Nitrogen Co-doped Carbon Nanotubes Research Articles

Nitrogen, phosphorus, and sulfur co-doped carbon nanotubes/melamine foam composite electrode for high-performance vanadium redox flow battery

The high cost and complex modification process of carbon felt electrodes limits its further popularization in vanadium redox flow batteries (VFBs). By introducing low-cost melamine foam, nitrogen, phosphorus, and sulfur co-doped carbon nanotubes/ melamine foam composite electrode (NPS-CNTs-CMF) is designed and fabricated via immersing melamine foam in a solution containing N, P, and S co-doped CNTs. The integration of modified CNTs significantly enhances the conductivity and hydrophilicity of the electrode. Moreover, the composite electrode also demonstrates outstanding electrocatalytic activity owing to the heteroatom doping that further inspired the electrocatalytic activity of CNTs. Density function theory calculations further uncover that introducing heteroatoms on CNTs not only promotes the adsorption of vanadium ions but also facilitates the electron transfer between vanadium ions and MF substrate. As a result, the battery loading with NPS-CNTs-CMF exhibits excellent battery performance, achieving energy efficiency of 80.12 % at 300 mA cm–2. Additionally, the long-term cycling stability is attained over 200 consecutive charge-discharge cycles at 300 mA cm−2. This study provides a novel melamine foam material with low cost and simple modification, and this new composite structure stimulates the development of high-performance electrodes in VFBs.

Lead and Nitrogen Co-Doped Multi-Walled Carbon Nanotube Electrocatalyst for Oxygen Reduction Reaction

The electrocatalysis of oxygen reduction reaction (ORR) on lead and nitrogen co-doped multi-walled carbon nanotube (Pb/N/MWCNT) composite catalyst has been investigated in the neutral, acidic and alkaline media. The mixture of lead phthalocyanine (PbPc) and MWCNTs was pyrolysed in nitrogen atmosphere to achieve co-doping of lead and nitrogen. The successful co-doping as well as formation of Pb nanoparticles were confirmed with the use of various physical and surface characterisation methods such as scanning and transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction analysis. This work brings forth the electrocatalytic effect of Pb and nitrogen co-doping of carbon by a detailed electrochemical analysis using rotating disk electrode (RDE) method. The Pb and nitrogen co-doped MWCNT material demonstrate a reasonable electrocatalytic ORR activity in acidic, neutral and alkaline media. The results indicate great potential of Pb to be employed in electrocatalyst design as co-doping agent to achieve superior cathode catalysts for microbial, proton and anion exchange membrane fuel cells.

Nitrogen and phosphorous co-doped carbon nanotubes for high-performance supercapacitors

Nitrogen and phosphorous co-doped carbon nanotubes for high-performance supercapacitors

Amorphous FeOOH Anchored on Boron and Nitrogen Codoped Carbon Nanotubes for Fenton-like Oxidation of Sulfamethoxazole

Amorphous iron oxide/hydroxides with structural disorder can be a potential alternative to typical crystalline structures when applied in environmental nanotechnology. In this work, novel amorphous FeOOH quantum dots (QDs) anchored on boron and nitrogen codoped graphene nanotubes (FeOOH@BNG) with different Fe loadings were synthesized and applied in the degradation of common antibiotic pollutant sulfamethoxazole (SMX). The as-fabricated catalysts were characterized by a series of physicochemical and thermal techniques, revealing the highly dispersive FeOOH QDs on the BNG surface. The as-prepared catalyst shows excellent catalytic ability toward SMX degradation via a Fenton-like approach. The excellent activity of the as-prepared FeOOH@BNG catalysts was ascribed to the enhanced textural properties and better exposure of active sites, thanks to the highly dispersive Fe sites on the BNG supports. The optimal catalyst, FeOOH-5@BNG, was further employed for the optimization of key reaction parameters such as catalyst loading, H2O2 dosage, pH, and reaction temperature. Moreover, electron paramagnetic resonance (EPR) and reactive species quenching tests were employed to reveal the responsive reactive oxygen species and the mechanism in the FeOOH@BNG/H2O2 system for SMX degradation. The current study not only opens new insights into the fabrication of amorphous but metallic nanomaterials but also leads to their potential application in environmental remediation.

"Setaria viridis"-like cobalt complex derived Co/N-doped carbon nanotubes as efficient ORR/OER electrocatalysts for long-life rechargeable Zn-air batteries.

