Visible-light-driven ZnIn2S4/CdIn2S4 composite photocatalyst with enhanced performance for photocatalytic H2 evolution

ZnIn₂S₄/CdIn₂S₄ composite photocatalysts (x = 0–1) were successfully synthesized via a hydrothermal route. Compositions of ZnIn₂S₄/CdIn₂S₄ composite photocatalysts were optimized according to the photocatalytic H₂ evolution rate. XRD patterns indicate the as-prepared samples are mixtures of hexagonal and cubic structures. FESEM and TEM images show that the as-prepared samples are composed of flower-like microspheres with wide distribution of diameter. There is obviously distinguishing distribution of Zn, Cd elements among the composite architectures. UV–vis absorption spectra of different compositions exhibit that absorption edges of ZnIn₂S₄/CdIn₂S₄ composites slightly move towards longer wavelengths with the increment of CdIn₂S₄ component. A typical time course of photocatalytic H₂ evolution from an aqueous Na₂SO₃ and Na₂S solution over unloaded and PdS-loaded ZnIn₂S₄/CdIn₂S₄ composite photocatalyst is carried out. The initial activity for H₂ evolution over 0.75 wt% PdS-loaded sample is up to 780 μmol h⁻¹. And the activity of unloaded sample also reaches 490 μmol h⁻¹ with consistent stability.     

Improving photocatalytic activity for hydrogen evolution over ZnIn2S4 under visible-light: A case study of rare earth modification

A series of rare earth (RE) ions (La³⁺, Ce³⁺, Gd³⁺, Er³⁺ or Y³⁺) modified ZnIn₂S₄ photocatalysts (RE-ZnIn₂S₄) were prepared using the hydrothermal method and characterized by various analysis techniques, such as UV–Vis diffusive reflectance spectroscopy, X-ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller surface analyzer, photoluminescence spectroscopy and X-ray photoelectron spectroscopy. The results indicated that the RE element exists as the oxide RE₂O₃ and their modification can reduce ZnIn₂S₄ crystallite size, inhibit ZnIn₂S₄ grain growth, promote ZnIn₂S₄ crystallite self-organization into a micro-sphere flower-like morphology, increase ZnIn₂S₄ surface area and total pore volume, and bring rich defects to ZnIn₂S₄. The photocatalytic activities of RE-ZnIn₂S₄ were evaluated based on photocatalytic hydrogen production from water under visible-light irradiation and the hydrogen production efficiency increased by 46%, 53%, 61%, 69%, and 106% after adding 2.0 wt% of Y, Gd, Er, Ce and La, respectively. The relationship between the photocatalytic activity of RE-ZnIn₂S₄ and the RE properties was discussed.     

Photocatalytic hydrogen generation in the presence of glucose over ZnS-coated ZnIn2S4 under visible light irradiation

ZnS coated ZnIn₂S₄ (ZnS–ZnIn₂S₄) photocatalysts were prepared in methanol by a facile solvothermal process. The photocatalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), UV–Vis diffusive reflectance spectroscopy (DRS), BET, and electrochemistry measurements. ZnS–ZnIn₂S₄ photocatalysts have hexagonal crystal phase and complex morphology such as micro-spheres, micro-tubes and micro-ribbons. Using glucose as an electron donor, photocatalytic hydrogen generation over Pt/ZnS–ZnIn₂S₄ was investigated. The results show that photoactivity of hydrogen generation over Pt/ZnS–ZnIn₂S₄ was improved notably with simultaneous degradation of glucose. The factors which affect photocatalytic hydrogen generation, such as composition of ZnS-ZnIn₂S₄, initial concentration of glucose and concentration of NaOH, were investigated. The prepared ZnS–ZnIn₂S₄ photocatalysts exhibit better activity for hydrogen generation than pure ZnIn₂S₄, which may be attributed to enhancement of the adsorption of glucose by ZnS on the ZnIn₂S₄ surface. The effect of glucose concentration on the hydrogen generation rate is consistent with a Langmuir model. The basic condition is favorable for the photocatalytic hydrogen generation. A large number of ·OH radicals generated in ZnS–ZnIn₂S₄ system, have been tested by a TA-FL (terephthalic acid-fluorescence) method. A possible mechanism was discussed.     

3D hierarchical ZnIn2S4: The preparation and photocatalytic properties on water splitting

Hexagonal ZnIn₂S₄ photocatalysts with 3D-hierarchical persimmon-like shape have been successfully synthesized via an oleylamine (OA)-assisted solvothermal method. Hydrogen evolution experiments revealed that the obtained hierarchical ZnIn₂S₄ possessed good photocatalytic activity, e.g. hydrogen production rate reached to 220.45 μmol h⁻¹ and the quantum yield was up to 13.16% when 3% Pt was loaded. Further delicate tuning the percentage of exposed facet of the obtained ZnIn₂S₄ crystals, it was found that the increase of {006} facets, terminated by metal ions, would improve their photocatalytic activity, and the relationship between the crystal structure and photocatalytic properties had been studied.     

