Carbon Nitride Research Articles

Visible light-induced synthesis of benzothiazole derivatives using graphitic carbon nitride as a recyclable metal-free photocatalyst

Visible light-induced synthesis of benzothiazole derivatives using graphitic carbon nitride as a recyclable metal-free photocatalyst

Polymerization Improvement of Graphitic Carbon Nitride Films Derived from Melamine and Thiourea.

Deposition of low-cost, efficient, and environmentally friendly graphitic carbon nitride (g-CN) films as photoanodes is a crucial step for constructing photoelectrochemical (PEC) cells and exploring their PEC performance. Currently, the improvement of the photocurrent density of g-CN films is badly needed for their practical applications in PEC water splitting. Enhancing the g-CN crystallinity by optimizing their synthesis conditions only through screening appropriate reactant precursors is insufficient for this purpose. Herein, using melamine and thiourea precursors with mass ratio 5:1, the degree of polymerization of g-CN thin films is successfully improved by a thermal vapor condensation method. The obtained pure g-CN exhibits a remarkably enhanced photocurrent density of 404.4µA cm-2 at 1.23V versus reversible hydrogen electrodes. Theoretical calculations reveal that the continuous attachment of small carbodiimide (HN═C═NH) mainly generated by thiourea to the melamine matrix facilitates the formation of large-area conjugated structure, which fundamentally determines better charge carrier separation and transfer thereby enhancing the PEC performance. This work realizes the synthesis of well-polymerized g-CN films with improved PEC activity and offers a computational understanding for the nucleation and growth mechanism of the polycrystalline g-CN.

SORPTION OF Fe(III) IONS ON CARBON NITRIDES SYNTHESIED FROM VARIOUS PRECURSORS

In the present work, graphitic carbon nitride powders synthesized from urea, melamine and dicyandiamide were ultrasonic exfoliated and used to evaluate their adsorption efficiency for iron ions –Fe(III) from aqueous solution. It has been established that the efficiency of sorption is significantly influenced by the pH of the medium, contact time, weight of the sorbent and the initial concentration of Fe(III). High adsorption of the iron ion (97–99%) occurs at pH4. It is shown that the Fe(III) sorption isotherm on the studied carbon nitride samples can be modeled by both Langmuir and Freundlich adsorption isotherms based on correlation coefficients

Sustainable Photocatalytic Mitigation of 2-Mercaptobenzothiazole by Expired Medicine Derived Metal-Free Graphitic Carbon Nitride Photocatalyst

Sustainable Photocatalytic Mitigation of 2-Mercaptobenzothiazole by Expired Medicine Derived Metal-Free Graphitic Carbon Nitride Photocatalyst

Unveiling N-doped carbon nitride aerogel for efficient electrocatalytic water splitting application

Unveiling N-doped carbon nitride aerogel for efficient electrocatalytic water splitting application

Large-Current CO2 Electromethanation Through Active Hydrogen Regulation Over Carbon Nitride.

Electromethanation of CO2 has received intensive attention due to its high calorific value and convenient storage along with transportation to accommodate industrial demands. However, it is limited by sluggish multi-step proton-coupled electron transfer kinetics and undesired *H coupling under high current density, posing great challenges to its commercialization. Herein, carbon nitride (CN) with superior hydrogen adsorption ability is used as an active-hydrogen adsorption and supply material. Through a facile liquid-assisted exfoliation and electrostatic self-assembly strategy to strengthen its interfacial contacts with Cu2O catalysts, yielding a strengthened CH4 production 52 times higher than that of pristine Cu2O. Flow-cell test ultimately achieved FECH4 and remarkably CH4 partial current density of 61% and 561mAcm-2, respectively. With in situ ATR-FTIR spectra and DFT calculations, it is established that strengthened interfaces enabled abundant *H tethered by ─C─N═C─ sites in CN nanosheets and oriented to the *CO hydrogenation to *CHO and *CHx on Cu species. This work reveals the profound influence of fine-expanded interfaces with dimensional materials on the product distribution and yield through the active-hydrogen management, which is of reference value for other small-molecule electro-polarization dominated by the proton-coupled electron transfer (PCET) process (e.g., N2, O2, etc.).

Enhanced Photocatalytic Hydrogen Peroxide Synthesis Performance of Polymeric Carbon Nitrides with a Controllable Carbonization Strategy

Enhanced Photocatalytic Hydrogen Peroxide Synthesis Performance of Polymeric Carbon Nitrides with a Controllable Carbonization Strategy

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.

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.

