Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

A green approach to the fabrication of titania–graphene nanocomposites: Insights relevant to efficient photodegradation of Acid Orange 7 dye under solar irradiation

Environment friendly and efficient strategy for the preparation of titanium dioxide (TiO₂)–graphene (GR) based hybrid nanocomposite has been demonstrated by simple chemical approach for the photodegradation of Acid Orange 7 (AO7) dye under solar irradiation. The resultant nanocomposite structure and composition has been characterized by Ultraviolet Diffusive Reflectance Spectroscopy (UV-DRS), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Raman spectroscopy and X-ray diffraction (XRD) studies. The incorporation of TiO₂ nanoparticles on the surface of GR was confirmed by High Resolution Transmission Electron Microscopy (HRTEM) and Field Emission Scanning Electron Microscopy (FESEM) studies. Electrochemical Impedance spectroscopy (EIS) and Cyclicvoltammetry (CV) studies revealed that the incorporation of GR with TiO₂ nanoparticles significantly enhanced the redox property and electrical conductivity. During photocatalysis, the TiO₂–GR nanocomposites have high photocatalytic activity compared with that of TiO₂ towards AO7 dye degradation under solar light irradiation. The enhanced photocatalytic activity might be attributed to the role GR played as an electron acceptor and transporter in the composite film, which effectively suppressed the charge recombination and promoted the charge transfer within the composite.     

Vanadium based zinc spinel oxides: Potential materials as photoanode for water oxidation and optoelectronic devices

In the recent past, layered zinc-based vanadium spinel oxides (ZnVOs) have shown an intriguing way to accomplish the challenges of energy conversion, storage, and utilization issues. Here, through first-principles calculations, a comprehensive study has been carried out to investigate the AV₂M (where A = Zn, Zn₂, Zn₃, Zn_4, and M = O₄, O₆, O₇, O₈, O₉ respectively) electronic, photocatalytic, and optical properties. Formation energies with a negative sign express that the final compounds from the pure elements are possible and cohesive energies revealed that compounds are energetically stable. Spin-polarized calculations are also taken into account for better approximation of the electronic properties (band structure and density of states). All layered structures show indirect bandgap for spin-up calculations in range 0.3 eV–2.4 eV, while spin-down calculations show mix trends in range 2.3 eV–3.50 eV. An appropriate band edge with large enough kinetic over-potentials of the oxygen evolution reaction (ΔE_V ≥ 1.244 eV) makes them potential candidates as photoanode for water splitting. ZnV₂O₄ is more suitable for OER as it has small kinetic overpotential as compared to the oxidation potential of water. Interestingly, all ZnVOs display a dramatically large coefficient (~10⁵ cm⁻¹) for optical absorption. Photogenerated electrons and holes on the layered zinc-based vanadium spinel oxide surfaces could make these spinel oxides promising materials for photocatalytic water splitting and solar energy conversion.     

A mixed phase lanthanum vanadate in situ induced by graphene oxide/graphite carbon nitride for efficient photocatalytic hydrogen generation

A mixed phase LaVO₄ with high dispersion was in situ induced and implanted in graphene oxide-graphite carbon nitride composite. The obtained nanocomposite (GO–C₃N₄–LaVO₄) showed high and stable photocatalytic activity for hydrogen evolution, which significantly benefited from the improved charge separation and light absorption in the special composite photocatalyst as evidenced by UV–vis spectra, fluorescence spectrum, photocurrent response and electrochemical impedance. The fabrication strategy of mixed phase LaVO₄ in the GO-C₃N₄ provides a new idea for constructing cheap and active organic-inorganic semiconductor photocatalysts for hydrogen generation.     

α-Fe2O3/Pt hybrid nanorings and their enhanced photocatalytic activities

In this paper, α-Fe₂O₃ nanorings were synthesized and used as a support to further synthesize hybrid Pt/α-Fe₂O₃ nanorings. Transmission electron microscopy (TEM) analyses clearly suggest that Pt nanoparticles are deposited on the surface of α-Fe₂O₃ nanorings in a well-dispersed state. This metal–semiconductor hybrid system is expected to show high photocatalytic activity towards the degradation of environmental pollutants. Because of the Schottky contact between semiconductor and metal particles, the holes prefer to localize in energetically lower semiconductor, whereas the electrons can move through the heterointerface. This interfacial charge transfer and separation facilitate the redox reactions, results in a high photocatalytic activity. In our case, the as obtained α-Fe₂O₃/Pt hybrids exhibit enhanced photocatalytic performance with a degradation rate of 86.7% for methyl orange, which is much higher than that of pure α-Fe₂O₃ (33.2%).     

