N-doped Carbon Materials Research Articles

NiCoP nanoparticles distributed on N-doped carbon-nanosheets loading on nickel phosphide as self-supporting electrode for efficient overall water splitting

The investigation of a bifunctional self-supporting catalytic electrode holds significant practical importance for the application of overall water splitting. In this paper, a precursor with a large specific surface is constructed by growing ZIF-67 nanosheets on nickel foam. Subsequently, Ni–Co bimetallic phosphide particles (NiCoP) are obtained through phosphating, which distributed in N-doped carbon material and loaded on nickel phosphide (NiCoP@NC-Ni3P/NF), facilitating the overall water splitting. Due to its large specific surface area, the double electron regulation of Ni and Co, as well as the synergistic interaction between NiCoP and Ni3P, NiCoP@NC-Ni3P/NF exhibits excellent hydrogen/oxygen evolution properties, only requiring 125.6/288.4 mV to achieve 20 mA cm−2. Its performance of overall water splitting only requires an applied voltage of 1.54 V to reach 10 mA cm−2. Moreover, the NiCoP particles embedded in the nitrogen-doped carbon can effectively reduce electrolyte corrosion, ensuring exceptional catalyst stability.

Performance and Mechanism of Porous Carbons Derived from Biomass as Adsorbent for Removal of Cr(VI)

To solve the problem of heavy metal hexavalent chromium (Cr(VI)) pollution in water bodies, this study was carried out to prepare nitrogen-doped porous carbon by using bamboo shoots as the raw material and KHCO3 as the activator, which has a good ability to remove Cr(VI) from water bodies. The prepared N-doped carbon materials were characterized by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), elemental analysis, and scanning electron microscopy (SEM). The results showed that the prepared carbon material had hierarchical pore structures and abundant functional groups, which is conducive to the adsorption of Cr(VI). The effects of various factors on the adsorption performance of Cr(VI), such as the carbon materials prepared under different conditions, the pH of the initial solution, the concentration of the initial solution, and the contact time between the carbon and Cr(VI), were explored. The results showed that the bamboo shoot-based nitrogen-doped carbon materials, especially BSNC-800 (prepared at 800 °C with a mass ratio of KHCO3 to bamboo shoot of 4:1), performed well in removing Cr(VI) from a water solution. The maximum adsorption of Cr(VI) by BSNC-800 under equilibrium conditions was 385.8 mg g−1 (conditions: at the pH of 2 with the initial concentration of 400 mg L−1). The adsorption kinetics and isotherms were analyzed, and the adsorption mechanism was discussed. It can be found that the adsorption of Cr(VI) by BSNC-800 fits better with the Langmuir isotherm model and the pseudo-second-order kinetic model. The adsorption mechanism between the Cr(VI)-containing solution and BSNC-800 was controlled by membrane diffusion and chemisorption. The results broaden the ways of utilizing biomass resources as precursors of carbon materials, which is significant and helpful for applying biomass carbon materials as adsorbents for wastewater treatment.

Recent Advances in Developing High-Performance Anode for Potassium-Ion Batteries based on Nitrogen-Doped Carbon Materials.

Owing to the low potential (vs K/K+), good cycling stability, and sustainability, carbon-based materials stand out as one of the optimal anode materials for potassium-ion batteries (PIBs). However, achieving high-rate performance and excellent capacity with the current carbon-based materials is challenging because of the sluggish reaction kinetics and the low capacity of carbon-based anodes. The doping of nitrogen proves to be an effective way to improve the rate performance and capacity of carbon-based materials as PIB anode. However, a review article is lacking in systematically summarizing the features and functions of nitrogen doping types. In this sense, it is necessary to provide a fundamental understanding of doped nitrogen types in nitrogen-doped(N-doped) carbon materials. The types, functions, and applications of nitrogen-doped carbon-based materials are overviewed in this review. Then, the recent advances in the synthesis, properties, and applications of N-doped carbon as both active and modification materials for PIBs anode are summarized. Finally, doped nitrogen's main features and functions are concluded, and critical perspectives for future research in this field are outlined.

