Carbon Nitride Research Articles

Exploring Flower-Structured Bifunctional VCu Layered Double Hydroxide and its Nanohybrid with g-C3N4for Electrochemical and Photoelectrochemical Seawater Electrolysis.

Seawater electrolysis holds great promise for sustainable green hydrogen generation, but its implementation is hindered by high energy consumption and electrode degradation. Two dimensional (2D) layered double hydroxide (LDH) exhibits remarkable stability, high catalytic activity, and excellent corrosion resistance in the harsh electrolytic environment. The synergistic effect between LDH and seawater ions enhances the oxygen evolution reaction, enabling efficient and sustainable green hydrogen generation. Here, we report a synthesis of low cost, novel 2D Vanadium Copper (VCu) LDH first time in the series of LDH's as a highly efficient bifunctional electrocatalyst. The electrochemical (EC) and photoelectrochemical (PEC) study of VCu LDH and VCu LDH/Graphite Carbon Nitride (g-C3N4) nanohybrid was performed in 0.5 M H2SO4 (acidic), 1 M KOH (basic), 0.5 M NaCl (artificial seawater), 0.5 M NaCl + 1 M KOH (artificial alkaline seawater), real seawater and 1 M KOH + real seawater (alkaline real seawater) electrolyte medium. It was found that VCu LDH shows a remarkable lower overpotential of 72 mV hydrogen evolution reaction (HER) and 254 mV oxygen evolution reaction (OER) at current density of 10 mA/cm2 under alkaline real seawater electrolysis exhibiting bifunctional activity and also showing better stability.

Enhancing the Activity of a Carbon Nitride Photocatalyst by Constructing a Triazine-Heptazine Homojunction.

Establishing homojunctions at the molecular level between different but physicochemically similar phases belonging to the same family of materials is an effective approach to promoting the photocatalytic activity of polymeric carbon nitride (CN) materials. Here, we prepared a CN material with a uniform distribution of homojunctions by combining two synthetic strategies: supramolecular assemblies as the precursor and molten salt as the medium. We designed porous CN rods with triazine-heptazine homojunctions (THCNs) using a melem supramolecular aggregate (Me) and melamine as the precursors and a KCl/LiBr salt mixture as the liquid reaction medium. The triazine/heptazine ratio is controlled by varying the relative amounts of the chosen precursors, and the molten salt treatment enhances the structural order of the interplanar packing units for the THCN skeleton, leading to rapid charge migration. The resulting built-in electric field induced by the triazine-heptazine homojunction enhances photogenerated charge separation; the optimal THCN catalyst exhibits an excellent H2 evolution rate via photocatalytic water splitting, which is ∼24 times as high as that of reference bulk CN, with long-term stability.

Photo-Induced Hydrophosphinylation Using Single-Atom Copper, Supported on Carbon Nitride

Photo-Induced Hydrophosphinylation Using Single-Atom Copper, Supported on Carbon Nitride

Silver Nanoparticle-Embedded Carbon Nitride: Antifungal Activity on Candida albicans and Toxicity toward Animal Cells.

The development of engineered nanomaterials has been considered a promising strategy to control oral infections. In this study, silver-embedded carbon nitrides (Ag@g-CN) were synthesized and tested against Candida albicans, investigating their antifungal action and biocompatibility in animal cells. Ag@g-CN was synthesized by a simple one-pot thermal polymerization technique and characterized by various analytical techniques. X-ray diffraction (XRD) analysis revealed slight alterations in the crystal structure of g-CN upon the incorporation of Ag. Fourier transform infrared (FT-IR) spectroscopy confirmed the presence of Ag-N bonds, indicating successful silver incorporation and potential interactions with g-CN's amino groups. UV-vis spectroscopy demonstrated a red shift in the absorption edge of Ag@g-CN compared with g-CN, attributed to the surface plasmon resonance effect of silver nanoparticles. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) confirmed the 2D layered sheet like morphology of both materials. The Ag 3d peaks found in X-ray photoelectron spectroscopy (XPS) confirmed the presence of metallic Ag0 nanoparticles in Ag@g-CN. The Ag@g-CN materials exhibited high antifungal activity against reference and oral clinical strains of C. albicans, with minimal inhibitory concentration (MIC) ranges between 16-256 μg/mL. The mechanism of Ag@g-CN on C. albicans was attributed to the disruption of the membrane integrity and disturbance of the biofilm. In addition, the Ag@g-CN material showed good biocompatibility in the fibroblastic cell line and in Galleria mellonella, with no apparent cytotoxicity observed at a concentration up to 1000 μg/mL. These findings demonstrate the potential of the Ag@g-CN material as an effective and safe antifungal agent for the treatment of oral fungal infections.

