One-pot synthesis of non-noble metal WS2/g-C3N4 photocatalysts with enhanced photocatalytic hydrogen production

As an increasing number of photocatalysis are developed, non-noble metal photocatalysts that can be synthesized from earth-abundant and low-cost materials have received a great deal of attention. In this study, non-noble metal WS₂/g-C₃N₄ photocatalysts were prepared by a facile one-pot synthesis. Varying masses of tungsten disulfide (WS₂) were successfully loaded onto g-C₃N₄ and characterized by X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). These results indicated that the WS₂ was successfully synthesized and immobilized closely on the surface of g-C₃N₄ to form a sheet-like nanostructure. The H₂ generation results showed that the optimal photocatalyst was 0.3-WCN because it had the highest photocatalytic H₂ production of 154 μmol h⁻¹g⁻¹, which is 34 times higher than bare g-C₃N₄ and even higher than 0.3 wt% platinum-loaded g-C₃N₄. Additionally, the possible mechanism of the photocatalyst was studied by photoluminescence (PL), UV–vis diffuse reflectance spectroscopy (UV–vis DRS) and photoelectrochemical tests, which showed that the WS₂ played a key role in improving the efficiency of separation and migration of the photogenerated carriers in g-C₃N₄.     

Metal chalcogenide based photocatalysts decorated with heteroatom doped reduced graphene oxide for photocatalytic and photoelectrochemical hydrogen production

Heteroatom (N, B and P) doped reduced graphene oxide (RGO)-metal chalcogenide nanocomposites (RGO-Cd_0.60Zn_0.40S) were prepared by the solvothermal method, and then they were characterized with X-ray diffraction, Raman spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, UV–Vis diffuse reflectance spectroscopy and photoluminescence techniques. Doping of RGO with heteroatoms of N, B and P increased charge-transfer capability of nanocomposites and thus, improved both photocatalytic and photoelectrochemical hydrogen production activities of them. N-doped RGO-Cd_0.60Zn_0.40S photocatalyst exhibited the highest photocatalytic hydrogen production rate (1114 μmolh⁻¹ g⁻¹) in photocatalytic (PC) system amongst other and it was 1.5 times higher than that of RGO-Cd_0.60Zn_0.40S photocatalyst. Having a current density of 0.92 mAcm⁻², photoelectrochemical hydrogen production activity of N-RGO-Cd_0.60Zn_0.40S electrode was found to be 3 times higher than RGO-Cd_0.60Zn_0.40S photoelectrode without any applied bias potential under visible light irradiation in photoelectrochemical system. In general, these results clearly showed that heteroatom doping of RGO led to promising materials for renewable hydrogen production in the photocatalytic and photoelectrochemical systems.     

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.     

Novel Janus 2D structures of XMoY (X,Y = O,S, Se,Te) composition for solar hydrogen production

The successful fabrication of H-phase Janus transition metal dichalcogenides (TMDs) has received considerable interest due to its great potential in photocatalytic applications. Here, new A′-XMoY (X/Y = O, S, Se, Te) Janus-type structures belonging to the family of TMDs were theoretically investigated for the first time in terms of photocatalytic water splitting via DFT calculations. For all compounds, the Raman spectra were calculated. The SMoO, SeMoO, SMoSe, SMoTe and SeMoTe compounds are dynamically stable and are semiconductors. Among all considered structures SMoTe is the most promising candidate for solar hydrogen production because valence and conduction bands perfectly engulf the redox potentials of water at both neutral and acidic media, opposite to SMoSe, SMoO, SeMoO suitable only in the acidic media, and SeMoTe – in the neutral media. Moreover, A′-SMoTe demonstrates the outstanding values of the solar-to-hydrogen (STH) conversion efficiencies of 54.0 and 67.1 for neutral and acidic media.     

Hollow heterostructure CoS/CdS photocatalysts with enhanced charge transfer for photocatalytic hydrogen production from seawater

In recent years, there have been many studies on photocatalytic water splitting, but there are still few high-efficiency photocatalysts for photocatalytic seawater splitting. In this study, a series of hollow Co sulphide-supported CdS catalyst (H–CoS/CdS) composite photocatalysts were prepared by loading CdS onto the surface of H–CoS, which can be used for efficient H₂ production in pure water and simulated seawater. The heterojunction H–CoS/CdS exhibited H₂ production of 572.4 μmol g^?1 (4 h) from simulated seawater, which is 97.7 and 2.96 times those of H–CoS and CdS, respectively. The h-CoS cocatalyst extended the light absorption range of CdS, improved the chemical stability, and significantly enhances the charge separation efficiency. This study provides guidance for the reasonable design of a photocatalytic seawater-based H₂ production catalyst with high efficiency and low cost.     

