Highly efficient photocatalytic conversion of CO_(2) into CH_(4) over Cu single atom promoted heterojunction:The effect of uplifted d-band center

Photoreduction of CO_(2) to solar fuels has caused great interest,but suffers from low catalytic efficiency and poor selectivity.Herein,we designed a S-scheme heterojunction(Cu-TiO_(2)/WO_(3))with Cu single atom to significantly boost the photoreduction of CO_(2).Notably,the developed Cu-TiO_(2)/WO_(3) achieved the solardriven conversion of CO_(2) to CH_(4) with an evolution rate of 98.69μmol g^(−1) h^(−1),and the electron selectivity of CH_(4) reached 88.5%.The yield was much higher than those of pristine WO_(3),TiO_(2)/WO_(3) and Cu-TiO_(2) samples.Experimental and theoretical analysis suggested that the S-scheme heterojunction accelerated charge migration and inhibited the recombination of electron-hole pairs.Importantly,the charge separation effect of the heterojunction meliorated the position of the d-band.The uplifted d-band centers of Cu and Ti on Cu-TiO_(2)/WO_(3) not only improved the electron interaction between Cu single atoms and substrate-TiO_(2),accelerated the adsorption and activation of CO_(2) on the active sites of Cu single atom,but also optimized the Gibbs free energies of CH 4 formation pathway,leading to excellent selectivity toward CH_(4).This work provides new insights into the design of photocatalyst systems with high photocatalytic performance.