Polyvinyl alcohol/polyethyleneimine grafted carbon oxynitride composite nanofiber membranes with the synergistical enhanced photocatalytic degradation and bactericidal performance

AbstractGraphitic carbon nitride (g‐C3N4) has received much attention as a metal‐free photocatalyst for dye degradation and sterilization. However, the low photocatalytic bactericidal activity and the difficulty in recycling have limited its applications. Here, oxidatively modified g‐C3N4 grafted with polyethyleneimine (PEI) nanofiber membranes (PVA/PEI‐OCN) was reported to enhance the photocatalytic activity. The modification by PEI grafting could reduce the recombination rate of photogenerated carriers and lead to more electrons for the photocatalytic reaction. In addition, electron spin resonance (ESR) results showed that the generation of reactive oxygen species (˙OH, ˙O2− and 1O2) were significantly enhanced in photocatalysis, leading to the significant enhancement of photocatalytic bactericidal activity and dye degradation. Furthermore, the PVA/PEI‐OCN nanofiber membranes prepared by electrospinning had smooth surfaces and uniform fiber formation, with an average diameter of 380 ± 60 nm. The tensile strength was about 73.5% higher than that of PVA nanofiber membranes. The inhibition diameter of PVA/PEI‐OCN‐4 against Escherichisa coli (E. coil) could reach 20 ± 0.2 mm, and the maximum degradation efficiency of methylene blue solution (10 mg/L) could reach 92.8% within 120 min. This work provided an effective paradigm for the rational design of metal‐free photocatalytic materials for elimination of bacterial and dye contamination.

Interlayer Potassium Single-Atom-Coordinated g-C3N4 for Significantly Boosted Visible Light Photocatalytic H2 Production.

In recent years, graphitic carbon nitride (g-C3N4) has attracted considerable attention because it includes earth-abundant carbon and nitrogen elements and exhibits good chemical and thermal stability owing to the strong covalent interaction in its conjugated layer structure. However, bulk g-C3N4 has some disadvantages of low specific surface area, poor light absorption, rapid recombination of photogenerated charge carriers, and insufficient active sites, which hinder its practical applications. In this study, we design and synthesize potassium single-atom (K SAs)-doped g-C3N4 porous nanosheets (CM-KX, where X represents the mass of KHP added) via supramolecular self-assembling and chemical cross-linking copolymerization strategies. The results show that the utilization of supramolecules as precursors can produce g-C3N4 nanosheets with reduced thickness, increased surface area, and abundant mesopores. In addition, the intercalation of K atoms within the g-C3N4 nitrogen pots through the formation of K-N bonds results in the reduction of the band gap and expansion of the visible-light absorption range. The optimized K-doped CM-K12 nanosheets achieve a specific surface area of 127 m2 g-1, which is 11.4 times larger than that of the pristine g-C3N4 nanosheets. Furthermore, the optimal CM-K12 sample exhibits the maximum H2 production rate of 127.78 μmol h-1 under visible light (λ ≥ 420 nm), which is nearly 23 times higher than that of bare g-C3N4. This significant improvement of photocatalytic activity is attributed to the synergistic effects of the mesoporous structure and K SAs doping, which effectively increase the specific surface area, improve the visible-light absorption capacity, and facilitate the separation and transfer of photogenerated electron-hole pairs. Besides, the optimal sample shows good chemical stability for 20 h in the recycling experiments. Density functional theory calculations confirm that the introduction of K SAs significantly boosts the adsorption energy for water and decreases the activation energy barrier for the reduction of water to hydrogen.

Chloride Ion-Induced Spatial Separation and Long Recombination Time of Photogenerated Electrons and Holes in Crystalline Carbon Nitride

Chloride Ion-Induced Spatial Separation and Long Recombination Time of Photogenerated Electrons and Holes in Crystalline Carbon Nitride

Accumulation of Long-Lived Photogenerated Holes at Indium Single Atom Catalysts via Two Coordinate Nitrogen Vacancy Defect Engineering for Enhanced Photocatalytic Oxidation.

