Aqueous Solution-Gel Synthesis of CuNb<sub>2</sub>O<sub>6</sub> and Cu<sub>3</sub>Nb<sub>2</sub>O<sub>8 </sub>and Exploring Their Potential as Precatalysts for Photothermal CO<sub>2</sub> Hydrogenation
Abstract Copper niobate metal oxides have gained significant attention in the field of CO2 reduction because of their great potential to address current energy and environmental challenges. Conventional solid-state synthesis methods generally suffer from poor cation homogeneity, whereas sol–gel processes facilitate molecular-scale mixing of precursors and enhanced compositional uniformity. However, many conventional sol–gel routes employ harmful or nonsustainable complexing agents, limiting their sustainability and scalability. Here, we report a facile citrate-complex aqueous solution–gel route for the controlled synthesis of CuNb2O6 and Cu3Nb2O8 phases. Citric acid functions as a chelating and polymerizing agent, facilitating the homogeneous complexation of Cu and Nb cations in aqueous solution while simultaneously promoting molecular-level mixing prior to gelation. The used precursor solution chemistry enables thermal decomposition and crystallization, leading to the reproducible formation of well-defined copper–niobate phases. The phase formation and purity of the target phases were confirmed using in situ high-temperature X-ray diffraction (HT-XRD), Raman spectroscopy, scanning electron microscopy (SEM), and UV–vis spectroscopy. The synthesized materials were further evaluated as precatalysts for photothermal CO2 hydrogenation, where CO was identified as the sole reaction product.