Biomass seaweed-derived n itrogen self-doped porous carb on anodes for sodium-ion batteries:Insights into the structure and electrochemical activity

Sustainable transformation and efficient utilization of biomasses and their derived materials are environ-mentally as well as economically compliant strategies.Biomass seaweed-derived nitrogen self-doped porous carbon with tailored surface area and pore structures are prepared through carb on izatio n and activation.The in fluence of carb on ization temperature on morphology,surface area,and heteroatom dopants are investigated to optimize sodium-ion storage capability.Seaweed-derived nitrogen selfdoped activated carbon(SAC)as anode materials for sodium-ion batteries exhibits remarkable reversible capacity of 303/192 mAh g^(-1) after 100/500 cycles at current densities of 100/200 mA g^(-1) respectively,and a good rate capability.The interconnected and porous conducting nature along with the heteroatom dopant role in creating defective sites and charge stabilization are favorable for ion storage and diffusion and electron transport,indicating the electrodes can offer improved electrochemical performances.In addition,post-mortem analysis of the cycled carbon electrodes through ex-situ tools demonstrates the sodium-ion storage mechanism.

Pyridinic nitrogen enriched porous carbon derived from bimetal organic frameworks for high capacity zinc ion hybrid capacitors with remarkable rate capability

Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.

Cu_(3)P nanoparticles confined in nitrogen/phosphorus dual-doped porous carbon nanosheets for efficient potassium storage

Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.

Study on Preparation of Nitrogen-Doped Hierarchically Porous and High-Performance Carbon Materials from Seaweed Biomass

Use Enteromorpha clathrate as a carbon and nitrogen precursor could obtain the N-doped porous carbon mate-rials by two-step pyrolysis.In this paper,the exogenous nitrogen(urea,melamine)and activating agents(KOH,ZnCl_(2))were employed for the production of higher-performance carbon materials from seaweed biomass.SEM,BET,FTIR,XRD,XPS,Raman and ultimate analyses were carried out to investigate the morpho-structural and elemental peculiarities of the carbonaceous materials.Moreover,cyclic voltammetry(CV),galvanostatic charge-discharge(GCD)and cyclic charge-discharge tests were carried out to examine the electrochemical properties of the samples.The results showed that electrochemical performance of the carbonaceous materials improved by adding the appropriate nitrogen sources.This improvement was observed under either condition,when the nitro-gen source and activating agent were melamine and ZnCl_(2) or urea and KOH,respectively.Specifically,under the condition with KOH as the activator,the nitrogen content of carbon material without exogenous nitrogen was initially 1.46%.After the addition of urea or melamine,the nitrogen content increased to 4.86%and 6.18%,respectively.Under the condition with ZnCl_(2) as the activator,and without exogenous nitrogen,the nitrogen con-tent of carbon materials was initially 3.75%.However,after adding urea or melamine,the nitrogen content increased to 12.11%and 14.76%,respectively.The carbonaceous materials(prepared from urea/KOH and mel-amine/ZnCl_(2))showed excellent gravimetric capacitances of 172 and 151.5 F/g at 1A/g.Moreover,at a current density of 5 A/g,their specific capacitance retention rate reached 78.3%and 82.6%respectively after 1000 cycles.

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.

A Molecular Foaming and Activation Strategy to Porous N-Doped Carbon Foams for Supercapacitors and CO2 Capture