Visible light-driven photocatalytic oxidation by photogenerated holes has immense potential for environmental remediation applications. While the electron-mediated photoreduction reactions are often at the spotlight, active holes possess a remarkable oxidation capacity that can degrade recalcitrant organic pollutants, resulting in non-toxic byproducts. However, the random charge transfer and rapid recombination of electron-hole pairs hinder the accumulation of long-lived holes at the reaction center. Herein, we report a novel method employing defect-engineered indium (In) single atom photocatalysts, dispersed in carbon nitride foam (In-Nv-CNF), to overcome these challenges and make further advances in photocatalysis. This Nv (nitrogen vacancy) defect-engineered strategy produces a remarkable extension in the lifetime of photogenerated holes and an increase in the concentration of photogenerated holes in In-Nv-CNF. Consequently, the optimized In-Nv-CNF demonstrates a remarkable 50-fold increase in photo-oxidative degradation rate compared to pristine CN, effectively breaking down two widely used antibiotics (tetracycline and ciprofloxacin) under visible light. The contaminated water treated by In-Nv-CNF has proven to be completely non-toxic based on the growth of E. coli before and after treatment. Structural-performance correlations between Nv defect engineering and long-lived hole accumulation in In-Nv-CNF are established and validated through experimental and theoretical agreement. This work has the potential to elevate the efficiency of overall photocatalytic reactions from a hole-centric standpoint. This article is protected by copyright. All rights reserved.

Engineering Built-In Electric Field Microenvironment of CQDs/g-C3N4 Heterojunction for Efficient Photocatalytic CO2 Reduction.

Graphitic carbon nitride (CN), as a nonmetallic photocatalyst, has gained considerable attention for its cost-effectiveness and environmentally friendly nature in catalyzing solar-driven CO2 conversion into valuable products. However, the photocatalytic efficiency of CO2 reduction with CN remains low, accompanied by challenges in achieving desirable product selectivity. To address these limitations, a two-step hydrothermal-calcination tandem synthesis strategy is presented, introducing carbon quantum dots (CQDs) into CN and forming ultra-thin CQD/CN nanosheets. The integration of CQDs induces a distinct work function with CN, creating a robust interface electric field after the combination. This electric field facilitates the accumulation of photoelectrons in the CQDs region, providing an abundant source of reduced electrons for the photocatalytic process. Remarkably, the CQD/CN nanosheets exhibit an average CO yield of 120µmol g-1, showcasing an outstanding CO selectivity of 92.8%. The discovery in the work not only presents an innovative pathway for the development of high-performance photocatalysts grounded in non-metallic CN materials employing CQDs but also opens new avenues for versatile application prospects in environmental protection and sustainable cleaning energy.

3D Tremella‐Like g‐C3N4/TiO2/HNTs Heterojunction Photocatalyst for Enhanced Photocatalytic Degradation of Rhodamine B From Water

AbstractAmong the traditional treatment processes for purifying wastewater contaminated with Rhodamine B (RhB), semiconductor photocatalysis is the most effective technology because it can oxidize organic pollutants and convert them into CO2, H2O, and other harmless molecules in a safe and efficient manner. According to literature research, it is feasible to enhance the performance of g‐C3 N4 as a photocatalyst by constructing a heterojunction with other photocatalytic materials. Morphological regulation of carbon nitride (g‐C3N4) is a viable strategy for improving its photocatalytic activities. By controlling the morphology of g‐C3N4, factors such as light absorption, specific surface area, charge separation, and reaction sites can be optimized to enhance its photocatalytic efficiency. Three‐dimensional tremella‐like carbon nitride (3DT‐CN) and 3D‐CN/TiO2/HNTs (halloysite nanotubes) were prepared using bubble templates and an impregnation method respectively. The Z‐scheme heterojunction structure constructed by 3D‐CN and TiO2 promotes electron‐hole separation. Catalytic experiments demonstrated that under irradiation for 120 min, the 3D‐CN/TiO2/HNTs catalyst could eliminate 86.48 % of Rhodamine B (RhB). Additionally, active radicals such as e‐, h+, ⋅OH, and ⋅O2‐ are involved in RhB degradation. Therefore, the three‐dimensional tremella‐like 3D‐CN/TiO2/HNTs heterojunction photocatalyst has great potential for environmental purification.

