Turning on Zn 4s Electrons in a N2‐Zn‐B2 Configuration to Stimulate Remarkable ORR Performance. Issue 1 (28th October 2020)

• Record Type: Journal Article
• Authors: Wang, Jing; Li, Hongguan; Liu, Shuhu; Hu, Yongfeng; Zhang, Jing; Xia, Meirong; Hou, Yanglong; Tse, John; Zhang, Jiujun; Zhao, Yufeng
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 1(2021)
• Page Start: 181
• Page End: 185
• Publication Date: 2020-10-28
• Subjects: co-doping -- M-Nx-C -- oxygen reduction -- s-band manipulation -- Zn single atoms; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202009991
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A zinc‐based single‐atom catalyst has been recently explored with distinguished stability, of which the fully occupied Zn 2+ 3d 10 electronic configuration is Fenton‐reaction‐inactive, but the catalytic activity is thus inferior. Herein, we report an approach to manipulate the s‐band by constructing a B, N co‐coordinated Zn‐B/N‐C catalyst. We confirm both experimentally and theoretically that the unique N2 ‐Zn‐B2 configuration is crucial, in which Zn + (3d 10 4s 1 ) can hold enough delocalized electrons to generate suitable binding strength for key reaction intermediates and promote the charge transfer between catalytic surface and ORR reactants. This exclusive effect is not found in the other transition‐metal counterparts such as M‐B/N‐C (M=Mn, Fe, Co, Ni and Cu). Consequently, the as‐obtained catalyst demonstrates impressive ORR activity, along with remarkable long‐term stability in both alkaline and acid media. This work presents a new concept in the further design of electrocatalyst. Abstract : A B, N co‐coordinated catalyst (denoted Zn‐B/N‐C) has been fabricated wherein the s‐band of Zn + has been manipulated. The ORR efficiency is maximized by the B2 ‐Zn‐N2 configuration, which holds enough Zn 4s electrons to guarantee favorable adsorption of O2 as well as visible charge transfer. The catalyst shows excellent long‐term stability in both acid and alkaline environment.