Nitrogen-doped Porous Carbon Research Articles

Nitrogen-doped coal-based microporous carbon material co-activated by HCOOK and urea for high performance supercapacitors

The doping of heteroatoms can adjust the surface chemical state of porous carbons, which is conducive to improving the surface activity, and enhancing the hydrophicity and conductivity of carbon electrodes. Herein, we developed a facile and green strategy to obtain nitrogen-doped coal-derived porous carbon dominated by micropores for high performance supercapacitor. The hydrothermal treatment of coal and urea can not only achieve the doping of nitrogen atoms, but also conducive to the subsequent activation process. Benefiting from the large micropore volume and specific surface area (0.68 cm3 g−1 and 1563 m2 g−1), suitable micropore size, and high content of surface CO, N-Q and N-5, the optimal sample exhibits a large capacitance of 371 F g−1 (1 A g−1), high capacitance retention of 67% (50 A g−1), and outstanding cyclic durability in a three-electrode system (aqueous electrolyte). Furthermore, the symmetrical supercapacitor in neat EMIM BF4 shows a high energy density of 40 Wh kg−1 (625 W kg−1). This work proposes a facile and potential strategy for preparing nitrogen-doped porous carbon materials with outstanding electrochemical property for supercapacitors and provides a novel insight for the efficient and low carbonization utilization of coal resources.

Honeycomb substrate carbon and nitrogen-doped coated carbon synergistically boost SnS/ZnS for efficient lithium storage

Metal sulfide has become an important anode electrode material for lithium-ion batteries due to its high theoretical specific capacity and low cost. In this work, nano-SnS/ZnS grown on a honeycomb substrate carbon were coated with nitrogen-doped carbon (EG@SnS@ZnS@N-C) by solvothermal and in situ thermal decomposition/sulfide reactions. Honeycomb carbon with good electrical conductivity and mechanical mechanism is loaded with SnS and ZnS with synergistic effects, combined with nitrogen-doped porous carbon with enhanced ion transport. These unique designs enable EG@SnS@ZnS@N-C to exhibit excellent lithium storage performance with a specific capacity of 880 mAh/g at 0.1 A/g and capacity retention of 98% after 100 cycles.

MOF-derived amorphous molybdenum trioxide anchored on nitrogen-doped porous carbon by facile in situ annealing for efficient oxidative desulfurization

Electron transfer between supports and metal oxides is of great significance in optimizing the catalytic activity, while this is still an open issue for understanding its real role in the oxidative desulfurization (ODS) process. Herein, the defective molybdenum trioxide derived from molybdenum-based metal–organic frameworks was highly dispersed on nitrogen-doped porous carbon (VO-MoO3@NPC) by a single-step carbonization treatment. The uniform integration of organic moieties and the unique porous structure of carbonaceous materials are conductive to the active site exposure and mass transfer process during the ODS reaction. Meanwhile, richer oxygen vacancies are generated due to the weakened Mo-O bonds, which is pertinent to the promoted electron transfer between nitrogen-doped porous carbon and molybdenum trioxide by shrinking the band gap. The results manifest that the obtained VO-MoO3@NPC realizes an extraordinary desulfurization efficiency of 99.1% within 20 min, as well as a stable recyclability of up to 9 times. Furthermore, the catalyst delivers an extremely remarkable turnover frequency of 96.2 h−1, which is far superior to that of previously reported molybdenum-based catalysts. This manuscript provides new inspiration for designing excellent ODS catalysts by introducing electron-rich nitrogen to construct strong metal-support interactions.

Phenol Adsorption Performance of Nitrogen-Doped Porous Carbon Derived from Silicon Oxycarbide Ceramics

Phenol Adsorption Performance of Nitrogen-Doped Porous Carbon Derived from Silicon Oxycarbide Ceramics

HKUST-1 derived one-dimensional Cu/N-doped carbon nanofibers for simultaneous detection of acetaminophen and sulfanilamide

The design of novel signal amplification elements was key to improving the sensing and analysis performance of electrochemical sensors. In this work, porous one-dimensional copper nitrogen-doped carbon nanofibers (Cu-NCNFs) were successfully prepared via the coupled process of electrospinning technology and high-temperature pyrolysis. This coupling of multiple processes and the introduction of heteroatoms pyrolyzed the HKUST-1 particles to generate three-dimensional Cu-doped carbon octahedra and mosaic them inside the one-dimensional carbon nitride channels, obtaining small-sized Cu particles while introducing a large number of N species, and constructing a three-dimensional MOFs-derived metal-carbon hybrid one-dimensional multistage carbon nitride structure. The resulting Cu-NCNFs sensor could simultaneously determine acetaminophen and sulfanilamide and exhibit superior electroanalytical performance, reproducibility, stability, and selectivity. This strategy provides a new approach to preparing novel signal amplification elements for the efficient monitoring of micropollutants.

