Abstract:
The primary factors that govern the selectivity and efficacy of CO2 photoreduction are the degree of activation of CO2 on the active surface sites of photocatalysts and charge separation/transfer kinetics. In this context, the rational synthesis of heterostructured MXene-coupled CeO2-based photocatalysts with different loading concentrations of Ti(3)C(2)MXene via a one-step hydrothermal approach has been undertaken. These photocatalysts exhibit a shift in X-ray diffraction peaks to higher 2 theta values and changes in stretching vibrations of 5 wt % Ti(3)C(2)MXene/CeO2(5-TC/Ce) that indicate interaction between Ti(3)C(2)MXene and CeO2. Moreover, XPS analysis confirms the presence of the Ce3+/Ce4+ states. A sharp band at 2335 cm(-1) observed during the CO2 photoreduction process corresponds to bidentate b-CO32-, which facilitates the adsorption of CO2 at the surface of the catalyst as revealed by the TPD analysis. Furthermore, the Schryvers test and NMR analysis were undertaken to confirm the formaldehyde intermediate formation during CO2 photoreduction to C2H5OH. The decrease in emission intensity, reduced lifetimes (2.68 ns), and lower interfacial resistance, as revealed by PL, TR-PL, and EIS analysis, imply an efficient charge separation and charge transfer in the case of the Ti(3)C(2)MXene/CeO2 heterojunction. The decrease in the intensity of peaks in the EPR spectrum in the case of 5-TC/Ce further confirms efficient charge transfer kinetics across the interface. The optimized 5-TC/Ce shows CO2 reduction with a drastically enhanced yield of ethanol on the order of 6127 mu mol g(-1) at 5 h with 98% selectivity and 7.54% apparent quantum efficiency, which is 6-fold higher than that of ethanol produced by bare CeO2. Herein, CeO2 that acts as a redox couple (Ce3+/Ce4+) when coupled with MXene having a metallic nature that reduces the electron transfer resistance is in unison, enabling an enhanced mobilization of electrons. Thereby, the synergistic coupling of Ti(3)C(2)MXene with CeO2 leads to an efficient photoreduction of CO2 under visible light illumination.