Electronic Communication Between Co and Ru Sites Decorated on Nitrogen-Doped Carbon Nanotubes Boosting the Alkaline Hydrogen Evolution Reaction

Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.

Pre-fixing defects in carbon framework for revealing the active sites of oxygen reduction reaction at nitrogen-doped carbon nanotubes

Nitrogen-doped carbon-based materials are promising non-platinum group metal electrocatalysts for the oxygen reduction reaction(ORR).Understanding their ORR active sites is vital for the rational design and development of nitrogen-doped carbon-based electrocatalysts with enhanced catalytic efficiency and selectivity.However,the conclusive analysis of the ORR mechanism of nitrogen-doped carbon-based electrocatalysts remains a grand challenge because the catalysts have a complex inhomogeneous structure.Here,we elucidate this problem using nitrogen-doped carbon nanotubes framework catalysts with fixed defect concentrations prepared by pre-thermal treatment at a low temperature.The generation of defects under high-temperature treatment was effectively suppressed to enable a simple model for ORR mechanism study.A correlation between ORR pathways and the different nitrogen species in the nitrogen-doped carbon catalysts was revealed through a combination of structural and electrochemical properties investigations.Besides,our results also demonstrate the importance of defects for ORR.We believe that the results will provide instructive guidance for designing and developing novel carbon nanomaterials for ORR.

Nickel nanoparticles supported on nitrogen-doped carbon nanotubes are a highly active,selective and stable CO_(2) methanation catalyst

CO_(2) methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route.Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation,calcination and reduction and characterized by elemental analysis,X-ray powder diffraction,H_(2) temperature-programmed reduction,CO pulse chemisorption and transmission electron microscopy.The Ni/NCNT catalysts were highly active in CO_(2) methanation at atmospheric pressure,reaching over 50% CO_(2) conversion and over 95% CH_(4) selectivity at 340℃ and a GHSV of50,000 mL g^(-1) h^(-1) under kinetically controlled conditions.The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs.The optimum loading of 30 wt%-40 wt% Ni was found to result in the highest Ni surface area,the highest degree of conversion and the highest selectivity to methane.A constant TOF of 0.3 s^(-1) was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt%to 50 wt% Ni loading.Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream.

Enhanced Electrochemical Capacitance of Nitrogen-Doped Carbon Nanotubes Synthesized from Amine Flames

This paper presents a new process for synthesizing a kind of nitrogen- doped carbon nanotubes (N-CNTs) with primarily a ‘graphite-like’ structure at N substitutions from flames using n-propylamine and n-butylamine as fuels. When the N-CNTs are used as the supercapacitor electrode materials, they exhibit a much larger capacitance than the regular carbon nanotubes (CNTs). It is proposed that the high proportional ‘graphite-like’ N dopant in the as-grown N-CNTs improves their surface chemical activity and conductivity and then results in a desirable performance for electro-chemical capacitors.

A reevaluation of the correlation between the synthesis parameters and structure and properties of nitrogen-doped carbon nanotubes

Nitrogen-doped carbon nanotubes（NCNTs） were synthesized by chemical vapor deposition using cobaltbased oxides as catalyst and ethylenediamine（EDA） as carbon/nitrogen precursor. The influence of growth time,EDA concentration and growth temperature on the morphology,yield,composition,graphitization and oxidation resistance of the NCNTs was systematically investigated by using Raman spectroscopy,temperature-programmed oxidation and other techniques. The NCNT growth from ethylenediamine with a high N/C ratio involves several processes including mainly（1） catalytic growth of NCNTs,（2） homogeneous gas-phase decomposition of EDA,（3） non-catalytic deposition of pyrolytic carbon/nitrogen species and（4）surface etching of amorphous carbon or carbon at defect sites through gasification. At a later growth stage the etching process appears to be dominating,leading to the thinning of nanotubes and the decrease of yield.Moreover,the surface etching through carbon gasification strongly influences the structure and degree of graphitization of NCNTs.

