Synergistic Thermal Energy and Charge Carriers in an Fe-MOF for Solar-Driven Scalable and Selective Aniline Production.

Aniline is a critical chemical feedstock for dyes, pharmaceuticals, and polymers, but its synthesis via nitroarene hydrogenation demands harsh conditions, precious metal catalysts, and incurs a substantial environmental footprint. Solar-driven catalysis offers a sustainable alternative, but suffer from limited efficiency. Photothermal catalysis simultaneously utilize photothermal energy and charge carriers to overcome the reaction kinetics barriers, and has become a promising strategy. Here, we show that an Fe-aminoterephthalate MOF (NM-101) enables photothermal catalytic aniline synthesis with exceptional efficiency by synergistically coupling thermal energy and charge carrier activation. Under sunlight irradiation, NM-101 achieves an aniline production rate of 303.13 mmol·g-1·h-1 with 100% selectivity and a turnover frequency (TOF) of 226.2 h-1, surpassing all reported nonnoble metal photo(thermal)catalysts. Mechanistic studies reveal a direct hydrodeoxygenation pathway for the aniline production. In this process, photons not only provide thermal energy to drive the reaction but also generate carriers to participate in the reaction and reduce the activation barrier. When immobilized on 3D Al2O3 foam, NM-101 operates for 180 h and produces 42.2 g of aniline with a turnover number of 8470. This synergistic thermal and carriers overcomes kinetic bottlenecks in photocatalytic aniline production, demonstrating the feasibility and scalability of chemical synthesis using solar energy.