Light-driven carbon dioxide reduction over the Ag-decorated modified TS-1 zeolite

Abstract

Light-driven reduction of CO₂ to high value-added fuel has shown great potential in reducing CO₂ emissions and solving the energy crisis. Herein, a Cu ion-exchanged mesoporous TS-1 zeolite (Cu-TS-1) with rich Ti³⁺–V_O defects was successfully prepared for the first time. Subsequently, Ag nanoparticles (2–10 nm) are highly dispersed on the surface of the zeolite by a photoreduction process, which greatly improves visible light absorption ability due to the localized surface plasmon resonance of Ag. Under UV-visible light irradiation, the Ag/Cu-TS-1 sample exhibits high and stable CO₂ reduction performance. The yield of CO reaches 6.93 μmol g⁻¹ while the competitive hydrogen evolution can be effectively inhibited. Interestingly, Ag/Cu-TS-1 as a photocathode can convert CO₂ into CH₃OH and C₂H₅OH, giving a rate of 5.64 and 2.62 μmol cm⁻² h⁻¹ at −0.6 V vs. RHE, respectively. In situ Raman tests reveal that the existence of intermediates containing C–H bonds, especially *CO intermediates, plays a key role in C–C coupling, thus promoting the formation of C2 products, indicating that the Ag cocatalyst-loaded Cu-modified zeolite can jointly accelerate the conversion of CO₂ into a hydrocarbon compound.