Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations. However, limited success has been achieved in applying oxide-supported atomically dispersed catalysts to semihydrogenation of alkynes under mild conditions. By utilizing various metal oxides (e.g., Cu2O, Al2O3, ZnO, and TiO2) as supports for atomically dispersed Pd catalysts, we demonstrate herein the critical role of the oxidation state and coordinate environment of Pd centers in their catalytic performance, thus leading to the discovery of an “oxide-support effect” on atomically dispersed metal catalysts. Pd atomically dispersed on Cu2O exhibits far better catalytic activity in the hydrogenation of alkynes, with an extremely high selectivity toward alkenes, compared to catalysts on other oxides. Pd species galvanically displace surface Cu(I) sites on Cu2O to create two-coordinated Pd(I), which is a critical step for the activation and heterolytic splitting of H2 into Pd-H− and O-H+ species for the selective hydrogenation of alkynes. Moreover, the adsorption of alkenes on H2-preadsorbed Pd(I) is relatively weak, preventing deeper hydrogenation and increased selectivity during semihydrogenation. We demonstrate that the local coordinate environment of active metal centers plays a crucial role in determining the catalytic performance of an oxide-supported atomically dispersed catalyst.

The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated surface and interface structures of heterogeneous catalysts make it challenging to identify the molecular-level structure of their active sites and thus precisely control their performance. To address this challenge, atomically dispersed metal catalysts (ADMCs) and ligand-protected atomically precise metal clusters (APMCs) have been emerging as two important classes of model heterogeneous catalysts in recent years, helping to build bridge between homogeneous and heterogeneous catalysis. This review illustrates how the surface and interface coordination chemistry of these two types of model catalysts determines the catalytic performance from multiple dimensions. The section of ADMCs starts with the local coordination structure of metal sites at the metal–support interface, and then focuses on the effects of coordinating atoms, including their basicity and hardness/softness. Studies are also summarized to discuss the cooperativity achieved by dual metal sites and remote effects. In the section of APMCs, the roles of surface ligands and supports in determining the catalytic activity, selectivity, and stability of APMCs are illustrated. Finally, some personal perspectives on the further development of surface coordination and interface chemistry for model heterogeneous metal catalysts are presented.

Heterogeneous hydrogenation with hydrogen spillover has been demonstrated as an effective route to achieve high selectivity towards target products. More effort should be paid to understand the complicated correlation between the nature of supports and hydrogenation involving hydrogen spillover. Herein, we report the development of the hydrogenation system of hexagonal boron nitride (h‐BN)‐supported Pd nanoparticles for the hydrogenation of aldehydes/ketones to alcohols with hydrogen spillover. Nitrogen vacancies in h‐BN determine the feasibility of hydrogen spillover from Pd to h‐BN. The hydrogenation of aldehydes/ketones with hydrogen spillover from Pd proceeds on nitrogen vacancies on h‐BN. The weak adsorption of alcohols to h‐BN inhibits the deep hydrogenation of aldehydes/ketones, thus leading to high catalytic selectivity to alcohols. Moreover, the hydrogen spillover‐based hydrogenation mechanism makes the catalyst system exhibit a high tolerance to CO poisoning.