Highly efficient Bi2O3/MoS2 p-n heterojunction photocatalyst for H2 evolution from water splitting

The design of p-n heterojunction photocatalysts to overcome the drawbacks of low photocatalytic activity that results from the recombination of charge carriers and narrow photo-response range is promising technique for future energy. Here, we demonstrate the facile hydrothermal synthesis for the preparation of Bi₂O₃/MoS₂ p-n heterojunction photocatalysts with tunable loading amount of Bi₂O₃ (0–15 wt%). The structure, surface morphology, composition and optical properties of heterostructures were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–visible absorption spectroscopy, Brunauer-Emmett-Teller (BET) surface area, photoluminescence (PL), electrochemical impedance spectroscopy (EIS). Compare to pure Bi₂O₃ and MoS_2, the Bi₂O₃/MoS₂ heterostructures displayed significantly superior performance for photocatalytic hydrogen (H₂) production using visible photo-irradiation. The maximum performance for hydrogen evolution was achieved over Bi₂O₃/MoS₂ photocatalyst (10 μmol h⁻¹g⁻¹) with Bi₂O₃ content of 11 wt%, which was approximately ten times higher than pure Bi₂O₃ (1.1 μmol h⁻¹g⁻¹) and MoS₂ (1.2 μmol h⁻¹g⁻¹) photocatalyst. The superior performance was attributed to the robust light harvesting ability, enhanced charge carrier separation via gradual charge transferred pathway. Moreover, the increased efficiency of Bi₂O₃/MoS₂ heterostructure photocatalyst is discussed through proposed mechanism based on observed performance, band gap and band position calculations, PL and EIS data.     

Highly efficient white-LED-light-driven photocatalytic hydrogen production using highly crystalline ZnFe2O4/MoS2 nanocomposites

Designing efficient photocatalytic systems for hydrogen evolution is extremely important from the viewpoint of the energy crisis. Highly crystalline heterostructure catalysts have been established, considering their interface electric field effect and structural features, which can help improve their photocatalytic hydrogen-production activity. In this study, we fabricated a highly crystalline heterojunction consisting of ZnFe₂O₄ nanobricks anchored onto 2D molybdenum disulfide (MoS₂) nanosheets (i.e., ZnFe₂O₄/MoS₂) via a hydrothermal approach. The optimized ZnFe₂O₄/MoS₂ photocatalyst, with a ZnFe₂O₄ content of 7.5 wt%, exhibited a high hydrogen-production rate of 142.1 μmol h⁻¹ g⁻¹, which was 10.3 times greater than that for the pristine ZnFe₂O₄ under identical conditions. The photoelectrochemical results revealed that the ZnFe₂O₄/MoS₂ heterojunction considerably diminished the recombination of electrons and holes and promoted efficient charge transfer. Subsequently, the plausible Z-scheme mechanism for photocatalytic hydrogen production under white-LED light irradiation was discussed. Additionally, the influence of cocatalysts on the photocatalytic hydrogen evolution for the ZnFe₂O₄/MoS₂ heterostructure was investigated. This work has demonstrated a simplified coupling of one-dimensional or zero-dimensional structures with 2D nanosheets for improving the photocatalytic hydrogen production activity as well as confirmed that MoS₂ is a viable substitute for precious metal-free photocatalysis.     

MoS2/Ti3C2 heterostructure for efficient visible-light photocatalytic hydrogen generation

The MoS₂/Ti₃C₂ catalyst with a unique sphere/sheet structure were prepared by hydrothermal method. The MoS₂/Ti₃C₂ heterostructure loading 30% Ti₃C₂ has a maximum hydrogen production rate of 6144.7  μmol g⁻¹ h⁻¹, which are 2.3 times higher than those of the pure MoS₂. The heterostructure maintains a high catalytic activity within 4 cycles. The heterostructure not only effectively reduce the recombination of photogenerated electrons and holes, but also provide more activation sites, which promotes the photocatalytic hydrogen evolution reaction (HER). These works can provide reference for the development of efficient catalysts in photocatalytic hydrogen evolution.     

