Boosting CO₂ Reduction with Spinel CoAl₂O₄ Anchored on N-Doped Graphitic Carbon

Efficient charge transfer and effective separation of photo-generated charge carriers are pivotal to the photocatalytic process. In this study, a novel CoAl₂O₄@nitrogen-doped graphitic carbon (CoAl₂O₄@NGC) composite photocatalyst was fabricated via a stepwise hydrothermal method coupled with high-temperature calcination, and its photocatalytic performance for CO₂ reduction was systematically investigated. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and photoelectrochemical measurements were employed to characterize the phase structure, microstructure, surface chemical state and photoelectrochemical properties of the catalyst. Spinel-structured CoAl₂O₄ nanoparticles were uniformly anchored on the NGC substrate, forming a well-integrated composite interface. XPS analysis confirmed the coexistence of Co²⁺/Co³⁺ mixed valence states in CoAl₂O₄ which provides abundant redox sites for CO₂ activation. Photocatalytic tests showed that CoAl₂O₄@NGC exhibits excellent catalytic activity and cycling stability, with CO and CH₄ yields of 27.88 μmol·g^-1·h^-1 and 23.90 μmol·g^-1·h^-1, respectively. The narrow bandgap (1.54 eV) enhances visible light absorption, while efficient electron-hole separation and reduced charge transfer resistance improve photocatalytic efficiency. Theoretical calculations further reveal that CoAl₂O₄@NGC lowers the adsorption free energy of CO₂ and the energy barrier for COOH formation, thus facilitating the photocatalytic CO₂ reduction. This work provides insights for the design of efficient and stable photocatalysts for CO₂ reduction and deepens the understanding of the synergistic catalytic mechanism in the spinel/nitrogen-doped carbon composite system.