No abstract

Artificial photosynthesis, light-driving CO2 conversion into hydrocarbon fuels, is a promising strategy to synchronously overcome global warming and energy-supply issues. The quaternary AgInP2S6 atomic layer with the thickness of ~ 0.70 nm were successfully synthesized through facile ultrasonic exfoliation of the corresponding bulk crystal. The sulfur defect engineering on this atomic layer through a H2O2 etching treatment can excitingly change the CO2 photoreduction reaction pathway to steer dominant generation of ethene with the yield-based selectivity reaching ~73% and the electron-based selectivity as high as ~89%. Both DFT calculation and in-situ FTIR spectra demonstrate that as the introduction of S vacancies in AgInP2S6 causes the charge accumulation on the Ag atoms near the S vacancies, the exposed Ag sites can thus effectively capture the forming *CO molecules. It makes the catalyst surface enrich with key reaction intermediates to lower the C-C binding coupling barrier, which facilitates the production of ethene.

Today's chemical industry is a pillar of our modern society, but it heavily relies on the consumption of non-renewable fossil fuels. The reaction conditions required to drive most of the chemical processes require high energy input, resulting in the consumption of significant amounts of dwindling reserves of fossil fuels. Therefore, more sustainable pathways are much sought after to reduce the dependence on fossil fuels and ameliorate the effects of climate change. Inspired by photosynthesis and its ability to convert CO 2 and H 2 O to hydrocarbons, this Perspective focuses on recent advances in catalytic small-molecule activation and conversion. It will consider reactions of C-H (CH 4 , benzene), C=O (CO and CO 2), NhN bonds, and other fine chemicals syntheses (e.g., CC and S-S bond coupling), driven by either solar or thermal energy. The paper also discusses the future opportunities and challenges by highlighting some strategies for the development of efficient solar or thermal catalysis processes.