The development of efficient and facile strategies to prepare metal and nitrogen codoped carbon (M-N-C) materials as oxygen electrocatalysts in rechargeable Zn-air batteries with high performance and a long life is challenging. Herein, we report a simple route to synthesize cobalt and nitrogen codoped carbon nanotubes (denoted as Co/N-CNT) as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries (ZABs). The Co/N-CNT are fabricated through the surface modification of carbon nanotubes with cobalt salt and melamine followed by pyrolysis, which delivers outstanding oxygen reduction/evolution reaction (ORR/OER) activity with a low overall potential gap (ΔE = 0.77 V) and remarkable durability. The home-made Zn-air batteries exhibit a high power density (130 mW cm-2vs. 82 mW cm-2), a large specific capacity of (864 mA h g-1Znvs. 785 mA h g-1Zn), and a long cycling life (1200 h vs. 60 h) in both aqueous and solid media. This work opens an avenue for the reasonable surface modification of carbon nanotubes with various metals and heteroatoms to achieve high-performance electrocatalysts for clean and sustainable energy conversion and storage devices.

Nitrogen-phosphorus codoped carbon nanotube sponges for detecting volatile organic compounds: experimental and DFT calculations.

The sensing of harmful gases and vapors is of fundamental interest to control the industrial emissions and environmental contamination. Nitrogen/phosphorus codoped carbon nanotube sponges (NP-CNTSs) were used to detect ethanol, acetone, cyclohexane, isopropanol, and methanol. The NP-CNTSs were produced through the aerosol-assisted chemical vapor deposition (AACVD) method using acetonitrile and triphenylphosphine as precursors at 1020 °C. The sensors based on NP-CNTSs were tested with varying operating temperatures (25-100 °C) and gas vapor concentrations (5-50 ppm). For instance, for a gas vapor concentration of 30 ppm and an operating temperature of 65 °C, the sensors showed changes in the electrical resistance of 1.12%, 1.21%, 1.09%, 2.4%, and 1.34% for ethanol, acetone, cyclohexane, isopropanol, and methanol, respectively. We found that the response and recovery times for isopropanol gas vapor are up to 43.7 s and 95 s, respectively. The current sensor outperformed the sensors reported in the literature by at least two times in the response measurement. Additionally, we performed van der Waals density functional theory calculations to elucidate the role of nitrogen and phosphorous codoped single-walled carbon nanotubes (SWCNTs) and their interaction with the considered gas molecule. We analyzed the molecular adsorption energy, optimized structures, and the density of states and calculated the electrostatic potential surface for N-doped, P-doped, NP-codoped, and OH-functionalized NP-codoped metallic SWCNTs-(6,6) and semiconducting SWCNTs-(10,0). Adsorption energy calculations revealed that in most cases the molecules are adsorbed to carbon nanotubes via physisorption. The codoping in SWCNTs-(6,6) promoted structural changes in the surface nanotube and marked chemisorption for acetone molecules.

Gram-scale production of in-situ generated iron carbide nanoparticles encapsulated via nitrogen and phosphorous co-doped bamboo-like carbon nanotubes for oxygen evolution reaction

Optimizing electrocatalytic activity and recognizing the most reactive sites for oxygen evolution reaction (OER) electrocatalysts are valuable to the order of renewable power. In this research article, we explored an innovative in-situ annealing technique for constructing iron carbide nanoparticles (Fe3C NPs) encapsulated via nitrogen and phosphorous doped bamboo-shape carbon nanotubes (NP-CNTs) for OER. Interestingly, the constructed Fe3C NPs@NP-CNT-800 composite exhibited remarkable electrochemical operation and offered a stable current density of 10 mA/cm2 at a lower overpotential (280 mV) in an alkaline solution. Furthermore, an innovative Fe3C NPs@N,P-CNT-800 hybrid surpassed the standard RuO2 electrocatalyst in terms of OER performance and showed negligible degradation in chronoamperometric (21 h) and chronopotentiometry (3000 cycles) analyses. The remarkable performance and stability are ascribed to the Fe3C NPs, novel tubular bamboo-like morphology of its carbon materials, and heteroatom doping, which contribute to the electrochemical interfaces, large surface area, active catalytic sites, and rapid charge transfer kinetics.

