N-rich Carbon Research Articles

In situ construction of Flowerlike bismuth oxide (BiO2-x)/N-rich carbon nitride (C3N5) S-scheme heterojunctions with enhanced structural defects for the efficient photocatalytic removal of tetracycline antibiotic and RhB

Efficient photocatalysts for the simultaneous removal of organic dyes and antibiotics are crucial for sustainable environmental management. In this study, we designed and synthesized a C3N5/BiO2-x S-type heterojunction photocatalyst with structural defects using a hydrothermal method, aimed at degrading both Rhodamine B (RhB) and tetracycline (TC). The degradation kinetic constants for RhB and TC were 0.0809 min−1 and 0.0535 min−1, respectively, showing improvements of 9.52 and 25.48 times over pure C3N5, and 2.90 and 1.49 times over BiO2-x. This enhanced performance is attributed to the unique electron transfer mechanism of the S-scheme heterojunction and the structural defects that facilitate efficient separation of electron-hole (e−-h+) pairs. Free radical trapping experiments indicated that the main reactive oxygen species (ROS) involved are ·O2− and h+. Additionally, electrochemical impedance spectroscopy (EIS) and transient photocurrent response (TPR) measurements confirmed improved separation and transfer of photogenerated e−-h+ pairs in the C3N5/BiO2-x heterojunction. The higher density of structural defects in C3N5/BiO2-x compared to individual BiO2-x counterparts enhances its ability to activate and photo-oxidize TC and degrade RhB. Consequently, C3N5/BiO2-x demonstrates significant potential as a photocatalyst for improving water quality.

Ultra-sensitive zinc cobaltate assembled on N-rich carbon nitride electrochemical sensor for the detection of paraquat in food samples

BackgroundParaquat (PQ) from agricultural waste cause contamination in water bodies, groundwater, soil, and foods has received increasing attention regarding health safety. On-site-based detection is much needed along with rapid results, selectivity and sensitivity, which can be achieved through an electrochemical-based sensor. MethodsThis work provides, an electrochemical sensor based on zinc cobaltite (ZnCo2O4) nanostructure strongly attracted through electrostatic interaction with the carbon nitride (C3N5; CN) nanosheets modified on a glassy carbon electrode (GCE) for the determination of paraquat (PQ). The strong immobilization of ZnCo2O4 over CN2 on GCE synergistically shows excellent sensing of PQ due to high interfacial charge transfer effect. Significant findingsIn addition, the electrochemical studies were performed using CV and DPV analysis which exhibits a good limit of detection (7.6 nM) and sensitivity (0.201 µA cm-2) towards PQ detection. Furthermore, the modified electrode was applied practically in real food samples for PQ detection with excellent recoveries.

Accelerating the Hydrogen Evolution Kinetics with a Pulsed Laser-Synthesized Platinum Nanocluster-Decorated Nitrogen-Doped Carbon Electrocatalyst for Alkaline Seawater Electrolysis.

Efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) in alkaline seawater environments are essential for sustainable hydrogen production. Zeolitic imidazolate framework-8 (ZIF-8) is synthesized through pulsed laser ablation in liquid, followed by pyrolysis, producing N-doped porous carbon (NC). NC matrix serves as a self-template, enabling Pt nanocluster decoration (NC-Pt) via pulsed laser irradiation in liquid. NC-Pt exhibits a large surface area, porous structure, high conductivity, N-rich carbon, abundant active sites, low Pt content, and a strong NC-Pt interaction. These properties enhance efficient mass transport during the HER. Remarkably, the optimized NC-Pt-4 catalyst achieves low HER overpotentials of 52, 57, and 53mV to attain 10mA cm-2 in alkaline, alkaline seawater, and simulated seawater, surpassing commercial Pt/C catalysts. In a two-electrode system with NC-Pt-4(-)ǀǀIrO2(+) as cathode and anode, it demonstrates excellent direct seawater electrolysis performance, with a low cell voltage of 1.63mV to attain 10mA cm-2 and remarkable stability. This study presents a rapid and efficient method for fabricating cost-effective and highly effective electrocatalysts for hydrogen production in alkaline and alkaline seawater environments.

