Advanced Structural and Functional Characterization
RESEARCH UNITS
Advanced Structural and Functional Characterization
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The Functional Surfaces and Interfaces Research Unit is formed by two Research Groups: the Functional Nanomaterials and Surfaces (FunNanoSurf) group and the Physical Chemistry of Surfaces and Interfaces (Surfaces) group.
Both groups have in common the study at the nanoscale of structural and electronic properties of nanostructures, surfaces and interfaces.
The FunNanoSurf group focuses more on molecular-based, supramolecular and polymeric aggregates.
The Surfaces group on the synthesis, characterization and manipulation of organic semiconductor surfaces and interfaces.
The Nanostructured Materials for Optoelectronics and Energy Harvesting Research Unit is formed by two Research Groups that focus their activities on materials for energy applications: the Nanostructured Materials for Optoelectronics and Energy Harvesting (NANOPTO) group and the Laser Processing (LASER) group.
The NANOPTO group studies the synthesis, characterization and application of semiconducting structures for organic and perovskite photovoltaics, organic thermoelectrics, and photonics.
The LASER group is focused on the preparation of nanostructures functional materials using multiple laser techniques.
The Smart Molecular Inorganic and Hybrid Materials Research Unit is formed by two groups who work especially with inorganic chemistry for biomedical applications, among others: the Inorganic Materials and Catalysis (LMI) group, and the Nanoparticles and Nanocomposites (NN) group.
The LMI group studies the synthesis, preparation and characterization of boron-based compounds, such as carboranes, borane clusters and MOFs, for energy and biomedical applications, such as BNCT for cancer treatment.
The NN group focuses its research in the synthesis and characterization of small inorganic nanoparticles or thin films for information technology or biomedical applications, and studies the interaction between these elements and the biological systems, such as cells or the model organism C. elegans.
The SOLID STATE CHEMISTRY research unit focuses on solid state transformations and processes that lead to new inorganic, polymeric, nanocarbon and nanostructured hybrid materials with direct applications in energy, electronics and biomedicine. The design of novel phases, based on crystal chemical criteria, and their modification by cationic and anionic chemical/electrochemical doping and by modulation of the microstructure, is among the major objectives, as well as the dynamic action of those materials through mixed valence changes and intercalation processes and the study of the reaction mechanisms including operando techniques. The development of new synthetic methodologies, specific for each targeted phase, is a defining feature of the research unit. The research lines focus on materials for high energy battery technologies, electroactive materials for neural growth, metal organic frameworks with applications as biomaterials, inorganic and carbon nanomaterials for biomedicine and (oxy)nitrides with photocatalytic and electronic properties.
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Research Scientist
Tenured Scientist
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Tenured Scientist
Postdoctoral Researcher
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Postdoctoral Researcher
Lab. Technician
Lab. Technician
Lab Technician
Project Manager
The Superconducting Materials and Large Scale Nanostructures (SUMAN) Research Unit is formed by a Research Group with the same name that focuses on the synthesis, preparation and characterization of high-temperature superconducting materials. The idea is to find low-cost processes to be able to scale up the production of this kind of materials and make them competitive for power applications.
Research Professor
Research Professor
Research Scientist
Tenured Scientist
Tenured Scientist
Emeritus Tenured Scientist
Tenured Scientist
Tenured Scientist
Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
The Molecular Nanoscience and Organic Materials (NANOMOL) Research Unit focuses on the study, synthesis and processing of molecular and polymeric materials with biomedical, electronic, magnetic and chemical properties.
NANOMOL is composed by two research groups: “Molecular Materials for Electronic Devices” (e-MolMat) and "Nanostructured Molecular Materials for Biomedicines" (NANOMOL-BIO).
eMolMat is focused on the design and synthesis of organic molecules and materials for their integration in electronic devices such as memories, switches, transistors or sensors. Both fundamental studies and proof-of-concept devices are pursued.
NANOMOL-BIO is devoted to the synthesis, physico-chemical characterization and development, up to pre-clinical regulatory phases, of molecular and polymeric (nano)materials for biomedical applications: (i) biomolecule and small molecule delivery, (ii) diagnosis, (iii) regenerative medicine and (iv) immunotherapy.
NANOMOL is member of the Biomedical Research Network (CIBER) in the area of Bioengineering, Biomaterials and Nanomedicine; and is awarded with the TECNIO label given to Catalan research groups with high innovative and tech transfer capacities.
In the Magnetic Material and Functional Oxides department at ICMAB, the activities of the Crystallography of Magnetic and Electronic Oxides and Surfaces group are addressed to explore, understand and develop new strongly correlated materials of interest in fundamental Condensed Matter research and as novel materials for the Information technologies.
The activities of the group are based on the application of chemical and magnetic crystallography methods to the investigation of emergent functional oxides. Combining an intensive use of Large Scale Facilities (such as neutron and synchrotron sources) with symmetry analysis methodologies, we investigate the symmetry-properties relationship associated to structural, magnetic or electronic orders in functional oxides.
Current research lines include the study of structure-properties relationship in new magnetic, multiferroic and magnetoelectric materials with special charge, spin or electronic orders, and the study of novel oxides with giant responses for technological applications. In addition to bulk materials and films, surface diffraction synchrotron techniques and surface characterization methods are also applied to the study of ordering related phenomena in low-dim systems.
The neutron scattering in the field of magnetic and electronic materials presents extraordinary importance. To probe magnetic properties on atomic scale, neutron diffraction is an established technique and a unique method of choice, which allows perfect quantitative data interpretation. The magnetic moment of the neutron makes it a unique probe for magnetic properties in condensed matter on atomic scale. It gives a direct access to the spin and orbital distribution in the unit cell. In particular, magnetic structure determination is the foyer to the understanding of many fundamental phenomena in Condensed Matter research. Neutron and synchrotron techniques can be applied to investigate spin-state transitions, charge and orbital ordering, giant magneto-resistance, magnetoelectric materials as well as other emergent phenomena in frustrated materials such as spin ice, spin liquid behavior or other promising topological defects.
Multiferroics are important functional materials featuring strongly coupled order parameters that can be manipulated by external fields. Magnetoelectric multiferroics are receiving enormous attention as they open the road to new forms of multifunctional devices. However, they challenge our fundamental understanding of magnetic and ferroelectric order because a strong magnetoelectric coupling is incompatible with traditional mechanisms of ferroelectricity. The recent discovery of a new class of materials (type-II multiferroics) in which the magnetic and electric properties are strongly coupled is attracting very much interest because of the possibility to manipulate magnetism and spins by electric fields and vice-versa, to magnetically control electric charges. Future applications in information technology require new multiferroic materials fulfilling all technological requirements. Along with its technological functionalities, multiferroics are also of great interest in fundamental research into strongly correlated oxides and quantum matter.
Cobalt oxides present a plethora of very interesting properties like metal-insulator transitions, spin-state changes, giant magnetoresistance, double-exchange, phase separation, high thermoelectric power, oxygen diffusivity, mixed-conduction, charge and orbital ordering or superconductivity among others. These properties are interesting not only from a fundamental point of view but also due to their potential applicability in different fields. One very remarkable characteristic of many cobalt compounds is the ability of Co ions to adopt different spin states. This makes that Co oxides have, in comparison with other transition metal oxides, an extra degree of freedom: the spin state of Co. So, the investigation of novel cobaltites with different structures and prepared in different forms is between the most attractive opportunities within strongly correlated systems: the spin state of Co at selected sites in the structure plays a key role in the structural, magnetic, magnetotransport properties, electronic and ion mobility or the thermoelectric power. This research is inscribed inside the wider objective of understand and control the spin state and electronics degrees of freedom of Co cations, especially with 3+ valence. Trivalent cobalt oxides exhibit unique electronic phases characterized by the interplay between nearly degenerate spin states.
The Molecular Materials for Electronic Devices (eMolMat) group is focused on the design and synthesis/preparation of new functional molecular materials for their application in organic/molecular electronic devices. This is an interdisciplinary group where researchers from different disciplines (i.e., chemistry, materials science, physics, engineering, etc.) are working together. Our work ranges from fundamental studies in order to better understand materials properties to a more applied perspective aiming at developing proof-of-principle devices.
Particularly, our areas of interest include synthesis of novel functional molecules (electroactive molecules, organic radicals, etc.), surface self-assembly, crystal engineering, molecular switches, organic field-effect transistors (OFETs) and electrolyte-gated field-effect transistors (EGOFETs), charge transport and organic-based (bio)-sensors.
Ramon y Cajal Researcher
Postdoctoral Researcher
The main scientific topics of the group are related to the preparation and characterization of novel organic molecular materials and their application in molecular electronic devices.
In particular, our interests include:
Research Professor
Research Professor
Research Professor
ALBA Scientist
The group interests relate to the fields of nanoscience and nanotechnology, particularly the areas of molecular electronics, molecular magnetism and biology. We design molecular systems capable of providing inputs at the nano-scale and focus our efforts in the control and organization of such species on different surfaces/nanodevices.
The main areas of expertise are
A main project in the group is the creation of advanced molecular systems that can be accomodated (hence, be inserted) within graphene electrodes toward the creation of robust hybrid three-terminal nanodevices. My view involves the synthesis of the desired molecules (curcuminoid (CCMoids)/porphyrinoid (PPDS) in nature), their characterization in bulk (solid state and studies in solution) and deposition on graphene electrodes. In a first stage such systems can act as nano-wires, capable exclusively of electronic transport however, coordination of such systems to metallic centers can provide additional propertie highly interesting in spintronics toward the creation of switches and memory nanodevices.
Our goal is the control of the properties and study of deposition of such molecules having as a final step the I-V measurements of the final nanodevices. With this in mind, we collaborate with international groups (STM, MCBJ and BJ techniques) and perform the measurements ourselves by the use of a cryogenic probe station.
This project is linked to an ERC-consolidator Grant (Acronym: Tmol4TRANS).
A major aim of crystal engineering and supramolecular chemistry is the rational synthesis of metallo-aggregates and self-assembled systems with new functions based on novel magnetic properties, light responsiveness, biomedical applications, catalytic activity, fluorescence, or redox properties, among others. These useful and interesting properties may lead to the application of such assemblies, as for example: in sensors, compact information storage devices for next-generation computers, catalysts in industrial processes and medical applications (such as implants, contrast agents for CAT scans,…).
The goal here is the design, synthesis and characterization, with a strong emphasis on the material properties, of these novel species. This approach involves the specific combination of polydentate ligands (curcuminoid (CCMoids)/porphyrinoid (PPDS)) that can accommodate a number of metallic/metalloid centers, providing interesting optic and/or electronic features. Additional bridging ligands may also be used to facilitate the creation of different architectures (1D (chains), 2D (layers) and 3D (MOFs, coordination polymers).
Considering this major aim, our projects include detailed spectroscopic characterizations of the final species by advanced techniques (SQUID, EPR, NMR, electrochemistry, fluorecence studies, …) as well as deposition in different surfaces/electrodes (functionalized or not, Au, graphene, Si/SiO2, using different techniques as for example µ-CP, micro-contact printing) of the final species, then studies of the created substrates (AFM, TEM, SEM, STM, XPS,…) and electronic/optical final properties (creation of three-terminal devices, confocal microscopy, etc).
Closely related to nanotechnology, many promising advanced materials are based on magnetic principles. At the nanoscale such features can be related to the paramagnetic behavior of coordination compounds (0D). Therefore, a most challenging project is the development of organic-inorganic hybrid materials, with emphasis in such property.
Here, I am interested in develop materials with 3d/4f centers with emphasis in the control of coordination of such systems, their magnetic characterization and nano-structuration. Regarding the last part, coordination molecules are soft-materials and it is crucial to determine the optimal deposition method/s toward the creation of robust systems.
The design, characterization and study of properties of such systems are closely related to the techniques described in the other lines. Overall. the three lines unify in the general idea of making functional materials based on molecules taking advantages on the properties of the organic ligand (curcuminoid (CCMoids)/ porphyrinoid (PPDS)) and/or the metallic center.
Focused on unraveling and controlling the nanoscale structural and electronic properties of nanostructures and interfaces through surface engineering. Devoting special effort to organic materials, part of our investigation centers on organic semiconductors with relevance as active layers for electronic devices (such as organic solar cells and organic field effect transistors).
Our research spans from fundamental issues in organic growth to the electronic response of metal-organic junctions within two main research activities:
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Tenured Scientist
Tenured Scientist
Research Scientist
Research group focused on the development and integration of new materials, basically nanometric oxide thin films, and the exploration of their use in photovoltaics, electronics, spintronics, data storage and computing. These broad and scientifically challenging objectives are currently major social demands, as silicon-based electronics is reaching its limit in size, speed and efficiency, and radically new approaches, energy sustainable, are needed.
Specifically, current activities include
Research Professor
Tenured Scientist
Tenured Scientist
Tenured Scientist
Tenured Scientist
Ramon y Cajal researcher
ICREA Research Professor – UAB
ERC Scientist
Posdoctoral Researcher
Posdoctoral Researcher
Posdoctoral Ramón y Cajal
Research Professor
Research Scientist
Research Scientist
Tenured Scientist
Tenured Scientist
The group focuses on producing and characterizing advanced semiconducting structures with the main objective of understanding their fundamental behavior in order to tailor and improve their functionalities and empower different applications in the areas of optoelectronics, energy-related, and sensing devices.
The group is divided into 4 different research activities:
Research Professor ICREA
Research Scientist
Research Scientist
Research Scientist
Tenured Scientist
Tenured Scientist
Postdoctoral Researcher
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Research Professor
Research Professor
Research Scientist
Tenured Scientist
Ramon y Cajal Researcher
Postdoctoral Researcher
Postdoctoral Researcher
Emeritus Research Professor
Research Scientist
Tenured Scientist
ICREA Research Professor
Tenured Scientist
Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
NANOMOL-BIO is devoted to the synthesis, physico-chemical characterization and development, up to pre-clinical regulatory phases, of molecular and polymeric (nano)materials for biomedical applications:
Molecular Materials for Therapy:
Molecular Materials for Diagnosis:
Research Scientist
Director of Nanomol-TECNIO
Principal Investigator of Nanomol at CIBER-BBN
Head of the Nanomol-Bio Group
Tenured Scientist
Tenured Scientist
Emeritus Research Professor
Ramon y Cajal Researcher and Max Planck Partner Grup Leader
CIBER- Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
Postdoctoral Researcher
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Executive Assistant
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Direction
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC
Carrer dels Til·lers s/n
Campus UAB
08193, Bellaterra
Catalunya, Spain
By email:
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By phone:
+34 935801853
CIC biomaGUNE
Spain
School of Chemical & Biomolecular Engineering - Georgia Institute of Technology
USA
Technische Universität München, Physik Department
Germany
Applied Superconductivity Center, National High Magnetic Field Laboratory
USA
Università di Trieste1 and CIC biomaGUNE2
1Italy, 2Spain
Lehigh University
USA
Director - W. M. Keck Smart Mat. Int. Lab.
