Metal Complex/ZnS-Modified Ni Foam as Magnetically Stirrable Photocatalysts: Roles of Redox Mediators and Carrier Dynamics Monitored by Operando Synchrotron X-ray Spectroscopy

Magnetically stirrable photocatalysts binding the ZnS-decorated Ni foam with the metal complex cocatalyst as a redox mediator and light-absorbing composition were investigated. Loading metal complex can improve light absorption, surface hydrophilicity, interfacial charge migration, and H-2 production activity. The variation of the metal valences of the composite photocatalysts in an operando environment (with sacrificial agent solution) with and without light irradiation was investigated by X-ray absorption near-edge structure (XANES) spectra and Fourier-transformed extended X-ray absorption fine structure (EXAFS) spectra to monitor the charge carrier dynamics of photocatalysis and explain how the macrocyclic Cu complex (CuC) acted as a redox mediator better than the Ni complex. The smaller valence difference of copper valence in ZS/CuC for dark and light states revealed that the Cu complex facilitates a reversible electron transfer between the ZnS photocatalyst and H+. Loading the Cu complex can improve the separation of photogenerated carriers by the redox couple of complexes, leading to a significantly improved photocatalytic H-2 production activity of 8150 mu mol h(-1) g(-1). The reactants can flow through these magnetically stirrable Ni foam-based photocatalysts by magnetic-field-driven stirring, which improves the contact between photocatalysts and the sacrificial agents. The operando synchrotron provides new insights for understanding the roles of redox mediators.