Effect of carbonization atmosphere on electrochemical properties of nitrogen-doped porous carbon

Effect of carbonization atmosphere on electrochemical properties of nitrogen-doped porous carbon

Room-Temperature Salt Template Synthesis of Nitrogen-Doped 3D Porous Carbon for Fast Metal-Ion Storage.

The water-soluble salt-template technique holds great promise for fabricating 3D porous materials. However, an equipment-free and pore-size controllable synthetic approach employing salt-template precursors at room temperature has remained unexplored. Herein, we introduce a green room-temperature antisolvent precipitation strategy for creating salt-template self-assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large-scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen-doped 3D porous carbon (N-3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium-ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g-1 at 4 A g-1 in the full cell. This study addresses the knowledge gap concerning the room-temperature synthesis of salt-template self-assembly precursors for the large-scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.

Porous W/N/C nanoframework: A trifunctionally effective cathodic electrocatalyst for rechargeable Zn-Air/iodide hybrid battery

Different from the conventional Zinc-Air batteries which only involves oxygen reduction and evolution (ORR/OER) in the cathode, the cathode of rechargeable zinc–air/iodide hybrid batteries (ZAIHBs), with the addition of I− species, involves I− electrooxidation (IOR) during charging and oxygen/iodate reduction (ORR and IDR) during discharging. This work reports the synthesis of a hierarchically porous tungsten-based nitrogen-doped carbon framework (W/N/C) with abundant WNx active sites and numerous ultrafine WN nanoclusters and explores their application as a trifunctional IOR/ORR/IDR electrocatalyst for ZAIHBs. The formation mechanism of ZIF-8-derived W/N/C framework as well as its structural and compositional features were investigated. The catalyst demonstrates high trifunctional catalytic activity and robust durability towards IOR/ORR/IDR in alkaline condition, owing to the uniform copresence of the numerous sub-nanometer-sized WN nanoclusters and the abundant single atom WNx sites in the hierarchically structured carbon framework. When applied in homemade ZAIHBs, it revealed a high peak energy density (141.9 mW cm−2) and remarkable cycling stability (65 h), outperforming the commercial Pt/C catalysts. This work demonstrates the multi-functional electrocatalytic activity of tungsten-based non-noble metal electrocatalyst for high-performance ZAIHBs.

Nitrogen-doped oxygen-rich porous carbon framework towards aqueous zinc ion hybrid capacitors and zinc-iodine batteries

Zinc ion hybrid capacitors (ZIHCs) and zinc-iodine batteries (ZIBs) have attracted significant attention as promising components for large-scale energy storage owing to their excellent security, environmental friendness and high theoretical capacity of Zn anode. However, there still exist some respective obstacles for commercial applications, such as limited specific capacity, poor cycling stability of ZIHCs or shuttle effect of polyiodide of ZIBs. Here, to enhance electrochemical properties, we report a synergistic one-step activation strategy using KMnO4 and Zn(NO3)2 for nitrogen-doped oxygen-rich three-dimensional hierarchical porous carbon (NOPC). Benefiting from its high specific surface area, three-dimensional porous morphology and improved redox sites from heteroatom doping, the as obtained NOPC exhibits desired electrochemical performance as cathode for ZIHCs and ZIBs. The NOPC-based electrode achieves an ultra-high specific capacity of 230 mAh g−1 at 0.1 A g−1, and 118 mAh g−1 can be maintained at 10 A g−1. Besides, a distinguished energy density of 213.0 Wh kg−1 and a high-power density of 11.2 kW kg−1 are also achieved with a constructed ZIHCs device. Furthermore, the NOPC/I2 composite exhibited excellent rate performance (54 mAh g−1 at 10 A g−1) and cycling performance (∼88.3 % retention upon 5000 cycles) in ZIBs device. This work provides a facile but effective strategy to develop 3D porous electrodes for ZIHCs and ZIBs with remarkable rate and cycling performance.