Facile Fabrication of Platinum Nanoparticles Supported on Nitrogen-doped Carbon Nanotubes and Their Catalytic Activity

A facile impregnation method under mild condition is designed for synthesis of highly dispersed Pt nanoparticles with a narrow size of 4-7 nm on nitrogen-doped carbon nanotubes （CNx）. CNx do not need any pre-surface modification due to the inherent chemical activity. The structure and nature of Pt/CNx were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy spectrum. All the experimental results revealed that the large amount of doped nitrogen atoms in CNx was virtually effective for capturing the Pt（IV） ions. The improved surface nitrogen functionalities and hydrophilicity contributed to the good dispersion and immobi- lization of Pt nanoparticles on the CNx surface. The Pt/CNx served as active and reusable catalysts in the hydrogenation of allyl alcohol. This could be attributed to high dispersion of Pt nanoparticles and stronger interaction between Pt and the supports, which prevented the Pt nanoparticles from aggregating into less active Pt black and from leaching as well.

Ni-Cu bimetallic alloy anchored on nitrogen-doped carbon nanotubes for CO_(2)-to-CH_(4) electrochemical conversion

Electrocatalytic CO_(2) reduction to CH_(4) remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbon nanotubes(NixCuy-NCNT)for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)via hydrothermal method followed by pyrolysis.The optimized Ni_(1)Cu_(1)-NCNT demonstrated a superior CO_(2)RR performance,achieving 99.7%FECH_(4)(FE=Faradaic efficiency)and 11.54 mA·cm^(−2) current density at−1.2 V vs.reversible hydrogen electrode(RHE),which outperformed single metal counterparts.Its outstanding performance was due to the electrons transferred from Cu to Ni and Ni-Cu alloy shifted the d-band center toward the Fermi level,which was more conducive to the intermediate formation.In situ electrochemical attenuated total reflection(EC-ATR)and density functional theory(DFT)calculations revealed the appearance of *CHO intermediate and the pathway during the CO_(2)RR process.The design of the bimetallic electrocatalyst in this study provides a new perspective for the highly selective reduction of CO_(2).

Selective glycerol oxidation using platinum nanoparticles supported on multi-walled carbon nanotubes and nitrogen-doped graphene hybrid

Selective oxidation of glycerol is a hot topic.Increased biodiesel production has led to glycerol oxidation over Au- and Pt-based catalysts being widely studied.However,Pt catalysts suffer from deactivation because of weak metal-support interactions.In this study,multi-walled carbon nanotube（MWCNTs）-pillared nitrogen-doped graphene（NG） was prepared by direct pyrolysis of melamine on MWCNTs,and the synthesized NG-MWCNT composite was used as the support for Pt.Characterization results showed that the surface area（173 m^2/g） and pore volume of the NG-MWCNT composite were greater than those of bare MWCNTs and the separated melamine pyrolysis product（CH_x）.Pt（1.4±0.4 nm） dispersion on the NG-MWCNTs was favorable and the Pt/NG-MWCNT catalyst was highly active and selective in the oxidation of glycerol to glyceric acid（GLYA） in base-free aqueous solution.For example,the conversion of glycerol reached 64.4% with a GLYA selectivity of 81.0%,whereas the conversions of glycerol over Pt/MWCNTs and Pt/CN_x were 29.0% and 31.6%,respectively.The unique catalytic activity of the Pt/NG-MWCNTs is attributed to well-dispersed Pt clusters on the NG-MWCNTs and the electron-donating effect of the nitrogen dopant in the NG-MWCNTs.

Synthesis of nitrogen-doped carbon nanotubes-FePO_4 composite from phosphate residue and its application as effective Fenton-like catalyst for dye degradation

Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nanotubes-FePO_4(NCNTs-FePO_4) composite was successfully synthesized from phosphate residue, and its application as an effective catalyst was explored. Firstly, an effective method was developed to recover FePO_4 from phosphate residue, achieving an impressive FePO_4 mass recovery rate of 98.14%. Then, the NCNTsFePO_4 catalyst was synthesized from the recovered FePO_4 by two main reactions, including surface modification and chemical vapor deposition. Finally, the synthesized NCNTs-FePO_4 was applied to photo-degrade 15 mg/L Rhodamine B(RhB) in a Fenton-like system. The results showed that 98.9% of RhB could be degraded in 60 min, closely following the pseudofirst-order kinetics model. It was found that even after six consecutive cycles, NCNTs-FePO_4 still retained a high catalytic capacity(>50%). Moreover, ·OH radicals participating in the RhB degradation process were evidenced using quenching experiments and electron paramagnetic resonance analysis, and a rational mechanism was proposed. It was demonstrated that the materials synthesized from hazardous phosphate residue can be used as an effective catalyst for dye removal.

