Turning Au Nanoclusters Catalytically Active for Visible-Light-Driven CO2 Reduction through Bridging Ligands

Xiaofeng Cui; Jin Wang; Bing Liu; Shan Ling; Ran Long; Yujie Xiong

doi:10.1021/jacs.8b06723

Turning Au Nanoclusters Catalytically Active for Visible-Light-Driven CO₂ Reduction through Bridging Ligands

J Am Chem Soc. 2018 Dec 5;140(48):16514-16520. doi: 10.1021/jacs.8b06723. Epub 2018 Nov 20.

Authors

Xiaofeng Cui^{1

2}, Jin Wang¹, Bing Liu³, Shan Ling², Ran Long¹, Yujie Xiong¹

Affiliations

¹ Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, and National Synchrotron Radiation Laboratory , University of Science and Technology of China , Hefei , Anhui 230026 , P. R. China.
² Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials, School of Chemistry and Chemical Engineering , Anqing Normal University , Anqing , Anhui 246011 , P. R. China.
³ School of Chemical and Material Engineering , Jiangnan University , Wuxi , Jiangsu 214122 , P. R. China.

PMID: 30407807
DOI: 10.1021/jacs.8b06723

Abstract

Development of visible-light photocatalytic materials is an ultimate goal for solar-driven CO₂ conversion. Au nanoclusters (NCs) may potentially serve as components for harvesting visible light but can hardly perform solar-driven CO₂ reduction due to the lack of catalytic sites. Herein, we report an effective strategy for turning Au nanoclusters catalytically active for visible-light CO₂ reduction, in which metal cations (Fe²⁺, Co²⁺, Ni²⁺, and Cu²⁺) are grafted to the Au NCs using l-cysteine as a bridging ligand. The metal-S bonding bridge facilitates the electron transfer from Au NCs to metal cations so that the grafted metal cations can receive photoinduced electrons and work as catalytic sites for CO₂ reduction. The varied d-band centers and binding energies with CO₂ for different metal cations allow tuning electron transfer efficiency and CO₂ activation energy. Furthermore, the photostability of Au NCs-based catalyst can be significantly enhanced through the encapsulation with metal-organic frameworks. This work opens a new door for the photocatalyst design based on metal clusters and sheds light on the surface engineering of metal clusters toward specific applications.