In this study, nitrogen and fluorine co-doped carbon nanocages (NF-CNCs) were synthesized as anode materials for potassium- ion batteries (KIBs), and their structural evolution with heat treatment and electrochemical behavior with different functional groups was investigated. NF-CNCs were prepared by physically mixing coal tar pitch (CTP) with a SiO2 template, followed by heat treatment and subsequent fluorination with NF3 gas. A systematic investigation of the structural properties revealed that graphitization increased with increasing heat treatment temperature as the carbon structure transitioned from amorphous at 500 and 1000 °C to graphite-like at 1500 °C. Furthermore, nitrogen and fluorine functional group analysis revealed significant changes, particularly in terms of covalent and semi-ionic C‒F bonds. Among the samples, NF-CNC 1000 displayed excellent electrochemical performance, with a specific capacity of 395.1 mAh g− 1 and a capacity retention rate of 94% during 1000 cycles at 50 mA g− 1. The exceptional performance of NF-CNC 1000 is attributed to its high porosity, amorphous carbon structure, and semi-ionic C‒F bonds, which facilitate the efficient adsorption and intercalation of potassium ions. These findings provide valuable insights into the design of advanced anode materials for next-generation KIBs.
Quantum dot nanocomposite-based luminescent materials have gained attention for solid-state lighting and optical displays. This study presents a one-step, eco-friendly hydrothermal process to synthesize nitrogen, potassium, and calcium-doped carbon quantum dots (N, K, Ca-doped CQDs) from the flower extract of Mesembryanthemum crystallinum L. (ice plant). The CQDs were characterized using HRTEM, EDX, SAED, XPS, XRD, NMR, FTIR, zeta potential, UV–Vis, and photoluminescence spectroscopy. HRTEM revealed an average particle size of 4.6 nm, with a range of 2 to 7 nm. The CQDs exhibited a quantum yield of 20%, excellent water solubility, photostability, and greenish fluorescence under UV (365 nm). The fluorescence spectra were analyzed using CIE (Commission Internationale de l’Eclairage) chromaticity coordinates to determine the emitted color. The fluorescence emission behavior was influenced by solvent polarity, locally excited (LE) states, intramolecular charge transfer (ICT) processes, and hydrogen bonding. The hydrogen bonds between N, K, Ca-doped CQDs and DI water likely enhanced the stability of the ICT state, resulting in a red shift in fluorescence. Additionally, we developed an eco-friendly wheat-starch-based bioplastic nanocomposite by embedding the CQDs. The effects of CQD concentration and pH sensitivity on luminescent properties were explored. Finally, we demonstrated a practical application by designing a conceptual nameplate-like calligraphy using the optimized CQDs@bioplastic nanocomposite film (CQD concentration: 240 mg/mL, pH: 2.7), highlighting its potential for luminescent film applications.
Ibuprofen (IBU), a common pharmaceutical and personal care product (PPCP), is a pervasive water pollutant with adverse ecological and human health effects after transformation and accumulation. In this study, we synthesized Fe, N-doped carbon quantum dots (Fe, N-CQDs) using pig blood and FeCl3 as a precursor via a one-step hydrothermal method. TEM, XRD, XPS, and UV–Vis were used to characterize the physical and chemical properties of Fe, N-CQDs. We investigated the feasibility of Fe, N-CQDs in activating peroxymonosulfate (PMS) for IBU degradation under visible light. The experimental results revealed that Fe in Fe, N-CQDs predominantly formed a stable complex through Fe–N and Fe-OH, with a high degree of graphitization and a sp2- hybridized graphitic phase conjugate structure. The Fe, N-CQDs/Light/PMS system exhibited strong activity, degrading over 87% of IBU, maintaining a wide pH range (3–10) adaptability. Notably, Fe, N-CQDs acted as visible-light catalysts, promoting Fe3+/ Fe2+ cycling and PMS activation, generating both free radicals ( SO4 •–, ·OH) and non-radicals (1O2, h+) to effectively degrade IBU. This study presents an innovative approach for the sustainable utilization of pig blood as a biomass precursor to synthesize Fe- and N-doped carbon materials. This study provides a new approach for the sustainable and value-added utilization of natural wastes and biomass precursors of Fe- and N-doped carbon materials, which can be used to treat pollutants in water while treating discarded pig blood.