Conjugated polymer-mediated synthesis of sulfur- and nitrogen-doped carbon nanotubes as efficient anode materials for sodium ion batteries

Heteroatom-doped carbon nanomaterials have attracted significant attention as anode materials for sodium-ion batteries （SIBs）. Herein, we demonstrate a conjugated polymer-mediated synthesis of sulfur and nitrogen co-doped carbon nanotubes （S/N-CT） via the carbonization of sulfur-containing polyaniline （PANI） nanotubes. It is found that the carbonization technique greatly influences the structural features and thus the Na-storage behavior of the S/N-CT materials. The carbon nanotubes developed using a two-step carbonization process （heating at 400℃ and then at 900℃） exhibit a high specific surface area, enlarged interlayer distance, small charge transfer resistance, enhanced reaction kinetics, as well as a large number of defects and active sites; further, they exhibit a high reversible capacity of 340 mAh·g^-1 at 0.1 A·g^-1 and a remarkable cycling stability with a capacity of 141 mAh·g^-1 at 5 A·g^-1 （94% retention after 3,000 cydes）. Direct carbonization of conjugated polymers with a specific morphology is an eco-friendly and low-cost technique for the synthesis of dual atom-doped carbon nanomaterials for application in energy devices. However, the carbonization process should be carefully controlled in order to better tune the structure-property relationship.

Nitrogen-doped carbon encapsulated in mesoporous TiO2 nanotubes for fast capacitive sodium storage

Controllable synthesis of insertion-type anode materials with beneficial micro-and nanostructures is a promising approach for the synthesis of sodium-ion storage devices with high-reactivity and excellent electrochemical performance.In this study,we developed a sacrificial-templating route to synthesize TiO_(2)@N-doped carbon nanotubes(TiO_(2)@NC-NTs)with excellent electrochemical performance.The asprepared mesoporous TiO_(2)@NC-NTs with tiny nanocrystals of anatase TiO_(2) wrapped in N-doped carbon layers showed a well-defined tube structure with a large specific surface area of 198 m^(2) g^(-1) and a large pore size of~5 nm.The TiO_(2)@NC-NTs delivered high reversible capacities of 158 m A h g^(-1) at 2 C(1 C=335 m A g^(-1))for 2200 cycles and 146 m A h g^(-1) at 5 C for 4000 cycles,as well as an ultrahigh rate capability of up to 40 C with a capacity of 98 m A h g^(-1).Even at a high current density of 10 C,a capacity of 138 m A h g^(-1) could be delivered over 10,000 cycles.Thus,the synthesis of mesoporous TiO_(2)@NC-NTs was demonstrated to be an efficient approach for developing electrode materials with high sodium storage and long cycle life.

Synthesis of nitrogen-doped single-walled carbon nanotubes and monitoring of doping by Raman spectroscopy

Nitrogen-doped single-walled carbon nanotubes （CNx-SWNTs） with tunable dopant concentrations were synthesized by chemical vapor deposition （CVD）, and their structure and elemental composition were characterized by using transmission electron microscopy （TEM） in combination with electron energy loss spectroscopy （EELS）. By comparing the Raman spectra of pristine and doped nanotubes, we observed the doping-induced Raman G band phonon stiffening and 2D band phonon softening, both of which reflect doping-induced renormalization of the electron and phonon energies in the nan- otubes and behave as expected in accord with the n-type doping effect. On the basis of first principles calculations of the distribution of delocalized carrier density in both the pristine and doped nanotubes, we show how the n-type doping occurs when nitrogen heteroatoms are substitutionally incorporated into the honeycomb tube-shell carbon lattice.

