Dual-Atom Catalyst with N-Colligated Zn1Co1 Species as Dominant Active Sites for Propane Dehydrogenation

Yicong Chai; Shunhua Chen; Yang Chen; Fenfei Wei; Liru Cao; Jian Lin; Lin Li; Xiaoyan Liu; Sen Lin; Xiaodong Wang; Tao Zhang

doi:10.1021/jacs.3c08616

Dual-Atom Catalyst with N-Colligated Zn₁Co₁ Species as Dominant Active Sites for Propane Dehydrogenation

J Am Chem Soc. 2024 Jan 10;146(1):263-273. doi: 10.1021/jacs.3c08616. Epub 2023 Dec 18.

Authors

Yicong Chai^{1

2}, Shunhua Chen³, Yang Chen¹, Fenfei Wei³, Liru Cao^{1

2}, Jian Lin¹, Lin Li¹, Xiaoyan Liu¹, Sen Lin³, Xiaodong Wang¹, Tao Zhang¹

Affiliations

¹ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
² University of Chinese Academy of Sciences, Beijing 100049, China.
³ State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, China.

PMID: 38109718
DOI: 10.1021/jacs.3c08616

Abstract

Dual-atom catalysts (DACs) with paired active sites can provide unique intrinsic properties for heterogeneous catalysis, but the synergy of the active centers remains to be elucidated. Here, we develop a high-performance DAC with Zn₁Co₁ species anchored on nitrogen-doped carbon (Zn₁Co₁/NC) as the dominant active site for the propane dehydrogenation (PDH) reaction. It exhibits several times higher turnover frequency (TOF) of C₃H₈ conversion and enhanced C₃H₆ selectivity compared to Zn₁/NC or Co₁/NC with only a single-atom site. Various experimental and theoretical studies suggest that the enhanced PDH performance stems from the promoted activation of the C-H bond of C₃H₈ triggered by the electronic interaction between Zn₁ and Co₁ colligated by N species. Moreover, the dynamic sinking of the Zn₁ site and rising of the Co₁ site, together with the steric effect of the dissociated H species at the bridged N during the PDH reaction, provides a feasible channel for C₃H₆ desorption through the more exposed Co₁ site, thereby boosting the selectivity. This work provides a promising strategy for designing robust hetero DACs to simultaneously increase activity and selectivity in the PDH reaction.