A Bifunctional Carbon-LiNO3 Composite Interlayer for Stable Lithium Metal Powder Electrodes as High Energy Density Anode Material in Lithium Batteries

Lithium metal remains a promising candidate for high-energy-density rechargeable batteries due to its exceptional specific capacity and low reduction potential. However, practical implementation of lithium metal anodes faces challenges such as dendrite formation, limited cycle life, and safety concerns. This study introduces a novel approach to enhance the performance of lithium metal powder (LMP)-based electrodes by embedding a LiNO3-carbon composite interlayer between the LMP electrode and the copper foil current collector. The N-rich carbon interlayer acts as a reservoir for LiNO3, enabling its gradual release to maintain prolonged stability of the interfacial reactions of the Li-metal and providing additional Li nucleation sites. Our findings demonstrate that the LiNO3-carbon composite effectively suppresses dendrite formation, improves reversible capacity, and stabilizes the solid electrolyte interphase. Additionally, we validated the fast-charging capabilities of the Li/NCM622 half-cell employing the LiNO3-carbon-coated Cu foil with LMP electrodes. Our results highlight the significant synergistic effect of the LiNO3 additive and carbon interlayer in enhancing the performance of lithium metal-based batteries.

Synthesis of nitrogen-rich porous carbon via a molecular confinement strategy for activating peroxymonosulfate in bisphenol A degradation: Role of singlet oxygen and electron transfer process

Nitrogen-doped porous carbon (NPC) catalysts show potential for activating peroxymonosulfate (PMS) to treat water pollution. However, nitrogen (N) experiences significant loss during pyrolysis, posing challenges for synthesizing N-rich carbon catalysts. This study innovatively proposed a molecular confinement strategy using the C−S−C bond formed between graphitic carbon nitride and mercaptan. Under this confinement, we successfully synthesized NPC-15 with a high N content (21.4 at%), surpassing most catalysts reported in the literature. NPC-15/PMS system showed excellent performance in degrading bisphenol A (BPA), achieving complete degradation within 3 min (kobs = 1.771 min−1), surpassing the effectiveness of most previously reported catalysts. The NPC-15/PMS system exhibited excellent performance and stability under various conditions, reducing BPA toxicity to ecological and human embryonic kidney cells. Moreover, it maintained stability during long-term continuous operation in a fixed-bed reactor, showing promise for practical applications. Through experiments and theoretical calculations, the mechanism of NPC-15 activating PMS was comprehensively investigated. The NPC/PMS system operated via a dual non-radical pathway involving singlet oxygen and electron transfer process induced by pyridinic N and graphitic N dual active sites. Pyridinic N promoted the generation of 1O2, while graphitic N supported the electron transfer process. This study introduced a new strategy for the preparation of N-rich carbon catalysts and proposed a novel method for the removal of emerging pollutants in water.

The Faradaic-Induced hybrid capacitive engine enables high-performance selective defluorination via capacitive deionization

Fluoride (F-) contamination has become a pressing environmental concern owing to its extensive origins and severe toxicity. Capacitive deionization (CDI) emerges as a promising technique for efficient defluorination, with the development of electrode materials being pivotal to its efficiency. Herein, we present a novel design of Sb-decorated N-rich carbon composites (SNTPCs) for the formation of a hybrid capacitive engine that integrates Faradaic-induced pseudocapacitance and electrical double layer capacitance, enabling efficient F- electrosorption. This approach features a distinctive N-rich carbonaceous laminar framework that not only guarantees rapid ion diffusion and electron transfer but also provides a dense electrical double layer for F- storage. The Sb sites are electrically stimulated to release the intrinsic affinity with F-, forming the Faradaic Sb-F bonds. The SNTPC2 electrode exhibits the exceptional saturation removal capability and dynamic electrosorption capacity for defluorination, reaching 178.58 and 34.77 mg F/g at 1.2 V respectively, which exceeds most reported F- capture electrodes. It also demonstrates excellent selectivity towards F- in complex conditions and exhibits effectiveness across a wide range of pH values. Additionally, the utilized electrode performs outstanding regeneration performance after 20 consecutive cycles. This study provides innovative perspectives for the effective elimination of fluoride pollution in aquatic environments.

