g-C3N4 particles with boron and oxygen dopants/carbon vacancies for efficient dehydrogenation in sodium borohydride methanolysis

In the study, metal-free boron and oxygen incorporated graphitic carbon nitride (B and O doped g-C₃N₄) with carbon vacancy was successfully prepared and applied as a catalyst to the dehydrogenation of sodium borohydride (NaBH₄) in methanol for the first time. The hydrogen generation rate (HGR) value was found to be 11,600 mL min^?1g^?1 by NaBH₄ of 2.5%. This is 2.53 times higher than the g-C₃N₄ catalyst without the addition of B and O. The obtained activation energy was 25.46 kJ mol^?1. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), energy dispersive X-Ray analyser (EDX), Transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR) analyses for characterization were performed. A possible mechanism of H₂ production from the reaction using metal-free B and O doped g-C₃N₄ catalyst with carbon vacancy has been proposed. This study showed that g-C₃N₄ and its composites with doping atoms can be used effectively in H₂ production by NaBH₄ methanolysis.     

Phosphorus and oxygen doped carbon-based on Spirulina microalgae as efficient metal-free catalysts to obtain H2 from methanolysis of NaBH4

Metal-free catalysts (SP–KOH–P) doped phosphorus and oxygen as a result of modification with H₃PO₄ to the surface of the activated carbon sample (SP–KOH) obtained by activation of KOH with Spirulina microalgae were used to obtain hydrogen (H₂) from methanolysis of NaBH₄. The characteristic structure of SP-KOH-P and SP-KOH metal-free catalysts were examined by XRD, TEM, elemental analysis, FTIR, and ICP-MS. The effects of the amount of catalyst, NaBH₄ concentration, reusability, and temperature on H₂ production rate from NaBH₄ methanolysis reaction were investigated. The hydrogen production rate (HGR) obtained with 25 mg SP-KOH-P was found to be 19,500 mL min^?1 g^?1. The activation energy (Ea) value of SP-KOH-P metal-free catalyst sample was calculated as 38.79 kJ mol^?1.     

Platinum deposition onto g-C3N4 with using of labile nitratocomplex for generation of the highly active hydrogen evolution photocatalysts

The chemisorption of the labile dimeric platinum nitratocomplex [Pt₂(μ-OH)₂(NO₃)₈]^2- onto graphene oxide doped graphitic C₃N₄ (g–C₃N₄–GO) was performed for the first time to prepare PtO_x/g–C₃N₄–GO composites with ionic platinum species (Pt(II)) bonded with N-donor groups of the g-C₃N₄. The thermal treatment of the obtained composites in the hydrogen atmosphere results in a gradual reduction of Pt(II) species with the formation of Pt/g–C₃N₄–GO photocatalysts. The Pt/g–C₃N₄–GO catalysts paired with TEOA sacrificing agent in an aqueous solution were tested in a photoinduced hydrogen evolution reaction under visible light (λ = 425 nm). The photocatalytic activity of prepared materials strongly influenced by the temperature of the reduction stage so that the maximal rate of H₂ evolution was revealed for the catalyst (0.5 wt% of Pt) reduced at 400 °C with a quantum efficiency of 3.0% and rate of HER of 5.1 mmol h^?1 per 1 g of photocatalysts. The photocatalytic activity of this sample was much higher than the activity of 0.5% Pt/g–C₃N₄–GO photocatalysts prepared by conventional photoreduction of H₂PtCl₆ or reduction of this precursor with NaBH₄. The Pt/g–C₃N₄–GO photocatalyst with Pt concentration of 0.1 wt% was prepared using the described protocol and shown specific activity of about 1.4 mol h^?1 per 1 g of Pt outperforming analogous material reported to date.     

