Non-Bonding Interaction of Neighboring Fe and Ni Single-Atom Pairs on MOF-Derived N-Doped Carbon for Enhanced CO2 Electroreduction

Long Jiao; Juntong Zhu; Yan Zhang; Weijie Yang; Siyuan Zhou; Aowen Li; Chenfan Xie; Xusheng Zheng; Wu Zhou; Shu-Hong Yu; Hai-Long Jiang

doi:10.1021/jacs.1c08050

Non-Bonding Interaction of Neighboring Fe and Ni Single-Atom Pairs on MOF-Derived N-Doped Carbon for Enhanced CO₂ Electroreduction

J Am Chem Soc. 2021 Nov 24;143(46):19417-19424. doi: 10.1021/jacs.1c08050. Epub 2021 Nov 15.

Authors

Long Jiao¹, Juntong Zhu², Yan Zhang¹, Weijie Yang³, Siyuan Zhou², Aowen Li², Chenfan Xie¹, Xusheng Zheng⁴, Wu Zhou^{2

5}, Shu-Hong Yu¹, Hai-Long Jiang¹

Affiliations

¹ Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Soft Matter Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
² School of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
³ Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding, Hebei 071003, P. R. China.
⁴ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, P. R. China.
⁵ CAS Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.

PMID: 34779627
DOI: 10.1021/jacs.1c08050

Abstract

Single-atom catalysts (SACs), featuring high atom utilization, have captured widespread interests in diverse applications. However, the single-atom sites in SACs are generally recognized as independent units and the interplay of adjacent sites is largely overlooked. Herein, by the direct pyrolysis of MOFs assembled with Fe and Ni-doped ZnO nanoparticles, a novel Fe₁-Ni₁-N-C catalyst, with neighboring Fe and Ni single-atom pairs decorated on nitrogen-doped carbon support, has been precisely constructed. Thanks to the synergism of neighboring Fe and Ni single-atom pairs, Fe₁-Ni₁-N-C presents significantly boosted performances for electrocatalytic reduction of CO₂, far surpassing Fe₁-N-C and Ni₁-N-C with separate Fe or Ni single atoms. Additionally, the Fe₁-Ni₁-N-C also exhibits superior performance with excellent CO selectivity and durability in Zn-CO₂ battery. Theoretical simulations reveal that, in Fe₁-Ni₁-N-C, single Fe atoms can be highly activated by adjacent single-atom Ni via non-bonding interaction, significantly facilitating the formation of COOH* intermediate and thereby accelerating the overall CO₂ reduction. This work supplies a general strategy to construct single-atom catalysts containing multiple metal species and reveals the vital importance of the communitive effect between adjacent single atoms toward improved catalysis.