Rational design of metal–nitrogen-codoped carbon nanotube catalysts for CO2 reduction based on NiZn-layered double hydroxides

CNT-N-NiZn was constructed by controlling the assembly, high-temperature nitriding between single-layer NiZn-LDH and CNT. This study elucidates the M-N-C catalyst activity source and provides new insights into the M-N-C structure design.

Exploring of catalytic oxygen reduction reaction activity of lattice carbons of vanadium and niobium doped nitrogen codoped carbon nanotubes by density functional theory

AbstractThe oxygen electroreduction mechanism on the V‐ and Nb‐doped nitrogen‐codoped (6,6)armchair carbon nanotube with incorporated MN4 fragment has been studied using the ωB97XD and PBE density functional theory approaches. The metal center in MN4 fragment and the adjacent NCCN double bond (C2 site) of the support have been revealed as active centers. The metal active centers turned out to be irreversibly oxidized at the first step of ORR affording stable O*, 2O*, or O*HO* adsorbates depending on the applied electrode potential U, that makes them no longer active in ORR. Therefore, the C2 site comes at the forefront in ORR catalysis. Among the metal oxidized forms M(O)N4, M(O)(O)N4, and M(O)(OH)N4CNT, the C2 site of the latter turned out to be most active for 4e dissociative ORR. For both metals the last protonation/electron transfer step, HO* + H* → H2O, is the rate‐limiting step. The alternative hydrogen peroxide formation is not only thermodynamically less favorable but also kinetically slower than the 4e dissociative ORR route on the C2 site of model M(O)(OH)N4CNT catalyst.

Insights into the electrocatalytic behavior of nitrogen and sulfur co-doped carbon nanotubes toward oxygen reduction reaction in alkaline media

This study examines the effect of pretreatment and doping to enhance the ORR activity of multiwalled carbon nanotubes (MWCNTs). Melamine and thio-urea are chosen as precursors for mono and co-doping, respectively. A series of samples with pristine and pretreated CNTs are prepared and characterized physicochemically by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) and electrochemically by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The obtained results show that co-doping is an effective way for improving ORR activity, due to the synergistic effect of N and S for changing the charge and spin density, respectively. Moreover, thio-urea favors the proportion of pyridinic and graphitic nitrogen configurations within doped samples. As a consequence, our synthesis method gives samples with superior ORR activity. The maximum ORR activity is obtained for NS-OX-CNTs which shows an over potential of 0.95 V vs RHE at 0.1 mA/cm2, which is comparable to Pt/C (0.98 V vs RHE). The electron transfer number (n) is calculated as 3.9 at 0.4 V which suggests that the ORR proceeds through a dominant 4 e− path. These comparable half-cell results to that of Pt/C pave the way for further testing as cathode materials for anion exchange membrane fuel cells (AEMFC).Graphical abstract

Nitrogen and phosphorous co-doped carbon nanotubes embedded via active Ni2P nanoparticles as an advanced in-situ generated electrocatalyst for water oxidation

• Ni 2 P NPs/N, P-CNT-850 prepared by a novel in-situ one-step carbonization strategy. • The optimized Ni 2 P NPs/N, P-CNT-850 electrocatalyst shows remarkable OER performance in the alkaline solution. • Electrocatalytic activity exceeds the benchmark RuO 2 electrocatalyst. • N,P co-doped CNTs can optimize the electronic structure to enhance electrocatalytic activity. • The enhanced performance resulted from the multicomponent synergetic effect. Earth-abundant nickel-based composites are of high concern as electrocatalysts for the oxygen evolution reaction (OER) which are significant to many sustainable chemical and energy transformation technologies. However, the realization of effective OER is still far away by the requirement of a high sustainable driving potential above thermodynamic requirements. In this work, we develop an innovative one-pot in-situ approach to synthesize nitrogen (N) and phosphorous (P) co-doped carbon nanotubes (CNTs) embedded with Ni 2 P nanoparticles. The structure of Ni 2 P nanoparticles in carbon nanotubes and their electrocatalytic activities have been studied in relation to varied carbonization temperatures. Benefiting from the in-situ designed Ni 2 P nanoparticles, N, P co-doped carbon nanotubes (NP-CNTs) with larger surface area, pore-rich structure, and optimized temperature, the as-prepared Ni 2 P NPs/NP-CNT-850 exhibits remarkable electrocatalytic activity for the OER in 1.0 M alkaline solution. In particular, the optimized Ni 2 P NPs/NP-CNT-850 can achieve a reference current density of 10 mA cm −2 at a very low overpotential of 298 mV and lower Tafel slope of 53 mV dec -1 . This electrocatalyst also shows long-term stability without significant degradation for 17 h. Our study opens innovative in-situ engineering to dramatically increase the electrocatalytic activity of Ni-based composite for other applications via rational design of architectures with multiple active sites.