Graphite carbon nitride loaded nitrogen-doped carbon and cobalt nanoparticles ternary photocatalyst for enhanced solar-driven hydrogen evolution

In this paper, we designed a composite photocatalytic system in which cobalt nanoparticles (Co NPs) are attached to nitrogen-doped carbon (N-d-C) and co-bonded to the surface of the noted photocatalyst graphite carbon nitride (g-C₃N₄), showing an excellent photocatalytic hydrogen production. The bulk g-C₃N₄ was formed in the first thermal treatment in air using melamine as a precursor. Subsequently, the secondary calcination under N₂ led to the synchronous fabrication of N-d-C/Co NPs and their combination with g-C₃N₄ to form a novel ternary photocatalyst (g-C₃N₄/N-d-C/Co NPs). Co NPs exposed on the surface of the nanomaterials endowed much more reaction sites than g-C₃N₄ for photocatalytic hydrogen production. Meanwhile, the embedded N-d-C provided an additional transfer approach for photocarriers. The as-prepared composite nanomaterials own a relatively high specific surface area of 97.45 m² g^?1 with an average pore size of 3.83 nm. As a result, compared with pristine g-C₃N₄ (～25.35 μmol g^?1 h^?1), the photocatalytic performance was increased by over 10 times (～270.05 μmol g^?1 h^?1). Our work gives a novel approach for highly active g–C₃N₄–based photocatalysts in the field of photocatalysis.     

Rich carbon vacancies facilitated solar light-driven photocatalytic hydrogen generation over g-C3N4 treated in H2 atmosphere

Graphite carbon nitride (g-C₃N₄) has caught far-ranging concern for its masses of advantages, for instance, the unique graphite-like two-dimensional lamellar structure, low cost, nontoxic, suitable bandgap of 2.7 eV and favorable stability. Whereas owing to the shortcomings of low solar absorptivity and fast recombination of photo-induced charge pairs, the overall quantum efficiency of photocatalysis for g-C₃N₄ is suboptimal, resulting in limited practicality of g-C₃N₄ (GCN). In our study, modified g-C₃N₄ materials (HCN) with ample carbon vacancies (CVs) were obtained through calcinating of g-C₃N₄ in H₂ atmosphere. Higher specific surface area and more active sites of HCN were induced by roasting of g-C₃N₄ in H₂. CVs that occurred in the N-(C₃) bond lead to the reduction of electron density around N, thus narrowing the bandgap of HCN-3h and enlarging corresponding light response capability. Under the synergistic function of abundant pore construction and CVs on HCN, the photo-excited e^?/h⁺ pairs can be memorably separated and transferred, which is favorable to photocatalytic efficiency. Among HCN, the HCN-3h sample has the highest H₂ generation rate of 4297.9 μmol h^?1 g^?1, which achieves 2.3-fold higher than that of GCN (1291.7 μmol h^?1 g^?1). This paper brings forward a meaningful method of boosting the photocatalytic performance of photocatalysts by constructing abundant CVs.     

Nickel–cobalt layered double hydroxide/NiCo2S4/g-C3N4 nanohybrid for high performance asymmetric supercapacitor

Graphitic carbon nitride (g-C₃N₄) with semiconducting nature can be considered for energy storage system by modifying its electrical conductivity and structural properties through formation of hybrid with materials such as bimetallic metal sulfide and nickel-cobalt layered double hydroxide (LDH). g-C₃N₄ as a N-rich compound with basic surface sites can change the surface properties of nanohybrid and impress the charge transfer. In this study, a nanohybrid based on nickel-cobalt LDH and sulfide and graphitic carbon nitride (NiCo LDH/NiCo₂S₄/g-C₃N₄) was synthesized through a three-step method. At first, Ni doped ZIF-67 was formed at the surface of g-C₃N₄ nanosheets and then the product was calcined in a furnace to form NiCo₂O₄/g-C₃N₄. At next step, the sample was hydrothermally converted to NiCo₂S₄/g-C₃N₄ using thioacetamide and finally modified with NiCo LDH nanoplates to form porous structure with high surface area. The NiCo LDH/NiCo₂S₄/g-C₃N₄ nanohybrid showed high specific capacitance of 1610 F g^?1 at current density of 1 A g^?1 and also excellent stability of 108.8% after 5000 cycles at potential scan rate of 50 mV s^?1, which makes it promising candidate for energy storage. An asymmetric system was prepared using nickel foams modified with NiCo LDH/NiCo₂S₄/g-C₃N₄ and g-C₃N₄ as positive and negative electrodes, respectively. The specific capacitance of 246.0 F g^?1 was obtained at 1 A g^?1 in 6 M KOH solution and system maintained 90.8% cyclic stability after 5000 cycles at potential scan rate of 50 mV s^?1. The maximum energy density and power density of the system were calculated as 82.0 Wh kg^?1 and 12,000 W kg^?1, respectively, which demonstrate its capability for energy storage.     

