Facile synthesis of anatase/rutile TiO2/g-C3N4 multi-heterostructure for efficient photocatalytic overall water splitting

Rational design of high-efficiency heterostructure photocatalyst is an effective strategy to realize photocatalytic H₂ evolution from pure water, but remains still a considerable challenge. Herein, an anatase/rutile TiO₂/g-C₃N₄ (A/R/CN) multi-heterostructure photocatalyst was prepared by a facile thermoset hybrid method. The combination of two type-II semiconductor heterostructures (i.e., A/R and R/CN) significantly improve the separation and transfer efficiency of photogenerated carriers of anatase TiO₂, rutile TiO₂ and g-C₃N₄, and A/R/CN photocatalyst with high activity is obtained. The optimal A/R/CN photocatalyst exhibits significantly increased photocatalytic overall water splitting activity with a rate of H₂ evolution of 374.2 μmol g⁻¹h⁻¹, which is about 8 and 4 times that of pure g-C₃N₄ and P25. Moreover, it is demonstrated to be stable and retained a high activity (ca. 91.2%) after the fourth recycling experiment. This work comes up with an innovative perspective on the construction of multi-heterostructure interfaces to improve the overall photocatalytic water splitting performance.     

Highly efficient visible-light-assisted photocatalytic hydrogen generation from water splitting catalyzed by Zn0.5Cd0.5S/Ni2P heterostructures

Development of heterostructured photocatalysts which can facilitate spatial separation of photo-generated charge carriers is crucial for achieving improved photocatalytic H₂ production. Consequently, herein, we report the synthesis of Zn_0.5Cd_0.5S/Ni₂P heterojunction photocatalysts with varying amount of Ni₂P, 0.5 (S1), 1 (S2), 3 (S3), 5 (S4) and 10wt% (S5) for the efficient visible-light-assisted H₂ generation by water splitting. The heterostructures were characterized thoroughly by PXRD, FE-SEM, EDS, HR-TEM and XPS studies. FE-SEM and HR-TEM analyses of the samples unveiled the presence of Zn_0.5Cd_0.5S microspheres composed of smaller nanocrystals with the surface of the microspheres covered with Ni₂P nanosheets and the intimate contact between the Zn_0.5Cd_0.5S and the Ni₂P. Further, visible-light-assisted photocatalytic investigation of the samples showed excellent water splitting activity of the heterostructure, Zn_0.5Cd_0.5S/1wt%Ni₂P (S2) with very high H₂ generation rate of 21.19 mmol h^?1g^?1 and the AQY of 21.16% at 450 nm with turnover number (TON) and turnover frequency (TOF) of 251,516 and 62,879 h^?1 respectively. Interestingly, H₂ generation activity of S2 was found to be about four times higher than that of pure Zn_0.5Cd_0.5S (5.0 mmol h^?1g^?1) and about 240 times higher than that of CdS/1wt%Ni₂P. The enhanced H₂ generation activity of S2 has been attributed to efficient spatial separation of photogenerated charge carriers and the presence of highly reactive Ni₂P sites on the surface of Zn_0.5Cd_0.5S microspheres. A possible mechanism for the enhanced photocatalytic H₂ generation activity of Zn_0.5Cd_0.5S/1wt%Ni₂P (S2) has been proposed and is further supported by photoluminescence and photocurrent measurements. Furthermore, the catalyst, S2 can be recycled for several cycles without significant loss of catalytic activity and photostability. Remarkably, the H₂ generation activity of S2 was found to be even higher than the reported examples of Zn_xCd_1-xS doped with noble metal cocatalysts. Hence, the present study highlights the importance of Zn_0.5Cd_0.5S/Ni₂P heterostructures based on non-noble metal co-catalyst for efficient visible-light-driven H₂ production from water splitting.     

