Direct growth of copper(I) oxide nanocubes on graphitic carbon nitrides enhancing aqueous carbon dioxide photoreduction

Semiconductor hybrid structures containing multiple components have been considered an ideal photocatalyst design to generate long-lived charge-separated states. Particularly for the reactions requiring high activation energies, such as a CO2 reduction reaction (CO2RR), the reaction activity is highly susceptible to the catalyst component and morphology. In this study, we selected g-C3N4 and Cu2O as photocatalytic components having bandgaps suitable for CO2RR. Then, we tried to form good electric junctions between two domains by direct growth of Cu on g-C3N4 using a polyol process. The resulting g-C3N4/Cu2O hybrid was employed as photocatalysts in an aqueous medium without hole acceptors. The catalyst exhibited a noticeable activity (5.4 mmol gcat-1h-1) and quantum yield (3.7%) with a nearly quantitative selectivity for CH4 production, superior to any other photocatalysts for CO2RR. The strong coordination of g-C3N4 to the Cu2O surface could form a conductive junction and induce effective electron transfer enforcing the Z-scheme process for CO2RR in high activity and selectivity. This result ensured the importance of junctions and interfaces in the hybrid catalyst structure to exhibit excellent photocatalytic CO2RR performances.

Investigation of carbon dioxide photoreduction process in a laboratory-scale photoreactor by computational fluid dynamic and reaction kinetic modeling

The production of solar fuels via the photoreduction of carbon dioxide to methane by titanium oxide is a promising process to control greenhouse gas emissions and provide alternative renewable fuels. Although several reaction mechanisms have been proposed, the detailed steps are still ambiguous, and the limiting factors are not well defined. To improve our understanding of the mechanisms of carbon dioxide photoreduction, a multi-physics model was developed using COMSOL. The novelty of this work is the computational fluid dynamic model combined with the novel carbon dioxide photoreduction intrinsic reaction kinetic model, which was built based on three-steps, namely gas adsorption, surface reactions and desorption, while the ultraviolet light intensity distribution was simulated by the Gaussian distribution model and Beer-Lambert model. The carbon dioxide photoreduction process conducted in a laboratory-scale reactor under different carbon dioxide and water moisture partial pressures was then modeled based on the intrinsic kinetic model. It was found that the simulation results for methane, carbon monoxide and hydrogen yield match the experiments in the concentration range of 10−4 mol·m−3 at the low carbon dioxide and water moisture partial pressure. Finally, the factors of adsorption site concentration, adsorption equilibrium constant, ultraviolet light intensity and temperature were evaluated.

Enhancing photocatalytic activity of defective titania for carbon dioxide photoreduction via surface-functionalization

The hydrophilic surface of defective titanium dioxide lowers its adsorption capacity towards CO2 molecules. To get rid of this drawback, we conducted surface-functionalization of defective titania by ammonium fluoride in...