Two dimensional N-doped ZnO-graphitic carbon nitride nanosheets heterojunctions with enhanced photocatalytic hydrogen evolution

The effective separation of photogenerated charge carriers, their transport and interfacial contact is of great significance for excellent performance of semiconductor based photocatalysts. Herein, we report the fabrication of two dimensional (2D) nanosheets heterojunction comprising of N-doped ZnO nanosheets loaded over graphitic carbon nitride (g-C₃N₄) nanosheets for enhanced photocatalytic hydrogen evolution. The prepared 2D-2D heterojunctions with varying amount of g-C₃N₄ nanosheets have been characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) techniques. The optimized heterojunction photocatalyst with 30 wt% of g-C₃N₄ nanosheets (NZCN30) exhibit hydrogen evolution rate of 18836 μmol h^?1 g_cat^?1 in presence of Na₂S and Na₂SO₃ as sacrificial agents under simulated solar light irradiation. The enhanced photocatalytic performance of NZCN30 heterojunction has been supported well by photoluminescence and photoelectrochemical investigations, which shows the minimum recombination rate and high photoinduced current density, respectively. In addition, the existence of 2D-2D interfacial contact plays a major role in enhanced H₂ evolution by high face-to-face contact surface area for separation of photogenerated charge carriers in space which facilitate their transfer for H₂ generation. This work paves way for the development of 2D-2D heterojunctions for diverse applications.     

Rationally designed ternary CdSe/WS2/g-C3N4 hybrid photocatalysts with significantly enhanced hydrogen evolution activity and mechanism insight

Excellent light harvest, efficient charge separation and sufficiently exposed surface active sites are crucial for a given photocatalyst to obtain excellent photocatalytic performances. The construction of two-dimensional/two-dimensional (2D/2D) or zero-dimensional/2D (0D/2D) binary heterojunctions is one of the effective ways to address these crucial issues. Herein, a ternary CdSe/WS₂/g-C₃N₄ composite photocatalyst through decorating WS₂/g-C₃N₄ 2D/2D nanosheets (NSs) with CdSe quantum dots (QDs) was developed to further increase the light harvest and accelerate the separation and migration of photogenerated electron-hole pairs and thus enhance the solar to hydrogen conversion efficiency. As expected, a remarkably enhanced photocatalytic hydrogen evolution rate of 1.29 mmol g⁻¹ h⁻¹ was obtained for such a specially designed CdSe/WS₂/g-C₃N₄ composite photocatalyst, which was about 3.0, 1.7 and 1.3 times greater than those of the pristine g-C₃N₄ NSs (0.43 mmol g⁻¹ h⁻¹), WS₂/g-C₃N₄ 2D/2D NSs (0.74 mmol g⁻¹ h⁻¹) and CdSe/g-C₃N₄ 0D/2D composites (0.96 mmol g⁻¹ h⁻¹), respectively. The superior photocatalytic performance of the prepared ternary CdSe/WS₂/g-C₃N₄ composite could be mainly attributed to the effective charge separation and migration as well as the suppressed photogenerated charge recombination induced by the constructed type-II/type-II heterojunction at the interfaces between g-C₃N₄ NSs, CdSe QDs and WS₂ NSs. Thus, the developed 0D/2D/2D ternary type-II/type-II heterojunction in this work opens up a new insight in designing novel heterogeneous photocatalysts for highly efficient photocatalytic hydrogen evolution.     