Preparation of direct Z-scheme Bi2WO6/TiO2 heterojunction by one-step solvothermal method and enhancement mechanism of photocatalytic H2 production

Direct Z-scheme Bi₂WO₆/TiO₂ heterojunction photocatalyst was prepared by one-step solvothermal method. The catalyst was characterized by XRD, TEM, XPS, UV–Vis DRS, photoluminescence spectroscopy and photoelectrochemical studies. The photocatalytic hydrogen production experiments show that Bi₂WO₆ did not generate H₂ and the H₂-production rate of TiO₂ is only 0.1 mmol⋅g⁻¹h⁻¹. The hydrogen production rate of the Bi₂WO₆/TiO₂ heterojunction photocatalyst reaches 12.9 mmol⋅g⁻¹h⁻¹, which is 129 times that of TiO₂. Compared with TiO₂, the enhanced H₂-production activity of the heterojunction catalyst can be attributed to the wider light absorption range and the efficient separation and migration of carriers at the close contact interface between Bi₂WO₆ and TiO₂. Based on the work functions of Bi₂WO₆, TiO₂ and their heterojunctions, combined with the results of electron paramagnetic resonance spectroscopy and Mott-Schottky measurements, the photocatalytic H₂ production mechanism of Z-scheme heterojunction Bi₂WO₆/TiO₂ was proposed. This work provides an easy and simple way to design a binary Z-scheme photocatalyst with efficient catalytic H₂-production activity without electron mediators.     

Boosted photogenerated carriers separation in Z-scheme Cu3P/ZnIn2S4 heterojunction photocatalyst for highly efficient H2 evolution under visible light

Developing low-cost, highly efficient and robust photocatalystic hydrogen evolution system is a promising solution to environmental and energy crisis. Herein, a Z-scheme Cu₃P/ZnIn₂S₄ heterojunction photocatalyst was successfully constructed for the first time via a facile solution-phase hybridization method. The optimized Cu₃P/ZIS composite exhibited the highest H₂ production rate of 2561.1 μmol g⁻¹ h⁻¹ under visible light irradiation (>420 nm), which was 5.2 times greater than that of bare ZnIn₂S₄ and even exceeded the photocatalytic performance of Pt/ZIS composite. The apparent quantum yield of 10 wt% Cu₃P/ZnIn₂S₄ can reach 22.3% at 420 nm. The huge boost of photocatalytic hydrogen evolution activity is ascribed to the formation of heterojunction with the built in electric field within Cu₃P/ZnIn₂S₄ and Z-scheme charge carriers transfer pathway, which result in efficient separation and migration of charge carriers. In addition, both experimental and theoretical calculation confirmed that the charge-carriers transfer pathway of Cu₃P/ZnIn₂S₄ photocatalyst follows the Z-scheme mechanism instead of conventional type-Ⅱ heterojunction mechanism. This work is considered helpful for getting a great deal of insight into constructing high-activity and cost-effective transition metal phosphides (TMPs) based photcatalytic hydrogen production system and rationally designing Z-scheme heterojunction photocatalyst.     

Facile approach for Z-scheme type Pt/g-C3N4/SrTiO3 heterojunction semiconductor synthesis via low-temperature process for simultaneous dyes degradation and hydrogen production

The platinum/graphite-like carbon nitride/strontium titanate (Pt/g-C₃N₄/SrTiO₃) heterojunction semiconductor was synthesized using a facile approach for simultaneous photocatalytic dye degradation and hydrolysis of hydrogen production from simulated dyeing wastewater. Using SrTiO₃, trace Pt, and the addition of an appropriate amount of electron donors, it can effectively absorb sunlight and achieve 93% dye degradation and 471 μmol h⁻¹ g⁻¹ hydrogen yield. The analysis result indicates that the semiconductor is a Z-scheme type composite. It was also showed that the addition of electron donors effectively promoted the degradation rate, whereas the addition of Pt changed the photocatalytic reaction pathway, which resulted in a reduced degradation rate and a significant improvement of hydrogen evolution. A reaction mechanism for this phenomenon is also proposed.     

An efficient ternary Mn0.2Cd0.8S/MoS2/Co3O4 heterojunction for visible-light-driven photocatalytic H2 evolution

An efficient ternary Mn_0.2Cd_0.8S/MoS₂/Co₃O₄ heterojunction was prepared and displayed excellent photocatalytic performance. The ternary Mn_0.2Cd_0.8S/MoS₂/Co₃O₄ heterojunction with 0.62 wt% of MoS₂ and 1.51 wt% of Co₃O₄ achieved the highest H₂ evolution activity (16.45 mmol g⁻¹ h⁻¹), which was well above Mn_0.2Cd_0.8S (2.72 mmol g⁻¹ h⁻¹). The improved H₂ evolution activity was ascribed to the synergistic effect of the Mn_0.2Cd_0.8S/Co₃O₄ p–n heterojunction and the modification of MoS₂ as a co-catalyst. This work can offer a new perspective for the application of Mn_xCd_1−xS-based ternary heterojunction towards solar energy conversion.     

