Dual Microenvironment Modulation of Pd Nanoparticles in Covalent Organic Frameworks for Semihydrogenation of Alkynes

Abstract The chemical microenvironment modulation of metal nanoparticles (NPs) holds promise for tackling the long‐lasting challenge of the trade‐off effect between activity and selectivity in catalysis. Herein, ultrafine PdCu 2 NPs incorporated into covalent organic frameworks (COFs) with diverse groups on their pore walls have been fabricated for the semihydrogenation of alkynes. The Cu species, as the primary microenvironment of Pd active sites, greatly improves the selectivity. The functional groups as the secondary microenvironment around PdCu 2 NPs effectively regulate the activity, in which PdCu 2 NPs encapsulated in the COF bearing −CH 3 groups exhibit the highest activity with >99 % conversion and 97 % selectivity. Both experimental and calculation results suggest that the functional group affects the electron‐donating ability of the COFs, which successively impacts the charge transfer between COFs and Pd sites, giving rise to a modulated Pd electronic state and excellent catalytic performance.