Triggering Water and Methanol Activation for Solar-Driven H₂ Production: Interplay of Dual Active Sites over...

Methanol steam reforming (MSR) is a promising reaction that enables efficient production and safe transportation of hydrogen, but it requires a relatively high temperature to achieve high activity, leading to large energy consumption. Here, we report a plasmonic ZnCu alloy catalyst, consisting of plasmonic Cu nanoparticles with surface-deposited Zn atoms, for efficient solar-driven MSR without additional thermal energy input. Experimental results and theoretical calculations suggest that Zn atoms act not only as the catalytic sites for water reduction with lower activation energy but also as the charge transfer channel, pumping hot electrons into water molecules and subsequently resulting in the formation of electron-deficient Cu for methanol activation. These merits together with photothermal heating render the optimal ZnCu catalyst a high H₂ production rate of 328 mmol g_catalyst^-1 h^-1 with a solar energy conversion efficiency of 1.2% under 7.9 Suns irradiation, far exceeding the reported conventional photocatalytic and thermocatalytic MSR. This work provides a potential strategy for efficient solar-driven H₂ production and various other energy-demanding industrial reactions through designing alloy catalysts.