Dynamic Proton Extraction from Supramolecular Functionalized Metal–Organic Framework/Ti3C2 MXene Hybrids for Efficient Solar Ammonia Synthesis

In N2 photoreduction, photogenerated holes and electrons are involved in H2O photolysis for proton supply and the weakening of the N≡N triple bond for N2 activation, respectively. Rationally regulating the structure–activity relationship of these catalytic sites for available generation of charge carriers is crucial for optimizing N2-to-NH3 conversion efficiency. Herein, a robust photothermal catalyst carboxyl-enriched supramolecular (perylene tetracarboxylic acid, PTA) functionalized MIL-125(Ti)/MXene having dynamic proton extraction sites is designed for efficient N2 photoreduction. Among these, MIL-125(Ti), PTA, and Ti3C2 MXene are, respectively, responsible for N2 activation, reliable proton supply through interconversion between Brønsted acid and its conjugated base, and a photothermal response for accelerated reaction kinetics. The synergistic collaboration of these functionally distinct modules enhances light harvesting and responsiveness for dynamic multielectron/proton extraction, thereby facilitating feasible photothermal catalytic ammonia production. Remarkably high solar-to-ammonia conversion rates of 314.5–654.7 μmol g–1 h–1 are achieved under 100–500 mW cm–2 illumination. This work provides insights into the rational design of an efficient solar ammonia synthesis system.