Synthesis and photocatalytic performance of MoS2/Polycrystalline black phosphorus heterojunction composite

As a promising catalyst for solar hydrogen production, black phosphorus (BP) has received widespread attention due to variable band gaps, high carrier mobility, and strong light absorption performance. Herein, we use MoS₂ as a cocatalyst to synthesize BP/MoS₂ catalyst with polycrystalline BP to improve photocatalytic performance under visible light irradiation. A small amount of MoS₂ can reduce the recombination of electron-hole pairs in the composite, increase carrier transport efficiency, and then improve photocatalytic performance. As expected, the 10/0.5 ratio of BP/MoS₂ catalyst exhibits the highest photocatalytic hydrogen evolution performance with a hydrogen evolution rate of 575.4 μmol h^?1 g^?1, which is 2.5 times of pure BP. Based on the results above, a simple method is provided to synthesize low-cost black phosphorus-based photocatalysts.     

ZnIn2S4 nanosheets decorating WO3 nanorods core-shell hybrids for boosting visible-light photocatalysis hydrogen generation

We here report the fabrication of a core-shell WO₃@ZnIn₂S₄ heterostructure by an interfacial seeding growth strategy, which is implemented by direct growth of ZnIn₂S₄ nanosheets on the surface of WO₃ nanorods with forming a strong electronic interaction between two semiconductors that are beneficial for promoting the interfacial charge transfer. Systematic studies demonstrate that the WO₃@ZnIn₂S₄ nanohybrids hold superior performance for photocatalytic hydrogen generation under visible light irradiation with a production rate of 3900 μmol g⁻¹ h⁻¹. This work provides an effective approach to construct the direct Z-scheme photocatalytic systems for efficient photocatalytic hydrogen evolution, which would be significant for the design of more direct Z-scheme system for various photocatalytic applications.     

Photocatalytic hydrogen evolution assisted by aqueous (waste)biomass under simulated solar light: Oxidized g-C3N4 vs. P25 titanium dioxide

Oxidized graphitic carbon nitride (o-g-C₃N₄) and Evonik AEROXIDE^® P25 TiO₂ were compared for lab-scale photocatalytic H₂ evolution from aqueous sacrificial biomass-derivatives, under simulated solar light. Experiments in aqueous starch using Pt or Cu–Ni as the co-catalysts indicated that H₂ production is affected by co-catalyst type and loading, with the greatest hydrogen evolution rates (HER) up to 453 and 806 μmol g⁻¹ h⁻¹ using TiO₂ coupled with 3 wt% Cu–Ni or 0.5 wt% Pt, respectively. Despite the lower surface area, o-g-C₃N₄ gave HERs up to 168 and 593 μmol g⁻¹ h⁻¹ coupled with 3 wt% Cu–Ni or 3 wt% Pt. From mono- and di-saccharide solutions, H₂ evolution was in the range 504–1170 μmol g⁻¹ h⁻¹ for Pt/TiO₂ and 339–912 μmol g⁻¹ h⁻¹ for Cu–Ni/TiO₂, respectively; o-g-C₃N₄ was efficient as well, providing HERs of 90–610 μmol g⁻¹ h⁻¹. The semiconductors were tested in sugar-rich wastewaters obtaining HERs up to 286 μmol g⁻¹ h⁻¹. Although HERs were lower compared to Pt/TiO₂, a cheap, eco-friendly and non-nanometric catalyst such as o-g-C₃N₄, coupled to non-noble metals, provided a more sustainable H₂ evolution.     

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.     

Co3O4/CeO2 p-n heterojunction construction and application for efficient photocatalytic hydrogen evolution

The construction of p-n type heterojunction is an effective way to enhance the efficiency of photocatalytic hydrogen evolution. In this work, Co₃O₄/CeO₂ p-n heterojunction was construct by a simple hydrothermal method. This heterojunction mainly uses the internal electric field formed and accelerate the separation of electrons and holes in the opposite direction. In addition, according to SEM and TEM characterization, it was found that the granular cobalt oxide nanoparticles prepared by in-situ hydrothermal method were firmly and uniformly dispersed in cerium oxide, which effectively increased the active sites of hydrogen evolution. And combined with the BET results, it shows that the growth of cobalt oxide effectively increases the specific surface area and increases the active sites for hydrogen evolution. By exploring the hydrogen evolution capacity of different ratios of the complex, the test results showed that in all different ratios of the catalyst, CC-0.16 showed the best performance, and the hydrogen production efficiency reached 2298.52 μmol g⁻¹h⁻¹, which was 71 times that of nanobelt CeO₂ and 2.72 times that of Co₃O₄. According to the characterization results, the photocatalytic water splitting mechanism of the p-n heterojunction was proposed, and the charge transfer mechanism in the process was discussed in depth.     

