Schiff-base polymer derived FeCo-N-doped porous carbon flowers as bifunctional oxygen electrocatalyst for long-life rechargeable zinc-air batteries

Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.

Nitrogen-doped porous carbon nanosheets as both anode and cathode for advanced potassium-ion hybrid capacitors

Potassium-ion hybrid capacitors(PIHCs)as a burgeoning research hotspot are an ideal replacement for lithium-ion hybrid capacitors(LIHCs).Here,we report nitrogen-doped porous carbon nanosheets(NPCNs)with enlarged interlayer spacing,abundant defects,and favorable mesoporous structures.The structural changes of NPCNs in potassiation and depotassiation processes are analyzed by using Raman spectroscopy and transmission electron microscopy.Due to the unique structure of NPCNs,the PIHC device assembled using NPCNs as both the anode and cathode material(double-functional self-matching material)exhibits a superior energy density of 128 Wh kg^(-1)with a capacity retention of 90.8%after 9000 cycles.This research can promote the development of double-functional self-matching materials for hybrid energy storage devices with ultra-high performance.

N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites as free-standing anodes for lithium-ion batteries

Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical conductivity.To mitigate these issues,free-standing N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites(Si/C-ZIF-8/CNFs)are designed and synthesized by electrospinning and carbonization methods,which present greatly enhanced electrochemical properties for lithium-ion battery anodes.This particular structure alleviates the volume variation,promotes the formation of stable solid electrolyte interphase(SEI)film,and improves the electrical conductivity.As a result,the as-obtained free-standing Si/C-ZIF-8/CNFs electrode delivers a high reversible capacity of 945.5 mAh g^(-1) at 0.2 A g^(-1) with a capacity retention of 64% for 150 cycles,and exhibits a reversible capacity of 538.6 mA h g^(-1) at 0.5 A g^(-1) over 500 cycles.Moreover,the full cell composed of a freestanding Si/C-ZIF-8/CNFs anode and commercial LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM)cathode shows a capacity of 63.4 mA h g^(-1) after 100 cycles at 0.2 C,which corresponds to a capacity retention of 60%.This rational design could provide a new path for the development of high-performance Si-based anodes.

N-doped porous carbon hollow microspheres encapsulated with iron-based nanocomposites as advanced bifunctional catalysts for rechargeable Zn-air battery

The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.

Novel Ag@Nitrogen-doped Porous Carbon Composite with High Electrochemical Performance as Anode Materials for Lithium-ion Batteries

A novel Ag@nitrogen-doped porous carbon(Ag-NPC) composite was synthesized via a facile hydrothermal method and applied as an anode material in lithium-ion batteries(LIBs). Using this method, Ag nanoparticles(Ag NPs) were embedded in NPC through thermal decomposition of Ag NO_3 in the pores of NPC. The reversible capacity of Ag-NPC remained at 852 m Ah g^(-1)after 200 cycles at a current density of 0.1 A g^(-1), showing its remarkable cycling stability. The enhancement of the electrochemical properties such as cycling performance,reversible capacity and rate performance of Ag-NPC compared to the NPC contributed to the synergistic effects between Ag NPs and NPC.

Controllable synthesis of nitrogen-doped porous carbon from metal-polluted miscanthus waste boosting for supercapacitors

High-value reclamation of metal-polluted plants involved in phytoremediation is a big challenge.In this study,nitrogen-doped nanoporous carbon with large specific area of 2359.1 m^(2)g^(-1) is facilely fabricated from metal-polluted miscanthus waste for efficient energy storage.The synergistic effect of KOH,urea and ammonia solution greatly improve the nitrogen quantity and surface area of the synthesized carbon.Electrodes fabricated with this carbon exhibit the excellent capacitance performance of 340.2 F g^(-1) at 0.5 A g^(-1) and a low combined resistance of 0.116Ω,which are competitive with most of previously reported carbon-based electrodes.In addition,the as-obtained carbon electrode shows a high specific capacitance retention of over 99.6%even after 5000 cycles.Furthermore,the symmetric supercapacitor fabricated using the synthesized carbon achieves a superior energy density of 25.3 Wh kg^(-1)(at 400 W kg^(-1))in 1 mol L^(-1) Na_(2)SO_(4)aqueous solution.This work provides an efficient route to upcycle metal-polluted plant waste for supercapacitor applications.

