A systematic theoretical study of hydrogen activation, spillover and desorption in single-atom alloys

• Published in: Applied catalysis. A, General Vol. 610; p. 117948
• Main Authors: Zhao, Guo-Chen, Qiu, Yong-Qing, Liu, Chun-Guang
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 25.01.2021; Elsevier Science SA
• Subjects: Activation analysis; Catalysis; Catalytic activity; Copper; Density functional theory; Desorption; Electronic structure; First principles; Free-atom-like d state; Hydrogen activation; Hydrogen desorption; Hydrogen spillover; Hydrogenation; Intermetallic compounds; Single atom catalysts; Single-atom alloys; Structural analysis; Hydrogen desorption; Hydrogen activation; Single-atom alloys; Hydrogen spillover; Free-atom-like d state
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2020.117948

[Display omitted] •The hydrogen activation, spillover and desorption in single-atom alloys have been systematically studied.•CuPd, CuMn, CuPt single-atom alloys possess excellent catalytic activity superior to pure metal Cu.•The rare electronic structure of CuMn single-atom alloy shows that Mn is even like a free atom. Towards the computational design of single-atom alloys (SAAs) catalysts, we systematically studied the hydrogen activation, spillover and desorption by density functional theory (DFT) and first-principles calculations. Herein, we designed a model with 27 individual isolated metals in Cu(111) slab and described the scaling relationships and meticulous electronic structures. The results show that CuPd, CuMn, CuPt SAAs possess appropriate H atom binding ability and lower H2 dissociation barrier superior to pure metal Cu. There have been many reports about the design of hydrogenation catalysts before, but most of them are about CuPd and CuPt SAAs. Here we found that CuMn SAAs exhibits excellent catalytic performance, even comparable to CuPd and CuPt SAAs. Based on exhaustive electronic structure analysis, we discovered a rare electronic structure on CuMn SAAs, where Mn has no obvious electronic interaction with the host metal Cu, even like a free atom. The incredible phenomenon promotes CuMn SAAs to possess extraordinary hydrogenation catalytic activity. This paper seeks to provide deep insights into chemistry, catalysis, and interfaces for people to design new catalysts.