Hierarchically porous carbon materials are promising for energy storage,separation and catalysis.It is desirable but fairly challenging to simultaneously create ultrahigh surface areas,large pore volumes and high N contents in these materials.Herein,we demonstrate a facile acid-base enabled in situ molecular foaming and activation strategy for the synthesis of hierarchically macro-/meso-/microporous N-doped carbon foams(HPNCFs).The key design for the synthesis is the selection of histidine(His)and potassium bicarbonate(PBC)to allow the formation of 3D foam structures by in situ foaming,the PBC/His acid-base reaction to enable a molecular mixing and subsequent a uniform chemical activation,and the stable imidazole moiety in His to sustain high N contents after carbonization.The formation mechanism of the HPNCFs is studied in detail.The prepared HPNCFs possess 3D macroporous frameworks with thin well-graphitized carbon walls,ultrahigh surface areas(up to 3200 m^2 g^-1),large pore volumes(up to 2.0 cm^3 g^-1),high micropore volumes(up to 0.67 cm^3 g^-1),narrowly distributed micropores and mesopores and high N contents(up to 14.6 wt%)with pyrrolic N as the predominant N site.The HPNCFs are promising for supercapacitors with high specific capacitances(185-240 F g^-1),good rate capability and excellent stability.They are also excellent for CO2 capture with a high adsorption capacity(~4.13 mmol g^-1),a large isosteric heat of adsorption(26.5 kJ mol^-1)and an excellent CO2/N2 selectivity(~24).

An integrated strategy towards the facile synthesis of core-shell SiC-derived carbon@N-doped carbon for high-performance supercapacitors

Porous active core-shell carbon material with excellent synergistic effect has been regarded as a prospective material for supercapacitors.Herein,we report an integrated method for the facile synthesis of carbide-derived carbon(CDC)encapsulated with porous N-doped carbon(CDC@NC)towards highperformance supercapacitors.Polydopamine(PDA)as nitrogen and carbon sources was simply coated on SiC nanospheres to form SiC@PDA,which was then directly transformed into CDC@NC via a onestep molten salt electro-etching/in-situ doping process.The synthesized CDC@NC with hierarchically porous structure has a high specific surface area of 1191 m^(2) g^(-1).The CDC core and NC shell are typical amorphous carbon and more ordered N-doped carbon,respectively.Benefitting from its unique dual porous structures,the CDC@NC demonstrates high specific capacitances of 255 and 193 F g^(-1) at 0.5 and20 A g^(-1),respectively.The reaction mechanism of the electro-etching/in-situ doping process has also been investigated through experimental characterizations and theoretical density functional theory calculations.It is suggested that the molten salt electro-etching/in-situ doping strategy is promising for the synthesis of active core-shell porous carbon materials with synergistic properties for supercapacitors without the need for additional doping/activation processes.

Porous nitrogen-doped carbon/MnO coaxial nanotubes as an efficient sulfur host for lithium sulfur batteries

As a promising candidate for next generation energy storage devices, lithium sulfur (Li-S) batteries still confrant rapid capacity degradation and low rate capability. Herein, we report a well-architected porous nitrogen-doped carbon/MnO coaxial nanotubes (MnO@PNC) as an efficient sulfur host material. The host shows excellent electron conductivity, sufficient ion transport channels and strong adsorption capability for the polysulfides, resulting from the abundant nitrogen-doped sites and pores as well as MnO in the carbon shell of MnO@PNC. The MnO@PNC-S composite electrode with a sulfur content of 75 wt.% deliveries a specific capacity of 802 mAh·g^-1 at a high rate of 5.0C and outstanding cycling stability with a capacity retention of 82% after 520 cycles at 1.0C.

N,P co-doped 3D porous carbon with self-assembled morphological control via template-free method for potassiumion battery anodes

The larger ionic radius of potassium ions than that of lithium ions significantly limits the accomplishment of rapid diffusion kinetics in graphite electrodes for potassium-ion batteries(PIBs),resulting in comparatively poor rate performance and cycle stability.Herein,we report a high-rate performance and cycling stability amorphous carbon electrode achieved through nitrogen and phosphorous co-doping.The as-prepared N,P co-doped carbon electrodes have distinct 3D structures with large surface areas,hierarchical pore architectures,and increased interlayer spaces resulting from the direct pyrolysis of supramolecular self-assembled aggregates without templates.The obtained electrode N3P1 exhibits a reversible specific capacity of 258 m Ah·g^(-1)at a current density of 0.1A·g^(-1)and a good long-term cycle performance(96.1%capacity retention after 800 cycles at 0.5 A·g^(-1)).Kinetic investigations show that the N3P1 electrode with the welldeveloped porous structure and large number of surface defects exhibits capacitive-driven behavior at all scan rates,which may be attributed by N and P co-doping.Ex-situ transmission electron microscopy analyses in the fully discharged and charged states demonstrate structural stability and reversibility owing to the expanded interlayer space.The suggested synthesis approach is simple and effective for producing heteroatom-doped carbon materials for PIBs and other advanced electrochemical energy storage materials.