Reusable metal-free mesoporous carbon-catalyzed reductive N-formylation of nitroarenes and quinolines

The high-value transformation of nitrogen-containing compounds through a facile, cost-effective, and eco-friendly one-pot strategy holds significant importance. However, this process typically involves the use of metal catalysts and is limited by low activity as well as the requirement of high temperature and pressure. Herein, we describe a general and efficient metal-free N-doped mesoporous carbon material using well-defined ligand 1,10-phenanthroline as the precursor and silica colloid as the hard template. Formic acid is both a reducing agent and a formylation reagent, and structurally distinct mono- or multi-substituted nitroarenes and quinolines can be selectively N-formylation in a one-pot method. The catalyst can be easily recovered without observable loss of efficiency for ten consecutive uses. The control experiments and density functional theory (DFT) calculations indicate that formic acid mainly obtains active hydrogen in the form of O–H bond cleavage, which benefits from the strong adsorption and enhanced activity generated by the interaction between graphitic nitrogen species in the catalyst and formic acid. The excellent catalytic performance of the meso-phen-X catalyst is attributed to the synergistic effect of graphitic N and large specific surface area, providing a promising method for the development of non-metallic catalyst-modified carbon materials.

The relationship between the high-frequency performance of supercapacitors and the type of doped nitrogen in the carbon electrode

Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors, particularly in terms of their high-frequency response. However, the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear. In this study, melamine foam carbons with different configurations of surface-doped N were formed by gradient carbonization, and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed. Using a combination of experiments and first-principle calculations, we found that pyrrolic N, characterized by a higher adsorption energy, increases the charge storage capacity of the electrode at high frequencies. On the other hand, graphitic N, with a lower adsorption energy, increases the speed of ion response. We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications, offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors

Pt3(CoNi) Ternary Intermetallic Nanoparticles Immobilized on N-Doped Carbon Derived from Zeolitic Imidazolate Frameworks for Oxygen Reduction.

Pt-based intermetallic compound (IMC) nanoparticles have been considered the most promising catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). Herein, we propose a strategy for producing ordered Pt3(CoNi) ternary IMC nanoparticles supported on N-doped carbon materials. Particularly, the Co and Ni are originally embedded into ZIF-derived carbon, which diffuse into Pt nanocrystals to form Pt3(CoNi) nanoparticles. Moreover, a thin layer of carbon develops outside of Pt3(CoNi) nanoparticles during the cooling process, which contributes to stabilizing the Pt3(CoNi) on carbon supports. The optimal Pt3(CoNi) nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential of 0.885 V vs reversible hydrogen electrode (RHE) and losing only 16 mV after 10,000 potential cycles between 0.6 and 1.0 V. Unlike the direct-use commercial carbon (VXC-72) for depositing Pt, we utilized ZIF-derived carbon containing dispersed Co and Ni nanocluster or nanoparticles to prepare ordered Pt3(CoNi) intermetallic catalysts.

Monolithic Nitrogen-Doped Carbon Electrode with Hierarchical Porous Structure for Efficient Electrochemical CO2 Reduction.

N-doped carbon materials have garnered extensive development in electrochemical CO2 reduction due to their abundant sources, high structural plasticity, and excellent catalytic performance. However, the use of powder carbon materials for electrocatalytic reactions limits their current density and mechanical strength, which pose challenges for industrial applications. In this study, we synthesized a monolithic N-doped carbon electrode with high mechanical strength for efficient electrochemical reduction of CO2 to CO through a simple pyrolysis method, using phenolic resin as the precursor and ZIF-8 as the sacrificial template. At 900 °C, the decomposition of ZIF-8 and the volatilization of Zn atoms promote the formation of a hierarchical porous structure in the carbon matrix, characterized by macropores with extended mesoporous channels. Simultaneously, N active species derived from ZIF-8 are effectively generated around the pores and fully exposed. The efficient mass transfer facilitated by the hierarchical porous structure and high activity of exposed nitrogen species enables efficient conversion of CO2 to CO. When the ZIF-8 content is 30%, the catalyst achieves a Faradaic efficiency of 88.9% for CO at a low potential of -0.7 V (vs RHE), with a CO production rate of 244.05 μmol h-1 cm-2. After 50 h of potentiostatic electrolysis, the current density and FECO remain stable. This work not only provides a strategy for the synergistic effects of hierarchical porous structures and nitrogen doping but also offers an effective method to avoid using powder binders and prepare integrated, stable monolithic electrodes.

