CO driven tunable syngas synthesis via CO2 photoreduction using a novel NiCo bimetallic metal-organic frameworks

Syngas has important industrial applications, and converting CO 2 to CO is critical for syngas production. Metal-organic frameworks (MOFs) have demonstrated significant potential in photocatalytic syngas conversion, although the impact of catalytic reactions on tunable H 2 /CO ratios remains unclear. Herein, we present a novel bimetallic NiCo-MOF catalyst, Ni 0.4 Co 0.6 , exhibiting high catalytic activity in syngas conversion due to the CO product self-drive effect. Our investigation, integrating experimental data with density functional theory (DFT) analysis, uncovers a high photocurrent response and a low charge-transfer resistance. Furthermore, the introduction of cobalt into Ni-MOF caused an upshift of the d -band center, which facilitated the conversion efficiency of *COOH intermediates, which has been identified as the rate-determining step in CO 2 conversion, resulting in increased CO yield. Additionally, the concentration of undesorbed CO rises, while CO co-adsorption diminishes the catalyst’s binding energy for *H, thereby enhancing H 2 generation. These combined effects contribute to a self-driven enhancement in the catalytic production of syngas. By adjusting the Ni/Co ratio, a tunable H 2 /CO ratio (0.21–0.85) was achieved, with Ni 0.4 Co 0.6 exhibiting optimal catalytic performance, yielding 17.6 mmol·g −1 ·h −1 gas products. This study provides a novel insight into the correlation between reaction products and catalyst design, offering a perspective on perspective on modulating syngas composition.