Nitrogen-doped carbon quantum dot as electron acceptor anchored on graphitic carbon nitride nanosheet for improving rhodamine B degradation

Carbon quantum dots (CQDs) hold significant promise for wastewater treatment because of their remarkable attributes, including robust stability, outstanding biocompatibility, minimal toxicity, superior water dispersibility, cost-effective production, and exceptional photo-stability.In this study, CQDs were synthesized using microplasma and tested for the degradation of rhodamine B (RhB) (5 mg/L) under different conditions, with a Solar simulator and UVA illumination. Specifically, graphitic carbon nitride nanosheets (NCN) in conjugation with carbon quantum dots (NCN@CQD) were prepared with different amounts of CQD. The synthesized CQD, NCN, and NCN@CQD underwent characterization using various compositional and structural analytical techniques. The results show that nitrogen species were effectively incorporated into the CQDs framework and CQDs are anchored on NCN forming NCN@CQD successfully. Subsequently, all samples were then investigated in degrading Rhodamin B, RhB, to assess the photocatalytic activity. The results reveal that the presence of CQDs substantially improved the photocatalytic efficiency of NCN. Specifically, the CQDs anchored on NCN exhibited a substantial enhancement in the photoactivity for RhB decomposition under a solar light simulator, surpassing that of pure NCN. The amount of CQD in the NCN@CQD sample exerted a strong influence on the photocatalytic activity. All NCN@CQD samples exhibited remarkable enhancements in both adsorption and photocatalytic performance compared to pure CQD and NCN samples. In an optimization study, a best NCN@CQ photocatalyst was identified, showing a 40 % enhancement of photocatalytic efficiency compared to the use of NCN alone. A visible light photocatalytic activity of 91 % can be attained within 150 min, exhibiting a reaction rate constant of 0.0135 min−1 toward RhB decomposition, which was double as for the individual NCN (0.0067 min−1). The boosted photocatalytic activity resulting from the synergistic effect between NCNs and CQDs can be attributed to the efficient function of CQD as an electron acceptor. The proposed mechanism of photocatalytic degradation of RhB is illustrated in detail.

Modified-TiO2 Nanotube Arrays as a Proficient Photo-Catalyst Nanomaterial for Energy and Environmental Applications

Recently, TiO2 nanotube arrays (TNTAs) have attracted researcher’s attention in the fields of energy production and environmental remediation applications; this is mainly due to their unique optoelectronic characteristics, corrosion resistance, chemical and mechanical stability. In this study, the ability of employing of TiO2 nanotube arrays-based catalysts in the field of photocatalytic CO2 reduction has been investigated. Possible modification strategies have been presented for improving the TNTAs performance by using different types of nanomaterials including graphitic carbon nitrides (g-C3N4), metal-organic frame work (MOF), reduced graphene oxide (RGO) and gold nanoparticles (Au NPs). The TNTAs composites were characterized using XRD and FESEM analyses and the results revealed the successful synthesis of these composites. The TNTAs and their composites exhibited good results for the photo-conversion of CO2 into CH4 gas product. This study gives new ideas for making and developing low-cost Ti metal-based nanomaterials which can be used in the future for recycling the CO2 gas emissions into useful solar fuels.

A DFT study on boron carbon nitride and in-plane graphene-boron nitride nanosheets for O3 and F2 gas sensing

In the industry era, nanostructures-based gas sensors have been more striking for environmental monitoring. In this research, we investigated the properties and the adsorption ability of boron carbon nitride (BCN) and in-plane graphene-boron nitride (G_BN) nanosheets for toxic (F2 and O3) gas molecules. The geometrical, electronic, and optical properties of the selected structures are analyzed using the density functional theory. The negative value of cohesive energy signifies that both BCN and G_BN are energetically stable. Both structures show strong attractive energy for the selected gas molecules with recovery times of 0.266 ps−5.482 ns. A significant change decrease in the band gap of the adsorbents occurred after gas adsorption. All the adsorbents show a high absorption coefficient of over 104 cm−1 in the visible wavelength range. A slight variation in the optical properties is observed after gas adsorption. Both the adsorbents demonstrate significant sensitivity toward F2 and O3 gases.

