Rational design of heterogenized molecular phthalocyanine hybrid single-atom electrocatalyst towards two-electron oxygen reduction

Wenjun Fan; Zhiyao Duan; Wei Liu; Rashid Mehmood; Jiating Qu; Yucheng Cao; Xiangyang Guo; Jun Zhong; Fuxiang Zhang

doi:10.1038/s41467-023-37066-y

Rational design of heterogenized molecular phthalocyanine hybrid single-atom electrocatalyst towards two-electron oxygen reduction

Nat Commun. 2023 Mar 14;14(1):1426. doi: 10.1038/s41467-023-37066-y.

Authors

Wenjun Fan¹, Zhiyao Duan², Wei Liu³, Rashid Mehmood^{1

4}, Jiating Qu^{1

4}, Yucheng Cao^{1

4}, Xiangyang Guo¹, Jun Zhong⁵, Fuxiang Zhang⁶

Affiliations

¹ State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.
² State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, 710072, Xi'an, P. R. China. zhiyao.duan@nwpu.edu.cn.
³ State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, 116024, Dalian, China.
⁴ University of Chinese Academy of Sciences, 100049, Beijing, China.
⁵ Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, 215123, Suzhou, Jiangsu, P. R. China.
⁶ State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China. fxzhang@dicp.ac.cn.

Abstract

Single-atom catalysts supported on solid substrates have inspired extensive interest, but the rational design of high-efficiency single-atom catalysts is still plagued by ambiguous structure determination of active sites and its local support effect. Here, we report hybrid single-atom catalysts by an axial coordination linkage of molecular cobalt phthalocyanine with carbon nanotubes for selective oxygen reduction reaction by screening from a series of metal phthalocyanines via preferential density-functional theory calculations. Different from conventional heterogeneous single-atom catalysts, the hybrid single-atom catalysts are proven to facilitate rational screening of target catalysts as well as understanding of its underlying oxygen reduction reaction mechanism due to its well-defined active site structure and clear coordination linkage in the hybrid single-atom catalysts. Consequently, the optimized Co hybrid single-atom catalysts exhibit improved 2e^- oxygen reduction reaction performance compared to the corresponding homogeneous molecular catalyst in terms of activity and selectivity. When prepared as an air cathode in an air-breathing flow cell device, the optimized hybrid catalysts enable the oxygen reduction reaction at 300 mA cm^-2 exhibiting a stable Faradaic efficiency exceeding 90% for 25 h.