RESUMEN
This work demonstrates the first example of interfacial manipulation in a hybrid photocatalyst based on poly(3-hexylthiophene-2,5-diyl) (P3HT) nanoparticle and graphene oxide (GO) bulk heterojunctions to efficiently reduce CO2 into selective industrial hydrocarbons under gas-phase reaction and visible-light illumination. High selectivity of chemical products (methanol and acetaldehyde) was observed. Moreover, the hybrid photocatalyst's solar-to-fuel conversion efficiency was 13.5 times higher than that of pure GO. The increased production yield stems from the co-catalytic and sensitizing role of P3HT in the hybrid system due to its ability to extend light absorption to the visible range and improve interfacial charge transfer to GO. The hybrid P3HT-GO formed a type II heterojunction, and its static and dynamic exciton behaviors were examined using fluorescence spectroscopy and exciton lifetime mapping. A reduced fluorescence decay time was observed by interfacial manipulation for improved dispersion, indicating a more efficient charge transfer from the excited P3HT to GO. Thus, the conducting polymer nanoparticles, 2D nanocarbon, have demonstrated superior performance as a metal-free, non-toxic, low-cost, and scalable heterogeneous photocatalyst for CO2 reduction to solar fuel, a solid-gas system.
RESUMEN
Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt-nitrogen-carbon (Co-Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co-O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications.
RESUMEN
In this study, biomimetic Mg-N x -C y from Pachira aquatica leaves were mixed with carbon black (L/C catalyst), in which the mixture was treated by a conventional microwave oven at 700 W and 2 min, exhibiting high catalytic activity for the oxygen reduction reaction (ORR). By using a microwave-assisted process, it not only offers a cheaper and faster way to synthesize the catalyst compared to the conventional furnace process but also avoids the decomposition of the N4-structure. Using the optimized conditions, the L/C catalyst exhibits an electron transfer number of 3.90 and an HO2 - yield of only 5% at 0.25 V vs. RHE, which is close to the perfect four electron-transfer pathway. Besides, the L/C catalyst offers superior performance and long-term stability up to 20 000 s. The L/C catalyst contains a high proportion of quaternary-type nitrogen, Mg-N x -C y , and -C-S-C- which can be the active sites for the ORR.