The application of Co3S4@NCNT/NCHS with excellent bifunctional catalytic activity in aqueous and flexible Zn-air batteries

In this work, we prepared a hybrid structure Co3S4@NCNT/NCHS using SiO2 nanospheres as a template. The structure is supported by hollow carbon spheres (NCHS), which are coated by Co3S4 nanoparticles and cross-linked N-doped carbon nanotubes. The combination of Co3S4 with N-doped carbon material significantly improves the electrocatalytic activity. In addition, the presence of N-doped carbon nanotubes induces more defects, which can regulate the electronic configuration of the material and improve its electrical conductivity. Therefore, Co3S4@NCNT/NCHS has good catalytic performance. At 10 mA cm−2, the OER overpotential of Co3S4@NCNT/NCHS is only 230 mV, which is lower than that of the commercial catalyst RuO2, and the ORR half-wave potential can reach 0.80 V. In the battery discharge test, Co3S4@NCNT/NCHS based ZABs can discharge continuously for 71.5 h, the specific capacity of 790.12 mA h g−1, power density of 113.09 m W cm−2, better than Pt/C+RuO2 battery. When the current density is 3 mA cm−2, ZABs assembled with Co3S4@NCNT/NCHS as catalyst can maintain a voltage gap of 0.62 V to 0.63 V within 300 h without significant change. When the current density is increased to 5 mA cm−2, ZABs based on Co3S4@NCNT/NCHS can be stably cycled for 300 h at a voltage gap between 0.80 V and 0.82 V.

Pt/C electrocatalysts based on N-doped carbon materials from waste plant biomass

The N-doped carbon material obtained by thermochemical conversion of a polycondensation product of a liquid fraction of humins (a waste product of plant biomass conversion into furan derivatives) with the nitrogen-containing crosslinking component melamine was investigated as a support in Pt/C electrocatalysts for the oxygen reduction reaction.

Fabrication of self-N-doped porous biochar by synergistic pyrolysis activation for efficient tetracycline and CO2 adsorption

The development of green and economical adsorption materials with high pollutant adsorption performance is of great significance to meet environmental challenges. Herein, self N-doped porous carbon materials with excellent tetracycline and CO2 adsorption properties are successfully prepared by synergistic pyrolysis activation of corn stalk and Chlorella mixture. The addition of N-riched Chlorella significantly affects the nanopore and surface chemical structure of biochar, forming rich micro-mesopores, changing the intrinsic N doping form and surface oxygen-containing functional groups. An ultra-high tetracycline adsorption capacity of 1159.7 mg/g can be achieved by using the prepared KBC-3:1 as an adsorbent. A series of kinetic isothermal adsorption models, thermodynamic calculations, as well as comparative characterization analysis show that multiple adsorption mechanisms coexist. The pore filling of micro-mesopores (1.5–3 nm), π-π interactions of CC bonds, H bonding interactions of CO and the strong electrophilicity of pyrrolic N contribute to the excellent tetracycline adsorption performance of KBC-3:1. Furthermore, the material shows great resistance to cationic (K+, Mg2+, Cu2+) interference and excellent cycling performance. In addition, KBC-3:1 also exhibits excellent adsorption capacity for CO2, and the adsorption capacity of 5.21 mmol/g can be achieved at 273 K and 1 bar, which could be attributed to the synergistic activation effect leading to KBC-3:1 having the most abundant pyrrolic and pyridinic N species as well as the rich microporous structure. This work can provide guidance for the development of green and economical high performance carbon materials based on the intrinsic characteristics of biomass.

Potassium single-atoms anchoring on three-dimensional porous N-doped carbon material as sensing material for boosting electrochemical sensing of hydrogen peroxide.

For thefirst time potassium single-atoms (K SA) are explored as the sensing material to boost electrochemical sensing of hydrogen peroxide (H2O2). The N-doped carbon material with a three-dimensional porous structure (3D NG) was prepared using NaCl as the template, and K SA were anchored to the surface of 3D NG through high-temperature pyrolysis. The structure of K SA/3D NG was characterized by TEM, HAADF-STEM, XPS, and XRD. The results of electrochemical studies indicate that K SA play a crucial role in promoting the electrocatalytic reduction of H2O2, which not only optimized the adsorption strength for H2O2 but also improved the electron transfer rate, therefore improving the sensitivity for detecting H2O2. This study demonstrates the excellent electrocatalytic activity of K SA, which provides a promising sensing material for the detection of H2O2 andlays the foundation for the application of alkali metal single-atoms in the field of electrochemical sensing.

Modulating N doping in cobalt-derived catalyst from zeolitic imidazolate frameworks for high performance zinc-air batteries

In this work, the N-content was varied using ammonium hydroxide (A), urea (U), and melamine (M) impregnated in a zeolitic imidazolate framework (ZIF-67) with a Co to Zn ratio of 7:93. The N-doped ZIF-derived carbon materials and the reference ZIF Co 7:93 underwent pyrolysis under identical conditions, yielding C-ZIF, CA-ZIF, CU-ZIF, and CM-ZIF. Different nitrogen sources mainly affected the surface area and graphitic-N content, yielding up to three times the N-content of the reference. All materials presented ORR onset potentials near 0.9 V and E10mA cm−2 near 1.6 V for the OER. However, CM-ZIF enabled rechargeability at different current densities, with a round-trip efficiency of 68.8 % at 5 mA cm−2, decreasing only to 54 % at 15 mA cm−2.