1T-phase MoS2/holey ultrathin g-C3N4 nanosheets based 2D/2D heterostructure for enhanced photocatalytic hydrogen production

Although graphitic carbon nitride (g-C₃N₄) is widely used for photocatalytic hydrogen production, its practical application is restricted by the high recombination rate of photoinduced electron-hole pairs and limited active sites. In this work, holey ultrathin g-C₃N₄ nanosheets (HCN NSs) with rich active sites are prepared, followed by the growth of 1T-MoS₂ NSs on their surfaces to construct 2D/2D 1T-MoS₂/HCN heterostructure. Due to the high surface area and abundant hydrogen active sites of the hybrid, large and intimate 2D nanointerface between MoS₂ and HCN, hydrogen ion adsorption and charge separation/transport ability are greatly enhanced. As a result, 1T-MoS₂/HCN-4 with the optimal 1T-MoS₂ content of 8 wt% displays the highest H₂ production rate of 2724.2 μmol^?1 h^?1 g^?1 under simulated solar light illumination with apparent quantum efficiency of 8.1% (λ = 370 nm). Moreover, the 1T-MoS₂/HCN-4 hybrid manifests improved stability after a long-time test. This study opens the door to design highly-efficient g-C₃N₄ based 2D/2D heterostructures for photocatalytic H₂ production.     

In-situ synthesis of Pd nanocrystals with exposed surface-active facets on g-C3N4 for photocatalytic hydrogen generation

Engineering surface-active facets of metal cocatalysts is one of the most widely explored strategies to develop advanced photocatalysts and promote photocatalytic solar energy conversion. Here, the surface-active facets of Pd nanocrystals in Pd/g-C₃N₄ photocatalyst was related to the injection flow rate of PdCl₂. When PdCl₂ was injected at a low flow rate of 7.5 mL/h (7.5-Pd/g-C₃N₄), the Pd nanocrystals were uniformly dispersed onto the g-C₃N₄ with exposed low-index {100} and {111} surface-active facets. However, increasing the injection flow rate to 150 mL/h (150-Pd/g-C₃N₄) formed Pd nanocrystals where only the {100} surface-active facet was exposed. Under visible light irradiation, the 7.5-Pd/g-C₃N₄ nanocomposite exhibited excellent water splitting activity for hydrogen production (7.61 mmol g⁻¹ h⁻¹), which was significantly better than with the 150-Pd/g-C₃N₄ nanocomposite (3.3 mmol g⁻¹ h⁻¹). Theoretical calculations and experimental results confirm the importance of the {111} surface-active facets in the 7.5-Pd/g-C₃N₄ nanocomposite for promoting photocatalytic activity.     

Enhanced photocatalytic hydrogen production from aqueous methanol solution using ZnO with simultaneous photodeposition of Cu

The enhanced photocatalytic hydrogen production from aqueous methanol solution using ZnO was investigated with aid of simultaneous metal deposition. The simultaneous deposition for such metals as Ag, Au, Cu, Ni, Pd, Pt, and Rh was evaluated for the H₂ production from aqueous methanol solution. As a result, the addition of Cu ion was effective improvement in photocatalytic hydrogen evolution. The photocatalytic hydrogen production using ZnO photocatalyst with aid of simultaneous deposition of Cu was approximately 130 times better than those obtained with bare ZnO. The Cu-deposited ZnO had the response to the visible light for the hydrogen formation. After the photocatalytic hydrogen production, the in-situ Cu-photodeposited ZnO sample was characterized by X-ray diffraction (XRD), UV–visible diffuse reflectance spectrometry (UV-DRS), and photoluminescence (PL) spectroscopy.     

Efficient solar hydrogen production by photocatalytic water splitting: From fundamental study to pilot demonstration

Photocatalytic water splitting with solar light is one of the most promising technologies for solar hydrogen production. From a systematic point of view, whether it is photocatalyst and reaction system development or the reactor-related design, the essentials could be summarized as: photon transfer limitations and mass transfer limitations (in the case of liquid phase reactions). Optimization of these two issues are therefore given special attention throughout our study. In this review, the state of the art for the research of photocatalytic hydrogen production, both outcomes and challenges in this field, were briefly reviewed. Research progress of our lab, from fundamental study of photocatalyst preparation to reactor configuration and pilot level demonstration, were introduced, showing the complete process of our effort for this technology to be economic viable in the near future. Our systematic and continuous study in this field lead to the development of a Compound Parabolic Concentrator (CPC) based photocatalytic hydrogen production solar rector for the first time. We have demonstrated the feasibility for efficient photocatalytic hydrogen production under direct solar light. The exiting challenges and difficulties for this technology to proceed from successful laboratory photocatalysis set-up up to an industrially relevant scale are also proposed. These issues have been the object of our research and would also be the direction of our study in future.     

