Highly Selective Photoreduction of CO2 with Suppressing H2 Evolution by Plasmonic Au/CdSe-Cu2 O Hierarchical Nanostructures under Visible Light.

Here, the photocatalytic CO2 reduction reaction (CO2 RR) with the selectivity of carbon products up to 100% is realized by completely suppressing the H2 evolution reaction under visible light (λ > 420 nm) irradiation. To target this, plasmonic Au/CdSe dumbbell nanorods enhance light harvesting and produce a plasmon-enhanced charge-rich environment; peripheral Cu2 O provides rich active sites for CO2 reduction and suppresses the hydrogen generation to improve the selectivity of carbon products. The middle CdSe serves as a bridge to transfer the photocharges. Based on synthesizing these Au/CdSe-Cu2 O hierarchical nanostructures (HNSs), efficient photoinduced electron/hole (e- /h+ ) separation and 100% of CO selectivity can be realized. Also, the 2e- /2H+ products of CO can be further enhanced and hydrogenated to effectively complete 8e- /8H+ reduction of CO2 to methane (CH4 ), where a sufficient CO concentration and the proton provided by H2 O reduction are indispensable. Under the optimum condition, the Au/CdSe-Cu2 O HNSs display high photocatalytic activity and stability, where the stable gas generation rates are 254 and 123 µmol g-1 h-1 for CO and CH4 over a 60 h period.