Ni@ETS‑10-catalyzed carboxylation of aryl and alkyl halides with CO2 in water: a green strategy for CO2 utilization

Abstract

A green, efficient and recyclable heterogeneous catalytic system for the carboxylation of aryl and alkyl halides, with CO₂ as sustainable C1 source, is reported using a bifunctional Ni@ETS‑10 catalyst. The reaction proceeds under clean and facile conditions without external ligands, additives, bases, or organic solvents, affording diverse aromatic, aliphatic, and heterocyclic carboxylic acids in up to 98% yield. The catalyst exhibits outstanding stability and recyclability, with no detectable metal leaching or structural degradation after ten cycles of reuse. Gram‑scale synthesis and drug precursor synthesis demonstrate the practical utility of this strategy. Mechanistic studies reveal that key steps such as halide activation and evolution followed by CO₂ insertion are all accomplished solely by the active sites composed of electron‑rich oxygen and Ni metal clusters, and the full catalytic cycle occurs on the catalyst, mechanistically rationalizing the clean and mild nature of this reaction system.