Porous carbon has been intensively used for microwave absorption in merits of its outstanding specific surface area and dielectric properties. This study investigates the microwave absorption capacity of saturated wood-based activated carbon (SWAC) which was used for methylene blue treatment. The results demonstrate that SWAC, subjected to high temperature calcination, exhibits excellent microwave absorption properties. The structure, composition, micro-morphology, and electromagnetic parameters of SWAC were comprehensively analyzed using various techniques. The findings reveal that after calcination, SWAC possesses a rich pore structure, optimized material impedance matching, and the introduction of N atoms from the organic substance methylene blue into the carbon lattice of SWAC, thereby providing dipole polarization loss. These properties significantly contribute to its microwave absorption performance. The optimal reflection loss of SWAC at 6 GHz reaches −50.29 dB with an effective absorption bandwidth of 2.01 GHz, achieved at a calcination temperature of 700 °C and a paraffin matrix additive amount of 25%. The one-step treatment of SWAC proves to be a competitive and cost-effective method for producing microwave absorbers, which holds significant importance for the recovery of SWAC.
Lithium-ion batteries (LIBs) are widely used as essential power sources for electric vehicles and energy storage systems. Among various cathode materials, Li[Ni0.9Mn0.1]O2 (NM90) has gained significant attention for enhancing the performance of LIBs due to its high energy density and nontoxicity. However, increasing the nickel content introduces challenges, including structural instability and cation mixing. To address these issues, we propose a surface coating strategy using nitrogendoped carbon quantum dots (NCQDs). NCQDs provide high electrical conductivity and electrochemically active sites, so the NCQDs coating effectively enhanced both structural stability and electrical/ionic conductivity. The NCQDs were synthesized via a hydrothermal method, and NM90 were synthesized by co-precipitation. The fabricated NCQD/NM_5 electrode exhibited superior electrochemical properties, including a high initial capacity of 189.6 mAh/g, excellent rate performance, and an outstanding capacity retention of 81.5 % after 200 cycles in 1C. These superior results demonstrate that surface modification using the NCQDs strategy for Li[Ni0.9Mn0.1]O2 cathode materials will contribute to the further development of cycle stability and ultrafast performance in energy storage systems.
For metal-free carbocatalysts, heteroatom doping and hierarchically porous structure are the significant factors to improve their catalytic performances. Herein, N-, P-co-doped hierarchically porous carbon fiber (NPC–2–800) was prepared by pyrolyzing bamboo pulp in combination with ( NH4)2HPO4 and activator K2CO3. It was found that ( NH4)2HPO4 not only provides N and P atoms, but also significantly affect the morphology and pore structure of the porous carbon. An appropriate dosage of ( NH4)2HPO4 facilitates the formation of hierarchically porous carbon fiber in NPC-2–800. Whereas, the carbon fragments with only micropores were obtained in absence of ( NH4)2HPO4. The hierarchical porosity and the co-doping of N and P atoms in the NPC-2–800 contribute to its outstanding catalytic performances in the 4-Nitrophenol (4-NP) reduction assisted by NaBH4. The NPC-2–800 exhibits an attractive turnover frequency (TOF) value of 4.29 × 10– 4 mmol mg− 1 min− 1, a low activation energy (Ea) of 24.76 kJ/mol, and an acceptable recyclability for 7 cycles without obvious decrease in activity. Kinetics analyses suggest that the 4-NP reduction proceeds through the Langmuir–Hinshelwood model. In addition, the NPC-2–800 can also efficiently catalyze the 2-NP and 3-NP reduction. Moreover, in the real water body, the NPC-2–800 also showed superior catalytic activity to catalyze 4-NP reduction. This study provides an efficient catalyst for pollutant conversion and elimination as well as guidelines for designing versatile carbon-based catalysts.
