Strong organic acid-assistant synthesis of holey graphitic carbon nitride for efficient visible light photocatalytic H2 generation

A facile and cost-effective method was developed for the synthesis of holey N-deficient graphitic carbon nitride nanosheets (FCN) using trifluoroacetic-acid-treated urea as a precursor. The role of trifluoroacetic acid on the composition, structure and photocatalytic performance of the prepared catalysts was carefully investigated. The obtained samples displayed laminated porous morphology with nitrogen defects, larger specific surface areas, extended range of spectral response and enhanced electron mobility of charge carriers. Consequently, the optimized catalyst FCN-400 exhibited superb photocatalytic performance and excellent cycling stability for hydrogen evolution. The hydrogen evolution rate over FCN-400 reached 309.3 μmol/h under visible light irradiation, which is 11.3-fold of that of urea-derived graphitic carbon nitride (27.3 μmol/h).     

Bamboo-charcoal-loaded graphitic carbon nitride for photocatalytic hydrogen evolution

Crystalline graphitic carbon nitride is an excellent photocatalyst for hydrogen production due to its non-toxicity, stability, elemental abundance, and visible-light response. Herein, we present a new type of composite photocatalysts, eco-friendly bamboo-charcoal-loaded graphitic carbon nitrides to accelerate the separation of electron-hole pairs. The suitable loading of bamboo charcoal on graphitic carbon nitrides shows an increased specific surface area from 85 to 120 m² g^?1, and excellent visible-light photocatalytic hydrogen production activity of 4.1 mmol g^?1 h^?1, which is 2.3 times higher than that of pristine carbon nitride (1.8 mmol g^?1 h^?1). Under irradiation, the photogenerated electrons fast migrate from graphitic carbon nitride to bamboo charcoal through an ohmic contact between them, reducing the recombination of electron-hole pairs. This study highlights the effect of carbonaceous material loading on photocatalytic activity of carbon nitrides and opens an avenue to design efficient loaded photocatalysts with natural abundant materials.     

Mixed-valence molybdenum ion incorporated graphitic carbon nitride with high photocatalytic H2 evolution activity

The graphitic carbon nitride (CN) incorporated with mixed-valence molybdenum ion has been prepared via in-situ copolymerization to improve the photocatalytic H₂ evolution performance. The introduced Mo species existed in mixed valence of Mo⁴⁺ and Mo²⁺ state and its content could be tuned by simply adjusting amount of added MoCl₅ in the preparation procedure. The incorporated mixed-valence Mo ions contributed to narrowed band gap, increased electron density and elevated electron motion kinetics, resulting in extended visible light response, promoted separation and transportation of photoexcited charge carriers. The obtained CN–Mo photocatalyst with an optimal content of Mo ions (0.41 wt%) exhibited a robust H₂ production activity up to 1.44 mmol h⁻¹ g⁻¹, 18 times higher than that of pristine counterpart.     

Organosilica-assisted superhydrophilic oxygen doped graphitic carbon nitride for improved photocatalytic H2 evolution

The regulation of surface wettability and heteroelement doping have been proved to be effective strategies to enhance photocatalytic H₂ evolution activity of graphitic carbon nitride (CN) based photocatalysts. Herein, we report, for the first time, an organosilica assisted method was adopted to synthesize the superhydrophilic oxygen doped graphitic carbon nitride (O–CN). The presence of organosilica induced simultaneous oxygen-containing groups grafting and oxygen doping within carbon nitride substrate. The grafted oxygen-containing groups improved the surface hydrophilicity and water adsorption. Oxygen doping tailored electronic structure and localized electron distribution, contributing to extended visible light harvesting and elevated photoelectric conversion efficiency. As a result, the H₂ generation rate of O–CN photocatalyst was 5.4 times higher than that of pristine CN photocatalyst attributed to the formation of hydrophilic groups and the oxygen doping.     

