Thermolysis of Noble Metal Nanoparticles into Electron‐Rich Phosphorus‐Coordinated Noble Metal Single Atoms at Low Temperature

Abstract Noble metal single atoms coordinated with highly electronegative atoms, especially N and O, often suffer from an electron‐deficient state or poor stability, greatly limiting their wide application in the field of catalysis. Herein we demonstrate a new PH 3 ‐promoted strategy for the effective transformation of noble metal nanoparticles (MNPs, M=Ru, Rh, Pd) at a low temperature (400 °C) into a class of thermally stabilized phosphorus‐coordinated metal single atoms (MPSAs) on g‐C 3 N 4 nanosheets via the strong Lewis acid–base interaction between PH 3 and the noble metal. Experimental work along with theoretical simulations confirm that the obtained Pd single atoms supported on g‐C 3 N 4 nanosheets exist in the form of PdP 2 with a novel electron‐rich feature, conceptionally different from the well‐known single atoms with an electron‐deficient state. As a result of this new electronic property, PdP 2 ‐loaded g‐C 3 N 4 nanosheets exhibit 4 times higher photocatalytic H 2 production activity than the state‐of‐art N‐coordinated PdSAs supported on g‐C 3 N 4 nanosheets. This enhanced photocatalytic activity of phosphorus‐coordinated metal single atoms with an electron‐rich state was quite general, and also observed for other active noble metal single atom catalysts, such as Ru and Rh.