Synthesis and characterization of composite visible light active photocatalysts MoS2–g-C3N4 with enhanced hydrogen evolution activity

Molybdenum disulfide (MoS₂) and graphitic carbon nitride (g-C₃N₄) composite photocatalysts were prepared via a facile impregnation method. The physical and photophysical properties of the MoS₂–g-C₃N₄ composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microcopy (HRTEM), ultraviolet–visible diffuse reflection spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. The photoelectrochemical (PEC) measurements were tested via several on–off cycles under visible light irradiation. The photocatalytic hydrogen evolution experiments indicate that the MoS₂ co-catalysts can efficiently promote the separation of photogenerated charge carriers in g-C₃N₄, and consequently enhance the H₂ evolution activity. The 0.5wt% MoS₂–g-C₃N₄ sample shows the highest catalytic activity, and the corresponding H₂ evolution rate is 23.10 μmol h⁻¹, which is enhanced by 11.3 times compared to the unmodified g-C₃N₄. A possible photocatalytic mechanism of MoS₂ co-catalysts on the improvement of visible light photocatalytic performance of g-C₃N₄ is proposed and supported by PL and PEC results.     

Carbon intercalated MoS2 cocatalyst on g-C3N4 photo-absorber for enhanced photocatalytic H2 evolution under the simulated solar light

Despite MoS₂ being a promising non-precious-metal cocatalyst, poor electronic conductivity and low activity for hydrogen evolution caused by serious agglomeration have been identified as critical roadblocks to further developing MoS₂ cocatalyst for photocatalytic water splitting using solar energy. In this work, the density functional theory calculations reveal that carbon intercalated MoS₂ (C-MoS₂) has excellent electronic transport properties and could effectively improve catalytic activity. The experiment results show that the prepared tremella-like C-MoS₂ nanoparticles have large interlayer spacing along the c-axis direction and high dispersion because of intercalation of the carbon between adjacent MoS₂ layers. Furthermore, the heterostructure photocatalyst of C-MoS₂@g-C₃N₄ formed by loading the cocatalyst of C-MoS₂ onto g-C₃N₄ nanosheets exhibits the H₂ evolution rate of 157.14 μmolg⁻¹h⁻¹ when containing 5 wt% C-MoS₂. The high photocatalytic H₂ production activity of the 5 wt% C-MoS₂@g-C₃N₄ can be attributed to the intercalated conductive carbon layers in MoS₂, which leads to efficient charge separation and transfer as well as increased activities of the edge S atoms for H₂ evolution. We believe that the C-MoS₂ will offer great potential as a photocatalytic H₂ evolution reaction cocatalyst 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.     

SnO2 promoted carrier separation in superior thin g-C3N4 nanosheets for enhanced photocatalytic degradation and H2 generation

The construction of heterostructures is an efficient approach to improve the photocatalystic performance of semiconductors. In this paper, SnO₂-g-C₃N₄ (SnO₂–CN) nanocomposites were created via thermal polymerization using SnO₂ nanoparticles and layered g-C₃N₄ nanosheets. A mechano-chemical pre-reaction and the second thermal polymerization of bulk g-C₃N₄ play important roles for the formation of SnO₂/g-C₃N₄ heterostructures with improved interface nature. The heterostructures with an optimized SnO₂ weight ratio of 10% was obtained by adjusting parameters for enhanced photocatalytic reactions in visible light region. Hydrogen generation and the degradation of rhodamine B (Rh B) were tested to characterize the photocatalytic performance of the SnO₂–CN nanocomposites. The degradation of a 20 mg/L Rh B solution was finished within 15 min, in which the degradation rate was about twice compared with superior thin g-C₃N₄ nanosheets prepared by a two-step polymerization procedure. The SnO₂–CN nanocomposite with 10% SnO₂ revealed a H₂ generation rate of 2569.5 μmol g⁻¹L⁻¹. The enhanced photocatalytic performance is ascribed to a type II heterostructure formed and improved interface properties between g-C₃N₄ and SnO₂. In addition, the improved conductivity of SnO₂ promoted the photogenerated carrier separation and transfer. The result provided a new idea for the construction of g-C₃N₄ heterostructures with improved interface characterization and the improvement of photocatalytic properties.     

