The Dynamic Formation from Metal‐Organic Frameworks of High‐Density Platinum Single‐Atom Catalysts with Metal‐Metal Interactions

Single‐atom catalysts (SACs) hold great promise for highly efficient heterogeneous catalysis, yet the practical applications require the development of high‐density active sites with flexible geometric structures. The lack of understanding in the dynamic formation process of single atoms in the host framework has been plaguing the controllable synthesis of next generation SACs. Here using Co‐based metal‐organic frameworks (MOFs) as a starting substrate, we fully elucidated the formation of high‐density Pt single atoms with inter‐site interactions in derived Co(3)O(4) host. The cation exchange process and dynamic evolution of Pt−Pt interactions, organic ligand cleavage and Pt‐oxygen coordination formation during the pyrolysis process have been unambiguously interpreted by a series of in situ/ex situ spectroscopic measurements and theoretical computation. These findings would direct the synthesis of high‐density SACs with metal‐metal interactions, which demonstrate significantly enhanced structural flexibility and catalytic properties.