N-doped Mesoporous Carbon Research Articles

Improved Energy Storage Performance of N-Doped Hollow Mesoporous Carbon Spheres as Substrate for MoS2

Improved Energy Storage Performance of N-Doped Hollow Mesoporous Carbon Spheres as Substrate for MoS2

Manganese nanoparticles catalyzed the formation of mesoporous helical nitrogen-doped carbon nanotubes enabled aldosterone biosensing

Primary aldosteronism (PA) is the foremost form of secondary hypertension that affects 5–20 % of healthy humans via the excessive secretion of aldosterone (ALD), which increases the level of potassium excretion and thus produces various critical combined diseases. Thus, determining trace-level ALD content in human blood or urine samples is a crucial factor in diagnosing a life-threatening disease called PA. Herein, nanosized manganese particles encapsulated within the tunable helical-shaped N-doped mesoporous carbon nanotubes (Mnx@H-NCNTs) are synthesized by a simple and facile ball-milling method at different reaction times (1, 6, 12, and 18 h). The influence of ball-milling process time on the final morphology of the as-synthesized Mnx@H-NCNTs nanostructures is systematically investigated. In order to fabricate an ALD biosensor electrode, the immobilization of Anti-ALD antibodies (Anti-ALD) on the surface of the Mn@H-NCNTs-12H electrode (Anti-ALD/Mn@H-NCNTs-12H) is achieved via the interactions of combined interactions of hydrogen bonds, Van der Waals’ force, negatively charged carboxylic acid functionalities of antibodies and positively charged metal centers, and π-π stacking interaction between nucleosides of Anti-ALD and mesoporous H-NCNTs. In addition, BSA was used as a blocking additive for covering non-specific adsorption sites of Anti-ALD/Mnx@H-NCNTs (BSA/Anti-ALD/Mn@H-NCNTs-12H) nanostructured electrodes. The BSA/Anti-ALD/Mn@H-NCNTs-12H can be used as an effective signal amplifying probe for ALD detection through a noticeable reduction in the amperometric i-t current response over a linear range from 1 to 2500 pM, with a LOD of 0.72 pM (S/N = 3). The practical applicability of BSA/Anti-ALD/Mn@H-NCNTs-12H is further demonstrated by the detection of ALD from 1 to 20 nM in human blood or urine samples with a recovery ranging from 90.5 to 97.0 %, indicating its potential use in clinical analysis.

Mesoporous carbon spheres modified with atomically dispersed iron sites for efficient electromagnetic wave absorption

Carbon materials have obtained some achievements in electromagnetic wave (EMW) absorption owing to their excellent electrical conductivity and low density. However, poor impedance matching and high electrical conductivity limit their EMW absorption properties. Metal single atoms absorbers have garnered considerable attention in EMW absorption, largely due to the high metal availability and special coordination structure, but the modulation of the EMW absorption properties still needs to be improved. Herein, atomically dispersed Fe sites embedded into the N-doped mesoporous carbon spheres (Fe–SAs/NC) were synthesized through a facile coordination-assisted polymerization assembly strategy without acid leaching treatment. Benefitting from abundant mesoporous structure, the Fe–SAs/NC displays large specific surface area (339 m2 g−1) and optimized impedance matching, which results in an effective reduction of the absorber density. The homogeneously dispersed Fe single atoms (Fe–SAs) on the carbon skeleton lead to the improvement in conduction and dipole polarization losses of Fe–SAs/NC, which endows Fe–SAs/NC with exceptional EMW absorption properties. Experimental results indicate that Fe–SAs/NC displays desirable EMW absorption properties with the minimal reflection loss of −52.5 dB at 2.8 mm and the effective absorption bandwidth of 4.8 GHz. The study provides valuable insights for the development of carbon materials modified with atomically dispersed metal sites to achieve high-efficient EMW absorbers.

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.

FeCo Alloy Nanoparticles Supported on N-doped Mesoporous Carbon Spheres for Hydrogen Evolution and Reduction of Organic Dyes

FeCo Alloy Nanoparticles Supported on N-doped Mesoporous Carbon Spheres for Hydrogen Evolution and Reduction of Organic Dyes

Aminotriazine derived N-doped mesoporous carbon with a tunable nitrogen content and their improved oxygen reduction reaction performance.