In-situ growth of mesoporous Nb2O5 microspheres on g-C3N4 nanosheets for enhanced photocatalytic H2 evolution under visible light irradiation

Large-surface-area mesoporous Nb₂O₅ microspheres were successfully grown in-situ on the surface of g-C₃N₄ nanosheets via a facile solvothermal process with the aid of Pluronic P123 as a structure-directing agent. The resultant g-C₃N₄/Nb₂O₅ nanocomposites exhibited enhanced photocatalytic activity for H₂ evolution from water splitting under visible light irradiation as compared to pure g-C₃N₄. The optimal composite with 38.1 wt% Nb₂O₅ showed a hydrogen evolution rate of 1710.04 μmol h^?1 g^?1, which is 4.7 times higher than that of pure g-C₃N₄. The enhanced photocatalytic activity could be attributed to the sufficient contact interface in the heterostructure and large specific surface area, which leads to effective charge separation between g-C₃N₄ and Nb₂O₅.     

Construction of g-C3N4/BCN two-dimensional heterojunction photoanode for enhanced photoelectrochemical water splitting

Two-dimensional heterojunction g-C₃N₄/BCN was constructed via thermal polymerization process. The formed two-dimensional heterostructure could enhance the interfacial contact area between BCN and porous g-C₃N₄ as well as shorten the photogenerated charge carriers transfer time and distance. The two-dimensional g-C₃N₄/BCN heterojunction photoanode shows enhanced photoelectrochemical (PEC) performance for water splitting under visible-light irradiation, which primarily originates from the improved charge transfer and separation, and prolonged lifetime of electrons. Under the visible light irradiation, the g-C₃N₄/BCN heterojunction sample yields a photocurrent density of ∼0.62 mA cm⁻² at 1.23 V vs. RHE, which is about eight times as many as that of CN (0.08 mA cm⁻²) electrode at the same conditions. In addition, the possible electron transfer model and mechanism of PEC water splitting for H₂ evolution have been discussed.     

Modification of the ultrasonication derived-g-C3N4 nanosheets/quantum dots by MoS2 nanostructures to improve electrocatalytic hydrogen evolution reaction

In this work, graphitic carbon nitride (g-C₃N₄) nanosheets/quantum dots (NS/QD) was prepared using a simple and low-cost procedure. By two steps exfoliation in a bath and tip sonicator, the g-C₃N₄ (NS/QD) was produced from bulk g-C₃N₄. To improve electrocatalytic hydrogen evolution reaction (HER), the g-C₃N₄ (NS/QD) were modified by the MoS₂ nanostructures. Nanocomposite of the g-C₃N₄ (NS/QD) with MoS₂ nanostructures was deposited on a flexible, conductive and three dimensional carbon cloth by a facile and binder-free electrophoretic technique. This electrode exhibited a Tafel slope of 88 mV/dec and an overpotential of 0.28 V vs RHE at −2 mA/cm², lower than that of the g-C₃N₄, and good stability after 1000 cycles and 100 days for HER. The enhanced electrocatalytic performance was attributed to the MoS₂ and g-C₃N₄ nanostructures on three dimensional carbon cloth, leading to high surface area and more number of the exposed active sites for HER. This heterostructure improved charge transport, proton adsorption and hydrogen evolution on the electrode. This work proposes cost-effective, stable and three dimensional g-C₃N₄ based electrode for hydrogen evolution reaction.     