Rational design of three-dimensional boron and nitrogen co-doped carbon nanotubes encapsulated with nickel nanoparticles composite for enhance electromagnetic wave absorbing

Three-dimensional boron, nitrogen co-doped carbon nanotubes encapsulated with nickel nanoparticles (3D Ni@BNCNTs) composite have been prepared by a simple pyrolysis process using flower-like Ni2B alloy nanosheets (Ni2B NS) as catalyst. This technique enables one-step regulation of the growth diameter and structure of CNTs as well as in situ doping of B atoms. The doping of B and N atoms generates dipolar polarization and increases the dielectric loss. The prepared 3D Ni@BNCNTs samples exhibit excellent electromagnetic wave absorption capacity due to the abundant interface polarization, rich defective polarization, good conduction loss and good magnetic loss synergistically. 3D Ni@BNCNTs has a minimum reflection loss of −63.7 dB with a matching thickness of 1.7 mm and a broad effective absorption bandwidth which can reach 4.56 GHz at 1.5 mm with the merely filler loading ratio of 20 wt%. Therefore, this work developed a promising electromagnetic wave absorber for ultra-lightweight, ultra-thin and high-efficiency.

Induced construction of large-area amorphous Li2O2 film via elemental co-doping and spatial confinement to achieve high-performance Li-O2 batteries

In aprotic lithium-oxygen batteries (LOBs), it is hard to simultaneously achieve both high specific capacity and good reversibility with the insulating solid Li2O2 formed via traditional surface or solution route. Tuning the structure of Li2O2 to construct a large-area amorphous film on the surfaces of catalysts is expected to break the above performance limitation. In this work, nitrogen and sulfur co-doped carbon nanotube (CNT) arrays grown on the three-dimensional graphene (NS-CNTA/3DG) was developed as the efficient catalysts for LOBs. Large-area thin amorphous Li2O2 film is induced through the synergistic effect between doping engineering and spatial confinement on CNT arrays, confirmed by theoretical calculation and in-situ Raman examination. Consequently, the NS-CNTA/3DG cathode delivers both high specific capacity (23778 mAh g−1 at 200 mA g−1) and a high round-trip coulombic efficiency (∼87.8%) in the first deep discharge-charge process. This work contributes a new approach to optimize the formation of Li2O2 film, which will inspire the design and fabrication of new catalysts for high-performance LOBs.

Transition Metal Oxides Anchored Onto Co-Doped Carbon Nanotubes As Bifunctional Electrocatalysts

It has been well established that rechargeable zinc-air batteries (ZABs) are safe, environmentally friendly, and have a high theoretical energy density, making them a promising battery technology. Like many technologies there are challenges that need to be overcome. The main setback for ZABs is the slow reaction kinetics for the oxygen reduction reaction and the oxygen evolution reaction (ORR/OER) at the air electrode. Traditionally, adding precious metal catalysts to the air electrode, like Pt/Ru, will improve the reaction kinetics. However, precious metal catalysts are expensive and unstable during cycling of the discharge and charge reactions. Transition metal oxides combined with nanocarbon materials have been shown to improve the ORR and OER kinetics while staying cost effective [1], [2]. Heteroatom doping, e.g. -N, -B, and -S, of carbon materials has the ability to improve ORR performance [3]. When co-doping carbon nanotubes with sulfur and nitrogen, sulfur has the ability to replace the carbon atoms easily, creating more active sites for catalyst material [3], [4].The purpose of this study is to investigate the effects that co-doping of carbon nanotubes with nitrogen and sulfur combined with transition metal oxides have on the reaction kinetics at the air electrode. Impregnating the combined transition metal oxides and N,S co-doped CNTs into a gas diffusion layer (GDL) made of porous carbon ensures that the catalyst is deposited throughout the GDL [2]. Previous work has been done on Zn- and Ni-based tri-metallic and tetra-metallic oxides with N-CNTs. Nickel-based oxides had high efficiency, while the Zn-based tetra-metallic oxides demonstrated poor ORR performance leading to poor overall efficiency. Based on the literature, it is predicted that using N,S-CNTs with tri-metallic and tetra-metallic oxides will improve ORR performance. Various electrochemical and microstructural characterization techniques; e.g., linear sweep voltammetry, electrochemical impedance spectroscopy, electron microscopy, and energy dispersive X-ray spectroscopy, will be used to examine each sample. The goal of this work is to improve the ORR performance of previously studied tri-metallic and tetra-metallic oxides and improve the cyclability of ZABs.[1] N. Xu et al., “Self-Assembly formation of Bi-functional Co 3 O 4 /MnO 2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-Air battery,” Sci. Rep., vol. 6, no. September, pp. 1–10, 2016.[2] D. Aasen, M. Clark, and D. G. Ivey, “ A Gas Diffusion Layer Impregnated with Mn 3 O 4 ‐Decorated N‐Doped Carbon Nanotubes for the Oxygen Reduction Reaction in Zinc‐Air Batteries ,” Batter. Supercaps, vol. 2, no. 10, pp. 882–893, 2019.[3] I. M. Patil, V. Reddy, M. Lokanathan, and B. Kakade, “Nitrogen and sulphur co-doped multiwalled carbon nanotubes as an efficient electrocatalyst for improved oxygen electroreduction,” Appl. Surf. Sci., vol. 449, pp. 697–704, 2018, doi: 10.1016/j.apsusc.2017.12.124.[4] J. Wang et al., “Nitrogen and Sulfur Co-Doping of Partially Exfoliated MWCNTs as 3-D Structured Electrocatalysts for the Oxygen Reduction Reaction,” J. Mater. Chem. A, vol. 4, no. 15, pp. 5678–5684, 2016, doi: 10.1039/c6ta00490c.