USA
Scuola Internazionale Superiore di Studi Avanzati (SISSA)
Italy
Laboratoire de Physico-Chimie, Pharmacotechnie et Biopharmacie
France
Helmholtz Zentrum Berlin Mat & Energie GmbH
Germany
University of Cambridge, Department of Materials Science & Metallurgy
UK
Collège de France, Chimie du solide et de l'énergie
France
Goethe-Universität Frankfurt am Main
Universitat Politècnica de València
Chalmers University of Technology
Karlsruhe Institute of Technology
Scientific Advisory Board
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC
Carrer dels Til·lers s/n
Campus UAB
08193, Bellaterra
Catalunya, Spain
By email:
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By phone:
+34 935801853
The Scientific Executive Board (SEB) is formed by the Direction team (Director and Deputy Directors), the members of the Severo Ochoa Strategic Managing Unit, and the coordinators of the 5 research lines (RL) of the Institute.
The SEB is in charge of taking decisions regarding the scientific strategy that the ICMAB follows. It also is in charge of deciding the strategic priority actions of the center and or organizing the Scientific Advisory Board (SAB) meeting, held once a year at ICMAB.
Scientific Executive Board
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC
Carrer dels Til·lers s/n
Campus UAB
08193, Bellaterra
Catalunya, Spain
By email:
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By phone:
+34 935801853
The Institute Governing Board is the governing body formed by Direction (as President), Deputy Direction, General Manager (as Secretary), by one member of each Department and by the Staff representatives.
The Institute Governing Board meets twice per year and is in charge of taking some important decisions concerning the Institute.
Institute Governing Board
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC
Carrer dels Til·lers s/n
Campus UAB
08193, Bellaterra
Catalunya, Spain
By email:
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By phone:
+34 935801853
The Scientific Board (el Claustre) is formed by the Direction team (Director and Deputy Directors), the General Manager and by all the permanent scientists (Research Professors, Research Scientists and Tenured Scientists) of the Institute.
Scientific Board
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC
Carrer dels Til·lers s/n
Campus UAB
08193, Bellaterra
Catalunya, Spain
By email:
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By phone:
+34 935801853
Dr. Arevik Musheghyan (Postdoctoral contract)
Dr. Chinwe Nwanya (Women for Africa Programme, University of Nigeria)
Mr. Pablo García Lebière (PhD, ICMAB - UAB)
Mr. Gerard Felipo i Esteve (Degree final project - UAB)
Mr. Roger Garreta Piñol (Degree final project - UAB)
Ms. Emma Poupard (Internship, Polytech Nantes)
Mr. Colin Duchassouy (Internship, Centrale Lille Institut)
Mr. Pablo Gómez Montañez (Joves i Ciencia, 2022)
Mr. Daniel Eduardo Monjaraz (Internship, CICESE Mexico)
Mr. Jeremy D'Arcangeli Escobar (Degree final project - UAB)
Dr. Yasmín Esqueda (Postdoc, CICESE, México)
Mr. Pablo García Lebière (PhD, ICMAB - UAB)
Mr. Alifhers Salim Mestra (PhD stay - PUCV, Chile)
Mr. Carlos García (Degree final project - UAB)
Mr. Roger Morales (Degree final project - UAB)
Mr. Faïz Attoumani (Internship, Polytech Nantes)
Ms. Blanca Gilabert López (Joves i Ciencia, F. Catalunya - La Pedrera)
Mr. Nick Toledo García (Internship, UB)
Ms. Anna Pérez Serrano (Internship, UB)
Mr. Alexandre Pinsach Gelabert (Internship, UB)
Mr. Gerard Felipo i Esteve (Degree final project - UAB)
Matrix Assisted Pulsed Laser Evaporation of hybrid nanocomposites
Laser Direct Write of nanostructured systems
Advanced nanomaterials for energy and environmental applications
"Temperature-modulated synthesis of vertically oriented atomic bilayer graphene nanowalls grown on stainless steel by inductively coupled plasma chemical vapour deposition"
E.Bertran-Serra, A. Musheghyan-Avetisyan, S. Chaitoglou, R. Amade-Rovira, I. Alshaikh, F. Pantoja-Suárez, J.L. Andújar-Bella, T. Jawhari, A. Perez del Pino, E. Gyorgy
Applied Surface Science 610 (2023) 155530
"Laser processing of graphene and related materials for energy storage: State of the art and future prospects"
R. Kumar, A. Pérez del Pino, S. Sahoo, R. K. Singh, W. K. Tan, K. K. Kar, A. Matsuda, E. Joanni
Progress in Energy and Combustion Science 91 (2022) 100981 .
"Unravelling the origin of the capacitance in nanostructured nitrogen-doped carbon - NiO hybrid electrodes deposited with laser"
P. García Lebière, E. György, C. Logofatu, D. Naumenko, H. Amenitsch, P. Rajak, R. Ciancio, A. Pérez del Pino
Ceramics International 48 (2022) 15877.
"Meteorite controlled ablation under low vacuum studied using emission spectroscopy: a technique to sample the bulk composition of asteroids"
J. M. Trigo-Rodriguez, A. Pérez del Pino, E. Peña-Asensio, A. Rimola.
52nd Lunar and Planetary Science Conference 2021. p. 1384
"Laser synthesis of NixZnyO/reduced graphene oxide/carbon nanotube electrodes for energy storage applications"
P. García Lebière, A. Pérez del Pino, C. Logofatu, E. György
Applied Surface Science 563 (2021) 150234
"Boost of Charge Storage Performance of Graphene Nanowall Electrodes by Laser-Induced Crystallization of Metal Oxide Nanostructures"
Y. Esqueda-Barrón, A. Pérez del Pino, P. García Lebière, A. Musheghyan-Avetisyan, E. Bertran-Serra, E. György, C. Logofatu
ACS Appl. Mater. Interfaces 13 (2021) 17957−17970
"Laser fabrication of hybrid electrodes composed of nanocarbons mixed with cerium and manganese oxides for supercapacitive energy storage"
P. García Lebière, A. Pérez del Pino, G. Domènech Domingo, C. Logofatu, I. Martínez-Rovira, I. Yousef, E. György
Journal of Materials Chemistry A 9 (2021) 1192
"Deposition and Growth of Functional Nanomaterials by LDW and MAPLE Techniques"
A. Pérez del Pino
Crystals 10 (2020) 1066
"Laser synthesis of TiO2–carbon nanomaterial layers with enhanced photodegradation efficiency towards antibiotics and dyes"
R. Ivan, A. Pérez del Pino, I. Yousef, C. Logofatu, E. György
Journal of Photochemistry & Photobiology A: Chemistry 399 (2020) 112616
"New fabrication method for producing reduced graphene oxide flexible electrodes by using low-power visible laser diode engraving system"
A. Chuquitarqui, L. C. Cotet, M. Baia, E. Gyorgy, K. Magyari, L. Barbu-Tudoran, L. Baia, M. Díaz-González, C. Fernandez Sanchez, A. Perez del Pino
Nanotechnology 31 (2020) 325402
"Enhanced UV-Vis Photodegradation of Nanocomposite Reduced Graphene Oxide/Ferrite Nanofiber Films Prepared by Laser-Assisted Evaporation"
A.Queraltó, E.György, R.Ivan, A.Pérez del Pino, R.Frohnhoven, S. Mathur
Crystals 10 (2020) 271
"Carbon–based nanomaterials and ZnO ternary compound layers grown by laser technique for environmental and energy storage applications"
R.Ivan, C.Popescu, A.Pérez del Pino, C.Logofatu, E. György
Applied Surface Science 509 (2020) 145359
"Laser-induced synthesis and photocatalytic properties of hybrid organic-inorganic composite layers"
R. Ivan, C. Popescu, A. Pérez del Pino, I. Yousef, C. Logofatu, E. György
Journal of Materials Science 54 (2019) 3927–3941
"Enhancement of supercapacitive properties of laser deposited graphene-based electrodes through carbon nanotube loading and nitrogen doping"
A. Pérez del Pino, M. Rodríguez López, M. A. Ramadan, P. García Lebière, C. Logofatu, I. Martínez-Rovira, I. Yousef, E. György
Physical Chemistry Chemical Physics 21 (2019) 25175 - 25186
"A review on synthesis of graphene, h-BN and MoS2 for energy storage applications: Recent progress and perspectives"
R. Kumar, S Sahoo, E. Joanni, R K Singh, R. M. Yadav, R. K. Verma, D. P. Singh, A. Pérez del Pino, S. A. Moshkalev
Nano Research 12 (2019) 2655–2694
"Mineralization-inspired synthesis of magnetic zeolitic imidazole framework composites"
M. Hoop, A. Terzopoulou, X. Z. Chen, A. M. Hirt, M. Charilaou, Y. Shen, F. Mushtaq, A. Pérez del Pino, C. Logofatu, L. Simonelli, A. J. deMello, P. Falcaro, C. J. Doonan, B. J. Nelson, J. Puigmartí-Luis, S. Pané
Angewandte Chemie 131 (2019) 13684–13689
E. György, C. Logofatu, A. Pérez del Pino, A. Datcu, O. Pascu, R. Ivan
Ceramics International 44 (2018) 1826-1835
"Ultrafast Epitaxial Growth of Functional Oxide Thin Films by Pulsed Laser Annealing of Chemical Solutions"
A. Queraltó, A. Perez del Pino, M. de la Mata, J. Arbiol, M. Tristany, X. Obradors, T. Puig
Chemistry of Materials 28 (2016) 6136-6145.
"Titanium oxide – reduced graphene oxide – silver composite layers synthesized by laser technique: wetting and electrical properties"
E. György, A. Perez del Pino, A. Datcu, L. Duta, C. Logofatu, I. Iordache, A.Duta
Ceramics International 42 (2016) 16191–16197.
"Laser-induced Chemical Transformation of Free-standing Graphene Oxide Membranes in Liquid and Gas Ammonia Environments"
A. Pérez del Pino, E. György, C. Cotet, L. Baia, C. Logofatu
RSC Advances 6 (2016) 50034.
"Direct multipulse laser processing of titanium oxide – graphene oxide nanocomposite thin films"
A. Pérez del Pino, A. Datcu, E. György
Ceramics International 42 (2016) 7278–7283.
"Ultraviolet pulsed laser crystallization of Ba0.8Sr0.2TiO3 films on LaNiO3-coated silicon substrates"
A. Queraltó, A. Pérez del Pino, M. de la Mata, M. Tristany, X. Obradors, T. Puig, S. Trolier-McKinstry
Ceramics International 42 (2016) 4039-4047.
"Growth of ferroelectric Ba0.8Sr0.2TiO3 epitaxial films by UV pulsed laser irradiation of chemical solution derived precursor layers"
A. Queraltó, A. Pérez del Pino, M. de la Mata, J. Arbiol, M. Tristany, A. Gómez, X. Obradors, T. Puig
Applied Physics Letters 106 (2015) 262903.
"One-step preparation of nitrogen doped titanium oxide / Au / reduced graphene oxide composite thin films for photocatalytic applications"
A. Datcu, L. Duta, A. Pérez del Pino, C. Logofatu, C. Luculescu, A. Duta, E. György
RSC Advances 5 (2015) 49771.
"Laser-induced chemical transformation of graphene oxide – iron oxide nanoparticles composites deposited on polymer substrates"
A. Pérez del Pino, E. György, C. Logofatu, J. Puigmartí-Luis, W. Gao
Carbon 93 (2015) 373-383.
"Ultrafast crystallization of Ce0.9Zr0.1O2-y epitaxial films on flexible technical substrates by pulsed laser irradiation of chemical solution derived precursor layers"
A. Queraltó, A. Perez del Pino, M. de la Mata, J. Arbiol, X. Obradors, T. Puig.
Crystal Growth & Design 15 (2015) 1957-1967.
"Wetting and photoactive properties of laser irradiated zinc oxide – graphene oxide nanocomposite layers"
A. Datcu, A. Pérez del Pino, C. Logofatu, A. Duta, E. György
2015 - NATO Science for Peace and Security Series A-Chemistry and Biology, 119-125.
"Resonant Infrared and Ultraviolet Matrix Assisted Pulsed Laser Evaporation of Titanium Oxide / Graphene Oxide Composites: A Comparative Study"
S. M. O’Malley, J. Tomko, A. Pérez del Pino, C. Logofatu, E. György
The Journal of Physical Chemistry C 118 (2014) 27911-27919.
"Simultaneous Laser-Induced Reduction and Nitrogen Doping of Graphene Oxide in Titanium Oxide / Graphene Oxide Composites"
E. György, A. Pérez del Pino, C. Logofatu, C. Cazan, A. Duta
Journal of the American Ceramic Society 97 (2014) 2718.
"Wetting and photoactive properties of laser processed zinc oxide - graphene oxide nanocomposite thin layers"
E. György, A. Pérez del Pino, C. Logofatu, A. Duta
Journal of Applied Physics 116 (2014) 024906.
"Ultraviolet pulsed laser irradiation of multi-walled carbon nanotubes in nitrogen atmosphere"
A. Pérez del Pino, E. György, B. Ballesteros, L. Cabana, G. Tobias
Journal of Applied Physics 115 (2014) 093501.
"Localized template growth of functional nanofibers from an amino acid-supported framework in a microfluidic chip"
J. Puigmartí-Luis, M. Rubio-Martínez, I. Imaz, B. Z. Cvetković, L. Abad, F. J. del Campo, A. Pérez del Pino, D. Maspoch, D. B. Amabilino
ACS Nano 8 (2014) 818-826
"Study of the deposition of graphene oxide sheets by matrix assisted pulsed laser evaporation"
A. Pérez del Pino, E. György, C. Logofatu, A. Duta
Journal of Physics D: Applied Physics 46 (2013) 505309.
"Effect of laser radiation on multi-wall carbon nanotubes: study of shell structure and immobilization process"
E. György, A. Pérez del Pino, J. Roqueta, B. Ballesteros, L. Cabana, G. Tobias
Journal of Nanoparticles Research 15 (2013) 1852.
"Laser-induced metal organic decomposition for doped CeO2 epitaxial thin film growth"
A. Queraltó, A. Pérez del Pino, S. Ricart, X. Obradors, T. Puig
Journal of Alloys and Compounds 574 (2013) 246-254.