The electrocatalytic activity of carbon materials is highly dependent on the controlled modulation of their composition and porosity. Herein, mesoporous N-doped carbon with different amounts of nitrogen was synthesized through a unique strategy of using a high nitrogen containing CN precursor, 3-amino 1,2,4 triazine (3-ATZ) which is generally used for the preparation of carbon nitrides, integrated with the combination of a templating method and high temperature treatment. The nitrogen content and the graphitisation of the prepared materials were finely tuned with the simple adjustment of the carbonisation temperature (800-1100 °C). The optimised sample as an electrocatalyst for oxygen reduction reaction (ORR) exhibited an onset potential of 0.87 V vs. RHE with a current density of 5.1 mA cm-2 and a high kinetic current density (Jk) of 33.1 mA cm-2 at 0.55 V vs. RHE. The characterisation results of the prepared materials indicated that pyridinic and graphitic nitrogen in the carbon framework promoted ORR activity with improved four-electron selectivity and excellent methanol tolerance and stability. DFT calculations demonstrated that the structural and planar defects in the N-doped carbon regulated the surface electronic properties of the electrocatalyst, leading to a reduction in the energy barrier for the ORR activity. This strategy has the potential to unlock a platform for designing a series of catalysts for electrochemical applications.

Enhanced stability in Co0.8Ni0.2/NDMCS catalysts: Carbon nitride encapsulation for robust hydrogen generation

Catalytic hydrolysis of NaBH4 is a promising method for "on-demand" hydrogen generation, with cobalt catalysts playing a key role due to their high hydrogen generation rates. However, rapid cobalt dissolution and poor recycling hinder stable hydrogen production. This study presents a dual-mode stabilization technique using carbon nitride encapsulation to address these challenges. Co0.8Ni0.2 alloy nanoparticles (NPs) are confined within N-doped mesoporous carbon spheres (NDMCS) and encapsulated with a carbon nitride shell (∼ 5 nm thick). XPS results reveal strong non-classical metal-support interaction, increasing activation energy from 38.82 to 44.6 kJ mol−1, which controls cobalt's reactivity, leading to excellent recycling efficiency (90 % retention of initial rate, no change in particle size) in high-concentration reactants (2 %NaBH4 + 2 %NaOH). The retention rate drops to 26.8 % without this stabilization due to rapid metal dissolution. This stability of Co0.8Ni0.2 alloy in alkaline conditions has significant practical implications for hydrogen generation and other electrochemical applications.

Modification of polypropylene separator with multifunctional layers to achieve highly stable sodium metal anode

Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries (SMBs) in practical applications, however, its success is mainly subject to surface modification. Herein, a separator with multifunctional layers composed of N-doped mesoporous hollow carbon spheres (HCS) as the inner layer and sodium fluoride (NaF) as the outer layer on commercial polypropylene separator (PP) is proposed (PP@HCS-NaF) to achieve stable cycling in SMB. At the molecular level, the inner HCS layer with a high content of pyrrolic-N induces the uniform Na+ flux as a potential Na+ redistributor for homogenous deposition, whereas its hollow mesoporous structure offers nano-porous buffers and ion channels to regulate Na+ ion distribution and uniform deposition. The outer layer (NaF) constructs the NaF-enriched robust solid electrolyte interphase layer, significantly lowering the Na+ ions diffusion barrier. Benefiting from these merits, higher electrochemical performances are achieved with multifunctional double-layered PP@HCS-NaF separators compared with single-layered separators (i.e. PP@HCS or PP@NaF) in SMBs. The Na||Cu half-cell with PP@HCS-NaF offers stable cycling (280 cycles) with a high CE (99.6%), and Na||Na symmetric cells demonstrate extended lifespans for over 6000 h at 1 mA cm−2 with a progressively stable overpotential of 9 mV. Remarkably, in Na||NVP full-cells, the PP@HCS-NaF separator grants a stable capacity of ∼81 mA h g−1 after 3500 cycles at 1C and an impressive rate capability performance (∼70 mA h g−1 at 15C).

Development of Iron-Based Single Atom Materials for General and Efficient Synthesis of Amines.

Earth abundant metal-based heterogeneous catalysts with highly active and at the same time stable isolated metal sites constitute a key factor for the advancement of sustainable and cost-effective chemical synthesis. In particular, the development of more practical, and durable iron-based materials is of central interest for organic synthesis, especially for the preparation of chemical products related to life science applications. Here, we report the preparation of Fe-single atom catalysts (Fe-SACs) entrapped in N-doped mesoporous carbon support with unprecedented potential in the preparation of different kinds of amines, which represent privileged class of organic compounds and find increasing application in daily life. The optimal Fe-SACs allow for the reductive amination of a broad range of aldehydes and ketones with ammonia and amines to produce diverse primary, secondary, and tertiary amines including N-methylated products as well as drugs, agrochemicals, and other biomolecules (amino acid esters and amides) utilizing green hydrogen.

