Atomistic Structure of Cobalt-Phosphate Nanoparticles for Catalytic Water Oxidation

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CNR-IOM Istituto Officina dei Materiali, Centro DEMOCRITOS, Scuola Internazionale Superiore di Studi Avanzati (SISSA), and Italian Institute of Technology (IIT-SISSA Unit), Via Bonomea 265, I-34136, Trieste, Italy
*Address correspondence to [email protected]; [email protected]
Cite this: ACS Nano 2012, 6, 12, 10497–10504
Publication Date (Web):November 12, 2012
https://doi.org/10.1021/nn3044325
Copyright © 2012 American Chemical Society
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Abstract

Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co–O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO6 octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ∼1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs—which are believed to be essential for the catalytic activity—display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

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Fitting and testing of the shell model parameters for Co-Pi; atomistic structures of crystallites in grains 4, 5, and 6; metadynamics trajectories using CV3; calculated radial distribution functions restricted to crystallites; total and projected density of electronic states for grain 6; and coordinates of the grains in Figures 1 and 2. This material is available free of charge via the Internet at http://pubs.acs.org.

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