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

Hasanvandian, F ; Sharif University of Technology | 2024

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  1. Type of Document: Article
  2. DOI: 10.1016/j.cej.2024.153771
  3. Publisher: 2024
  4. Abstract:
  5. Sustainability is a key issue in developing stable and efficient catalysts for solar-catalyzed CO2 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 CO2 photoreduction (CO2-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)S2 high-entropy metal sulfide nanoparticles (HEMS-Nps) were grown in situ on crossed ultrathin g-C3N4 (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 CO2 adsorption. These features are combined with synergistic electronic multimetallic interactions, facilitating a heterogeneous valence electron distribution and atomic disorder. The CO2-PR power of the (CoFeNiMnCu)S2@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 CO2-PR materials. © 2024 Elsevier B.V
  6. Keywords:
  7. Carbon dioxide ; Charge transfer ; Copper compounds ; Free energy ; Gibbs free energy ; Iron compounds ; Metal ions ; Metal nanoparticles ; Methane ; Redox reactions ; Sulfur compounds ; Synthesis gas ; CO2 photoreduction ; Fine tuning ; G-C3N4 photocatalyst ; Glycerates ; High-entropy material ; Metal sulfides ; Photo reduction ; Sulphide-based material ; Syn gas ; Ultra-thin ; Entropy
  8. Source: Chemical Engineering Journal ; Volume 496 , 2024 ; 13858947 (ISSN)
  9. URL: https://www.sciencedirect.com/science/article/abs/pii/S1385894724052604