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

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.