Synthesis and characterization of α/β-Bi2O3 with enhanced photocatalytic activity for 17α-ethynylestradiol

The α/β-Bi₂O₃ photocatalyst was successfully synthesized by a novel solvothermal-calcination method. The physical and chemical properties of as-prepared samples were characterized based on XRD, XPS, SEM, TEM, EDS, BET, UV–vis DRS and PL techniques. The synthesized α/β-Bi₂O₃ photocatalyst exhibited enhanced photocatalytic activity for 17α-ethinylestradiol (EE2), and 96.9% of EE2 was degraded after only 24 min of visible-light irradiation using α/β-Bi₂O₃ as photocatalyst. The reaction rate constant over α/β-Bi₂O₃ photocatalyst was 1.42, 2.23, 9.22 and 54.1 times higher than pure β-Bi₂O₃, α-Bi₂O₃+β-Bi₂O₃, α-Bi₂O₃ and P25 respectively. Effect of catalyst dosage and pH value was investigated. The possible photocatalytic mechanism has been discussed on the basis of the theoretical calculation and the experimental results. α/β-Bi₂O₃ was a fairly stable and efficient photocatalyst under the studied experimental conditions, proving that the α/β-Bi₂O₃ photocatalyst was a promising photocatalyst for the practical application.     

An excellent universal catalyst support-mesoporous silica: Preparation,modification and applications in energy-related reactions

As a kind of versatile, excellent catalyst carriers, mesoporous silicas (mSiO₂) have been widely applied for preparing various supported catalysts with ideal catalytic properties due to their uniform and regular channels, adjustable medium pore size, big surface area, controllable wall composition, high hydrothermal stability, easy functional modification and good accessibility of larger reactant molecules. mSiO₂ not only enhances the dispersity of the active phase and generates more active sites for superior catalytic activity but also improves resulted selectivity and cyclic lifespan for enhanced interaction. And high adsorption capacity of mSiO₂ also increases the reactant molecule enrichment. In addition, mesoporous feature of the mSiO₂ pore wall can ensure diffusion of the substrate molecules and prevent leaching of active components. Thus, related investigation and application have been rapidly growing in the past decades. In this review, the development of mesoporous silica based catalysts on preparation, modification, pore size tune and energy-related applications, especially in hydrogenation reaction, esterification reaction, hydrogen production by alkane dry reforming and alcohol steam reforming and photocatalytic water splitting, is introduced in detail and the design ideas, preparation strategies and corresponding mechanism of different composite catalysts are discussed.     

Fabrication of direct Z-scheme MoO3/N–MoS2 photocatalyst for synergistically enhanced H2 production

A novel visible-light active MoO₃/N–MoS₂ heterostructure photocatalyst was fabricated via hydrothermal process. The structure, morphology and optical characteristics were studied using X-ray diffraction (XRD) technique, scanning electron microscopy (SEM), UV–visible and photoluminescence (PL) spectroscopies. The results indicated that loading pf MoO₃ and nitrogen doping played main influence role in advancing the morphology and optical characteristics. Upon visible photo-illumination, the MoO₃/N–MoS₂ sample displayed superior photocatalytic H₂-production activity (118 μ mol h⁻¹g⁻¹), which was about four-time higher than that of pure MoS₂ (30 μ mol h⁻¹g⁻¹). The enhancement in photocatalytic performance of MoO₃/N–MoS₂ photocatalyst can be ascribed to the development of direct Z-scheme heterostructure, which promoted the photo-excited electrons/holes transfer and separation. The recycling experiment verified that the MoO₃/N–MoS₂ photocatalyst had superior cyclic activity and stability, implying promising applications in energy field.     

Photocatalytic performance of β-Ga2O3 microcubes towards efficient degradation of malachite green

In this work, the photocatalytic degradation of malachite green (MG) solutions by β-Ga₂O₃ was investigated. The latter was synthetized by reacting gallium nitrate with concentrated formic acid, which produced gallium formate. The thermal decomposition of this compound at 850 °C produced single-phase β-Ga₂O₃. The resulting morphology corresponds to non-agglomerated microcubes, with a size in the range of 0.8 and 2.3 μm. The surface chemical composition and bandgap energy of this oxide were determined by X-ray photoelectron spectroscopy (XPS) and the Tauc method, respectively. The photodegradation of MG was carried out under violet light (λ = 405 nm), at room temperature, using the as-prepared powder. The results revealed a fast degradation of the dye during the first 20 min, which attenuates over time. The rate of photodegradation depends on the amount of β-Ga₂O₃ used and can be fitted by an exponential equation. The role of free hydroxyl radicals and reactive oxygen species in photocatalysis was addressed by using analytic techniques (FTIR and XPS).     

Direct Z-Scheme NiWO4/CdS nanosheets-on-nanorods nanoheterostructure for efficient visible-light-driven H2 generation

Exploiting efficient catalysts is of interest for solar-driven water splitting. Herein, a novel NiWO₄/CdS nanosheets-on-nanorods direct Z-Scheme heterostructure was developed by using a facile in-situ approach. The optimized NiWO₄/CdS heterostructure shows a H₂ evolution rate of 26.43 mmol g^?1 h^?1 exceeding that of bare CdS by more than 75 folds. Systematic investigations reveal the nanostructures with numerous active sites, intimate contact interface, and enhanced charge separation rate synergistically account for the outstanding performance of the NiWO₄/CdS. Moreover, the band structures were detailedly analyzed and the tentative photocatalytic mechanism was proposed, which could contribute to deeply understanding the catalytic process and guide the synthesis of the efficient heterostructure. These findings and strategies may have great significance in promoting the development of highly efficient and low-cost photocatalysts.