Engineered disorder in CO2 photocatalysis

Zhao Li; Chengliang Mao; Qijun Pei; Paul N Duchesne; Teng He; Meikun Xia; Jintao Wang; Lu Wang; Rui Song; Feysal M Ali; Débora Motta Meira; Qingjie Ge; Kulbir Kaur Ghuman; Le He; Xiaohong Zhang; Geoffrey A Ozin

doi:10.1038/s41467-022-34798-1

Engineered disorder in CO₂ photocatalysis

Nat Commun. 2022 Nov 23;13(1):7205. doi: 10.1038/s41467-022-34798-1.

Authors

Zhao Li^#^{1

2

3}, Chengliang Mao^#², Qijun Pei⁴, Paul N Duchesne⁵, Teng He⁴, Meikun Xia², Jintao Wang⁴, Lu Wang⁶, Rui Song^{1

2

3}, Feysal M Ali², Débora Motta Meira^{7

8}, Qingjie Ge⁴, Kulbir Kaur Ghuman⁹, Le He^{1

3}, Xiaohong Zhang^{10

11}, Geoffrey A Ozin¹²

Affiliations

¹ Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, 199 Ren'ai Road, Suzhou, 215123, Jiangsu, PR China.
² Solar Fuels Group, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada.
³ Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou, 215123, Jiangsu, PR China.
⁴ Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, Liaoning, PR China.
⁵ Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON, K7L 3N6, Canada.
⁶ The Chinese University of Hong Kong, Shenzhen, 518172, Shenzhen, Guangdong, People's Republic of China.
⁷ CLS@APS, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, 60439, USA.
⁸ Canadian Light Source Inc., 44 Innovation Boulevard, Saskatoon, SK, S7N 2V3, Canada.
⁹ Institut National de la Recherche Scientifique, Centre Énergie, Matériaux et Télécommunications, 1650 Boul. Lionel Boulet, Varennes, QC, J3X 1S2, Canada. kulbir.ghuman@inrs.ca.
¹⁰ Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, 199 Ren'ai Road, Suzhou, 215123, Jiangsu, PR China. xiaohong_zhang@suda.edu.cn.
¹¹ Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou, 215123, Jiangsu, PR China. xiaohong_zhang@suda.edu.cn.
¹² Solar Fuels Group, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada. g.ozin@utoronto.ca.

^# Contributed equally.

Abstract

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO₂ can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO₂ forms a core-shell c-TiO₂@a-TiO_2-x(OH)_y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO₂ reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO₂ photocatalysts.