"Processing and immobilization of chondroitin-4-sulphate by UV laser radiation"
E. György, A. Pérez del Pino, J. Roqueta,A.S. Miguel, C. Maycock, A. G. Oliva
Colloids and Surfaces B: Biointerfaces 104 (2013) 169-173.
"Laser processing and immobilisation of CdSe/ZnS core-shell quantum dots"
E. György, J. Roqueta, B. Ballesteros, A. Pérez del Pino, A.S. Miguel, C. Maycock, A. G. Oliva
Physica Status Solidi A 11 (2012) 2201-2207
"Deposition of Functionalized Single Wall Carbon Nanotubes through Matrix Assisted Pulsed Laser Evaporation"
A. Pérez del Pino, E. György, L. Cabana, B. Ballesteros, G. Tobias
Carbon 50 (2012) 4450 - 4458
"Polycarbonate films metalized with a single component molecular conductor suited to strain and stress sensing applications"
E. Laukhina, Lebeded, V. Laukhin, A. Pérez del Pino, E. B. Lopes, A. I.S. Neves, D. Belo, M. Almeida, J. Veciana, C. Rovira
Organic Electronics 13 (2012) 894-898
"Synthesis and characterization of Ag nanoparticles and Ag loaded TiO2 photocatalysts"
G. Sauthier, A. Pérez del Pino, A. Figueras, E. György
Journal of American Ceramic Society 94 (2011) 3780
"Synthesis and laser immobilisation onto solid substrates of CdSe/ZnS core-shell quantum dots"
E. György, A. Pérez del Pino, J. Roqueta, B. Ballesteros, A.S. Miguel, C. Maycock, A. G. Oliva
Journal of Physical Chemistry C 115 (2011) 15210
"Effects of Pulsed Laser Radiation on Epitaxial Self-assembled Ge Quantum Dots Grown on Si Substrates"
A. Pérez del Pino, E. György, I. C. Marcus, J. Roqueta, M. I. Alonso
Nanotechnology 22 (2011) 295304
"Processing and immobilization of Ribonuclease A through laser irradiation"
C. Popescu, J. Roqueta, A. Pérez del Pino, M. Moussaoui, M. V. Nogués, E. Gyorgy
Journal of Materials Research 26 (2011) 815
"Guided Assembly of Metal and Hybrid Conductive Probes Using Floating Potential Dielectrophoresis"
Josep Puigmartí-Luis, Johannes Stadler, Daniel Schaffhauser, Ángel Pérez del Pino, Brian R. Burgcand Petra S. Dittrich
Nanoscale 3 (2011) 937-940
"Boosting electrical conductivity in a gel-derived material by nanostructuring with trace carbon nanotubes"
D. Canevet, A. Pérez del Pino, D. B. Amabilino, M. Sallé
Nanoscale 3 (2011) 2898-2902
"Nanocomposites combining conducting and superparamagnetic components prepared via an organogel"
E. Taboada, L. N. Feldborg, A. Pérez del Pino, A. Roig, D. B. Amabilino, J. Puigmartí-Luis
Soft Matter 7 (2011) 2755-2761
"Tunable optical and electrical properties of pulsed laser deposited WO3 and Ag-WO3 nanocomposite thin films"
E. Gyorgy, A. Pérez del Pino
Journal of Materials Science 46 (2011) 3560
ummary: The use of electrochemical methods in the preparation of new materials and the tuning of their properties by cation and anion doping in soft synthesis conditions. —– Applications in new concepts in energy storage, new mixed conducting phases, or electrostimulation of biological systems
The electrochemical doping, intercalation in mixed valence systems and synthesis of oxides was initiated in the origin of the Department , led then by three researchers. Then, the specific line, supported up to three fourths of the Department budget thanks to National and European Grants, as well as Marato TV3 projects and industry contracts.
With a focus in mixed valence, mixed ionic-electronic conducting systems, the line has developed:
a) new solid state transformations and materials (AgCuO2)
b) large changes in physical properties of materials by electrochemical reduction (polyoxometalates, vanadates), electrochemical oxygen intercalation (La2CuO4, LnCaMnO4,…), electrocatalysis in O2 evolution and CO2 reduction
c) electrodeposition (YBa2Cu3O7, IrOx, polypyrrole-PEDOT-X, hybrids IrOx-nanocarbons, Bi in Xray detectors)
d) use of electrochemistry in neural cell development
e) and bipolar electrochemistry effects inducing non contact electrochemistry and its application in energy storage and bioelectrochemistry effects.
Direct applications of those studies are found in 2D materials exfoliation, energy storage (supercapacitors with enhanced charge capacity, electrocatalysts in nanoform (POM) or coatings), and electroestimulation bioelectrodes. But also in fundamental aspects of the use of electrochemical processes to study the physicochemistry of materials.
CONTACT
1.- Intercalation processes that lead to notable changes in physical properties in bulk and thin layer forms lead to electrodes of various configurations that can be applied in tuning of materials properties, structure, energy storage, transport or in biological applications.
La2-xSrxCuO4 structure in which oxygen intercalation is possible by electrochemical oxidation resulting in induction of superconducting properties with higher Tc values. The Mn equivalent behaves equally, resulting in dramatic changes in its magnetic properties
Direct RT electrochemical solid state transformation of Ag2Cu2O3 into Ag2Cu2O4
The same electrochemical treatment induces structure transformations in solid state at room temperature. Ej. Ag2Cu2O3 to Ag2Cu2O4 as shown below 1 O atom “intercalated” per unit formula. Pass from a 3D structure to a 2D one at r.t. !!!!; The final phase is a peculiar case where all elements are shown to be in mixed valence states.
Ag2CuMnO4 represents the first delafossite with Cu/Mn ordered with a 2D structure . Ferromagnetic coupling within the layers is coupled with Antiferromagnetic exchange among layers joined by Ag ions
Dalton Transactions, 2016, DOI: 10.1039/C6DT03986C
Oxidazing conditions render layered Silver-Copper oxides . In some cases are metallic, Ag2Cu2O4, in some others , ferromagnetic, Ag2CuMnO4 or Ag2Cu3Cr2O8(OH)4. In the last two cases, a significant difference lies on the connection among Cu-O layers. In one case direct bonding through Ag orbitals allows further antiferromagnetic coupling at lower temperatires, rendering a ferro-antiferrotransition. In the other Cu-O layers behave as completely isolated from each other.
Ag2CuMnO4 represents the first delafossite with Cu/Mn ordered with a 2D structure . Ferromagnetic coupling within the layers is coupled with Antiferromagnetic exchange among layers joined by Ag ions
Electrochemically exfoliated graphene in non -surfactant aqueous media
Anodic exfoliation in presence of surfactants or without them , has been possible from Carbon in the form of graphite. The pristine graphene obtained shows no defects as compared with the reduced graphene oxide, and has yielded a series of hybrid materials with a superior charge capacity useful in supercapacitors and electrostimulation electrodes
2.- Electrochemical reduction of Polyoxometalates, nanoclusters of W and Mo , have allowed to elucidate the influence of delocalized electrons in the magnetic properties at the nanoscale. Such study has been the base of the new studies of the role of POM as mediators in O2 evolution, and in M-O2 cells
Magnetic Properties of Mixed-Valence Heteropoly Blues. Interactions within Complexes Containing Paramagnetic Atoms in Various Sites as Well as “Blue” Electrons Delocalized over Polytungstate Frameworks” N. Casañ-Pastor and L.C.W. Baker, J. Am. Chem. Soc., (1992), 114, 10384-94.
Using polyoxometalates to enhance the capacity of lithium-oxygen batteries.Tom Homewooda, James T. Fritha, Nieves Casañ-Pastorb, Dino Tontib ,John R. Owena, Nuria Garcia-Araeza.Chem. Comm. 54 (69) , 2018, 9599-9602
Electrochemically exfoliated graphene in non -surfactant aqueous media
3.- Electrodeposition methods
Reduction of metal precursors in presence of complexing agents, and further annealing has allowed the synthesis of YBa2Cu3O7 on Ag wires. As an alternative electrophoresis of suspensions of the preformed oxide also yields coatings of the oxide as shown in the figure. The opposite electrodeposition, Ag on the oxide , difficult for the rich redox chemistry of the oxide , is also possible in certain conditions
4. Electroactive materials for biological applications.
Interfase studies with neural systems and Electrostimulation
IrOx electrodeposited transparent coatings as the best substrates for neural growth in absence of electric fields and in presence of them when amorphous. Thermal evolution results in rutile structures. A channel spongy- like original oxohydroxide results: IrOx(OH)y.nH2O with a local rutile-like structure. Dynamic deposition has allowed a fourfould increase in charge capacity for this iridium oxide, and fully improved adhesion to the substrate
Electrochemically exfoliated graphene in non -surfactant aqueous media
Cell culture studies on neural cortex cells from rat embryo , show survival above controls
(collaboration with HNP Toledo and IIBB-CSIC)
Conducting polymers based on polypyrrole or PEDOT with various counterions. Best cell growth when counterion is an aminoacid.
Thin coatings and interdigitated patterns as substrates for cell growth in absence and presence of electric fields
Cells survive significantly better in aminoacid containing polymers (collaboration with IIBB-CSIC)
Neuronal scratch response to ELECTRIC FIELD DC applications. And neurotransmitters release under field effects using IrOx-Graphene nanostructured electrodes
Large charge capacity electrodes such as IrOx-graphene allow DC electrostimulation without secondary effects due to radical formation. In that case, neurite extension is greatly enhanced above the effects of standard electrodes. Neurotransmitter release shows an enhancement in neural function under the electric field. http://dx.doi.org/10.1016/j.apmt.2016.12.002
5.- Bipolar electrochemistry effects in biosystems and electrochemical energy storage devices: Electrostimulation may be induced indirectly with a conducting un-connected substrate , an observation that opens up a new way of thinking on implants in biological systems
6. Redox Gradient Materials and Bipolar Electrochemistry
Iridium oxide redox gradient material: Operando X Ray absorption of Ir gradient oxidation states during IrOx bipolar electrochemistry. Laura Fuentes-Rodriguez, Llibertat Abad, Laura Simonelli, Dino Tonti, N. Casañ-Pastor* J. Phys. Chem. C, in press , july 2021
The Vanadyl Phosphate Dihydrate, a Solid Acid: The Role of Water in VOPO4.2H2O and Its Sodium Derivatives Nax(V(IV)xV(V)1-xO)PO4.(2-x)H2O.” N. Casan, P. Amorós, R. Ibañez, E. Martinez-Tamayo, A. Beltran-Porter and D. Beltran-Porter. J. Inclusion Phenomena, (1988), 6, 193-211.
Ring Currents in Wholly Inorganic Heteropoly Blue Complexes. Evaluation by a Modification of Evans’s Susceptibility Method.”, M. Kozik, N. Casan-Pastor, C.F. Hammer and L.C.W. Baker, J. Am. Chem. Soc., (1988), 110, 7697-7701
“Magnetic Properties of Mixed-Valence Heteropoly Blues. Interactions within Complexes Containing Paramagnetic Atoms in Various Sites as Well as “Blue” Electrons Delocalized over Polytungstate Frameworks” N. Casañ-Pastor and L.C.W. Baker, J. Am. Chem. Soc., (1992), 114, 10384-94
“First Ferromagnetic Interaction in a Heteropoly Complex: [Co4O14(H2O)2(PW9O27)2]10-. Experiment and Theory for Intramolecular Anisotropic Exchange Involving the Four Co(II) Atoms.” N. Casan-Pastor, J. Bas-Serra, E. Coronado, G. Pourroy and L.C.W. Baker, J. Am. Chem. Soc., (1992), 114, 10380-3.
“Electrochemical Oxidation of Lanthanum Cuprates. Superconductivity vs Thermal Treatment in La2CuO4+d. N. Casañ-Pastor, P. Gomez-Romero, A. Fuertes, J.M. Navarro, M.J. Sanchis, S. Ondoño-Castillo Physica C, (1993), 216 478-490
“Superconducting YBa2Cu3O7-d Wires by Simultaneous Electrodeposition of Y, Ba and Cu in Presence of Cyanide” S.Ondoño-Castillo, A. Fuertes, F. Perez, P. Gomez-Romero, N. Casañ-Pastor. Chem. Materials (1995), 7, 771
“Chemical Polymerization of Polyaniline and Polypyrrole by Phosphomolybdic Acid. In situ Formation of Hybrid Organic-Inorganic Materials” P. Gómez-Romero, N. Casañ-Pastor, M. Lira-Cantú Solid State Ionics (1997) 101-103, 875
“Dramatic Change in Magnetic Properties of Manganates Ca2-xLnxMnO4 by Low Temperature Electrochemical Oxidation in Fused Nitrates” C.R. Michel, R. Amigó and N. Casañ-Pastor. Chem. Materials (1999), 11, 195-197
“Evidence of Oxygen Mobility at low temperature by Electrochemical Oxidation of oxides. A Quartz Microbalance Study” N. Casañ-Pastor, C.R. Michel, C. Zinck, E.M. Tejada-Rosales.Chem. Mater.. (2001) 13, 2118-2126
Electrochemically induced reversible solid state reversible transformations: Electrosynthesis of Ag2Cu2O4 by room temperature oxidation of Ag2Cu2O3 D. Muñoz-Rojas, J. Oró, J. Fraxedas, P. Gómez-Romero, J. Fraxedas, N. Casañ-Pastor Electrochem. Comm. 4, (2002) , 684-689
“POLYOXOMETALATES: FROM INORGANIC CHEMISTRY TO MATERIALS SCIENCE” (review) N. Casañ-Pastor, P. Gómez-Romero. Frontiers in Bioscience 9, 1759-1770, 2004
Electronic Structure of Ag2Cu2O4 and its precursor Ag2Cu2O3. Oxidized mixed valence silver and copper and internal valence fluctuations” D. Muñoz-Rojas, G. Subías, J. Fraxedas, P. Gómez-Romero, N. Casañ-Pastor, J. Phys. Chem B (2005), 109, 6193-6203
“High Quality Silver Contacts on Ceramic Superconductors Obtained by Electrodeposition from Non aqueous Solvents” L. Angurel, J.M. Andrés, D. Muñoz- Rojas, N. Casañ-Pastor, .Supercond. Sci. Tecn. (2005), 18, 135-141
Ag2CuMnO4 : A new Silver Copper Oxide with Delafossite Structure.D. Muñoz-Rojas, G. Subías, M. Casas-Cabanas, J. Fraxedas, J. Oro-Sole, R. I. Walton, E. García, J. Gonzalez-Calbet, B. Martínez, and N. Casañ-Pastor* J. Solid State Chem. (2006) 179, 3883-3892
Electrochemically Functionalized Carbon Nanotubes and their Application to Rechargeable Lithium Batteries,M. Baibarac,* M. Lira-Cantú, J. Oró Sol, N. Casañ-Pastor and P. Gomez-Romero* Small:, 2006 , 2, 1075-1082
“Transport properties and Lithium Insertion study in the p-type Semiconductors AgCuO2 and AgCu0.5Mn0.5O2” F. Sauvage, D Muñoz-Rojas, K. Poeppelmeier, N. Casañ-Pastor. J. Solid State Chemistry , 2009, 182 , 374-382.
