Nitrogen-doped carbon nanomaterials (N-CNMs) were prepared using Ni(NO3)2 as a catalyst in the laminar diffusion flame. Doping the structure of carbon nanomaterials (CNMs) with nitrogen can significantly change the characteristics of CNMs. The purpose of this research is to study the effect of adding ammonia ( NH3) on the evolution of CNMs structure in the laminar flame of ethylene. Raman analysis shows that the intensity ratio ( ID/IG) of the D-band and G-band of N-CNMs increases and then decreases after the addition of NH3. The intensity ratio is a maximum of 0.99, which has a good degree of disorder and defect density. The binding distribution of nitrogen was analyzed by X-ray photoelectron spectroscopy (XPS), and a correlation was found between the amount of nitrogen and the morphology of N-CNMs. Nitrogen atoms predominantly present in the forms of pyrrolic-N, pyridinic-N, graphitized-N and oxidized-N, with a doping ratio of nitrogen atoms reaching up to 2.44 at.%. This study found that smaller nickel (Ni) nanoparticles were the main catalysts for carbon nanotubes (CNTs), and their synthesis followed the ‘hollow growth mechanism’ and carbon nanofibers (CNFs) were synthesized from larger Ni nanoparticles according to the ‘solid growth mechanism’. Furthermore, a growth mechanism for the synthesis of bamboolike CNTs using a specific particle size of the Ni catalyst is proposed. It is noteworthy that the synthesis and modulation of high-performance N-CNMs by flame method represents a simple and efficient approach.
Graphitic nitrogen-doped carbon film/nanoparticle composite, in which the films were wrapped and separated by the nanoparticles, was prepared through a simple co-calcination route. Due to its unique porous structure and improved nitrogen content, the as-prepared electrode material could exhibit high specific capacitances of 317.5 F g− 1 at 0.5 A g− 1 and 200.0 F g− 1 at 20 A g− 1, and stable cycling behavior with no capacitance decline after 10,000 cycles in three-electrode system. When assembled in two-electrode capacitor, its specific capacitance could be well kept at 265.5 F g− 1 at 0.5 A g− 1, and thus the supercapacitor with a high energy density of 9.22 Wh kg− 1 was obtained. The superior energy storage properties of the as-prepared material indicate its promising application as high-performance carbon-based electrode for supercapacitors.
Electrochemical oxidation and reduction reactions are fundamental in various conversion and energy storage devices. Functional materials derived from MOFs have been considered promising as electrical catalysts for ORR, HER, and OER, which can be used in Zinc-air batteries and water electrolysis. Herein, we designed a novel approach to fabricating the ultrafine Co9S8 embedded nitrogen-doped hollow carbon nanocages ( Co9S8@N-HC). The method involved a process of sulfidation of cobalt-based metal–organic frameworks (ZIF67) and then coating them with polypyrrole (PPy). PPy has notable properties such as high electrical conductivity and abundant nitrogen content, rendering it highly promising for catalytic applications. The Co9S8@ N-HC catalyst was successfully synthesized via the carbonization of CoSx@ PPy. Remarkably, the Co9S8@ N-HC catalyst demonstrated exceptional electrocatalytic activity, requiring only low overpotentials of 285 mV and 201 mV at 10 mA cm‒ 2 for OER and HER, respectively, and exhibited high activity for ORR, with an onset potential ( Eonset) of 0.923 V and half-wave potential ( E1/2) of 0.879 V in alkaline media. The electrocatalytic efficiency displayed by Co9S8@ N-HC opens a new line of research on the synergistic effect of MOF-PPy materials on energy storage and conversion.
With the wide application of portable wearable devices, a variety of electronic energy storage devices, including microsupercapacitors (MSCs), have attracted wide attention. Laser-induced graphene (LIG) is widely used as electrode material for MSCs because of its large porosity and specific surface area. To further improve the performance of MSCs, it is an effective way to increase the specific surface area and the number of internal active sites of laser-induced graphene electrode materials. In this paper, N-doped polyimide/polyvinyl alcohol (PVA) as precursor was used to achieve in situ doping of nitrogen atoms in laser-induced graphene by laser irradiation. Through the addition of N atoms, nitrogen-doped laser-induced threedimensional porous graphene (N-LIG) exhibits large specific surface area, many active sites, and good wettability all of which are favorable conditions for enhancing the capacitive properties of laser-induced graphene. After assembly with PVA/H2SO4 as gel electrolyte, the high surface capacitance of the MSC device with N-LIG as electrode material is 16.57 mF cm− 2 at the scanning rate of 5 mV s− 1, which is much higher than the 2.89 mF cm− 2 of the MSC device with LIG as electrode material. In addition, MSC devices with N-LIG as electrode materials have shown excellent cyclic stability and flexibility in practical tests, so they have a high application prospect in the field of flexible wearable microelectronics.
