Graphitic carbon nitride/few-layer graphene heterostructures for enhanced visible-LED photocatalytic hydrogen generation

Few-layer graphene (FLG, 2–7 nm thickness) prepared by catalytic chemical vapour deposition (c-CVD), and bulk graphitic carbon nitride (g-C₃N₄; GCN) were assembled to develop novel 2D/2D xFLG_y/GCN heterostructures. The impact of FLG loading and morphology on the activity of GCN has been evaluated towards H₂ generation from water splitting under visible-LED irradiation. The heterostructures, characterised by UV–vis DRS, photoluminescence, EPR, Raman, AFM, XRD, XPS, SEM/TEM/STEM and photocurrent, present strong interfacial interaction and show higher photocatalytic activity than pure GCN. The best performing material, 2FLG₁₀/GCN, generated 1274 g^?1 h^?1 of H₂, i.e., 4-times higher than pure GCN. The improved photoactivity was ascribed to a synergistic effect between GCN and FLG, owing to: i) efficient charge separation of photoinduced electron-hole pairs through electron transfer from GCN to FLG, ii) increased surface area, and iii) enhanced visible light absorption. Moreover, the best performing composite presents high stability after four successive cycles with no significant change in its activity.     

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.     

Noble metal-free cuprous oxide/reduced graphene oxide for enhanced photocatalytic hydrogen evolution from water reduction

Cu₂O loaded reduced graphene oxide (Cu₂O/RGO) was prepared via a one-step in-situ reduction method. Composition and structure of the Cu₂O/RGO were characterized by X-ray diffraction, high resolution transmission electron microscope and X-ray photoelectron spectroscopy. With eosin Y (EY) and rose bengal (RB) as co-sensitizers, the activity of hydrogen evolution over the Cu₂O/RGO dramatically increased and achieved a maximum when the loading amount of Cu on the RGO was about 3 wt.%. It exceeded that of RGO and Cu₂O by a factor of 7.3 and 4.2 at the same conditions, respectively. It could be even comparable to that of the Pt/RGO under the same reaction conditions. This work showed a possibility of utilizing Cu₂O as an alternative for noble metals (such as Pt) due to its low cost and high performance in photocatalytic hydrogen production.     

Based on amorphous carbon C@ZnxCd1-xS/Co3O4 composite for efficient photocatalytic hydrogen evolution

In this work, C@Zn_xCd_1-xS/Co₃O₄ catalyst which with high hydrogen production activity was prepared and the catalyst was characterized by SEM, TEM, XRD, XPS, Uv–vis DRS characterization. After two-step modification, the light absorption intensity of C@Zn_xCd_1-xS and C@Zn_xCd_1-xS/Co₃O₄ showed an increasing trend compared with pure Zn_xCd_1-xS, such phenomenon was beneficial to the visible light absorption and utilization of photocatalyst. In addition, Mott-Schottky proved that Zn_xCd_1-xS catalyst formed p-n heterojunction with Co₃O₄ nanoparticles, which further demonstrated that the modification of Zn_xCd_1-xS by Co₃O₄ was successful. And the hydrogen production of C@Zn_xCd_1-xS/Co₃O₄ (30%) (1405.1 μmol) was 6.9 times that of pure Zn_xCd_1-xS. The improvement of photocatalytic performance can be attributed to that carbon particles accelerate the storage and transfer of electrons, and the formation of p-n heterojunction between Co₃O₄ and Zn_xCd_1-xS promotes the separation of photogenerated carriers effectively. In this study, the introduction of amorphous carbon and Co₃O₄ promoted the transfer and separation of electrons and holes greatly, thereby inhibited the recombination of carriers and provided the favorable conditions for the preparation of highly efficient and stable photocatalysts.     

In situ modification of Co-MOF with graphene oxide for enhanced photocatalytic hydrogen production

Metal-organic frameworks (MOFs) are one of the most promising precursors for the fabrication of advanced photocatalysts. In this report, we present a stable in water MOF based on earth-abundant cobalt (Co-BDC) as a highly active catalyst for visible-light-driven H₂ generation. The rate of H₂ production sensitized by eosin Y (EY) over Co-BDC reached 14.5 mmol g^?1 h^?1. By in situ addition of graphene oxide suspension to the photocatalytic system, the hydrogen production efficiency was further enhanced by a factor of 6.6.     