Neural Cell growth on Anatase TiO2 Coatings ” J. Collazos-Castro, A.M. Cruz, LL. Abad, J. Fraxedas, M. Lira-Cantú, M. Carballo-Vila, A. Pego, C. Fonseca, A. Sanjoan, N. Casañ-Pastor* Thin Solid Films , 518, (2009) 160-170
Rutile substrata for Neural Cell Growth. Mónica Carballo-Vila, Berta Moreno-Burriel, Jose R. Jurado, Eva Chinarro, A. Perez, Nieves Casañ-Pastor, and Jorge E. Collazos-Castro*Journal of Biomedical Materials Research: Part A, 90 (2009) 94-105
High Conductivity in hydrothermally-grown AgCuO2 single crystals verified using FIB-deposited nanocontacts. D. Muñoz-Rojas, R. Cordoba, A. Fern¡ndez-Pacheco, J. M. De Teresa, G. Sauthier, J. Fraxedas, R. I. Walton, N. Casañ-Pastor. Inorganic Chemistry, 49, 2010, 10977
The synthesis of graphene sheets with controlled thickness and order using surfactant-assisted electrochemical processes M. Alanyologlu, J. Oró, N. Casañ-Pastor. Carbon, 50, 2012 , 142. MOST CITED
Iridium Oxohydroxide, a Significant Member in the Family of Iridium Oxides. Stoichiometry, Characterization, and Implications in Bioelectrodes.A. M. Cruz, Ll. Abad, N. M. Carretero, J. Moral-Vico, J. Fraxedas, P. Lozano, G. Subias, V. Padial, M. Carballo, J. E. Collazos-Castro, and N. Casañ-Pastor*;J. Phys. Chem. C , 116 , 2012, 5155-5168
Iridium Oxide sensor for biomedical applications. Case urea-urease in real urine samplesElisabet Prats-Alfonso; Llibertat Abad; Nieves Casan-Pastor; Javier Gonzalo-Ruiz; Eva Baldrich Biosensors and Bioelectronics, 39, 2013, 163-169
Graded conducting titanium-iridium oxide coatings for bioelectrodes in neural systemsA.M. Cruz, N. Casañ-Pastor Thin Solid Films, 534, 2013, 316-324
Dynamic electrodeposition of aminoacid-polypyrrole on aminoacid-PEDOT substrates: Conducting polymer bilayers as electrodes in neural systems.“J. Moral-Vico, N. M. Carretero, E. Perez, C. Suñol, M. Lichtenstein, N. Casañ-Pastor , Electrochim. Acta 111 (2013), 250-260
Nanocomposites of iridium oxide and conducting polymers as electroactive phases in biological media.J. Moral-Vico,, S. Sanchez-Redondo, E. Perez, M. Lichtenstein, C. Suñol, N. Casañ-Pastor. Acta Biomaterialia, 10 (2014) 2177-218
IrOx-Carbon Nanotubes Hybrid:A Nanostructured Material for Electrodes with Increased Charge Capacity in Neural systems. Nina M. Carretero, Mathieu P. Lichtenstein, Estela Perez, Laura Cabana, Cristina Suñol,Nieves Casañ-Pastor*, Acta Biomaterialia, 10, 2014, 4548-4558 .
Enhanced charge capacity in Iridium Oxide-Graphene Oxide Hybrids. N. M. Carretero , M. P. Lichtenstein , E. Perez , S. Sandoval , G. Tobias , C. Suñol , N. Casan-Pastor * Electrochimica Acta, 157 (2015) 369-377
Coatings of Nanostructured Pristine Graphene-IrOx Hybrids for Neural Electrodes: Layered Stacking and the role of non-oxygenated Graphene.E. Perez, M. P. Lichtenstein, C. Suñol , N. Casan-Pastor*. Materials Science & Engineering C, 55, 2015, 218-226
A comparative study on surface treatments in the immobilization improvement of hexahistidine-tagged protein on the indium tin oxide surface. M.B. Ismail, N. Casañ-Pastor, E. Pérez, A. Soltani, A. Othmane J. Nanomed. Nanotechnol. 7 (372), 2016, 1-6. http://dx.doi.org/10.4172/2157-7439.1000372.
Short term electrostimulation enhancing neural repair in vitro using large charge capacity nanostructured electrodes. M.P. Lichtenstein, E. Pérez, L. Ballesteros, C. Suñol, N. Casañ-Pastor* Applied Materials Today 6, 2017, 29-43
Ag2Cu3Cr2O8(OH)4:A new bidimensional silver-copper mixed -oxyhydroxide with in-plane ferromagnetic coupling. Nieves Casañ-Pastor*, Jordi Rius, Oriol Vallcorba, Inma Peral, Judith Oró-Solé, Daniel S. Cook, Richard I. Walton, Alberto García, David Muñoz-Rojas. Dalton Transactions, 46, 2017, 1093-1104, DOI: 10.1039/C6DT03986C
Controlling Nerve Growth with an Electric Field Induced Indirectly in Transparent Conductive Substrate Materials. Ann M. Rajnicek, Zhiqiang Zhao, Javier Moral-Vico, Ana M. Cruz, Colin D. McCaig and Nieves Casañ-Pastor*. Advanced HealthCare Mat. Accepted June 2018. DOI: 10.1002/ adhm.20180047
Microstructure and electrical transport in electrodeposited Bi films. J.Moral-Vico, N.Casañ-Pastor, A.Camón, C.Pobes, R.M.Jáudenes, P.Strichovanec and L.Fàbrega. J. Electroanal. Chem. , 832, (2019), 40-47
Using polyoxometalates to enhance the capacity of lithium-oxygen batteries. Tom Homewood, James T. Frith, Nieves Casañ-Pastor, Dino Tonti ,John R. Owen, Nuria Garcia-Araez. Chem. Comm. 54 (69) , 2018, 9599-9602 .
Electric Field Gradients and Bipolar Electrochemistry effects on Neural Growth. A finite element study on inmersed electroactive conducting electrode materials. Ll. Abad, A. Rajnicek, N. Casañ-Pastor*. Electrochimica Acta , 317 (2019) 102-111 .
Charge delocalization, oxidation states and silver mobility in the mixed silver-copper oxide AgCuO2. Abel Carreras, Sergio Conejeros, Agustín Camón, Alberto García, Nieves Casañ-Pastor*, Pere Alemany*, Enric Canadell*. Inorg Chem, 58, 2019, 7026-7035. https://doi.org/10.1021/acs.inorgchem.9b00662
Nitro-graphene oxide in Iridium Oxide hybrids: Electrochemical modulation of N-graphene redox states and Charge capacities. E. Pérez, N. M. Carretero, S. Sandoval, A. Fuertes, G. Tobias, N. Casañ-Pastor*. Materials Chemistry Frontiers, 4, 2020, 1421 – 143
Nanocarbon-Iridium Oxide Nanostructured Hybrids as Large Charge Capacity Electrostimulation Electrodes for Neural Repair. N. Casañ-Pastor. Molecules 2021, 26, 4236.. Special issue: Electrochemical Applications of Carbon-Based Nanomaterials
Iridium oxide redox gradient material: Operando X Ray absorption of Ir gradient oxidation states during IrOx bipolar electrochemistry. Laura Fuentes-Rodriguez, Llibertat Abad, Laura Simonelli, Dino Tonti, N. Casañ-Pastor*. J. Phys. Chem. C, 2021 , 125 (30), 16629-16642. DOI: 10.1021/acs.jpcc.1c05012.
Induced dipoles and Possible modulation of Wireless effects in implanted electrodes. Effects of implanting insulated electrodes on an animal test to screen antidepressant activity. Perez-Caballero, H. Carceller, J. Nacher, V. Teruel-Marti, E. Pujades , N. Casañ-Pastor*, E. Berrocoso* J. Clinical Medicine, 2021, 10, 4003. https://doi.org/10.3390/jcm10174003. Special issue: “Advances in Neurostimulation: Understanding of the Mechanisms and Clinical Applications”
Dramatic drop in cell resistance through induced dipoles and bipolar electrochemistry. Fuentes-Rodríguez, Ll. Abad, E. Pujades, P. Gómez-Romero, D. Tonti, N. Casañ-Pastor*.J. Electrochem. Soc., 2022 , 169, 016508. https://doi.org/10.1149/1945-7111/ac492d
Nanostructured Electroactive Materials with Large Charge Capacity: Direct Field Electrostimulation through Connected and Non-connected Electrodes. Ann M. Rajnicek, Cristina Suñol and Nieves Casan-Pastor*. in BOOK “Engineering Biomaterials for Neural Applications. Targeting traumatic Brain and spinal cord Injuries”. Ed. Lopez-Dolado, Serrano MC, Springer Nature. In press. 11/04/2022 release. Online ISBN978-3-030-81400-7. Print ISBN978-3-030-81399-4
Pedro Gomez-Romero, Monica Lira, Nieves Casañ-Pastor. “Reversible electrochemical cells using hybrid organic-inorganic electrodes formed by organic conducting polymers and active inorganic species” Patente N. 9500599, OEPM 1995,
P. Gomez-Romero, E. Tejada- Rosales, D. Muñoz-Rojas, N. Casañ-Pastor, G. Mestl, H. J. Wohl. Preparacion de nuevos catalizadores basados en Oxidos de cobre y plata y su uso en catalizadores de oxidacion. Patente N. 20020 309 OEP 8 junio 2002.
N. Casañ-Pastor, M. Lichtenstein, E. Pérez Soler, C. Suñol Esquirol, PROCEDIMIENTO PARA LA IDENTIFICACION DE ELECTRODOS UTILES PARA EL TRATAMIENTO DE LESIONES NEURONALES MEDIANTE UN MODELO DE LESION IN VITRO Y PROTOCOLOS DE ACCIÓN DE CAMPO ELECTRICO. P201531912, presentada 24 dic 2015.
Proyecto Intramural CSIC Ref. 201560E053. Electrodos biocompatibles nanoestructurados, electrodeposición 3D de híbridos de IrOx y carbón y extensión a otros metales. Supercondensadores en bio y energía.
The SFFM group focuses its research in the use of Supercritical CO2 for the design and preparation of functional materials for a wide variety of applications ranging from energy and environment to biomedical applications
scCO2 is a non-toxic and environmentally benign green solvent that has been widely used in the food and pharmaceutical industries. However, scCO2 (which reaches its supercritical conditions at 31.1 °C and 7.4 MPa) also has many outstanding properties, which give it a great potential for advanced synthesis and materials processing. In particular, it is an attractive alternative to organic solvents that are widely recognized as pollutant or toxic. ScCO2 is a non-destructive fluid with null surface tension, thus adequate to create or manipulate complex primary nanoparticles, functional nanomaterials and nanostructures. Moreover, the low viscosity of the compressed fluid and its high diffusivity allow for exceptionally effective penetration in nanopores.
The overall objective of the SFFM group is to use this clean supercritical fluid technology, coupled with other chemical processing approaches, as a platform to develop flexible manufacturing routes for the cost-effective production of nanoporous materials as well as 3D nanostructures using sustainable processes. scCO2 technology is used for the production of high performance existing and new products with unique characteristics in regard to composition (purity), size (micro or nanoscale) and architecture (fibres, foams).
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Our current interest is largely focused on the preparation of porous polymers, coordination polymers and graphene-based aerogel composites. These research lines interlink to create further advanced and more sophisticated structures.
Godoy-Gallardo, Maria; Portolés-Gil, Núria; López-Periago, Ana M; Domingo, Concepción; Hosta-Rigau, Leticia, Materials Science and Engineering C, 2020, 117,11124
Materials employed for the fabrication of scaffolds have mainly relied on bioceramics and biodegradable polymer
In our group, we propose the use of scCO2for the preparation of composite scaffolds made from bioceramics and polymers such as hydroxyapatite (HA) and polycraprolactone (PCL) matrix.
The scaffolds are fabricated using scCO2technology and controlled pressurization/depressurization regimens, which help to display a highly interconnected network of pores with a multimodal pore size distribution. This architecture can mimic the extracellular matrix of natural tissue, in which the macropores can promote cell growth, proliferation and migration, and the microporous network allows the diffusion of the necessary oxygen, nutrients and waste.
The SFFM research group pioneered the synthesis of coordination polymers in scCO2, showing that this fluid can act simultaneously as solvent and activation agent.
MOFs are hybrid network structures formed by self-assembly of metal ions or clusters and organic linking groups. These structures have a great variety of applications in catalysis, drug delivery, or gas separation and storage.
In this research topic, we propose an attractive synthetic method for the preparation of MOFs and coordination polymers. These hybrid materials can be obtained by using bidentate and tridentate N donor ligands, such as bipyridyl and triazine derivative organic linkers, respectively. Among the coordination polymers based on M2+ transition metals, there is a large variety of structural motifs when reacted with the different linkers, including simple and sinusoidal 1D chains, 2D double helices with simple and interpenetrating layers and even 3D frameworks.
Since the first synthesis of a coordination polymer using scCO2, more than 25 structures have been synthesised, from rigid to flexible structures, as well as very well known MOFs using carboxylate linkers such as ZIF-8, H-Kust-1 or MIL-100 (Fe).
Nuria Portoles-Gil, Arianna Lanza, Nuria Aliaga-Alcalde, José A Ayllón, Mauro Gemmi, Enrico Mugnaioli, Ana M López-Periago*, Concepción Domingo, “Crystalline curcumin bioMOF obtained by precipitation in supercritical CO2 and structural determination by electron diffraction tomography”. ACS Sustainable Chemistry & Engineering. 2018, 6, 12309-12319
A promising field of application of MOFs is the biomedical one. In this case, it is a bioactive molecule, such a curcumine, the linker in the MOF network
We own a patented technology for producing GO aerogels starting from an alcoholic dispersion of graphene oxide. The procedure is developed under isothermal and isobaric conditions, and it is readily reproducible, scalable and cost-effective, leading to a non-reduced end-product.