Polyacrylonitrile-based 3D N-rich activated porous carbon synergized with Co-doped MoS2 for promoted electrocatalytic hydrogen evolution

MoS2 is a promising electrocatalyst for the hydrogen evolution reaction (HER), but it is limited by its own agglomeration, low conductivity, and surface inertness. In this study, we report a well-organized 3D hybrid structure of N-rich active porous carbon (CN) synergized with Co-doped molybdenum disulfide (Co-MoS2@CN) for promoted electrocatalytic hydrogen evolution. MoS2 nanosheets were grown vertically on CN and the pore structure was improved, which exposed abundant edge active sites. The N-rich graphite structure and abundant pore structure of CN enhanced the electron transfer ability and stability of the 3D hybrid structure. Meanwhile, doping of Co atoms optimized the catalytic activity of the in-plane sulfur sites and induced a partial transition from 2H-MoS2 to 1 T-MoS2. The resulting Co-MoS2@CN 3D hybrid structure exhibited excellent HER electrocatalytic performance, had a current density of 10 mA cm−2 in a 0.5 M H2SO4 aqueous solution by an overpotential of 137 mV, and showed excellent stability in a 24 h HER test. DFT calculations confirmed that the heterogeneous interface constructed by CN and Co-MoS2 effectively optimized Gibbs free energy (ΔGH*) of the MoS2 hydrogen adsorption site and enhanced the interfacial electron transfer capacity, which ensured rapid HER kinetics during the electrocatalytic process.

Surface confinement boosts the in-situ formation of peroxydisulfate metastable complexes on assembled hollow N-rich carbon plates for water purification

Herein, an innovative solution was proposed by engineering the pore-confinement microenvironment in hollow nanoporous carbon to enhance the enrichment and diffusion kinetics of reactants for an efficient peroxydisulfate-based electron transfer process (PDS-ETP). Specifically, hollow N-rich carbon plate-assembled flowers (NCU900) with accessible surface area and abundant nano-confined channels (< 4 nm) were synthesized via a secondary N doping strategy to activate PDS. The confined system (0.42 min−1) exhibits a 21-fold higher catalytic degradation kinetics than the unconfined system (0.02 min−1) toward bisphenol A, along with an outstanding stability (45 h, 94.59 %) evaluated by the continuous flow reactor. Density functional theory calculations show that the kinetics enhancement is attributed to the stronger PDS adsorption and electron transfer at active sites caused by sufficient confined space. This work aims to promote the rational design of carbon-based catalysts with a confinement effect for high-performance PDS-ETP.

Fe3O4 Nanoparticles Embedded into Pyridinic-N-Rich Carbon Nanohoneycomb with Strong dx2-Pz Orbital Hybridization for High-Performance Electromagnetic Wave Absorption.

Carbon-based magnetic nanocomposites as promising lightweight electromagnetic wave (EMW) absorbents are expected to address critical issues caused by electromagnetic pollution. Herein, Fe3O4 nanoparticles embedded into a 3D N-rich porous carbon nanohoneycomb (Fe3O4@NC) were developed via the pyrolysis of an in-situ-polymerized compound of m-phenylenediamine initiated by FeCl2 in the presence of NaCl crystals as templates. Results demonstrate that Fe3O4@NC features highly dispersed Fe3O4 nanoparticles into an ultrahigh specific pyridinic-N doping carbon matrix, resulting in excellent impedance matching characteristics and electromagnetic wave absorbing capability with the biggest effective absorption bandwidth (EAB) of up to 7.1 GHz and the minimum reflective loss (RLmin) of up to -65.5 dB in the thin thickness of 2.5 and 2.3 mm, respectively, which also outperforms the majority of carbon-based absorbers reported. Meanwhile, its high absorption performance is further demonstrated by an ethylene propylene diene monomer wave absorbing patch filled with 8.0 wt % Fe3O4@NC, which can completely shield a 5G signal in a mobile phone. In addition, theory calculation reveals that there is a strongest dx2-Pz orbital hybridization interaction between Fe3O4 clusters and pyridinic-N dopants in the carbon network, compared with other kinds of N dopants, which can not only generate more dipoles of carbon networks but also increase net magnetic moments of Fe3O4, thereby leading to a coupling effect of efficient dielectric and magnetic losses. This work provides new insights into the precise design and synthesis of carbon-based magnetic composites with specific interface interactions and morphological effects for high-efficiency EMW absorption materials.