PtS2/g-C3N4 van der Waals heterostructure: A direct Z-scheme photocatalyst with high optical absorption,solar-to-hydrogen efficiency and catalytic activity

Using two-dimensional semiconductors to build heterojunction as photocatalyst for water splitting is an important green and clean energy technology and has wide development prospects. Here, the monolayered PtS₂ and g-C₃N₄ are used to build the direct Z-scheme van der Waals (vdW) heterostructure, and the structure, electrical, Bader charge, optical properties and solar-to-hydrogen efficiency are calculated in detail through first-principle calculations. The direct Z-scheme PtS₂/g-C₃N₄ vdW heterostructure has an inherent type-II band alignment that enables it to reduce the photogenerated carriers aggregation, and it also possesses a decent band edge position to fully induce the redox reactions of decomposed water. The charge density shows that PtS₂ monolayer is negatively charged while g-C₃N₄ monolayer is positively charged, and the interface potential drop of PtS₂/g-C₃N₄ vdW heterostructure forms a built-in electric field with the direction from g-C₃N₄ to PtS₂. The PtS₂/g-C₃N₄ vdW heterostructure has suitable optical property, outstanding solar-to-hydrogen efficiency, high catalytic activity and thus a promising application prospect for photocatalytic water splitting.     

Redox couple mediated charge carrier separation in g-C3N4/CuO photocatalyst for enhanced photocatalytic H2 production

Graphitic carbon nitride (g-C₃N₄) is one of the promising two-dimensional metal-free photocatalysts for solar water splitting. Regrettably, the fast electron-hole pair recombination of g-C₃N₄ reduces their photocatalytic water splitting efficiency. In this work, we have synthesized the CuO/g-C₃N₄ heterojunction via wet impregnation followed by a calcination method for photocatalytic H₂ production. The formation of CuO/g-C₃N₄ heterojunction was confirmed by XRD, UV–vis and PL studies. Notably, the formation of heterojunction not only improved the optical absorption towards visible region and also enhanced the carrier generation and separation as confirmed by PL and photocurrent studies. The photocatalytic H₂ production results revealed that CuO/g-C₃N₄ photocatalyst demonstrated the increased photocatalytic H₂ production rate than bare g-C₃N₄. The maximum H₂ production rate was obtained with 4 wt % CuO loaded g-C₃N₄ photocatalyst. Importantly, the rate of H₂ production was further improved by introducing simple redox couple Co²⁺/Co³⁺. Addition of Co²⁺ during photocatalytic H₂ production shuttled the photogenerated holes by a reversible conversion of Co²⁺ to Co³⁺ with accomplishing water oxidation. The effective shuttling of photogenerated holes decreased the election-hole pair recombination and thereby enhancing the photocatalytic H₂ production rate. It is worth to mention that the addition of Co²⁺ with 4 wt % CuO/g-C₃N₄ photocatalyst showed ∼7.5 and ∼2.0 folds enhanced photocatalytic H₂ production rate than bare g-C₃N₄/Co²⁺ and CuO/g-C₃N₄ photocatalysts. Thus, we strongly believe that the present simple redox couple mediated charge carrier separation without using noble metals may provide a new idea to reduce the recombination rate.     

Construction of heterostructured g-C3N4@TiATA/Pt composites for efficacious photocatalytic hydrogen evolution

Construction of heterostructured photocatalysts is a feasible method for improving hydrogen production from water splitting because of its good charge transport efficiency. Herein, we coupled the Ti-MOFs (TiATA) with metal-free graphitic carbon nitride (g-C₃N₄) to synthesize composites, g-C₃N₄@TiATA, in which a heterostructure was formed between g-C₃N₄ and TiATA. The establishment of heterojunctions not only broadens the light absorption range of g-C₃N₄@TiATA (490 nm) by contrast with g-C₃N₄ (456 nm), but also greatly accelerates charge migration. Photocatalytic studies present that the construction of heterostructure steering the charges flow from g-C₃N₄ to TiATA and then delivery to the cocatalyst of Pt nanoparticles, exhibiting an impressively photocatalytic hydrogen production rate (265.8 μmol·h⁻¹) in assistance of 300 W Xenon lamp, which is about 3.4 times as much as g-C₃N₄/Pt.     