Highly efficient and selective CO2 electro-reduction with atomic Fe-C-N hybrid coordination on porous carbon nematosphere

Carbon dioxide reduction(CO2RR)has become a promising way to address the energy and environmental crisis,of which the fundamental development of the optimal electrocatalysts is the crucial part.Herein,we develop Fe and N doping porous carb on n ematosphere(FeNPCN)as an excellent CO2RR electrocatalyst in aqueous electrolyte.Featuring with the high conductivity,pore structure and abundant Fe and N doping,FeNPCN exhibits high catalytic activity with a high faradaic selectivity of CO(94%)and long-term durability.Moreover,the ratio of CO and H2 can be changed by the applied potential for the different syngas related industry.Density functional theory(DFT)calculation results also reveal that the excellent catalytic activity is likely attributed to C and N hybrid coordination with atomic Fe.

Porous carbon framework nested nickel foam as freestanding host for high energy lithium sulfur batteries

Constructing 3 D multifunctional conductive framework as stable sulfur cathode contributes to develop advanced lithium-sulfur(Li-S)batteries.Herein,a freestanding electrode with nickel foam framework and nitrogen doped porous carbon(PC)network is presented to encapsulate active sulfur for Li-S batteries.In such a mutually embedded architecture with high stability,the interconnected carbon network and nickel foam matrix can expedite ionic/electro nic tra nsport and sustain volume variations of sulfur.Furthermore,rationally designed porous structures provide sufficient internal space and large surface area for high active sulfur loading and polar polysulfides anchoring.Benefiting from the synergistic superiority,the Ni/PC-S cathode exhibits a high initial capacity of around 1200 mAh/g at 0.2 C,excelle nt rate perfo rmance,and high cycling stability with a low decay rate of 0.059%per cycle after 500 cycles.This work provides a useful strategy to exploit freestanding porous framework for diverse applications.

S-enriched porous polymer derived N-doped porous carbons for electrochemical energy storage and conversion

Porous polymers have been recently recog- nized as one of the most important precursors for fabrication of heteroatom-doped porous carbons due to the intrinsic porous structure, easy available heteroatom- containing monomers and versatile polymerization meth- ods. However, the heteroatom elements in as-produced porous carbons are quite relied on monomers. So far, the manipulating of heteroatom in porous polymer derived porous carbons are still very rare and challenge. In this work, a sulfur-enriched porous polymer, which was prepared from a diacetylene-linked porous polymer, was used as precursor to prepare S-doped and/or N-doped porous carbons under nitrogen and/or ammonia atmo- spheres. Remarkably, S content can sharply decrease from 36.3% to 0.05% after ammonia treatment. The N content and specific surface area of as-fabricated porous carbons can reach up to 1.32% and 1508 m^2·g^-1, respectively. As the electrode materials for electrical double-layer capacitors, as-fabricated porous carbons exhibit high specific capacitance of up to 431.6 F·g^-1 at 5 mW·s^-1 and excellent cycling stability of 99.74% capacitance retention after 3000 cycles at 100 mV·s^-1. Furthermore, as the electro- chemical catalysts for oxygen reduction reaction, as- fabricated porous carbons presented ultralow half-wave- potential of 0.78 V versus RHE. This work not only offers a new strategy for manipulating S and N doping features for the porous carbons derived from S-containing porous polymers, but also paves the way for the structure- performance interrelationship study of heteroatoms co- doped porous carbon for energy applications.

