Nowadays, the study of environmentally friendly ways of producing hydrogen as a green energy source is an increasingly important challenge. One of these potential processes is the heterogeneous photocatalytic splitting of water or other hydrogen sources such as H₂S or its alkaline solution. The most common catalysts used for H₂ production from Na₂S solution are the CdS-ZnS type catalysts, whose efficiency can be further enhanced by Ni-modification. In this work, the surface of Cd_0.5Zn_0.5S composite was modified with Ni(II) compound for photocatalytic H₂ generation. Besides two conventional methods, impregnation was also applied, which is a simple but unconventional modification technique for the CdS-type catalysts. Among the catalysts modified with 1% Ni(II), the impregnation method resulted in the highest activity, for which a quantum efficiency of 15.8% was achieved by using a 415 nm LED and Na₂S-Na₂SO₃ sacrificial solution. This corresponded to an outstanding rate of 170 mmol H₂/h/g under the given experimental conditions. The catalysts were characterized by DRS, XRD, TEM, STEM-EDS, and XPS analyses, which confirmed that Ni(II) is mainly present as Ni(OH)₂ on the surface of the CdS-ZnS composite. The observations from the illumination experiments indicated that Ni(OH)₂ was oxidized during the reaction, and that it therefore played a hole-trapping role.

Kaolin-based graphitic carbon nitride (g-CNx) composite photocatalysts were synthesized from a urea precursor using a commercial kaolin. Structural characterization by X-ray diffraction and infrared spectroscopy (FTIR) verified the successful thermal polycondensation of g-CNx along the thermal dehydroxylation of kaolinite to metakaolin at 550 °C. The g-CNx content of the composites were estimated by thermogravimetry and CHN analysis, ranging from ca. 87 m/m% to ca. 2 m/m% of dry mass. The addition of kaolin during the composite synthesis was found to have a significant effect: the yield of in situ formed g-CNx drastically decreased (from ca. 4.9 m/m% to 3.8–0.1 m/m%) with increasing kaolin content. CHN and FTIR indicated the presence of nitrogen-rich g-CNx, having a specific surface area of 50 m²/g, which synergistically increased after composite synthesis to 67–82 m²/g. Estimated optical band gaps indicated the affinity to absorb in the visible light spectrum (λ < 413 nm). Photocatalytic activity upon both UV and artificial sunlight irradiation was observed by hydroxyl radical evolution, however, without the synergistic effect expected from the favorable porosity.