N-rich carbon nanosphere as fluorescent nanoprobe for intracellular iron

Nitrogen rich carbon nanoparticles are known to provide higher fluorescence stokes shift, and thereby are potential candidates for fluorescent sensors. Herein, a facile one-step hydrothermal synthesis is reported for N-rich carbon nanospheres (G-CNS) from caffeine and o-phenylenediamine as precursors. The as-synthesized G-CNS showed high fluorescence with λem at 509 nm, with a highly selective fluorescence turn-off response towards Fe2+/Fe3+, rendering these carbon nanospheres as potential candidates to detect intracellular labile iron pool in live cells. The intracellular labile iron pool in iron-overloaded cells was sensed using the synthesized G-CNS. Mechanistically, the fluorescence quenching via dynamic pathway involves the formation of an excited state charge transfer process, which undergoes non-radiative decay.

Green synthesis of N-rich carbon dot-derived crosslinked covalent organic nanomaterial for multipurpose chromatographic applications.

Carbon dots (CDs) derived crosslinked covalent organic nanomaterials (CONs) possessing high specific surface area and abundant surface functional groups are considered to be potential candidates for multimodal chromatographic separations. Typically, the synthesis of CDs and CONs requires harsh reaction conditions and toxic organic solvents, hence, the pursuit of facile and mild preparation strategies is the goal of researchers. In this work, 3-aminopropyltriethoxysilane and D-glucose were used as nitrogen and carbon sources, respectively, to prepare amino-CDs (AmCDs) by rapid low-temperature polymerization rather than the common high-temperature and high-pressure reaction. Then, surface functionalization of the aminated silica gel was carried out in a deep eutectic solvent by using hydrophilic AmCDs and 1,3,5-triformylbenzene (TFB) as the functional monomers. Consequently, a novel N-rich CDs derived CON surface-functionalized silica gel (AmCDs-CON@SiO2) was obtained under mild reaction conditions. The combination of AmCDs and TFB created an ideal CON based chromatographicstationary phase. The incorporation of TFB not only contributed to the successful construction of a crosslinked CON, but also enhanced the interaction forces. The developed AmCDs-CON@SiO2 has a great potential for versatile applications in liquid chromatography. This study proposes a simple stationary phase preparation strategy by the surface modification of silica gel with CDs-based CON. Moreover, this study verified the application potential of CDs derived CON in chromatographic separation. This not only promotes the development of CDs in the field of liquid chromatographic stationary phase, but also provides some reference value for the wide application of cross-linked CON.

In situ construction of N-rich carbon nitride (C3N5)/silver phosphate (Ag3PO4) S-scheme heterojunctions for the efficient photocatalytic removal of levofloxacin antibiotic and RhB

In situ construction of N-rich carbon nitride (C3N5)/silver phosphate (Ag3PO4) S-scheme heterojunctions for the efficient photocatalytic removal of levofloxacin antibiotic and RhB

Sulfur doped N-rich nitrogen carbon nanocatalysts for enhancing photocatalytic reduction of uranium(VI)

Sulfur doped N-rich nitrogen carbon nanocatalysts for enhancing photocatalytic reduction of uranium(VI)

Low-crystallinity conductive multivalence iron sulfide-embedded S-doped anode and high-surface area O-doped cathode of 3D porous N-rich graphitic carbon frameworks for high-performance sodium-ion hybrid energy storages

