Amorphous Strategy and Doping Copper on Metal-Organic Framework Surface for Enhanced Photocatalytic CO₂ Reduction to...

Amorphous photocatalysts are characterized by numerous grain boundaries and abundant unsaturated sites, which enhance reaction efficiency from both kinetic and thermodynamic perspectives. However, amorphization strategies have rarely been used for photocatalytic CO₂ reduction. Doping copper onto a metal-organic framework (MOF) surface can regulate the electronic structure of photocatalysts, promote electron transfer from the MOF to Cu, and improve the separation efficiency of electron-hole pairs. In this study, an amorphous photocatalyst MOF_w-p/Cu containing highly dispersed Cu (0, I, II) sites was designed and synthesized by introducing a regulator and in situ copper species during the nucleation process of MOF (UiO-66-NH₂). Various characterizations confirmed that the Cu species were anchored to the organometallic skeleton of the surface amorphization MOF structure. The synergistic effect of Cu doping and surface amorphization in MOF_w-p/Cu can significantly enhance the CO and CH₄ yields while promoting the formation of the multicarbon product C₂H₄. The approach holds promise for developing novel, highly efficient MOFs as photocatalysts for CO₂ photoreduction, enabling the production of high-value-added C₂ products.