Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO2 photocatalytic hydrogenation

Tingjiang Yan; Na Li; Linlin Wang; Weiguang Ran; Paul N Duchesne; Lili Wan; Nhat Truong Nguyen; Lu Wang; Meikun Xia; Geoffrey A Ozin

doi:10.1038/s41467-020-19997-y

Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO₂ photocatalytic hydrogenation

Nat Commun. 2020 Nov 30;11(1):6095. doi: 10.1038/s41467-020-19997-y.

Authors

Tingjiang Yan^{1

2}, Na Li³, Linlin Wang⁴, Weiguang Ran⁴, Paul N Duchesne⁵, Lili Wan⁵, Nhat Truong Nguyen⁵, Lu Wang⁵, Meikun Xia⁵, Geoffrey A Ozin⁶

Affiliations

¹ The Key Laboratory of Life-Organic Analysis, College of Chemistry and Chemical Engineering, Qufu Normal University, 273165, Qufu, Shandong, People's Republic of China. tingjiangn@163.com.
² Materials Chemistry and Nanochemistry Research Group, Solar Fuels Cluster, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada. tingjiangn@163.com.
³ Qufu Normal University Library, Qufu Normal University, 273165, Qufu, Shandong, People's Republic of China. chessmantj@163.com.
⁴ The Key Laboratory of Life-Organic Analysis, College of Chemistry and Chemical Engineering, Qufu Normal University, 273165, Qufu, Shandong, People's Republic of China.
⁵ Materials Chemistry and Nanochemistry Research Group, Solar Fuels Cluster, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada.
⁶ Materials Chemistry and Nanochemistry Research Group, Solar Fuels Cluster, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada. gozin@chem.utoronto.ca.

Abstract

The surface frustrated Lewis pairs (SFLPs) on defect-laden metal oxides provide catalytic sites to activate H₂ and CO₂ molecules and enable efficient gas-phase CO₂ photocatalysis. Lattice engineering of metal oxides provides a useful strategy to tailor the reactivity of SFLPs. Herein, a one-step solvothermal synthesis is developed that enables isomorphic replacement of Lewis acidic site In³⁺ ions in In₂O₃ by single-site Bi³⁺ ions, thereby enhancing the propensity to activate CO₂ molecules. The so-formed Bi_xIn_2-xO₃ materials prove to be three orders of magnitude more photoactive for the reverse water gas shift reaction than In₂O₃ itself, while also exhibiting notable photoactivity towards methanol production. The increased solar absorption efficiency and efficient charge-separation and transfer of Bi_xIn_2-xO₃ also contribute to the improved photocatalytic performance. These traits exemplify the opportunities that exist for atom-scale engineering in heterogeneous CO₂ photocatalysis, another step towards the vision of the solar CO₂ refinery.