Biomass derived porous nitrogen doped carbon for electrochemical devices

Biomass derived porous nanostructured nitrogen doped carbon(PNC) has been extensively investigated as the electrode material for electrochemical catalytic reactions and rechargeable batteries. Biomass with and without containing nitrogen could be designed and optimized to prepare PNC via hydrothermal carbonization, pyrolysis, and other methods. The presence of nitrogen in carbon can provide more active sites for ion absorption, improve the electronic conductivity, increase the bonding between carbon and sulfur, and enhance the electrochemical catalytic reaction. The synthetic methods of natural biomass derived PNC, heteroatomic co-or tri-doping into biomass derived carbon and the application of biomass derived PNC in rechargeable Li/Na batteries, high energy density Li-S batteries, supercapacitors, metal-air batteries and electrochemical catalytic reaction(oxygen reduction and evolution reactions, hydrogen evolution reaction) are summarized and discussed in this review. Biomass derived PNCs deliver high performance electrochemical storage properties for rechargeable batteries/supercapacitors and superior electrochemical catalytic performance toward hydrogen evolution, oxygen reduction and evolution, as promising electrodes for electrochemical devices including battery technologies, fuel cell and electrolyzer.

Modulating the CO methanation activity of Ni catalyst by nitrogen doped carbon

Nitrogen doping has been proved to be an effective way to modify the properties of graphene and other carbon materials. Herein, we explore a composite with nitrogen doped carbon overlayers wrapping Si C substrate as a support for Ni（Ni/CN-Si C） and evaluate its effects on the methanation activity. The results show that both the activity and stability of Ni are enhanced. Characterization with STEM, XRD, XPS, Raman and H2-TPR indicates that nitrogen doping generates more defects in the carbon overlayers, which benefit the dispersion of Ni. Furthermore, the reduction of Ni is facilitated.

Cu,N codoped carbon nanosheets encapsulating ultrasmall Cu nanoparticles for enhancing selective 1,2-propanediol oxidation

In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.

Efficient Fe based catalyst with nitrogen doped carbon material modification for propane non-oxidative dehydrogenation

Nitrogen doped carbon species(NC)was introduced into Fe based catalyst and applied into propane non-oxidative dehydrogenation.With characterizations of XRD,TEM and XPS,it was deduced that the NC modification induces the electrons transferred from NC species to Fe species,leading to electron-rich Fe species.Consequently,propane conversion and propene selectivity were increased by suppressing the by-products formation.It was also confirmed that such a modification strategy could be also extended to ones with different supports,iron precursors,and NC precursors.

Reinforcing epoxy resin with nitrogen doped carbon nanotube:A potential lightweight structure material

The outstanding mechanical properties of nanocarbon materials, especially carbon nanotube（CNT）, make them one of the most promising reinforcing nanofillers for the high-performance lightweight structural material. However, the complicated but not eco-friendly surface functionalization processes（e.g. HNO3 oxidation） are generally necessary to help disperse nanocarbon materials into epoxy or build chemical bonds between them. Herein, nitrogen doped carbon nanotube（NCNT） was used to replace CNT to reinforce the epoxy resin, and the mechanical properties of the NCNT/epoxy nanocomposite showed significant superiorities over the CNT/epoxy nanocomposites. The fabrication process was simple and environmentally friendly, and avoided complicated, polluting and energy intensive surface functionalization processes. Moreover, the NCNT/epoxy suspension exhibited a relative low viscosity, which was favorable for the subsequent application. The reinforcing mechanism of NCNT was also proposed. The present work gives out an easy solution to the preparation of a high-performance nanocomposite as a potential lightweight structure material.

Co/CoO heterojunction rich in oxygen vacancies introduced by O2 plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.

Structure and Mechanical Performance of Nitrogen Doped Diamond-like Carbon Films

Nitrogen doped diamond-like carbon （DLC：N） films were prepared by electron cyclotron resonance chemical vapor deposition （ECR-CVD） on polycrystalline Si chips. Film thickness is about 50 nm. Auger electron spectroscopy （AES） was used to evaluate nitrogen content, and increasing N2 flow improved N content from 0 to 7.6%. Raman and X-ray photoelectron spectroscopy （XPS） analysis results reveal CN-sp^3C and N-sp^2C structure. With increasing the N2 flow, sp^3C decreases from 73.74% down to 42.66%, and so does N-sp^3C from 68.04% down to 20.23%. The hardness decreases from 29.18 GPa down to 19.74 GPa, and the Young＇s modulus from 193.03 GPa down to 144.52 GPa.

