The roles of gold and silver nanoparticles on ZnIn₂S₄/silver (gold)/tetra(4-carboxyphenyl)porphyrin iron(III) chloride hybrids in carbon dioxide photoreduction

The construction of hybrid catalysts composed of inorganic semiconductors and molecular catalysts shows great potential for achieving high photocatalytic carbon dioxide (CO₂) conversion efficiency. In this study, ZnIn₂S₄ was first synthesized via a solvothermal route. Gold (Au) and silver (Ag) nanoparticles were then deposited on ZnIn₂S₄ via the reduction of noble metal precursor by sulfur vacancy defects. The obtained composite was further combined with tetra(4-carboxyphenyl)porphyrin iron(III) chloride (FeTCPP) molecular catalyst for efficient photocatalytic CO₂ conversion. The roles of different noble metal nanoparticles in charge separation and interfacial electron transfer have been comprehensively studied. The photocatalytic performance and photoelectrochemical characterizations demonstrate that the introduction of Ag or Au nanoparticles is beneficial for charge separation. More importantly, the presence of Ag nanoparticles plays a crucial role in promoting the interfacial charge transfer between ZnIn₂S₄ and FeTCPP, whereas, Au nanoparticles function as active sites for the water reduction reaction.