Synthesis of mesoporous g-C3N4/S-PAN π-conjugation heterojunction via sulfur-induced cyclization reaction for enhanced photocatalytic H2 production

Simultaneously extended π-conjugated system and provide abundant pore structure of semiconductor photocatalysts for hydrogen (H₂) production is highly desirable. Hence, a novel mesoporous sulfurized polyacrylonitrile modified g-C₃N₄ (g-C₃N₄/S-PAN) π-conjugation heterojunction is firstly fabricated by one-step strategy under the sulfur-induced cyclization reaction and pore-creating effect. Excitedly, the g-C₃N₄/S-PAN π-conjugation heterojunction extends the π-conjugated system in favor of speeding up the photogenerated electron transfer, which is due to strengthen the π-π interactions between the S-PAN and g-C₃N₄ and S-PAN is more apt to accept electrons. And the obtained g-C₃N₄/S-PAN π-conjugation heterojunction with mesoporous structure also provide abundant active sites for proton reduction. Accordingly, the g-C₃N₄/S-PAN-2 π-conjugation heterojunction shows the optimal photocatalytic H₂ evolution (PHE) activity (736.24 μmol h⁻¹g⁻¹), which is approximately 2.15 times higher than pristine g-C₃N₄. In addition, the relationships of the optical and photoelectrochemical properties with photocatalytic activity are revealed in depth based on the first-principles calculations of band structure and density of states (DOS). This work provides a new one-step strategy to obtain g-C₃N₄-based π-conjugation heterojunction with the unique microstructure for improving PHE activity.     

A latest overview on photocatalytic application of g-C3N4 based nanostructured materials for hydrogen production

Photocatalytic H₂ production is a hopeful technology to solving the environment problems and global energy. Consequently, it is essential to develop high efficient, nonprecious and stable photocatalysts. Graphitic carbon nitride (g-C₃N₄) was fascinated much concentration owed to this metal free n-type semiconductor possesses appropriate bandgap, unique two dimensional (2D) layered structures, low toxicity, high thermal and chemical stability, lowcost, facile preparation and visible light response. Moreover, the g-C₃N₄ composites are having huge promise on photocatalytic H₂ production but, the efficiency of pure g-C₃N₄ is at present limited by its poor visible light absorption and suffers from high recombination rate of g-C₃N₄ photogenerated electron/hole pairs resulting in low photocatalytic performance. Furthermore, the g-C₃N₄ has unique electronic structure, therefore renowned candidates have been coupled with different functional components to improve photocatalytic activity. In this contribution, we review the recent research progresses of transition metals, non metals, noble metals, semiconductor compounds, graphene, carbon nanotubes (CNTs), carbon dots and quantum dots, supported on g-C₃N₄ nanosheets, which were applied to photocatalytic H₂ production. In addition, different techniques used to synthesis the g-C₃N₄ based photocatalyst including with their corresponding examples have been described. We hope that this review will encourage the readers to extend the applications of g-C₃N₄ based heterostructure in the field of H₂ production in a green manner.     

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.     

A facile one-step strategy to construct 0D/2D SnO2/g-C3N4 heterojunction photocatalyst for high-efficiency hydrogen production performance from water splitting

Fabricating 0D/2D heterojunctions is considered to be an efficient mean to improve the photocatalytic activity of g-C₃N₄, whereas their applications are usually restricted by complex preparation process. Here, the 0D/2D SnO₂/g-C₃N₄ heterojunction photocatalyst is prepared by a simple one-step polymerization strategy, in which SnO₂ nanodots in-situ grow on the surface of g-C₃N₄ nanosheets. It shows the outstanding photocatalytic H₂ production activity relative to g-C₃N₄ under the visible light, which is due to the formation of 0D/2D heterojunction significantly contributing to the separation of photogenerated charge carriers. In particular, the H₂ production rate over the optimal SnO₂/g–C₃N₄–1 sample is 1389.2 μmol h⁻¹ g⁻¹, which is 6.06 times higher than that of g-C₃N₄ (230.8 μmol h⁻¹ g⁻¹). Meanwhile, the AQE value of H₂ production over the SnO₂/g–C₃N₄–1 sample reaches up to a maximum of 4.5% at 420 nm. This work develops a simple approach to design and fabricate g–C₃N₄–based 0D/2D heterojunctions for the high-efficiency H₂ production from water splitting.     

