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

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‐C3N4 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 4d orbitals for high activity in H2 activation. The precise synthesis of Pd SACs on BCN supports with varied B contents substantiated the theoretical prediction. A zero‐valence Pd1/BCN SAC was achieved on a BCN support with a relatively low B content. It exhibited much higher stability in a H2 reducing environment, and more strikingly, a hydrogenation activity, approximately 10 and 34 times greater than those high‐valence Pd1/g‐C3N4 and Pd1/BCN with a high B content, respectively. Doping boron atoms with lower electronegativity into g‐C3N4 can substantially change the local electronic structures at metal anchor sites to achieve zero‐valence Pd SACs with reinforced metal‐support orbital hybridizations for high stability and upshifted Pd 4d orbitals for high hydrogenation activity.