Flower-like CoMoS x Micro/Nanoparticles for the Chemoselective Hydrogenation of Halonitroaromatics

Selective hydrogenation of halogenated nitroarenes is often limited by competitive hydrodehalogenation and insufficient control over the active site structure in conventional sulfide catalysts. In this work, we report a precursor intercalation engineering strategy to construct predominantly amorphous Co–Mo–S coordination motifs via sulfidation of molybdate-intercalated Co-based layered double hydroxides. Systematic characterization analyses confirm the preservation of local Co–Mo–S ensembles, leading to modified electronic structure and increased accessible active sites. The optimized catalyst affords >99% conversion of p -chloronitrobenzene with >99% selectivity toward p -chloroaniline under mild conditions (1.6 MPa H 2, 150 °C). The Co–Mo ensembles facilitate −NO 2 activation while suppressing C–Cl cleavage, demonstrating that short-range ordering can regulate active sites for high-performance chemoselective hydrogenation.