Preparation of nitrogen doped clews-like carbon materials and their application as the electrode in supercapacitor

In this work, nitrogen doped clews-like carbon materials were successfully fabricated through hydrothermal polymerization method, followed by post treatment that integrated the carbonization,activation and post-nitrogen doping into one process. This preparation method can form particular hierarchical porous structure without using any sacrificial templates. The experimental results show that the nitrogen doped clews-like hierarchical porous carbon materials possess a relatively high specific surface area of 815 m^2/g with the nitrogen content of 10.58 at%. The electrochemical properties show that the resulting sample delivers 258 F/g at a 0.5 A/g and excellent capacity retention of 79% at 20 A/g. After conducting 10,000 charge-discharge cycles at 10 A/g, the capacitance retention of 98.3% is achieved.These intriguing results demonstrate that the obtained nitrogen doped clews-like carbon materials will be promising electrode materials for supercapacitor and other energy storage devices.

Scalable synthesis of macroscopic porous carbon sheet anode for potassium-ion capacitor

Carbon materials hold the great promise for application in energy storage devices owing to their low cost, high thermal/chemical stability, and high electrical conductivity. However, it remains challenging to synthesize high-performance carbon electrodes in a simple, scalable and sustainable way. Here, we report a facile method for scalable synthesis of porous carbon anode by using cheap and easily accessible zeolitic imidazolate framework-8 as a template and polyvinylpyrrolidone as an additional carbon source. The obtained porous carbon shows the macroscopic sheet-like morphology, which has the highly disordered structure, expanded interlayer spacing, abundant pore structure, and nitrogen doping properties. This porous carbon anode is demonstrated to have the excellent K^(+) charge storage properties in specific capacity, rate capability, and cycling stability. A potassium-ion capacitor assembled by using this porous carbon as the anode, delivers a maximum energy density of 85.12 Wh/kg and power density of 11860 W/kg as well as long cycle life exceeding 3000 cycles. This represents a critical advance in the design of low cost and scalable carbon material for applications in energy storage devices.

Defect-rich porous tubular graphitic carbon nitride with strong adsorption towards lithium polysulfides for high-performance lithium-sulfur batteries

The commercialization of the lithium-sulfur(Li-S)batteries is severely hampered by the shuttle effect and sluggish kinetics of lithium polysulfides(Li PSs).In this study,porous tubular graphitic carbon nitride(PTCN)was synthesized as the sulfur host by hydrothermal treatment,thermal shock and etching methods.By etching technology,the hollow nanotube tentacles grow on the tube wall of PTCN,the mesoporous appears on the inner wall,and a large number of nitrogen defects are introduced.The verticallyrooted hollow nanotube tentacles on the PTCN surface facilitate electron conduction for sulfur redox reactions.The hollow and porous architecture exposes plentiful active interfaces for accelerated redox conversion of polysulfide.Furthermore,the nitrogen defects in PTCN enable more excellent intrinsic conductivity,higher adsorbability and conversion catalytic activity to Li PSs.Based on the above synergetic effect,the batteries with PTCN/S cathodes realize a high discharge capacity of 504 m Ah g^(-1) at 4 C and a stable cycling behavior over 500 cycles with a low capacity decay of 0.063%per cycle.The results indicate a promising approach todesigning a high performance electrode material for Li-S batteries.

Phenolic Based Porous Carbon Fibers with Superior Surface Area and Adsorption Efficiency for Radioactive Protection