Fabrication of hollow g-C3N4@α-Fe2O3/Co-Pi heterojunction spheres with enhanced visible-light photocatalytic water splitting activity

For the first time, g-C₃N₄@α-Fe₂O₃/Co-Pi heterojunctional hollow spheres were successfully fabricated via thermal condensation method followed by solvothermal and photo-deposition treatment, which showed excellent photocatalytical property. Except for the Z-scheme charge transfer between α-Fe₂O₃ and g-C₃N₄, the Co-Pi could further reduce the combination of photogenerated electrons and holes as a hole storage agent, resulting in remarkably enhanced visible-light photocatalytic water splitting activity with the H₂ production rate of 450 μmol h⁻¹g⁻¹, which is 15.7 times higher than that of g-C₃N₄. Moreover, the photocatalytic activity of the prepared ternary hollow photocatalysts showed almost no significant weakness after five cycles, which indicated their good performance stability. The as-prepared g-C₃N₄@α-Fe₂O₃/Co-Pi also possessed good activity for overall water splitting with the hydrogen production rate reaching 9.8 μmol h⁻¹g⁻¹. This synthesized g-C₃N₄@α-Fe₂O₃/Co-Pi composite is expected to be a promising candidate for water splitting.     

Green synthesized carbon quantum dots as TiO2 sensitizers for photocatalytic hydrogen evolution

Carbon quantum dots (CQDs) have attracted growing interest due to their superior luminescent properties, which make them excellent photosensitizers for TiO₂. This study presents the green-synthesis of CQDs from edible mushroom Agaricus bisporus through microwave irradiation. In the study as-synthesized CQDs were used as a sensitizer for TiO₂ in photocatalytic hydrogen evolution in aqueous triethanolamine (sacrificial reagent) under visible-light irradiation. Photocatalytic hydrogen production activity of CQD-sensitized TiO₂ was found to be 472 μmol g⁻¹ h⁻¹ (without loading any noble metal co-catalyst) and 1458 μmol g⁻¹ h⁻¹ (with loading Pt co-catalyst). The study revealed that the CQDs from mushroom A. bisporus can be used as an efficient sensitizer for TiO₂ in photocatalytic hydrogen production.     

Construction of ternary Z-scheme covalent triazine framework@Au@TiO2 for enhanced visible-light-driven hydrogen evolution activity

One key challenge in photocatalytic hydrogen production is how to construct high-performance photocatalyst. Covalent triazine framework (CTF) based polymers as photocatalysts show great application potential because of their good photocatalytic activity, high chemical stability, tunable electronic and optical properties, and easy synthesis process. In this paper, we designed the ternary Z-scheme heterojunction Au@TiO₂-X%TrTh based on CTF polymer TrTh, TiO₂ and Au nanoparticle, which exhibit higher photocatalytic hydrogen production rate compared with the corresponding binary heterojunction Au@TiO₂ and TiO₂-12%TrTh. The results of photocatalytic hydrogen production show that the optimized Au@TiO₂-12%TrTh has a remarkable hydrogen production rate of 4288.54 μmol g^?1 h^?1, which is about 312.3 times of Au@TiO₂ and 9.1 times of the TiO₂-12%TrTh. The enhanced hydrogen production activity of the ternary heterojunction comes from the local surface plasmonic resonance effect of Au nanoparticle, lower recombination efficiency of photogenerated electron-holes pairs and Z-scheme electron transfer pathway of Au@TiO₂-12%TrTh. The work provides a new strategy for designing efficient and practical photocatalyst.     

