Nitrogen Co-doping Research Articles

The effect of carbon supports on the electrocatalytic performance of Ni-N-C catalysts for CO2 reduction to CO

Carbon-supported nickel and nitrogen co-doped (Ni-N-C) catalysts have been extensively studied as selective and active catalysts for CO2 electroreduction to CO. Most studies have focused on adjusting the coordination structure of Ni-Nx active sites, while the impact of the carbon supports has often been overlooked. In this study, a series of Ni-N-C catalysts on different carbon supports, including carbon black (CB), multi-walled carbon nanotubes (CNT), and activated nitrogen-doped biochar (ANBC), were synthesized using a ligand-mediated method. The effect of the carbon support on the electrocatalytic performance for CO2 reduction was investigated at both low current densities, in a H-cell, and high current densities, in a MEA electrolyzer. All of the prepared Ni-N-C catalysts show good faradaic efficiencies (FE) toward CO production (up to ~90%), however, the onset potentials and partial current densities for CO production vary greatly. The textural properties of the carbon support and the distribution of Ni-Nx active sites on the carbon support are demonstrated as the main factors behind the performance differences. In particular, hierarchical porous structures with large specific surface area are helpful to facilitate mass transport and improve the dispersion of active sites, which allows for a better CO2 reduction performance of Ni-N-ANBC compared to Ni-N-CB and Ni-N-CNT. This study demonstrates the importance of the carbon support for Ni-N-C catalysts and provides new insights into the design of efficient Ni-N-C catalysts for the CO2RR.

Magnetic coal gangue-based catalysts for peroxymonosulfate activation and benzo[a]pyrene degradation: The construction of Fe and N dual active sites

The magnetic coal gangue (CG)-based catalysts were successfully prepared by impregnation-calcination method with iron (Fe) and nitrogen (N) co-doping for peroxymonosulfate (PMS) activation, illustrating excellent catalytic property with 100.00 % removal rate of benzo[a]pyrene (BaP). Additionally, Fe/N co-doped CG catalysts (Fe-N-CG) possess desirable performance against co-existing anions and organic matter (HA), with a nearly 80.00 % removal rate in actual water systems. The mechanism of activating PMS and removing BaP was comprehensively analyzed through a series of characterizations and experiments, proving that the Fe and N double reaction sites could enhance the contribution of radical paths and non-radical paths for BaP degradation. Finally, the safety and prospects for practical environmental remediation via Fe-N-CG for PMS activation were further evaluated by ECOSAR toxicity analysis software and mung bean growth experiments. In summary, the development of Fe-N-CG widened the high-value utilization of CG and supplied a deep insight into the restoration of organically polluted environments.

Electrolytic conversion of CO2 to proportionally tunable syngas using nickel-nitrogen doped carbon materials derived from Chlorella sp.

Chlorella sp., a common type of algae found in global surface waters, is prone to causing "blooms" and can accumulate significant amounts of nutrients such as nitrogen, phosphorus, and carbon. While carbon materials derived from Chlorella sp. are widely used in the field of adsorption, there are relatively few reports focused on electrocatalysis. This study utilized Chlorella sp. as a raw material to synthesize functional carbon materials, and prepared nitrogen-doped (CN), nickel-doped (CNi), and nitrogen-nickel co-doped (CNNi) carbon-based catalysts with both metal and non-metal elements. The results showed that the CN, CNi and CNNi catalysts possessed certain electrocatalytic properties, among which the CNNi material had the best electrocatalytic activity towards CO2 reduction (CO2RR). In 1.0 M KHCO3, the CNNi catalyst exhibited an instantaneous current density of 15.4 mA/cm2 under the potential of -0.82V (vs. RHE). In terms of product selectivity, the Faraday efficiency of CO on the CNNi electrode was up to 90% when the electrode potential was -0.62 V (vs. RHE), while the selectivity of the CN and CNi catalysts for CO was only 59% under the optimal conditions. The co-doping of nitrogen and nickel significantly enhanced the electrocatalytic activity and the selectivity towards CO of Chlorella-based carbon materials.

Sulfur and Nitrogen Codoped Hard Carbon with Expanded Interlayer Distance as an Effective Anode Material for Sodium-Ion Batteries

Sulfur and Nitrogen Codoped Hard Carbon with Expanded Interlayer Distance as an Effective Anode Material for Sodium-Ion Batteries

S/N Co-Doped Ultrathin TiO2 Nanoplates as an Anode Material for Advanced Sodium-Ion Hybrid Capacitors.

