Search Results
Relations between Structure, Activity and Stability in C3N4 Based Photocatalysts Used for Solar Hydrogen Production
Solar hydrogen production from water could be a sustainable and environmentally friendly alternative to fossil energy carriers, yet so far photocatalysts active and stable enough for large-scale applications are not available, calling for advanced research efforts. In this work, H2 evolution rates of up to 1968 and 5188 μmol h−1 g−1 were obtained from aqueous solutions of triethanolamine (TEOA) and oxalic acid (OA), respectively, by irradiating composites of AgIn5S8 (AIS), mesoporous C3N4 (CN, surface area >150 m2/g) and ≤2 wt.% in-situ photodeposited Pt nanoparticles (NPs) with UV-vis (≥300 nm) and pure visible light (≥420 nm). Structural properties and electron transport in these materials were analyzed by XRD, STEM-HAADF, XPS, UV-vis-DRS, ATR-IR, photoluminescence and in situ-EPR spectroscopy. Initial H2 formation rates were highest for Pt/CN, yet with TEOA this catalyst deactivated by inclusion of Pt NPs in the matrix of CN (most pronounced at λ ≥ 300 nm) while it remained active with OA, since in this case Pt NPs were enriched on the outermost surface of CN. In Pt/AIS-CN catalysts, Pt NPs were preferentially deposited on the surface of the AIS phase which prevents them from inclusion in the CN phase but reduces simultaneously the initial H2 evolution rate. This suggests that AIS hinders transport of separated electrons from the CN conduction band to Pt NPs but retains the latter accessible by protons to produce H2.
Influence of MoS2 on activity and stability of carbon nitride in photocatalytic hydrogen production
MoS2/C3N4 (MS-CN) composite photocatalysts have been synthesized by three different methods, i.e., in situ-photodeposition, sonochemical, and thermal decomposition. The crystal structure, optical properties, chemical composition, microstructure, and electron transfer properties were investigated by X-ray diffraction, UV-vis diffuse reflectance spectroyscopy, X-ray photoelectron spectroscopy, electron microscopy, photoluminescence, and in situ electron paramagnetic resonance spectroscopy. During photodeposition, the 2H MoS2 phase was formed upon reduction of [MoS4]2− by photogenerated conduction band electrons and then deposited on the surface of CN. A thin crystalline layer of 2H MoS2 formed an intimate interfacial contact with CN that favors charge separation and enhances the photocatalytic activity. The 2H MS-CN phase showed the highest photocatalytic H2 evolution rate (2342 µmol h−1 g−1, 25 mg catalyst/reaction) under UV-vis light irradiation in the presence of lactic acid as sacrificial reagent and Pt as cocatalyst.
Room temperature synthesis of an amorphous MoS2 based composite stabilized by N-donor ligands and its light-driven photocatalytic hydrogen production
Herein an entirely new and simple room temperature synthesis of an amorphous molybdenum sulfide stabilized by complexing ammonia and hydrazine is reported. The resulting material exhibits an outstanding activity for the photocatalytic hydrogen evolution driven by visible light. It is chemically stable during the reaction conditions of the photocatalysis and shows unusual thermal stability up to 350 °C without crystallization. The new material is obtained by a reaction of solid ammonium tetrathiomolybdate and gaseous hydrazine. In the as-prepared state Mo atoms are surrounded by μ2-briding S2−, NH3 and hydrazine, the latter being coordinated to Mo(IV) in a bridging or side-on mode. Heating at 450 °C or irradiation with an electron beam generates nanosized crystalline MoS2 slabs. The two modes for crystallization are characterized by distinct mechanisms for crystal growth. The stacking of the slabs is low and the material exhibits a pronounced turbostratic disorder. Heat treatment at 900 °C yields more ordered MoS2 but structural disorder is still present. The visible-light driven hydrogen evolution experiments evidence an outstanding performance of the as-prepared sample. The materials were thoroughly characterized by optical spectroscopy, chemical analysis, in situ HRTEM, XRD, 1H and 15N solid-state NMR, XPS, and thermal analysis.