Heterostructure based on exfoliated graphitic carbon nitride coated by porous carbon for photocatalytic H2 evolution

In this contribution, the heterostructure based on exfoliated graphitic carbon nitride (ex-gCN) coated by a porous carbon layer was fabricated by a simple approach and tested as a photocatalyst for hydrogen evolution under simulated solar light illumination. Bulk-gCN was firstly exfoliated and annealed under a hydrogen atmosphere in carefully selected conditions. The catalyst with the highest photoactivity was fabricated at 400 °C for 4 h. This material exhibited about a 23-fold higher amount of photogenerated hydrogen (18.2 μmol/g) compared to reference ex-gCN (0.8 μmol/g). Boosted photoactivity could be attributed to the (i) highly developed Specific Surface Area leading to more active sites on the surface due to the porous carbon layer, (ii) better transfer, and separation of photogenerated carriers, and (iii) sufficient suppression of the recombination process. Moreover, the mechanism of photocatalytic H₂ evolution from water splitting based on a full physicochemical characterization of the studied materials was proposed.     

High efficiency photocatalytic CO2 reduction realized by Ca2+ and HDMP group Co-modified graphitic carbon nitride

The development of highly efficient and visible-light responsive carbon nitride (CN) photocatalysts is desirable to address energy shortages and environmental pollution challenges. Herein, we synthesized novel 2-hydroxy-4,6-dimethylpyrimidine (HDMP) group and Ca²⁺ co-modified carbon nitride (CN) photocatalyst (CN-CAA) using a facile in situ copolymerization procedure employing urea and calcium acetylacetonate (CAA) as precursors. The HDMP group and Ca²⁺ co-modification contributed to increased electron density and modulated electronic structure, resulting in extended visible light harvesting and accelerated separation and migration of photoinduced charge carriers. Benefiting from the enhanced visible light utilization and improved photoexcited carriers separation and transportation, the CN-CAA exhibited significantly elevated visible-light-driven photocatalytic activity for CO₂ reduction. This work provided a new insight into the photocatalytic performance promotion of CN through molecular engineering and metal ions incorporation co-modification.     

Cobalt oxide on mesoporous carbon nitride for improved photocatalytic hydrogen production under visible light irradiation

Cobalt oxide (Co₃O₄) nanoparticles decorated on mesoporous carbon nitride (Co₃O₄/MCN) nanocomposites for photocatalytic hydrogen evolution were investigated in this work. MCN was prepared using 3-amino-1,2,4-triazole, high nitrogen content, as a single molecular carbon and nitrogen precursor and SiO₂ nanoparticles as the hard template. Complementary characterization techniques were employed to understand the textural and chemical properties of the nanocomposites. The bare MCN showed high photocatalytic activity under visible light irradiation without using any co-catalyst. The photocatalytic activity of Co₃O₄/MCN with a Co₃O₄ mass content of 5 wt % presented two times higher than the bare MCN, which is attributed to the enhanced visible-light harvesting and more efficient charge separation. Mechanistic study shows lower electron-hole recombination rate, higher charge separation efficiency occurs after the formation of p-n type heterojunction.     

Synthesis of graphitic carbon nitride by directly heating sulfuric acid treated melamine for enhanced photocatalytic H2 production from water under visible light

Herein we report the synthesis of graphitic carbon nitride (g-C₃N₄) by directly heating sulfuric acid treated melamine precursor. Thermoanalytical methods (TG-DSC) in combination with XRD, XPS and elemental analysis were used to characterize the condensation steps of the precursor. The TG-DSC curves clearly show significant difference in thermal behavior between the treated and untreated melamine. The sublimation of melamine during condensation was significantly suppressed by treating melamine with sulfuric acid. The decomposition of melamine sulfuric acid and the condensation of melamine occur simultaneously. The N/C ratio of the prepared carbon nitride (1.53) is slight higher than that of the ideal crystal g-C₃N₄ (1.33), indicating the incomplete condensation of amino groups in the material. The XPS and elemental analysis show that there is no sulfur residue in the final product. The sample synthesized from sulfuric acid treated melamine shows relatively higher BET surface area. The photocatalytic performance of the as prepared carbon nitride was evaluated under visible light irradiation (λ > 420 nm). The photocatalytic H₂ production rate on sample synthesized from sulfuric acid treated melamine is 2 times higher than that on sample synthesized from untreated melamine.     

