Ligand–Metal Charge Transfer Induced via Adjustment of Textural Properties Controls the Performance of Single-Atom Catalysts during Photocatalytic Degradation

[Image: see text] Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts. However, the relation between catalysts’ textural properties and their photophysical–photocatalytic properties is rarely elaborated. Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic C(3)N(4). We show that adjustment of materials textural properties and therefore metal single-atom coordination mode enables ligand-to-metal charge transfer (LMCT) or ligand-to-metal-to-ligand charge transfer (LMLCT), properties that were long speculated in single-atom catalysis but never observed. We employ the developed materials in the degradation of organic pollutants under irradiation with visible light. Kinetic investigations under flow conditions show that single atoms of Ag and Cu decrease the number of toxic organic fragmentation products while leading to a higher selectivity toward full degradation. The results correlate with the selected mode of charge transfer in the designed photocatalysts and provide a new understanding of how the local environment of a single-atom catalyst affects the surface structure and reactivity. The concepts can be exploited further to rationally design and optimize other single-atom materials.