2D MOFs enriched g-C3N4 nanosheets for highly efficient charge separation and photocatalytic hydrogen evolution from water

Here we report a 2D-2D heterostructure of g-C₃N₄/UMOFNs photocatalysts via mechanical grinding two kinds of two-dimensional nanosheets of g-C₃N₄ nanosheets and UMOFNs, which exhibits enhanced H₂ evolution from water with simulated solar irradiation. g-C₃N₄ nanosheets are in close contact with UMOFNs, and there is a certain interaction between them, showing the effect of superimposition on the two-dimensional layer. The 2D-2D heterostructure offers a maximal photocatalytic hydrogen production activity of 1909.02 μmol g⁻¹ h⁻¹ with 3 wt% of UMOFNs, which is 3-fold higher than that of g-C₃N₄ nanosheets (628.76 μmol g⁻¹ h⁻¹) and 15-flod higher than that of bulk g-C₃N₄ (124.30 μmol g⁻¹ h⁻¹). The significant increasement of photocatalysis is due to 2D-2D heterostructure possessing a short charge transfer distance and large contact area between g-C₃N₄ and UMOFNs. The highly dispersed NiO, CoO and π-π bonds in UMOFNs of 2D-2D structure also promote charge transfer and enhance the photocatalytic activity.     

Photo-assisted splitting of water into hydrogen using visible-light activated silver doped g-C3N4 & CNTs hybrids

Herein, highly efficient and cost effective solar photocatalytic water splitting for hydrogen (H₂) generation was achieved by modified g-C₃N₄. Visible light absorption of g-C₃N₄ was enhanced by decorating g-C₃N₄ matrix with silver nanoparticles (Ag). Moreover, incorporation of carbon nanotubes (CNTs) in Ag/g-C₃N₄ facilitated photocatalytic performance through efficient separation and transfer of photogenerated e-h pairs (charges) in Ag/g-C₃N₄ that consequently generated very pure and significant H₂. Among several tested ratios (wt. %) of Ag/g-C₃N₄/CNTs, 1.82 (Ag/g-C₃N₄) and 2.00 (and Ag/g-C₃N₄/CNTs) were found to be highly efficient that harvested maximum visible-light and produced H₂ @1.48 mmol h⁻¹ and 1.78 mmol h⁻¹. We witnessed distinctive role of CNTs as an electron collector and carrier to separate photogenerated e-h pairs to facilitate photocatalysis for H₂ generation together with possible utility of Ag and CNTs doped materials with regard to energy transformation.     

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.     

One-pot sulfurized synthesis of ZnIn2S4/S,N-codoped carbon composites for solar light driven water splitting

To enhance the intrinsic active sites and to suppress the recombination of charge carriers, ZnIn₂S₄ modified with S,N-codoped carbon (ZIS/SN-C) composites were prepared for solar light driven water splitting via the one-pot sulfurized route. Compared with g-C₃N₄ and S-doped g-C₃N₄, the combined effect between S,N-codoped carbon and ZnIn₂S₄ can greatly enhance the photocatalytic activity of ZIS/SN-C. The optimal 4-ZIS/SN-C with the Zn(II) content of 13.78% and the calculated In/Zn molar ratio of 2.03:1 presents the H₂ evolution rate of 2937.1 μmol g^?1 h^?1, which is 2.98 and 23.42 times higher than that of one-pot sulfurized ZnIn₂S₄ and S-doped g-C₃N₄, respectively. However, long-term photo-corrosion induces to the declined durability of 4-ZIS/SN/C for water splitting after three cycles. S vacancies of ZnIn₂S₄ serve as the efficient active sites of H₂ evolution reaction, and S, N-codoped carbon acts as the photo-induced electrons trapper. The one-pot sulfurized approach is thus a potential strategy to fabricate metal sulfide-based photocatalysts.     