Simultaneously Geometrical and Electronic Modulation of L10-PtZn by Trace Ge Boosts High-performance Oxygen Reduction Reaction.

Developing a highly active, durable, and low-platinum-based electrocatalyst for the cathodic oxygen reduction reaction (ORR) is for breaking the bottleneck of large-scale applications of proton exchange membrane fuel cells (PEMFCs). Herein, ultrafine PtZn intermetallic nanoparticles with low Pt-loading and trace germanium (Ge) involvement confined in the nitrogen-doped porous carbon (Ge-L10-PtZn@N-C) are reported. The Ge-L10-PtZn@N-C exhibit superior ORR activity with a mass activity of 3.04 A mg-1 Pt and specific activity of 4.69mA cm-2, ≈12.2- and 10.2-times improvement compared to the commercial Pt/C (20%) at 0.90V in 0.1m KOH. The cathodic catalyst Ge-L10-PtZn@N-C assembled in the PEMFC shows encouraging peak power densities of 316.5 (at 0.86V) and 417.2mW cm-2 (at 0.91V) in alkaline and acidic fuel-cell, respectively. The combination of experiment and density functional theory calculations (DFT) results robustly reveal that the participation of trace Ge can not only trigger a "growth site locking effect" to effectively inhibit nanoparticle growth, bring miniature nanoparticles, enhance dispersion uniformity, and achieve the exposure of the more electrochemical active site, but also effectively modulates the electronic structure, hence optimizing the adsorption/desorption of the oxygen intermediates.

Domain-Limited Sub-Nanometer Co Nanoclusters in Defective Nitrogen Doped Carbon Structures for Non-Invasive Drug Monitoring.

In this work, sub-nanometer Co clusters anchored on porous nitrogen-doped carbon (C─N─Co NCs) are successfully prepared by high-temperature annealing and pre-fabricated template strategies for non-invasive sensing of clozapine (CLZ) as an efficient substrate adsorption and electrocatalyst. The introduction of Co sub-nanoclusters (Co NCs) provides enhanced electrochemical performance and better substrate adsorption potential compared to porous and nitrogen-doped carbon structures. Combined with ab initio calculations, it is found that the favorable CLZ catalytic performance with C─N─Co NCs is mainly attributed to possessing a more stable CLZ adsorption structure and lower conversion barriers of CLZ to oxidized state CLZ. An electrochemical sensor for CLZ detection is conceptualized with a wide operating range and high sensitivity, with monitoring capabilities validated in a variety of body fluid environments. Based on the developed CLZ sensing system, the CLZ correlation between blood and saliva and the accuracy of the sensor are investigated by the gold standard method and the rat model of drug administration, paving the way for non-invasive drug monitoring. This work provides new insights into the development of efficient electrocatalysts to enable drug therapy and administration monitoring in personalized healthcare systems.

A hierarchical porous N-doped carbon material as catalyst derived from the folic acid-Zn/KBr hydrogel: Reaction network and kinetics and mechanism for the oxidation of furfural to maleic acid

A novel hydrogel (named FA-Zn/KBr) was prepared, by taking advantage of the hydrogen-bonding and π-π stacking interactions between the pterin heterocycles of the folic acid (FA) molecules. The hydrogel is composed of highly dispersed KBr, coordinated zinc ions, and stacked arrays of folate tetramers. Due to the presence of KBr, a hierarchical porous nitrogen-doped carbon (PNC-800) material with a specific surface area 2807.9 m2/g can be formed through the calcination of the FA-Zn/KBr xerogel under N2. PNC-800 is used to catalyze the oxidation of furfural to maleic acid in the presence of H2O2. Representative nine reactions constitute the reaction network. The reaction rate constants and apparent activation energy were obtained for each reaction. Based on the kinetics parameters, the simulated results are in good agreement with the experimental data. The mechanism of the reaction catalyzed by PNC-800 is proposed based on ample experimental evidence. The graphitic nitrogen species in PNC-800 are the active sites. PNC-800 catalyzes the decomposition of hydrogen peroxide to generate hydroxyl radical (HȮ), which oxidizes furfural to furfural radical, and the furfural radical is subsequently converted to 5-hydroxy-furan-2(5H)-one (HFONE). The conversion of furfural to maleic acid via the formation of HFONE is the main reaction pathway. In addition, the hierarchical porous structure with a high specific surface area facilitates the interaction of reactant with the active sites. PNC-800 has been shown an excellent catalytic activity for the production of maleic acid from furfural. For the oxidation of 1000 mM furfural using 50 mg PNC-800 at 80 °C within 9 h, the conversion of furfural is 100 % with a maleic acid yield 67.5 %.

