Discovery of Electronic Structure and Interfacial Interaction Features in Catalytic Activity.

The selective transformation of inert bonds (C-H, C-O, C-C, C-F, etc.) via various catalysts is one of the most challenging areas, with applications in organic synthesis, materials science, and biological and pharmaceutical chemistry. The catalytic performance of homogeneous and heterogeneous catalysts can be rationally controlled in two ways: (i) electronic structure modulation of the active site, such as the metal center, ligands, and coordination modes, to improve the catalytic activity and stability and (ii) tuning intermolecular or interfacial interactions to promoting the reaction kinetics by accelerating the transmission of electrons between the catalyst and solvents or support. The rational design of catalysts based on adjustable features, such as metal (monometallic or bimetallic) active sites, crystal phase, ligands, solvents, and supports for inert bond activation under mild conditions remains a challenge. This Perspective summarizes the features of electronic structures, interfacial interactions, and their effects on molecular catalysis, metal-organic frameworks (MOFs), and natural mineral catalysis. The discovery of efficient catalysts could be promoted using machine-learning methods with high-performance descriptors. More attention should be paid to high-throughput quantum-chemical computations and experiments, automatic searches of chemical reaction pathways, and efficient machine-learning or deep-learning methods to accelerate catalyst design and synthesis in the future.