Facial synthesis of dandelion-like g-C3N4/Ag with high performance of photocatalytic hydrogen production

Nowadays, energy shortage is one of the major problems in the world. Photocatalytic hydrogen production is a new type of energy technology with good application prospect. As a new type of photocatalytic semiconductor material, g-C₃N₄ has attracted much attention as a photocatalyst. By ultrasonic treatment of a mixed solution of g-C₃N₄ and bovine serum albumin, followed by adding a certain amount of silver nitrate solution and then directly hydrothermal treatment, a special dandelion-like g-C₃N₄/Ag (D-g-C₃N₄/Ag) was prepared. The scanning electronic microscopy, transmission electronic microscopy, X-ray diffraction, Fourier transform infrared, fluorescence and physicochemical adsorption methods were used to characterize the morphology and structure of D-g-C₃N₄/Ag. In addition, the photocatalytic H₂ production of D-g-C₃N₄/Ag with different Ag loadings or in different sacrificial agents and different pH conditions were investigated. The results indicated that when triethanolamine was used as sacrificial agent, photocatalytic hydrogen efficiency was the best, and the rate of photocatalytic hydrogen production reached 862 μmol g⁻¹ h^{− 1} as the Ag loading was 4%.     

g-C3N4/CoAl-LDH 2D/2D hybrid heterojunction for boosting photocatalytic hydrogen evolution

In this work, a 2D/2D heterojunction composed of CoAl layered double hydroxide (LDH) and graphitic carbon nitride nanosheets (CNNS) was designed and fabricated for boosting photocatalytic hydrogen generation. The as-prepared 20 mol% CoAl-LDH/CNNS exhibited a remarkable photocatalytic hydrogen evolution rate of 680.13 μmol h⁻¹ g⁻¹, which was 21 times higher than that of pure CoAl-LDH (32.91 μmol h⁻¹ g⁻¹). The enhanced activity could be mainly attributed to its unique structure and high surface area. Distinct from ordinary heterojunction photocatalysts, two-dimensional (2D) heterojunctions with abundant 2D coupling interfaces and strong interfacial interaction could efficiently suppress the recombination of photo-induced charge carriers and shorten charge transmission distance. Particularly, compared with other concentrations, the increased surface area (138.70 m² g⁻¹) of 20 mol% CoAl-LDH/CNNS, which is 3.94 times of pure CNNS (35.48 m² g⁻¹), is more favorable for enhanced photocatalytic activity. Increasing the surface area of sheet-on-sheet heterostructure is an effective and novel strategy to facilitate the photocatalytic hydrogen evolution from water splitting.     

Kinetic performance of TiO2/Pt/reduced graphene oxide composites in the photocatalytic hydrogen production

Among the different alternatives to generate hydrogen, photocatalysis can play an important role since it is based on the use of solar radiation and a suitable semiconductor. Starting from the most commonly researched TiO₂ catalyst, many efforts have been devoted to improve its efficacy. This work, based on the potential of reduced graphene oxide (rGO) to carry charges and platinum nanoparticles to act as efficient traps for photogenerated electrons, assesses the performance of synthesized binary and ternary photocatalysts (TiO₂/rGO, TiO₂/Pt and TiO₂/rGO/Pt) for hydrogen generation. The addition of rGO to TiO₂ almost duplicates (1.95 factor) the hydrogen production rate compared to bare TiO₂. Moreover, the binary TiO₂/Pt photocatalyst reported the best performance, with an increase in the hydrogen production rate by a factor of 15.26 compared to TiO₂. However, the ternary catalyst performed worse than the binary TiO₂/Pt probably due to the use of non-optimized co-catalyst ratios. Since the addition of rGO reduces the cost of the catalyst, the trade-off between the catalyst performance and cost is worth of future research.     

