Coordination tailoring of Cu single sites on C3N4 realizes selective CO2 hydrogenation at low temperature

Tang Yang; Xinnan Mao; Ying Zhang; Xiaoping Wu; Lu Wang; Mingyu Chu; Chih-Wen Pao; Shize Yang; Yong Xu; Xiaoqing Huang

doi:10.1038/s41467-021-26316-6

Coordination tailoring of Cu single sites on C₃N₄ realizes selective CO₂ hydrogenation at low temperature

Nat Commun. 2021 Oct 15;12(1):6022. doi: 10.1038/s41467-021-26316-6.

Authors

Tang Yang¹, Xinnan Mao^{2

3}, Ying Zhang¹, Xiaoping Wu³, Lu Wang⁴, Mingyu Chu^{2

3}, Chih-Wen Pao⁵, Shize Yang⁶, Yong Xu⁷, Xiaoqing Huang⁸

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
² Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou, China.
³ Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, Collaborative Innovation Center of Advanced Energy Materials, School of Materials and Energy, Guangdong University of Technology, Guangzhou, China.
⁴ Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou, China. lwang@suda.edu.cn.
⁵ National Synchrotron Radiation Research Center, Hsinchu, Taiwan.
⁶ Eyring Materials Center, Arizona State University, Tempe, AZ, USA.
⁷ Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, Collaborative Innovation Center of Advanced Energy Materials, School of Materials and Energy, Guangdong University of Technology, Guangzhou, China. yongxu@gdut.edu.cn.
⁸ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. hxq006@xmu.edu.cn.

Abstract

CO₂ hydrogenation has attracted great attention, yet the quest for highly-efficient catalysts is driven by the current disadvantages of poor activity, low selectivity, and ambiguous structure-performance relationship. We demonstrate here that C₃N₄-supported Cu single atom catalysts with tailored coordination structures, namely, Cu-N₄ and Cu-N₃, can serve as highly selective and active catalysts for CO₂ hydrogenation at low temperature. The modulation of the coordination structure of Cu single atom is readily realized by simply altering the treatment parameters. Further investigations reveal that Cu-N₄ favors CO₂ hydrogenation to form CH₃OH via the formate pathway, while Cu-N₃ tends to catalyze CO₂ hydrogenation to produce CO via the reverse water-gas-shift (RWGS) pathway. Significantly, the CH₃OH productivity and selectivity reach 4.2 mmol g^-1 h^-1 and 95.5%, respectively, for Cu-N₄ single atom catalyst. We anticipate this work will promote the fundamental researches on the structure-performance relationship of catalysts.

Abstract

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