Tuning the Electronic Structures of Anchor Sites to Achieve Zero‐Valence Single‐Atom Catalysts for Advanced Hydrogenation

Abstract Single‐atom catalysts (SACs) have recently become highly attractive for selective hydrogenation reactions owing to their remarkably high selectivity. However, compared to their nanoparticle counterparts, atomically dispersed metal atoms in SACs often show inferior activity and are prone to aggregate under reaction conditions. Here, by theoretical calculations, we show that tuning the local electronic structures of metal anchor sites on g‐C 3 N 4 by doping B atoms (BCN) with relatively lower electronegativity allows achieving zero‐valence Pd SACs with reinforced metal‐support orbital hybridizations for high stability and upshifted Pd 4 d orbitals for high activity in H 2 activation. The precise synthesis of Pd SACs on BCN supports with varied B contents substantiated the theoretical prediction. A zero‐valence Pd 1 /BCN SAC was achieved on a BCN support with a relatively low B content. It exhibited much higher stability in a H 2 reducing environment, and more strikingly, a hydrogenation activity, approximately 10 and 34 times greater than those high‐valence Pd 1 /g‐C 3 N 4 and Pd 1 /BCN with a high B content, respectively.