The raw material selected for this research was Brazil chestnut shells (BCs), which were utilized to gain porous carbon as a positive electrode for lithium–sulfur batteries (LSBs). The effects of N/S co-doped on the electrochemical properties of porous carbon materials were studied using thiourea as nitrogen and sulfur sources. The experimental results indicate that the N/S co-doped carbon materials have a higher mesopore ratio than the undoped porous carbon materials. The porous carbon material NSPC-2 has a lotus-like structure with uniform pore distribution. The N and S doping contents are 2.5% and 5.4%. The prepared N/S co-doped porous carbon materials were combined with S, respectively, and three kinds of sulfur carbon composites were obtained. Among them, the composite NSPC-2/S can achieve the initial specific discharge capacity of 1018.6 mAh g− 1 at 0.2 C rate. At 1 C rate, the initial discharge capacity of the material is 730.6 mAh g− 1, and the coulomb efficiency is 98.6% and the capacity retention rate is 71.5% after 400 charge–discharge cycles.
Heavy metal ions pollution has become of worldwide critical concern, thus, it is particularly important to monitor it in the environment and food for ensuring human health. In this study, p-phenylenediamine and 2-mercaptothiazoline were used to prepare nitrogen (N) and sulfur (S) co-doped carbon dots (N/SCDs) for fluorescent and colorimetric detection of Cu2+. The fabricated N/SCDs with bright green fluorescence showed excellent optical characteristics and favorable water solubility. In an aqueous system, a significant fluorescence quenching of N/SCDs at 512 nm is obtained in the presence of Cu2+. It also caused a significant colorimetric response with the color of prepared N/SCDs solution changed from colorless to yellow. Under optimal conditions, the analytical results showed that the linear range spanning from 5 to 400 μM, with a detection limit of 0.215 μM in fluorescence and 0.225 μM in colorimetric detection. In addition, N/SCDs displayed high selectivity toward Cu2+. No obvious interference was observed over other metal ions. Furthermore, we have also used N/SCDs to monitor Cu2+ in tap and lake water. The recovery of Cu2+ ranged between 89.6% and 113.1%. Exhibiting remarkable sensitivity and selectivity, the designed sensor offers a promising detection method for Cu2+ detection in the real sample.
The presence of tetracycline (TC) has been detected in the human living environment, and its complex structure makes it difficult to degrade. The green and efficient utilization of electroactivated persulfate advanced oxidation technology for the degradation of tetracycline remains a challenge. In this study, N-doped reduced graphene oxide (N-rGO) was prepared using a hydrothermal treatment method with urea as the nitrogen source. Four different mass ratios of graphene oxide (GO) to urea were synthesized, and the optimal mass ratio was determined through degradation experiments of tetracycline. The N-rGO/EC/PMS three-dimensional electrocatalytic system was constructed, and the influence of the experimental data on TC degradation, such as initial pH, PMS dosage and voltage, was determined. Characterization analysis using scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and other methods was conducted. The efficient catalytic ability of N-rGO was demonstrated through the generation of hydrogen peroxide ( H2O2) and consumption of peroxymonosulfate (PMS). The superiority of the three-dimensional (3D) electrochemical advanced oxidation process was proposed by combining different systems. Furthermore, the presence of hydroxyl radicals (.OH), persulfate radicals ( SO4 ·−), and singlet oxygen (1O2) was identified using electron spin resonance (ESR) technology. The utilization of N-rGO as a three-dimensional electrode, coupled with the advantages of PMS activation and electrochemical oxidation processes, is a promising method for treating organic pollutants in wastewater.
