In a lab just outside of Barcelona, tiny particles are arranging themselves into ordered 3D structures, like little animated Lego bricks clicking themselves into place frame by frame. And not just any particles, but highly-porous organic-inorganic hybrids whose size and shape can be controlled to tune the properties of the resulting ensemble.
Self-assembly has long been ubiquitous in chemistry, materials science and biology, but it emerges now as an efficient route to a range of materials with uniform structures, particularly at the nanoscale. Many studies to date have reported the synthesis of polymeric and metal-based particles that spontaneously self-assemble into ordered 3D superstructures. Today researchers at the Catalan Institute of Nanoscience and Nanotechnology (ICN2) and the Institute of Materials Science of Madrid (ICMM-CSIC) present their findings in relation to hybrid metal-organic particles and, in doing so, add a new family to the list of compounds that can be synthesised for 3D self-assembly: metal-organic frameworks (MOFs).
A condition for this stop-motion Lego effect is that all synthesised particles present the same size (monodispersity) and shape, so that when they click into place, the resulting arrangement is well-ordered, well-packed and functional. Think of cannonballs: they pile up easily because of their shape, fitting into place regardless of their orientation. Bricks, however, need to be in the right place and facing the right direction to create an orderly pile.
Until now this had never been achieved for crystalline hybrid compounds like MOFs, despite their sharing the same polyhedral geometries as their metal-based counterparts. But in this latest work, published this week in Nature Chemistry, researchers led by ICREA Prof. Daniel Maspoch of the ICN2 and by Prof. Cefe López of the ICMM, with lead author Civan Avci (ICN2), report the successful synthesis, with the required homogeneity of size and shape, of the MOFs known as “ZIF-8” and “UiO-66”.
The resulting 3D superstructures, made up of many billions of identical particles arranged into crystals several millimetres across, present properties typical of photonic crystals, a promising new material that is finding applications in the manipulation of light. As such, the new structures scatter light in a way that provides colour without the use of pigments or dyes, known as structural colour. Furthermore, by controlling the size and shape of the particles at synthesis, we can tune the material’s photonic band gap to determine what colour is achieved.
Built from MOFs, the new structures also boast high porosity, a feature that can be exploited in sensing applications: different substances adsorbed into the pores cause the light to be refracted into different colours. This effect can be tuned such that a given colour indicates the presence of a given substance. The ability to form 3D superstructures from porous units also opens the door to applications based on the alignment of the pores on a large scale, for instance, to produce improved membranes for gas adsorption and catalysis.
This work is the result of a multi-disciplinary collaboration between research centres in Spain and Holland. Led by the ICN2 and ICMM, researchers from the Debye Institute for Nanomaterials Science of Utrecht University and the Institute of Materials Science of Barcelona (ICMAB) also lent their practical and theoretical expertise. The ICN2 and ICMAB are both based at the Autonomous University of Barcelona (UAB).
Civan Avci, Inhar Imaz, Arnau Carné-Sánchez, Jose Angel Pariente, Nikos Tasios, Javier Pérez-Carvajal, Maria Isabel Alonso
, Alvaro Blanco, Marjolein Dijkstra, Cefe Lopez, and Daniel Maspoch. Self-Assembly of Polyhedral Metal-Organic Framework Particles into Three-Dimensional Ordered Superstructures
. Nature Chemistry
. DOI: 10.1038/nchem.2875This article has been published originally at ICN2, and has been featured in R+D CSIC, Agencia SINC, madridmasd, La Vanguardia, and El Periódico.