Study of oxygen evolution reaction on amorphous Au13@Ni120P50 nanocluster

• Published in: Physical chemistry chemical physics : PCCP Vol. 2; no. 21; pp. 14545 - 14556
• Main Authors: Wang, Yanzhou, Gao, Panpan, Wang, Xiaoxu, Huo, Jinrong, Li, Lu, Zhang, Yajing, Volinsky, Alex A, Qian, Ping, Su, Yanjing
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 2018
• Subjects: Adsorption; Catalysis; Clusters; First principles; Free energy; Industrial applications; Kinetic energy; Nanoclusters; Oxygen evolution reactions; Potential energy; Water splitting
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/c8cp00784e

The pursuit of catalysts to promote effective water oxidization to produce oxygen has become a research subject of high priority for water splitting. Here, first-principles calculations are employed to study the water-splitting oxygen evolution reaction (OER) on ∼1.5 nm diameter Au 13 @Ni 120 P 50 core-shell nanoclusters. Water splitting to produce oxygen proceeds in four intermediate reaction steps (OH*, O*, OOH* and O 2 ). Adsorption configurations and adsorption energies for the species involved in OER on both Au 13 @Ni 120 P 50 cluster and Ni 12 P 5 (001) supported by Au are presented. In addition, thermodynamic free energy diagrams and kinetic potential energy changes are systematically discussed. We show that the third intermediate reaction (O* reacting with H 2 O to produce OOH*) of the four elementary steps is the reaction-determining step, which accords with previous results. Also, the catalytic performance of OER for Au 13 @Ni 120 P 50 is better than that for Ni 12 P 5 (001) supported by Au in terms of reactive overpotential (0.74 vs. 1.58 V) and kinetic energy barrier (2.18 vs. 3.17 eV). The optimal kinetic pathway for OER is further explored carefully for the Au 13 @Ni 120 P 50 cluster. The low thermodynamic overpotential and kinetic energy barrier make Au 13 @Ni 120 P 50 promising for industrial applications as a good OER electrocatalyst candidate. Potential energy changes of the four consecutive elementary reaction steps for OER on the surfaces of both bumpy Au 13 @Ni 120 P 50 nanocluster and clean Ni 12 P 5 (001) supported by bulk Au, respectively.