Encapsulating a Ni(II) molecular catalyst in photoactive metal-organic framework for highly efficient photoreduction of CO2

Zhi-Hao Yan; Bo Ma; Shu-Rong Li; Junxue Liu; Rong Chen; Ming-Hao Du; Shengye Jin; Gui-Lin Zhuang; La-Sheng Long; Xiang-Jian Kong; Lan-Sun Zheng

doi:10.1016/j.scib.2019.05.014

Encapsulating a Ni(II) molecular catalyst in photoactive metal-organic framework for highly efficient photoreduction of CO₂

Sci Bull (Beijing). 2019 Jul 30;64(14):976-985. doi: 10.1016/j.scib.2019.05.014. Epub 2019 May 18.

Authors

Affiliations

¹ Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
² State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
³ State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China. Electronic address: sjin@dicp.ac.cn.
⁴ College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
⁵ Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. Electronic address: xjkong@xmu.edu.cn.

PMID: 36659809
DOI: 10.1016/j.scib.2019.05.014

Abstract

Photocatalytic reduction of CO₂ to CO is a promising strategy for reducing atmospheric CO₂ levels and storing solar radiation as chemical energy. Here, we demonstrate that a molecular catalyst [Ni^II(bpet)(H₂O)₂] successfully encapsulated into a highly robust and visible-light responsive metal-organic framework (Ru-UiO-67) to fabricate composite catalysts for photocatalytic CO₂ reduction. The composite Ni@Ru-UiO-67 photocatalysts show efficient visible-light-driven CO₂ reduction to CO with a TON of 581 and a selectivity of 99% after 20-h illumination, because of the facile electron transfer from Ru-photosensitizer to Ni(II) active sites in Ni@Ru-UiO-67 system. The mechanistic insights into photoreduction of CO₂ have been studied based on thermodynamical, electrochemical, and spectroscopic investigation, together with density functional theory (DFT) calculations. This work shows that encapsulating molecular catalyst into photoactive MOF highlights opportunities for designing efficient, stable and recyclable photocatalysts.

Keywords: CO(2) reduction; DFT calculations; Metal-organic frameworks; Photocatalysis; Transient absorption.