Titania - Supported transition metals sulfides as photocatalysts for hydrogen production from propan-2-ol and methanol

A series of transition metals sulfides deposited on anatase titania (MS_x/TiO₂) were prepared by precipitation of transition metals salts with thioacetamide in aqueous medium under reflux. The solids were characterized by XRD, XPS, temperature programmed reduction and transmission electron microscopy. The properties of as obtained catalysts were compared for the photocatalytic hydrogen evolution reaction (PHER) in pure methanol and water-isopropanol mixture. The sequences of PHER activity were compared with electrochemical HER and thiophene hydrodesulfurization (HDS) activity of the corresponding sulfides prepared by the same technique. For PHER, in both alcohols the most active photocatalysts contain hydrogenating sulfides of Co and Ru. However the PHER activity does not follow the same trend as electrocatalytic HER and thiophene HDS. Some sulfides, such as HgS or CuS, show poor activity in HDS and electrocatalytic HER, but have the PHER activity comparable with that of the best samples. This difference suggests that the PHER rate is not merely related to the hydrogen activating properties of the co-catalyst, but is enhanced by the transfer of photogenerated electrons from TiO₂ towards the sulfide. The ranking of the co-catalysts and the PHER activity depend also on the nature of the alcohol molecule, the overall PHER rates in water-isopropanol mixture being lower than in methanol.     

Photocatalytic hydrogen production using Fe2O3-based core shell nano particles with ZnS and CdS

Stability and efficiency of photocatalysts are important to realize the practical applications of them for photocatalytic hydrogen production from industrial sulfide effluent. Novel, magnetically separable core–shell nano photocatalysts viz., CdS/Fe₂O₃, ZnS/Fe₂O₃ and (CdS + ZnS)/Fe₂O₃ were prepared and their hydrogen evolution activity under visible light was examined. The XRD result shows that CdS and ZnS were very well coated on the surface of the iron oxide core shell particles. The HR-TEM result also confirms the core shell formation. (CdS + ZnS)/Fe₂O₃ evolved higher volume of hydrogen than the other catalysts. It is ascribed to rapid migration of excited electrons from (CdS + ZnS) toward Fe₂O₃ suppressing electron hole annihilation compared to other catalysts. The catalysts can be easily recovered from the reaction medium using external magnetic bar and so the photocatalyst can be reused without any mass loss. Hence, it can be a potential catalyst for recovery of hydrogen from industrial sulfide containing waste streams.     

Hydrogen production from the splitting of H2S by visible light irradiation of vanadium sulfides dispersion loaded with RuO2

The possibility of using aqueous vanadium sulfides dispersions loaded with RuO₂ under illumination by visible light for cleavage of hydrogen sulfide has been studied at room temperature and 35°C at different pH and different concentration of Na₂S, Na₂SO₃ and Na₂S₂O₃ solutions. Hydrogen generation and activities of the colloidal semiconductor have been measured and examined in the presence of RuO₂ catalyst for above conditions.The photogeneration of hydrogen from the splitting of hydrogen sulfide was very efficient when 0.1 M Na₂S or Na₂SO₃ at pH = 11 is used in aqueous media at 35°C, with 0.3 g of vanadium sulfide and 0.9 mg RuO₂ dissolved in 300 ml water, thus thiosulphate was formed as a replacement of particles.     

Sulfur-poisoned Ni-based solid oxide fuel cell anode characterization by varying water content

The 0.2% hydrogen sulfide (H₂S) poisoning of Ni/YSZ anode-supported solid oxide fuel cells (SOFCs) is investigated by varying water content in fuel. The degradation extent of the cell voltage decreases with increasing water content (from 0% to 10%). Water can be generated at the anode side through an electrochemical reaction, and the content of water product augments upon the addition of fuel. However, our results indicate that an increase in fuel utilization significantly aggravates H₂S poisoning behavior. The results of X-ray analysis suggest that the presence of water in fuel cannot affect the final forms of nickel sulfides, but microstructural inspection reveals different attack modes upon the injection of vapor (from 0 to 10%) into fuel containing 0.2% H₂S.     

