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Updated: Jan 8, 2026
Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Orbital-level insights into multifunctional electrocatalysis of transition-metal single atoms anchored on WS2
Bingling He1,2, Mingyang Ren1,3, Qianyi Bu1
1School of Electronic Engineering, Chaohu University, Hefei 238000, China.
Abstract:
A comprehensive understanding of single-atom catalysts (SACs) from an orbital-level perspective will provide a simple and direct method for the selection of SACs. Here, using first-principles calculations, we reveal the orbital-level origins of catalytic activity with WS2-supported transition-metal single atoms (TM@WS2, TM = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt) using the hydrogen evolution reaction (HER), oxygen reduction (ORR) and oxygen evolution (OER) as examples. We show that, for the HER, the activity is primarily determined by the orbital hybridization characteristics and the covalency between the TM atom and adsorbed hydrogen. In contrast, the activities are governed by orbital-specific spin-polarized occupation of antibonding states, which modulates TM-OH bond strength and intermediate adsorption. Among the catalysts, Fe@WS2, Co@WS2, Ru@WS2, and Pt@WS2 exhibit excellent HER performance, with Fe@WS2 and Ru@WS2 achieving particularly low energy barriers via the Volmer-Tafel pathway. Ni@WS2 exhibits outstanding OER activity, Pd@WS2 serves as a bifunctional catalyst for the ORR/OER, and Pt@WS2 demonstrates remarkable trifunctional activity for overall water splitting and metal-air batteries. These insights provide a fundamental orbital-level understanding of catalytic activity, thereby guiding the development of efficient multifunctional electrocatalysts.
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