A Covalent Organic Framework Bearing Single Ni Sites as a Synergistic Photocatalyst for Selective Photoreduction of CO2 to CO

Wanfu Zhong; Rongjian Sa; Liuyi Li; Yajun He; Lingyun Li; Jinhong Bi; Zanyong Zhuang; Yan Yu; Zhigang Zou

doi:10.1021/jacs.9b02997

A Covalent Organic Framework Bearing Single Ni Sites as a Synergistic Photocatalyst for Selective Photoreduction of CO₂ to CO

J Am Chem Soc. 2019 May 8;141(18):7615-7621. doi: 10.1021/jacs.9b02997. Epub 2019 Apr 24.

Authors

Wanfu Zhong¹, Rongjian Sa², Liuyi Li¹, Yajun He¹, Lingyun Li¹, Jinhong Bi¹, Zanyong Zhuang¹, Yan Yu¹, Zhigang Zou^{1

3}

Affiliations

¹ Key Laboratory of Eco-materials Advanced Technology, College of Materials Science and Engineering , Fuzhou University , Fuzhou 350108 , China.
² Institute of Oceanography, Ocean College , Minjiang University , Fuzhou , Fujian 350108 , China.
³ Eco-materials and Renewable Energy Research Center, College of Engineering and Applied Sciences , Nanjing University , Nanjing 210093 , China.

PMID: 30998334
DOI: 10.1021/jacs.9b02997

Abstract

Photocatalytic reduction of CO₂ into energy-rich carbon compounds has attracted increasing attention. However, it is still a challenge to selectively and effectively convert CO₂ to a desirable reaction product. Herein, we report a design of a synergistic photocatalyst for selective reduction of CO₂ to CO by using a covalent organic framework bearing single Ni sites (Ni-TpBpy), in which electrons transfer from photosensitizer to Ni sites for CO production by the activated CO₂ reduction under visible-light irradiation. Ni-TpBpy exhibits an excellent activity, giving a 4057 μmol g^-1 of CO in a 5 h reaction with a 96% selectivity over H₂ evolution. More importantly, when the CO₂ partial pressure was reduced to 0.1 atm, 76% selectivity for CO production is still obtained. Theoretical calculations and experimental results suggest that the promising catalytic activity and selectivity are ascribed to synergistic effects of single Ni catalytic sites and TpBpy, in which the TpBpy not only serves as a host for CO₂ molecules and Ni catalytic sites but also facilitates the activation of CO₂ and inhibits the competitive H₂ evolution.