Implementing an“Impracticable”Copolymerization to Fabricate a Desired Polymer Precursor for N-doped Porous Carbons

It is common that a proof-of-concept of a desired reaction,which might generate materials with new functions or application potential,is eventually proved impracticable or commercially unfeasible.Considerable efforts have been made but wasted in searching for unknown reaction conditions in solvent environments because it was believed that the activity of reactants can be enhanced to facilitate reactions by dissolving them in solvents.However,an abnormal case was discovered in this study.A desired copolymerization reaction between 1,3,5-tris(chloromethyl)-2,4,6-trimethylbenzene and melamine was confirmed to be impracticable under various solvent conditions;however,it was successfully implemented using a solvent-free method.Using first-principle calculations and molecular dynamics simulations,two decisive factors that the reaction in solvents cannot possess,namely the reaction equilibrium being pushed by the timely release of by-products and the confined thermal motions of the activated monomer molecules in the solid phase,were demonstrated to make the copolymerization successful in the solvent-free method.Owing to the high aromaticity and azacyclo-content,the as-synthetic copolymer exhibited good application potential as a precursor to fabricate N-doped porous carbons with satisfactory carbon yields,ideal N contents,desired textural properties,and competitive CO_(2)capture abilities compared to other representative counterparts reported recently.

Bi Nanoparticles Anchored in N-Doped Porous Carbon as Anode of High Energy Density Lithium Ion Battery

A novel bismuth–carbon composite, in which bismuth nanoparticles were anchored in a nitrogen-doped carbon matrix(Bi@NC), is proposed as anode for high volumetric energy density lithium ion batteries(LIBs).Bi@NC composite was synthesized via carbonization of Zn-containing zeolitic imidazolate(ZIF-8) and replacement of Zn with Bi, resulting in the N-doped carbon that was hierarchically porous and anchored with Bi nanoparticles. The matrix provides a highly electronic conductive network that facilitates the lithiation/delithiation of Bi.Additionally, it restrains aggregation of Bi nanoparticles and serves as a buffer layer to alleviate the mechanical strain of Bi nanoparticles upon Li insertion/extraction.With these contributions, Bi@NC exhibits excellent cycling stability and rate capacity compared to bare Bi nanoparticles or their simple composites with carbon. This study provides a new approach for fabricating high volumetric energy density LIBs.

Hierarchical N-doped porous carbon hosts for stabilizing tellurium in promoting Al-Te batteries

Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.

Hierarchical N-Doped Porous Carbons for Zn–Air Batteries and Supercapacitors

Nitrogen-doped carbon materials with a large specific surface area,high conductivity,and adjustable microstructures have many prospects for energy-related applications.This is especially true for N-doped nanocarbons used in the electrocatalytic oxygen reduction reaction(ORR)and supercapacitors.Here,we report a low-cost,environmentally friendly,large-scale mechanochemical method of preparing N-doped porous carbons(NPCs)with hierarchical micro-mesopores and a large surface area via ball-milling polymerization followed by pyrolysis.The optimized NPC prepared at 1000°C(NPC-1000)offers excellent ORR activity with an onset potential(Eonset)and half-wave potential(E1/2)of 0.9 and 0.82 V,respectively(vs.a reversible hydrogen electrode),which are only approximately 30 mV lower than that of Pt/C.The rechargeable Zn–air battery assembled using NPC-1000 and the NiFe-layered double hydroxide as bifunctional ORR and oxygen evolution reaction electrodes offered superior cycling stability and comparable discharge performance to RuO2 and Pt/C.Moreover,the supercapacitor electrode equipped with NPC prepared at 800℃ exhibited a high specific capacity(431 F g^−1 at 10 mV s^−1),outstanding rate,performance,and excellent cycling stability in an aqueous 6-M KOH solution.This work demonstrates the potential of the mechanochemical preparation method of porous carbons,which are important for energy conversion and storage.

