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 Ti3C2MXene via a one-step hydrothermal approach has been undertaken. These
photocatalysts exhibit a shift in X-ray diffraction peaks to higher
2θ values and changes in stretching vibrations of 5 wt % Ti3C2MXene/CeO2(5-TC/Ce) that indicate
interaction between Ti3C2MXene 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-CO3
2–, 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 Ti3C2MXene/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 μmol 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 Ti3C2MXene with CeO2 leads to
an efficient photoreduction of CO2 under visible light
illumination.