Iron Oxide Clusters as Electron Donors Under Light Enhance Oxygen Reduction Kinetics at Atomically Dispersed Fe for Photocatalytic CH4 Partial Oxidation

AbstractPhotocatalytic CH4 oxidation to CH3OH emerges as a promising strategy to sustainably utilize natural gas and mitigate the greenhouse effect. However, there remains a significant challenge for the synthesis of methanol by using O2 at low temperature. Inspired by the catalytic structure in soluble methane monooxygenase (MMO) and the corresponding reaction mechanism, we prepared a biomimetic photocatalyst with the decoration of Fe2O3 nanoclusters and satellite Fe single atoms immobilized on carbon nitride. The catalyst demonstrates an excellent CH3OH productivity of 5.02 mmol ⋅ gcat−1 ⋅ h−1 with CH3OH selectivity of 98.5 %. Mechanism studies reveal that the synergy between Fe2O3 nanoclusters and Fe single atoms establishes a dual‐Fe site as MMO for O2 activation and subsequent CH4 partial oxidation. Moreover, the light excitation of Fe2O3 nanoclusters with a relative narrow band gap could deliver the electrons and protons to atomic Fe that facilitating the oxygen reduction kinetics for the robust of CH3OH synthesis.

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

Solar 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 30min. Additionally, the photocatalyst can be integrated into a continuous-flow fixed-bed reactor, facilitating clean water production for up to 60h at a rate of 121Lm-2day-1, highlighting its significant potential for POU applications.

Oriented and Continuous Phase Epitaxy Enabled by A Highly Dendrite‐Resistant Plane Toward Super‐High Areal Capacity Zinc Metal Batteries

AbstractUnstable Zn metal anodes with dendrites/side reactions are becoming the main obstacle to the practical application of zinc‐based aqueous batteries. Epitaxial growth has been considered to be an effective strategy for solving these issues, especially for inducing the (002) plane growth. Nonetheless, the (002)‐textured Zn is difficult to achieve highly stable Zn anode under high capacity resulting from its large lattice distortion. Herein, the Cu single atom anchored polymeric carbon nitride (Cu@PCN) is synthesized by a facile thermal polymerization method. Serving as multifunctional protective layer on Zn surface, the Cu@PCN can provide massive nucleation sites at a nano‐level and uniformize the electron distribution through coordination engineering. Optimizing the coordination structures of single Cu and N atoms within the carbon matrix enables a redistribution for electric field and regulates ion flux. More importantly, this coordination strategy with single atoms is first reported to customize oriented and continuous phase epitaxy along highly dendrite‐resistant Zn(101) plane by reducing (101) surface energy. This pattern of oriented dense deposition leads to stable and reversible Zn plating/stripping is achieved, which delivers an extended cycling life of 550 h at 10 A cm−2, 20 mAh cm−2. The practical full cell also displays stable performance for 1200 cycles.

Metal Single Atom-Hydroxyl Incorporation in Poly(heptazine imide) to Create Active Sites for Photocatalytic Water Oxidation.

Poly(heptazine imide) (PHI) salts are extensively researched crystalline carbon nitride photocatalysts, but their photocatalytic water oxidation (PWO) performance is scarcely researched because of the difficulty in creating efficient active sites. Interference of metal ion (e.g., Na+ and K+) loss from the PHI salts in their PWO research has hardly been considered. Herein, metal single atom─OH (e.g., Co─OH) groups are incorporated into PHI to create efficient PWO active sites, via simple ion metathesis, hydrolysis, and deprotonation. The Co─OH modified PHI exhibits 9.3-fold higher PWO (oxygen evolution) activity than PHI, with an external quantum yield reaching 0.44% even at 600 nm. Excluding interference of the metal ion loss, the function of the Co─OH incorporation is evidenced mainly to facilitate the oxygen evolution reaction, as well as to promote photogenerated charge separation and raise visible light absorption, with the role of the OH especially revealed. Moreover, it is discovered that Na+ loss from sodium PHI will decrease its PWO activity, protonation of PHI has a detrimental effect on its PWO performance, and some other metal single atom─OH incorporation in PHI can also enhance its PWO activity. Overall, this work provides a general way to create PWO active sites in PHI.

XPS investigation of CuxO-functionalized amorphous carbon nitride

In this work, we report the x-ray photoelectron spectroscopy characterization of a novel nanocomposite (photo)electrocatalyst for the oxygen evolution reaction, based on amorphous carbon nitride (aCN) functionalized with CuxO nanoparticles (NPs). The specimen has been fabricated employing two sequential plasma-assisted processes, involving the initial aCN deposition onto conductive glass via magnetron sputtering, followed by carbon nitride functionalization with CuxO (x = 1, 2) NPs by radio frequency-sputtering. The results reported herein include the survey spectrum and the high-resolution C 1s, N 1s, O 1s, Cu 2p, and Cu LMM signals. The most significant spectral features are analyzed and critically discussed.

