INPhINIT Incoming Fellowship – Electronic Engineering of 2D materials for Efficient Oxygen, Hydrogen and Carbon Electrocatalysis
The Computational Electrocatalysis Group (CEG) led by Dr Federico Calle Vallejo uses Density Functional Theory (DFT), atomistic thermodynamics and kinetics, and house-made descriptors to create predictive, structure-sensitive models of electrocatalytic reactions (see a recent review in Chem. Sci. 10, 2019, 8060). Our models are based on conventional and “generalized” coordination numbers (Nat. Chem. 7, 2015, 403; Science 350, 2015, 185), “outer” electrons (Chem. Sci. 4, 2013, 1245; Phys. Rev. Lett. 108, 2012, 116103) and “electrocatalytic symmetry” (ACS Catal. 9, 2019, 4218).We are interested in extended surfaces and nanoparticles of transition metals, their alloys and oxides. We model reactions of interest in fuel cells, electrolyzers and pollution control devices such as O2 reduction and evolution, H2 evolution, CO oxidation and reduction, and NOx reduction. CEG actively collaborates with experimenters in The Netherlands, Germany, Singapore and Madrid.
The Nanoclusters and Nanostructured Materials (2NM) group is headed by Prof. Stefan Bromley and focusses on modelling the properties of low dimensional nanoscale materials (e.g. inorganic nanoclusters – Chem. Soc. Rev. 38, 2009, 2657, organic 2D materials – Nat. Commun. 8, 2017, 1957). Such materials often display novel size-dependent properties compared to materials at everyday length scales. Employing classical atomistic and quantum chemical methods implemented on powerful supercomputers, we provide detailed and predictive insights into the structural, electronic and chemical properties of nanomaterials. Our main goals are to understand how nanomaterials evolve with respect to their size, and to design viable new materials from nanoscale building blocks. The 2NM group focusses on two classes of materials: i) nanoclusters and nanostructured inorganic materials for energy applications (e.g TiO2, ZnO), ii) nanostructured 2D materials built from organic molecular building blocks for electronics/spintronics.
The colossal imbalance in the carbon cycle calls for a portfolio of interconnected solutions. For instance, automotive CO2 emissions can be substantially reduced by combining electrolyzers and fuel cells. H2 can be “greenly” produced from H2O splitting in electrolyzers powered by solar or wind energy, and fuel-cell vehicles can use H2 to generate power, without burning any fossil fuels (PNAS 103, 2006, 15729).However, a major problem of this approach is that O2 reduction (namely, transforming of O2 into H2O by using protons and electrons) in fuel cells and H2 evolution (namely, combining of protons and electrons to produce H2) in electrolyzers, are catalyzed by Pt, a tremendously scarce and expensive metal (Science 350, 2015, 185). Besides, O2 reduction is kinetically slow, even when using Pt, resulting in large power losses (Appl. Cat. B 56, 2005, 9). Thus, new, stable and active catalysts based on Earth-abundant elements are now sought to replace Pt.
Two-dimensional covalent radical organic frameworks (2D-CORFs) were initially proposed by the 2NM group (Chem. Sci. 8, 2017, 1027). Soon afterwards, experimental groups synthesized the first 2D-CORFs and showed their promise in electrocatalysis (Angew. Chem. Int. Ed. 57, 2018, 8007). However, these new 2D materials remain largely unexplored and the electronic factors modulating their catalytic activities are still unknown.
In this interdisciplinary project, the CEG and 2NM groups will join forces to study the electrocatalytic activities of 2D-CORFs in a holistic way. The analysis will consider intrinsic factors such as stretching and compressive strain, and external factors such as support, solvent and pH effects. The result will be a comprehensive picture of 2D-CORFs that can guide experimenters toward the synthesis of next-generation electrocatalysts for O2 reduction and H2 evolution. To further help balance the C cycle, CO2 electrolysis to industrially useful compounds such as CO and CH4 will also be considered.
https://scholar.google.com/citations?hl=en&user=Ehc5tVAAAAAJ
Google scholar profile of Prof. Stefan Bromley
https://scholar.google.com/citations?hl=en&user=GRcDA5cAAAAJ
Personal web page (Stefan Bromley) as group leader at ICREA. ICREA is an institution that offers permanent, tenured positions to researchers from all over the world to come and work in Catalonia. Over the years these positions have become a synonym of global academic excellence.
https://www.icrea.cat/Web/ScientificStaff/stefan-t.-bromley-441