Red-blood-cell-like nitrogen-doped porous carbon as an efficient metal-free catalyst for oxygen reduction reaction

A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%)and specific surface area(631.46 m^2/g)was prepared by using melamine cyanuric acid and glucose as sacrificial template and carbon source,respectively.This catalyst has a comparable onset potential and a higher diffusion-limiting current density than the commercial 20 wt%Pt/C catalyst in alkaline electrolyte.The oxygen reduction reaction mechanism catalyzed by this catalyst is mainly through a 4e pathway process.The excellent catalytic activity could origin from the synergistic effect of the in-situ doped nitrogen(up to 9.81%)and three-dimensional(3D)porous network structure with high specific surface area,which is conducive to the exposure of more active sites.It is interesting to note that the catalytic activity of oxygen reduction strongly depends on the proportion of graphic N rather than the total N content.

Pyrolyzing soft template-containing poly(ionic liquid)into hierarchical N-doped porous carbon for electroreduction of carbon dioxide

Heteroatom-doped carbon materials have demonstrated great potential in the electrochemical reduction reaction of CO_(2)(CO_(2)RR)due to their versatile structure and function.However,rational structure control remains one challenge.In this work,we reported a unique carbon precursor of soft template-containing porous poly(ionic liquid)(PIL)that was directly synthesized via free-radical self-polymerization of ionic liquid monomer in a soft template route.Variation of the carbonization temperature in a direct pyrolysis process without any additive yielded a series of carbon materials with facile adjustable textural properties and N species.Significantly,the integration of soft-template in the PIL precursor led to the formation of hierarchical porous carbon material with a higher surface area and larger pore size than that from the template-free precursor.In CO_(2)RR to CO,the champion catalyst gave a Faraday efficiency of 83.0%and a current density of 1.79 mA·cm^(-2)at-0.9 V vs.reversible hydrogen electrode(vs.RHE).The abundant graphite N species and hierarchical pore structure,especially the unique hierarchical small-/ultramicropores were revealed to enable better CO_(2)RR performance.

Nitrogen-Doped Porous Carbon Nanofiber Supported Platinum as Promising Oxygen Reduction Reaction Electrocatalysts

Heteroatoms doped Carbon materials have been proved as promising catalyst support material for oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC). In this paper, nitrogen-doped porous nanofibers (N-PCNF) were fabricated via cost effective electrospinning technique by blending the PI and PAN as precursors, followed by heat treatment procedures. The N-PCNFs were used as support to prepare platinum (Pt) catalyst (Pt/N-PCNFs). SEM figure indicated that the porous structures not only existed on the surface but also in the cross session of the fibers. XPS and TEM displayed that with the help of heteroatoms nitrogen, the fiber had rougher surface and more defective structure, contributing to the dispersion of Pt nanoparticles. The catalytic performance for ORR was evaluated by cyclic voltammetry (CV) and liner sweep voltammetry (LSV) with a rotating disk electrode (RDE). According to the results, Pt/N-PCNF exhibited superior property (more positive onset potential and half-wave potential) than that of JM20. The excellent ORR activity of Pt/N-PCNF was attributed to the enriched nitrogen heteroatoms coordinated within the microstructure which increased the exposure of more active sites and dispersion of Pt nanoparticles.

Hydrogel-derived nitrogen-doped porous carbon framework with vanadium nitride decoration for supercapacitors with superior cycling performance

Transition metal nitrides(TMNs)and their composites with carbon materials hold tremendous potential for supercapacitor(SC)electrodes because of their excellent electronic conductivity and electrochemical activity.However,realizing cycling stable TMN/carbon-based supercapacitors with economically viable and environmentally-friendly approaches remains a significant challenge.Significantly,polyacrylamide(PAM)hydrogel,as a water-soluble linear polymer electrolyte,is expected to be a remarkable candidate precursor for preparing N-doped porous carbon(NPC)due to the high contents of carbon and nitrogen elements.In this study,vanadium nitride(VN)embedded in PAM hydrogel-derived NPC was fabricated successfully via an ammonia-free process.The VN/NPC delivers a high specific capacitance of 198.3 F g^(−1)at a current density of 1 A g^(−1),with a remarkable cycling stability of 107%after 16,000 cycles.The electrochemical performances of VN/NPC compared to bare VN nanoparticles are strongly improved due to the composite structure.Additionally,the VN/NPC-based solid-state symmetric device delivers an excellent energy density of 21.97µWh cm^(−2)at a power density of 0.5 mW cm^(−2),and an outstanding cycling durability of 90.9%after 18,000 cycles.This work paves the way to design metal nitride/porous carbon materials,which also opens up unique horizons for the recovery of hydrogel electrolyte.