N-doping content and configurations have a significant effect on the electrochemical performance of carbon anodes. Herein, we proposed a simple method to synthesize highly N self-doped chitosan-derived carbon with controllable N-doping types by introducing 2ZnCO3 ·3Zn(OH)2 into the precursor. The as-synthesized NC-CS/2ZnCO3·3Zn(OH)2 electrode exhibited more than twice the reversible capacity (518 mAh g− 1 after 100 cycles at 200 mA g− 1) compared to the NC-CS electrode, superior rate performance and outstanding cycling stability. The remarkable improvement should be mainly attributed to the increase of N-doping content (particularly the pyrrolic-N content), which provided more active sites and favored Li+ diffusion kinetics. This study develops a cost-effective and facile synthesis route to fabricate high-performance N self-doped carbon with tunable doping sites for rechargeable battery applications.
In this work, norepinephrine (NE) was determined by an electrochemical sensor represented by a carbon paste electrode boosted using nitrogen-doped porous carbon (NDPC) derived from Spirulina Platensis microalga anchored CoFe2O4@ NiO and 1-Ethyl-3-methylimidazolium acetate (EMIM Ac) ionic liquid. The morphological characteristics of the catalyst were recorded by field emission scanning electron microscope (FE-SEM) images. Moreover, the electrochemical behavior of norepinephrine on the fabricated electrode was checked using various voltammetric methods. All tests were done at pH 7.0 as the optimized condition in phosphate buffer solution. The results from linear sweep voltammetry revealed that the electro-oxidation of norepinephrine was diffusion, and the diffusion coefficient value was obtained by chronoamperometry (D⁓6.195 × 10– 4). The linear concentration of the modified electrode was obtained from 10 to 500 μM with a limit of detection of 2.26 μM using the square wave voltammetry (SWV) method. The sensor selectivity was investigated using various species, and the results from stability and reproducibility tests showed acceptable values. The sensor's efficiency was tested in urine and pharmaceutical as real samples with recovery percentages between 97.1% and 102.82%.
Nitrogen and phosphorous dual-doped carbon nanotubes (N,P/CNT) have been grown in a single-step direct synthesis process by CVD method using iron-loaded mesoporous SBA-15 support, as an electrode material for the energy storage device. For comparison, pristine nanotubes, nitrogen and phosphorous individually doped nanotubes were also prepared. The basic characterization studies clarify the formation of nanotubes and the elemental mapping tells about the presence of the dopant. Under three-electrode investigations, N,P/CNT produced a maximum specific capacitance of about 358.2 F/g at 0.5 A/g current density. The electrochemical performance of N,P/CNT was further extended by fabricating as a symmetric supercapacitor device, which delivers 108.6 F/g of specific capacitance for 0.5 A/g with 15 Wh/kg energy density and 250 W/kg power density. The observed energy efficiency of the device was 92.3%. The capacitance retention and coulombic efficiency were 96.2% and 90.6%, respectively, calculated over 5000 charge–discharge cycles.
The development of functional carbon materials using waste biomass as raw materials is one of the research hotspots of lithium-sulfur batteries in recent years. In this work, used a natural high-quality carbon source—coffee grounds, which contain more than 58% carbon and less than 1% ash. Honeycomb-like S and N dual-doped graded porous carbon (SNHPC) was successfully prepared by hydrothermal carbonization and chemical activation, and the amount of thiourea used in the activation process was investigated. The prepared SNHPC showed excellent electrochemical energy storage characteristics. For example, SNHPC-2 has a large pore volume (1.85 cm3·g− 1), a high mesoporous ratio (36.76%), and a synergistic effect (S, N interaction). As the cathode material of lithium-sulfur batteries, SNHPC-2/S (sulfur content is 71.61%) has the highest specific capacity. Its initial discharge-specific capacity at 0.2 C is 1106.7 mAh·g−1, and its discharge-specific capacity after 200 cycles is still as high as 636.5 mAh·g−1.
Lead sulfide ( PbS ) nanocrystals anchored on nitrogen-doped multiwalled carbon nanotubes ( CNx ) have been synthesized employing an environmentally friendly and inexpensive wet chemistry process. CNx∕PbS composites have been examined by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. Theorical ab initio calculations have been developed to determine the samples structural, morphological and optical properties to explain the experimental evidences. The PbS nanoparticles exhibit of 4 nm to 27 nm particle size with a face-centered cubic crystal structure and are homogeneously distributed along the carbon nanotubes. The nitrogen-doped CNTs acts as binding sites for the PbS clusters as ab initio theoretical study suggests.