Synergetic effect of nitrogen‐doped carbon catalysts for high‐efficiency electrochemical CO_(2) reduction

The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.

Cobalt nanoparticles encapsulated in nitrogen-doped carbon for room-temperature selective hydrogenation of nitroarenes

Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized by pyrolyzing a mixture of a cobalt salt,an inexpensive organic molecule,and carbon nitride.Using the Co@NC catalyst,a turnover frequency of^12.3 h?1 and selectivity for 4‐aminophenol of>99.9%were achieved for hydrogenation of 4‐nitrophenol at room temperature and 10 bar H2 pressure.The excellent catalytic performance can be attributed to the cooperative effect of hydrogen activation by electron‐deficient Co nanoparticles and energetically preferred adsorption of the nitro group of nitroarenes to electron‐rich N‐doped carbon.In addition,there is electron transfer from the Co nanoparticles to N‐doped carbon,which further enhances the functionality of the metal center and carbon support.The catalyst also exhibits stable recycling performance and high activity for nitroaromatics with various substituents.

Atomic modulation of Fe‐Co pentlandite coupled with nitrogen‐doped carbon sphere for boosting oxygen catalysis

Reversible oxygen reaction plays a crucial role in rechargeable battery systems,but it is limited by the slow reaction kinetics.Herein,the ionic modulation of cobalt pentlandite coupled with nitrogen‐doped bowl‐like hollow carbon sphere is well designed on octahedral and tetrahedral sites.The robust FexCo9−xS8‐NHCS‐V with iron replacing at the octahedron possesses prolonged metal sulfur bond and exhibits excellent bifunctional electrocatalytic performance towards oxygen reduction reaction(ORR,E_(1/2)=0.80 V vs.RHE)and excellent oxygen evolution reaction(OER,E_(j=10)=1.53 V vs.RHE)in 0.1 mol/L KOH.Accordingly,a rechargeable Zn‐air battery of Fe_(x)Co_(9−x)S_(8)‐NHCS‐V cathode endows high energy efficiency(102 mW cm^(−2)),and a microbial fuel cell achieves a high‐power density(791±42 mW m^(−2)),outperforming the benchmark Pt/C catalyst.

Mechanochemical Synthesis of Visible-light Induced Photocatalyst with Nitrogen and Carbon Doping

Nitrogen and/or carbon doped titania photocatalysts were prepared by a novel mechanochemical method. The prepared powders possessed two absorption edges around 400 and 540 nm wavelengths and showed excellent photocatalytic ability for nitrogen monoxide oxidation under visible light irradiation. Under the irradiation of visible light of wavelength >510 nm,37% of nitrogen monoxide could be continuously removed by the carbon and nitrogen co-doped titania prepared by planetary ball milling of P-25 titania–10% hexamethylenetetramine mixture followed by calcination in air at 400-C.

Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction

Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Nitrogen doped hollow carbon nanospheres as efficient polysulfide restricted layer on commercial separators for high-performance lithium-sulfur batteries

The polysulfide shuttle limits the development of lithium-sulfur(Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres(NHCS) derived from polymerization of dopamine on SiO_(2)nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators(PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.

High lithiophilic nitrogen-doped carbon nanotube arrays prepared by in-situ catalyze for lithium metal anode

Lithium metal has a very outstanding theoretical capacity(3860 mAh/g)and is one of the most superior anode materials for high energy density batteries.However,the uncontrollable dendrite growth and the fo rmation of"dead lithium"are the important hidden dangers of short cycle life and low safety.However,the uncontrollable dendrite growth and the fo rmation of dead lithium leads to short cycle life and hidden dange r,which hinder its practical application.Controlling the nucleation and growth process of lithium is an effective strategy to inhibit lithium dendrite.Herein,a simple in situ self-catalytic method is used to construct nitrogen doped carbon nanotube arrays on stainless steel mesh(N-CNT@SS)as a lithium composite anode.The N-doped CNTs provide a great number of N-functional groups,which enhance the lithiophilic of anode and provide a large number of uniform nucleation sites,hence it has excellent structural stability for cycles.The arrays provide neat lithium-ion transport channels to uniform lithiumion flux and inhibits dendrite generation,revealed by the COMSOL multi-physics concentration field simulation.The N-CNT@SS composite anode sustain stable at 98.9%over 300 cycles at 1 mA/cm2.NCNT@SS as the anode is coupled LiFePO_(4)(LFP)as the cathode construct a full battery,demonstrating excellent cycling stability with a capacity of 152.33 mAh/g and capacity retaining ratio of 95.4%after 100 cycles at 0.5 C.