The aerogel obtained combines stability and robustness with a high functionalization capacity granted by the large number of functional groups maintained from the starting graphene oxide. Aerogels obtained have a high surface area, ca. 250 m2/g, and a high pore volume, between 0.9 and 1.5 mL/g.
The possibility of preparing multifunctional composites using graphene oxide as a basic unit for the controlled self-assembly of 3D carbon macrostructures by supercritical CO2 is enormous. Possible applications include adsorption material in membrane technologies, batteries, supercapacitors, metal catalyst supports, among others.
In particular, composites of metal nanoparticles and GO aerogels are promising for a myriad of applications. As an example, the development of an all-green synthesis approach allowed the preparation of hybrid materials shaped into aerogels with large mesoporosity, involving the loading of SPIONs onto a GO surface via a simple one-pot supercritical CO2 technique for MRI applications
European
The similarities in electronegativity, polarizability, ionic radii and coordination numbers of oxygen and nitrogen allow the formation of the same structural types when combined with cations as well as the mutual substitution of both anions at the same crystallographic sites. This can result in the formation of solid solutions where the formal valence of one or more cations may change according to the O/N ratio. The design of new nitrides based on phases and crystal structures already known for oxides is a useful tool for exploring and/or modifying a large variety of physical properties, either through the formation of completely new compounds or of solid solutions.
We have investigated hafnium nitride halide superconductors that show high critical temperatures within non oxidic compounds. We investigate the effect of nitrogen on the properties of important materials such as CeO2 and TiO2, and we design new oxynitrides with magnetic, electrical, photocatalytic and luminescent properties. Oxynitrides of transition metals, alkaline earth metals and rare earth metals are an important group of materials to expand and tune the properties of oxides. The differences in polarizability, electronegativity and anion charge of nitrogen and oxygen induces changes in the physical and chemical properties by nitrogen introduction. The effects on properties arise from the higher covalency of metal-nitrogen bond and the changes in the energies of electronic levels, and are important in slightly doped nitrogen metal oxides as in stoichiometric oxynitrides. The stabilization of new perovskite oxynitrides, with the oxidation states of cations tuned by O/N stoichiometry, has lead to new photocatalysts, magnetic and dielectric materials. The lower electronegativity of nitrogen and larger crystal field splitting induced by N3- shifts the emission wavelenghts of phosphors to the red, and oxynitridosilicates have been investigated as components of white LED’s.
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Mechanism of intercalation of Na in beta-HfNCl
We have investigated the influence of the nature of the transition metal, the co-intercalated molecules, the staging and the doping level on the superconducting properties of intercalated zirconium and hafnium nitride halides. We have discovered an unprecedent re-entrant mechanism during synthesis of superconducting Na0.5HfNCl by ultra slow electrochemical intercalation of sodium. HfNCl host layers transform to an alternative geometry and then revert to their original structure, revealing that intercalation reactions may proceed by very different mechanisms to those expected in the conventional slab-gliding picture.
Nitrogen doping is an important method for modifying the properties of oxides, for example, tuning the band gap of the photocatalyst TiO2 from the UV to the visible region. We have prepared mesoporous films of N-TiO2 showing photocatalytic activity under visible light. We have shown for the first time that ceria (CeO2), a relevant material with important applications as oxide ion-conducting and oxygen-storage component in catalysts, can be doped with nitrogen that would be a significant defect when this material is exposed to reducing, nitrogen-rich atmospheres. Films of CeO2-x-yNx show photocatalytic activity under visible light in the decomposition of acetaldehyde.
Our research in perovskite oxynitrides has lead to the discovery of large/colossal magnetoresistance in EuNbO2N, EuWO2-xN1+x and in the double perovskite Sr2FeMoO4.9N1.1. We have discovered new vanadium and chromium perovskites RVO3-xNx and RCrO3-xNx (R= rare earth), showing the effect of nitride introduction on the magnetic interactions between the spins of the transition metal or the rare earth and on the electrical properties. New antiferromagnetic double perovskites Sr2FeWO5N have been prepared by topochemical ammonolysis of cation ordered Sr2FeWO6.
We have discovered new hafnium oxynitride perovskites RHfO2N that show photocatalytic activity under visible light in water oxidation or reduction. Anion order in pseudocubic perovskite oxynitrides has been investigated by neutron diffraction indicating a cis distribution of nitrides confined in planes, which is induced by the higher covalency of B-N bonds.
The new compound BaWON2 is the first example of a hexagonal perovskite oxynitride. It crystallizes in the non centrosymmetric space group P63mc and shows complete order of N and O in hexagonal and cubic layers. Synergetic second order Jahn- Teller effect, anion order and electrostatic repulsion between hexavalent W cations induce large distortions at two inequivalent face sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.
Phosphors based on rare earth-doped silicon oxynitrides attract attention because of their good luminescent properties, low toxicity, thermal stability and colour tunability. We have discovered new oxynitridosilicates with apatite and beta-K2SO4 structure that show orange and red emission wavelengths under excitation with blue or UV light. The new oxynitride orthosilicates LaMSiO3N (M=Sr, Ba) are isotypic to alpha’-M2SiO4 (M= Sr, Ba) with beta-K2SO4 structure and can be activated either with Ce3+ or Eu2+. Under excitation with UV-blue light the emission wavelengths are red shifted with respect to the high efficient phosphors Sr2SiO4:Eu or Ba2SiO4:Eu, from c.a. 550 nm to 650-700 nm.
Solid state chemistry and electrochemistry applied to battery materials, covering a wide diversity of technologies with either aqueous or organic electrolytes. These include already commercial (e.g. Ni or Li-ion) or pre-commercial (Na-ion) concepts, as well as new emerging chemistries such as those based on Mg or Ca. Emphasis is placed on developing fertile cooperation scenarios between fundamental research and industry.
Current projects are focused on post Li-ion sustainable technologies based on abundant elements. While for the Na-ion case fast progress is expected as a result of chemical similarities with lithium and the cumulated Li-ion battery know-how over the years, for Ca and Mg the situation is radically different. On one hand, the possibility to use Ca or Mg metal anodes would bring a breakthrough in terms of energy density,9 on the other, development of suitable electrolytes and cathodes with efficient multivalent ion diffusion are bottlenecks to overcome
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Electrode materials investigated for multivalent battery concepts typically exhibit a transition metal as redox center. A priori, the use of more covalent electrode would be preferred, as the coulombic interactions with divalent ions would be less important. Development of suitable experimental protocols is mandatory, as know-how gained in the field of Li-ion cannot be blindly adopted. Thus, the use of characterization techniques complementary to electrochemistry is mandatory.19 These have enabled, for instance, to assess reversible electrochemical Ca2+ intercalation in TiS2, forming a range of different phases depending on the electrolyte and conditions used, some of them exhibiting co-intercalated solvent molecules.2,13
The screening of positive electrode materials being strongly limited by the absence of standard electrolyte with adequate anodic stability, theoretical calculations using DFT have been very useful in unraveling suitable electrode materials for divalent cation intercalation.3 Yet, the topic is complex as some hosts that have been predicted to enable low migration barriers for calcium, such as a hypothetical CaMn2O4 spinel, come to the expense of phase stability and hence, the polymorphs that can be synthesized experimentally are different and exhibit larger migration barriers.27 In other cases, such as 1D-structure Ca3Co2O6,15 or ternary nitride CaTaN2,7 electrochemical extraction of calcium takes place, with reversibility being very limited, if any, which might be related to high desolvation energies or unstability of the phases formed.
In contrast to what happens for multivalent chemistries, progress in the sodium-ion battery (SIB) field is achieved at a quicker pace, catalysed by the chemical analogies between lithium and sodium and the wide accumulated know-how of LIBs. The materials choice on the negative side is relatively restricted, and today only hard carbon exhibit realistic application prospects.32 The most critical issue for hard carbon is the irreversible capacity loss upon the first cycle which severely penalizes the practical cell energy density achievable. This can at least partly be explained by the lower stability of the passivation layer formed at the negative electrode/electrolyte interface when compared to the one formed for LIB (commonly termed Solid Electrolyte Interphase, SEI).1,28
Hard carbon can be prepared from different precursors (phenolic resin and commercially available cellulose and lignin) under different pyrolysis and processing conditions using industrially adapted syntheses protocols. The study of their microstructural features enabled to assess that the nature of the precursor and the temperature of pyrolysis are the major factors determining the carbon yield and the surface area, the latter one having a major effect on the electrochemical capacity.18 When coupled to Na3V2(PO4)2F3, full cells exhibit performances comparable to State-of-the-art Li-ion batteries.39
The electrolyte is sometimes called “passive”, “only” being responsible for containing and shuttling the charge carrier ion of choice (H+, Li+, Na+, Ca2+, Mg2+, etc.) between the electrodes. Yet, the electrolyte has a relevant influence in the life-length of a battery and the practically accessible capacity, rate capability, safety, etc.12 Indeed, the composition of the electrolyte is responsible for the parasitic degradation reactions, wettability of the electrodes and separator, mobility of solvated cations, flammability, etc.31 Our research mostly focuses in controlling post-Li battery electrolyte formulations (combination of salt, solvent and additive) in order to tune their physico-chemical properties (ionic conductivity, viscosity, electrochemical stability window, solvation structure …).6,39,47
The nature, composition and homogeneity of the interface between the electrode and the electrolyte are other crucial parameters determining the battery performances. Electrolyte reduction or oxidation often result in insoluble products adhering to the electrode surface and forming solid passivation layer (the so-called SEI) on the negative electrode or surface layer (SL on the positive). Long term cell operation will only be enabled if such passivation layers are electronically insulating (preventing further electrolyte decomposition), while allowing for cation diffusion through it. Such behaviour is not trivial for post-Li systems and, for instance, salts present in Na based passivation layers possess higher solubility when compared with Li analogues, due to the difference in Lewis acidity of the two cations, possibly resulting in poor stability and cycle life.1,20,28 On the other hand, Ca salts are usually much less soluble and better stability of the interface is expected. However, passivation layers were generally thought to be the reason preventing Ca plating due to lack of divalent cation transport through them. Challenging that assumption, we were able to demonstrate that calcium can be reversibly plated and stripped through a stable SEI layer at moderate temperature (> 75°C) evidencing that crucial parameters impacting the electrodeposition process are not only the SEI composition but also the formation of ion pairs within the electrolyte. The latter hinders Ca2+ migration and results in a high energy barrier for cation desolvation.6,22 Efforts are now being devoted to control the solvation structure of the cation, investigating its impact on: (i) the cation mobility within the electrolyte, (ii) the formation of the SEI layer and (iii) the desolvation energy at the electrolyte/SEI interface.
Finally, we are also interested in the engineering of the electrode/electrolyte interface by means of coating. For instance, carbon coating on both negative and positive electrodes was found to results in (i) improved electronic conductivity (and thus power performance) and (ii) increased electrochemical stability window (longer cycle life) due to a decrease in catalytic activity with respect to electrolyte decomposition when carbon is directly in contact with the electrolyte instead of the electrode material (often containing transition metal).42
Research takes advantage of the technical and analytical resources in the ICMAB and of the shared facilities at the Solid State Chemistry Department. Additional specific equipment includes:
[1] SEI Composition on Hard Carbon in Na-Ion Batteries after Long Cycling: Influence of Salts (NaPF6, NaTFSI) and Additives (FEC, DMCF). J. Fondard, E. Irisarri, C. Courrèges, M. R. Palacin, A. Ponrouch, R. Dedryvère. J. Electrochem. Soc. 2020, 167, 070526. https://doi.org/10.1149/1945-7111/ab75fd.
[2] Steps Towards the Use of TiS2 Electrodes in Ca Batteries. R. Verrelli, A. Black, R. Dugas, D.Tchitchekova, A.Ponrouch, M.R. Palacin. J. Electrochem. Soc. 2020, 167, 070532. https://doi.org/10.1149/1945-7111/ab7a82.
[3] Appraisal of calcium ferrites as cathodes for calcium rechargeable batteries: DFT, synthesis, characterization and electrochemistry of Ca4Fe9O17. A. P. Black, A. Torres, C. Frontera, M. R. Palacín, M. E. Arroyo-de Dompablo. Dalton Trans. 2020, 49, 2671. https://doi.org/10.1039/C9DT04688G.
[4] Review-Achievements, Challenges, and Prospects of Calcium Batteries. M.E. Arroyo-de Dompablo, A.Ponrouch, P. Johansson, M.R. Palacín. Chem. Rev. 2019 https://doi.org/10.1021/acs.chemrev.9b00339.
[5] Methods and Protocols for Reliable Electrochemical Testing in Post-Li Batteries (Na, K, Mg, and Ca). R. Dugas, J. D. Forero-Saboya, A. Ponrouch. Chem. Mat. 2019, 31 (21) 8613. https://doi.org/10.1021/acs.chemmater.9b02776.
[6] Cation Solvation and Physicochemical Properties of Ca Battery Electrolytes. J. D. Forero-Saboya, E. Marchante, R. B. Araujo, D. Monti, P. Johansson, A. Ponrouch. J. Phys. Chem. C 2019, 123 (49) 29524. https://doi.org/10.1021/acs.jpcc.9b07308.
[7] On the Study of Ca and Mg Deintercalation from Ternary Tantalum Nitrides. R. Verrelli, A. P. Black, C. Frontera, J. Oró-Solé, M. E. Arroyo-de Dompablo, A. Fuertes, M. R. Palacín. ACS Omega 2019, 4 8943. https://doi.org/10.1021/acsomega.9b00770.
[8] Review-Post-Li batteries: promises and challenges. A.Ponrouch, M.R. Palacin. Phil. Trans. R. Soc. A 2019, 377, 20180297. http://dx.doi.org/10.1098/rsta.2018.0297.
[9] Multivalent Batteries—Prospects for High Energy Density: Ca Batteries. D. Monti, A. Ponrouch, R. B. Araujo, F. Barde, P. Johansson, M.R. Palacin. Front. Chem. 2019, 7, 79. https://doi:10.3389/fchem.2019.00079.
[10] Review-Multivalent rechargeable batteries. A. Ponrouch, J. Bitenc, R. Dominko, N. Lindahl, P. Johansson, M.R. Palacín. Energy Storage Materials 2019, 20, 253. https://doi.org/10.1016/j.ensm.2019.04.012.
[11] Review-Rechargeable aqueous electrolyte batteries: from univalent to multivalent cation chemistry. R. Demir-Cakan, M. R. Palacín, L. Croguennec. J. Mater. Chem. A 2019, 7, 20517. https://doi.org/10.1039/C9TA04735B.
[12] Review-Understanding ageing in Li-ion batteries: a chemical issue. M.R. Palacín Chem. Soc. Rev. 2018, 47 (13) 4924. https://doi.org/10.1039/C7CS00889A.