Synergistic effects of hierarchical porous structures and ultra-high pyridine nitrogen doping enhance the oxygen reduction reaction electrocatalytic performance of metal-free laminated lignin-based carbon

Construction of non-metallic biomass-carbon based catalysts for fuel cell air cathode applications has attracted great attention in recent years. In this work, a convenient and clean technique was developed to fabrication nitrogen-doped lignin-based hierarchical porous lamellar carbon (N-LHPC) via lignin as the carbon precursor, melamine/urea as the nitrogen source and ZnC2O4.2H2O as the chemical activator. The N-LHPC has a high specific surface area (491.5 m2 g−1) and macroporous/mesoporous/microporous structures. The nitrogen doping of N-LHPC can reach 16.37 wt%, with a high pyridinic nitrogen content of 41.39 at.%. N-LHPC exhibits a high half-wave potential (0.87 V) and a large limiting current density (5.75 mA cm−2) in 0.1 mol KOH media which is comparable to the commercial Pt/C catalysts. Furthermore, N-LHPC was assembled as air cathode catalyst for Zn-air batteries to evaluate its practical catalytic performance, and the power density was as high as 191 mW cm−2, which was superior to the 20 wt% Pt/C electrocatalyst. This research demonstrates that lignin is a promising carbon source for the fabrication of high catalytic activity and economical electrocatalysts for energy storage systems.

One-Step Synthesis of Nitrogen-Doped Porous Carbon Derived from Biomass for Lithium-Ion Battery

Bamboo shoot is renewable biomass rich in carbon and nitrogen. To take advantage of its sources of carbon and nitrogen, hierarchical porous nitrogen-doped carbon materials derived from bamboo shoot were acquired via a one-step method in this study. The obtained carbons were characterized by using XRD, Raman, N2 sorption, SEM, TEM, XPS, etc. The carbon calcinated at 700 °C with KHCO3 treatment (BSC) displays a large surface area (1475.5 m2 g−1) and typically porous structure from micro- to macropores, a self-nitrogen content, and many defects, which could offer transport channels and active sites for lithium ions while used as carbon anode. Based on the above features and the synergistic effects among them, BSC exhibits the typical electrochemical performance of a carbon-based anode material, with a specific capacity as high as 611.3 mA h g−1 (a Coulombic efficiency of 98.7%) after 100 cycles at a current density of 0.1 A g−1. Meanwhile, it also has a good rate performance and excellent cycling properties (436.1 mA h g−1 after 300 cycles at 0.1 A g−1) compared with NBSC (carbon directly carbonized at 700 °C). Thus, it is promising for further improvements made to porous carbon derived from biomass and used as anode in the application of energy storage, and could be a guideline for the preparation of high-value-added carbon materials derived from biomass.

Metal–organic framework-derived cobalt nanoparticles modified nitrogen-doped porous carbon hybrids for efficient hydrogenation and one-pot reductive acetylation of nitroarenes

Metal–organic framework-derived cobalt nanoparticles modified nitrogen-doped porous carbon hybrids for efficient hydrogenation and one-pot reductive acetylation of nitroarenes

N-doped EG@MOFs derived porous carbon composite phase change materials for thermal optimization of Li-ion batteries at low temperature

Electric vehicles often encounter the challenge of battery capacity reduction in cold environments. Existing thermal conductive patches and partial short-circuiting for electrical heating can address the above issues. In this paper, a method to increase battery capacity was proposed by phase change material (PCM) assisted heating. Specifically, a nitrogen-doped hierarchical porous carbon (NPC) was synthesized through a combination of “low-temperature calcination + concentrated nitric acid treatment” to treat the chrysanthemum-shaped MOF-199@EG, and impregnated with stearic acid (SA) to form a stable composite PCM. With its well-developed pore structure and N-adsorbed active sites, the NPC prevents the leakage of molten SA, maintains stability effect and significantly improves the thermal properties of SA composites. The SA/NPC has a loading rate of 80.15 wt%, closely approaching the theoretical values of latent heat (137.89 J·g-1). It also demonstrates enhanced thermal conductivity (1.873 W·m-1·K-1) and thermal diffusivity (1.024 mm2·s-1). Thermal conductivity and thermal diffusivity of SA/NPC are 8.56 times and 14.06 times higher, respectively, than those of SA. Furthermore, when the lithium-ion battery is discharged 2C at −20 °C, the utilization of SA/NPC as an insulation material can increase the discharge energy by 7.89 %. Consequently, this novel composite PCM holds significant promise for the thermal optimization of batteries at low temperature.

