Engineering phase-selective gel composites presents a promising route to enhance both CO
2 adsorption and conversion efficiency in photocatalytic systems. In this work, Cu
9S
5/TiO
2 gel composites were synthesized via a hydrazine-hydrate-assisted hydrothermal method, using TiO
2 derived from
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Engineering phase-selective gel composites presents a promising route to enhance both CO
2 adsorption and conversion efficiency in photocatalytic systems. In this work, Cu
9S
5/TiO
2 gel composites were synthesized via a hydrazine-hydrate-assisted hydrothermal method, using TiO
2 derived from a microwave-assisted sol–gel process. The resulting materials exhibit a porous gel-derived morphology with highly dispersed Cu
9S
5 nanocrystals, as confirmed by XRD, TEM, and XPS analyses. These structural features promote abundant surface-active sites and interfacial contact, enabling efficient CO
2 adsorption. Among all samples, the optimized 0.36Cu
9S
5/TiO
2 composite achieved a methane production rate of 34 μmol·g
−1·h
−1, with 64.76% CH
4 selectivity and 88.02% electron-based selectivity, significantly outperforming Cu
9S
8/TiO
2 synthesized without hydrazine hydrate. This enhancement is attributed to the dual role of hydrazine: facilitating phase transformation from Cu
9S
8 to Cu
9S
5 and modulating the interfacial electronic environment to favor CO
2 capture and activation. DFT calculations reveal that Cu
9S
5/TiO
2 effectively lowers the energy barriers of critical intermediates (*COOH, *CO, and *CHO), enhancing both CO
2 adsorption strength and subsequent conversion to methane. This work demonstrates a gel-derived composite strategy that couples efficient CO
2 adsorption with selective photocatalytic reduction, offering new design principles for adsorption–conversion hybrid materials.
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