Organic-Modulated Inorganic Catalysts: Interactions, Structures, and Applications in Heterogeneous Catalytic Reactions

The development of efficient catalysts relies on the precise design of their structures. Traditional heterogeneous catalysts often suffer from limited active sites and difficulty in their precise description and construction. Homogeneous catalysts have defined structures and can regulate the electronic and spatial environment through organic ligands, thus establishing a well-defined structure–activity relationship. Due to the difficulty in separating homogeneous catalysts, anchoring homogeneous catalysts onto supports, often referred to as heterogenized homogeneous catalysts, can recover these homogeneous moieties, but the low loading density and deactivation of the active sites by aggregation into nanoparticles have yet to be solved. Alternatively, it is beneficial to effectively and precisely regulate the inorganic components by organic molecules, which maintain the active inorganic components and possess systematic tuning capabilities due to the plethora of organic molecules. In this review, we focus on organic-modulated inorganic catalysts, in which the organic ligand can effectively tune inorganic components through different modes of action (such as assembly, modification, and intercalation) to improve the accessibility and high activity of metal centers for creating diverse catalytic properties. Organic-modulated inorganic catalysts feature an inherently inorganic core with high metal densities that enable enhanced gravimetric activities. Crucially, their organic ligands permit flexible modulation, while the inorganic scaffold maintains structural integrity during postsynthetic modifications without framework degradation. This review contributes to the rational design and targeted application of advanced catalyst design via the merging of organic ligands and inorganic nanomaterials.