A phenylboric acid functionalized carbon dot (2-FPBA-CD) for rapid fluorescent sensing of glucose in blood was synthesized by simply mixing N, S-doped carbon dots (CDs) with phenylboric acid at room temperature. At pH 7.4, the response of 2-FPBA-CD to glucose could reach equilibrium in a very short time (10 min), with a wide responsive linear range of 19.70 μM to 2.54 mM, which can be applied to the detection of glucose in serum. The mechanism studies showed that the layered carbon film of 2-FPBA-CD aggregated after adding glucose, thereby leading to the fluorescence quenching of 2-FPBA-CD.
4-Nitrophenol (4NP) is a vital intermediate in organic industries, and its exploitation creates serious environmental issues. We propose a fluorescence quenching-based strategy with nitrogen and sulfur co-doped carbon dots (NS-CDs) for highly sensitive 4NP detection with excellent selectivity. The NS-CDs are produced through the hydrothermal process, in which citric acid serves as a carbon source and cysteamine hydrochloride as a source of N and S. The effect of doping was also studied by synthesizing undoped CDs and examining their properties. As-developed NS-CDs exhibit a bright cyan blue color with maximum emission centered at 465 nm. The fluorescence of NS-CDs is significantly quenched in an approximately linear fashion with increasing 4NP concentration (7.5–97.5 μM). The inner filter effect (IFE) and static quenching (SQ) between NS-CDs and 4NP are responsible for such fluorescence reduction. The fluorimetry technique enables the quantification of 4NP with a limit of detection (LOD) of about 0.028 μM. Moreover, the fluorescence quenching is tested for several other chemical compounds but they generate false quenching signals; only 4NP leads to fluorescence quenching of NS-CDs, demonstrating excellent selectivity. The “turn-off” fluorescence properties and visually apparent color change of the fluorescent probe reveal the excellent performance for 4NP sensing. The NS-CDs’ capability of quantifying 4NP in real water samples (tap water and drinking water) produces an excellent recovery rate ranging between 96.24 and 98.36%.
Sulfur and nitrogen co-doped carbon dots (NSCDs) were quickly synthesized by the microwave-assisted method from triammonium citrate and thiourea. NSCDs showed a quantum yield of 11.5% with excitation and emission bands at 355 and 432 nm, respectively. Also, a fluorescence quenching was observed in the presence of Pb(II) ions, and the as-synthesized CDs were used as a sensitive probe for detecting Pb(II) in water and food samples. The results showed the optimal conditions for Pb(II) determination were CDs concentration of 0.02 mg mL− 1 at pH 6.0–7.0 and an incubation time of 20 min. The relative fluorescence intensity of NSCDs was proportional to Pb(II) concentrations in the range of 0.029–2.40 and 2.40–14.4 μmol L− 1 with a correlation coefficient (R2) of 0.998 and 0.955, respectively, and a detection limit of 9.2 × 10– 3 μmol L− 1. Responses were highly repeatable, with a standard deviation below 3.5%. The suggested method demonstrates the potential of a green, fast, and low-cost approach for Pb(II) determination in water, tea, and rice samples with satisfying results.
The disposal of organic pollutants is one of the important research topics. Some of the studies in this field are based on the degradation of organic pollutants with a catalytic agent. The cobalt tetraoxide/peroxymonosulfate system is an important catalytic system used for the radical degradation of organic pollutants. To increase the catalytic efficiency of such reactions, graphitization of activated carbon used as a support solid and nitrogen doping to the carbon structure are commonly used methods. In this study, cobalt tetraoxide production, N-doping and graphitization were carried out in a single step by heat treatment of activated carbon doped with the phthlocyanine cobalt (II) complex. The catalytic performance of the catalyst/ peroxymonosulfate system was investigated by changing the pH, catalyst, and PMS concentration parameters on rhodamine B and 1,3,5 trichlorophenol, which were used as models. It was seen that the catalysts had 97% activity on rhodamine B in 16 min and 100% on 1,3,5 trichlorophenol in 6 min. It was observed that the catalysts continued to show high catalytic activity for five cycles in reusability studies and had a very low cobalt leaching rate. These results are in good agreement with previously published studies. In line with these results, the synthesized N-doped graphitic carbon/Co3O4 catalyst can be used as an effective catalyst for wastewater treatments.
