Graphitic Carbon Research Articles

The effect of filler distribution on electromagnetic properties of nanocarbon/magnetic particles/polymer composites

The type of multi-component fillers and their spatial distribution in conductive polymer-based composites greatly influenced their electrical properties, electromagnetic shielding efficiency (SE), and absorption capability, which require a deep understanding of how these properties improve with changes in the phase composition, content, and distribution of these fillers in the composite. In this study, three-phase polymer composite materials (CMs) with random (epoxy-based) and segregated (polyethylene-based) distribution of nanocarbon (graphite nanoplatelets GNP and carbon nanotubes CNTs) and magnetic (Fe and Co3O4) fillers have been developed. It was found that permittivity εr′ in the frequency range (40–60 GHz) increases sufficiently with the nanocarbon content and their values are slightly higher for random GNP-filled CMs (εr′=10–15 for 3–5 wt. % GNP) compared to CNT-filled CMs and much higher compared to segregated CMs (εr′=4–7 for 3–5 wt. % of nanocarbon). Dielectric loss tangent tanδ is increased with the nanocarbon content (especially for Fe-filled CMs) and sufficiently higher in segregated CMs compared to similar random composites. These enhanced tanδ values correlate with higher electromagnetic shielding efficiency due to absorption of segregated nanocarbon/magnetic/polyethylene CMs, for example, SEAd ≈ 18–23 dB/mm for 5 wt. %GNP. The most preferable for microwave absorption are random and segregated CMs with 2–3 wt. % GNP/30 wt. % magnetic filler: RLmin = −(27–35) dB, effective absorption bandwidth (EAB) Δf10dB=11.5–12.5GHz at a sample thickness of 0.5–0.7 mm. In CNT-based segregated CMs, |RLmin| and EAB values are lower compared with GNP-based CMs. The ability to manipulate these characteristics is important for obtaining good shielding and absorptive properties in the microwave range of electromagnetic radiation.

Potassium and Boron Co-Doping of g-C3N4 Tuned CO2 Reduction Mechanism for Enhanced Photocatalytic Performance: A First-Principles Investigation

Graphitic phase carbon nitride (g-C3N4, abbreviated as CN) can be used as a photocatalyst to reduce the concentration of atmospheric carbon dioxide. However, there is still potential for improvement in the small band gap and carrier migration properties of intrinsic materials. K-B co-doped CN (KBCN) was investigated as a promising photocatalyst for carbon dioxide reduction via the Density Functional Theory (DFT) method. The electronic and optical properties of CN and KBCN indicate that doping K and B can improve the catalytic performance of CN by promoting charge migration and separation. In terms of the Gibbs free energy change, the CO2 reduction reaction catalysed by KBCN results in CH3OH, and its optimal pathway is CO2 → *CO2 → *COOH → CO → *OCH → HCHO → *OCH3 → CH3OH. Compared with CN, the doping elements K and B shift the rate-determining step from CO2 → *CO2 to *CO2 → *COOH. The K and B elements co-doping tuned the charge distribution between the catalyst and the adsorbate and reduced the Gibbs free energy of the rate-determining step from 1.571 to 0.861 eV, suggesting that the CO2 reduction activity of KBCN is superior to that of CN. Our work provides useful insights for the design of metallic–nonmetallic co-doped CN for photocatalytic CO2 reduction (CO2PR) reactions.

Conductive Islands Assisted Resistive Switching in Biomimetic Artificial Synapse for Associative Learning and Image Recognition

AbstractSolution‐processed memristor devices hold significant potential for advancing synaptic applications, offering scalable, cost‐effective, and efficient solutions for next‐generation neuromorphic systems. These devices replicate the behavior of biological synapses with their gradual and continuous changes in resistance, making them promising for neuromorphic computing and artificial neural networks. However, understanding the temporal characteristics and cumulative effect of successive pulses on the devices is essential for emulating the dynamics of biological synapses. This study proposes a hybrid materials‐based conductive islands‐assisted resistive switching (CIARS) in a solution‐processed active layer consisting of thermally exfoliated graphitic carbon nitride (g‐C3N4 abbreviated as CN) nanosheets embedded with silver nanoparticles (Ag NPs). The fabricated devices demonstrate repeatable and bipolar memory features with a lower operating voltage (≤0.5 V), emulating the frequency and amplitude‐dependent synaptic plasticities. The threshold switching occurs due to the formation of conduction filaments (CFs) of silver ion (Ag+), whereas the analog behavior results from the voltage pulse‐dependent modulation of Schottky barrier height combined with metallic CFs formation. The experimental findings demonstrate the efficacy of the CIARS mechanism within the material platform, highlighting its potential for applications in associative learning, Morse code detection, and image recognition.