Accelerating photocatalytic hydrogen evolution of Ta2O5/g-C3N4 via nanostructure engineering and surface assembly

Despite that several strategies have been demonstrated to be effective for improving the catalytic hydrogen evolution activity of bulky g-C₃N₄, the large-scale hydrogen production over g–C₃N₄–based photocatalysts still confronts a big challenge. Here, a two-step calcination method is presented in constructing metal oxide/two-dimensional g-C₃N₄, i.e., Ta₂O₅/2D g-C₃N₄ photocatalyst. Thanks to the superiority of the synthetic method, nanostructure engineering forming 2D structure, and surface assembly with another semiconductor, can be realized simultaneously, in which ultrathin structure of 2D g-C₃N₄ and strong interfacial coupling between two components are two important characteristics. As a result, the structure engineered Ta₂O₅/2D g-C₃N₄ induces high photocatalytic hydrogen evolution half reaction rate of ~19,000 μmol g^?1 h^?1 under visible light irradiation (λ > 400 nm), and an external quantum efficiency (EQE) of 25.18% and 12.48% at 405 nm and 420 nm. The high photocatalytic performance strongly demonstrates the advance of the synchronous engineering of nanostructure and construction of heterostructure with tight interface, both of which are beneficial for the fast charge separation and transfer.     

Phosphorus doped carbon nanodots particles based on pomegranate peels for highly active dehydrogenation of sodium borohydride in methanol

Here, the carbon nanodots were successfully synthesized from pomegranate peels (PPCD). This obtained PPCD was treated by a hydrothermal process with phosphoric acid for P doping (P doped PPCD) and used as a metal-free catalyst to obtain hydrogen(H₂) from sodium borohydride (NaBH₄) methanolysis for the first time. The characteristics of the samples obtained by ultraviolet, fluorescence, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and Inductively coupled plasma mass spectrometry (ICP-MS) analyses were examined. NaBH₄ concentration effect, temperature effect and catalyst reusability experiments were carried out. Using 10 mg of the catalyst with 2.5% NaBH₄, an HGR value of 13000 mL min^?1g^?1 was obtained. The activation energy (Ea) for the P-doped PPCD catalyst was 30.96 kJ mol^?1.     

One-pot calcination preparation of graphene/g–C3N4–Co photocatalysts with enhanced visible light photocatalytic activity

Photocatalytic technology for hydrogen evolution from water splitting and pollutant degradation is one of the most sustainable methods. Here, the graphene/g–C₃N₄–Co composite materials have been prepared by one-pot calcination method. The results show that g-C₃N₄ grow on the surface of graphene and form a sandwich structure, meanwhile, the introduction of Co increases the active sites, which promotes the photocatalytic performance. The influences of graphene and Co content on photocatalytic activity were also studied by UV–visible spectrophotometry (DRS), photoluminescence spectroscopy (PL), photocurrent, degradation MB, and hydrogen production. The apparent reaction rate constant k of graphene/g–C₃N₄–Co (3%) is 0.946 h⁻¹, which is 4.90 and 2.18 times faster than g-C₃N₄ and graphene/g-C₃N₄, respectively. And the hydrogen production rate of graphene/g–C₃N₄–Co (3%) (892.3 μmol h⁻¹ g⁻¹) is 3.53 and 1.61 times higher than g-C₃N₄ and graphene/g-C₃N₄, respectively.     

