This article provides a review of heterojunction-based (type-II and Z-scheme) photocatalytic nitrogen fixation, including fundamental principles, current progress, and prospects.

In this paper, we report the preparation of visible-light active direct Z-scheme Cu₂O/WO₃ nanocomposite photocatalyst by a solid-state reaction avoiding the otherwise inevitable formation of CuWO₄ phase in wet syntheses. Structure, morphology, and thermal and optical properties of prepared WO₃ nanoplatelets decorated by Cu₂O were investigated by XRD, Raman spectroscopy, SEM/TEM, combined thermogravimetric (TG)/differential scanning calorimetry (DSC) analysis, and UV–VIS spectroscopy. The photocatalytic performance of the prepared samples under UV and visible light was studied through monitoring discoloration of methylene blue under illumination by selected wavelengths, allowing for the distinguishing between the contributions of the two semiconductive components. Experimental results showed that the decoration of WO₃ nanoplates by Cu₂O nanoparticles led to an improvement in photocatalytic performance, regardless of used LED (Light-Emitting Diode) wavelength, even at low concentrations. By using scavengers selectively blocking reactive species involved in the discoloration reaction, we determined that the Cu₂O/WO₃ nanocomposite exhibited the characteristics of direct Z-scheme-type photocatalyst.

The impact of geometric features, light absorption spectra, and electrochemical active surface area on photoelectrochemical properties was investigated in this work. Nanoforests of ZnO nanorods with rationally controlled morphologies were grown on ITO substrates by the hydrothermal method and utilized as a model for this purpose. The size of the nanorods was systematically adjusted by varying the concentration of polyethyleneimine as a cation surfactant in the growth solution. It was found that the emergent geometric characteristics (i.e. the aspect ratio) increased almost at the same pace as the electrochemically active surface area, but the light scattering effect slightly increased as a result of the random spatial orientation of the nanorods. The large surface area and the void space between nanorods increased the photon-to-current conversion efficiency by promoting the hole transfer process at the electrode/electrolyte interface. A maximum photocurrent density of 0.06 mA cm⁻² (0.5 V vs. NHE) for smaller diameter and length ZnO nanorods (ZnO–P1) was obtained under 365 nm UV light illumination. Additionally, we provide visual evidence that a shorter photogenerated hole diffusion distance results in improved charge separation efficiency using Mn²⁺ as the photogenerated hole imaging agent. Therefore, the present work demonstrates a facile strategy for nanoforest morphology improvement for generating strong contact at the ZnO NR electrode/electrolyte interface, which is favourable in energy conversion and storage technologies.