Facile synthesis of AuPd/g-C3N4 nanocomposite: An effective strategy to enhance photocatalytic hydrogen evolution activity

AuPd bimetallic nanoparticle (NP) modified ultra-thin graphitic carbon nitride nanosheet photocatalysts were synthesized via photochemical deposition-precipitation followed by hydrogen reduction. The crystal structure, chemical properties, and charge carrier behavior of these photocatalysts were characterized by X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS), transient photovoltage spectroscopy (TPV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and UV-Vis diffuse-reflectance spectroscopy (DRS). Photocatalytic H₂ evolution experiments indicate that the hydrogen treated AuPd nanoparticles can effectively promote the separation efficiency of electron-hole pairs photo-excited in the g-C₃N₄ photocatalyst, which consequently promotes photocatalytic H₂ evolution. The 1.0 wt% AuPd/g-C₃N₄ (H₂) composite photocatalyst showed the best performance with a corresponding photocatalytic H₂ evolution rate of 107 μmol h^?1. The photocatalyst can maintain most of its photocatalytic activity after four photocatalytic experiment cycles. These results demonstrate that the synergistic effect of light reduction and hydrogen reduction of AuPd and g-C₃N₄ help to greatly improve the photocatalytic activity of the composite photocatalyst.     

WO3/g-C3N4 two-dimensional composites for visible-light driven photocatalytic hydrogen production

WO₃/g-C₃N₄ two-dimensional (2D) composite photocatalysts were prepared through a simple hydrothermal method followed by a post thermal treatment. The H₂ generation activity of these photocatalysts in the visible light was evaluated. The photocatalysts were characterized by X-ray powder diffraction, Fourier transform infrared spectra, transmission electron microscopy and UV–vis diffuse reflectance spectroscopy et al. These results show that the orthorhombic-phase WO₃ nanoparticles with a grain size from 5 to 80 nm were successfully anchored on g-C₃N₄ nanosheets surface with intimate contact. Furthermore, the charge separation mechanisms of photo-generated charge carriers of the 2D WO₃/g-C₃N₄ photocatalysts were further studied by photoelectrochemical response and electrochemical impedance spectroscopy. The result shows that the 2D WO₃/g-C₃N₄ photocatalyst with 10 wt% WO₃ possesses the maximum photocatalytic performance for H₂ generation, as high as of 1853 μmol h^?1 g^?1, which is about 6.5 times higher than that of bare g-C₃N₄, indicating the fast injection of interface interaction between 2D g-C₃N₄ and WO₃. The increased photocatalytic performance of the composite photocatalyst can be attributed to the enhanced absorption of visible light, the higher photo-generated electrons and holes separation efficiency and low recombination rate of electrons and holes generated by photoexcitation.     

Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production

In this paper, a novel Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture has been successfully constructed by integrating Au/g-C₃N₄ plasmonic photocatalyst composite with 3D ZnIn₂S₄ nanosheet through a simple hydrothermal process. The Au nanoparticles were firstly anchored on the surface of pristine g-C₃N₄ material to get Au/g-C₃N₄ plasmonic photocatalyst. Ascribing to the surface plasmon resonance of Au nanoparticles, the obtained Au/g-C₃N₄ plasmonic photocatalyst shows a significant improved photocatalytic activity toward hydrogen production from water with visible light response comparing with pristine g-C₃N₄. Further combining Au/g-C₃N₄ plasmonic photocatalyst with 3D ZnIn₂S₄ nanosheet to construct a heterojunction composite. Owing to the synergistic effect of the surface plasmon resonance of Au nanoparticles in Au/g-C₃N₄ and the heterojunction structure in the interface of Au/g-C₃N₄ and ZnIn₂S₄, the prepared Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite shows an excellent photocatalytic activity toward hydrogen production from water with visible light response, which is around 7.0 and 6.3 times higher than that of the pristine C₃N₄ and Znln₂S₄ nanosheet, respectively. The present work might provide some insights for exploring other efficient heterojunction photocatalysts with excellent properties.     

