Monitoring Electron Flow in Nickel Single-Atom Catalysts during Nitrogen Photofixation

An efficient catalytic system for nitrogen (N-2) photofixation generally consists of light-harvesting units, active sites, and an electron-transfer bridge. In order to track photo generated electron flow between different functional units, it is highly desired to develop in situ characterization techniques with element-specific capability, surface sensitivity, and detection of unoccupied states. In this work, we developed in situ synchrotron radiation soft X-ray absorption spectroscopy (in situ sXAS) to probe the variation of electronic structure for a reaction system during N-2 photoreduction. Nickel single-atom and ceria nano particle comodified reduced graphene oxide (CeO2/Ni-G) was designed as a model catalyst. In situ sXAS directly reveals the dynamic interfacial charge transfer of photogenerated electrons under illumination and the consequent charge accumulation at the catalytic active sites for N-2 activation. This work provides a powerful tool to monitor the electronic structure evolution of active sites under reaction conditions for photocatalysis and beyond.