Reduced graphene oxide-supported boron and nitrogen co-doped carbon nanotubes with embedded cobalt nanoparticles for absorption of electromagnetic wave

We develop a facile method to fabricate Co nanoparticles-embedded N, B co-doped carbon nanotubes on reduced graphene oxide sheets (Co@BNCNT/rGO). The prepared Co@BNCNT/rGO has high electrical conductivity, a large number of defects, and a three-dimensional structure with multiple interfaces. The experimental results show that the introduction of rGO can adjust the dielectric loss and impedance matching characteristics of the Co@BNCNT/rGO. Density functional theory calculations indicate that the electrons transfer from metallic Co to N,B-doped CNT, leading to interfacial polarization relaxation that favors the improvement of the electromagnetic wave absorption property of the Co@BNCNT/rGO. As a result, the Co@BNCNT/rGO exhibits excellent electromagnetic wave absorption properties with a minimum reflection loss exceeding −20 dB even if the matching thickness is lower than 2.0 mm. Moreover, the filler mass load of the Co@BNCNT/rGO is merely 20 wt%. Our results highlight a new method for synthesizing high-performance electromagnetic wave absorbers.

Experimental and DFT insights into nitrogen and sulfur co-doped carbon nanotubes for effective desulfurization of liquid phases: Equilibrium & kinetic study

Herein, nitrogen and sulfur co-doped carbon nanotubes (NS-CNT) adsorbents were synthesized via the chemical vapor deposition technique at 1000°C by employing the camphor, urea and sulfur trioxide pyridine. In this study, desulfurization of two types of mercaptans (dibenzothiophene (DBT) and tertiary butyl mercaptan (TBM) as nonlinear and linear forms of mercaptan) was studied. In this regard, a maximum capacity of NS-CNT was obtained as 106.9 and 79.4 mg/g and also the removal efficiencies of 98.6% and 88.3% were achieved after 4 h at 298K and 0.9 g of NS-CNT for DBT and TBM, respectively. Characterization of the NS-CNTs was carried out through exploiting scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and elemental analysis (CHN). The isotherm equilibrium data could be ascribed to the Freundlich nonlinear regression form and the kinetic data was fitted by nonlinear form of the pseudo second order model. The negative values of ΔS0, ΔH0 and ΔG0 specify that the adsorption of both types of mercaptans was a natural exothermic process with a reduced entropy. Maintenance of more than 96% of the adsorption capacity even after nine cycles suggest the NS-CNT as a superior adsorbent for mercaptans removal in the industry. Density functional theory (DFT) calculations were also performed to peruse the effects of S/N co-doping and carbon monovacancy defects in CNTs toward the adsorption of DBT and TBM.