Facile strategy to fabricate Ni2P/g-C3N4 heterojunction with excellent photocatalytic hydrogen evolution activity

Transition metal phosphides are considered as the most prospective replacements for noble metal cocatalysts used for H₂ evolution during photocatalytic water splitting. In this work, Ni₂P/g-C₃N₄ composite photocatalyst was synthesized using a simple in-situ hydrothermal method by one step. Benefiting from the excellent light trapping, efficient transfer of charge carriers and strong stability of Ni₂P nanoparticles, as well as the stable interface contact between Ni₂P and g-C₃N₄, the Ni₂P/g-C₃N₄ exhibit greatly enhanced H₂ evolution performance during photocatalytic water splitting. The optimized H₂ evolution rate can reach 3344 μmol h^?1 g^?1 over 17.5 wt% Ni₂P/g-C₃N₄, which is 68.2 times greater than that of pure g-C₃N₄ and even much greater than that of 15 wt% Pt/g-C₃N₄. The apparent quantum efficiency (QE) is about 9.1% under 420 nm monochromatic. The enhancement mechanism was demonstrated in detail by transient photocurrent responses, photoluminescence spectra and electrochemical impedance spectroscopy. This work develops a facile strategy to fabricate transition metal phosphide/semiconductor heterojunction systems with potential application for photocatalytic H₂ evolution.     

The 2D RGO-NiS2 dual co-catalyst synergistic modified g-C3N4 aerogel towards enhanced photocatalytic hydrogen production

The two-dimension RGO (reduced graphene oxide)-NiS₂ dual co-catalyst synergistic modified g-C₃N₄ nanosheets aerogel is synthesized via the continuous thermal oxidation etching-hydrothermal method-freeze drying process. The results of scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) imply that the RGO-NiS₂ dual co-catalyst is introduced into the aerogel system successfully. The photocatalytic activity of the RGO-NiS₂ synergistic modified g-C₃N₄ aerogel remarkably exhibits an enhancement of 67 times than that of simplicial g-C₃N₄. Further, the photocatalytic process and the mechanism of the photocatalytic hydrogen production enhancement are studied, which is ascribed to RGO-NiS₂ dual co-catalyst synergistic modification, including the Pt-like behavior of the NiS₂ and the high conductivity and large specific surface area of the RGO.     

Sol-gel synthesis of Er3+:Y3Al5O12/TiO2Ta2O5/MoO2 composite membrane for visible-light driving photocatalytic hydrogen generation

By using TiO₂ and Ta₂O₅ colloids, a stable and efficient visible-light driven photocatalyst, Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane, was successfully prepared via sol–gel dip coating method at room temperature. The XRD, FTIR, SEM, TEM and EDX results confirm that approximately spherical Er³⁺:Y₃Al₅O₁₂ nanoparticles were embedded in TiO₂Ta₂O₅ matrix. UV–vis absorption and PL spectra of Er³⁺:Y₃Al₅O₁₂ were also determined to confirm the visible absorption and ultraviolet emission. The photocatalytic hydrogen generation was carried out by using methanol as sacrificial reagent in aqueous solution under visible-light irradiation. Furthermore, some main influence factors such as heat-treated temperature, heat-treated time and molar ratio of TiO₂ and Ta₂O₅ on visible-light photocatalytic hydrogen generation activity of Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane were studied in detail. The experimental results showed that the photocatalytic hydrogen generation activity of Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ composite membrane heat-treated at 550 °C for 3.0 h was highest when the molar ratio of TiO₂ and Ta₂O₅ was adopted as 1.00:0.50. And that a high level photocatalytic activity can be still maintained after four cycles. In addition, a possible mechanism for the visible-light photocatalytic hydrogen generation of the Er³⁺:Y₃Al₅O₁₂/TiO₂Ta₂O₅/MoO₂ membrane was proposed based on PL spectra.     

An efficient photocatalytic system containing Eosin Y, 3D mesoporous graphene assembly and CuO for visible-light-driven H2 evolution from water

In the present work, 3D mesoporous graphene assembly was fabricated in a hydrothermal process using triethylenetetramine molecules as cross-linkers. And CuO nanoparticles were introduced in the graphene assembly via in-situ photodeposition. Then, a photocatalytic system containing Eosin Y as a sensitizer, graphene assembly as a supporter material and electron transfer channel, and CuO nanoparticles as an active center of H₂ evolution from water was prepared. Meanwhile, photocatalytic hydrogen evolution from water over the as-prepared photocatalytic system was explored under visible irradiation. Furthermore, for practical purposes, the durability of the photocatalytic system was also studied. And the photocatalytic mechanism was preliminarily discussed. The experimental results indicate that the as-prepared photocatalytic system is an efficient photocatalyst for visible-light-driven H₂ evolution from water. The rate of H₂ evolution over the photocatalytic system is up to 5.85 mmol g^?1 h^?1 under optimal conditions, which is 2.3 times higher than that over reduced graphene oxide loaded with CuO. The 3D porous graphene assembly plays an important role in the photocatalytic process. It can not only efficiently enhance the electron transfer in the photocatalytic system, but also result in fast diffusion of sacrificial reagent and timely release of H₂ bubbles. This work provides us with new possibility for designing an efficient Pt-free visible photocatalyst for H₂ evolution from water.     