Hydrogen and Solid Carbon Production via Methane Pyrolysis in a Rotating Gliding Arc Plasma Reactor

Plasma‐induced methane pyrolysis is a promising hydrogen production method. However, few studies have focused the decomposition of pure methane as a discharge gas. Herein, a rotating gliding arc reactor was used for the conversion of methane (discharge gas and feedstock) into hydrogen and solid carbon. Methane conversion, gaseous product selectivity, and energy usage efficiency(specific energy requirement for hydrogen production(SER)) were investigated as functions of operating parameters, e.g., specific energy input(SEI), residence time, and reactor design. SEI was positively(almost linearly) correlated with methane conversion and hydrogen yield and negatively correlated with SER. Conversion and efficiency of energy usage increased when reactor designs providing higher thermal densities were used. With the increasing flow rate of methane at constant SEI, the reaction volume and, hence, the residence time of the gas inside the reaction zone increased, which resulted in methane conversion and hydrogen selectivity enhancement. The solid carbon featured four distinct domains, namely graphitic carbon, turbostratic carbon, few‐layer graphene, and amorphous carbon, which indicated a nonuniform temperature distribution in the reaction zone. But it seems that graphitic carbon dominates amorhphous one. This study highlights the potential of rotating gliding arc plasma systems for efficient methane conversion into hydrogen and valuable solid carbon products

Interlayer-Functionalized Graphene with Phosphorus–Silicon-Containing Elements for Improving Thermal Stability and Flame Retardance of Polyacrylonitrile

Highly-effective non-halogenated flame retardants have received widespread attention because they are environmentally friendly, with low toxicity and low smoke density. In this work, interlayer-functionalized graphene (fRGO) containing silicon and phosphorus elements was synthesized via hydrolytic condensation with 3-(methacryloyloxy)propyltrimethoxysilane and addition reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Interlayer spacing and oxygen-containing groups of reduced graphene oxide (RGO) were regulated by controlling the hydrazine hydrate dosage. Then, phosphorus–silicon-containing organic molecules were inserted into RGO interlayers; this was verified by FTIR, XPS, TEM, etc. The fRGO was added to a polyacrylonitrile (PAN) matrix using a solution blending method to prepare polyacrylonitrile (PAN) composites. The fRGO addition caused the significant decrease in cyclization heat and the considerable increase in char residues, indicating improved thermal stability. Importantly, PAN composites exhibited outstanding flame-retardant properties, with the peak heat release rate reduced by 45%, which is ascribed to the dense graphitic carbon layers induced by phosphorus–silicon-containing organics and the 2D barrier effect of RGO layers to prevent the heat and mass transfer.

Visible‐Light‐Induced Rapid Elimination of Antibiotic Resistance Contaminations Using Graphitic Carbon Nitride Tailored with Carrier Confinement Domains

AbstractSolar water disinfection facilitated by photocatalyst has been considered a viable point‐of‐use (POU) method for mitigating antibiotic resistance contaminations at the household or community levels. Here, density functional theory calculations are used to guide the fabrication of a carrier confinement domains (CCD)‐decorated graphitic carbon nitride (CN) photocatalyst. The CCD integration effectively disrupts the electron distribution symmetry of CN, amplifies its local electron density, and facilitates the formation of long‐range ordered structure, thereby enhancing charge separation efficiency. Importantly, the CCD directs the migration of photogenerated carriers to specific regions upon light illumination, effectively minimizing their spatial proximity. As a result, the overall reactive oxygen species level of the photocatalytic system is markedly elevated, with a twelvefold increase in H2O2 concentration, alongside a nearly two‐order‐of‐magnitude rise in •O2− and •OH steady‐state concentrations. Remarkably, a record‐high disinfection efficiency is attained, successfully inactivating 7 log of antibiotic‐resistant bacteria within 30 min. Additionally, the photocatalyst can be integrated into a continuous‐flow fixed‐bed reactor, facilitating clean water production for up to 60 h at a rate of 121 L m−2 day−1, highlighting its significant potential for POU applications.