Potassium doped and nitrogen defect modified graphitic carbon nitride for boosted photocatalytic hydrogen production

Controlling the structure of semiconductors to tailor are physicochemical and photoelectronic structure features. Graphitic carbon nitride has triggered a new impetus in the field of photocatalysis. However, the rapid recombination of charge carriers limited its photocatalytic activity. Herein, we demonstrate that potassium doped and nitrogen defects into graphitic carbon nitride (KCN_x) framework are favorable for visible light harvesting, charge separation and have highly efficient photocatalytic behavior for water splitting. It exhibits a high hydrogen evolution activity of 59.9 mmol·g^?1·h^?1 (66.6 times much higher than that of pristine g-C₃N₄), and remarkable apparent quantum efficiency of 57.17% at 420 nm. The superior photocatalytic performance of the KCNx sample was attributed to the less recombination rate of photogenerated electron and hole, and enhanced conductivity, which was proven by photoelectrochemical and PL. This work reveals the synergistic mechanism of introducing foreign elements and defects into the framework of graphitic carbon nitride to improve its photocatalytic activity.     

One-pot annealing preparation of Na-doped graphitic carbon nitride from melamine and organometallic sodium salt for enhanced photocatalytic H2 evolution

Na-doped graphitic carbon nitride was successfully developed by a one-pot preparation, that was, by simply annealing the mixture of melamine and organometallic sodium salt (ethylenediamine tetraacetic acid disodium salt). Visible-light-driven photocatalytic H₂-evolution activity of graphitic carbon nitride was effectively enhanced by Na doping (9.2 times). It was found based on comprehensive analysis that, the absorption of visible light was improved due to the structural change of graphitic carbon nitride by Na doping, thereby promoting the generation of more photo-generated carriers. Meanwhile, the separation and transfer of photo-generated carriers were greatly enhanced by coordination of Na into big C-N rings of the triazine units. Moreover, more active sites for photocatalytic H₂-evolution reaction were provided by the increased surface areas.     

Co,Ni-based nanoparticles supported on graphitic carbon nitride nanosheets as catalysts for hydrogen generation from the hydrolysis of ammonia borane under broad-spectrum light irradiation

From the viewpoint of tailoring the atomic and nanoscale structures of semiconductors to enhance the solar-to-hydrogen energy conversion, we employed an in-situ gas template-assisted co-polymerization route, where melamine and 2,4,6-triaminopyrimidine were co-monomers and NH₄Cl was the in-situ gas template, to synthesize porous broad-spectrum light-responsive carbon nitride nanosheet (termed as CNN) species with increased π-electron availability. Then we developed CNN-supported Co and Ni nanoparticles (NPs) for catalytic hydrogen generation from aqueous ammonia borane (NH₃BH₃) under light irradiation (λ ≥ 420 nm) at room temperature. Though all the Co-based catalysts had the similar activities with total turnover frequency (TOF) values of 37.5–44.1 min⁻¹ in the dark, they exhibited significantly different and enhanced photocatalytic activities. Remarkably, the optimized catalyst had a total TOF value of 123.2 min⁻¹, exceeding the values of reported non-noble metal catalysts. Moreover, the porous CNN species possessed the C-substitution for N, tunable narrow bandgaps of 0.71–2.34 eV and efficient separation of photogenerated charge carriers. This resulted in the enriched electron density of metal NPs and the apparent quantum yield of 66.9% at 420 nm.     

ZnCr LDH nanosheets modified graphitic carbon nitride for enhanced photocatalytic hydrogen production

ZnCr layered double hydroxides (ZnCr LDH) nanosheets modified graphitic carbon nitride (g-C₃N₄) nanohybrids were fabricated via a self-assembly procedure through electrostatic interaction between these two components. Such 2D-2D inorganic-organic hybrid material was employed for photocatalytic hydrogen production under visible light for the first time. The physical and photophysical properties of the hybrid nanocomposites were investigated to reveal the effect of ZnCr LDH nanosheets on the photocatalytic activities of g-C₃N₄. It was found that 1 wt% ZnCr LDH nanosheets modified g-C₃N₄ was optimal for the formation of intimate interfacial contact. The visible light photocatalytic H₂ production activity over g-C₃N₄ was enhanced about 2.8 times after ZnCr LDH nanosheets modification. The significant enhancement in photocatalytic performance for ZnCr LDH/g-C₃N₄ heterojunction should be attributed to the promoted charge transfer and separation efficiency, resulting from the intimate interfacial contact and Type II band alignment between ZnCr LDH and g-C₃N₄.     