[13] Electrochemical Intercalation of Calcium and Magnesium in TiS2: Fundamental Studies Related to Multivalent Battery Applications. D. Tchitchekova, A. Ponrouch, R. Verrelli, T. Broux, C. Frontera, A. Sorrentino, F. Barde, N. Biskup, M.E. Arroyo-de Dompablo, M.R. Palacin. Chem. Mat. 2018, 30 (3) 847. https://doi.org/10.1021/acs.chemmater.7b04406.
[14] The nickel battery positive electrode revisited: stability and structure of the β-NiOOH phase. M. Casas-Cabanas, M. D. Radin, J. Kim, C. P. Grey, A. Van der Ven, M. R. Palacín. J. Mater. Chem. A 2018, 6, 19256. https://doi.org/10.1039/C8TA07460G.
[15] Electrochemical calcium extraction from 1D-Ca3Co2O6. D. Tchitchekova, C. Frontera, A. Ponrouch, C. Krich, Barde, M.R. Palacin. Dalton Trans. 2018, 47, 11298. https://doi.org/10.1039/C8DT01754A.
[16] Review-On the road toward calcium-based batteries. A. Ponrouch, M.R. Palacin. Current Opinion in Electrochemistry 2018, 9, 1. https://doi.org/10.1016/j.coelec.2018.02.001.
[17] Diglyme Based Electrolytes for Sodium-Ion Batteries. K. Westman, R. Dugas, P. Jankowski, W. Wieczorek, G. Gachot, M. Morcrette, E. Irisarri, A. Ponrouch, M. R. Palacín, J.-M. Tarascon, P. Johansson. ACS Appl. Energy Mater. 2018, 1, 6, 2671. https://doi.org/10.1021/acsaem.8b00360.
[18] Optimization of large scale produced hard carbon performance in Na-ion batteries: effect of precursor, temperature and processing conditions. E. Irisarri, N. Amini, S. Tennison, C. Matei-Ghimbeu, J. Gorka, C. Vix-Guterl, A. Ponrouch, M.R. Palacin. J. Electrochem. Soc. 2018, 165(16) A4058. https://doi.org/10.1149/2.1171816jes.
[19] On the strange case of divalent ions intercalation in V2O5. R. Verrelli, A.P. Black, C. Pattanathummasid, D.S. Tchitchekova, A. Ponrouch, J. Oro-Sole, C. Frontera, F. Barde, M.R. Palacin. J. Power Sources 2018, 407, 162. https://doi.org/10.1016/j.jpowsour.2018.08.024.
[20] On the Reliability of Half-Cell Tests for Monovalent (Li+, Na+) and Divalent (Mg2+, Ca2+) Cation Based Batteries. D. S. Tchitchekova, D. Monti, P. Johansson, F. Bardé, A. Randon-Vitanova, M. R. Palacín, A. Ponrouch. J. Electrochem. Soc. 2017, 164, A1384. https://doi.org/10.1149/2.0411707jes.
[21] On the viability of Mg extraction in MgMoN2: a combined experimental and theoretical approach. R. Verrelli, M. E. Arroyo-de-Dompablo, D. Tchitchekova, A. P. Black, C. Frontera, A. Fuertes, M. R. Palacín. Phys. Chem Chem. Phys. 2017, 19, 26435. https://doi.org/10.1039/C7CP04850E.
[22] Towards a calcium-based rechargeable battery. A. Ponrouch, C. Frontera, F. Barde, M.R. Palacín. Nat. Mater. 2016, 15, 169. https://doi.org/10.1038/nmat4462.
[23] Na Reactivity toward Carbonate-Based Electrolytes: The Effect of FEC as Additive. R. Dugas, A. Ponrouch, G. Gachot, R. David, M. R. Palacín, J. M. Tarascon. J. Electrochem. Soc. 2016, 163, A1. https://doi.org/10.1149/2.0981610jes.
[24] Towards safer sodium-ion batteries via organic solvent/ionic liquid based hybrid electrolytes. D. Monti, A. Ponrouch, M. R. Palacín, P. Johansson. J. Power Sources 2016, 324, 712. http://dx.doi.org/10.1016/j.jpowsour.2016.06.003.
[25] Review-Why do batteries fail? M.R. Palacín, A. de Guibert. Science 2016, 351(6273) 1253292. https://doi.org/10.1126/science.1253292.
[26] Assessing Si-based anodes for Ca-ion batteries: Electrochemical decalciation of CaSi2. A. Ponrouch, D. Tchitchekova, C. Frontera, F. Bardé, M.E. Arroyo-de Dompablo, M.R. Palacín. Electrochem. Commun. 2016, 66, 75. http://dx.doi.org/10.1016/j.elecom.2016.03.004.
[27] A Joint Computational and Experimental Evaluation of CaMn2O4 Polymorphs as Cathode Materials for Ca Ion Batteries. M. E. Arroyo-de Dompablo, C. Krich, J. Nava-Avendaño, N. Biškup, M. R. Palacín, F. Bardé. Chem. Mat. 2016, 28, 6886. https://doi.org/10.1021/acs.chemmater.6b02146.
[28] On the Comparative Stability of Li and Na Metal Anode Interfaces in Conventional Alkyl Carbonate Electrolytes. D. I. Iermakova, R. Dugas, M. R. Palacín, A. Ponrouch. J. Electrochem. Soc. 2015, 162, A7060. https://doi.org/10.1149/2.0091513jes.
[29] Review-Recent achievements on inorganic electrode materials for Lithium-ion batteries. L. Croguennec, M.R. Palacin J. Am. Chem. Soc. 2015, 137, 3140-56. https://doi.org/10.1021/ja507828x.
[30] Taking steps forward in understanding the electrochemical behavior of Na2Ti3O7. J. Nava-Avendaño, A. Morales-García, A. Ponrouch, G. Rousse, C. Frontera, P. Senguttuvan, J.-M. Tarascon, M. E. Arroyo-de Dompablo, M. R. Palacín, J. Mater. Chem. A 2015, 3, 22280. https://doi.org/10.1039/C5TA05174F.
[31] Review-Non-aqueous electrolytes for sodium-ion batteries. A. Ponrouch, D. Monti, A. Boschin, B. Steen, P. Johansson, M. R. Palacín, J. Mater. Chem. A 2015, 3, 22. https://doi.org/10.1039/C4TA04428B.
[32] Review-Hard Carbon Negative Electrode Materials for Sodium-Ion Batteries. E. Irisarri, A. Ponrouch, M. R. Palacin, J. Electrochem. Soc. 2015, 162, A2482. https://doi.org/10.1149/2.0091514jes.
[33] On the high and low temperature performances of Na-ion battery materials: Hard carbon as a case study. A. Ponrouch, M.R. Palacín. Electrochem. Commun. 2015, 54, 51. http://dx.doi.org/10.1016/j.elecom.2015.03.002.
[34] Low temperature synthesis and characterization of Na-M-(O)-F phases with M = Ti, V. J. Nava Avendaño, J. A Ayllón, C. Frontera, J. Oro-Solé, M. Estruga, E. Molins, M.R. Palacín. J. Solid State Chem. 2015, 226, 286-94. https://doi.org/10.1016/j.jssc.2015.03.006
[35] High temperature electrochemical performance of hydrothermally prepared LiMn1 − xMxPO4 (M = Fe, Mg). J. Nava-Avendaño, M.R. Palacín, J. Oró-Solé, A. Ponrouch, J.-M. Tarascon, N. Recham. Solid State Ionics 2014, 263, 157. https://doi.org/10.1016/j.ssi.2014.06.007.
[36] Electroanalytical study of the viability of conversion reactions as energy storage mechanisms. A. Ponrouch, J. Cabana, R. Dugas, J. L. Slack, M. R. Palacín. RSC Adv., 2014, 4, 35988. https://doi.org/10.1039/C4RA05189K.
[37] Ionic liquid based electrolytes for sodium-ion batteries: Na+ solvation and ionic conductivity. D. Monti, E.Jónsson, M. R. Palacín, P. Johansson. J. Power Sources, 2014, 245, 630. https://doi.org/10.1016/j.jpowsour.2013.06.153.
[38] The Li–Si–(O)–N system revisited: Structural characterization of Li21Si3N11 and Li7SiN3O. M. Casas-Cabanas, H. Santner, M. R. Palacín. J. Solid State Chem., 2014, 213, 152. https://doi.org/10.1016/j.jssc.2014.02.022.
[39] Towards high energy density sodium ion batteries through electrolyte optimization. A.Ponrouch, R. Dedryvere, D. Monti, A.E. Demet, J.M. Ateba Mba, L. Croguennec, C. Masquelier, P. Johansson, M R. Palacín. Energy Environ. Sci. 2013, 6, 2361. https://doi.org/10.1039/C3EE41379A
[40] Low potential sodium insertion in a NASICON-type structure through the Ti(III)/Ti(II) redox couple. P. Senguttuvan, G. Rousse, M.E. Arroyo y de Dompablo, H. Vezin, J.M. Tarascon, M. R. Palacín. J. Am. Chem. Soc. 2013, 135, 3897. https://doi.org/10.1021/ja311044t.
[41] High capacity hard carbon anodes for sodium ion batteries in additive free electrolyte. A. Ponrouch, A.R. Goñi, M. R. Palacín. Electrochem. Comm. 2013, 27, 85-8. https://doi.org/10.1016/j.elecom.2012.10.038.
[42] A new room temperature and solvent free carbon coating procedure for battery electrode materials. A. Ponrouch, A. R. Goñi, M. T. Sougrati, M. Ati, J.-M. Tarascon, J. Nava-Avendaño, M. R. Palacín. Energy Environ. Sci. 2013, 6, 3363. https://doi.org/10.1039/C3EE41243A.
[43] Rationalization of Intercalation Potential and Redox Mechanism for A2Ti3O7 (A = Li, Na). G. Rousse, M. E. Arroyo-de Dompablo, P. Senguttuvan, A. Ponrouch, J.-M. Tarascon, M. R. Palacín. Chem. Mater. 2013, 25, 4946. https://doi.org/10.1021/cm4032336.
[44] A low temperature TiP2O7 polymorph exhibiting reversible insertion of lithium and sodium ions. P. Senguttuvan, G. Rousse, J. Oró-Solé, J. M. Tarascon, M. R. Palacín. J. Mater. Chem. A 2013, 1, 15284. https://doi.org/10.1039/C3TA13756B.
[45] Synthesis and Characterization of a Novel Sodium Transition Metal Oxyfluoride: NaMnMoO3F3·H2O. J. Nava-Avendaño, C. Frontera, J. A. Ayllón, J. Oró-Solé, P. Senguttuvan, M. R. Palacín. Inorg. Chem. 2013, 17, 9791. https://doi.org/10.1021/ic401447p.
[46] Titanium(III) Sulfate as New Negative Electrode for Sodium-Ion Batteries. P. Senguttuvan, G. Rousse, H. Vezin, J.-M. Tarascon, M. R. Palacín. Chem. Mater. 2013, 25, 2391. https://doi.org/10.1021/cm401181b.
[47] In search of an optimized electrolyte for Na-ion batteries. A. Ponrouch, E. Marchante, M. Courty, J.M. Tarascon, M. R. Palacín Energy Environ. Sci. 2012, 5, 8572. https://doi.org/10.1039/C2EE22258B.
[48] Optimisation of performance through electrode formulation in conversion materials for lithium ion batteries: Co3O4 as a case example. A. Ponrouch, M. R. Palacín. J. Power Sources 2012, 212, 233. https://doi.org/10.1016/j.jpowsour.2012.04.005.
[49] On the origin of the extra capacity at low potential in materials for Li batteries reacting through conversion reaction. A. Ponrouch, P.-L. Taberna, P. Simon, M. R. Palacín. Electrochim. Acta 2012, 61, 13. https://doi.org/10.1016/j.electacta.2011.11.029.
[50] Na2Ti3O7: Lowest voltage ever reported oxide insertion electrode for sodium ion batteries. P. Senguttuvan, G. Rousse, V. Seznec, J.M. Tarascon, M.R. Palacín. Chem. Mater. 2011, 23, 4109. https://doi.org/10.1021/cm202076g
[51] Review-Beyond intercalation-based Li-ion batteries: State of the art and challenges of electrode materials reacting through conversion reactions J. Cabana, L. Monconduit, D. Larcher, M.R. Palacín. Adv. Mater. 2010, 22, E170-92. https://doi.org/10.1002/adma.201000717.
[52] Review-Recent advances in rechargeable battery materials: a chemist’s perspective Chem. Soc. Rev. 2009, 38 2565-2575. https://doi.org/10.1039/B820555H
Cancer is one of the most relevant diseases worldwide because of its incidence, prevalence and mortality. During the past decades, considerable efforts have been devoted to understand the origin of the disease, find early detection methods that could improve the survival rate of cancer patients or develop treatments and devices that could reduce or eradicate cancer. The application of nanotechnology for the rational design of biomaterials is providing alternative solutions to classical treatments, thus expanding the toolbox available for biomedical imaging and therapy. Nanomaterials offer a unique platform to adjust essential properties such as solubility, diffusivity, blood-circulation half-life, pharmacokinetic profile and cytotoxicity. Nanoencapsulation of biomedically relevant payloads into porous materials is of special interest for the development of contrast agents and smart therapeutic systems. Most of our research activity is in the area of nanooncology, by developing nanomaterials for both diagnosis and treatment of cancer in the framework of the ERC Consolidator Grant NEST.
From the wide range of nanomaterials available, our focus is on the exploitation of the unique properties that both, carbon and inorganic nanomaterials offer. When combined, the synergies of both types of materials results in novel or enhanced properties that are of interest not only in the biomedical field but also in other research areas as highlighted below.
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We have developed radioactive nanocapsules that allow nuclear imaging in an ultrasensitive manner and lung cancer therapy. Two different strategies have been employed for the preparation of ‘hot’ radioactive nanocapsules. The first strategy consists in the direct encapsulation of radionuclides in their cavities of the carbon nanocapsules. The second strategy goes via the initial encapsulation of a ‘cold’ isotopically enriched isotope (152Sm), which can then be activated on demand to their ‘hot’ radioactive form (153Sm) by neutron irradiation. The use of ‘cold’ isotopes avoids the need for radioactive facilities during the preparation of the nanocapsules, reduces radiation exposure to personnel, prevents the generation of nuclear waste, and evades the time constraints imposed by the decay of radionuclides. A high specific radioactivity (up to 11.37 GBq/mg) has been achieved by neutron irradiation, making the “hot” nanocapsules useful not only for in vivo imaging but also therapeutically effective against lung cancer metastases after intravenous injection. The external surface remains available and can be funtionalized to increase the dispersability, biocompatibility and for targeting purposes. Glycans, peptides and antibodies have been employed in the performed studies. The high in vivo stability of the radioactive payload, selective toxicity to cancerous tissues, and the elegant preparation method offer a paradigm for application of nanomaterials in radiotherapy.
