Configuration Matching Strategy to Control Selectivity in Heterogeneous Catalysis

ConspectusHeterogeneous catalysis is a fundamental process in the chemical industry, enabling the efficient transformation of reactants into valuable products across a wide range of chemical reactions. Selectivity in catalysis is critical for maximizing the desired products, minimizing byproducts, and enhancing the overall process efficiency, making it a cornerstone of green and sustainable chemical processes. While significant advances have been made in designing high-performance catalysts over the past few decades, achieving high selectivity remains a fundamental challenge due to the complexity of multiple competing reaction pathways. This issue is especially evident in reactions including hydrogenation, hydrogenolysis, and oxidation, where selective transformations, such as partial hydrogenation of alkynes to alkenes, require catalysts tailored to specific conditions. It has been well indicated that the reaction pathway in catalysis is strongly influenced by the adsorption configurations of reactants on the catalyst surface, underscoring the importance of designing catalysts capable of precisely regulating these configurations. However, achieving control over selectivity via the manipulation of adsorption configurations remains a significant challenge, as it requires the delicate tuning of active sites to selectively promote or suppress specific interactions.In recent years, our group has concentrated on the precise manipulation of adsorption configurations to achieve high selectivity in heterogeneous catalysis, particularly in hydrogenation, oxidation, and hydrogenolysis. In this Account, we highlight our recent progress in configuration matching, a design principle that aligns active-site properties with the structural features of the substrate to favor productive adsorption modes while suppressing competing ones. Importantly, different substrate classes demand distinct strategies. For small unsaturated molecules such as alkynes, the key is to prevent multisite adsorption that favors overhydrogenation. By enlarging the adjacent metal-metal distance through site isolation, we disrupt multi-σ ensembles, enforce π-adsorption, and direct acetylene hydrogenation toward ethylene while suppressing formations of ethane and C₄ byproducts. For polyfunctional molecules, such as glycerol or dimethyl oxalate, the challenge is to discriminate among multiple reactive groups. Metal-oxide interfaces provide oxophilic perimeters that preferentially anchor selected functionalities and coactivate hydrogen, enabling transformations to dihydroxyacetone or methyl glycolate with high selectivity. Yet such interfaces are not universally beneficial: overly oxophilic features can coactivate multiple groups, eroding chemoselectivity and underscoring the need for balanced design. For bulky aromatics and cyclic molecules, extended π-systems favor flat-lying adsorption that promotes ring hydrogenation and deep deoxygenation. Here, nanopore confinement and porous overlayers act as geometric gates, forcing upright orientations and regulating hydrogen diffusion, thereby channeling reactions along hydrodeoxygenation or partial hydrogenation pathways with exceptional selectivity.Together, these strategies underscore the importance of configuration matching as a strategy to control selectivity in heterogeneous catalysis. By matching the adsorption configurations of reactants with the structural and electronic properties of active sites, we have demonstrated significant improvements in selectivity and efficiency. This systematic approach to catalyst design not only provides a robust framework for controlling reaction pathways but also highlights the broader potential of configuration-driven catalysis in addressing challenges across a wide range of chemical transformations.