Sodium-ion hybrid energy storages (SIHESs) are promising electrochemical energy storages for many applications, but their low energy and power densities are yet to be overcome. Herein, we report a strategy to realize ultrahigh-energy density and fast-rechargeable SIHESs. Ultrafine iron sulfide-embedded S-doped carbon/graphene (FS/C/G) anode materials are synthesized from iron-based metal-organic framework (MOF)/graphene oxide heterostructures via graphitic carbon formation and sulfidation. Operando and ex-situ analyses reveal that cycled iron sulfides are rescaled into low-crystallinity conductive fragments with Fe vacancies and multivalence Fe2+/Fe3+ states. Size reduction to fragments inside a 3D porous S-doped N-rich graphitic carbon framework induces high-capacity/high-rate FS/C/G performance. Moreover, 3D porous O-doped carbon cathode materials are synthesized from zeolitic imidazolate frameworks (ZIFs) via pyrolysis-assisted micropore and KOH-assisted mesopore formations. This ZIF-derived porous carbon (ZDPC) has a ∼20-fold higher surface area (3972 m2/g) than conventional ZDCs, O-induced micropores/N-rich sites for high capacity, heteroatom-induced ion-accessible defects/mesopores, and N-rich conductive graphitic carbon networks. Additionally, FS/C/G//ZDPC SHHES benefits from diffusion-controlled and capacitive reactions, as demonstrated by its hitherto highest energy density of 247 Wh kg-1 outperforming state-of-the-art SIHESs, fast-rechargeable power density (up to 34,748 W kg-1) exceeding battery-type reactions by more than 100 folds, and cycle stability with ∼100 % Coulombic efficiency over 5000 charge-discharge cycles.

Bimetallic FeCo nanoparticles embedded N-rich porous ZIF-derived carbon as highly active heterogeneous Fenton catalyst for degradation of tetracycline and organic dyes

Peroxymonosulfate (PMS) based advanced oxidation process (AOP) is used for the degradation of the organic molecules due to ease of reactive oxygen species (ROS) generation through activation. In this study, bimetallic FeCo nanoparticles (NPs) supported on N-doped porous carbons are prepared for the first time by in-situ co-precipitation of metal ions in ZIF-67 followed by carbonization. The prepared nanocomposite, denoted as Fe(x)Co@N-CZ-67, is used to activate PMS for Fenton-like degradations of tetracycline (TC) and dyes. The results reveal that about 96% of TC is degraded by Fe(0.4)Co@N-CZ-67 in 4 min. The catalyst can also degrade three organic dyes, namely methylene blue, neutral red and methyl orange with outstanding reaction rates of 1.75, 1.80 and 2.62 min−1, respectively. The excellent catalytic activities of the catalysts can be ascribed to the synergistic effects between Fe and Co that enhance the electron transfer rate, uniform dispersion of NPs, presence of N in support, and generation of surface PMS complexes with high oxidation activity. Based on the quench experiments, SO4•–, •OH, O2•− and 1O2 are determined to be the ROS responsible for degradations organic molecules. Fe(x)Co@N-CZ-67 shows excellent catalytic activity over ten consecutive cycles with negligible metal leaching and remarkable structural stability.

Synergistic electronic structure modulation in single-atomic Ni sites dispersed on Ni nanoparticles encapsulated in N-rich carbon nanotubes synthesized at low temperature for efficient CO2 electrolysis

Ni, N-doped carbon materials (Ni–N–C) are prosperous candidates for the electrochemical CO2 reduction reaction (CO2RR) due to their outstanding activity and selectivity. However, the role of the coexisting uncoordinated N-doped sites and Ni nanoparticles (Ni-NPs) in overall CO2RR has been overlooked in prior studies. To address this gap, a low temperature synthesis method developed for Ni-NP-encapsulated Ni–N–C nanotube (Ni-NCNT) catalysts with atomically dispersed Ni–N4 and abundant uncoordinated N-doped sites, where Ni-NPs increase the electron density on Ni–N–C nanotube through carbon network and synergistically enhances the CO2RR activity. The systematic analysis reveals the cooperative role of Ni-NPs and uncoordinated N-doped sites in altering the electronic structure of Ni–N4 sites. The results of control experimental studies confirm the synergistic interaction of uncoordinated N-doped sites boost the CO2RR activity of Ni–N4 sites. Additionally, density functional theory calculations show that the strong interaction between the Ni-NPs and Ni–N–C did not affect the electronic structures of the Ni–N4 centers, but rather alter the electronic structure of uncoordinated pyridinic-N sites. This variation led to decreased the energy barriers of rate-limiting steps of COOH* formation on Ni–N4 and N-doped sites, resulting in excellent CO2RR performance.