CuS-modified ZnO rod/reduced graphene oxide/CdS heterostructure for efficient visible-light photocatalytic hydrogen generation

Solar energy utilization is a promising strategy for the photocatalytic generation of H₂ from water. Herein, a CuS-modified ZnO rod/reduced graphene oxide (rGO)/CdS heterostructure was fabricated via Cu-induced electrochemical growth with Zn powder at room temperature. The resulting powder revealed good interfacial bonding and promoted photoexcited carrier transport. The CuS nanoparticles played a pivotal role in enhancing visible-light responses and demonstrated excellent catalytic performance. A high visible-light photocatalytic H₂ generation rate of 1073 μmol h⁻¹ g⁻¹ was obtained from the CuS–ZnO/rGO/CdS heterostructure containing 0.23% CuS and 1.62% CdS. Increased photoexcited electron lifetimes, improved carrier transport rates, and decreased fluorescence intensities confirmed the synergistic effects of each of the components of the heterostructure. This study provides an innovative strategy for constructing multi-component heterostructures to achieve efficient visible-light H₂ evolution.     

Nanocomposite of BiPO4 and reduced graphene oxide as an efficient photocatalyst for hydrogen evolution

Nanocomposites of BiPO₄ and reduced graphene oxide (BiPO₄/RGO) synthesized by hydrothermal method, hydrazine reduction, and UV-assisted photoreduction method were studied as photocatalysts for hydrogen evolution from ethanol aqueous solution under irradiation. The incorporation of RGO into BiPO₄ significantly enhanced the photocatalytic activity for H₂ evolution, and the photocatalytic activity increases in the order of BiPO₄/RGO-hydrothermal > BiPO₄/RGO-photoreduction > BiPO₄/RGO-hydrazine. The optimum proportion of GO is 2 wt% for all the samples prepared by different methods. The rate of H₂ production calculated for BiPO₄/RGO-hydrothermal (with 2 wt% GO) nanocomposite was about 306 μmol/h/g, which was almost 2 times as high as that for bare BiPO_4. The XRD, Raman and XPS characterization suggested that the original GO was successfully reduced to RGO. The more intimate contact between BiPO₄ and RGO, the higher photocurrent responses and the higher reduction degree of RGO was consistent with the higher photocatalytic performance.     

Regulated effect of organic small molecular doped in carbon nitride skeleton for boosting photocatalytic hydrogen evolution

Organic small molecules doping in polymer carbon nitride (PCN) skeleton can dramatically improve photocatalytic performance owing to its effective regulation effect on molecular and electronic structure. Here, a new PCN-based photocatalyst is obtained via polymerization of urea with 1-benzyl-3-phenylthiourea (BPT). The doping effect of BPT in PCN skeleton directly adjusts the hybridization states and delocalization of molecular orbitals, so that the visible light harvest ability, adsorption capacity, charge separation efficiency and transfer kinetics are improved significantly. Consequently, the photocatalytic hydrogen evolution reaction (HER) rate reaches to 125.0 μmol h⁻¹ over the optimal PCN-BPT₁₅ photocatalyst, which is as 13.9 times as PCN (9.0 μmol h⁻¹). Noteworthily, a high apparent quantum efficiency (AQE) of 24.2% is achieved at 420 nm for photocatalytic HER. This work enriches the functionalized investigations of PCN-like photocatalysts by insight into regulated effect of organic small molecules in the skeleton for photocatalytic applications.     

High UV/visible light activity of mixed phase titania: A generic mechanism

Synergistic effect of the mixed phase in titania photocatalyst on its performance compared to the pristine phases has been investigated in terms of the bulk and interfacial behavior of the phases in contact. The experiments were conducted under both UV and visible light irradiations. The photoactivity variation has been correlated with the changes in the ratio of anatase to rutile phases (A/R ratio), and their unique response to UV and visible radiations. For this, a set of pure (rutile or anatase) and mixed phases (with varying A/R ratio) titania nanoparticles were synthesized. The physico-chemical characterization was done using SEM, XRD, EDAX, UV-DRS, PL and FTIR analyses. The activity of catalysts in UV and visible light was investigated by monitoring the degradation of phenol. The results show that the mixed phase catalysts show enhanced photoactivity compared to pristine phases across the irradiation wavelength range. Further, the catalysts having a narrow range of high A/R ratio (>1) around 5.0 show high UV activity while those having low A/R ratio (<1) around 0.5 show high visible light activity. A mechanism is proposed based on the influence of interfacial phenomena under both UV and visible light irradiations. It explains the differences observed in the behavior of the catalyst irradiated with UV and visible light and also the high activity of mixed phase catalysts compared to the pristine phases across the wavelength ranges.     

