Non-Photochemical Origin of Selectivity Difference between Light and Dark Catalytic Conditions

Lin Zhang; Xingda An; Kai Feng; Juan Li; Jingjing Liu; Jinxing Chen; Chaoran Li; Xiaohong Zhang; Le He

doi:10.1021/acsami.4c02425

Non-Photochemical Origin of Selectivity Difference between Light and Dark Catalytic Conditions

ACS Appl Mater Interfaces. 2024 May 1;16(17):21987-21996. doi: 10.1021/acsami.4c02425. Epub 2024 Apr 18.

Authors

Lin Zhang¹, Xingda An^{1

2}, Kai Feng^{1

2}, Juan Li¹, Jingjing Liu³, Jinxing Chen^{1

2}, Chaoran Li^{1

4}, Xiaohong Zhang^{1

2}, Le He^{1

2}

Affiliations

¹ Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China.
² Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, Jiangsu, P. R. China.
³ Institute of Information Technology, Suzhou Institute of Trade and Commerce, Suzhou 215009, Jiangsu, P. R. China.
⁴ Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, Jiangsu, P. R. China.

PMID: 38636167
DOI: 10.1021/acsami.4c02425

Abstract

The interest in introducing light into heterogeneous catalysis is driven not only by the urgent need of replacing fossil energy but also by the promise of controlling product selectivity by light. The product selectivity differences observed in recent studies between light and dark reactions are often attributed to photochemical effects. Here, we report the discovery of a non-photochemical origin of selectivity difference, at essentially the same CO₂ conversion rate, between photothermal and thermal CO₂ hydrogenation reactions over a Ru/TiO_2-x catalyst. While the presence of the photochemical effect from ultraviolet light is confirmed, it merely enhances the catalytic activity. Systematic investigation reveals that the gradual formation of an adsorbate-mediated strong metal-support interaction under catalytic conditions is responsible for the variation in the catalytic selectivity. We demonstrate that differences in product selectivity under light/dark reactions do not necessarily originate from photochemical effects. Our study refines the basis for determining photochemical effects and highlights the importance of excluding non-photochemical effects in mechanistic studies of light-controlled product selectivity.

Keywords: CO2 hydrogenation; adsorbate-mediated strong metal−support interaction; nonphotochemical effect; photothermal catalysis; selectivity modulation.