Synergistic enhancement of photocatalytic H2 production by Ni decorated 2D bubble-like carbon nitride

In this paper, a novel 2D bubble-like g-C₃N₄ (B–CN) with a highly porous and crosslinked structure is successfully synthesized via a cost-effective bottom-up process. The as-prepared B–CN photocatalyst delivers a considerably expanded specific surface area and increased active sites. Moreover, the 2D bubble-like structure can afford shortened diffusion paths for both photogenerated charge carriers and reactants. As a result, the photocatalytic H₂ evolution rate of B–CN reached 268.9 μmol g^?1 h^?1, over 5 times more than that of bulk C₃N₄. The Ni ions were further deposited on B–CN as a cocatalyst to enhance the photocatalytic activity. Benefit from the synergy of 2D bubble-like structure and Ni species cocatalyst, recombination of photoinduced charges was greatly inhibited and the hydrogen evolution reaction (HER) was significantly accelerated. The resulted catalyst achieved a dramatically high H₂ evolution rate of 1291 μmol g^?1 h^?1. This work provides an alternative way to synthesize novel porous carbon nitride together with non-noble metal cocatalysts toward enhanced photocatalytic activity for H₂ production.     

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.     

Construction of carbon dots modified hollow g-C3N4 spheres via in situ calcination of cyanamide and glucose for highly enhanced visible light photocatalytic hydrogen evolution

In this work, a series of carbon dots (CDs) modified hollow g-C₃N₄ spheres (HCNS-C_x) were constructed via a double in situ approach using cyanamide and glucose as precursors, respectively. As HCNS-C_x was synthesized by one-step in situ thermal polymerization of two precursors, which could make CDs and g-C₃N₄ keep tight connection and increase the separation of the photogenerated electron-hole pairs. The average diameter and wall thickness of the HCNS-C_x are about 355 nm and 55 nm, respectively. Under the visible light irradiation, the H₂ evolution rate (HER) of HCNS-C_1.0 (2322 μmol g^?1 h^?1) was 19 times that of bulk g-C₃N₄ (122 μmol g^?1 h^?1) and 1.8 times that of HCNS without CDs modification (1289 μmol g^?1 h^?1), respectively. And its apparent quantum efficiency is 17.93% at 420 nm. The specific surface area, light absorption capacity, and charge carrier mobility of HCNS-C_x could be dramatically improved due to the introduction of CDs and hollow structures of g-C₃N₄ spheres, resulting in a significant improvement of photocatalytic activity.     

Co/CuO–NiO–Al2O3 catalyst for hydrogen generation from hydrolysis of NaBH4

This paper presents hydrogen generation measurements from the hydrolysis of NaBH₄ aqueous solutions catalyzed by Co doping on single, bimetallic and trimetallic oxide supports (Co/CuO, Co/NiO, Co/Al₂O₃, Co/NiO–Al₂O₃, Co/CuO–Al₂O_3, and Co/CuO–NiO–Al₂O₃). Support materials are synthesized by the co-precipitation method. Then, Co is doped into support materials by the impregnation method. It is found that Co/CuO–NiO–Al₂O₃ catalyst exhibited high reaction activity with a maximum hydrogen generation rate (HGR) of 2067.2 ml min^?1 g_cat^?1 at 25 °C. The effect of temperature of the solution, Co amount, and recyclability of the catalyst on hydrogen generation with Co/CuO–NiO–Al₂O₃ catalyst is investigated in detail. In addition, the highest HGR for Co/CuO–NiO–Al₂O₃ catalyst is obtained at 55 °C as 6460.0 ml min^?1 g_cat^?1. The activation energy is calculated to be 31.59 kJ mol^?1 using Co/CuO–NiO–Al₂O₃ catalyst. Co/CuO–NiO–Al₂O₃ catalyst exhibits zero-order reaction kinetics concerning NaBH₄ concentration. In addition, the Co/CuO–NiO–Al₂O₃ catalyst provided high reusability after 5 cycles.     