Atomically dispersed ternary FeCoNb active sites anchored on N-doped honeycomb-like mesoporous carbon for highly catalytic degradation of 4-nitrophenol

In the last decades, 4-nitrophenol is regarded as one of highly toxic organic pollutants in industrial wastewater, which attracts great concern to earth sustainability. Herein, atomically dispersed ternary FeCoNb active sites were incorporated into nitrogen-doped honeycomb-like mesoporous carbon (termed FeCoNb/NHC) by a two-step pyrolysis strategy, whose morphology, structure and size were characterized by a set of techniques. Further, the catalytic activity and reusability of the as-prepared FeCoNb/NHC were rigorously examined by using 4-NP catalytic hydrogenation as a proof-of-concept model. The influence of the secondary pyrolysis temperature on the catalytic performance was investigated, combined by illuminating the catalytic mechanism. The resultant catalyst exhibited significantly enhanced catalytic features with a normalized rate constant (kapp) of 1.2 × 104 min-1g−1 and superior stability, surpassing the home-made catalysts in the control groups and earlier research. This study provides some constructive insights for preparation of high-efficiency and cost-effectiveness single-atom nanocatalysts in organic pollutants environmental remediation.

The synthesis of Ni-Co@NOMC and the regulation of its active sites for the selective conversion of furfural to cyclopentanone

Catalysts play a critical role in the selective conversion of furfural (FAL) in the aqueous-phase hydrogenation-rearrangement tandem reaction (AP-HRT). Herein, the N-doped bimetallic Ni-Co@NOMC was synthesized by solvent volatilization self-assembly method. The morphology and structure of the APF precursors were effectively controlled through adjustments in the synthesis and the presence of numerous pore channels and the substantial specific surface areas contributed to enhancing catalytic efficiency. Furthermore, this study also examined the synergistic interaction between the acid-base sites of the novel mesoporous N-doped carbon (NOMC) carrier and metal active sites to advance the succession of the furan ring hydrogenation and rearrangement processes. Specifically, the 99.9 % conversion of 8 wt% FAL solution was successfully accomplished with the 90.5 % selectivity of cyclopentanone catalyzed by 1.2-Ni-Co@NOMC catalysts. Therefore, this research holds significant importance for advancing the sustainable utilization of biomass resources in the future.

Photocatalytic degradation of antibiotics by N-doped carbon nanoflakes-nickel ferrite composite derived from algal biomass

This work reports the synthesis of nickel ferrite (NiFe) nanoparticles, N-doped mesoporous carbon nanoflakes (NCF) and novel nickel ferrite-carbon nanoflakes (NiFe@NCF) nanocomposite using solvothermal method. NCF was derived from a cyanobacterial consortium consisting of Anabaena, Lyngbya and Weistiellopsis, rich in carbon and nitrogen. The synthesized nanoparticles were used as heterogeneous photocatalyst for degradation of two harmful water pollutants, ciprofloxacin (CIP) and levofloxacin (LEV). 99.91% LEV and 98.86% CIP were degraded within 50 and 70 min of visible light irradiation using NiFe@NCF following pseudo first order kinetics. This improved efficiency of the nanocomposite may be attributed to its higher surface area, reduction of band gap (from 2.42 to 2.19 eV), more active sites as well as charge carrier mobility with decreasing agglomeration tendency of the magnetic nickel nanoparticles upon being embedded on NCF. N-doping improves light harvesting property, retards charge recombination and extends as well as delocalises ᴨ-conjugated system resulting in enhanced photocatalytic activity. The scavenging experiments and EPR analysis reveal that O2−• and •OH are the main active species taking part in the degradation process. The material performs well within a wide range of pH and can be effectively used up to 5 repetitive cycles. A feasible photocatalytic degradation mechanism of the antibiotics against NiFe@NCF nanocomposite is also put forwarded along with their possible degradation pathways from LCMS studies.

