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.

Perilli, D., Selli, D., Liu, H., & Di Valentin, C. (2019). Computational Electrochemistry of Water Oxidation on Metal-Doped and Metal-Supported Defective h-BN. CHEMSUSCHEM, 12(9), 1995-2007 [10.1002/cssc.201802499].

Computational Electrochemistry of Water Oxidation on Metal-Doped and Metal-Supported Defective h-BN

Perilli, D;Selli, D;Liu, H;Di Valentin, C
2019

Abstract

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.
No
Articolo in rivista - Articolo scientifico
Scientifica
computational electrochemistry; DFT; metal clusters; nitrides; water oxidation;
computational electrochemistry; DFT; metal clusters; nitrides; water oxidation
English
1995
2007
13
Perilli, D., Selli, D., Liu, H., & Di Valentin, C. (2019). Computational Electrochemistry of Water Oxidation on Metal-Doped and Metal-Supported Defective h-BN. CHEMSUSCHEM, 12(9), 1995-2007 [10.1002/cssc.201802499].
Perilli, D; Selli, D; Liu, H; Di Valentin, C
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10281/232848
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