Noble metal free efficient photocatalytic hydrogen generation by TaON/CdS semiconductor nanocomposites under natural sunlight

Tantalum oxynitride have narrow band gap and its band potentials are suitable for visible light induced hydrogen generation. However, due to fast electron-hole recombination, the efficiency of photocatalytic hydrogen evolution reaction is very low. Herein, we have synthesized semiconductor heterojunction photocatalyst, i.e., TaON/CdS with suitable band positions by a simple precipitation method. Ratio between two semiconductors is optimized to obtain maximum hydrogen evolution. XRD, XPS and TEM analysis demonstrate the formation of heterojunction between these semiconductors. Among the synthesized catalysts, 3% TaON/CdS heterostructure exhibits the highest hydrogen evolution activity with H₂ production rate of 7.5 mmol h⁻¹ under natural solar light, whereas the rate is 11 mmol h⁻¹ under the visible light generated by xenon (Xe) lamp without the addition of any noble metal as the co-catalyst. The CdS and 3% TaON/CdS nanomaterials show an AQE of 5.1% and 12.2%, respectively. Combination of Mott-Schottky, UPS and DR UV–visible spectroscopy studies revealed the formation of S scheme semiconductor heterojunction between these nanomaterials with valence, conduction band positions, i.e., 1.46, −0.78 eV for CdS and 2.19, −0.66 eV for TaON, respectively. These band positions help in efficient e-h pair separation to produce hydrogen from water.     

Enhancement of photocatalytic hydrogen production by liquid phase plasma irradiation on metal-loaded TiO2/carbon nanofiber photocatalysts

Enhanced hydrogen production by photocatalytic decomposition was assessed using liquid phase plasma over metal-loaded photocatalysts. Effects of irradiation of the liquid phase plasma were evaluated in the photocatalytic hydrogen production of hydrogen. Carbon nanofiber was introduced as photocatalytic support for the Ni-loaded TiO₂ photocatalyst. The influence of addition of organic reagents into water on hydrogen evolution was also evaluated. The photocatalytic decomposition by irradiation of the liquid phase plasma without photocatalyst produced some hydrogen evolution. The rate of hydrogen evolution was improved by the metal loading on the TiO₂ surface. The carbon nanofiber acted as a useful photocatalytic support for the fixation of TiO₂. Hydrogen evolution was enhanced by the Ni loading on the TiO₂ nanocrystallites supported on the carbon nanofiber support. Hydrogen evolution was increased significantly by the addition of organic reagents, which acted as a type of sacrificial reagent promoting photocatalysis.     

A 3D peony-like sulfur-doped carbon nitride synthesized by self-assembly for efficient photocatalytic hydrogen production

Photocatalytic hydrogen evolution reaction (HER) provides a new way for the development of clean energy. Herein, a high-performance peony-like 3D structure S-doped carbon nitride (SCNx) with a large specific surface area was synthesized through a universal and non-thermal polymerization template-free approach. As an additional component, the introduction of trithiocyanuric acid in the raw material led to the formation of supramolecular intermediates through hydrogen bond self-assembly, and the sulfur was introduced into the framework of g-C₃N₄ subsequently. The charge separation lifetime of SCNx was studied by transient absorption spectroscopy, and the reason for its excellent optical performance was revealed from a dynamic perspective. Furthermore, the resulting SCNx composite material shows significant photocatalytic hydrogen release performance under visible light irradiation. In particular, the photocatalytic hydrogen rate of SCN1.0 reached 567.7 μmol/h, which was almost 53 times that of BCN, and was also 2.3 times that of SCN0 obtained by the binary self-assembly of melamine and cyanuric acid. Our finding advances the application of simple, environmentally friendly, and scalable strategy for the synthesis of high-performance sulfur-doped g-C₃N₄ photocatalysts.     

Microwave-assisted synthesis of edge-grafted carbon nitride by triazole rings for efficient photocatalytic hydrogen evolution

Copolymerization of conjugated nitrogen heterocycles within carbon nitride nowadays is proven to be a successful strategy to promote charge separation. Here, a novel edge-grafted carbon nitride nanosheets by triazole rings were synthesized from the copolymerization of dicyandiamide and 3-amino-1, 2, 4-triazole via microwave-assisted heating with improved yield. Based on the building of a feasible donor-acceptor (D-A) system by such edge grafting, the rapid charge transfer pathways were formed. Benefiting from the thin-layer structure of carbon nitride via microwave-assisted heating and abundant π electrons by intramolecular doping, the system showed enhanced visible light absorption from n-π1 electrons transition, facile charge separation and transfer, and then an increased H₂ evolution rate (637.58 μmol h⁻¹ g⁻¹), which is 17.43 times than the triazole modified sample from conventional thermal condensation method. This work enlightens an innovative pathway for the regulation of carbon nitride photocatalysts by conjugated nitrogen heterocycles for efficient solar energy conversion applications.     