Neutron capture therapy (NCT) is a high-linear energy transfer form of radiotherapy that exploits the potential of some specific isotopes for cancer treatment, based on the neutron capture and emission of short-range charged particles, which occur at low energies. The nuclear reaction that takes place when some isotopes are irradiated with low-energy thermal neutrons, produces high linear energy transfer (LET) particles suitable for cancer cell eradication. The limited path lengths of the LET particles (5-9 µm) produced in NCT can limit the destructive effects to isotopes that are localized in cells. Thus, conferring high therapeutic precision to this type of radiotherapy. We are developing several nanocarriers with the aim to increase the amount of neutron capture elements that are delivered to cancer cells (patent application 202230271).
Although optical imaging is still the leading imaging modality in laboratory-based biomedical research mainly due to its convenience and low cost, magnetic resonance imaging (MRI) and nuclear imaging are currently the mainstream clinical diagnostic approaches. MRI is already a standard medical imaging technique which offers excellent spatial and temporal resolution, and good soft tissue contrast. In this field, we have combined the outstanding properties of superparamagnetic iron oxide nanoparticles (SPION) as positive contrast agents for MRI along with those of carbon nanomaterials, namely graphene and carbon nanotubes that are employed as nanocarriers. The resulting hybrid materials offer high r2 relaxivities in both phantom and in vivo MRI compared to clinically approved SPION. We have also shown that not only the characteristics of the SPION but also the employed nanocarrier might play a key role in the resulting properties. For instance, short carbon nanotubes reveal enhanced MRI properties compared to their long counterparts. We are also exploring the contrast imaging properties of 3D scaffolds of graphene oxide (using a patented technology, WO 2019/158794 A1) bearing SPION.
The electronic and optical properties of two-dimensional layered materials allow the miniaturization of nanoelectronic and optoelectronic devices in a competitive manner. Even larger opportunities arise when two or more layers of different materials are combined. We have observed that the cavities of carbon nanotubes can be employed for the template assisted growth of inorganic metal halide nanotubes in their interior, thus forming 1D tubular van der waals heterostructures. We have developed strategies that result in a high selectivity toward the growth of such 1D heterostructures. A decrease of the resistivity as well as a significant increase in the current flow upon illumination has been observed in a PbI2@CNT bulk matrix. Both effects are attributed to the presence of single-walled lead iodide nanotubes in the cavities of carbon nanotubes (CNTs), which dominate the properties of the whole matrix.
Theragnostic nanocapsules
Functionalization of filled radioactive multi-walled carbon nanocapsules by arylation reaction forin vivodelivery of radio-therapy. Gajewska A., Wang J.T., Klippstein R., Martincic M., Pach E., Feldman R., Saccavini J.-C., Tobias G., Ballesteros B., Al-Jamal K.T., Da Ros T., J. Mater. Chem. B. 2022, 10 (1), 47-56. https://doi.org/10.1039/d1tb02195h.
Neutron-irradiated antibody-functionalised carbon nanocapsules for targeted cancer radiotherapy. Wang J.T.-W., Spinato C., Klippstein R., Costa P.M., Martincic M., Pach E., Ruiz de Garibay A.P., Ménard-Moyon C., Feldman R., Michel Y., Šefl M., Kyriakou I., Emfietzoglou D., Saccavini J.-C., Ballesteros B., Tobias G., Bianco A., Al-Jamal K.T., Carbon. 2020, 162, 410-422. https://doi.org/10.1016/j.carbon.2020.02.060.
Neutron Activated 153Sm Sealed in Carbon Nanocapsules for in Vivo Imaging and Tumor Radiotherapy. Wang J.T.-W., Klippstein R., Martincic M., Pach E., Feldman R., Šefl M., Michel Y., Asker D., Sosabowski J.K., Kalbac M., Da Ros T., Ménard-Moyon C., Bianco A., Kyriakou I., Emfietzoglou D., Saccavini J.-C., Ballesteros B., Al-Jamal K.T., Tobias G., ACS Nano. 2020, 14 (1) 129-141. https://doi.org/10.1021/acsnano.9b04898.
In vivo behaviour of glyco-NaI@SWCNT ‘nanobottles’. De Munari S., Sandoval S., Pach E., Ballesteros B., Tobias G., Anthony D.C., Davis B.G., Inorg. Chim. Acta. 2019, 495, 118933. https://doi.org/10.1016/j.ica.2019.05.032.
Non-cytotoxic carbon nanocapsules synthesized via one-pot filling and end-closing of multi-walled carbon nanotubes. Martincic M., Vranic S., Pach E., Sandoval S., Ballesteros B., Kostarelos K., Tobias G., Carbon 2019, 141, 782-793 https://doi.org/10.1016/j.carbon.2018.10.006.
Evaluation of the immunological profile of antibody-functionalized metal-filled single-walled carbon nanocapsules for targeted radiotherapy. Perez Ruiz De Garibay A., Spinato C., Klippstein R., Bourgognon M., Martincic M., Pach E., Ballesteros B., Ménard-Moyon C., Al-Jamal K.T., Tobias G., Bianco A., Sci. Rep. 2017, 7, 42605 https://doi.org/10.1038/srep42605.
Carbon nanotubes allow capture of krypton, barium and lead for multichannel biological X-ray fluorescence imaging. Serpell C.J., Rutte R.N., Geraki K., Pach E., Martincic M., Kierkowicz M., De Munari S., Wals K., Raj R., Ballesteros B., Tobias G., Anthony D.C., Davis B.G., Nat. Commun. 2016, 7, 13118 https://doi.org/10.1038/ncomms13118.
Design of antibody-functionalized carbon nanotubes filled with radioactivable metals towards a targeted anticancer therapy. Spinato C., Perez Ruiz De Garibay A., Kierkowicz M., Pach E., Martincic M., Klippstein R., Bourgognon M., Wang J.T.-W., Ménard-Moyon C., Al-Jamal K.T., Ballesteros B., Tobias G., Bianco A., Nanoscale. 2016, 8 (25), 12626-12638 https://doi.org/10.1039/c5nr07923c.
Filled and glycosylated carbon nanotubes for in vivo radioemitter localization and imaging. Hong S.Y., Tobias G., Al-Jamal K.T., Ballesteros B., Ali-Boucetta H., Lozano-Perez S., Nellist P.D., Sim R.B., Finucane C., Mather S.J., Green M.L.H., Kostarelos K., Davis B.G., Nat. Mater. 2010, 9 (6), 485-490 https://doi.org/10.1517/17425247.2015.971751.
Magnetic resonance imaging
Green and Solvent-Free Supercritical CO2-Assisted Production of Superparamagnetic Graphene Oxide Aerogels: Application as a Superior Contrast Agent in MRI. Borrás A., Fraile J., Rosado A., Marbán G., Tobias G., López-Periago A.M., Domingo C., ACS Sustainable Chem. Eng. 2020, 8 (12), 4877-4888 https://doi.org/10.1021/acssuschemeng.0c00149.
Particle size determination from magnetization curves in reduced graphene oxide decorated with monodispersed superparamagnetic iron oxide nanoparticles. Bertran A., Sandoval S., Oró-Solé J., Sánchez À., Tobias G., J. Colloid Interface Sci. 2020, 566, 107-119 https://doi.org/10.1016/j.jcis.2020.01.072.
Microwave-assisted synthesis of SPION-reduced graphene oxide hybrids for magnetic resonance imaging (MRI). Llenas M., Sandoval S., Costa P.M., Oró-Solé J., Lope-Piedrafita S., Ballesteros B., Al-Jamal K.T., Tobias G., Nanomaterials. 2019, 9 (10), 1364 https://doi.org/10.3390/nano9101364.
Novel Fe3O4@GNF@SiO2 nanocapsules fabricated through the combination of an: In situ formation method and SiO2 coating process for magnetic resonance imaging. Lu C., Sandoval S., Puig T., Obradors X., Tobias G., Ros J., Ricart S., RSC Adv. 2017, 7 (40), 24690-24697 https://doi.org/10.1039/c7ra04080f.
The Shortening of MWNT-SPION Hybrids by Steam Treatment Improves Their Magnetic Resonance Imaging Properties in Vitro and in Vivo. Wang J.T.-W., Cabana L., Bourgognon M., Kafa H., Protti A., Venner K., Shah A.M., Sosabowski J.K., Mather S.J., Roig A., Ke X., Van Tendeloo G., De Rosales R.T.M., Tobias G., Al-Jamal K.T., Small. 2016, 12 (21), 2893-2905 https://doi.org/10.1002/smll.201502721.
Magnetically decorated multiwalled carbon nanotubes as dual MRI and SPECT contrast agents. Cabana L., Bourgognon M., Wang J.T.-W., Protti A., Klippstein R., De Rosales R.T.M., Shah A.M., Fontcuberta J., Tobías-Rossell E., Sosabowski J.K., Al-Jamal K.T., Tobias G., Adv. Funct. Mater. 2014, 24 (13), 1880-1894 https://doi.org/10.1002/adfm.201302892.
1D tubular van der Waals heterostructures
Structure of inorganic nanocrystals confined within carbon nanotubes. Sandoval S., Tobias G., Flahaut E., Inorg. Chim. Acta. 2019, 492, 66-75 https://doi.org/10.1016/j.ica.2019.04.004.
Selective Laser-Assisted Synthesis of Tubular van der Waals Heterostructures of Single-Layered PbI2 within Carbon Nanotubes Exhibiting Carrier Photogeneration. Sandoval S., Kepić D., Pérez Del Pino Á., György E., Gómez A., Pfannmoeller M., Tendeloo G.V., Ballesteros B., Tobias G., ACS Nano. 2018, 12 (7), 6648-6656 https://doi.org/10.1021/acsnano.8b01638.
Encapsulation of two-dimensional materials inside carbon nanotubes: Towards an enhanced synthesis of single-layered metal halides. Sandoval S., Pach E., Ballesteros B., Tobias G., Carbon. 2017, 123, 129-134 https://doi.org/10.1016/j.carbon.2017.07.031.
Synthesis of PbI2 single-layered inorganic nanotubes encapsulated within carbon nanotubes. Cabana L., Ballesteros B., Batista E., Magén C., Arenal R., Orõ-Solé J., Rurali R., Tobias G., Adv. Mater. 2014, 26 (13), 2016-2021 https://doi.org/10.1002/adma.201305169.
Gil Gonçalves and Gerard Tobias (Editors)
Nanooncology: Engineering nanomaterials for cancer therapy and diagnosis
(Springer, 2018). ISBN: 978-3319898773.
Gerard Tobias, Emmanuel Flahaut.
Smart carbon nanotubes
Smart materials for drug delivery (Royal Society of Chemistry)
Vol. 2, p. 90-116 (2013). ISBN: 978-1-84973-552-0.
Gerard Tobias, Ernest Mendoza, Belén Ballesteros.
Functionalisation of carbon nanotubes
Encyclopedia of Nanotechnology (Springer)
Part 7, 911-919 (2012). ISBN: 978-90-481-9750-7.
Several new and emergent chemistries for electrochemical energy storage are based on the understanding and the engineering of the electrode/electrolyte interface. The approach followed in this line to bring these concepts closer to practical reality involves the preparation of nanostructured materials to use in batteries, and the study of the electrode processes by electrochemical and physical techniques.
The great success of the lithium-ion battery is based on the intercalation reaction, which involves the bulk of the active electrode material and is compatible with a static interface, allowing a large cycle life. Novel concepts and chemistries pursue improving the established Li-ion technology, in one or more properties of such as energy density, cost, sustainability. Use of metallic anodes, air or sulfur cathodes, or flow batteries imply the deposition and dissolution of the active material, and therefore an evolving interface and/or redox catalytic processes at the interface. Controlling composition and nanostructure of the interface is the main focus in this line.
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Binder-free inverse opal carbons with pores of different sizes to study the effects of architecture on the electrochemistry of Li-air cathodes
The challenges of novel electrochemical energy storage systems are often related to more difficult reactions, i.e. slower or less reversible electrochemical processes. The development of appropriate material architectures that multiply the number of reactions sites by expanding the interface area and providing appropriate ionic channels and electron wiring without compromising density or cost is critical for efficient devices. However, the use of well-defined controlled structures is also a strategy for the understanding of fundamental phenomena and the experimental localization of possible system bottlenecks, which serves as guide for the further design of improved materials.
Based on these concepts, we have been developing materials mainly for metal-air batteries. Aprotic Li/O2 batteries are based on the precipitation of insulating Li2O2 in the porous conducting matrix of the cathode during discharge. Li2O2 formation and removal need to be properly managed to ensure effective operation. To understand what parameters of the porous network optimize discharge capacity, rate capability and reversibility, two approaches have been followed: 1) using model systems with well-defined pore structure and 2) modeling pore filling of practical carbons based on their experimental pore size distribution (PSD). To determine the degree of utilization of the cathode porosity we fabricate ideal structures where we exactly know pore sizes and their arrangements, such as inverse opals.
Another path for the production of attracting materials for energy storage is based on the control of nanostructuration through low cost and sustainable raw materials and routes. Our studies center on processes of drying and carbonization in specific environments to obtain appropriate porous structures from widely available renewable precursors such as bacterial nanocellulose.
Enhancement of the discharge capacity of a Li-O2 battery by adding a novel radical molecule in the electrolyte.
The nanostructured, mostly carbonaceous materials described above are developed mainly for application in metal-air and redox flow batteries. These systems target high energy density and large scale storage respectively, and can encompass a wide array of specific chemistries. However they have in common that generally the required redox processes take place by electron transfer at the electrode surface and may involve a product deposition. The related problems of electrocatalysis and of the deposition distributions may be influenced by supply of active species, solvation and soluble catalysts. Therefore the influence of all components in the full system is investigated, which includes electrolyte formulations, redox mediators and other additives, as well as design and study of novel cell concepts. The main focus is currently on the reversibility of Li- and Zn-air batteries, as well as the kinetics in V redox flow batteries.