1D/2D carbon-doped nanowire/ultra-thin nanosheet g-C3N4 isotype heterojunction for effective and durable photocatalytic H2 evolution

It is still challenging to design effective g-C₃N₄ photocatalysts with high separation efficiency of photo-generated charges and strong visible light absorption. Herein, a simple, template-free and “bottom-up” strategy has been developed to prepare 1D/2D g-C₃N₄ isotype heterojunction composed of carbon-doped nanowires and ultra-thin nanosheets. The ethanediamine (EE) grafted on melamine ensures the growth of 1D g-C₃N₄ nanowires with high carbon doping, and the ultra-thin g-C₃N₄ nanosheets were produced through HCl-assisted hydrothermal strategy. The apparent grain boundary between 2D nanosheets and 1D carbon-doped nanowires manifested the formation of the isotype heterojunction. The built-in electric field provide strong driving force for photogenerated carriers separation. Meanwhile, the doping carbon in g-C₃N₄ nanowires promotes visible light absorption. As a result, the photocatalytic H₂ evolution activity of 1D/2D g-C₃N₄ isotype heterojunction is 8.2 time that of the pristine g-C₃N₄, and an excellent stability is also obtained. This work provides a promising strategy to construct isotype heterojunction with different morphologies for effective photocatalytic H₂ evolution.     

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.     

Direct Z-scheme CoS/g-C3N4 heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen generation

Facilitating the separation of photoexcited electron-hole pairs and enhancing the migration of photogenerated carriers are essential in photocatalytic reaction. CoS/g-C₃N₄/NiS ternary photocatalyst was prepared by hydrothermal and physical stirring methods. The optimized ternary composite achieved a hydrogen yield of 1.93 mmol g^?1 h^?1, 12.8 times that of bare g-C₃N₄, with an AQE of 16.4% at 420 nm. The enhanced photocatalytic activity of CoS/g-C₃N₄/NiS was mainly ascribed to the synergistic interaction between the Z-scheme heterojunction constructed by CoS and g-C₃N₄ and the NiS co-catalyst featuring a large amount of hydrogen precipitation sites, which realized the efficient separation and migration of photogenerated carriers. In addition, the CoS/g-C₃N₄/NiS heterojunction-co-catalyst system exhibited excellent photocatalytic stability and recyclability.     

Phosphorylation of NiAl-layered double hydroxide nanosheets as a novel cocatalyst for photocatalytic hydrogen evolution

In previous studies, it has been shown that phosphorus and phosphate can improve the conductivity, change the electronic structure, and accept electrons from catalysts. In this study, we obtained phosphorylated NiAl-layered double hydroxide (P-LDH) nanosheets and used them as a novel cocatalyst in photocatalytic hydrogen evolution. After assembly with g-C₃N₄ via an in situ process, these noble-metal-free composite photocatalysts showed superior photocatalytic hydrogen evolution activity. It was also found that the efficiency of H₂ production on the optimal composite was 1.5 times that of Pt-modified g-C₃N₄. Characterization of the photocatalysts revealed that the effects of P-LDH were different from those of other bimetallic LDHs, showing a lower overpotential and faster reaction kinetics of H₂ evolution. Moreover, it was found that P-LDH has a higher surface work function than that of g-C₃N₄, leading to the formation of an interfacial electric field from CN toward P-LDH. Therefore, modifying P-LDH can efficiently improve the interfacial charge transfer rate, suppress photogenerated charge recombination, and lower the surface overpotential of g-C₃N₄. This study serves as guidance on the design of more effective cocatalysts for photocatalytic hydrogen evolution reactions.     

