With the development of photocatalytic hydrogen production technology, the effective transport of photogenerated carrier electrons is still one of the main factors affecting the performance of photocatalytic hydrogen evolution. In this work, graphdiyne was prepared by ball milling method. The CoMo-MOF with polyhedral structure was introduced into graphdiyne to construct S-scheme heterojunction to promote the efficient transfer of photogenerated carriers and enhanced hydrogen evolution activity. Graphdiyne is a new carbon material with adjustable band gap, which is synthesized from the hybrid of sp and sp2, and has excellent electrical conductivity. CoMo-MOF is a polyhedral structure that can provide more active sites and promote photocatalytic hydrogen evolution. The weak point of poor conductivity in CoMo-MOF has been successfully improved by combining CoMo-MOF with graphdiyne, and the migration rate of photogenerated carriers has been accelerated. The hydrogen evolution property of graphdiyne/CoMo-MOF is 300 μmol, which is 19.61 times that of graphdiyne and 9.03 times that of CoMo-MOF. Therefore, the construction of S-scheme heterojunction provides a transport channel for electron transfer and improves the efficiency of photogenerated carrier separation. This work provides a new train of thought of design to introduce MOFs materials into carbon materials for photocatalytic hydrogen evolution.

Photocatalytically splitting water into hydrogen upon semiconductors has tremendous potential for alleviating environmental and energy crisis issues. There is increasing attention on improving solar light utilization and engineering photogenerated charge transfer of TiO2 photocatalyst because it has advantages of low cost, non-toxicity, and high chemical stability. Herein, oxygen vacancies and cocatalysts (Cu and MoS2) were simultaneously introduced into TiO2 nanoparticles from protonic titanate by a one-pot solvothermal method. The composition and structure characterization confirmed that the pristine TiO2 nanoparticle was rich in oxygen vacancies. The photocatalytic performances of the composites were evaluated by solar-tohydrogen evolution test. The results revealed that both Cu-TiO2 and MoS2- TiO2 could improve the photocatalytic hydrogen evolution ability. Among them, 0.8% Cu-TiO2 showed the best hydrogen evolution rate of 7245.01 μmol·g−1·h−1, which was 3.57 and 1.34 times of 1.25% MoS2- TiO2 (2726.22 μmol·g−1·h−1) and pristine TiO2 material (2028.46 μmol·g−1·h−1), respectively. These two kinds of composites also had good stability for hydrogen evolution. Combined with the results of photocurrent density and electrochemical impedance spectra, the incorporation of oxygen vacancies and cocatalysts (Cu and MoS2) could not only enhance the light-harvesting of TiO2 but also improve the separation and transfer capabilities of light-induced charge carriers, thus promoting water splitting to hydrogen.

Photocatalytic green energy H2 production utilizing inexhaustible solar energy has been considered as a potential solution to problems of energy scarcity and environmental contamination. However, the design of a cost-effective photocatalyst using simple synthesis methodology is still a grand challenge. Herein, a low-cost transition metal, Cu-loaded one-dimensional TiO2 nanorods (Cu/TNR) were fabricated using an easy-to-use synthesis methodology for significant H2 production under simulated solar light. X-ray photoelectron spectral studies and electron microscopy measurements provide evidence to support the successful formation of the Cu/TNR catalyst under our experimental conditions. UV-vis DRS studies further demonstrate that introducing Cu on the surface of TNR substantially increases light absorption in the visible range. Notably, the Cu/TNR catalyst with optimum Cu content, achieved a remarkable H2 production with a yield of 39,239 μmol/g after 3 h of solar light illumination, representing 7.4- and 27.7-fold enhancements against TNR and commercial P25, respectively. The notably improved H2 evolution activity of the target Cu/TNR catalyst was primarily attributed to its excellent separation and efficiently hampered recombination of photoexcited electron-hole pairs. The Cu/TNR catalyst is, therefore, a potential candidate for photocatalytic green energy applications.