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,

MoS_(2) wrapped MOF-derived N-doped carbon nanocomposite with wideband electromagnetic wave absorption

Designing electromagnetic wave absorption(EMWA)materials with wide bandwidth,strong absorption,and light weight is still a great challenge for practical applications.Herein,the novel nitrogen doped carbon(NDC)/MoS_(2) composite with rationally designed composition and structure was developed.The NDC particles were introduced into MoS_(2) nanosheets through the calcination of ZIF-8 precursor and consequent hydrothermal process.A series of characterizations were carried out to investigate the physical properties of the as-prepared nanocomposites.The NDC particles exhibited the shape of rhombic dodecahedron with the size of about 500 nm,which were decorated on flower-shaped MoS_(2) with the size of about 3μm.With the increasing NDC content,the absorbing properties of NDC/MoS_(2) composites increased firstly and then decreased.The features of NDC/MoS_(2) composite including interconnected porous structure,nitrogen dopant,and appropriate electrical conductivity gave rise to the polarization,multiple reflection,multiple scattering,and impedance matching,resulting in the outstanding EMWA performance.With a filler loading ratio of 30 wt.%,the optimized EMWA property can be achieved when the mass ratio of NDC to MoS_(2) was adjusted to be 1:1.At a coating thickness of 3.0 mm,the effective EMWA bandwidth(<−10 dB)reached 6.08 GHz(8.56–14.64 GHz).These satisfactory achievements provide a way for the reasonable design of high-performance EMWA and new ideas for future research on wideband EMWA.

Advanced non-precious electrocatalyst of the mixed valence CoO_x nanocrystals supported on N-doped carbon nanocages for oxygen reduction

Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybrid exists in the mixed valence with predominant Co O over Co3O4 and demonstrates superb oxygen reduction reaction activity and stability remaining^94%current density even after operation over 100 h.These results suggest a promising strategy to develop advanced electrocatalysts with the novel NCNCs or even beyond.

Boosting the photocatalytic performance of Ag_2CO_3 crystals in phenol degradation via coupling with trace N-CQDs

A series of N‐CQDs/Ag2CO3composite crystals(where N‐CQDs=Nitrogen doped carbon quantumdots)were prepared by adding different volumes of a solution of N‐CQDs during Ag2CO3crystalgrowth.Under irradiation from a350‐W Xe lamp light(with optical filter,λ≥420nm),the performanceof N‐CQDs/Ag2CO3in photocatalytic degradation of phenol was evaluated.The as‐preparedsamples were analyzed by XRD,SEM,TEM,BET,element mapping,UV‐vis DRS,FT‐IR,XPS,transientphotocurrent response and EIS testing.The results showed that after coupling with trace amountsof N‐CQDs,both the photocatalytic activity and stability of Ag2CO3were greatly boosted.The additionof N‐CQDs solution influenced the crystallization of Ag2CO3,resulting in a distinct decrease inAg2CO3crystal size and an obvious increase in surface area.Moreover,the charge transfer resistancewas greatly reduced,and the separation efficiency of photogenerated electrons and holes wasstrongly promoted.The presence of NCQDs on the surface of the catalysts facilitates the transfer ofphotogenerated electrons,slowing the photocorrosion rate of Ag2CO3,and then resulting in higherstability than bare Ag2CO3in degradation.The synergistic effect of the improvement of morphologyand charge transfer rate thus accounted for the superior photocatalytic performance ofN‐CQDs/Ag2CO3.

Pyrolysis transformation of ZIF-8 wrapped with polytriazine to nitrogen enriched core-shell polyhedrons carbon for supercapacitor

This work presents a simple effective strategy to synthesize N-doped and shell-controlled carbon nanocages through a package baking approach.A green approach to synthesize core-shell ZIF-8@PTZ nanoparticles involves zinc contained ZIF-8 core wrapped by a N-enriched polytriazine(PTZ).Synthesized core-shell ZIF-8@PTZ nanoparticles are calcinated to further sublime zinc through PTZ shell and washed by HC1,leaving a porous carbon structure.At the meantime,hollow cavities were introduced into N-doped carbon polyhedrons via the sacrifice of ZIF-8 template(noted as ZIF-8@C/N-x).The electrochemical performance of the ZIF-8@C/N-x as supercapacitor electrode has demonstrated high energy density and specific capacitance,as well as a long-term cycleability showing 92%capacitance retention after 10000 cycles.There is a systematic correlation between micro-/meso-porosity of ZIF-8@C/N-x and their electrochemical performances.