Spherical g-C3N4@PDA nanocarrier for synergistic chemo-photothermal tumor therapy

In this paper, by wrapping the near-infrared (NIR) response polydopamine (PDA) as a nanocoating on the surface of spherical nano graphitic phase carbon nitride (g-C3N4), a multifunctional g-C3N4/PDA (CNP) nanocarrier platform was prepared. The π-conjugation system in PDA and the electronegative hydroxyl groups on the surface of CNP promote the creation of abundant active sites, which had a high drug loading rate of about 98.5 % for the electropositive GA. Due to the strong NIR reaction of CNP, the release of GA from CNP/GA can be greatly accelerated by the rising temperature, bonding disruption and charge transfer. Moreover, the photo-generated electron-hole pairs could be excited by the NIR effect of CNP, which promotes the production of ROS (·OH, ·O2– and 1O2) to induce apoptosis in HepG2 cells. Thus, the present spherical CNP nanocarrier with a combination of enzyme-mimic activity and NIR-responsive properties has a great potential for chemo-photothermal synergistic tumor therapy.

Magnetic soft centirobot to mitigate biological threats

AbstractSoft robots have drawn a lot of interest in the field of human–robot interfaces because they can mimic the propulsion of soft bodies and archive complex tasks that cannot be made by rigid robots such as performing the complex motion, avoiding collisions by absorbing impacts, and shape adaptation by elastic deformation. Herein, drawing inspiration from creatures in the Cambrian period, such as Hallucigenia, we develop a centimeter‐sized soft robot with multiple magnetic legs (referred to as a soft centirobot). This robot is equipped with graphitic carbon nitride (g‐C3N4) nanosheets to kill biological threats by photogenerated reactive oxygen species under black light illumination. The motion of g‐C3N4 soft centirobot is controlled by magnetic actuation even in complex wastewater samples (with a relative speed of 0.12 body lengths per second). The magnetic multilegs work as a propeller to walk across and cover large regions, and water disinfection is more efficient than what could be achieved by nano/micrometer scale sheets of g‐C3N4. Finally, factors affecting the accelerated propulsion of g‐C3N4 soft centirobot such as design principle, structure geometry, body mass, driving mechanism, and magnetic sensitivity, have been investigated. We envision that such a photoactive 2D material‐based integrated centimeter‐sized robot shall find application in many areas where pathogen removal is required.

Heavily Doped Carbon Nitride Nanocrystal Promotes Visible-Near-Infrared Photosynthesis of Hydrogen Peroxide with Near-Unit Photon Utilization.

Direct photosynthesis of hydrogen peroxide (H2O2) from water and oxygen represents an intriguing alternative to the current indirect process involving the reduction and oxidation of quinones. However, limited light utilization and sluggish charge transfer largely impede overall photocatalytic efficiency. Herein, we present a heavily doped carbon nitride (CNKLi) nanocrystal for efficient and selective photoproduction of H2O2 via a two-electron oxygen reduction reaction (ORR) pathway. CNKLi induces metal-to-ligand charge transfer (MLCT) and electron trapping, which broadens the light absorption to the visible-near-infrared (vis-NIR) spectrum and prolongs the photoelectron lifetime to the microsecond time scale with an exceptional charge diffusion length of ∼1200 nm. Near-unit photoutilization with an apparent quantum yield (AQY) of 100% for H2O2 generation is achieved below 420 nm. Impressively, CNKLi exhibits an appreciable AQY of 16% at 700 nm, which reaches the absorption capacity (∼16%), thus suggesting a near-unit photon utilization <700 nm. In situ characterization and theoretical calculations reveal the facilitated charge transfer from K+ to the heptazine ring skeleton. These findings provide an approach to improve the photosynthetic efficiency of direct H2O2 preparation in the vis-NIR region and expand applications for driving kinetically slow and technologically desirable oxidations or high-value chemical generation.