Anatase titanium dioxide (TiO2) has emerged as a potential anode material for sodium-ion hybrid capacitors (SICs) in terms of its nontoxicity, high structure stability and cost-effectiveness. However, its inherent poor electrical conductivity and limited reversible capacity greatly hinder its practical application. Here, ultrathin TiO2 nanoplates were synthesized utilizing a hydrothermal technique. The electrochemical kinetics and reversible capacity were significantly improved through sulfur and nitrogen co-doping combined with carbon coating (SN-TiO2/C). Sulfur and nitrogen co-doping generated oxygen vacancies and introduced additional active sites within TiO2, facilitating accelerated Na-ion diffusion and enhancing its reversible capacity. Furthermore, carbon coating provided stable support for electron transfer in SN-TiO2/C during repeated cycling. This synergistic strategy of sulfur and nitrogen co-doping with carbon coating for TiO2 led to a remarkable capacity of 335.3 mAh g-1 at 0.1 A g-1, exceptional rate property of 148.3 mAh g-1 at 15 A g-1 and a robust cycling capacity. Thus, the SN-TiO2/C//AC SIC delivered an impressive energy density of 177.9 W h kg-1. This work proposes an idea for the enhancement of reaction kinetics for energy storage materials through a synergistic strategy.

Long cycle life Zn-I2 batteries: Utilizing Co/N Co-doped carbon matrix derived from zeolitic imidazolate framework-67 as a bifunctional iodine host

Zinc-iodine batteries (ZIBs) emerge as a clean energy transfer device with very excellent application prospects due to its abundant natural reserves, environmental friendliness, low cost, and good safety. However, the severe shuttle effect of soluble polyiodide in aqueous medium and the sluggish reaction kinetics of iodine substances restrict the application potential of ZIBs. Herein, we report a promising iodine host material for ZIBs by deriving from zeolite imidazole framework-67 (ZIF-67) with co-doping of cobalt and nitrogen. The synergistic effect of porous carbon and cobalt and nitrogen co-doping is revealed by employing in-situ Raman spectroscopy and UV–vis absorption spectroscopy. It is found that the outstanding electrochemical behavior could be attributed to the efficient adsorption for polyiodide and catalyzing the conversion reaction between iodine substances, inhibiting the shuttle effect of polyiodide, and ensuring cycling stability. Consequently, the resultant ZIBs possess a high specific capacity of 152.4 mAh g−1 at rate of 5 C (1 C = 211 mA g−1), and long cycle stability of 24,000 cycles with more than 80 % capacity retention. This work provides a feasible and efficient strategy to realize high-performance ZIBs.

Nitrogen and Oxygen Codoped Hierarchically Porous Carbon Derived from Tannic Acid and Reed Straw for High-Performance Supercapacitors

Nitrogen and Oxygen Codoped Hierarchically Porous Carbon Derived from Tannic Acid and Reed Straw for High-Performance Supercapacitors

Synthesis of carbon dots with tailored heteroatomic structure for achieving ultrahigh effectiveness in persulfate activation

Carbon dots (CDs) are normally feature with zero-dimensional structure, excellent solubility, good biosafety, and exceptional photoelectronic properties, thus, awakening the homogeneous-like photocatalytic potency of CDs in peroxymonosulfate (PMS) activation can afford new idea for water body remediation. Herein, we presented a facile nitrogen and sulfur co-doping strategy for the development of high-performance CDs-based photocatalysts. Through the deep investigation on the structure-activity relationship, we proposed that the incorporated pyridinic N within CDs structure could serve as efficient Lewis basic sites for PMS confinement. Importantly, the co-existence of oxidized sulfur groups and specific nitrogen speciation (pyridine N and pyrrolic N) induced unique “push-pull” effect on the photogenerated carriers within the surface state of S,N co-doped CDs. The unique synergy sites and surface hydrophilic nature conferred the CDs exceptional photocatalytic effectiveness, presenting a remarkable PMS consumption ratio of 7.62 per gram of the CDs photocatalyst within just 20 min. Profited from the improved kinetics of interfacial reactions, the CDs-photocatalyzed oxidation system that consisted largely of sulfate radicals can completely degrade rhodamine B within 12.5 min, and hold great potential in long-term operation without needing to regenerate CDs catalyst.