Rational design of plasmonic Ag@CoFe2O4/g-C3N4 p-n heterojunction photocatalysts for efficient overall water splitting

Highly efficient and direct photocatalytic H₂ evolution from water via water splitting without using sacrificial reagents is a challenging approach to convert solar energy into renewable and storable chemical energy. Herein, by amalgamating the architecture recommendations and energy band engineering principles into the design formulation, a novel Ag@CoFe₂O₄/g-C₃N₄ plasmonic p-n heterojunction photocatalytic system is designed and constructed for the first time. The Ag@CoFe₂O₄/g-C₃N₄ photocatalyst so designed, under the illumination of the visible-light (λ > 420 nm), produced H₂ and O₂ in 2:1 stoichiometric amount at the rates of 335 μmol h^?1 and 186 μmol h^?1, respectively, with an apparent quantum yield reaching 3.35% at 420 nm, demonstrating that Ag@CoFe₂O₄ dimer colloids are responsible for oxidation and g-C₃N₄ for reduction. Moreover, in the presence of triethanolamine, the apparent quantum yield achieved by Ag@CoFe₂O₄/g-C₃N₄ is 16.47% with hydrogen produced at the rate 3.5 times higher than the CoFe₂O₄/g-C₃N₄ heterojunction photocatalyst with AQY of 5.49%. The combination of Ag plasmonic effect and internal electric field established at the interface of p-type CoFe₂O₄ and n-type g-C₃N₄ boosts the separation efficiency of photoexcitons from CoFe₂O₄ to g-C₃N₄, extending the visible-light absorption capacity of the systems. The generation of optimum amount of defects like oxygen vacancies at the p-n heterojunction interface due to the structural distortion of CoFe₂O₄ also plays a prominent photocatalytic enhancement by providing active sites for the adsorption of water molecules for the light driven catalytic reactions. Our work introduces a potential avenue to design efficient photocatalysts by constructing several other suitable p-n heterojunction semiconductor photocatalysts toward practical application in solar energy conversion.     

Graphitic carbon nitride heterojunction photocatalysts for solar hydrogen production

Photocatalytic hydrogen production is considered as an ideal approach to solve global energy crisis and environmental pollution. Graphitic carbon nitride (g-C₃N₄) has received extensive consideration due to its facile synthesis, stable physicochemical properties, and easy functionalization. However, the pristine g-C₃N₄ usually shows unsatisfactory photocatalytic activity due to the limited separation efficiency of photogenerated charge carriers. Generally, introducing semiconductors or co-catalysts to construct g–C₃N₄–based heterojunction photocatalysts is recognized as an effective method to solve this bottleneck. In this review, the advantages and characteristics of various types of g–C₃N₄–based heterojunction are analyzed. Subsequently, the recent progress of highly efficient g–C₃N₄–based heterojunction photocatalysts in the field of photocatalytic water splitting is emphatically introduced. Finally, a vision of future perspectives and challenges of g–C₃N₄–based heterojunction photocatalysts in hydrogen production are presented. Predictably, this timely review will provide valuable reference for the design of efficient heterojunctions towards photocatalytic water splitting and other photoredox reactions.     

Morphology and defects design in g-C3N4 for efficient and simultaneous visible-light photocatalytic hydrogen production and selective oxidation of benzyl alcohol

Small surface area, deficient reaction sites, and poor visible-light harvest ability of the original graphitic carbon nitride (g-C₃N₄) severely restrict its photocatalytic H₂ production activity. Here, an ultrathin porous and N vacancies rich g-C₃N₄ (V_N-UP-CN) was fabricated by thermal oxidation exfoliation and high-temperature calcination under the Ar atmosphere. The ultrathin porous morphology increases the surface area and reaction sites of original g-C₃N₄, moreover, the produced N vacancies greatly broaden the light harvest ability of ultrathin porous g-C₃N₄ (UP–CN). Therefore, V_N-UP-CN displays the maximal H₂ production rate of 2856.7 μmol g^?1 h^?1 in triethanolamine solution under visible-light, and adding 0.5 M of K₂HPO₄ can further improve its H₂ production rate to 4043.9 μmol g^?1 h^?1. Importantly, V_N-UP-CN also shows good performance in simultaneous photocatalytic H₂ production and benzyl alcohol oxidation to benzaldehyde with the activities of 196.08 and 198.28 μmol g^?1 h^?1, respectively, which avoids the waste of sacrificial agent and photogenerated holes. This work affords an achievable way to design the efficient g-C₃N₄ photocatalyst by morphology and defect regulation, which can effectively utilize both photogenerated electrons and holes for H₂ and value-added chemical production.     

