An efficient catalytic system for nitrogen (N2) photofixation
generally consists of light-harvesting units, active sites, and an
electron-transfer bridge. In order to track photogenerated 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 N2 photoreduction. Nickel single-atom and ceria
nanoparticle 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 N2 activation. This work
provides a powerful tool to monitor the electronic structure evolution
of active sites under reaction conditions for photocatalysis and beyond.