The photocatalytic CO2 reduction by abundant water to chemical fuels such as hydrocarbons or alcohols is considered to be a promising technology for renewable generation of energy. Immense efforts have been made in improving the CO2 conversion efficiency of the currently known photocatalytic systems, nonetheless, developing CO2 photoreduction kinetics are required to intensify this process up to industrial-scale applications. The scaling up of the CO2 photoreduction process is restricted using the conventional kinetic models because they are reliant on different photoreactor geometries and light transport behavior. On the contrary, the intrinsic kinetic model that is independent of photoreactor geometry is crucial for scaling up CO2 photoreduction reactors. In this work, we proposed an intrinsic kinetic model for CO2 photoreduction reaction and solved the non-linear function to determine the kinetic parameter coefficients using the multistart (MS) median algorithm. The reaction rate constant, absorption equilibrium constants of CO2 and H2O and the reaction order of the light intensity were estimated to be 17.963, 1.764 bar-1, 0.321 bar-1, and 0.967, respectively. Then, these results were compared and validated with the reported experimental data and found to be a good fit. Furthermore, we provided a perspective to create a link between the intrinsic kinetic model and extrinsic kinetic model through photoreactor modelling. This study can be a valuable reference to understand the impact of CO2 photoreduction reaction parameters and enable the research community to bridge the technology gap between lab-scale setups and industrial photocatalytic systems.

Photocatalytic reduction of CO2 with H2O: Reactor modelling, process intensification and kinetic studies

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