Template-assisted formation of atomically dispersed iron anchoring on nitrogen-doped porous carbon matrix for efficient oxygen reduction

Isolated active metal atoms anchored on nitrogen-doped carbon matrix have been developed as the efficient catalyst for accelerating sluggish reaction kinetics of oxygen reduction reaction(ORR).The facile rational structure engineering with abundant isolated active metal atoms is highly desirable but challenging.Herein,we demonstrate that atomically dispersed Fe sites(Fe-N4 moieties)on the hierarchical porous nitrogen-doped carbon matrix(Fe-SA-PNC)for high ORR activity can be achieved by a dual-template assisted strategy.By thermal decomposition of NH_(4)Cl template,the nitrogen-doped carbon matrix is generated based on the interaction with carbon precursor of citric acid.Meanwhile,the introduction of NaCl template facilitates the formation of hierarchical porous structures,which enable more active sites exposed and improve the mass transfer.Interestingly,the dual-template strategy can inhibit the formation of iron carbide nanoparticles(NPs)by generating porous structures and avoiding of the rapid loss of nitrogen during pyrolysis.The as-made Fe-SA-PNC catalysts with well-defined Fe-N_(4)active sites exhibit highly efficient ORR activity with a half-wave potential of 0.838 V versus the reversible hydrogen electrode,as well as good stability and methanol tolerance,outperforming the commercial Pt/C.The zinc-air battery(ZAB)constructed by Fe-SA-PNC also shows a higher peak power density and specific discharging capacity than that of Pt-based ZAB.The present work provides the facile strategy for tailoring nitrogen doping and porous structures simultaneously to prevent the formation NPs for achieving the well-dispersed and accessible single-atom active sites,paving a new way to design efficient electrocatalysts for ORR in fuel cells.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

High-efficiency sodium storage of Co_(0.85)Se/WSe_(2) encapsulated in N-doped carbon polyhedron via vacancy and heterojunction engineering

With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.

Effect of carbonization atmosphere on electrochemical properties of nitrogen-doped porous carbon

Nitrogen atom doping has been found to enhance the electrochemical performance of porous carbon(PC).In this study,hollow tubular nitrogen-doped porous carbon(N/PC)was synthesized using polyvinylpyrrolidone as the carbon–nitrogen source and fibrous brucite as the template through carbonization.The effects of nitrogen and argon protective atmospheres on the nitrogen content,the specific surface area(SSA),and electrochemical properties of N/PC were investigated.The results showed that compared with N/FBC-Ar,N/FBC-N2 prepared in nitrogen protective atmosphere had a higher nitrogen content and a larger proportion of pyrrolic nitrogen(N-5)and pyridinic nitrogen(N-6).N/FBC-N2 displayed a specific capacitance(C)of 194.1 F·g^(−1)at 1 A·g^(−1),greater than that of N/FBC-Ar(174.3 F·g^(−1)).This work reveals that the nitrogen doping with a higher nitrogen content in nitrogen protective atmosphere is more favorable.Furthermore,a larger proportion of pyrrolic nitrogen and pyridinic nitrogen in the doped nitrogen atoms significantly enhances the electrochemical performance.

The preparation and properties of N-doped carbon materials and their use for sodium storage

Defect engineering by heteroatom doping gives carbon materials some new characteristics such as a different electronic structure and a high electrochemical activity,making them suitable for high-performance applications.N-doping has been widely investigated because of its similar atom radius to carbon,high electronegativity as well as many different configurations.We summarize the preparation methods and properties of N-doped carbon materials,and discuss their possible use in sodium ion storage.The relationships between N content/configuration and crystallinity,electronic conductivity,wettability,chemical reactivity as well as sodium ion storage performance are discussed.

Enhanced stability of nitrogen-doped carbon-supported palladium catalyst for oxidative carbonylation of phenol

Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.