Fluorine and Nitrogen Codoped Carbon Nanosheets In Situ Loaded CoFe2O4 Particles as High-Performance Anode Materials for Sodium Ion Hybrid Capacitors

Fluorine and Nitrogen Codoped Carbon Nanosheets In Situ Loaded CoFe₂O₄ Particles as High-Performance Anode Materials for Sodium Ion Hybrid Capacitors

Insights into the roles of nitrogen and phosphorus co-doping for efficient methanol electrooxidation

Anchoring Pt onto multi-heteroatom doped carbon materials has been recognized as an effective approach to improve the performance of electrocatalytic methanol oxidation. However, distinct contributions and specific behavior mechanisms of different heteroatoms, notably N and P, the specific behavior mechanisms in synergistically promoting Pt NPs remain elusive. In this work, we construct 1D N and P co-doped carbon nanotube (N, P-CNTs) supports with abundant defect anchors for Pt. The as-prepared Pt/N, P-CNTs exhibit outstanding activity and exceptional stability in methanol oxidation reaction (MOR), achieving high mass activity up to 6481.3 mA mg−1Pt. Moreover, they can retain 90.5 % of their initial current density even after 800 cycles tests. Detailed characterizations and theoretical calculations indicate that the robust strong metal-support interactions (SMSI) effect caused by N doping within the unique N and P co-doped coordination structure controllably regulate the coordination environment of Pt, reduce the d-band center of Pt, thus promoting the adsorption and decomposition of CH3OH. However, P doping weakens the adsorption strength of CO on the Pt active site by sacrificing partial electron transfer, accelerating the oxidative conversion of the CO-like poisoning species (COads). Significantly, the synergistic mechanism of N and P species on the modification of Pt’s electronic structure and its subsequent impact on the electrocatalytic methanol oxidation behaviors on the Pt surface was thoroughly elucidated, providing a constructive route for designing robust MOR electrocatalysts with high MOR activity and durability.

Activation of inert surface of monolayer MoS2 by transition metal and nitrogen co-doping to promote hydrogen evolution reaction

In this work, we systematically investigate the possible H adsorption sites, charge density difference, partial density of states, p-band center and Bader charge of transition metal (TM) and nitrogen (N) co-doped monolayer MoS2. The results show that the equilibrium of H adsorption and desorption can be achieved in TM-N co-doped monolayer MoS2. The ΔGH at the S site of Co-N co-doped system is −0.05 eV, which is better than that of traditional Pt site (ΔGH=-0.09 eV) and Mo site at the MoS2 edge (ΔGH=0.08 eV). This work has important implications for designing more efficient electrocatalysts.

Highly Sensitive and Selective Fluorescence and Smartphone-Based Sensor for Detection of Rutin Using Boron Nitrogen Co-doped Graphene Quantum Dots.

This research explores the fluorescence properties and photostability of boron nitrogen co-doped graphene quantum dots (BN-GQDs), evaluating their effectiveness as sensors for rutin (RU). BN-GQDs are biocompatible and exhibit notable absorbance and fluorescence characteristics, making them suitable for sensing applications. The study utilized various analytical techniques to investigate the chemical composition, structure, morphology, optical attributes, elemental composition, and particle size of BN-GQDs. Techniques included X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The average particle size of the BN-GQDs was determined to be approximately 3.5 ± 0.3nm. A clear correlation between the emission intensity ratio and RU concentration was identified across the range of 0.42 to 4.1μM, featuring an impressively low detection limit (LOD) of 1.23nM. The application of BN-GQDs as fluorescent probes has facilitated the development of a highly sensitive and selective RU detection method based on Förster resonance energy transfer (FRET) principles. This technique leverages emission at 465nm. Density Functional Theory (DFT) analyses confirm that FRET is the primary mechanism behind fluorescence quenching, as indicated by the energy levels of the lowest unoccupied molecular orbitals (LUMOs) of BN-GQDs and RU. The method's effectiveness has been validated by measuring RU concentrations in human serum samples, showing a recovery range between 97.8% and 103.31%. Additionally, a smartphone-based detection method utilizing BN-GQDs has been successfully implemented, achieving a detection limit (LOD) of 49nM.

Effects of nitrogen and oxygen co-doping on α to β phase transition in tungsten

Effects of nitrogen and oxygen co-doping on α to β phase transition in tungsten

Self-Powered Electrochemical CO2 Conversion Enabled by a Multifunctional Carbon-Based Electrocatalyst and a Rechargeable Zn-Air Battery.