Enabling highly concentrated tetracycline degradation with tailored FeCo nanocrystals in porous graphitic carbon fiber

Enabling highly concentrated tetracycline degradation with tailored FeCo nanocrystals in porous graphitic carbon fiber

Fire-Induced Multiple Changes in Electron Transfer Properties of Peat Soil Organic Matter: The Role of Functional Groups, Graphitic Carbon, and Iron.

Peatland fires induced changes in electron transfer properties and relevant electroactive structures of peat soil organic matter (PSOM) remain ambiguous, impeding comprehension of postfire biogeochemical processes. Here, we revealed temperature-dependent electron exchange capacity (EEC) of PSOM dynamics through simulated peat soil burning (150-500 °C), which extremely changed postfire microbial Fe-nanoparticles reduction and methanogenesis. EEC diminished significantly (60-75% loss) due to phenolic-quinone moieties depletion with increasing temperature, regardless of oxygen availability. The final EEC in oxic burning surpassed that of anoxic burning by 1.5 times, attributed to additional quinones from oxygen incorporation. Notably, EEC exhibited heat resistance up to 200 °C and stabilized above 350 °C. Additionally, fire reshaped the EEC-relevant redox-active moieties. Heterocyclic-N generated from burning predominantly contributed to the electron-accepting capacity (EAC) alongside quinones, while phenolic moieties and bonded Fe(II) enhanced the electron-donating capacity (EDC). However, the preferential binding of heterocyclic-N to Fe(II) restricted the EDC of Fe(II). Interestingly, the decrease in EAC declined its electron-shuttling effects in microbial Fe nanoparticle reduction, but fire-induced graphitic carbon formation increased the electrical conductivity (EC) of PSOM, promoting electron transfer. Further, enhanced EC may facilitate methanogenesis in postfire peatlands. These findings advance our understanding of elemental biogeochemical cycles and greenhouse emission mechanisms in postfire peatlands.

Efficient uranium removal by amidoxime functionalized graphitic carbon nitride and its potential mechanism

Efficient uranium removal by amidoxime functionalized graphitic carbon nitride and its potential mechanism

Research on Graphitic Carbon Nitride (g-C3N4) prepared by template-based method and its photocatalytic properties

Abstract. The Graphitic Carbon Nitride (g-C3N4), a non-metallic polymer photocatalytic material, has a wide range of raw materials and a simple preparation process. Due to its unique electronic structure and excellent photocatalytic performance, g-C3N4 has attracted wide attention in the field of environmental purification and energy conversion in recent years. However, g-C3N4 faces a lot of challenges, including a wide band gap, many interlayer defects, and poor interlayer electron transport. Nevertheless, its unique semiconductor structure and chemical stability still provide the possibility to explore the effect of its piezoelectric properties on photocatalysis, which paves the way for a novel approach to environmentally friendly hydrogen production. Therefore, the paper delves into the application of different template methods in the preparation of g-C3N4 by reviewing the related literature, and analyzes the role of different template materials in the preparation. In addition, in this paper, the photocatalytic properties of g-C3N4 are explored, which are mainly reflected in the photocatalytic water separation performance and photocatalytic degradation of organic dyes. It is found that the g-C3N4 shows great potential in the fields of photocatalytic water decomposition for hydrogen production and degradation of organic pollutants due to its unique band gap, nontoxicity, low cost and wide range of sources. Future research should continue to explore more kinds of template materials and their preparation processes, with the aim of realizing further enhancement of the performance of g-C3N4 photocatalysts and promoting their practical applications in the fields of environment and energy.