Hollow ZIF-67-derived Co@N-doped carbon nanotubes boosting the hydrogenation of phenolic compounds to alcohols

The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.

Effects of bimetallic catalysts on synthesis of nitrogen-doped carbon nanotubes as nanoscale energetic materials

Well aligned nitrogen-doped carbon nanotubes （CNx-NTs）, as energetic materials, are synthesized on a silicon substrate by aerosol-assisted chemical vapor deposition, Tungsten （W） and molybdenum （Mo） metals are respectively introduced to combine with iron （Fe） to act as a bimetallic co-catalyst layer. Cor- relations between the composition and shape of the co-catalyst and morphology, size, growth rate and nitrogen doping amount of the synthesized CNx-NTs are investigated by secondary and backscattered electron imaging in a field emission scanning electron microscope （FESEM） and X-ray photoelectron spectrometer （XPS）. Compared to pure iron catalyst, W-Fe co-catalyst can result in lower growth rate, larger diameter and wider size distribution of the CNx-NTs; while incorporation of molybdenum into the iron catalyst layer can reduce the diameter and size distribution of the nanotubes. Compared to the sole iron catalyst, Fe-W catalyst impedes nitrogen doping while Fe-Mo catalyst promotes the incorporation of nitrogen into the nanotubes. The present work indicates that CNx-NTs with modulated size, growth rate and nitrogen doping concentration are expected to be synthesized by tuning the size and composition of co-catalysts, which may find great potential in producing CNx-NTs with controlled structure and properties,

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO_2 Hydrogenation

Nitrogen-doped carbon nanotubes （NCNTs） were used as a support for iron （Fe） nanoparticles applied in car- bon dioxide （CO_2） hydrogenation at 633 K and 25 bar （1 bar = 10-5 Pa）. The Fe/NCNT catalyst promoted with both potassium （K） and manganese （Mn） showed high performance in CO_2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity （GHSV） of 3.1 L-（g·h）-1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promot- ed with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction （XRD）, temperature-programmed reduction （TPR） with molecular hydrogen （H2）, and in situ X-ray absorption near-edge structure （XANES） analysis. The Mn pro- moter stabilized wtistite （FeO） as an intermediate and lowered the TPR onset temperature. Catalytic ammo- nia （NH_3） decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

Influence of the aspect ratio of nitrogen-doped carbon nanotubes on their piezoelectric properties

Recent studies have shown that nitrogen doping of carbon nanotubes(CNTs)can lead to the formation of piezoelectric properties in them,not characteristic of pure CNTs.In this work,nitrogen-doped CNTs were grown by plasma-enhanced chemical vapor deposition and the effect of the aspect ratio of the nanotube length to its diameter on its piezoelectric coefficient d33 was shown.It was observed that as the aspect ratio of the nanotube increased from 7 to 21,the value of d33 increased linearly from 7.3 to 10.7 pm/V.This dependence is presumably due to an increase in curvature-induced polarization because of an increase in the curvature and the number of bamboo-like“bridges”in the nanotube cavity formed as a result of the incorporation of pyrrole-like nitrogen into the nanotube structure.The obtained results can be used in the development of promising elements of nanopiezotronics(nanogenerators,memory elements,and strain sensors).

Nitrogen-doped carbon nanotubes by multistep pyrolysis process as a promising anode material for lithium ion hybrid capacitors

Lithium-ion hybrid capacitors(LIHCs) is a promising electrochemical energy storage devices which combines the advantages of lithium-ion batteries and capacitors.Herein,we developed a facile multistep pyrolysis method,prepared an amorphous structure and a high-level N-doping carbon nanotubes(NCNTs),and by removing the Co catalyst,opening the port of NCNTs,and using NCNTs as anode material.It is shows good performance due to the electrolyte ions enter into the electrode materials and facilitate the charge transfer.Furthermore,we employ the porous carbon material(APDC) as the cathode to couple with anodes of NCNTs,building a LIHCs,it shows a high energy density of 173 Wh/kg at 200 W/kg and still retains 53 Wh/kg at a high power density of 10 kW/kg within the voltage window of 0-4.0 V,as well as outstanding cyclic life keep 80% capacity after 5000 cycles.This work provides an opportunity for the preparation of NCNTs,that is as a promising high-performance anode for LIHCs.

