Breaking the scaling relationship of ORR on carbon-based single-atom catalysts through building a local collaborative structure. Issue 23 (3rd November 2021)

• Record Type: Journal Article
• Authors: Fu, Cehuang; Luo, Liuxuan; Yang, Lijun; Shen, Shuiyun; Wei, Guanghua; Zhang, Junliang
• Is Part Of: Catalysis science & technology. Volume 11:Issue 23(2021)
• Page Start: 7764
• Page End: 7772
• Publication Date: 2021-11-03
• Subjects: Catalysis -- Periodicals; 541.395
• DOI: 10.1039/d1cy01195b
• Languages: English
• ISSNs: 2044-4753

Abstract

Abstract : The local collaborative structure further stabilizes the OOH*/OH* and weakens the on metal site by hydrogen bond and repulsive interaction, for which the scaling relationship of ORR could be broken. Abstract : The structure of M–N4, in which one metal atom is anchored by 4 N atoms, is the main active structure of N-doped carbon-based single-atom catalysts (SACs). However, we still lack efficient strategies for improving their activity. In this DFT study, M–N4 is doped with phosphorus or sulfur, which can be realized in many experiments by the addition of a P/S source. Previous studies simply attributed the improved activity of the metal site to the electronic effect of non-metal doping using the d-band center theory, which is inaccurate for understanding the ORR performance in the P/S-doped M–N4 . We found that the strong interactions between P/S and O cause the doping site to be occupied by adsorbed O atoms, whose effects on the ORR process have been ignored for a long time. The local collaborative structure further stabilizes OOH*/OH* and weakens on metal sites by hydrogen bond and repulsive interactions, for which the scaling relationship of ORR could be broken. In our P/S-doped models, the onset potentials of ORR in the 4e − mechanism on M 1 –N4 (M 1 = Co, Ni, Cu, Rh, Ir, and Pt) and those in the 2e − mechanism on M 2 –N4 (M 2 = Ni, Cu, Pd, Ag, Pt, and Au) has increased.