Adsorption performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the removal of pharmaceutical contaminants: a molecular dynamics simulation study

The rising presence of drug-related contaminants in water sources is a major environmental and public health concern. Several studies have addressed the hazardous influence of these pollutants on the lives of over 400 million people worldwide. In this study, we used molecular dynamics simulations to evaluate the efficacy of two promising composite materials for the removal of pharmaceutical contaminants by using the adsorption technique. Graphitic carbon nitride/graphene (g-C3N4/graphene) and metal-organic framework (MIL-101(Fe))/graphene have been simulated for the first time for the removal of three of the most common pollutants (acetaminophen (AC), caffeine (CAF), and sulfamethoxazole (SMZ)). The nanocomposite structure has been created and optimized using the geometry optimization task in the DFTB Modules in the Amsterdam Modeling Suite. We summarized the condition of the essential parameters (Temperature, pressure, and density) of the simulation box during the MD-simulation to ensure the accuracy of our MD-simulation results. The adsorption process, van der Waals interactions, and the adsorption capacity have been calculated by using the Reactive Forcefield (ReaxFF) software. We found that the combination of MIL-101(Fe)/graphene had a higher adsorption capacity for the removal of pharmaceutical contaminants than g-C3N4/graphene. At 40 Picosecond (Ps), 80 molecules of each pharmaceutical contaminants (AC, CAF and SMZ) have been adsorbed by MIL-101(Fe)/graphene with higher exothermic energy equated to (−1174, −1630, and − 2347) MJ/mol respectively. While for g-C3N4/graphene at 40 Ps, 70 molecules of each pharmaceutical contaminants have been adsorbed with exothermic energy equated to (−924, −966, and − 1268) MJ/mol respectively. Also, our results showed that the combination of g-C₃N₄/graphene and MIL-101(Fe)/graphene both have remarkable properties that make them effective at resisting surface clogging. Finally, the results showed that the adsorption kinetics followed a pseudo-first order model, while the adsorption isotherms for AC, CAF and SMZ adhered to Freundlich model.

A High-Performance and Flexible Electrothermal Heater with Bending Tolerance from Layer-by-Layer Self-Assembled Graphite Nanoplates and Carbon Black on Paper

A High-Performance and Flexible Electrothermal Heater with Bending Tolerance from Layer-by-Layer Self-Assembled Graphite Nanoplates and Carbon Black on Paper

Optical properties of carbon dots generated in liquid by pulsed IR laser at 1064 nm

Biocompatible carbon dots (CDs) have been synthesized by the laser ablation of graphite and vegetable carbon (charcoal) placed in a phosphate-buffered saline (PBS) solution. The carbon nanoparticles are produced by a pulsed IR laser beam, operating at 1064 nm, 100 mJ energy, and 3 ns pulse duration, interacting with the carbon matrix placed in the liquid at a 0.2 Hz repetition rate. The ablation rate, in terms of removed carbon mass per laser shot, was evaluated to be about 75.8 ng/pulse and 758 ng/pulse for graphite and charcoal, respectively. Optical and electronic microscopy, UV-Vis spectroscopy, and luminescence measurements were employed to evince the CDs dispersion through its photoluminescence emission. The UV excitation at a 365 nm wavelength induces CDs luminescence in the visible region, as a result of electron transition, at a wavelength band depending on the laser spot size, i.e., of the laser fluence. CDs luminescence emission obtained from charcoal is independent of the laser fluence, showing a major emission peak around 475 nm and a secondary emission peak at 515 nm. CDs luminescence emission obtained from graphite depends on the laser fluence, showing a minor wavelength band, around 474 nm, at high laser fluences and a major wavelength band, around 670 nm, at low laser fluence. The CDs luminescence of the produced biocompatible solution finds many applications in the bio-medical field, as will be presented and discussed.