Synthesis of (CuIn)xCd2(1−x)S2 photocatalysts for H2 evolution under visible light by using a low-temperature hydrothermal method

A new series visible-light driven photocatalysts (CuIn)_xCd_2(1−x)S₂ was successfully synthesized by a simple and facile, low-temperature hydrothermal method. The synthesized materials were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV–Vis DRS). The results show that the morphology of the photocatalysts changes with the increase of x from 0.01 to 0.3 and their band gap can be correspondingly tuned from 2.37 eV to 2.30 eV. The (CuIn)_xCd_2(1−x)S₂ nanocomposite show highly photocatalytic activities for H₂ evolution from aqueous solutions containing sacrificial reagents, SO₃²⁻ and S²⁻ under visible light. Substantially, (CuIn)_0.05Cd_1.9S₂ with the band gap of 2.36 eV exhibits the highest photocatalytic activity even without a Pt cocatalyst (649.9 μmol/(g h)). Theoretical calculations about electronic property of the (CuIn)_xCd_2(1−x)S₂ indicate that Cu 3d and In 5s5p states should be responsible for the photocatalytic activity. Moreover, the deposition of Pt on the doping sample results in a substantial improvement in H₂ evolution than the Pt-loaded pure CdS and the amount of H₂ produced (2456 μmol/(g h)) in the Pt-loaded doping system is much higher than that of the latter (40.2 μmol/(g h)). The (CuIn)_0.05Cd_1.9S₂ nanocomposite can keep the activity for a long time due to its stability in the photocatalytic process. Therefore, the doping of CuInS₂ not only facilitates the photocatalytic activity of CdS for H₂ evolution, but also improves its stability in photocatalytic process.     

Electronic structure and water splitting under visible-light irradiation of Zn and Ag co-doped In(OH)ySz photocatalysts

Zinc and silver co-doped In(OH)_yS_z with nanocubic blocks morphology were prepared by a one-step hydrothermal method and their photocatalytic activities were investigated. The as-synthesized products were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) and UV–visible spectroscopy. The electron microscope observations revealed that the particle sizes of Zn-doped In(OH)_yS_z crystals were smaller than that of the non-doped In(OH)_yS_z, which accords with BET results. While Zn–Ag co-doped In(OH)_yS_z showed the nanocubic blocks with different particle sizes. The UV–vis spectra indicate that the single Zn ions doping leads to the absorbance band shifts toward lower wavelength upon increasing the Zn doping. Consequently, the band gap of In(OH)_yS_z also increases gradually with increasing the Zn doping. In contrast, an obvious red-shift is observed for Zn–Ag co-doped In(OH)_yS_z solid solution, which mainly attributed to the transition from Ag 4d + S 3p orbitals to Zn 4s + In 5s orbitals. The sample doped with 4 mol% Ag and Zn was found to have the highest activity, which is 20 times that of the In(OH)_yS_z.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Photocatalytic H2 evolution on a novel CaIn2S4 photocatalyst under visible light irradiation

A novel visible-light-driven photocatalyst CaIn₂S₄ was synthesized using a facile hydrothermal method followed by a post-calcination process. The influence of the calcination temperature and time on the activities of the photocatalyst was investigated. CaIn₂S₄ exhibits optical absorption predominantly in visible region with an optical band gap of 1.76 eV. Considerable activity for hydrogen evolution from pure water was observed without any sacrificial agents or cocatalysts under visible light irradiation. The maximum hydrogen evolution rate achieved was 30.92 μmol g⁻¹ h⁻¹ without obvious deactivation of the photocatalytic activity for four consecutive runs of 32 h.     