Cu/S Co-anchoring junction boosted the photogenerated carrier separation efficiency in g-C3N5 for enhanced H2 evolution

C3N5 is emerging as an important visible light catalyst because of its narrow band gap, nontoxicity and thermal stability. Herein, sulfur-doped g-C3N5 (SCN) was prepared by copolymerization of thioacetamide (TAA) and 3-amino-1,2,4-triazole (3-AT). Then copper nanoparticles (Cu NPs) were anchored onto the SCN framework, resulting in the formation of Cu/SCN. It was found that the average H2 production rate of SCN and Cu/SCN was 0.76 and 1.34 mmol g−1 h−1, which was much higher than that of C3N5, respectively. Acting as a new active spots, sulfur doping effectively reduces the band gap of g-C3N5, and the formation of S-Cu bonds further creates an efficient electron transport pathway. As a result, Cu/SCN possesses a broader visible light absorption spectrum, stronger reduction capability, and greater efficiency in photo-induced carrier separation and transfer. Therefore, this work introduces a novel strategy for design of high efficiency photocatalytic H2 evolution carbon nitride through non-noble metal and sulfur anchoring junction.

Carbon Nitride‐Supported Zinc Oxide Nanocomposite for the Electrochemical Detection of Dopamine and the Development of Disposable Sensors

AbstractThe carbon nitride‐supported zinc oxide (CNZO) nanocomposite was synthesized through a high‐temperature synthesis method, resulting in zinc oxide nanoparticles with an average size of ~44 nm, dispersed on a carbon nitride matrix. X‐ray diffraction confirmed the formation of the hexagonal wurtzite phase of zinc oxide, with a space group of P63mc. X‐ray photoelectron spectroscopy and Fourier‐transform infrared analysis further verified the presence of both zinc oxide and carbon nitride. The CNZO nanocomposite served as a catalyst for the electrochemical detection of dopamine, achieving limit of detection and sensitivity of 2.66 μM and 6.23 μA μM−1 cm−2 respectively, using square wave voltammetry technique. Cyclic voltammetry experiments demonstrated excellent electroactivity of the CNZO nanocomposite in a neutral pH environment. An electrochemical paper‐based analytical device (EPAD) was designed and successfully employed for the electrochemical analysis of dopamine in pharmaceutical samples using CNZO nanocomposites. Additionally, CNZO was used as an active material in the development of a disposable dopamine sensor based on an extended gate field‐effect transistor (EG‐FET). This sensor exhibited a sensitivity and limit of detection 18.22 μA μM−1 cm−2 and 0.36 μM, respectively, with a correlation coefficient of 0.99.

In situ Monitoring of Photocatalysis on Polymeric Carbon Nitride Thin Films.

Polymeric carbon nitride has attracted significant interest in heterogeneous photocatalysis due to its activity under visible-light irradiation. Herein, we report on using carbon nitride-coated NMR tubes for in situ studies of photocatalytic reaction mechanisms. In a first step, we exploited carbon nitride-coated crimp vials as batch photoreactors for visible photocatalytic fluorinations of unactivated C(sp3)-H bonds, with moderate to excellent yields and reusability over multiple cycles. Eventually, carbon nitride-coated NMR tubes were used as a photoreactor by coupling them with optical fiber irradiation directly inside the spectrometer. This enabled us to follow the reaction with in situ NMR spectroscopy identifying reactive intermediates otherwise elusive in conventional analyses. The method provides advantages for the study of photocatalytic mechanisms of complex reactions and substantially reduces the need of comparative tests for depicting reaction intermediates and conversion pathways.

Phase Reconstruction‐Assisted Electron‐Li+ Reservoirs Enable High‐Performance Li‐S Battery Operation Across Wide Temperature Range

AbstractLithium‐sulfur batteries (LSBs) are known as high energy density, but their performance deteriorates sharply under high/low‐temperature surroundings, due to the sluggish kinetics of sulfur redox conversion and Li+ transport. Herein, a catalytic strategy of phase reconstruction with abundant “electron‐Li+” reservoirs has been proposed to simultaneously regulate electron and Li+ exchange. As a demo, the 1T‐phase lithiation molybdenum disulfide grown on hollow carbon nitride (1T‐LixMoS2/HC3N4) is achieved via in situ electrochemical modulation, where the 1T‐LixMoS2 serves as an auxiliary “Li+ source” for facilitating Li+ transport and the HC3N4 acts as an electron donor for electronic supplier. From the theoretical calculations, experimental and post‐modern analyses, the relationship between the catalytic behaviors and mechanism of “electron‐Li+” reservoirs in accelerating the rate‐determining kinetics of sulfur species are deeply understood. Consequently, the cells with 1T‐LixMoS2/HC3N4/PP functional separator demonstrate excellent long‐term electrochemical performance and stabilize the areal capacity of 6 mAh cm−2 under 5.0 mg cm−2. Even exposed to robust surroundings from high (60 °C) to low (0 °C) temperatures, the optimized cells exhibit high‐capacity retention of 76.2% and 90.4% after 100 cycles, respectively, pointing out the potential application of catalysts with phase reconstruction‐assisted “electron‐Li+” reservoirs in LSBs.

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

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