Revitalizing CO2 photoreduction: Fine-tuning electronic synergy in ultrathin g-C3N4 with amorphous (CoFeNiMnCu)S2 high-entropy sulfide nanoparticles for enhanced sustainability.

[Display omitted] • Visible light-assisted CO 2 -PR) studied by (CoFeNiMnCu)S 2 embedded in ultrathin g-C 3 N 4. • An excellent activity toward generation of CH 4 and CO was attained by CO 2 -PR). • Composite showed a long-term reusability during photocatalytic reduction of CO 2. • The mechanism of CO 2 -PR) over (CoFeNiMnCu)S 2 /ultrathin g-C 3 N 4 was studied in detail. Sustainability is a key issue in developing stable and efficient catalysts for solar-catalyzed CO 2 conversion. The concept of structural stabilization by quenching the Gibbs free energy, which is achieved by increasing the configurational entropy level of the system, introduced high-entropy materials. However, because alloying immiscible multimetallic atoms into a unit system is still an arduous process, the potential of high-entropy materials has not yet been fully exploited. Surprisingly, although metal sulfide photocatalysts have an enviable reputation for CO 2 photoreduction (CO 2 -PR) owing to their optical/electronic merits and more negative redox potential than other materials, the capability of high-entropy metal sulfides has been completely disregarded. Herein, an adaptable, self-templating metal alkoxide appropriately addresses the immiscibility of metallic constituents by the well-blended metal ions with polyalcohol in the metal glycerate. Consequently, (CoFeNiMnCu)S 2 high-entropy metal sulfide nanoparticles (HEMS-Nps) were grown in situ on crossed ultrathin g-C 3 N 4 (UCN) monolayers during the sulfidation of the metal glycerate. The as-synthesized HEMS-Np has a crystalline–amorphous structure, which is conducive to the acceleration of charge transfer to/from reaction sites, and a convincing orientation for CO 2 adsorption. These features are combined with synergistic electronic multimetallic interactions, facilitating a heterogeneous valence electron distribution and atomic disorder. The CO 2 -PR power of the (CoFeNiMnCu)S 2 @UCN nanostructure was noticeable in realizing added-value products in both the liquid–solid (1063 µmol/g h of syngas and 250 µmol/g h of methane) and gas–solid phases (1883 µmol/cm2 h of syngas and 321 µmol/cm2 h of methane). To prove its utility, long-term and corresponding time-equivalent cycling experiments were conducted, demonstrating a highly stable system that endured for a long time. Overall, this approach simultaneously exploits the advantages of sulfide-based materials and high-entropy materials in stable structures to generate sustainable CO 2 -PR materials. [ABSTRACT FROM AUTHOR]