Multifunctional electrocatalysts are required for diverse clean energy-related technologies (e.g., electrochemical CO2 reduction reaction (CO2RR) and metal-air batteries). Herein, a nitrogen and fluorine co-doped carbon nanotube (NFCNT) is reported to simultaneously achieve multifunctional catalytic activities for CO2RR, oxygen reduction reaction (ORR), and oxygen evolution reaction (OER). Theoretical calculations reveal that the superior multifunctional catalytic activities of NFCNT are attributed to the synergistic effect of nitrogen and fluorine co-doping to induce charge redistribution and decrease the energy barrier of rate-determining step for different electrocatalytic reactions. Furthermore, the rechargeable Zn-air battery (ZAB) with NFCNT electrode delivers a high peak power density of 230mWcm-2 and superior durability over 100 cycles, outperforming the ZAB with Pt/C+RuO2 based electrodes. More importantly, a self-driven CO2 electrolysis unit powered by the as-assembled ZABs is developed, which achieves 80% CO Faraday efficiency and 60% total energy efficiency. This work provides a new insight into the exploration of highly efficient multifunctional carbon-based electrocatalysts for novel energy-related applications.

A networked iron and nitrogen-doped ZIF-8/MWCNTs heterostructure for oxygen reduction reaction.

Zeolitic Imidazolate Frameworks-8 (ZIF-8) is commonly used as an ideal precursor for non-noble metal catalysts because of its high specific surface area, ultra-high porosity, and N-rich content. Upon pyrolyzing ZIF-8 at 900 °C in Ar, the resulting material, referred to as Z8, displayed good activity toward the oxygen reduction reaction (ORR). Then the ZIF-8 was mixed with various conductive carbon materials, such as multiwall carbon nanotubes (MWCNTs), Acetylene black (ACET), Vulcan XC-72R (XC-72R), and Ketjenblack EC-600JD (EC-600JD), to form Z8 composites. The Z8/MWCNTs composite exhibited enhanced ORR activity owing to its network structure, meso-/microporous hierarchical porous structure, improved electrical conductivity, and graphitization. Subsequently, iron and nitrogen co-doping is achieved through the pyrolysis of a mixture comprising Fe, N precursor, and ZIF-8/MWCNTs, which is denoted as FeN-Z8/MWCNTs. The intrinsically high electrical conductivity of MWCNTs facilitated efficient electron transfer during the ORR, while the meso-/microporous hierarchical porous structure and network structure of Fe, N co-doped ZIF-8/MWCNTs promoted oxygen transport. The presence of Fe-containing species in the catalyst acted as activity centers for ORR. This strategy of preparing Z8 composites and modifying them with Fe, N co-doping offers an insightful approach to designing cost-effective electrocatalysts.

Enhanced activity of Ru-based catalysts for ammonia decomposition through nitrogen doping of hierarchical porous carbon carriers

Activated carbon (AC) materials, renowned for their high specific surface area, excellent conductivity, and customizable functional groups, are widely employed as catalyst carriers. However, enhancing the activity of Ru-based catalysts supported on AC (Ru/AC) for ammonia decomposition remains a challenge. In this study, commercial AC was utilized as a substrate, with glucose and urea employed as modifiers. Specifically, the surface of the AC was modified via a hydrothermal pyrolysis method, resulting in the successful post-treatment in situ co-doping of nitrogen (AC-GN). Experimental results revealed that Ru/AC-GN exhibited a hydrogen production rate 46% higher than that of Ru/AC at 475 °C, indicating improved activity and stability. The characterization of AC-GN demonstrated that nitrogen doping primarily occurred on the external surface and macropores of the AC, increasing the nitrogen content in the carrier, particularly pyrrolic nitrogen content, while preserving the original structural and morphological integrity of the AC. The enhanced dispersion of Ru, combined with the improved electronic transmission capabilities and strengthened interactions between the metal and the modified carrier, were identified as pivotal factors contributing to the enhanced low-temperature efficacy of Ru/AC-GN. This paper presents a novel direction for the large-scale preparation of efficient catalysts for ammonia decomposition.

Boron and Nitrogen Co-Doped Porous Graphene Nanostructures for the Electrochemical Detection of Poisonous Heavy Metal Ions

Heavy metal poisoning has a life-threatening impact on the human body to aquatic ecosystems. This necessitates designing a convenient green methodology for the fabrication of an electrochemical sensor that can detect heavy metal ions efficiently. In this study, boron (B) and nitrogen (N) co-doped laser-induced porous graphene (LIGBN) nanostructured electrodes were fabricated using a direct laser writing technique. The fabricated electrodes were utilised for the individual and simultaneous electrochemical detection of lead (Pb2+) and cadmium (Cd2+) ions using a square wave voltammetry technique (SWV). The synergistic effect of B and N co-doping results in an improved sensing performance of the electrode with better sensitivity of 0.725 µA/µM for Pb2+ and 0.661 µA/µM for Cd2+ ions, respectively. Moreover, the sensing electrode shows a low limit of detection of 0.21 µM and 0.25 µM for Pb2+ and Cd2+ ions, with wide linear ranges from 8.0 to 80 µM for Pb2+ and Cd2+ ions and high linearity of R2 = 0.99 in case of simultaneous detection. This rapid and facile method of fabricating heteroatom-doped porous graphene opens a new avenue in electrochemical sensing studies to detect various hazardous metal ions.

