Unraveling the selectivity puzzle of H-2 evolution over CO2 photoreduction using ZnS nanocatalysts with phase junction

摘要

Catalytic reduction of CO2 is usually accompanied by competitive H-2 evolution. However, the selectivity between CO2 reduction and H-2 evolution is not completely understood hitherto. Here ZnS is chosen as the model catalyst to study this and are prepared by hydrothermal treatment of ZnS(en)(0)(.5) precursor. ZnS nanoparticles exhibit high production yield of solar fuels due to the formation of internal Sphalerite-Wurtzite phase junction within a single particle. The predominant product of H-2 can reach a yield as high as 31.5 mmol/g-cat after 4-h reaction, meanwhile with a high CO yield of 279.3 mu mol/g-cat. The mechanism is proposed from both dynamic (adsorption/desorption of reactants/products) and thermodynamic (redox potential, change in Gibbs free energy of key intermediates) point of view. This work not only provides useful information on the reaction selectivity between CO2 reduction and H-2 evolution, but also pave a way to adjust the yield of a specific product upon photocatalysis.