One single-atom Mn doping strategy enabling two functions of oxygen reduction reaction and pseudocapacitive performance

Single-atom metal species as highly effective active sites are crucial for enhancing energy storage and conversion properties. However, achieving the simultaneous construction of single-atom sites and the regulation of matrix structures to enable their application in both energy storage and conversion remains a challenge. Here, we have successfully developed unique MnN2C2 active sites, atomically dispersed on N-doped mesoporous graphitic carbon sheets (MnSAs/NMC). This is accomplished through the strategic utilization of MnCl2 salt, which serves dual roles of a pore-forming agent and a template. The MnSAs/NMC catalyst demonstrates compelling electrocatalytic activity for the oxygen reduction reaction (ORR), with an impressive half-wave potential (E1/2 = 0.90 V), alongside superior capacitance reaching 444 F g-1 at 0.5 A g-1 for supercapacitors. Crucially, both experimental and theoretical simulations validate that the single-atom dispersed MnN2C2 optimizes the adsorption energy of reactants and intermediates in the ORR process and pseudocapacitive behavior, leading to excellent ORR activity and capacitive performance. Interestingly, MnSAs/NMC-based Zn-air batteries exhibit concurrently high-power density derived from capacitive property and high energy density enhanced by ORR process. This study presents a novel preparation method for single-atom catalysts, which paves the way for the commercial application of super energy storage and conversion devices.

Electrospun MOF-derived N-doped mesoporous carbon fibers embedded with ultrafine vanadium oxide as an ultralong cycling stability for potassium ion storage

Potassium-ion batteries (KIBs) are promising options for large-scale energy storage because of their low cost and low redox potential. The use of anodes with porous structures is an attractive strategy to improve the electrochemical properties of KIBs. However, the development of KIB anodes has been hindered by their low capacity and difficulty in synthesizing porous structures. Herein, ultrafine vanadium oxide nanoparticles embedded in porous N-doped carbon nanofibers (VO@PNCNFs) using electrospinning and one-step heat treatment are reported. The uniform growth of vanadium oxide crystals is facilitated by the porous structure of the carbon nanofiber. The numerous pores play a crucial role in the transfer of electrons and ions and provide structural stability to the N-doped carbon matrix. As a result, the VO@PNCNF electrode demonstrates a high reversible capacity (∼205 mA h g−1 at 1.0 A g−1), good cycle stability over 3000 cycles, and excellent rate performance (95 mA h g−1 at 3.0 A g−1).

A novel mesoporous carbon pocket with single atom Cr sites for high performance Lithium-Sulfur battery

Lithium-sulfur batteries (LSBs) are considered one of the most promising next-generation energy storage devices. However, their practical application is limited by the sluggish conversion kinetics and shuttle behavior of lithium polysulfides (LiPSs). In this work, we employ a facile salt template and micelle-mediated co-assembly strategy to synthesize atomic Cr dispersed mesoporous N-doped carbon pocket (denoted as Cr-mNC pocket). The designed Cr-mNC pocket exhibits uniform and ordered mesoporous caged morphology with a high surface area (843.5 m2/g), large pore volume (0.184 cm3 g−1), and uniform mesopore size (3.7 nm). The mesoporous structure offers a facilitated pump to promote electron/ion transportation while exposing more catalytic sites. These advantages enable the Cr-mNC pocket modified membrane to facilitate Li+ diffusion, enhance LiPSs adsorption, and accelerate electrochemical reaction kinetics for polysulfide conversion. Consequently, LSBs with Cr-mNC modified separator show a high sulfur utilization (1405 mAh g−1 at 0.2 C), a remarkable rate performance (776 mAh g−1 at 5 C), a low capacity decay rate of 0.047 % per cycle at 2 C over 1000 cycles, and even remain at 4.47 mAh cm−2 after 100 cycles with a high sulfur load of 5.0 mg cm−2.

Algae derived N-doped mesoporous carbon nanoflakes fabricated with nickel ferrite for photocatalytic removal of Congo Red and Rhodamine B dyes

A hydrothermal approach was employed to synthesize nickel ferrite (NiFe2O4) nanoparticles and its composite (NiFe2O4–NCF) with N-doped mesoporous carbon nanoflakes (NCF) where NCF acts as the catalytic support. The N-doped carbon nanoflakes were derived by pyrolyzing algae under Nitrogen atmosphere. These prepared materials were later probed with XRD, FESEM, TEM, BET, VSM, PL and UV–Vis spectrophotometry for their structural, morphological, magnetic and optical properties. The materials were used as photocatalysts to degrade two harmful textile dyes viz. Congo Red (CR) and Rhodamine B (RhB) under visible light at room temperature. Under optimized conditions, the pristine NiFe2O4 nanoparticle could degrade 95.34% and 98.24% CR and RhB respectively within 70 min while, the NiFe2O4–NCF nanocomposite showed degradation efficiency of 96.51% and 98.83% within 40 and 35 min of light irradiation respectively for CR and RhB dyes. The radical scavenging experiments indicated that electron and hole are the main reacting species that initiate the degradation of the dyes against the catalyst.