Enhancing photovoltaic performance of dye-sensitized solar cells through TiO2/g-C3N4 nanocomposite photoanodes for improved charge carrier management

This study explores the enhancement of dye-sensitized solar cells (DSSCs) through the modification of porous TiO2 photoanodes by incorporating two-dimensional graphitic carbon nitride (g-C3N4) synthesized from urea. The combination of wide-bandgap TiO2 with narrow-bandgap g-C₃N₄ extends the optical response range of the TiO2 heterostructure composites from ultraviolet to visible light. The introduction of g-C3N4 with TiO2 to form a heterojunction significantly boosts the photovoltaic performance of the device by minimizing charge recombination at the photoanode-electrolyte interface. Upon optimizing the g-C3N4 loading, a peak power conversion efficiency (PCE) of 10.79 % is achieved, representing an impressive 42 % improvement over the pristine TiO2-based device. This enhancement is primarily attributed to the efficient separation of photogenerated charge carriers, facilitated by the type II band alignment between g-C3N4 and TiO2. This alignment, enabled by favorable conduction and valence band offsets, accelerates the separation of photogenerated carriers and prolongs electron lifetime.

NiPd Nanoparticles on Nanoporous Carbon Embedded in Graphitic Carbon Nitride for Transfer Hydrogenation and Suzuki–Miyaura Coupling Reactions

NiPd Nanoparticles on Nanoporous Carbon Embedded in Graphitic Carbon Nitride for Transfer Hydrogenation and Suzuki–Miyaura Coupling Reactions

A Z-scheme g-C3N4/TiO2 heterojunction for enhanced performance in protecting magnesium and nickel couple from galvanic corrosion

Large interfacial contact is crucial for designing novel heterostructure materials to achieve good photoelectrochemical performance. Herein, we prepared a composite photoanode consisting of titanium dioxide (TiO2) nanotubes and graphitic carbon nitride (g-C3N4) nanosheets for enhancing the photocathodic protection (PCP) capability of the nickel-coated Mg alloy (Mg/Ni). The composite g-C3N4/TiO2 (CN/TiO2) photoanode was achieved by depositing g-C3N4 on the TiO2 nanotubes grown titanium foil via a one-step thermal polymerization of melamine and thiourea mixture. A series of characterizations, including transmission electron microscope, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectra, manifested the successful deposition of g-C3N4 at the inner wall of the TiO2 nanotubes to achieve sufficient interfacial contact and the formation of a Z-scheme heterojunction to promote the charge carriers’ transfer and separation. Compared with the pure TiO2 photoanode, the heterojunction exhibited enhanced photoelectrochemical and photocathodic protection performances, which was confirmed by the electrochemical measurements. The heterojunction achieved a duration of 6.5 h to protect the Mg-Ni couple from galvanic corrosion, representing a tenfold enhancement compared with the uncoupled Mg/Ni electrode. These findings demonstrate the great potential of constructing a unique Z-scheme heterojunction with a sizeable interfacial contact area to enhance the PCP capability of metals.

A Well‐Coupled Supramolecular System Accelerates Photophosphorylation

AbstractSupramolecular assembly allows multiple chemical/bio‐components integrated as one system for cascade biochemical reactions. Herein the graphitic carbon nitrides (g‐C3N4) as photocatalyst trapped in a dipeptide hydrogel covering adenosine triphosphate (ATP) synthase accelerates the photophosphorylation through ATP synthesis. Self‐assembled N‐fluorenylmethoxycarbonyl diphenylalanine (Fmoc‐FF) as nanofibrils to allow g‐C3N4 nanosheets are embedded as a complex Fmoc‐FF/g‐C3N4 hydrogel. Fmoc‐FF gel exhibits good electronic coupling with g‐C3N4, which enables a photo‐induced proton generation. The transmembrane proton gradient can be established by ATP synthase‐lipid reconstituted on the surface of the Fmoc‐FF/g‐C3N4 hydrogel to enhance the ATP synthesis. It indicates that the Fmoc‐FF/g‐C3N4/ATP synthase‐lipid film can possess a longer‐term ATP production capability and allow repeated immersion for sustained ATP production. Such a hydrogel‐supported ATP synthesis platform is achieved by a procedure at a larger scale.

Oxygen-Doped Porous Ultrathin Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Evolution and Rhodamine B Degradation.