Restricted growth of molybdenum carbide nanoparticles in hierarchically porous nitrogen-doped carbon matrix for boosting electromagnetic wave absorption performance

With the development of electronic science and technology, electromagnetic pollution is becoming increasingly serious, which urgent people to develop wave-absorbing materials with the features of “thin, light, strong and wide”. In this paper, restricted growth of molybdenum carbide nanoparticles in hierarchically porous nitrogen-doped carbon matrix (Mo2C/NC) was designed and prepared via a salt-assisted template route and carbonization process, whose morphology and the wave-absorbing properties are regulated by changing the content of Mo2C/NC nanoparticles. The honeycomb porous Mo2C/NC composites with large specific surface area and smooth surface can optimize the impedance matching and allow the entrance, multiple reflections and scattering of incident electromagnetic waves (EMW), which effective enhance the electromagnetic wave consumption. Meanwhile, the honeycomb cross-linked carbon matrix facilitates the construction of the conductive network and enhances its conductive loss. Furthermore, numerous Mo2C/NC nanoparticles dispersed restricted growth in carbon matrix induces interfacial polarization. In addition, the heteroatom nitrogen doping acts as dipole centers to induce dipole polarization under electromagnetic field. The uniquely designed Mo2C/NC absorbers show satisfactory EMW absorption behaviors of a minimum reflection loss (RLmin) of −61.53 dB at 1.5 mm and an effective absorption bandwidth (EAB) of 9.6 GHz at 3.5 mm. This work enriches the variety of EMW absorbers and offers the route to promote the EMW absorption performance, especially large effective absorption bandwidth.

Titanium metal–organic framework-derived nanocrystalline TiO2-supported nitrogen-doped carbon nanostructures as highly efficient antibiotic adsorbents

Metal-organic frameworks (MOFs) are explored extensively as a distinctive precursor for producing porous metal oxide-supported nitrogen-doped carbon nanomaterials. MOF-derived materials can offer tailored porosity, structure, and elemental composition so they are gaining prominence as a new-generation adsorbent for emerging antibiotic contaminant removal in aqueous solutions. In this study, we demonstrate the fabrication of nanocrystalline titanium dioxide-supported nitrogen-doped carbon nanostructures (TiO2@NC) obtained from a titanium metal–organic framework (NH2-MIL-125(Ti)) as a starting precursor. When applied as an adsorbent, TiO2@NC nanospheres efficiently removed high concentrations of tetracycline (TC) in aqueous solutions. The TiO2@NC adsorption process obeyed the Langmuir model and pseudo-second-order kinetics. The optimum adsorption capacity of the TiO2@NC nanospheres is estimated to be 1187.08 mg g−1, which is remarkably superior to several previously reported adsorbents for TC removal. The TiO2@NC adsorbent performs efficiently in a broad pH range (3–8) and shows excellent stability. The post-adsorption characterization signifies the crucial role of the adsorbent's nitrogen sites, surface area, and porous sphere morphology in achieving efficient TC removal through hydrogen bonding, π-π interactions, and surface complexation.

Single-step Synthesis of Highly Porous Nitrogen-doped Carbon by Solid–gas Mechanochemical Treatment as an Oxygen Reduction Electrocatalyst

Single-step Synthesis of Highly Porous Nitrogen-doped Carbon by Solid–gas Mechanochemical Treatment as an Oxygen Reduction Electrocatalyst

Metal-Free Nitrogen-Doped Porous Carbons for Nitriles and Amides Synthesis from 1,2-Diols via Oxidative Cleavage of C–C Bonds

Metal-Free Nitrogen-Doped Porous Carbons for Nitriles and Amides Synthesis from 1,2-Diols via Oxidative Cleavage of C–C Bonds