Towards an advanced electrochemical horizon: ion selectivity and energy harnessing through hybrid capacitive deionization with carbon-coated NaTi2(PO4)3 and N-rich carbon nests

Dual potent functionality of selective water softening and charge storage from resource recovery with fabricated NTP-C//NCN IEM-HCDI device.

N-rich chitosan-derived porous carbon materials for efficient CO2 adsorption and gas separation.

Capturing and separating carbon dioxide, particularly using porous carbon adsorption separation technology, has received considerable research attention due to its advantages such as low cost and ease of regeneration. In this study, we successfully developed a one-step carbonization activation method using freeze-thaw pre-mix treatment to prepare high-nitrogen-content microporous nitrogen-doped carbon materials. These materials hold promise for capturing and separating CO2 from complex gas mixtures, such as biogas. The nitrogen content of the prepared carbon adsorbents reaches as high as 13.08wt%, and they exhibit excellent CO2 adsorption performance under standard conditions (1 bar, 273K/298K), achieving 6.97mmol/g and 3.77mmol/g, respectively. Furthermore, according to Ideal Adsorption Solution Theory (IAST) analysis, these materials demonstrate material selectivity for CO2/CH4 (10 v:90 v) and CO2/CH4 (50 v:50 v) of 33.3 and 21.8, respectively, at 1 bar and 298K. This study provides a promising CO2 adsorption and separation adsorbent that can be used in the efficient purification process for carbon dioxide, potentially reducing greenhouse gas emissions in industrial and energy production, thus offering robust support for addressing climate change and achieving more environmentally friendly energy production and carbon capture goals.

A Data-Driven Approach to Molten Salt Synthesis of N-Rich Carbon Adsorbents for Selective CO2 Capture.

Applying a design of experiments methodology to the molten salt synthesis of nanoporous carbons enables inverse design and optimization of nitrogen (N)-rich carbon adsorbents with excellent CO2 /N2 selectivity and appreciable CO2 capacity for carbon capture via swing adsorption from dilute gas mixtures such as natural gas combined cycle flue gas. This data-driven study reveals fundamental structure-function relationships between the synthesis conditions, physicochemical properties, and achievable selective adsorption performance of N-rich nanoporous carbons derived from molten salt synthesis for CO2 capture. Taking advantage of size-sieving separation of CO2 (3.30 Å) from N2 (3.64 Å) within the turbostratic nanostructure of these N-rich carbons, while limiting deleterious N2 adsorption in a weaker adsorption site that harms selectivity, enables a large CO2 capacity (0.73mmol g-1 at 30.4Torr and 30 °C) with noteworthy concurrent CO2 /N2 selectivity as predicted by the ideal adsorbed solution theory(SIAST = 246) with an adsorbed phase purity of 91% from a simulated gas stream containing only 4% CO2 . Optimized N-rich porous carbons, with good physicochemical stability, low cost, and moderate regeneration energy, can achieve performance for selective CO2 adsorption that competes with other classes of advanced porous materials such as chemisorbing zeolites and functionalized metal-organic frameworks.

In-situ preparation of N-rich nano-activated carbon on negative-charged montmorillonite with enhanced activation of peroxymonosulfate for antibiotics degradation

N-rich nano-activated carbon/montmorillonite nanosheet with high ability for PMS activation and TC degradation was prepared via in-situ polymerization of ANI and calcination, creating open access for PMS to react with the fully exposed active sites. The prepared catalyst exhibited comparable catalytic ability to metal-based catalysts, achieving 86% degradation of TC (40 mg/L) in just 10 min using 0.3 g/L catalyzer and 0.3 g/L PMS. The degradation rate of TC reached 0.35 min−1, which was higher than that of most catalyst. The reason was attributed to the abundant active sites of graphitic N, pyridinic N, pyrrolic N, nitric oxide, and defects, improving the charge distribution and electron transfer of catalyst, and promoting the self-decomposition of PMS into the radical (•OH, •SO4−) and non-radical (1O2, predominant) species for TC degradation. Such catalyzer provided a novel design of metal-free catalysts with significant improvements, achieving the efficient bio-safety disposal of antibiotics from wastewater.