Synthesis,characterization and application of silver doped graphitic carbon nitride as photocatalyst towards visible light photocatalytic hydrogen evolution

In this study, the series of silver doped graphitic carbon nitride composites (GCN-Agx) were prepared by varying the amount of silver nitrate added in urea for thermal polymerisation reaction among the two precursors. The characterisation study of GCN-Agx composites so obtained was performed using X-ray diffraction, fourier transform infrared spectroscopy, diffused reflectance spectra and Brunauer–Emmett–Teller analysis to explore the effect of silver doping on the various structural, morphological and optical aspects of pure graphitic carbon nitride (GCN-P). In addition, the GCN-Agx composites were analysed for their photoactivity potential and it was found that silver doping can noticeably enhance the photoactivity potential of GCN-P. The phenomenon of enhanced photoactivity was ascribed to the synergistic effect of silver nanoparticles and GCN-P resulting in the increased ability towards visible light absorption, delayed recombination and better separation of photogenerated charge carriers. The synthesized catalyst could be considered as a potential photocatalyst for environmental and energy applications.     

First-principles study on hydrogen storage by graphitic carbon nitride nanotubes

First-principles calculations based on density functional theory were carried out to investigate the hydrogen storage capacity of graphitic carbon nitride nanotubes. Graphitic carbon nitride nanotubes could be attractive hydrogen sorbent for two reasons: firstly, its porous structure allows easy access of hydrogen into the interior of the nanotubes; and secondly, the doubly bonded nitrogen at its pore edges provides active sites for either the adsorption of hydrogen (chemically and physically), or functionalization with metal catalysts. Our calculations show that an isolated nanotube can uptake up to 4.66 wt. % hydrogen, with an average overall hydrogen adsorption energy of about −0.22 eV per H atom. In the form of a bulk bundle, the hydrogen storage capacity is enhanced due to the increased availability of space among the tubes. We predict that the hydrogen storage capacity in the bundle is at least 5.45 wt. %. Importantly, hydrogen molecules can easily access the tube’s interior due to the low energy barrier (∼0.54 eV) for their passage through the pores, indicating a fast uptake rate at relatively low pressure and temperature. Our findings show that graphitic carbon nitride nanotubes should be applicable to practical hydrogen storage because of the high gravimetric capacity and fast uptake rate.     

An efficient exfoliation method to obtain graphitic carbon nitride nanosheets with superior visible-light photocatalytic activity

Graphitic carbon nitride (g-C₃N₄) has a promising application in the photocatalytic field due to its large aspect ratio and the favorable band gap energy. Herein, g-C₃N₄ nanosheets (g-C₃N₄ NS) with high photoactivity are obtained with the aid of isopropanol (IPA) in the synthesis process. The introduced IPA causes a more intense oxidation in the exfoliation process and the obtained g-C₃N₄ NS owns its unique properties of a broaden absorption range of visible light, an enlarged surface area and the irregular surface. As a result, the g-C₃N₄ NS has good photocatalytic activity in the degradation of organic pollutant. Moreover, the photocatalytic hydrogen evolution rate of g-C₃N₄ NS is three times as that of g-C₃N₄ NS* synthesized without IPA using the same method.     

Graphitic carbon nitride tetragonal hollow prism with enhanced photocatalytic hydrogen evolution

Graphitic carbon nitride tetragonal hollow prism (GCN-THP) with nitrogen vacancies was prepared by a simple two-step calcination method. Based on the characterizations of the as-prepared GCN-THP and the intermediate precursor, a possible mechanism was proposed for the formation of GCN-THP. The as-prepared GCN-THP exhibits superior activity and excellent stability during photocatalytic hydrogen evolution under visible light irradiation. The photocatalytic hydrogen evolution rate of GCN-THP was measured to be 1990 μmol g⁻¹ h⁻¹, which is 6.2 times as that of GCN. The enhanced photocatalytic activity could be attributed to unique 1D tetragonal hollow prism morphology and the presence of nitrogen vacancies in the as-prepared GCN-THP, which could increase the surface area, expand the visible light absorption, and promote the charge separation during photocatalytic hydrogen evolution. Our work could provide a new route to synthesize highly efficient photocatalysts with 1D hollow structures.     

