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.
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.
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.
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.
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
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
Cell culture studies on neural cortex cells from rat embryo , show survival above controls
(collaboration with HNP Toledo and 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.