Microwave-assisted hydrothermal synthesis of transition-metal doped ZnIn2S4 and its photocatalytic activity for hydrogen evolution under visible light

Aiming at the enhancement of photocatalytic activity for hydrogen evolution over ZnIn₂S₄, different transition metals (Cr, Mn, Fe, Co) are doped into the lattices of ZnIn₂S₄ to narrow the band gap. The doped ZnIn₂S₄ is characterized by XRD, Raman, UV-vis spectra, photoluminescence spectra, SEM and XPS techniques. The photocatalytic evaluation shows that Mn-doped ZnIn₂S₄ performs photocatalytic activity 20% higher than undoped ZnIn₂S₄, while Cr-, Fe-, and Co-doped ZnIn₂S₄ perform poorer activities in an order of Cr > Fe > Co. Based on the combined characterization results, the band structures of doped ZnIn₂S₄ are schematically depicted, which illustrates the different effects of transition-metal doping on the photocatalytic activity for hydrogen evolution. For Mn-doped ZnIn₂S₄, the enhancement of photocatalytic activity could be due to narrowed band gap induced by Mn doping. However, for Cr-, Fe-, and Co-doped ZnIn₂S₄, the suppressed photocatalytic activities should be attributed to the dopant-related impurity energy levels localizing the charge carriers or acting as non-radiative recombination centers for photoexcited electrons and holes. Hence, this study indicates that it is of great importance to make the in-depth investigation on the effects of band structures on the photocatalytic activity, especially for the doped semiconducting photocatalysts.     

ZnmIn2S3+m (m = 1–5, integer): A new series of visible-light-driven photocatalysts for splitting water to hydrogen

A new series of Zn_mIn₂S_3+m (m = 1–5, integer) photocatalysts was synthesized via a simple hydrothermal method. X-ray diffraction (XRD), Raman spectra, UV–vis–near-IR diffuse reflectance spectra (UV–vis), X-ray fluorescence (XRF) and scanning electron microscope (FESEM) were used to characterize these photocatalysts. These Zn_mIn₂S_3+m photocatalysts had a similar layered crystal structure. The absorption edge of Zn_mIn₂S_3+m shifted to shorter wavelength as the atomic ratio of Zn/In in the synthetic solution was increased (i.e. m increased from 1 to 5). Additionally, the morphology of Zn_mIn₂S_3+m greatly depended on the atomic ratio of Zn/In. The photocatalytic activity of Zn_mIn₂S_3+m was evaluated by photocatalytic hydrogen production from water under visible light. The Zn₂In₂S₅ product, with quantum yield at 420 nm determined to be 11.1%, had the highest photocatalytic activity among these Zn_mIn₂S_3+m (m = 1–5, integer) photocatalysts.     

Effects of cocatalysts on photocatalytic properties of La doped Cd2TaGaO6 photocatalysts for hydrogen evolution from ethanol aqueous solution

La doped Cd₂TaGaO₆ photocatalyst was successfully synthesized for the first time by a sol–gel method. Several metal oxides and noble metals involving NiO, CuO, Cr₂O₃, Pt, and Ru were respectively loaded onto La doped Cd₂TaGaO₆ as cocatalyst. NiO and noble metal co-loaded photocatalyst was also prepared. The obtained products were characterized by X-ray diffraction (XRD), ultraviolet–visible spectra (UV–Vis), scanning electron microscope (SEM), etc. The results showed that most of cocatalyst loaded photocatalysts exhibited much higher activities for hydrogen evolution from ethanol aqueous solution than single La doped Cd₂TaGaO₆. Compared with sole NiO or noble metal loaded photocatalyst, NiO and noble metal co-loaded La doped Cd₂TaGaO₆ showed superior activity. It is revealed that the loaded NiO and noble metal can interact with each other and cooperate on improving the photocatalytic activity. The effect of the cocatalyst loading amount on photocatalytic properties was discussed. Especially, 0.5 wt% NiO and 0.5 wt% Pt co-loaded La doped Cd₂TaGaO₆ displayed the highest hydrogen production rate of 2.93 mmol h⁻¹, which was ca. 33 times that of single La doped Cd₂TaGaO₆.     

Synthesis,characterization and photocatalytic performances of Cu2MoS4

A novel visible-light-driven Cu₂MoS₄ photocatalyst was prepared by a facile hydrothermal method using Ammonium Tetrathiomolybdate reacting with cuprous chloride in aqua ammonia. The synthetic catalysts were characterized by XRD, UV–vis spectra, XRF and SEM techniques. The influence of the reaction temperature and time on the activities of the catalysts and the morphology of particles was investigated. The results showed that the catalysts exhibited strong absorption in visible light region. It was found that the photocatalyst prepared under hydrothermal condition at 140 °C for about 24 h showed good crystallinity with regular shape, and the highest activity for hydrogen production under visible light irradiation in an aqueous Na₂S–Na₂SO₃ solution. The reason for its better performance has been discussed in detail.     