Effect of precursor on the hydrogen evolution activity and recyclability of Pd-Supported graphitic carbon nitride

The examination of graphitic carbon nitride (GCN) synthesis and its catalytic activity in hydrogen production from potassium formate was done as a function of the precursor selection. Four different precursors were assessed, namely urea, dicyandiamide, melamine and thiourea. The catalytic activity of the catalysts fabricated from different GCN precursors and palladium (Pd) was compared. The catalyst prepared from dicyandiamide, Pd-GCN(D), was found to be the most active of the four precursors tested during the first reaction cycle. Nonetheless, the catalyst prepared from urea, Pd-GCN(U), has been attributed by us as the preferred catalyst due to its excellent catalytic activity as well as its phenomenal stability over multiple cycles, which was not observed for the other three catalysts. The better catalytic activity of Pd-GCN(U) is correlated to the high surface area and pore volume of the material. Both the GCN and Pd-GCN samples were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, Brunauer-Emmett-Teller methods, scanning tunneling electron microscopy, and X-ray photoelectron spectroscopy.     

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.     

Phosphorus and sulphur co-doping of g-C3N4 nanotubes with tunable architectures for superior photocatalytic H2 evolution

Non-metal doping not only optimizes the energy band structure of g-C₃N₄ to improve the absorption of visible light, but also exacerbates the distortion of lowest and highest unoccupied molecular orbital plane, causing polarization, thereby improving photocatalytic activity. For the first time, S and P are co-introduced into g-C₃N₄ network to enhance photocatalytic performance and create various tubular morphologies. The ratio of S to P is crucial to control the tubular morphology and property. In the photocatalytic process, the separation of electrons and holes causes by the polarization of the S and P elements and the synergy of the tubular morphology results in new migration paths for photogenerated electrons and holes. Using optimized preparation conditions, g-C₃N₄ tubes co-doped with S and P (CNSP) reveal very high H₂ generation efficiency (163.27 μmol/h), which is two orders of magnitude higher compared to that of pure g-C₃N₄ and apparent quantum yield is 18.93% at 420 nm. Fast degradation of Rhodamine B by using CNSP occurs within 5 min under visible light irradiation. Because of the reproducible process, the synthetic strategy provides a novel method for controlling the morphology of g-C₃N₄-based materials with super activity.     

Nano-structured palladium impregnate graphitic carbon nitride composite for efficient hydrogen gas sensing

Nanoparticles of palladium (Pd) were incorporated into graphitic carbon nitride (g-C₃N₄) matrix with a view to improving hydrogen sensing efficiency of g-C₃N₄, by a fairly new chemical process that uses ammonium tetrachloropalladate as a Pd metal nanoparticle source along with an appropriate reducing agent. Researchers have explored g-C₃N₄ for various applications such as a catalyst for water splitting, photoluminescence, storage because of its relatively low cost, easy synthesis, and ready availability. For the synthesis of g-C₃N₄, urea was used as a precursor at 550 °C and at atmospheric pressure under a muffle furnace without add-on support. The final solution of the Pd/g-C₃N₄ nanocomposite was then centrifuged and dried for use as a hydrogen-sensing material. g-C₃N₄ and Pd/g-C₃N₄ were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), UV-VIS-NIR spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and energy dispersive X-ray spectroscopy (EDS). Pd-dispersed graphitic carbon nitride film was deposited on an inter digited carbon electrode by using a screen printing technique. From the qualitative analysis by I–V measurement, a significant change in the resistance was observed during the presence and absence of the hydrogen gas. The results show Pd/g-C₃N₄ nanocomposite as an efficient hydrogen sensing material.