Fabrication of nano N-doped In2Ga2ZnO7 for photocatalytic hydrogen production under visible light

N-doped In₂Ga₂ZnO₇ photocatalysts were fabricated by solid state reaction route. All the prepared photocatalysts were successfully characterised by PXRD, optical absorption spectra, SEM, TEM, XPS, BET surface area and photoresponse studies. The formation of In₂Ga₂ZnO₇ was confirmed by the PXRD pattern. Optical absorption spectra showed that the visible light absorption of all the photocatalysts were enhanced by nitrogen doping. Among all the prepared photocatalysts, 1 wt% Pt loaded N-GaInZn-500 showed enhanced photocatalytic activity towards hydrogen evolution under visible light irradiation in presence of 10 vol% methanol solution as sacrificial agent. The excellent photocatalytic activity of N-GaInZn-500 is in agreement with N-content, bandgap energy, PL intensity and Surface area.     

TiO2 hollow spheres with separated Au and RuO2 co-catalysts for efficient photocatalytic water splitting

Hollow mesoporous TiO₂ photocatalysts with dual co-catalysts, located at specific positions, were prepared using Polystyrene (PS) as sacrificial templates. Au nanoparticles (NPs) were in situ loaded on the surface of PS spheres and the resulting nanocomposites were coated with TiO₂ shell using sol-gel reaction. The outer surface of core-shell spheres was impregnated with Ru and the subsequent calcination produced hollow anatase spheres with Au and RuO₂ dual co-catalysts. The hollow mesoporous spheres of Au@TiO₂@RuO₂ were proved by various techniques such as TEM, EDX, and SEM images. Photocatalysts were applied for hydrogen generation from water splitting and that with dual co-catalysts showed efficient catalytic activity under simulated solar light. The catalytic activity of photocatalysts with both oxidation and reduction co-catalysts (Au@TiO₂@RuO₂) showed hydrogen evolution (3165 μmol g⁻¹) almost two times more than that Au@TiO₂ and TiO₂@RuO₂ with single co-catalysts. And the hydrogen evolved is more than three times as compared to TiO₂ (935 μmol g⁻¹) without any co-catalyst. Hollow mesoporous morphology with different co-catalysts on inner and outer surfaces is believed to enhance photocatalytic activity which is due to better separation of photo-generated charges.     

Review of photocatalytic water‐splitting methods for sustainable hydrogen production

This paper examines photocatalytic hydrogen production as a clean energy solution to address challenges of climate change and environmental sustainability. Advantages and disadvantages of various hydrogen production methods, with a particular emphasis on photocatalytic hydrogen production, are discussed in this paper. Social, environmental and economic aspects are taken into account while assessing selected production methods and types of photocatalysts. In the first part of this paper, various hydrogen production options are introduced and comparatively assessed. Then, solar‐based hydrogen production options are examined in a more detailed manner along with a comparative performance assessment. Next, photocatalytic hydrogen production options are introduced, photocatalysis mechanisms and principles are discussed and the main groups of photocatalysts, namely titanium oxide, cadmium sulfide, zinc oxide/sulfide and other metal oxide‐based photocatalyst groups, are introduced. After discussing recycling issues of photocatalysts, a comparative performance assessment is conducted based on hydrogen production processes (both per mass and surface area of photocatalysts), band gaps and quantum yields. The results show that among individual photocatalysts, on average, Au–CdS has the best performance when band gap, quantum yield and hydrogen production rates are considered. From this perspective, TiO₂–ZnO has the poorest performance. Among the photocatalyst groups, cadmium sulfides have the best average performance, while other metal oxides show the poorest rankings, on average. Copyright © 2016 John Wiley & Sons, Ltd.     