Preparation of ZnIn2S4/fluoropolymer fiber composites and its photocatalytic H2 evolution from splitting of water using Xe lamp irradiation

This paper focuses on the preparation of ZnIn₂S₄/fluoropolymer fiber composites and their performance for H₂ evolution from splitting of water using Xe lamp irradiation. Hexafluorobutyl acrylate-co-methacrylic acid (poly(HFBA-co-MAA)) is synthesized by a solution polymerization. Next, the fluoropolymer fibers, which have around 100 nm in average diameter, of poly(HFBA-co-MAA) and polyvinylidene fluoride (PVDF) mixtures are obtained by electrospinning. Then, zinc and indium ions are introduced onto the fiber surface by coordinating with carboxyls of MAA. After that, sulfide ions are incorporated to react with zinc and indium ions by a hydrothermal synthesis. Thus, ZnIn₂S₄ particles of around 800 nm in average size, are obtained and well loaded on the fiber surface. The absorption edge of ZnIn₂S₄/fluoropolymer fiber composites is at 510 nm within the visible-light region. Photocatalytic H₂ evolution from water was investigated using Xe lamp. It was found that the average rate of H₂ evolution of ZnIn₂S₄ powders gradually decreased, while the average rate of H₂ evolution of ZnIn₂S₄/fluoropolymer fiber composites increased from the first to the third run. The average rate of H₂ evolution using the ZnIn₂S₄/fluoropolymer fiber composites as the catalyst achieved 9.1 mL/h in the third run.     

Efficient photocatalytic hydrogen production under visible light over a novel W-based ternary chalcogenide photocatalyst prepared by a hydrothermal process

Decahedral Cu₂WS₄ was synthesized by a facile hydrothermal method and employed as photocatalyst for photocatalytic hydrogen production for the first time. The hydrothermal method avoids the traditional use of H₂S for the preparation of such chalcogenide, which guarantees an environmental-friendly process. The properties of the Cu₂WS₄ samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–Vis reflectance spectra, etc. The results showed that the decahedral Cu₂WS₄ possessed a band gap of ca. 2.1ev. The photocatalyst was demonstrated to be very active under visible light for hydrogen production. Especially, Cu₂WS₄ synthesized at 200 °C for 72 h showed the highest activity with the apparent quantum yield of 11% at 425 nm. The correlation between the preparation parameters and the photocatalytic properties were investigated. It was expected this first report of W-based chalcogenide photocatalyst would add to the photocatalyst group and lead to the finding of new photocatalyst with much higher activity.     

Photocatalytic hydrogen generation through water splitting on nano-crystalline LaFeO3 perovskite

Visible light active ABO₃ type photocatalyst with LaFeO₃ composition was synthesized by sol-gel method. The photocatalyst was characterized by different techniques such as X-ray diffraction, BET surface area analysis, particle size analysis, scanning electron microscopy, UV–visible diffuse reflectance spectroscopy (UV–Visible DRS), and photoluminescence spectroscopy. LaFeO₃ photocatalyst exhibited an optical band gap of 2.07 eV with the absorption spectrum predominantly in visible region of the spectrum. The BET surface area of photocatalyst LaFeO₃ was observed as 9.5 m²/g, with the crystallite size of 38.8 nm as calculated by the Debye-Scherer equation. The photocatalytic activity of LaFeO₃ was investigated for hydrogen generation through sacrificial donor assisted photocatalytic water splitting reaction by varying conditions in feasible parametric changes using visible light source, ethanol as a sacrificial donor and Pt solution of H₂PtCl₆ as a co-catalyst. The rate of photocatalytic hydrogen evolution was observed to be 3315 μmol g⁻¹ h⁻¹ under optimized conditions and using 1 mg dose of photocatalyst with reaction time of 4 h and illumination of 400 W.     

Ag3PO4 photocatalyst: Hydrothermal preparation and enhanced O2 evolution under visible-light irradiation

Visible-light-driven semiconducting photocatalysts of Ag₃PO₄ were prepared by a hydrothermal method, and were optimized by adjusting reaction conditions, i.e., temperature, pH of reaction solution, concentration of feedstock, and time of hydrothermal process. The obtained photocatalysts were then systematically characterized by different instruments, such as XRD, UV–vis, FESEM, and BET, to reveal the physicochemical properties. Furthermore, activities of photocatalysts for visible-light-driven O₂ evolution were evaluated, demonstrating that the photocatalytic activity of Ag₃PO₄ prepared by hydrothermal reaction (initial rate of O₂ evolution, 1156 μmol g⁻¹ h⁻¹) was more than two times as that of sample prepared by room-temperature reaction (initial rate of O₂ evolution, 533 μmol g⁻¹ h⁻¹), which could be attributed to its better ability to utilize visible light and more regulated morphology.     