When a product precipitates during the electrochemical process, the precise knowledge of composition and morphology of the nano-sized deposits provides valuable information on their formation process that need to be understood in detail to obtain true reversible operation. Within this activity, we introduced the use of energy-dependent full field transmission soft x-ray microscopy (TXM) using synchrotron radiation to study the reactions in the oxygen electrode of Li-air batteries. The TXM high energy and space resolution provide semiquantitative chemical information at the scale of few tens of nm. The unique access to the oxygen chemical state allowed detecting the critical superoxide component and its interplay with the other compounds present in the precipitate. The use of this technique has been extended to the mapping of the intercalation state in other battery active materials and complemented with hard x-ray absorption, allowing to observe core-shell effects or insurgence of local heterogeneities among particles, providing relevant insights on the charge redistribution and the irreversible processes to guide the development of more reliable battery systems..
The Thermal Analysis and Surface Area Analysis Service is used for the study of the behavior of materials when temperature changes under different conditions and atmospheres, and for studies of surface area and porosity. The Service allows for simultaneous thermogravimetric analysis (TGA- DSC/DTA), differential scanning calorimetry (DSC), as well as Brunauer–Emmett–Teller (BET) Surface Area Analysis.
Thermal Analysis Technician
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BET Surface Area Analysis Technician
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The Thermal Analysis Service of ICMAB includes two equipments, a simultaneous thermogravimetric analysis (TG)- differential scanning calorimetry/differential thermal analysis (heat flow DSC /DTA) system NETZSCH -STA 449 F1 Jupiter, and a differential scanning calorimeter (power compensation DSC) Perkin Elmer DSC8500 LAB SYS (N5340501) equipped with a Liquid N2 controller CRYOFILL (N534004)
To request this service, please fill the application form in the link left and leave it together with the sample in the closet located at in the ground floor. For further information please contact the service technician Roberta Ceravola This email address is being protected from spambots. You need JavaScript enabled to view it.
Thermal Analysis Laboratory
ICMAB
Campus UAB
(in front of Firehouse)
08193, Bellaterra
Spain
By email:
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By phone:
+34 935801853
Ext. 270
IMB-CNM-CSIC
ICN2-CSIC
UAB
Molecular Beam
Epitaxy
ICMAB
Campus UAB
(in front of Firehouse)
08193, Bellaterra
Spain
By email:
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By phone:
+34 935801853
Ext. 281
Technical support
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Spectrophotometer Jasco 4700. Energy range: 300-7800 cm-1. The Service is provided with a Attenuated Total Reflectance accessory (ATR) for powder samples, films, polymers, liquids, etc. Powder samples can also be measured making KBr pellets.
This equipment is of self-service management for internal users, who have been previously trained by the technicians. However, the technicians are needed for the external users
There are two double beam UV-Vis-NIR spectrophotometer, a by Jasco V-780 and a Jasco V-770 with operational range of 190-3300 nm and also a Shimadzu UV-Vis 1700 spectrophotometer with operational range of 200-800 nm.
Liquid samples can be measured in absorbance or transmittance mode mainly using 1 cm or 1 mm quartz cuvettes. The three equipments are of self-service management for internal users, who have been previously trained by the technicians. However, the technicians are needed for the external users.
For solid samples it is available a Diffuse Reflectance Sphere DRA-2500 accessory in the UV-Vis-NIR Jasco V-770 spectrophotometer, with operational range of 190-3300 nm. Solid samples can be measured mainly in reflectance or transmittance mode.
A qualified technician is always needed for running the DRA-2500 accessory.
INTERNAL USERS
First contact with the Service Technicians Vega Lloveras (This email address is being protected from spambots. You need JavaScript enabled to view it., ext. 300, 311). They will train the users to manage the equipment by themselves because it works in a self-service regime for internal users.
All users must register in the database registration of the equipment every time they use it, pointing out the time they have spent doing the measurement, the group's IP and the project's number.
EXTERNAL USERS
First contact with the Service Technicians Vega Lloveras (This email address is being protected from spambots. You need JavaScript enabled to view it., ext. 300, 311) in order to arrange the details of the measurements. At the same time, a service form must be filled in. Every equipment has its own service form. There exists the possibility of working with the apparatus in a self-service regime.
In addition to this, all users must also register in the database of the equipment every time they use it.
Follow the general procedure
1. Liquid measurements.
Follow the general procedure.
2. Solid measurements using Diffuse Reflectance Sphere (DRA-2500) accessory.
The technicians are always needed for running the DRA-2500 accessory, for internal as well as for external users. Contact with them (This email address is being protected from spambots. You need JavaScript enabled to view it., ext. 300, 311) in order to arrange the details of the measurements.
At the same time, a service form must be filled in.
In addition to this, all users must also register in the database of the equipment every time they use it.
First contact with the Service Technician Vega Lloveras (This email address is being protected from spambots. You need JavaScript enabled to view it., ext. 300, 311) in order to arrange the details of the measurements. At the same time, a service form must be filled in.
Contact with Prof. Narcís Mestres (This email address is being protected from spambots. You need JavaScript enabled to view it., ext. 227)
Spectroscopic Techniques Laboratory
ICMAB
Campus UAB
(in front of Firehouse)
08193, Bellaterra
Spain
By email:
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By phone:
+34 935801853
Ext. 436100
The Service of Thin Films has been created to offer to the researchers the capability of fabrication of complex oxides thin films and heterostructures combining oxides and metals.
The deposition techniques are pulsed laser deposition (PLD) for oxides and sputtering for metals. Currently there are two PLD set-ups installed, and in short time both systems will be connected to a chamber with several sputtering units. PLD is a physical vapour deposition technique that uses ultraviolet laser radiation to vaporize material that is transferred to the substrate. The plot in Figure 1 is a sketch illustrating a PLD set-up.
Technician
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Technician
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Tel. 93 580 18 53 (ext. 303)
The technique is very suitable for oxides, and compared with other techniques is particularly useful to obtain films with complex stoichiometry and to grow epitaxial films and heterostructures. Moreover, PLD is highly versatile to optimize the deposition conditions of new materials, and the films can be grown in relatively fast processes. These characteristics favour the use of the technique by research groups having interest in different materials.
The pulsed beam of an ultraviolet laser (usually an excimer) is focused on a ceramic target placed in a vacuum chamber. The combination of pulsed irradiation, high photon energy, and high energy density can cause the ablation of the material. Ablation refers to the etching and emission of material under conditions totally out of the equilibrium. The plasma created expands fast along the perpendicular direction of the target (see the photography in Figure 2). A substrate is placed front the target, and inert or reactive gases are usually introduced during the deposition process.
Scientific Manager
Technician
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Tel. 935801853 (ext. 323-262)
Thin Films Laboratory
ICMAB
Campus UAB
(in front of Firehouse)
08193, Bellaterra
Spain
By email:
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By phone:
+34 935801853
Ext. 323-262
The SPM Lab offers 2.300 hours yearly of SPM related experiments to people inside and outside the ICMAB, without including maintenance, development of new equipment, setups, calibration and implementation of new modes.
The ICMAB groups who use the service are:
Superconducting Materials & Large Scale
Nanostructured Molecular Nanoscience and Organic Materials (NANOMOL)
Multifunctional Oxides and Complex Structures
Molecular Chirality
Surfaces and Nanomaterials
These groups make up 65% of the work done by the service. To a lesser extent, the service is also used by the following groups Nanoparticles and Nanocomposites, Inorganic Materials and Catalysis and Optoelectronic Nanostructured Materials. Besides ICMAB groups, service groups performs measurements of the Institute of Microelectronics of Barcelona (Micro & Nano Tools group, Integrated Circuits and Systems (ICAS), Department of Micro i Nanosistemes. Grup Biosensors & BioMEMs) groups the Autonomous University of Barcelona (Sensors and Biosensors Group, Department of Chemistry, Reliability of electronic devices and circuits) as well as to outside companies such as Henkel (Chemical sector) or Kostal (automotive sector). In total, more than 60 different users ICMAB and 13 have used the SPM external service over the past two years.
We also carry on outreach activities inside the ICMAB that brought international attention.
Training personnel (mainly PhD) in the AFM technique is another part of the tasks done at the lab.
Technician
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Tel. +34 935801853 Ext. 388
Technician
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Tel. +34 935801853 Ext. 388
Keysight 5100 AFM comprises a scanner of 60 x 60 microns in X / Y and 6 microns in the Z axis. The equipment can use a special liquid cell and controlled environment chamber for conducting scanners at low humidity or in nitrogen. The maximum sample size is 3x3 cm in X / Y and 2 cm thick. The equipment works in the Constant Amplitude Dynamic mode for obtaining topographic images, however Contact mode is also a possibility. The equipment uses an external generator module that can apply in-plane magnetic fields upto + -800 Oe. The equipment is specifically employed to acquired topographic images, having a low noise architecture that allow the acquisition of 500 nm size images.
We offer a broad range of services, including Topography, PFM, EFM, KPFM, CSAFM, PCAFM and SThM. Send us the Request Form to get a quotation.
[18] Iglesias, L., Gómez, A., Gich, M., Rivadulla, F., (2018) . Tuning Oxygen Vacancy Diffusion through Strain in SrTiO3 Thin Films. ACS Appl. Mater. Interfaces, 2018, 10 (41), pp 35367–35373
[17] del Moral, A., González-Rosillo, J. C., Gómez, A., Puig, T., & Obradors, X. (2018). Thermoelectric stack sample cooling modification of a commercial atomic force microscopy. Ultramicroscopy. https://doi.org/10.1016/j.ultramic.2018.10.014
[16] Daniel Suarez, Eden Steven, Elena Laukhina, Andres Gomez, Anna Crespi, Narcis Mestres, Concepció Rovira, Eun Sang Choi & Jaume Veciana (2018) 2D organic molecular metallic soft material derived from BEDO-TTF with electrochromic and rectifying properties. npj Flexible Electronicsvolume 2, Article number: 29 (2018) https://doi.org/10.1038/s41528-018-0041-1
[15] Vila-Fungueiriño, J. M., Gómez, A., Antoja-Lleonart, J., Gázquez, J., Magén, C., Noheda, B., & Carretero-Genevrier, A. (2018). Direct and converse piezoelectric responses at the nanoscale from epitaxial BiFeO 3 thin films grown by polymer assisted deposition. Nanoscale. 10.1039/c8nr05737k
[14] Sandoval, S., Kepic, D., Pérez del Pino, A., Gyorgy, E., Gómez, A., Pfannmoeller, M., … & Tobias, G. (2018). Selective Laser-Assisted Synthesis of Tubular van der Waals Heterostructures of Single-Layered PbI2 within Carbon Nanotubes Exhibiting Carrier Photogeneration. ACS nano, 12(7), 6648-6656. 10.1021/acsnano.8b01638
[13] A.Gomez, T.Puig, X.Obradors, Diminish electrostatic in piezoresponse force microscopy through longer or ultra-stiff tips, Applied Surface Science
Volume 439, 1 May 2018, Pages 577-582, https://doi.org/10.1016/j.apsusc.2018.01.080
[12] A.Gomez, S.Sanchez, Mariano Campoy-Quiles, A.Abate, Topological distribution of reversible and non-reversible degradation in perovskite solar cells, Nano Energy Volume 45, March 2018, Pages 94-100, https://doi.org/10.1016/j.nanoen.2017.12.040
[11] A. Gomez, M. Gich, A. Carretero-Genevrier, T. Puig, X. Obradors, Piezo-generated charge mapping revealed through direct piezoelectric force microscopy, Nature Communicationsvolume 8, Article number: 1113 (2017) doi:10.1038/s41467-017-01361-2
[10] Alberto Quintana, Andrés Gómez, Maria Dolors Baró, Santiago Suriñach, Eva Pellicer, Jordi Sort, Self-templating faceted and spongy single-crystal ZnO nanorods: Resistive switching and enhanced piezoresponse, In Materials & Design, Volume 133, 2017, Pages 54-61, ISSN 0264-1275, https://doi.org/10.1016/j.matdes.2017.07.039.
[9] Gómez, A., Vila-Fungueiriño, J. M., Moalla, R., Saint-Girons, G., Gázquez, J., Varela, M., Bachelet, R., Gich, M., Rivadulla, F. and Carretero-Genevrier, A. (2017), Semiconducting Films: Electric and Mechanical Switching of Ferroelectric and Resistive States in Semiconducting BaTiO3–δ Films on Silicon (Small 39/2017). Small, 13: n/a. doi:10.1002/smll.201770208
[8] A Carretero‐Genevrier, R Bachelet, G Saint‐Girons, R Moalla, JM Vila‐Fungueiriño, B Rivas‐Murias, F Rivadulla, J Rodriguez‐Carvajal, A Gomez, J Gazquez, M Gich, N Mestres, Ashutosh Tiwari, Rosario A Gerhardt, Magdalena Szutkowska. Development of Epitaxial Oxide Ceramics Nanomaterials Based on Chemical Strategies on Semiconductor Platforms (2016) Advanced Ceramic Materials
[7] David Kiefer, Liyang Yu, Erik Fransson, Andrés Gómez, Daniel Primetzhofer, Aram Amassian, Mariano Campoy-Quiles, Christian Müller (2016). A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics Advanced Science
[6] Marta Riba-Moliner, Narcis Avarvari, David. B. Amabilino , Arántzazu González-Campo, and Andrés Gómez* (2016). Distinguishing between Mechanical and Electrostatic Interaction in Single Pass Multi Frequency Electrostatic Force Microscopy Measurements on a Molecular Material. Langmuir, 2016, 32 (51), pp 13593–13599, DOI: 10.1021/acs.langmuir.6b03390
[5] Marta Riba-Moliner, Andrés Gómez-Rodríguez, David B. Amabilino, Josep Puigmartí-Luis, Arántzazu González-Campo, (2016). Functional supramolecular tetrathiafulvalene-based films with mixed valences states. Polymer
[4] Oliveras-González, C., Di Meo, F., González-Campo, A., Beljonne, D., Norman, P., Simón-Sorbed, M., … & Amabilino, D. B. (2015). Bottom-up hierarchical self-assembly of chiral porphyrins through coordination and hydrogen bonds. Journal of the American Chemical Society.
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[1] Coll, M., Gomez, A., Mas-Marza, E., Almora, O., Garcia-Belmonte, G., Campoy-Quiles, M., & Bisquert, J. (2015). Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites. The Journal of Physical Chemistry Letters, 6(8), 1408-1413.
Piezoresponse Phase image over the topography roughness, image acquired at low humidity environment. Sample courtesy of Joan Bisquert
Current image of a Carbon nano tube doped thermoelectric film obtained with a solid platinum tip, sample biased and at low humidity environment. The data can be used to correlate topography image with current image, obtained information on the local current distribution or compare the images with different samples, using histograms from the images. Sample courtesy of Bernhard Dörling
Scanning Probe
Microscopy
ICMAB
Campus UAB, delante de caseta de Bomberos
08193, Bellaterra
Spain