Visible light response photocatalytic water splitting over CdS-pillared zirconium–titanium phosphate (ZTP)

With an attempt to extend the light absorption towards the visible range and inhibit the rapid recombination of excited electrons/holes, a new type photocatalysts, cadmium sulfide intercalated zirconium–titanium phosphate (CdS–ZTP) was synthesized. The photocatalysts were characterized by small angle X-ray diffraction studies (SAXS), N₂ adsorption–desorption studies, diffused reflectance UV–vis (DRUV–vis) spectroscopic analysis, photoluminescence studies (PL), scanning electron microscopic/energy dispersive spectroscopic (SEM/EDS), X-ray photoelectron spectroscopic (XPS) studies etc. The samples exhibit a unique property of optical absorption in UV and visible regions with a wavelength, λ ≤ 450 nm followed by a clear long tail up to 700 nm. The pillared materials showed excellent activity for UV–visible light driven hydrogen production from photocatalytic splitting of water without using any co-catalyst. The photocatalytic activity of this cadmium sulfide pillared catalyst, as well as that of neat cadmium sulfide powder, was monitored for the visible light-induced evolution of hydrogen from water in the presence of hole scavenger, sulfide (S²⁻).     

Z-scheme MoO3-2D SnS nanosheets heterojunction assisted g-C3N4 composite for enhanced photocatalytic hydrogen evolutions

In this work, the 2D SnS/g-C₃N₄ nanosheets have been successfully prepared by a facile ultrasonic and microwave heating approach, which formed intimate interfacial contact and suitable energy band structure. The optimized sample displayed enhanced photocatalytic hydrogen evolution from water assisted with Pt co-catalyst, which is much higher than that of pure g-C₃N₄. After loaded with MoO₃ particles, the stability of photocatalysts displayed significate improvement due to the formed Z-scheme heterojunction. With the characterization, the enhanced hydrogen evolution reaction (HER) performance might be ascribed to the improved light-harvesting capability of the composite, lowered charge-transfer resistance, increased electrical conductivity and the co-catalyst effect of SnS. This study provides insights about SnS assisted HER photocatalysts and a new strategy to improve the stability of metal sulfides photocatalysts.     

Atomic interface engineering: Strawberry-like RuO2/C hybrids for efficient hydrogen evolution from ammonia borane and water

Efficient hydrogen production plays a key role in establishing hydrogen economy in the current world. In this study, we fabricated ultrafine RuO₂ nanoparticles on carbon black to form a strawberry-like RuO₂/C hybrid, using by a solid-phase grinding and subsequent low-temperature annealing. The synthesized hybrid displays very low reaction activation energy (28.5 KJ mol^?1) for hydrogen evolution from ammonia borane. In case of hydrogen evolution from alkaline water, it also exhibits a remarkably improved electrocatalytic activity than a commercial Pt/C, with an ultra-low overpotential of 8 mV (at 10 mA cm^?2). For the above bifunctional catalyst, the formed C–Ru–C bonds between the ruthenium oxide and carbon result in the ultrahigh activity of the hybrid, as evidenced by DFT results. This work offers a guideline to synthesize efficient metal-based (Ru, Pd, Rh, Ir, Au, etc.) catalysts with smart structures for catalysis.     

Structural, optical and photoelectrochemical properties of screen-printed and sintered (CdS)x(ZnS)1−x (0<x<1) films

Sulfides of zinc and cadmium have been used effectively in various optolectronic devices and recently as photocatalysts in the production of molecular hydrogen in photoelectrochemical processes. We have prepared sintered CdZnS films by the screen printing method without the presence of the typical flux material. The formation of crystalline ternary compounds is inferred from the X-ray diffraction pattern of these films. Their structural and optical properties are studied by reflection spectra in a wavelength range of 300–600 nm. The films have a direct band gap, which varies from 3.7 eV for zinc sulfide to 2.45 eV for cadmium sulfide. Films with a narrow range of composition were found to be stable in Na₂SO₃ solution under cathodic or anodic polarization in dark and illuminated conditions. This potential interval allowed to determine the flat band potentials from capacity measurements in the dark, which indicated strong contribution of double layer capacitance, surfaces states, and non-uniform doping concentration. Electrochemical impedance measurements where further performed, giving detailed information about the relevance of these factors and the optimum composition of coupled semiconductor films for photocatalytic purposes.     