Graphite phase carbon nitride (g-C3N4) is a highly promising metal-free photocatalyst, but its low activity, due to limited quantum efficiency and small specific surface area, restricts its practical application. While exfoliating bulk crystals into porous thin-layer nanosheets and incorporating dopants have been shown to improve photocatalytic efficiency, these methods are typically complex, time-consuming, and costly processes. In this study, we developed a simple approach to synthesize oxygen-doped porous g-C3N4 (OCN) nanosheets. The resulting OCN exhibited significantly enhanced light absorption and visible-light photocatalytic activity compared to bulk g-C3N4 (BCN) and g-C3N4 (CN). The OCN achieved an impressive hydrogen evolution reaction (HER) rate of 8.02 mmol g-1 h-1, eight times greater than BCN, and demonstrated a high Rhodamine B (RhB) degradation rate of 97.3 % owing to the generation of abundant singlet oxygen. These improvements in photocatalytic performance are attributed to the narrow band gap and enhanced electron transfer properties, suggesting a promising route for the efficient design of g-C3N4-based photocatalysts.

Development of engineered Zn-MOF/g-C3N4 based photoelectrochemical system for real-time sensors and removal of naproxen in wastewater

Naproxen-contaminated water may lead to the accumulation of the drug in aquatic organisms and can pose high risks to an aquatic environment and human beings. Therefore, this work aimed to develop photoelectrochemical sensing and degradation of naproxen (NPX) using zinc-metal organic framework /graphitic carbon nitride thin film-based fluorine-doped tin oxide (Zn-MOF/g-C3N4/FTO) as anode material for the sensing and degradation of naproxen (NPX). The surface morphology, structure, surface property, surface area, optical property, photocurrent, and charge transfer kinetics abilities were studied using different techniques. The nanocomposites showed a superior photocurrent response (0.815 mA cm-2) compared to the original g-C3N4 (0.328 mA cm-2). The photo-anode made of Zn-MOF@g-C3N4/FTO displayed the highest photocurrent value, indicating that the alignment of the two semiconductor bands prevented the quick recombination of electron-hole pairs. Owing to these attractive features, the Zn-MOF/g-C3N4/FTO electrode was applied for photoelectrochemical detection of NPX using chronoamperometry. Interestingly, the nanocomposites-based FTO ascribed a lower detection limit (2.3 ng l-1) with a wide linear range concentration of NPX (0.5 to 200 µg l-1). Additionally, the analytical assessment of repeatability and reproducibility demonstrated robust performance, with commendable relative standard deviations (RSD%) of 2.54 % and 2.40 %, respectively. On the other hand, a remarkable degradation efficiency of 97.52 % was attained when employing a bias potential of 0.1 V during a 2 h photoelectrocatalytic oxidation of NPX. The degradation process was primarily driven by the active participation of holes and hydroxyl radicals in ring opening and subsequent cleavage of by-products. The notable effectiveness of this degradation can be attributed to the combined and synergistic effects of both electrochemical and photocatalytic degradation techniques. The current state demonstrates its effectiveness in the photoelectrochemical sensing and removal of NPX using MOF/g-C3N4 nanocomposites-based electrode materials in wastewater.

Polarized electric field-mediated graphitic carbon nitride-based S-scheme heterostructure for efficient photocatalytic removal of bisphenol A

Tuning interface charge transfer is considered as a feasible way to promote electron migration and separation in heterojunction system, but the role of in-plane electron behavior in single phase has received little attention. Here, a carboxyl functionalized graphitic carbon nitride (CCN) coupled PbBiO2Br (PBOB) S-scheme heterostructure is elaborately designed for investigation. Compared with pristine CN/PBOB, although the existence of carboxyl group weakens the built-in electric field strength of CCN/PBOB (ΔΦ = 0.44 eV), the formed polarized electric field (µ = 3.18 Debye) is conducive to the pre-separation of photogenerated electrons and holes in CCN, thereby improving interface charge transfer. In addition, the introduced carboxyl group can also serve as an O2 adsorption site to enhance its activation, and generate reactive oxygen species (ROS) through a two-step single-electron O2 reduction route. Thus, the optimized CCN/PBOB exhibits excellent photocatalytic ROS generation ability, which can remove 88.7 % of bisphenol A and significantly reduce the acute toxicity of the formed intermediates. This work provides a new perspective for the development of advanced heterojunction photocatalyst by regulating in-plane/interface charge dynamics, and helps to fully understand the pollutant detoxification/degradation process initiated by molecular oxygen activation.