Coal tar pitch derived N-doped mesoporous carbon through "carbonization in air" strategy for high performance supercapacitor electrode

In the present work, the N-doped mesoporous carbon was prepared through an easy solid phase milling and "carbonization-in-air" strategy from coal tar pitch (CTP). A novel NaCl-KCl-NaF composite salt was used as the additive and acted as a flame-retardant coating and pore template during the heating process. This strategy achieved high carbon production rates from CTP without using inert atmosphere. The prepared products were characterized by mesopores, high specific surface area (1362.26 m2 g−1), and nitrogen doping. The synthesized CKNF700–2-3 achieved a carbon yield up to 43.02 wt%, with the specific capacitance reaching 343.9 F g−1 at 1 A g−1. The CKNF700–2-3//CKNF700–2-3 symmetric supercapacitor showed the ultra-high energy density (33.4 Wh kg−1) at the 600.1 W kg−1 power density.

D-band center engineering of single Cu atom and atomic Ni clusters for enhancing electrochemical CO2 reduction to CO

The rational design of catalysts with atomic dispersion and a deep understanding of the catalytic mechanism is crucial for achieving high performance in CO2 reduction reaction (CO2RR). Herein, we present an atomically dispersed electrocatalyst with single Cu atom and atomic Ni clusters supported on N-doped mesoporous hollow carbon sphere (CuSANiAC/NMHCS) for highly efficient CO2RR. CuSANiAC/NMHCS demonstrates a remarkable CO Faradaic efficiency (FECO) exceeding 90% across a potential range of −0.6 to −1.2 V vs. reversible hydrogen electrode (RHE) and achieves its peak FECO of 98% at −0.9 V vs. RHE. Theoretical studies reveal that the electron redistribution and modulated electronic structure—notably the positive shift in d-band center of Ni 3d orbital—resulting from the combination of single Cu atom and atomic Ni clusters markedly enhance the CO2 adsorption, facilitate the formation of *COOH intermediate, and thus promote the CO production activity. This study offers fresh perspectives on fabricating atomically dispersed catalysts with superior CO2RR performance.

Amino-Induced CO2 Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production.

A considerable challenge in CO2 reduction reaction (CO2RR) to produce high-value-added chemicals comes from the adsorption and activation of CO2 to form intermediates. Herein, an amino-induced spillover strategy aimed at significantly enhancing the CO2 adsorption and activation capabilities of CdS supported on N-doped mesoporous hollow carbon sphere (NH2-CdS/NMHCS) for highly efficient CO2RR is presented. The prepared NH2-CdS/NMHCS exhibits a high CO Faradaic efficiency (FECO) exceeding 90% from -0.8 to -1.1V versus reversible hydrogen electrode (RHE) with the highest FECO of 95% at -0.9V versus RHE in H cell. Additional experimental and theoretical investigations demonstrate that the alkaline -NH2 group functions as a potent trapping site, effectively adsorbing the acidic CO2, and subsequently triggering CO2 spillover to CdS. The amino modification-induced CO2 spillover, combined with electron redistribution between CdS and NMHCS, not only readily achieves the spontaneous activation of CO2 to *COOH but also greatly reduces the energy required for the conversion of *COOH to *CO intermediate, thus endowing NH2-CdS/NMHCS with significantly improved reaction kinetics and reduced overpotential for CO2-to-CO conversion. It is believed that this research can provide valuable insights into the development of electrocatalysts with superior CO2 adsorption and activation capabilities for CO2RR application.

Exploring nitrogen doped mesoporous carbon spheres for superior microwave absorption

Mesoporous carbon materials hold significant promise for usage in microwave absorption due to their wide and unique advantages stemming from their mesoporous structure. This study synthesizes N-doped mesoporous carbon spheres (NMCs) by carbonizing mesoporous silica nanospheres (MSN). By controlling the annealing temperature, the resulting NMCs exhibit a significant increase in pore size. The exceptional microwave absorption capability of multifunctional carbon with a mesoporous structure result from its appropriate composition. The minimum reflection loss (RL) can reach −58.04 dB with a thickness of 3.3 mm, and the corresponding effective absorption bandwidth (EAB) reaches up to 8.19 GHz, outperforming the many previously documented microwave absorbing materials. The material's practical application potential was evaluated using computer simulation technology (CST), resulting in a simulated RCS value of 32.88 dBm2.The microwave absorption process of this material has been extensively studied and thoroughly described. Our study offers valuable guidance for developing and producing efficient microwave absorbers doped with nitrogen and possessing a unique mesoporous structure.