Manganese phosphorous trifulfide nanosheets and nitrogen doped carbon dot composites with manganese vacancies for a greatly enhanced hydrogen evolution.

As a novel chalcogenide photocatalyst, MnPS3 suffered from limited visible light absorption, high photogenerated electron-hole recombination, and low hole oxidation capability due to its high valence band (VB) potential. In this work, the novel MnPS3 nanosheets-Nitrogen-doped carbon dots (NCDs) composites were fabricated by immobilizing NCDs with terminal amine groups on Na+ intercalated MnPS3 nanosheets for a greatly enhanced photocatalytic hydrogen production activity. MnPS3 nanosheets of 400 nm with Mn2+ vacancies are produced in high yield by NaCl intercalation and subsequent exfoliation in N-methylpyrrolidone (NMP). NCDs with 5 nm are evenly loaded on the surface of MnPS3 nanosheets of 400 nm via strong chemical interactions of ammonium sulfate salts formed at the interface. The MnPS3-NCDs composites exhibit enhanced light absorption at 500-600 nm, reduced charge recombination and notably promoted photocatalytic activity in relative to neat MnPS3 nanosheets. MnPS3-NCDs composite with the NCDs content of 16.5% possessed the highest photocatalytic hydrogen evolution rate of 339.63 µmol·g-1·h-1 with good cycling stability, which is 9.17 times that of exfoliated MnPS3 nanosheets. The type-II MnPS3-NCDs heterojunction is conducive to the efficient interfacial carrier transport and the significantly improved photocatalytic hydrogen generation activity. Our work confirmed that the non-toxic MnPS3 could possess photocatalytic performance comparable to CdS, which will be promising to become an attractive visible-light driven photocatalyst in environmental purification and energy applications.

Fabrication of graphitic carbon Nitride/Nonstoichiometric molybdenum oxide nanorod composite with the nonmetal plasma enhanced photocatalytic hydrogen evolution activity.

The extended light absorption and the prevented charge recombination are crucial for the graphitic carbon nitride (g-C3N4) based photocatalytic materials. Herein, nonstoichiometric molybdenum oxide (MoO3-x) nanorods with oxygen vacancies were synthesized by a hydrothermal method with trace amount of oleylamine, and the Z-scheme two-dimentional (2D)/one-dimentional (1D) g-C3N4/MoO3-x composites were prepared by a facile electrostatic assembling approach. The blue MoO3-x nanorods with oxygen vacancies are loaded uniformly on the g-C3N4 nanosheets. The g-C3N4/MoO3-x composite materials exhibit strong absorption in the visible and near-infrared light regions, and the improved charge separation efficiency through the Z-scheme charge transfer mechanism. The g-C3N4/MoO3-x composite presents a significantly improved photocatalytic hydrogen generation activity with good cycling stability compared with sonicated g-C3N4 nanosheets. The best hydrogen generation activity of 209.2 µmol·h-1 under solar light irradiation and the highest apparent quantum efficiency of 4.4% irradiated at 365 nm are obtained by the g-C3N4/MoO3-x composite with a mass percent of 27.5%, which is 2.63 times of g-C3N4. The weight ratios and the content of oxygen vacancies in the small-size MoO3-x nanorods have a significant influence on the photocatalytic hydrogen performance. Moreover, effective photocatalytic overall water splitting can be achieved with the H2 and O2 evolution rates of 0.755 and 0.368 µmol∙h-1 by the g-C3N4/MoO3-x composite. The novel g-C3N4/MoO3-x composite will have broad prospects in the field of photocatalytic applications.