Surfactant tunable hierarchical nanostructures of CdIn2S4 and their photohydrogen production under solar light

The hierarchical nanostructures of CdIn₂S₄ were selectively prepared through hydrothermal process in the presence of different surfactants. Structural study demonstrated existence of cubic spinel structure and micro structural study shown a pretty marigold flower like morphology without any surfactant. The effect of surfactants on the morphology and microstructure of CdIn₂S₄ has been studied by using Polyvinyl pyrrolidone (PVP) and Cetyltrimethyl ammonium bromide (CTAB) as a surfactants. The CdIn₂S₄ bipyramids with length of 0.7-1 μm have been obtained using PVP. Interestingly, the nanopetals (thin and transparent) of CdIn₂S₄ are self assembled into hollow spheres in the presence of CTAB. Considering the importance of these unique nanostructures, the growth mechanism has also been proposed. The optical properties demonstrated the band gap in the range of 2.12-2.29 eV which is well within the visible region. In this contest, photocatalytic activity for hydrogen production using the above nanostructures under visible light was also demonstrated. The prima-fascia observations shows that the bipyramidal CdIn₂S₄ exhibit excellent photocatalytic activity for hydrogen production (3238 μmolh⁻¹) than other nanostructures. Being a nanostructured semiconductor chalcogenide with a good stability will also have potential applications in solar cells and LED.     

Hydrothermally stabilized Fe(III) doped titania active under visible light for water splitting reaction

Fe³⁺ doped TiO₂ photocatalysts were prepared by hydrothermal treatment for the photocatalytic water splitting to produce stoichiometric hydrogen and oxygen under visible light irradiation. It was found that hydrothermal treatment at 110 °C for 10 h was essential for the synthesis of highly stabilized Fe³⁺ doped TiO₂ photocatalysts. The synthesized photocatalysts were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS) and BET surface area techniques. The doping of highly stabilized Fe³⁺ in the titania matrix leads to significant red shift of optical response towards visible light owing to the reduced band gap energy. Optimum amount of Fe³⁺ doped TiO₂, 1.0 wt% Fe/TiO₂, showed drastically improved hydrogen production performance of 12.5 μmol-H₂/h in aqueous methanol and 1.8 μmol-H₂/h in pure water, respectively. This Fe/TiO₂ photocatalyst was stable for 36 h without significant deactivation in the water splitting reaction.     

Photocatalytic water splitting with In-doped H2LaNb2O7 composite oxide semiconductors

The In-doped HLaNb₂O₇ oxide semiconductors synthesized by solid-state reaction followed by an ion-exchange reaction were found to be a novel composite photocatalyst system with enhanced activity for water splitting. Pt was incorporated in the interlayer of In-doped HLaNb₂O₇ by the stepwise intercalation reaction. The In-doped HLaNb₂O₇ powder samples were characterized with X-ray diffraction (XRD) and UV-vis diffuse reflectance spectrometry. The photocatalytic activities of Pt-loaded In-doped HLaNb₂O₇ and individual precursor materials were evaluated by H₂ evolution from aqueous CH₃OH solution under UV light irradiation. It was found that the composite In-doped HLaNb₂O₇ showed a higher H₂ evolution rate in comparison with individual materials. The hydrogen production activity of In-doped HLaNb₂O₇ was greatly enhanced by Pt co-incorporation. The In content in the In-doped HLaNb₂O₇ system was discussed in relation to the photophysical and photocatalytic properties. As In content equal 5 mol%, the HLaNb₂O₇:In/Pt showed a photocatalytic activity of 354 cm³ g⁻¹ hydrogen evolution in 10 vol% methanol solution under irradiation from a 100 W mercury lamp at 333 K for 3 h.     

High-rate performance of all-solid-state lithium secondary batteries using Li4Ti5O12 electrode

The all-solid-state Li–In/Li₄Ti₅O₁₂ cell using the 80Li₂S·20P₂S₅ (mol%) solid electrolyte was assembled to investigate rate performances. It was difficult to obtain the stable performance at the charge current density of 3.8 mA cm⁻² in the all-solid-state cell. In order to improve the rate performance, the pulverized Li₄Ti₅O₁₂ particles were applied to the all-solid-state cell, which retained the reversible capacity of about 90 mAh g⁻¹ at 3.8 mA cm⁻². The 70Li₂S·27P₂S₅·3P₂O₅ glass–ceramic, which exhibits the higher lithium ion conductivity than the 80Li₂S·20P₂S₅ solid electrolyte, was also used. The Li–In/70Li₂S·27P₂S₅·3P₂O₅ glass–ceramic/pulverized Li₄Ti₅O₁₂ cell was charged at a current density higher than 3.8 mA cm⁻² and showed the reversible capacity of about 30 mAh g⁻¹ even at 10 mA cm⁻² at room temperature.