In-situ growth of Zn–AgIn5S8 quantum dots on g-C3N4 towards 0D/2D heterostructured photocatalysts with enhanced hydrogen production

Photocatalytic water splitting for hydrogen production represents an ideal pathway for solar energy harvesting and conversion, for which narrow bandgap multinary sulfides play an important role. Here, series of Zn–AgIn₅S₈/g-C3N4 0D/2D nanocomposites were prepared by in-situ growth of the Zn–AgIn₅S₈ quantum dots (QDs) on g-C3N4 nanosheets for improved charge separation. To our surprise, rather than a photoactive component, here g-C3N4 nanosheets act as a charge transfer mediator, where only a relatively low ratio is required. The as-fabricated Zn–AgIn₅S₈/g-C3N4 nanocomposites were systematically studied. When the mass ratio of g-C3N4 was 10%, the hydrogen production rate was maximized, which was 1.39 times higher than pure Zn–AgIn₅S₈ QDs and 138.6 times higher than g-C3N4. The enhanced photocatalytic activity of the Zn–AgIn₅S₈/g-C3N4 nanocomposites is attributed to the intimate interface contact, which results in the effective separation and transfer of the photogenerated charge carriers as proved by the PL lifetime, transient photocurrent and electrochemical impedance spectra measurements. The Zn–AgIn₅S₈/g-C3N4 nanocomposites also exhibit excellent cycle stability. A plausible mechanism was proposed for the 0D/2D Zn–AgIn₅S₈/g-C3N4 composite photocatalysts. This work provides a relatively simple method for constructing high-quality 0D/2D heterostructure of QDs/nanosheets, as well as new insight for the efficiency improvement of narrow-bandgap sulfide photocatalysts.     

Application of a photostable silver-assisted Z-scheme NiTiO3 nanorod/g-C3N4 nanocomposite for efficient hydrogen generation

The performance and reaction mechanism of a silver (Ag)-assisted one-dimensional NiTiO₃ nanorod/CN heterostructure nanocomposite (NTACN) photocatalyst for hydrogen (H₂) production were explored with simulated sunlight. The physicochemical properties of the synthesized catalysts were examined using various spectrophotometers. The newly developed NTACN samples displayed an enhanced photocatalytic activity in producing hydrogen. Specifically, the H₂ production rate of NTACN-5 (with a NT-to-ACN weight ratio of 5) was 3351 μmol/g-h, which was 1.42 times higher than that of ACN-4 with a Ag-to-CN ratio of 4 (2325 μmol/g-h). The effects of the Ag-to-CN and NiTiO₃-to-ACN ratios on the photocatalytic activity of NTACN photocatalysts were determined. The NTACN photocatalysts exhibited a high long-term photostability under simulated sunlight irradiation. The increased photocatalyst performance and photostability were primarily ascribed to an improved charge separation efficiency due to a Z-scheme reaction mechanism as well as the assistance provided by Ag as a charge transfer shuttle and in the surface plasmon resonance effect. A photocatalytic mechanism for hydrogen generation over the NTACN photocatalysts under simulated sunlight irradiation is suggested.     

A green and facile synthesis of TiO2/graphene nanocomposites and their photocatalytic activity for hydrogen evolution

This work reports a green and facile approach to synthesize chemically bonded TiO₂/graphene sheets (GS) nanocomposites using a one-step hydrothermal method. The as-prepared composites were characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and ultraviolet visible (UV-Vis) diffuse reflectance spectra. The photocatalytic activity was evaluated by hydrogen evolution from water splitting under UV-Vis light illumination. An enhancement of photocatalytic hydrogen evolution was observed over the TiO₂/GS composite photocatalysts, as 1.6 times larger for TiO₂/2.0 wt%GS than that of Degussa P25. This fabrication process features the reduction of graphene oxide and formation of TiO₂ simultaneously leading to the well dispersion of generated TiO₂ nanoparticles on the surface of GS.     

