Direct Visualization of the Evolution of a Single‐Atomic Cobalt Catalyst from Melting Nanoparticles with Carbon Dissolution

Transition metal single-atom catalysts (SACs) are of immense interest, but how exactly they are evolved upon pyrolysis of the corresponding precursors remains unclear as transition metal ions in the complex precursor undergo a series of morphological changes accompanied with changes in oxidation state as a result of the interactions with the carbon support. Herein, the authors record the complete evolution process of Co SAC during the pyrolysis a Co/Zn-containing zeolitic imidazolate framework. Aberration-corrected environmental TEM coupled with in-situ EELS is used for direct visualization of the evolution process at 200-1000 °C. Dissolution of carbon into the nanoparticles of Co is found to be key to modulating the wetting behavior of nanoparticles on the carbon support; melting of Co nanoparticles and their motion within the zeolitic architecture leads to the etching of the framework structure, yielding porous C/N support onto which Co-single atoms reside. This uniquely structured Co SAC is found to be effective for the oxidation of a series of aromatic alkanes to produce selective ketones among other possible products. The carbon dissolution and melting/sublimation-driven structural dynamics of transition metal revealed here will expand the methodology in synthesizing SACs and other high-temperature processes.