In this article, nitrogen (N) doped porous carbon nanofibers (N-PCNF) were prepared by carbonization of polymer-silica nanocomposite precursor, and its application for heavy metal ion removal was demonstrated. Carbon–silica composite nanofibers were obtained by carbonization of electrospun polyacrylonitrile (PAN)-silica nanofiber composites. Subsequent selective etching of silica porogen produced porous carbon nanofibers (PCNF). It was revealed by surface characterization with X-ray photoelectron spectroscopy (XPS) that the surface of the PCNF was nitrogen-doped because N atom from cyanide group in PAN chains remained in the hexagonal carbon structure. The use of the obtained N-PCNF for heavy metal ion ( Hg2+) removal was demonstrated using a simple adsorption test apparatus and 5, 10, 15, 20-tetraphenylporphine tetrasulfonic acid (TPPS) as an indicator. The N-PCNF showed a removal efficiency of 96 and 99% in 10 and 120 min, respectively, indicating a maximum heavy metal ion adsorption capacity at pH 7.0. In addition, heavy metal ion adsorption behavior was also analyzed using common adsorption isotherms. This article provides important information for future research activities regarding control over hazardous substances.
Here, a novel nitrogen-doped carbon nano-material (N-CGNM) with hierarchically porous structure was prepared from spent coffee ground for efficient adsorption of organic dyes by a simple one-step carbonization process (the uniform mixture consists of spent coffee ground, urea, and CaCl2 with the ratio of 1:1:1, which was heated to 1000 °C with a rate of 10 °C min− 1 and held at 1000 °C for 90 min in N2 atmosphere to carry out carbonization, activation, and N-doping concurrently). The morphology and structure analysis show that the prepared N-CGNM exhibits hierarchical pore structure, high specific surface area (544 m2/ g), and large numbers of positively charged nitrogen-containing groups. This unique structure and chemical composition endow N-CGNM with an excellent adsorption capacity toward anion Congo red (623.12 ± 21.69 mg/g), which is obviously superior to that (216.47 ± 18.43 mg/g) of untreated spent coffee ground-based carbon nano-materials (CGM). Oppositely, the adsorption capacity of N-CGNM towards cation methylene blue is inferior to that of CGM due to the existence of electrostatic repulsion. These findings show a great guidance for the development of low-cost but efficient selective adsorbent.
Doped porous carbon materials have attracted great interest owing to their excellent electrochemical performance toward energy storage applications. In this report, we described the synthesis of nitrogen-doped porous carbon (N-PC) via carbonization of a triazine-based covalent organic framework (COF) synthesized by Friedel–Crafts reaction. The as-synthesized COF and N-PC were confirmed by X-ray diffraction. The N-PC exhibited many merits including high surface area (711 m2 g−1), porosity, uniform pore size, and surface wettability due to the heteroatom-containing lone pair of electron. The N-PC showed a high specific capacitance of 112 F g−1 at a current density of 1.0 A g−1 and excellent cyclic stability with 10.6% capacitance loss after 5000 cycles at a current density of 2.0 A g−1. These results revealed that the COF materials are desirable for future research on energy storage devices.
Hierarchically porous carbon materials with high nitrogen functionalities are extensively studied as highperformance supercapacitor electrode materials. In this study, nitrogen-doped porous carbon textile (N-PCT) with hierarchical pore structures is prepared as an electrode material for supercapacitors from a waste cotton T-shirt (WCT). Porous carbon textile (PCT) is first prepared from WCT by two-step heat treatment of stabilization and carbonization. The PCT is then nitrogendoped with urea at various concentrations. The obtained N-PCT is found to have multi-modal pore structures with a high specific surface area of 1,299 m2 g−1 and large total pore volume of 1.01 cm3 g−1. The N-PCT-based electrode shows excellent electrochemical performance in a 3-electrode system, such as a specific capacitance of 235 F g−1 at 1 A g−1, excellent cycling stability of 100 % at 5 A g−1 after 1,000 cycles, and a power density of 2,500 W kg−1 at an energy density of 3.593 Wh kg−1. Thus, the prepared N-PCT can be used as an electrode material for supercapacitors.
