Abstract
Solar-driven CO(2) reduction into value-added C(2+) chemical fuels, such as C(2)H(4), is promising in meeting the carbon-neutral future, yet the performance is usually hindered by the high energy barrier of the C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms-modified W(18)O(49) nanowires (Cu(1)/W(18)O(49)) photocatalyst with asymmetric Cu─W dual sites is reported for selective photocatalytic CO(2) reduction to C(2)H(4). The interconversion between W(V) and W(VI) in W(18)O(49) ensures the stability of Cu(I) during the photocatalytic process. Under light irradiation, the optimal Cu(1)/W(18)O(49) (3.6-Cu(1)/W(18)O(49)) catalyst exhibits concurrent high activity and selectivity toward C(2)H(4) production, reaching a corresponding yield rate of 4.9 µmol g(-1) h(-1) and selectivity as high as 72.8%, respectively. Combined in situ spectroscopies and computational calculations reveal that Cu(I) single atoms stabilize the *CO intermediate, and the asymmetric Cu─W dual sites effectively reduce the energy barrier for the C─C coupling of two neighboring CO intermediates, enabling the highly selective C(2)H(4) generation from CO(2) photoreduction. This work demonstrates leveraging stabilized atomically-dispersed Cu(I) in asymmetric dual-sites for selective CO(2)-to-C(2)H(4) conversion and can provide new insight into photocatalytic CO(2) reduction to other targeted C(2+) products through rational construction of active sites for C─C coupling.