title: Gold Nanoclusters Promote Electrocatalytic Water Oxidation at the Nanocluster/CoSe2Interface.
abstract: Electrocatalytic water splitting to produce hydrogen comprises the hydrogen and oxygen evolution half reactions (HER and OER), with the latter as the bottleneck process. Thus, enhancing the OER performance and understanding the mechanism are critically important. Herein, we report a strategy for OER enhancement by utilizing gold nanoclusters to form cluster/CoSe2composites; the latter exhibit largely enhanced OER activity in alkaline solutions. The Au25/CoSe2composite affords a current density of 10 mA cm-2at small overpotential of ∼0.43 V (cf. CoSe2: ∼0.52 V). The ligand and gold cluster size can also tune the catalytic performance of the composites. Based upon XPS analysis and DFT simulations, we attribute the activity enhancement to electronic interactions between nanocluster and CoSe2, which favors the formation of the important intermediate (OOH) as well as the desorption of oxygen molecules over Aun/CoSe2composites in the process of water oxidation. Such an atomic level understanding may provide some guidelines for design of OER catalysts.
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Shuo
authors.initials: S
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Renxi
authors.initials: R
authors.lastname: Jin
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Hadi
authors.initials: H
authors.lastname: Abroshan
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Chenjie
authors.identifier: 0000-0002-2904-5590
authors.initials: C
authors.lastname: Zeng
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Hui
authors.initials: H
authors.lastname: Zhang
authors.affiliation: Chemical and Petroleum Engineering, and Physics, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Stephen D
authors.identifier: 0000-0003-2035-6373
authors.initials: SD
authors.lastname: House
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Eric
authors.initials: E
authors.lastname: Gottlieb
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.|School of Computational Sciences, Korea Institute for Advanced Study , Seoul 02455, Korea.
authors.forename: Hyung J
authors.identifier: 0000-0003-4334-1879
authors.initials: HJ
authors.lastname: Kim
authors.affiliation: Chemical and Petroleum Engineering, and Physics, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Judith C
authors.initials: JC
authors.lastname: Yang
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Rongchao
authors.identifier: 0000-0002-2525-8345
authors.initials: R
authors.lastname: Jin