Porous g-C3N4/TiO2 S-scheme heterojunction photocatalyst for visible-light driven H2-production and simultaneous wastewater purification

In this work, photocatalysts with a novel S-scheme heterojunction were fabricated by coupling MOF-derived TiO₂ with porous g-C₃N₄ (MTO/PCN). The S-scheme heterojunction with matching band gap possesses different advantageous properties, which can not only inhibit photo-generated charge recombination, but also reserve outstanding redox ability. As expected, superior hydrogen evolution efficiency of 40-MTO/PCN was obtained in a TEOA-containing aqueous solution and pure water, which were 5252.9 and 974.6 μmol h⁻¹ g⁻¹, respectively. Meanwhile, the hybrid can also serve as a bifunctional catalyst for H₂ generation (2137.3 μmol h⁻¹ g⁻¹) and organic contaminant removal (the RhB purification efficiency: 35.24%). This work furnishes a feasible method for devising bifunctional photocatalysts that can simultaneously produce hydrogen and purify wastewater to provide both energy-saving and environmental restoration functions.     

0D/3D ZnIn2S4/Ag6Si2O7 nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H2 evolution under visible light

Constructing heterojunction structure is a feasible way to realize an efficient and durable photocatalysts. Herein, a novel Z-scheme zero/three dimensional (0D/3D) ZnIn₂S₄/Ag₆Si₂O₇ (ZIS/ASO) composite was rationally designed, synthesized and analyzed. ZIS/ASO composite possesses a layer structure for increasing light response, a special 0D/3D structure for reducing the photo-induce carriers migration path, and numerous active sites for absorbing H₂O and producing H₂. This composite retains the high oxidation and reduction ability by facilitating separation and migration as well as limiting recombination of photo-induced carriers via the intimate interface between ZIS and ASO. Undoubtedly, the synthesized ZIS/ASO photocatalyst achieved a high photocatalytic H₂ activity, and the optimum sample shows a satisfactory H₂ evolution rate of 590.56 μmol g⁻¹ h⁻¹, distinctly better than that of pure ZIS. More importantly, this composite exhibits high stability and recyclability and is expected to be applied in practical application. Based on the H₂ evolution experimental results and electrochemical tests, the Z-scheme heterostructure construction of the composite was confirmed. This work expects to inspire a unique protocol for synthesizing Z-scheme photocatalysts for water splitting under visible light irradiation.     

Rationally construct of CoSx/MoS2/g-C3N4 double heterojunction with promoting the separation of carriers for enhanced photocatalysis

g-C₃N₄ (CN) has attracted extensive attention in photocatalysis field, but its weak visible light absorption and rapid charge recombination limit its application. In this, MoS₂ and CoSx (ZIF67 derivatives) as cocatalyst grew on the surface of semiconductor CN in situ to construct CoSx/MoS₂/CN double heterojunction. Then the activities of photocatalytic hydrogen evolution and degradation MB were researched. The hydrogen production rate of 5%CoSx/MoS₂/CN-2 photocatalyst is 9800 μmol h^?1 g^?1 and is about 6.5 times as great as CN, 46 times than MoS₂ and 98 times than CoSx, respectively. Under natural sunlight and simulated sunlight, the degradation efficiency of MB is 99.95% and 99.50% after 4 h, respectively. Catalyst characterizations have pointed out that CoSx/MoS₂/CN catalyst has abundant active sites and larger specific surface area, which increase absorption of water and oxygen. At the same time, internal electric field and S vacancy enhance electrons transfer rate, which effectively inhibit the recombination of e^?-h⁺. This work provides a new idea into the creation of steady, high-efficiency and continuable photocatalytic catalyst for visible light.     

Improving hydrogen evolution activity of perovskite BaTiO3 with Mo doping: Experiments and first-principles analysis

Hydrogen production through photocatalytic water splitting attracts great attention in fields of energy conversion. To improve the hydrogen evolution efficiency, narrowing the bandgap of photocatalysts by introducing dopant atoms is widely investigated for increasing light absorption. Herein, Mo-doped BaTiO₃ samples are synthesized by a traditional solid-state reaction method and all the samples are modified with Pt by a photo-reduction method. Compared with pure BaTiO₃, Mo doping into BaTiO₃ samples realizes the band-to-band visible-light absorption and shows remarkable improvement in hydrogen production efficiency. Under simulated sunlight irradiation and with 0.4 wt% Pt deposition, BaTiO₃ doped with 2 at% Mo exhibits a hydrogen evolution rate of 63 μmol g⁻¹ h⁻¹, about 2 times improvement in comparison to pure BaTiO₃ (35 μmol g⁻¹ h⁻¹). Further first-principles calculations based on density-function theory demonstrates an apparent downward movement of the conduction band minimum due to the coupling between the Ti 3d and Mo 3d states, leading to the significant bandgap narrowing and enhancement of the visible-light photocatalytic activity.