Effect of mechanochemical preparation of 2D g-C3N4 on electronic properties and efficiency of photocatalytic hydrogen evolution

A comparative study of morphology, spectral and photocatalytic properties of graphene-like C₃N₄ samples prepared by liquid-phase exfoliation of the bulk (l-C₃N₄) and mechanochemically delaminated g-C₃N₄ (m-C₃N₄) was performed for the first time. It was established that the particles of the mechanochemically prepared m-C₃N₄ are predominantly monolayer whereas the particles of l-C₃N₄ possess few-layer morphology. It was shown that m-C₃N₄ exhibits higher photocatalytic activity in the photocatalytic hydrogen evolution from aqueous solution of lactic acid under AM1.5G irradiation due to monolayer morphology, higher reduction potential, as well as more efficient separation and transfer of the photogenerated charges.     

CoCO3 hierarchical structure embedded on g-C3N4 nanosheets to assemble 3D/2D Z-scheme heterojunction towards efficiently and stably photocatalytic hydrogen production

Structure and interface control of heterojunction is usually a challenging issue to improve the photocatalytic performance. Herein, a new 3D/2D CoCO₃/g-C₃N₄ heterojunction is assembled by embedding hexahedral CoCO₃ on g-C₃N₄ nanosheets. The unique step-like hierarchical structure of CoCO₃, the formed built-in electric field and Z-scheme charge transfer behavior at the interface jointly drive the high-efficient separation of photogenerated carriers to boost the photocatalytic H₂ production. It achieves the optimal H₂ production rate that is almost 2.6 times than g-C₃N₄, apparent quantum efficiency (AQE) of 10.1% at 400 nm and continuous running of 60 h over the 3D/2D CoCO₃/g-C₃N₄ heterojunction. This work endows a fresh structural control strategy for the fabrication of 3D/2D Z-scheme heterojunction to improve the photocatalytic H₂ production performance.     

Photocatalytic hydrogen production with CuS/ZnO from aqueous Na2S + Na2SO3 solution

The photocatalytic hydrogen production in the sacrificial S²⁻–SO₃²⁻ anions was investigated with ZnO in the addition of metal sulfides containing Ag₂S, CuS, Fe₂S₃, and NiS. In the absence of metal sulfides, the photocatalytic H₂ evolution using ZnO was observed with 255 μmol g⁻¹. The CuS amount and the concentrations of S²⁻ and SO₃²⁻ ions were optimized. It was found that ternary component semiconductor CuS/ZnS/ZnO was formed during the photocatalytic hydrogen production in the aqueous Na₂S + Na₂SO₃ solution. The photocatalytic hydrogen evolution with CuS/ZnS/ZnO in the 0.4 M Na₂S–0.4 M Na₂SO₃ solution was more than about 8.5 times better compared with those obtained with only ZnO. The CuS clusters on the surface of ZnS/ZnO seem to play an important role on the separation for electron–hole pair and the enhancement of H₂ production. Nano-sized ZnS/ZnO photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.     

Phosphorus-doped Fe3O4 nanoflowers grown on 3D porous graphene for robust pH-Universal hydrogen evolution reaction

It is extremely necessary to develop highly efficient and low-cost non-noble metal electrocatalysts for hydrogen evolution reaction (HER) under a pH-universal condition in the realm of sustainable energy. Herein, we have successfully prepared phosphorus doped Fe₃O₄ nanoflowers on three-dimensional porous graphene (denoted as P–Fe₃O₄@3DG) via a simple hydrothermal and low-temperature phosphating reaction. The P–Fe₃O₄@3DG hybrid composite not only demonstrates superior performance for HER in 1.0 M KOH with low overpotential (123 mV at 10 mA/cm²), small Tafel slope (65 mV/dec), and outstanding durability exceeding 50 h, but also exhibits satisfying performances under neutral and acidic medium as well. The 3D graphene foam with large porosity, high conductivity, and robust skeleton conduces to more active sites, and faster electron and ion transportation. The phosphorus dopant provides low Gibbs free energy and ability of binging H⁺. The synergistic effect of 3DG substrate and P–Fe₃O₄ active material both accelerates the catalytic activity of Fe-based hybrid composite for HER.