Modulation of Exposed Active Sites and Electronic Structure of Co-Doped Carbon Nitride Achieving Enhanced Activity toward Peroxymonosulfate Activation for Antibiotic Degradation

Modulation of Exposed Active Sites and Electronic Structure of Co-Doped Carbon Nitride Achieving Enhanced Activity toward Peroxymonosulfate Activation for Antibiotic Degradation

Localized surface-plasmon resonance effect as a new driver of Z-scheme electron transfer in cerium dioxide–graphitic carbon nitride heterojunctions

The intersecting interface between the two semiconductors of cerium dioxide (CeO2)–graphitic carbon nitride (g-C3N4) heterojunctions, which have demonstrated excellent photocatalytic activity, inhibits the rapid compounding of the photogenerated electron–hole pairs of g-C3N4. CeO2–g-C3N4 heterojunctions with Z-scheme and type-II electron-transfer routes were prepared via calcination in argon and air atmospheres, respectively. The built-in electric field theory cannot be used to explain the presence of a type-II electron-transfer route in CeO2–g-C3N4 heterojunctions. According the femtosecond transient absorption spectra, the localized surface-plasmon resonance (LSPR) effect of CeO2 drove the Z-scheme electron transfer in CeO2–g-C3N4 heterojunctions. The CeO2–g-C3N4 heterojunction exhibited a type-II electron-transfer route when the particle size of CeO2 increased, which attenuated the LSPR effect. The CeO2–g-C3N4 heterojunction with the Z-scheme electron-transfer route exhibited 4.4 times higher degradation efficiency for bamboo pulping wastewater than g-C3N4, and this result was attributed to the reduced complexation of photogenerated electron–hole pairs and extended photogenerated electron lifetime. Overall, this research provides a new idea for constructing Z-scheme electron-transfer heterojunctions.

Sensitizer created defective metal organic framework as a new platform for boosting visible-light photocatalysis of g-C3N4

We developed herein for the first time a sensitizer created defective MOF (SCD-MOF), simultaneously possessing sensitizers and defects as visible-light harvester and electron trapper, respectively, which can synergistically improve the visible-light photocatalysis of polymeric graphitic carbon nitride (g-C3N4). Based on this discovery, the resulting 5.0 wt% FeTCPP⊂UiO-66@g-C3N4 shows a significant 6.6 and 3.9 times improvement in catalytic efficiency compared with its parent materials of FeTCPP⊂UiO-66 and g-C3N4 in degrading organic pollutants. Moreover, it shows a 10.4 times enhancement in catalytic efficiency compared with commercial TiO2 (P25). Mechanism studies suggest that sensitizer molecules and defects in SCD-MOF can synergistically improve photocatalytic efficiency because of broadening the visible-light response and strengthening the charge carrier separation. This work illustrates a remarkably triple synergetic effect among visible-light harvester, electron/hole separator, and semiconductor and thus established SCD-MOF as a class of new platform to greatly improve the visible-light photocatalytic performance of conventional semiconductors.

Cascade Self-Generation of Carbon Monoxide Triggered by Photoinduced Holes for Efficient Hypoxic Tumors Therapy.

It still remains challenging to design multifunctional therapeutic reagents for effective cancer therapy under a unique tumor microenvironment including insufficient endogenous H2O2 and O2, low pH, and a high concentration of glutathione (GSH). In this work, a CO-based phototherapeutic system triggered by photogenerated holes, which consisted of ionic liquid (IL), the CO prodrug Mn2(CO)10, and iridium(III) porphyrin (IrPor) modified carbonized ZIF-8-doped graphitic carbon nitride nanocomposite (IL/ZCN@Ir(CO)), was designed for cascade hypoxic tumors. Upon light irradiation, the photogenerated holes on IL/ZCN@Ir(CO) oxidize water into H2O2, which subsequently induces Mn2(CO)10 to release CO. Meanwhile, IrPor can convert H2O2 to hydroxyl radical (•OH) and subsequent singlet oxygen (1O2), which further triggers CO release. Moreover, the degraded MnO2 shows activity for glutathione (GSH) depletion and mimics peroxidase, leading to GSH reduction and •OH production in tumors. Thus, this strategy can in situ release high concentrations of CO and reactive oxygen species (ROS) and deplete GSH to efficiently induce cell apoptosis under hypoxic conditions, which has a high inhibiting effect on the growth of tumors, offering an attractive strategy to amplify CO and ROS generation to meet therapeutic requirements in cancer treatment.