Evidence for H2S gas as an intermediate species in the reaction mechanism of trapping hydrogen by cobalt disulfide

Cobalt sulfide prepared by aqueous precipitation using Na₂S and a Co(II) salt is known to trap hydrogen at room temperature and low pressure. The importance of oxidation of the primary CoS precipitate with atmospheric oxygen with respect to its efficiency as a hydrogen absorber is demonstrated. This stage of oxidation produces a mixture of two solid phases: a partially crystallized cobalt hydroxide Co(OH)₂ and an amorphous cobalt sulfide CoS₂ with a Co(OH)₂/CoS₂ molar ratio of 1 as predicted by thermodynamics. This biphasic product is probably the basic cobalt sulfide CoSOH considered in older and even more recent work. This product traps molecular hydrogen with a H₂/Co molar ratio of 0.5 whereas unoxidized CoS precipitate traps almost no hydrogen (H₂/Co = 0.025). Moderate acidic treatment of the absorber at room temperature leads to the selective dissolution of Co(OH)₂. The remaining cobalt sulfide has CoS₂ stoichiometry and reacts with hydrogen to form H₂S gas and CoS. We showed that H₂S released is reactive toward bases: CoS or Na₂S were formed when H₂S reacted with Co(OH)₂ or NaOH, respectively. This proves that the hydrogen trapping reaction mechanism implies H₂S as an intermediate species.     

Recent advances in non-metals-doped TiO2 nanostructured photocatalysts for visible-light driven hydrogen production,CO2 reduction and air purification

The generation of hydrogen and oxygen from the photocatalytic water splitting reaction under visible light is a promisingly renewable and clean source for H₂ fuel. The transition metal oxide semiconductors (e.g. TiO₂, WO_3, ZnO, and ZrO₂) are have been widely used as photocatalysts for the hydrogen generation. Because of safety, low cost, chemical inertness, photostability and other characteristics (bandgap, corrosion resistance, thermal and environmental stability), TiO₂ is considered as a most potential catalyst of the semiconductors being investigated and developed. However, the extensive applications of TiO₂ are hampered by its inability to exploit the solar energy of visible region. Other demerits are lesser absorbance under visible light, and recombination of photogenerated electron-hole pairs. In this review, we focus on the all the possible reactions taking place at the catalyst during photo-induced H₂ from water splitting reaction, which is green and promising technology. Various parameter affecting the photocatalytic water splitting reactions are also studied. Predominantly, this review is focussed on bandgap engineering of TiO₂ such as the upward shift of valence band and downward shift of conduction bands by doping process to extend its light absorption property into the visible region. Furthermore, the recent advances in this direction including various new strategies of synthesis, multiple doping, hetero-junction, functionalization, perspective and future opportunities of non-metals-doped TiO₂-based nanostructured photocatalysts for various photocatalytic applications such as efficient hydrogen production, air purification and CO₂ reduction to valuable chemicals have been discussed.     

Hydrogen production from water splitting under UV light irradiation over Ag-loaded mesoporous-assembled TiO2-ZrO2 mixed oxide nanocrystal photocatalysts