Rational Design of Three-Dimensional Boron and Nitrogen Co-Doped Carbon Nanotubes Encapsulated with Nickel Nanoparticles Composite for Enhance Electromagnetic Wave Absorbing

Rational Design of Three-Dimensional Boron and Nitrogen Co-Doped Carbon Nanotubes Encapsulated with Nickel Nanoparticles Composite for Enhance Electromagnetic Wave Absorbing

Pt supported on boron, nitrogen co-doped carbon nanotubes (BNC NTs) for effective methanol electrooxidation

The research for electrocatalyst with high electroactivity and great CO-resistance ability for direct methanol fuel cells (DMFCs) is still a huge challenge. In this report, we develop Boron, Nitrogen co-doped carbon nanotubes (BNC NTs) as a support for Pt. Owing to the doping of boron, the catalyst not only provides extremely active sites for methanol oxidation reactions (MOR) but also protects Pt nanoparticles from agglutinating, performing superior electroactivity and excellent ability to anti CO poisoning. The X-ray photoelectron spectroscopy (XPS) results demonstrate the strong electron effect between Pt and B. Notably, the Pt/BNC NTs catalyst exhibits higher catalytic activity towards MOR and more superior durability in comparison with Pt/NC NTs and commercial JM Pt/C catalyst. The accelerated durability test (ADT) illustrates that Pt/BNC NTs catalyst can improve the issue of electrochemical surface area (ECSA) conservation, with only 30% diminish in comparison with the initial ECSA after 5000 cycles. The experiment result demonstrate that boron doping is the key step to improve the catalytic activities and CO-resistance ability due to the combination effects, involving firm B–C and N–C bonds, the stronger electron transfer in the nanotube structure among Pt, B and N, the stronger adsorption intensity of oxygen species from doped B.

CoP-embedded nitrogen and phosphorus co-doped mesoporous carbon nanotube for efficient hydrogen evolution

Hydrogen evolution reaction (HER) through the electrochemical process at low overpotentials is vital for sustainable energy production. However, the fabrication of non-precious materials with high efficiency for the HER remains a challenge. Here, a new catalyst that consists of cobalt (Co) species embedded nitrogen (N) and phosphorus (P) co-doped carbon nanotubes (CNT) is fabricated by the polymerization of dopamine on the cobalt-nitrilotriacetic coordination polymer nanowire surface, followed by the phosphidation and carbonization under high temperature. After the pretreatment by potassium hydroxide (KOH) and the removal of metallic Co nanoparticles by sulfuric acid (H2SO4), the activated catalyst (A-Co/N,P-CNT-700) exhibits an overpotential of 44 mV to obtain 10 mA cm−2 current density , approaching the value of commercial Pt/C catalyst (27 mV). The catalyst could easily maintain ~ 95% of its original HER activity after 15–hour stability test. The superior performance arises from the unique N-Co-P surface bonding states at the interface between CoP nanoparticles (1–4 nm) and N,P co-doped CNT. To the best of our knowledge, such HER performance is the best among noble metal free electrocatalysts in acidic electrolytes.

Incorporating Fe3C into B, N co-doped CNTs: Non-radical-dominated peroxymonosulfate catalytic activation mechanism

Boron and Nitrogen co-doped carbon nanotubes incorporated iron carbide (Fe3C) nanoparticles (Fe3C@BN-C) were successfully prepared by one-step pyrolysis method employing melamine, ferric chloride and boric acid as precursors. Characterizations indicate that the catalyst has large specific surface area (258.17–305.74 m2/g) and abundant defect sites, which are closely related to the adsorption performance and catalytic efficiency of the catalysts. In the presence of peroxymonosulfate (PMS), the removal rates of Fe3C@BN-C-7, Fe3C@BN-C-8 and Fe3C@BN-C-9 for doxycycline hydrochloride (DOX-H) are 87.0%, 91.9% and 86.0% within 120 min. Fe3C nanoparticles, oxygen-containing functional groups, pyridinic N, pyrrolic N, graphite N and B, N dopants play a vital role in the improvement of catalytic activity. Quenching experiments and electron paramagnetic resonance (EPR) studies show that singlet oxygen (1O2) is dominant reactive oxygen species, demonstrating that the degradation reaction predominantly follows the non-radical oxidation pathway. The possible degradation pathway of DOX-H is proposed and 14 intermediate products are reported for the first time. This work not only provides a novel and valuable catalyst for pharmaceutical wastewater treatment, but also reveals a new perspective for the study of activated PMS dominated by non-radical pathway.