Nanocomposite of graphene oxide with nitrogen-doped TiO2 exhibiting enhanced photocatalytic efficiency for hydrogen evolution

The application of hydrogen energy potentially addresses energy and environmental problems. In order to improve the photocatalytic efficiency, nanocomposite of N-doped TiO₂ with graphene oxide (NTG) is prepared and characterized with Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), photoluminescent spectra. The application of NTG to hydrogen evolution exhibits high photocatalytic efficiency of 716.0 or 112.0 μmol h⁻¹ g⁻¹ under high-pressure Hg or Xenon lamp, which is about 9.2 or 13.6 times higher than P25 photocatalyst. This is mainly attributed to the N-doping of TiO₂ and the incorporation of graphene oxide resulting in narrow band gap, together with the synergistic effect of fast electron-transporting of photogenerated electrons and the efficient electron-collecting of graphene oxide retarding charge recombination. These results provide a significant theoretical foundation for the potential application of N-doping photocatalysts to hydrogen evolution.     

Functionalized role of highly porous activated carbon in bismuth vanadate nanomaterials for boosted photocatalytic hydrogen evolution and synchronous activity in water

Energy crises and water pollution have become the key challenges in current era of technology. In this research work, activated carbon modified BiVO₄ photocatalysts have been prepared using simple hydrothermal methods for efficient hydrogen evolution through water splitting under visible light irradiation and degradation, simultaneously. The properties of the synthesized photocatalysts were studied through SEM, UV, XRD, BET and PL emission spectroscopy. The 4%AC/BiVO₄ exhibited highest degradation efficiency ≈98% in 60 min and production of hydrogen energy ≈510 h⁻¹g⁻¹ which is much higher when compared to pure BiVO₄. The enhancement in the efficiency was due to large surface area, large absorption region. High crystallinity, small band gap and synergetic effect between the composites. The activated carbon based BiVO₄ composites showed high stability which shows its vital role in practical applications.     

Increasing electron transfer and light absorption in graphited nanocarbon-conjugated g-C3N4 nanosheet heterostructure for photocatalytic hydrogen evolution

Accelerating the charge separation and transfer as well as increasing the visible light absorption is of great importance for photocatalysts to realize efficient photocatalytic hydrogen evolution via water splitting. Herein, for the first time, we fabricated in-plane graphited nanocarbon-conjugated polymeric carbon nitride (GNC-C₃N₄) nanosheet heterostructure photocatalyst from melamine and hexaketocyclohexane octahydrate mixture via an amino-carbonyl reaction. The incorporation of GNC into conjugate network of C₃N₄ can not only dramatically enhance the light harvesting but also significantly promote the charge separation and transfer by the built-in electric field and intimate interface in the coplanar GNC-C₃N₄ heterostructure. Accordingly, the optimal GNC-C₃N₄ photocatalyst demonstrates a more than 15-fold enhancement for photocatalytic hydrogen evolution from water under visible light irradiation, compared to C₃N₄.     

A critical review on core/shell-based nanostructured photocatalysts for improved hydrogen generation

Photocatalytic water splitting into gaseous hydrogen and oxygen in the presence of semiconductor photocatalysts under a visible spectrum of solar irradiation is one of the most promising processes for plummeting energy demands and environmental pollution. Among the successful photocatalytic materials, the core/shell nanostructures show promising results owing to their fascinating morphology that protects the surface features of the core besides the effective separation of photo-excitons resulting in an enhanced rate of hydrogen production up to 162 mmol h⁻¹g⁻¹_cat, which is a notable highest value reported in the literature. In this review, we have focused on the basic characteristics of the core-shell structure-based semiconductor photocatalytic systems and their efficient water-splitting reactions under light irradiation. Comprehensive detail on various synthesis methods of core-shell nanostructures, shell thickness-dependent properties, charge-transfer reaction mechanisms, and photocatalytic stability are highlighted in this review. Core-shell nanostructured materials have been extensively used as a photocatalyst, co-catalyst, and by coupling with supporting materials to improve the apparent quantum efficiency up to 45.6%. Besides, important photocatalytic properties that influence the redox reactions i.e., effective exciton separation, the effect of different light sources/wavelengths, surface charge modeling, photocatalytic active sites, and turnover frequency (TOF) have also been focused on and extensively described. Finally, the present and future prospects of the core-shell nanostructured photocatalysts for solar energy conversion into green hydrogen production have been expounded.     

