Copper(II)-Doped Two-Dimensional Titanium-Based Metal-Organic Frameworks toward Light-Driven CO₂ Reduction to...

Recently, metal-organic framework (MOF)-based photocatalysts for an efficient CO₂ reduction reaction have drawn wide attention in multidisciplinary fields and sustainable chemistry. In this work, a series of Cu²⁺-doped two-dimensional Ti-based MOFs were fabricated by a facile in situ solvothermal method. Cu²⁺ ions were doped in equal proportions and uniformly dispersed in the crystal structure of the MOF matrix. Interestingly, the doping content of Cu²⁺ ions and the photocatalytic performance displayed an obvious volcanic relationship, the medium-concentration Cu²⁺-doped sample (T1-2Cu) held the greatest activity with 100% carbonaceous product (CH₄ and CO) formation, and the CH₄ production rate was 3.7 μmol g^-1 h^-1 with 93% electron selectivity. The band structure, local electronic structure, carrier separation kinetics, and CO₂ adsorption studies demonstrated that the excellent photocatalytic activity of T1-2Cu benefited from the appropriate amount of Cu²⁺ ion doping: (1) a doping amount of 2 atom % optimized the conduction band position of the MOF substrate and endowed T1-2Cu with strong reduction potential in thermodynamics, (2) doping Cu²⁺ ions tuned the local electronic environment around titanium oxide clusters and optimized the generation, separation, and migration processes of photoinduced carriers, and (3) the introduction of Cu²⁺ ions also provided more accessible active sites and more probabilities for the adsorption and activation of CO₂ reactants.