Nitrogen-Doped Carbon Nanotube-Supported Pd Catalyst for Improved Electrocatalytic Performance toward Ethanol Electrooxidation

In this study, hydrothermal carbonization(HTC)was applied for surface functionalization of carbon nanotubes(CNTs) in the presence of glucose and urea. The HTC process allowed the deposition of thin nitrogen-doped carbon layers on the surface of the CNTs. By controlling the ratio of glucose to urea, nitrogen contents of up to 1.7 wt%were achieved. The nitrogen-doped carbon nanotube-supported Pd catalysts exhibited superior electrochemical activity for ethanol oxidation relative to the pristine CNTs.Importantly, a 1.5-fold increase in the specific activity was observed for the Pd/HTC-N1.67%CNTs relative to the catalyst without nitrogen doping(Pd/HTC-CNTs). Furtherexperiments indicated that the introduction of nitrogen species on the surface of the CNTs improved the Pd(0)loading and increased the binding energy.

Ultrafine VN nanodots induced generation of abundant cobalt single-atom active sites on nitrogen-doped carbon nanotube for efficient hydrogen evolution

Development of highly active and stable non-noble electrocatalysts with well-defined nanostructures is crucial for efficient hydrogen evolution reaction(HER). Herein, a novel three-dimensional(3D) selfsupported electrode consists of vanadium nitride(VN) nanodots and Co nanoparticles co-embedded and highly active single Co atoms anchored in N-doped carbon nanotubes supported on carbon cloth(VN-Co@CoSAs-NCNTs/CC) is fabricated via a one-step in situ nanoconfined pyrolysis strategy, which shows remarkable enhanced HER electrocatalytic activity in acidic medium. During pyrolysis, the formed VN nanodots induce the generation of atomic Co Nxsites in NCNTs, contributing to superior electrocatalytic activity. Experimental and density functional theory(DFT) calculation results reveal that the electrode has multiple accessible active sites, fast reaction kinetics, low charge/mass transfer resistances,high conductivity, as well as downshifted d-band center with a thermodynamically favorable hydrogen adsorption free energy(△G_(H·)), all of which greatly boost the HER performance. As a result, the VNCo@CoSAs-NCNTs/CC electrode displays superb catalytic performance toward HER with a low overpotential of 29 mV at 10 mA cm^(-2) in acidic medium, which could maintain for at least 60 h of stable performance. This work opens a facile avenue to explore low-cost, high performance, but inexpensive metals/nitrogen-doped carbon composite electrocatalysts for HER.

Enhancing the Interaction of Carbon Nanotubes by Metal-Organic Decomposition with Improved Mechanical Strength and Ultra-Broadband EMI Shielding Performance

The remarkable properties of carbon nanotubes(CNTs)have led to promising applications in the field of electromagnetic inter-ference(EMI)shielding.However,for macroscopic CNT assemblies,such as CNT film,achieving high electrical and mechanical properties remains challenging,which heavily depends on the tube-tube interac-tions of CNTs.Herein,we develop a novel strategy based on metal-organic decomposition(MOD)to fabricate a flexible silver-carbon nanotube(Ag-CNT)film.The Ag particles are introduced in situ into the CNT film through annealing of MOD,leading to enhanced tube-tube interactions.As a result,the electrical conductivity of Ag-CNT film is up to 6.82×10^(5) S m^(-1),and the EMI shielding effectiveness of Ag-CNT film with a thickness of~7.8μm exceeds 66 dB in the ultra-broad frequency range(3-40 GHz).The tensile strength and Young’s modulus of Ag-CNT film increase from 30.09±3.14 to 76.06±6.20 MPa(~253%)and from 1.12±0.33 to 8.90±0.97 GPa(~795%),respectively.Moreover,the Ag-CNT film exhibits excellent near-field shield-ing performance,which can effectively block wireless transmission.This innovative approach provides an effective route to further apply macroscopic CNT assemblies to future portable and wearable electronic devices.