Unraveling the Role of Orbital Interaction in the Electrochemical HER of the Trimetallic AgAuCu Nanobowl Catalyst

Rathindranath Biswas; Saptarshi Ghosh Dastider; Imtiaz Ahmed; Sourabh Barua; Krishnakanta Mondal; Krishna Kanta Haldar

doi:10.1021/acs.jpclett.3c00011

Unraveling the Role of Orbital Interaction in the Electrochemical HER of the Trimetallic AgAuCu Nanobowl Catalyst

J Phys Chem Lett. 2023 Apr 6;14(13):3146-3151. doi: 10.1021/acs.jpclett.3c00011. Epub 2023 Mar 24.

Authors

Rathindranath Biswas¹, Saptarshi Ghosh Dastider^{1

2}, Imtiaz Ahmed¹, Sourabh Barua², Krishnakanta Mondal², Krishna Kanta Haldar¹

Affiliations

¹ Department of Chemistry, Central University of Punjab, Bathinda 151401, India.
² Department of Physics, Central University of Punjab, 151401 Bathinda, Punjab, India.

PMID: 36961305
DOI: 10.1021/acs.jpclett.3c00011

Abstract

Unraveling the origins of the electrocatalytic activity of composite nanomaterials is crucial but inherently challenging. Here, we present a comprehensive investigation of the influence of different orbitals' interaction in the AuAgCu nanobowl model electrocatalyst during the hydrogen evolution reaction (HER). According to our theoretical study, AgAuCu exhibits a lower energy barrier than AgAu and AgCu bimetallic systems for the HER, suggesting that the trimetallic AgAuCu system interacts optimally with H*, resulting in the most efficient HER catalyst. As we delve deeper into the HER activity of AgAuCu, it was observed that the presence of Cu allows Au to adsorb the H* intermediate through the hybridization of s orbitals of hydrogen and s, d_x²_-y², and d_z² orbitals of Au. Such orbital interaction was not present in the cases of AgAu and AgCu bimetallic systems, and as a result, these bimetallic systems exhibit lower HER activities.