A set of novel photocatalysts, i.e., copper-zirconia imidazolate (CuZrIm) frameworks, were synthesized using different zirconia molar ratios (i.e., 0.5, 1, and 1.5 mmol). The photoreduction process of CO2 to methanol in a continuous-flow stirred photoreactor at pressure and temperature of 1 atm and 25 °C, respectively, was studied. The physicochemical properties of the synthesized catalysts were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. The highest methanol activity of 818.59 µmol/L.g was recorded when the CuZrIm1 catalyst with Cu/Zr/Im/NH4OH molar ratio of 2:1:4:2 (mmol/mmol/mmol/M) was employed. The enhanced yield is attributed to the presence of Cu2+ oxidation state and the uniformly dispersed active metals. The response surface methodology (RSM) was used to optimize the reaction parameters. The predicted results agreed well with the experimental ones with the correlation coefficient (R2) of 0.99. The optimization results showed that the highest methanol activity of 1054 µmol/L.g was recorded when the optimum parameters were employed, i.e., stirring rate (540 rpm), intensity of light (275 W/m2) and photocatalyst loading (1.3 g/L). The redox potential value for the CuZrIm1 shows that the reduction potential is −1.70 V and the oxidation potential is +1.28 V for the photoreduction of CO2 to methanol. The current work has established the potential utilization of the imidazolate framework as catalyst support for the photoreduction of CO2 to methanol.
Cooperative valorization of lignin and residual sugar to polyhydroxyalkanoate (PHA) for enhanced yield and carbon utilization in biorefineries