Hydrogen production from the photocatalytic water splitting reaction is very attractive because it is an environmentally friendly process, where hydrogen is produced from two abundantly renewable sources, i.e. water and solar energy, with the aid of photocatalysts. TiO₂ is the most widely investigated photocatalyst; however, it alone still exhibits low performance to photocatalytically produce hydrogen. Hence, the aim of this work focused on the enhanced photocatalytic hydrogen production over Ag-loaded mesoporous-assembled TiO₂-ZrO₂ mixed oxide nanocrystal photocatalysts under UV light irradiation. The TiO₂-ZrO₂ mixed oxides with various TiO₂-to-ZrO₂ molar ratios were synthesized by a sol-gel process with the aid of a structure-directing surfactant, followed by Ag loading via a photochemical deposition method. The influences of photocatalyst preparation parameters, i.e. calcination temperature, phase composition, and Ag loading, were studied. The results revealed that the mesoporous-assembled TiO₂-ZrO₂ mixed oxide nanocrystal photocatalyst with a TiO₂-to-ZrO₂ molar ratio of 93:7 calcined at 500 °C exhibited the highest photocatalytic hydrogen production activity, and the Ag loading of 0.5 wt.% further greatly enhanced the photocatalytic activity of such TiO₂-ZrO₂ mixed oxide photocatalyst.     

Strong anion exchange for improved NiCo2S4 oxygen reduction reaction via interlayer spacing manipulation

Transition metal sulfides as high-performance, cost-effective, and stable electrocatalysts for oxygen reduction reaction (ORR) have attracted much attention. The replacement of sulfur atom by oxygen atom in metal sulfides was considered to be the fundamental reason for its decreased activity. Adequate anion exchange can greatly reduce the generation of oxygen species in transition metal sulfide, which further enhances the intrinsic electrical conductivity and stability of transition metal sulfides. Herein, a novel and simple approach to larger interlayer spacing was provided by introducing interlayer water in layered hydroxides precursor. The NCS-O₁ with treated layered hydroxides precursor exhibits few oxygen impurities and excellent activity for the ORR in alkaline electrolyte, presenting the close limiting diffusion current density and lower Tafel slope (reaches 56 mV dec^?1, vs. Pt/C 70) in comparison to 20% commercial Pt/C. Hence, our results provide an interesting design path for such catalysts.     

Green synthesis of well dispersed TiO2/Pt nanoparticles photocatalysts and enhanced photocatalytic activity towards hydrogen production

Deposition of Pt NPs with preferred dispersion and morphologies on TiO₂ have been the focus of studies in photocatalytic and photoelectrochemical hydrogen production. Green synthesis of TiO₂/Pt NPs nanocomposites with narrow size distribution of Pt NPs still remain a challenge. Herein, we report that sucrose is highly efficient for the preparation of well-dispersed TiO₂/Pt NPs photocatalysts. Moreover, the sucrose could act as an electron donor, showing higher hydrogen production activity under simulated sunlight than pure water. The as-synthesized photocatalysts have been characterized by techniques of transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDX), and diffuse reflectance spectroscopy (DRS). Compared with TiO₂/Pt NPs photocatalysts prepared through conventional photodeposition, the photocatalysts as prepared showed higher photocatalytic efficiency. Moreover, the catalyst could be reused easily without apparent degradation of their original photocatalytic activities. This approach presents a promising and low-cost strategy to improve the photocatalytic performance of TiO₂ from biomass.     

Electrocatalyst of RuO2 decorating TiO2 nanowire arrays for acidic oxygen evolution

Oxygen evolution reaction (OER) at the anode limits the efficiency of hydrogen production from water electrolysis substantially. A novel electrocatalyst of RuO₂ decorating TiO₂ nanowire arrays for OER was successfully prepared using a cyclic voltammetric method with electrodeposition of RuO₂ nanoparticles on the TiO₂ nanowire (TNW) arrays synthesized hydrothermally. Even though the electrodes with the composite electrocatalyst have a lower loading of RuO₂, they have higher electrocatalytic activity and stability for acidic oxygen evolution than the Ti/RuO₂ electrode prepared by conventional thermal decomposition method. The core-shell structure of the TNW@RuO₂ electrocatalyst not only increases the specific surface area of the electrodes, but also inhibits the adverse effect of the poor conductivity of TiO₂. This novel OER electrocatalyst can improve the efficiency and reduce the cost of hydrogen production from electrolytic water splitting.