Polylactic acid electrospun membrane loaded with cerium nitrogen co-doped titanium dioxide for visible light-triggered antibacterial photocatalytic therapy.

Wound infection caused by multidrug-resistant bacteria poses a serious threat to antibiotic therapy. Therefore, it is of vital importance to find new methods and modes for antibacterial therapy. The cerium nitrogen co-doped titanium dioxide nanoparticles (N-TiO2, 0.05Ce-N-TiO2, 0.1Ce-N-TiO2, and 0.2Ce-N-TiO2) were synthesized using the hydrothermal method in this study. Subsequently, electrospinning was employed to fabricate polylactic acid (PLA) electrospun membranes loaded with the above-mentioned nanoparticles (PLA-N, PLA-0.05, PLA-0.1, and PLA-0.2). The results indicated that cerium and nitrogen co-doping tetrabutyl titanate enhanced the visible light photocatalytic efficiency of TiO2 nanoparticles and enabled the conversion of ultraviolet light into harmless visible light. The photocatalytic reaction under visible light irradiation induced the generation of ROS, which could effectively inhibit the bacterial growth. The antibacterial assay showed that it was effective in eliminating S. aureus and E. coli and the survival rates of two types of bacteria under 30 min of irradiation were significantly below 20% in the PLA-0.2 experimental group. Moreover, the bactericidal membranes also have excellent biocompatibility performance. This bio-friendly and biodegradable membrane may be applied to skin trauma and infection in future to curb drug-resistant bacteria and provide more alternative options for antimicrobial therapy.

One Precursor, Two Different Outcomes: SnO-Graphite Composite and Anion-Doped SnO2 with Ester Surface Functionality.

The technological importance of SnO2 and SnO has invited scientists to explore various aspects, including their synthesis in the nanosize regime, surface functionalization, and composite formation. In the present work, a binuclear Sn2-EDTA complex has been demonstrated to produce a SnO-graphite composite and C, N-codoped SnO2 nanocrystals with ester functionality in quantitative yields by thermal and solvothermal dissociation processes. The products were characterized extensively. While SnO in the SnO-graphite composite exhibited tetragonal symmetry, graphitic carbon had defects. The composite had 12 wt % of graphitic carbon. The role of the SnO-graphite composite as an anode in lithium-ion batteries (LIB) has been evaluated. Solvothermal dissociation of the Sn2-EDTA complex in a propylene glycol medium yielded nanocrystalline SnO2 with yellow color. Agglomerated crystallites had ester functionality on their surfaces. The surface functionality was thermally stable up to 200 °C, and its complete removal yielded tetragonal white-colored SnO2. Co-doping of carbon and nitrogen in yellow SnO2 reduced its optical band gap (2.9 eV). Despite the negative surface charge of the functionalized SnO2, its affinity to rapidly adsorb anionic azo dyes (Congo red and Eriochrome black T) from aqueous solutions has been validated. Following pseudo-second-order kinetics, adsorption data analysis revealed chemisorption as the primary driving force in this process.

Sulfur and nitrogen co-doping of peanut shell-derived biochar for sustainable supercapacitor applications

To enhance the biochar produced from biomass and utilize it in the development of electrodes for applications in supercapacitors, doping the biochar with multiple or double heteroatom elements could be more beneficial than single-element doping. The search for the right heteroatom doping sources and synthesis techniques is difficult but necessary. This study exhibited the synthesis of peanut shell-derived biochar doped with sulfur (S) and nitrogen (N) through carbonization, activation, and ex-situ doping with affordable melamine and thiourea as S and S/N sources. Characterizations such as XPS, XRD, TEM, Raman, EDS mapping revealed that the S and N co-doped biochar has multilayered nanosheet-like morphology, uniform heteroatom doping, and hierarchical pore structure. Electrochemical characterization showed that the S and N co-doped electrode material has a specific capacitance of 224 F/g, higher than those of 200 F/g and 178.94 F/g of N-doped and pristine biochar at 1 A/g, respectively. The supercapacitor fabricated by the developed electrodes at 1 A/g has a specific capacitance of 80.25 F/g with a density of energy of 11.15 Wh/Kg. It is considered that S and N co-doping can enhance the active regions and pore arrangement of peanut shell-derived biochar to improve the passage of ions of the electrolyte and transfer of charge to the electrode surface in supercapacitor applications.