ZnIn2S4/In(OH)3 hollow microspheres fabricated by one-step l-cysteine-mediated hydrothermal growth for enhanced hydrogen production and MB degradation

An intervening barrier for photocatalytic water decomposition and pollutant degradation is the frustratingly quick recombination of e⁻ - h⁺ pairs. Delicate design of heterojunction photocatalysts by coupling the semiconductors at nanoscale with well-matched geometrical and electronic alignments is an effective strategy to ameliorate the charge separation. Here a facile and environment-friendly l-cysteine-assisted hydrothermal process under weakly alkaline conditions is demonstrated for the first time to fabricate ZnIn₂S₄/In(OH)₃ hollow microspheres with intimate contact, which are verified by XRD, SEM, (HR)TEM, XPS, N₂ adsorption-desorption, UV–Vis DRS and photoluminescence spectra. ZnIn₂S₄/In(OH)₃ heterostructure (L-cys/Zn²⁺ = 4, molar ratio) with a band-gap of 2.50 eV, demonstrates the best photocatalytic performance for water reduction and MB degradation under visible light, outperforming its counterparts (In(OH)₃ and ZnIn₂S₄). The excellent activity of ZnIn₂S₄/In(OH)₃ heterostructure arises from the intercrossed band-edge positions as well as the unique hollow structure with large surface area and wide pore-size distribution, which are beneficial for the efficient charge migration from bulk to surface as well as at the interface between ZnIn₂S₄ and In(OH)₃. This work provides an efficient and eco-friendly strategy for one-pot synthesis of heterostructured composites with intimate contact for photocatalytic application.     

In situ growth of nickel phosphide nanoparticles on inner wall of graphitic carbon nitride tubes for efficient photocatalytic hydrogen evolution

A facile two-step approach is employed to prepare novel Ni₂P@CNT hybrid photocatalyst, which is assembled by nickel phosphide (Ni₂P) nanoparticles on the inner wall of graphitic carbon nitride tube (CNT). This unique microstructure endows Ni₂P@CNT with close interfacial interaction, promotes efficient separation of photoexcited charge carriers and provides enriched sites for photocatalytic reaction. Moreover, the hybrid system is found to exhibit more superior photocatalytic hydrogen evolution activity than pure CNT and Pt-decorated CNT (Pt@CNT). As a consequence, the work illustrates the essential role of experimental process on the final morphology and performance, which is expected to pave a new method to construct various kind of excellent photocatalyst.     

Properly aligned band structures in B-TiO2/MIL53(Fe)/g-C3N4 ternary nanocomposite can drastically improve its photocatalytic activity for H2 evolution: Investigations based on the experimental results

The development of new tools that could meet the demand of sustainable energy production has attracted worldwide scientific attention. Over the past few decades, significant research efforts have been carried out to efficiently reduce water to H₂ (green fuel) over semiconductor photocatalysts. Numerous semiconductor photocatalysts have been employed in photocatalysis for optimum H₂ production. All the techniques were chosen based on their flexibility, cost-effectiveness, and ease of availability. Recently, polymeric carbon nitride (g-C₃N₄) received worldwide attention in visible light photocatalysis for energy and environmental applications due to its low price, robust nature, and superior thermal stability. Nevertheless, g-C₃N₄ (CN) exhibits shortfalls such as high charge carrier's recombination rate and weak reduction ability. To overcome these drawbacks, herein, for the first time we have fabricated B-TiO₂/MIL-53(Fe)/CN ternary composite via hydrothermal and wet-chemical methods. The resultant B-TiO₂/MIL53(Fe)/CN ternary composite shows drastically improved photocatalytic activity for hydrogen evolution compared to the bare CN, B-TiO_2, and MIL53(Fe) components. The B-TiO₂/MIL53(Fe)/CN ternary composite produced approximately 166.3 and 581.2 μmol h^?1 g^?1 of hydrogen under visible light and UV–visible light irradiations, respectively, with the assistance of co-catalyst Pt. Photo-luminescence (PL) and the fluorescence (FL) spectroscopy measurements reveal that the enhanced photoactivity is due to the greatly promoted charge carrier's separation and transfer at the interfacial contact of the well-aligned three-component systems. This work will promote the design and development of efficient photocatalyst based on CN for clean energy production and environmental purification.