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.     

Boosting photocatalytic hydrogen evolution of g-C3N4 via enhancing its interfacial redox activity and charge separation with Mo-doped CoSx

To achieve low-cost photocatalytic hydrogen (H₂) production, it is necessary to develop low-priced transition metal co-catalysts to replace the roles of noble metals for photocatalytic H₂ evolution. Herein, a co-catalyst of Mo-doped CoS_x (Mo-CoS_x) was synthesized by using the hydrothermal procedure, then attached to g-C₃N₄ to construct a composite photocatalyst. As a co-catalyst, Mo-CoS_x can work as an electron acceptor, it is utilized to receive electrons generated by g-C₃N₄ photocatalyst on the surface of the catalyst, and inhibit the recombination of those electrons, thus showing enhanced charge transfer ability as well as reduction ability. The optimized Mo-CoS_x/g-C₃N₄ delivered a prominent photocatalytic H₂ evolution rate of 2062.4 μmol h^?1 g^?1, which was ～193 times higher than g-C₃N₄. Its AQE at 400 nm and 420 nm were 11.05% and 6.83%, respectively. This work provides a novel non-precious metal co-catalyst/g-C₃N₄ photocatalyst that is expected to be an acceptable cost route to solar energy conversion.     

Free-standing CuS–ZnS decorated carbon nanotube films as immobilized photocatalysts for hydrogen production

Free-standing carbon nanotube films (CNTF) with entangled carbon nanotubes (CNT) were used as conductive supports for the preparation of CuS–ZnS/CNTF composite as immobilized photocatalysts for H₂ production. The surface morphology, crystalline property, surface chemistry, and optical properties of the CuS–ZnS/CNTF photocatalysts were investigated. The effects of forming CuS–ZnS heterojunction and conductive CNTF on the separation of photogenerated charges and photocatalytic hydrogen production activity of CuS–ZnS/CNTF photocatalysts were evaluated by the photocatalytic hydrogen production tests. Conductive CNT films can prevent the recombination of photogenerated electron–hole pairs. The deposition of CuS nanoparticles on the ZnS/CNTF leads to higher photocatalytic activity which can be attributed to the effective electron–hole separation. Introducing ZnS and CuS makes the photocatalyst surface more hydrophilic. The porous structure contributed to the effective contact between the sacrificing agents and the photocatalysts, leading to enhanced H₂ production activity.     

Carbon vacancies improved photocatalytic hydrogen generation of g-C3N4 photocatalyst via magnesium vapor etching

Vacancies engineering was widely reported as the promising strategy for the improvement of the photocatalytic performance of semiconductor photocatalysts. In current work, carbon vacancies are constructed successfully in graphitic carbon nitride (g-C₃N₄) photocatalyst via magnesium vapor etching. Experimental results show that the formed carbon vacancies in g-C₃N₄ photocatalyst can significantly improve the photocatalytic H₂ generation performance. XRD, FTIR, SEM/TEM, XPS and PL characterization data are employed to evidence the construction of carbon vacancies, which are revealed to be the reason for the enhancement of photocatalytic H₂ evolution. This work develops an alternative route to construct carbon vacancies in g-C₃N₄ materials and gives an insight into the influence of vacancies on the photocatalytic performance of photocatalysts.