Young‐Woong Suh

In heterogeneous catalysis, heterolytic H 2 activation for (selective) hydrogenation and hydroprocessing reactions involves the dissociation of adsorbed H 2 molecules into proton (H δ+ ) and hydride (H δ− ) on the catalyst surface. This approach offers several advantages, including high selectivity for polar bond (s), a low energy barrier for H 2 dissociation, a high capacity for reaction‐favorable H 2 adsorption, and reduced catalyst poisoning. This requires the construction of frustrated Lewis pairs on the catalyst surface, satisfying specific criteria, such as having an abundant quantity of Lewis pairs with steric hindrance and maintaining a certain distance of 3–5 Å between the pairs. This review highlights intrinsic catalyst properties for heterolytic H 2 activation based on state‐of‐the‐art reports. The main components necessary for this activation include supports with strong basic sites and/or oxygen vacancies, and/or metals of single atom. For this purpose, designed catalytic materials aim to strengthen the Lewis acidity and basicity, improve the polarization of Lewis pairs, enrich oxygen vacancies, maximize the interfacial area between metal species and Lewis base, and enhance metal–support interaction. Therefore, heterogeneous catalysts retaining such heterolytic H 2 activation characteristics will be significantly effective in various hydrogenation and hydroprocessing reactions.