Crystallinity and phase controlling of g-C3N4 /CdS hetrostructures towards high efficient photocatalytic H2 generation

The heterostructures of graphitic carbon nitride (g-C₃N₄) and CdS were synthesized by controlling the crystalline degree of g-C₃N₄ and the phase composition of CdS. A thermal polycondensation process of N precursors was adjusted to get amorphous and crystalline g-C₃N₄. A multistep adsorption method was used to deposit CdS nanoparticles on g-C₃N₄. An annealed process was used to adjust the phase composition of CdS from cubic to hexagonal. The morphology of CdS was changed to rod. Amorphous g-C₃N₄/CdS heterostructures revealed enhanced photocatalytic activity because the amorphous g-C₃N₄ has a lower crystallinity, it is easier to form a heterojunction with the CdS. Further, an annealing process resulted in the phase transfer and morphology change of CdS. The high stability and rod morphology of CdS make the heterostructures with high H₂ generation rate to 5440 μmol h-1 g-1 which is ~5 times high compared with g-C₃N₄.     

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.     

Vanadium (V) and Niobium (Nb) as the most promising co-catalysts for hydrogen sulfide splitting screened out from 3d and 4d transition metal single atoms

The options of transition metals as co-catalysts for photocatalytic H₂S splitting are restricted to some noble metals and related compounds which have noticeable achievements despite their high prices. Substituting with cheap transition metals and downsizing the size to single atom level are economic ways to lower the cost. Herein, the s-triazine graphite-like carbon nitride sheet g-C₃N₄ (001) is chosen as the model to study the performances of 3d and 4d transition metal single atoms (TMSA = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd) in H₂S splitting based on density functional theory (DFT) calculations. It is found that low-cost transition metals with industrial relevance (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Cd) are completely comparable with noble metals (Ru, Rh, Pd, Ag). Among them, V and Nb are the most promising co-catalysts with good thermodynamic stabilities, favorable responses to visible light, high photoinduced electron-hole separation efficiencies, sufficient potentials for H₂S splitting, and low energy barriers for H₂S dissociation into H₂ and S. The noticeable improved activities of V/g-C₃N₄ and Nb/g-C₃N₄ are attributed to the formation of strong interfacial chemical bonds which could promote electrons transferring to H₂S derivates. In addition, the introduction of photoinduced electrons could further improve the activities of V/g-C₃N₄ and Nb/g-C₃N₄ with more electrons transferring to H₂S derivates. It is expected that this work could provide a helpful guidance to choose appropriate TMSA co-catalysts as references for H₂S splitting.     

Facile preparation and photocatalytic hydrogen production of WS2 and its composites

Two-dimensional transition metal dichalcogenides, MoS₂ and WS₂ have been widely considered as promising materials for photocatalytic hydrogen production. However, compared with the widely investigated MoS₂, researches on WS₂ are much less. Besides, for the synthesis of WS₂, methods suitable for large-scale preparation are still rare. Then in this paper, a facile method for the preparation of WS₂ was developed based on the liquid-phase precipitation-calcination method reported previously. In specific, thiourea was introduced in the calcination process to realize the in-situ conversion of impurity WO₃ to WS₂. As a result, WS₂ was successfully prepared. More interestingly, a series of photocatalysts with different compositions and performances were easily obtained only through changing the thiourea amount. When no thiourea was used, a WS₂/WO₃ heterostructure was constructed, while when excessive thiourea was introduced, an efficient WS₂/g-C₃N₄ heterostructure (g-C₃N₄ = graphitic carbon nitride) was fabricated. Moreover, their hydrogen production performances were investigated with Erythrosine B (ErB) and triethanolamine (TEOA) as photosensitizer and sacrificial agent, respectively. The results showed that the as-obtained WS₂ has a comparable H₂-evolving activity (1686.3 μmol h^?1 g^?1) to the WS₂/WO₃ (1637.8 μmol h^?1 g^?1), and the WS₂/g-C₃N₄ owns the highest performance (2428.7 μmol h^?1 g^?1). This work provides a facile and feasible route for the preparation of efficient WS₂-based photocatalysts.