One-step preparation of N-doped porous carbon materials with excellent microwave absorption properties based on methylene blue saturated wood-based activated carbon

One-step preparation of N-doped porous carbon materials with excellent microwave absorption properties based on methylene blue saturated wood-based activated carbon

Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction

N-doped carbon materials, with their applications as electrocatalysts for the oxygen reduction reaction (ORR), have been extensively studied. However, a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxidation potential of carbon, possibly leading to the oxidation of carbon materials. Consequently, the influence of the structural oxidation evolution on ORR performance and the real active sites are not clear. In this study, we discover a two-step oxidation process of N-doped carbon during the ORR. The first oxidation process is caused by the applied potential and bubbling oxygen during the ORR, leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups. This oxidation process also converts the reaction path from the four-electron (4e) ORR to the two-electron (2e) ORR. Subsequently, the enhanced 2e ORR generates oxidative H2O2, which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups, such as quinones to dicarboxyls, further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species. We also reveal the synergistic effect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*, thus leading to high efficiency and durability in electrocatalytic H2O2 production.

Core/shell Ni@C particle-supported N-doped carbon with hollow capsules for efficient electrocatalytic reduction of oxygen

To replace the noble metal catalysts for oxygen reduction reaction (ORR), a Ni@C-supported N-doped carbon material (Ni@C/NC) is in-situ prepared via one-step pyrolyzing the polymerizable ionic liquid of vinyl imidazole combined with Ni(NO3)2. Systemic investigations demonstrate that these nanosized Ni particles are tightly wrapped with a thin carbon layer to form the core/shell structure, meanwhile carbon capsules are synchronously yielded on the carbon matrix. As a result, both the carbon shell and the carbon capsule jointly increase the active sites of the Ni@C/NC, while the carbon shell also contributes the fast electron-transfer from Ni particle. Compared with the normal Ni-supported carbon catalyst, the Ni@C/NC shows the respectable ORR performance with the onset and half-wave potentials of 0.96 and 0.84 VRHE. After the long-term electrocatalysis (10 h), the Ni@C/NC is found to possess the great structural and electrocatalytic stabilities, which maintains 93 % of the initial current density and the well-dispersed and uniform Ni@C particles. Subsequently, a Zn-Air battery with the Ni@C/NC cathode is assembled and exhibits a peak power density of 200 mW cm−2. Therefore, the as-obtained Ni@C/NC with the high electroactivity and stability can be expected as an ideal candidate to apply in the metal-air batteries and fuel cells in the future.

A broad-spectrum oxidation capability Ru-CeO2 catalyst for efficient synergistic selective oxidation of benzyl alcohol

Selective oxidation of alcohols to aldehydes by molecular oxygen is one of the most important transformations in multiphase catalysis. In this paper, a catalyst with selective oxidation ability was designed and synthesized for the selective catalytic oxidation of benzyl alcohol. N-doped carbon materials were prepared by high-temperature calcination using hydrothermal reaction products of citric acid and melamine as a carbon source, and a bimetallic catalyst supported by Ru-CeO2 was constructed using the mixture as the carrier for the selective oxidation of benzyl alcohol to benzaldehyde. The results showed that the introduction of CeO2 could effectively improve the oxidizing ability and catalytic activity of the catalyst. The Ru-Ce0.05/NC170–600 catalyst was able to convert 85.5 % benzyl alcohol into benzaldehyde at 140 °C, 6 h, and 2 MPa, and the selectivity for benzaldehyde was 100 %. It was demonstrated by DFT that it was theoretically feasible to generate benzaldehyde by extracting hydrogen atoms from benzyl alcohol molecules. Further, the selective oxidation experiments on other alcohols showed that the catalyst has high activity for the oxidation of various alcohols to generate the corresponding carbonyl products, and it is a catalyst with broad-spectrum selective oxidation ability. In this study, a green synthesis route of benzaldehyde was proposed to solve the problems in the traditional process. Meanwhile, it provides a new idea for the synthesis of carbonyl products by selective oxidation of alcohols.

