Computational Electrochemistry of Water Oxidation on Metal-Doped and Metal-Supported Defective h-BN
| Autor: | Cristiana Di Valentin, Hongsheng Liu, Daniele Perilli, Daniele Selli |
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| Přispěvatelé: | Perilli, D, Selli, D, Liu, H, Di Valentin, C |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Materials science
General Chemical Engineering 02 engineering and technology Electron Nitride Overpotential 010402 general chemistry Electrochemistry computational electrochemistry DFT water oxidation hexagonal boron nitride 01 natural sciences Redox DFT Catalysis Metal Lattice (order) Environmental Chemistry General Materials Science computational electrochemistry metal cluster 021001 nanoscience & nanotechnology nitride 0104 chemical sciences General Energy Chemical engineering water oxidation visual_art visual_art.visual_art_medium 0210 nano-technology |
| Popis: | Metal-doped and metal-supported two-dimensional materials are attracting a lot of interest as potentially active electrocatalysts for reduction and oxidation processes. Previously, when a non-regular 2 D h-BN layer was grown on a Cu(111) surface, metal adatoms were found to spontaneously emerge from the bulk to fill the atomic holes in the structure and become available for surface catalysis. Herein, computational electrochemistry is used to investigate and compare the performance of Cu-doped and Cu-supported pristine and defective h-BN systems for the electrocatalytic water oxidation reaction. For the various model systems, the intermediate species of this multistep oxidation process are identified and the free-energy variations for each step of reaction are computed, even for those steps that do not involve an electron or a proton transfer. Both associative and O2 direct evolution mechanisms are considered. On this thermodynamic basis, the potential-determining step, the thermodynamic-determining step, and consequently the theoretical overpotential are determined for comparison with experiments. Small Cu clusters (tetramers) trapped in the h-BN defective lattice on a Cu(111) support are found to be very active for the water oxidation reaction since such systems are characterized by a low overpotential and by a small energy cost for O2 release from the catalyst, which is often observed to be a major limit for other potential electrocatalysts. |
| Databáze: | OpenAIRE |
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