Recently, hollow carbon spheres (HCS) have aroused great interests in the field of energy storage and conversion owing to their unique morphology, structure and other charming properties. Nevertheless, unsatisfactory electrical conductivity and relatively poor volumetric energy density caused by inevitable gaps between discrete carbon spheres greatly impede the practical application of HCS. In this work, for the first time we propose a novel dual-template strategy and successfully fabricate interconnected 3D hollow N-doped carbon network (HNCN) by a facile and scalable pyrolysis process. By systematical characterization and analysis, it can be found that HNCN is assembled by HCS and lots of mesoporous carbon. Compared to the counterparts, the obtained HNCN exhibits unique 3D interconnected architecture, larger specific surface area, hierarchical meso/macropore structure, higher structure defects, higher N doping amount and more optimized N configurations (especially for pyridinic-N and graphitic-N). As a result, these advantageous features endow HNCN with remarkably promoted electrochemical performance for supercapacitor and oxygen reduction reaction. Clearly, our proposed dual-template strategy provides a good guidance on overcoming the intrinsic shortcomings of HCS, which undoubtedly broadens their application in energy storage and conversion.
Hydrogen energy is a promising source of renewable and clean energy for various industries, such as chemical, automobile, and energy industries. Electrolysis of water is one of the basic methods for the production of hydrogen energy. However, the high overpotential of the oxygen evolution reaction (OER) in water electrolysis has hindered the effective production of hydrogen using this method. Thus, the development of high-efficiency non-precious metal-based electrocatalysts for OER is extremely significant. In this study, we adopted a one-step hydrothermal method to fabricate Ni-based catalysts with N/Sdual doped graphene oxide/carbon nanotube (GO/CNT) supports using thiourea ( CH4N2S) and urea as the S source and the N source. It was observed that the amount of thiourea utilized in the synthesis of the catalyst affected the morphology, composition, and the electrochemical properties of the catalyst. For a GO/CNT-to-thiourea mass ratio of 1:10, the catalyst exhibited the highest activity, where the OER overpotential was 320 mV at a current density of 10 mA/cm2. This was attributed to the high specific surface area, high conductivity, and fast electron transport channels of the N/S-dual doped GO/ CNT composite. Furthermore, sulfurization of the Ni particles to form nickel sulfide played a significant role in enhancing the catalytic performance.
A promising approach to enhance catalytic performance of supported heterogeneous nano-metal catalysts is to uniformly disperse active nanoparticles on the support. In this work, N-doped carbon-modified graphene (G@NC) nanosheet is designed and prepared to anchor Pd–Fe bimetallic nanoparticles (Pd–Fe/G@NC). The N-doped carbon modification on graphene surface could construct a sandwich-like structure (G@NC), which not only prevented the re-stacking of graphene nanosheets but also provided confined space for stable anchoring of bimetallic Pd–Fe nanoparticles. Benefitted from the unique structural property and synergetic effect of metal Pd and Fe species, the as-obtained Pd–Fe/G@NC composite displays excellent catalytic activity toward 4-nitrophenol reduction reaction with a turnover frequency of 613.2 min− 1, which is far superior to that of the mono-metal counterparts (Fe/G@NC and Pd/G@NC). More importantly, Pd–Fe/G@NC catalyst also exhibits favorable catalytic performance in the reduction of other nitroaromatic compounds (nitrobenzene, 4-nitrotoluene, 4-chloronitrobenzene, and so on). In addition, Pd–Fe/G@NC can catalyze the oxidation of furfuraldehyde to furoic acid with a high yield of 88.64%. This work provides a new guide for rationally designing and developing advanced supported heterogeneous bimetallic catalyst.
Electrochemical water splitting is an important process for next generation of eco-friendly energy systems. The oxygen evolution reaction (OER), which occurs at an anode during the process, requires efficient electrocatalysts to reduce activation energies. Although Ru- or Ir-containing materials show excellent electrocatalytic activities, their high cost is a critical drawback. Consequently, the development of efficient electrocatalysts composed of low-cost metal components is a great challenge. In this study, we develop a new route to produce a hybrid material (Fe–NC) containing Fe3C particles dispersed on the surface of N-doped carbon (NC) materials by heat treatment of a mixture of urea and Fe(II)Cl2(H2O)4. Microscopic analyses prove that the Fe3C particles are placed on the surfaces of thin NC materials. Additionally, various characterizations reveal that the particles contain Fe3C structure. Fe–NC shows good electrocatalytic properties with onset and overpotentials of 1.57 V and 545 mV, respectively, for OER in KOH electrolyte. This study suggests the possibility of the use of Fe3C- based composites as OER electrocatalysts.