Facile construction of composition-tuned ruthenium-nickel nanoparticles on g-C3N4 for enhanced hydrolysis of ammonia borane without base additives

Developing high-efficiency and low-cost catalysts for hydrogen evolution from hydrolysis of ammonia borane (AB) is significant and critical for the exploitation and utilization of hydrogen energy. Herein, the in-situ fabrication of well-dispersed and small bimetallic RuNi alloy nanoparticles (NPs) with tuned compositions and concomitant hydrolysis of AB are successfully achieved by using graphitic carbon nitride (g-C₃N₄) as a NP support without additional stabilizing ligands. The optimized Ru₁Ni_7.5/g-C₃N₄ catalyst exhibits an excellent catalytic activity with a high turnover frequency of 901 min^?1 and an activation energy of 28.46 kJ mol^?1 without any base additives, overtaking the activities of many previously reported catalysts for AB hydrolysis. The kinetic studies indicate that the AB hydrolysis over Ru₁Ni_7.5/g-C₃N₄ is first-order and zero-order reactions with respect to the catalyst and AB concentrations, respectively. Ru₁Ni_7.5/g-C₃N₄ has a good recyclability with 46% of the initial catalytic activity retained even after five runs. The high performance of Ru₁Ni_7.5/g-C₃N₄ should be assigned to the small-sized alloy NPs with abundant accessible active sites and the synergistic effect between the composition-tuned Ru–Ni bimetals. This work highlights a potentially powerful and simple strategy for preparing highly active bimetallic alloy catalysts for AB hydrolysis to generate hydrogen.     

Active-center-enriched Ni0.85Se/g-C3N4 S-scheme heterojunction for efficient photocatalytic H2 generation

Photocatalysts with abundant active sites are essential for photocatalytic H₂ evolution from water. Herein, Ni_0.85Se-deposited g-C₃N₄ was obtained by a physical solvent evaporation method. The investigation shows that Ni_0.85Se with unsaturated active Se atoms can significantly improve the photocatalytic activity of g-C₃N₄, and the H₂ production rate of Ni_0.85Se/g-C₃N₄ can reach 8780.3 μmol g^?1 h^?1, which is 3.5 and 92.9 times higher than that of Ni_0.85+xSe/g-C₃N₄ (2497.9 μmol g^?1 h^?1) and pure g-C₃N₄ (94.5 μmol g^?1 h^?1), respectively. This improvement can be attributed to the quick charge transfer between Ni_0.85Se and g-C₃N₄ with S-scheme heterojunction feature based on a series of trapping experiments and photoelectrochemical analysis. Moreover, abundant unsaturated Se atoms could provide more H₂ evolution active sites. This work sheds light on the construction of heterojunctions with abundant active sites for H₂ production.     

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.     

Visible-light-enhanced catalytic hydrolysis of ammonia borane using RuP2 quantum dots supported by graphitic carbon nitride

Hydrolytic dehydrogenation of ammonia borane (AB) driven by efficient catalysts has attracted considerable attention and is regarded as a promising strategy for hydrogen generation. Herein, RuP₂ quantum dots supported on graphitic carbon nitride (g-C₃N₄) were successfully prepared by in-situ phosphorization, yielding a highly efficient photocatalyst toward AB hydrolysis. The catalysts were characterized by field-emission scanning electron microscopy, transmission electron microscopy, x-ray diffraction, x-ray photoelectron microscopy, inductively coupled plasma atomic emission spectroscopy, UV–visible diffuse reflectance spectroscopy and photoluminescence spectroscopy. A conventional water-displacement method was employed to record the hydrogen volume as a function of reaction time. Owing to visible-light irradiation, the initial turnover frequency of the AB hydrolysis was significantly enhanced by 110% (i.e., 134 min^?1) at room temperature. Furthermore, the apparent activation energy decreased from 67.7 ± 0.9 to 47.6 ± 1.0 kJ mol^?1. The photocatalytic hydrolysis mechanism and catalyst reusability were also investigated.     