Highly luminescent carbon quantum dots (CQDs) are developed as fluorescent probes for selective detection of the heavy-ion Fe3+, where the CQDs exhibit excellent nontoxicity, functionalizability, sensitivity, and selectivity. Biomass-based CQDs and nitrogen-doped CQDs (N-CQDs) are synthesized for the selective detection of Fe3+ by using H2O2 as an oxidant and polyetherimide (PEI) as a nitrogen precursor by a green hydrothermal synthesis method. The prepared CQDs and N-CQDs exhibit an elliptical morphology and with an average particle size of 7 and 4 nm, respectively, and emit blue photoluminescence at 445 and 468 nm under excitation at 367 and 343 nm, respectively. The CQDs and N-CQDs exhibit good water solubility because of the abundant hydroxyl and carboxyl/carbonyl groups and graphic/pyrrolic/pyridinic nitrogen on the surfaces, giving rise to a quantum yield of about 24.2% and 30.7%, respectively. Notably, the Matrimony vine-PEI-based CQDs exhibit excellent Fe3+ selectivity and sensitivity relative to the Matrimony vine-based CQDs due to complexation of the numerous phenolic hydroxyl groups and nitrogen-containing groups with Fe3+, leading to increased fluorescence quenching, which greatly improves the sensitivity of detection. The minimum detection limit was 2.22 μmol L− 1 with a complexation constant of 44.7.
Nitrogen-doped carbon dots (N-CDs), derived from the biomass (anthocyanin), are the novel additive to the nanocarbon materials, which is expected to bring a wide spectrum of novel applications. Moreover, metallic oxides are emerging for their unique potential for electrocatalysis. Herein, we report the synthesis of N-CDs for the selective detection of Fe3+ with a limit of detection of 2.57 μM in the range of 5–60 μM using ethylenediamine and H2O2 by a hydrothermal method. The obtained N-CDs displayed a spherical morphology with a particle size range of 2–7 nm and emitted blue luminescence at 394 nm under excitation at 319 nm. Meanwhile, we have demonstrated the fabrication of cost-efficient electrocatalysts for oxygen evolution reaction (OER) in an alkaline medium, employing N-CDs. Owing to the successful incorporation of N-CDs into NiO nanospheres, the resulting N-CDs/NiO with large surface areas, fast charge transfer, and increased conductivity vastly improved the catalytic activity. Remarkably, the optimal of N-CDs/NiO composite requires the overpotential of only 380 mV at a current density of 10 mA cm− 2 and a relatively low Tafel slope of 57.96 mV dec− 1 compared with pure NiO. These results open up a facile route for the application of N-CDs and offer prospects for CD-metal hybrids as high OER catalysts in electrochemical energy devices.
The simultaneous use of KOH and nitrogen to manufacture carbon materials provides these materials with properties that the presence of only one of these additives would not give them, such as high porosity and reactivity. However, it is difficult to obtain nitrogen-doped carbon materials with both high porosity and high nitrogen content, as the KOH significantly reduces the nitrogen content. In this review the complex relationships between nitrogen content and nitrogen precursor amount, KOH amount and the activation temperature are discussed, with a focus on the different N-functional groups and the porosity of the fabricated carbons. Generally, increasing activation temperature and increasing KOH amount decrease the nitrogen content due to reactions with the N-containing substructures of carbon, resulting in the release of nitrogen as N2, HCN and other N gases. Increasing these parameters can also result in the reduction of pyridine-N while the amount of quaternary-N increases simultaneously. Besides this, an increase in the amount of nitrogen precursor leads to an increase in the porosity of N-doped materials. However, too high amounts of the nitrogen precursor generate an excess of nitrogen which blocks the pore system and consequently reduces the porosity of the doped carbons.
Nitrogen-doped carbon dots (CDts) with tunable fluorescence properties in aqueous media were synthesized hydrothermally. The excitation wavelength variation to obtain the maximum emission produced a blue shift in the emission peaks upon dilution in an aqueous solution. The shift can be explained by a re-absorption phenomenon in a concentrated solution. The interparticle interaction within was responsible to show dilution-dependent optical behavior. The as-synthesized solution of CDts did not show any prominent absorption peak over a wide range. However, upon dilution, two peaks became predominant. The concentration-dependent behavior was observed during the interaction with metal cations. Cationic salts of Co(II) and Hg(II) caused quenching at different dilutions of CDts. This might be explained by the exposure of different surface functional groups during dilution and metal-ion–CDts charge transfer. The quenched fluorescence of CDts was rescued using ascorbic acid. Therefore, the one-pot detection of Co(II)/Hg(II) and ascorbic acid was designed through a ‘Turn Off/On’ phenomenon.