Enhanced bimetallic CuCo nanoparticles on nitrogen-doped carbon for selective hydrogenation of furfural to furfuryl alcohol through strong electronic interactions

Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials (N-C) were achieved using impregnation method and applied in the hydrogenation of furfural (FAL) to furfuryl alcohol (FOL). The high hydrogenation activity of FAL over Cu1Co1/N-C was originated from the synergistic interactions of Cu and Co species, where Co0 and Cu0 simultaneously adsorb and activate H2, and Cu+ served as Lewis acid sites to activate C═O. Meanwhile, electrons transfer from Cu to Co promoted the formation of Cu+. In situ Fourier transform infrared spectroscopy analysis indicated that Cu1Co1/N-C adsorbed FAL with a tilted η1-(O) configuration. The superior Cu1Co1/N-C showed excellent adsorbed ability towards H2 and FAL, but weak adsorption for FOL. Therefore, Cu1Co1/N-C possessed 93.1% FAL conversion and 99.0% FOL selectivity after 5 h reaction, which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.

Nitrogen-Doped Porous Carbons Derived from Peanut Shells as Efficient Electrodes for High-Performance Supercapacitors.

The doping of porous carbon materials with nitrogen is an effective approach to enhance the electrochemical performance of electrode materials. In this study, nitrogen-doped porous carbon derived from peanut shells was prepared as an electrode for supercapacitors. Melamine, urea, urea phosphate, and ammonium dihydrogen phosphate were employed as different nitrogen dopants. The optimized electrode material PA-1-1 prepared by peanut shells, with ammonium dihydrogen phosphate as a nitrogen dopant, exhibited a N content of 3.11% and a specific surface area of 602.7 m2/g. In 6 M KOH, the PA-1-1 electrode delivered a high specific capacitance of 208.3 F/g at a current density of 1 A/g. Furthermore, the PA-1-1 electrode demonstrated an excellent rate performance with a specific capacitance of 170.0 F/g (retention rate of 81.6%) maintained at 20 A/g. It delivered a capacitance of PA-1-1 with a specific capacitance retention of 98.8% at 20 A/g after 5000 cycles, indicating excellent cycling stability. The PA-1-1//PA-1-1 symmetric supercapacitor exhibited an energy density of 17.7 Wh/kg at a power density of 2467.0 W/kg. This work not only presents attractive N-doped porous carbon materials for supercapacitors but also offers a novel insight into the rational design of biochar carbon derived from waste peelings.

Synergistic Interaction between the Ni-Center and Glycine-Derived N-Doped Porous Carbon Material Boosts Electrochemical CO2 Reduction

Synergistic Interaction between the Ni-Center and Glycine-Derived N-Doped Porous Carbon Material Boosts Electrochemical CO₂ Reduction

Pyrolysis of folic acid: Identification of gaseous/volatile products and structural evolution of N-doped graphitic carbon

Folic acid (FA) is a low-cost and suitable source for producing different N-doped carbon materials by pyrolysis. However, the pyrolytic steps of FA are not entirely understood, particularly above 350 °C, which hampers the intelligent design of tailor-made carbon materials by a one-pot route. In this work, the pyrolytic decomposition steps of FA were investigated by simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (TGA-DSC). The released gaseous/volatile products were probed by coupling TGA to infrared spectroscopy and mass spectrometry (TGA-FTIR-MS). Considering the thermal analysis data, FA was pyrolysed in a furnace at 350, 430, 570, 800, and 1000 °C, and the products were analysed by X-ray diffractometry (XRD), vibrational spectroscopy, and X-ray photoelectron spectroscopy. In situ high-temperature X-ray diffractometry (HT-XRD) experiments were also conducted under the nitrogen atmosphere. According to the data set, insights about FA decomposition steps could be proposed, including gaseous/volatile products released during the process and the structural evolution of N-doped graphitic carbon. The formation of carbonaceous material initiated between 200 and 350 °C through polymerisation/condensation reactions, and this step was marked by the release of 2-pyrrolidone and aniline. The graphitisation was enhanced above 350 °C, increasing graphitic nitrogen while the amide groups vanished. The process was accompanied by deoxygenation (i.e., CO and CO2 release) and denitrogenation (e.g., NH3, HNCO, and HCN) reactions. In the 570–800 °C range, the N-enrichment of carbon material (N-pyridine, N-pyrrole/Csp2-N in 5,7-membered rings, and nitrile) could occur by the reaction of released NH3 over the char surface. Graphitic-like structures containing mainly N-graphite and N-pyridine were obtained above 800 °C. The original data about the thermal decomposition steps of FA allow for optimising the synthesis of N-doped carbon materials suitable for applications in adsorption, sensing, catalysis, and energy storage.