Magnetic Fe3C@C nanoparticles as a novel cocatalyst for boosting visible-light-driven photocatalytic performance of g-C3N4

In photocatalytic field, it is a significant challenge to synthesize cocatalyst with high performance, noble-metal free and facile methods to recycle. Herein, carbon layer coated Fe₃C (Fe₃C@C) nanoparticles were prepared by one-step method and for the first time utilized as highly efficient cocatalysts for improving visible-light-driven hydrogen evolution activity of g-C₃N₄. The photocatalytic hydrogen evolution rate of optimal Fe₃C@C/g-C₃N₄ was about 27.2 times of bare g-C₃N₄ samples. Furthermore, the Fe₃C@C/g-C₃N₄ composite catalyst showed excellent stability and reusability. The apparent quantum yield (AQY) of the optimized FeC@C/g- C₃N₄ reaches 0.501% and 0.124% at 400 nm and 420 nm, respectively. The AQY of the FeC@C/g- C₃N₄ is 26.2 times higher than that of g-C₃N₄ at 400 nm Fe₃C@C has an extraordinary cocatalytic effect for g-C₃N₄ photocatalytic hydrogen evolution mainly due to three aspects: Firstly, the Fe₃C acts as a trap to lure electrons because of its lower Fermi energy level and higher conductivity, which can increase the hydrogen production activity by trapping the photogenerated electrons produced by g-C₃N₄; Secondly, the coated carbon layer can provide chemical protection for Fe₃C nanoparticles and promote the transfer of photogenic electrons, thus further improving the efficiency and stability of photocatalytic hydrogen production; Thirdly, the strong magnetic property of Fe₃C@C nanoparticles gives Fe₃C@C/g-C₃N₄ photocatalysts the advantages of low cost and high recovery efficiency. It is believed that this work provides a new strategy and possibility for the application of photocatalytic hydrogen production.     

Exfoliated and plicated g-C3N4 nanosheets for efficient photocatalytic organic degradation and hydrogen evolution

Exfoliated and plicated g-C₃N₄ nanosheets (CNsF) were prepared through a thermal-chemical exfoliation in which the bulk g-C₃N₄ was obtained first under thermal exfoliation, and then was exposed to an acidic etching using hydrofluoric acid under hydrothermal condition. The acidic etching not only exfoliated g-C₃N₄ nanosheets by disrupting weak van der Waals forces between layers, which led to formation of a monolayer or a few layers of g-C₃N₄ nanosheets, but also made disordered defects on its surface and created plicated g-C₃N₄ nanosheets. Under visible-light illumination, the optimized sample (CNsF-6%) showed a hydrogen evolution rate of 54.13 μmol h^?1g^?1 (without co-catalyst) and a specific surface area of 121.4 m² g^?1, which were about 4.7 and 2.5 times, respectively, higher than pristine g-C₃N₄. It also showed remarkably enhanced photocatalytic performance in removing various organic pollutants. This remarkable improvement probably arises from the porous nanosheets and an increased number of active sites resulting from the CNsF, which subsequently enhanced the charge separation efficiency. This work provided an alternative way to obtain highly active g-C₃N₄ photocatalysts.     

In-situ synthesis of ternary heterojunctions via g-C3N4 coupling with noble-metal-free NiS and CdS with efficient visible-light-induced photocatalytic H2 evolution and mechanism insight

The two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) nanosheets based composites are prepared in the form of the NiS/g-C₃N₄, CdS/g-C₃N₄ and CdS/NiS/g-C₃N₄ using a facile and reliable method of chemical deposition. The TEM and HRTEM images demonstrated a spectacular representation of the 2D lamellar microstructure of the g-C₃N₄ with adequately attached CdS and NiS nanoparticles. The changes in crystallinity and the surface elemental valence states of composites with the incorporation of two metal sulphides are studied, which confirmed the formation of composites. The photocatalytic response of the composites was estimated by photodegradation of Rhodamine B (C₂₈H₃₁ClN₂O₃–RhB), and the ternary composite CdS/NiS/g-C₃N₄ samples exhibited the superior photocatalytic performance. Further, the free radical capture and electron paramagnetic resonance (EPR) spectroscopy experiments identified the main active species that contributed to the photocatalytic reaction. Besides, the samples’ photocatalytic performance was evaluated by photocatalytic hydrogen production. The stability of the performance-optimized composite was determined by employing cyclic experiments over five cycles. The CdS/NiS/g-C₃N₄ showed the highest efficiency of hydrogen production i.e. about 423.37 μmol.g^?1.h^?1, which is 2.89 times that of the pristine g-C₃N₄. Finally, two types of heterojunction structures were proposed to interpret the enhanced photocatalytic efficiency.