In this study, N/S co-doped carbon felt (N/S-CF) was prepared and characterized as an electrode material for electric double-layer capacitors (EDLCs). A commercial carbon felt (CF) was immersed in an aqueous solution of thiourea and then thermally treated at 800 oC under an inert atmosphere. The prepared N/S-CF showed a large specific surface area with hierarchical pore structures. The electrochemical performance of the N/S-CF-based electrode was evaluated using both 3- electrode and 2-electrode systems. In the 3-electrode system, the N/S-CF-based electrode showed a good specific capacitance of 177 F/g at 1 A/g and a good rate capability of 41% at 20 A/g. In the 2-electrode system (symmetric capacitor), the freestanding N/S-CF-based electrode showed a specific capacitance of 275 mF/cm2 at 2 mA/cm2, a rate capability of 62.5 % at 100 mA/cm2, a specific power density of ~ 25,000 mW/cm2 at an energy density of 23.9 mWh/cm2, and a cycling stability of ~ 100 % at 100 mA/cm2 after 20,000 cycles. These results indicate the N/S co-doped carbon felts can be a promising candidate as a new electrode material in a symmetric capacitor.
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.
To meet the increased performance and cost requirements of commercial supercapacitor, a N and O self-doped hierarchical porous carbon is fabricated via a green and simple self-activation route utilizing leaves of wild hollyhock as raw materials. Comparing to commercial activated carbon, the reported material exhibits some marked merits, such as simple and green fabrication process, low cost, and superior capacitance performance. The specific surface area of the obtained N and O codoped hierarchical porous carbon arrives 954 m2 g−1, and the content of the self-doped nitrogen and oxygen reaches 2.64 at.% and 7.38 at.%, respectively. The specific capacitance of the obtained material reaches 226 F g− 1 while the specific capacitance of the symmetric supercapacitor arrives 47.3 F g− 1. Meanwhile, more than 90.3% of initial specific capacitance is kept under a current density of 20 A g− 1, and no arresting degradation is observed for capacitance after 5000 times cycle, perfectly demonstrating the excellent cycle and rate capability of the obtained material. The obtained N and O co-doped hierarchical porous carbon are expected to be an ideal substitution for commercial activated carbon.
Oxygen evolution reaction (OER) is an essential step at an anode in electrochemical water-splitting process and requires efficient electrocatalysts to reduce overpotentials. Although precious metal-based materials, such as RuO2, IrO2 and their hybrids with other components, performed excellently as OER electrocatalysts, their high cost has limited practical applications. Consequently, earth-abundant metal components including Fe, Co, and Ni have been investigated as alternatives. In this work, the hybridization of Ni-containing species with conductive carbon-based materials was used to prevent aggregation of active species and improve electrochemical catalytic performance. A new hybrid material composed of NiO nanoparticles and N-doped carbon materials was prepared. The NiO particles with a narrow size distribution were well dispersed on the surface of carbon-based materials. The hybrid showed improved electrocatalytic performance for OER than single components of NiO and N-doped carbon materials.
Nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a dual transition metal system were synthesized as non-Pt catalysts for the ORR. The highly nitrogen doped OMCs were prepared by the precursor of ionic liquid (3-methyl-1-butylpyridine dicyanamide) for N/C species and a mesoporous silica template for the physical structure. Mostly, N-doped carbons are promoted by a single transition metal to improve catalytic activity for ORR in PEMFCs. In this study, our N-doped mesoporous carbons were promoted by the dual transition metals of iron and cobalt (Fe, Co), which were incorporated into the N-doped carbons lattice by subsequently heat treatments. All the prepared carbons were characterized by via transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). To evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The dual transition metal promotion improved the ORR activity compared with the single transition metal promotion, due to the increase in the quaternary nitrogen species from the structural change by the dual metals. The effect of different ratio of the dual metals into the N doped carbon were examined to evaluate the activities of the oxygen reduction reaction.