Radioactive iodine element mainly in CH3I is a key fission product of concern in the nuclear fuel cycle,which directly threat-ens human health if released into the environment.Effective capture of the I element is essential for human health protection.The iodine filter,consisting of an activated carbon inner core and cotton filter,is the most common radioactive iodine pro-tection product.Currently,the activated carbon inside the iodine filter suffers from the weak adsorption efficiency and high cost.Herein,a process based on a strong alkali activation method was developed to significantly improve iodine absorption and reduce the cost.A series of flexible porous carbon fibers with a high specific surface area(up to about 1,500~2,200 m^(2)/g)were prepared by carbonation of the phenolic resin fibers(PF,prepared through melt spinning and crosslink)followed by activation via KOH treatment.Meanwhile,the nitrogen-doped sp^(2)-heterogeneous carbon atoms were prepared by add-ing nitrogen sources such as urea which led to a high surface area nano-porous fibers with an average pore size of~2.4 nm.The nitrogen-doped porous carbon fibers exhibit very high adsorption for liquid iodine and iodine vapor.The liquid iodine adsorption capacity of nitrogen-doped porous carbon NDAC-4 prepared under 800°C reaches 2,120 mg/g,which is 2.1 times higher than that of the commercial iodine filter,and for iodine vapor the capacity can reach 5,330 mg/g.Meanwhile,the CH_(3)I adsorption capacity is 510 mg/g,which is 3.4 times higher than that of commercial unmodified viscose fibers and has greater stability and circularity.Importantly,the research has met the requirements of industrial production,and the fabrication of phenolic-fibers-based protection equipment can be widely used in the nuclear radiation industry.

Facile synthesis of Fe single-atom porous photocatalysts via direct metal atomization achieving efficient photocatalytic nitrogen fixation

Photocatalytic nitrogen fixation has been explored as a feasible pathway for ammonia synthesis.How-ever,the convenient and efficient preparation of photocatalysts for nitrogen fixation remains a challenge.Meanwhile,the reaction pathway and mechanism of photocatalytic nitrogen fixation are unclear.Herein,single-atom Fe-porous g-C_(3)N_(4)(FPx)samples were manufactured using a one-step anneal technique via bubble template and direct metal atomization.Characterization results indicate that FPx has a porous structure and single-atom Fe.The porous structure exposed more active centers.Simultaneously,single-atom Fe changes the adsorption mode of N_(2)from physical to chemical and turns the photocatalytic ni-trogen fixation from the associative distal pathway to the associative alternating pathway.Consequently,without any sacrificial agent or cocatalysts,FPx presents a prominent increase in photocatalytic activ-ity,reaching 62.42μmol h^(−1)g^(−1),over fivefold larger than that of bulk g-C_(3)N_(4).This work provides new insights into photocatalytic nitrogen fixation and achieves efficient N_(2)photoreduction by constructing single-atom photocatalysts.

Regeneration of photovoltaic industry silicon waste toward high-performance lithium-ion battery anode

The diamond-wire sawing silicon waste(DWSSW)from the photovoltaic industry has been widely considered as a low-cost raw material for lithium-ion battery silicon-based electrode,but the effect mechanism of impurities presents in DWSSW on lithium storage performance is still not well understood;meanwhile,it is urgent to develop a strategy for changing DWSSW particles into high-performance electrode materials.In this work,the occurrence state of impurities presents in DWSSW was carefully analyzed using in situ Ar ion etching technology Then,the novel Si@C@SiO_(x)@PAl-NDC composite was designed through in situ encapsulation strategy.The obtained Si@C@SiO_(x)@PAl-NDC electrode shows a high first capacity of 2343.4 mAh·g^(-1)with an initial Coulombic efficiency(ICE)of 84.4%under current density of 1.0 A·g^(-1),and can deliver an impressive capacity of 984.9 mAh·g^(-1)after 200 cycles.Combined numerical simulation modeling calculations,the increase in proportion of Si^(4+)/Si^(0)and Si^(3+)/Si^(0)valence states in SiO_(x)layer leads to a decrease in von Mises stress,which ultimately improves the cycling structural stability.Meanwhile,the porous 2D-3D aluminum/nitrogen(Al/N)co-doped carbon layer and nanowires on SiO_(x)layer can provide abundant active sites for lithium storage due to its developed hierarchical pores structure,which facilitates ion transport What is more,the performance of Si@C@SiO_(x)@PAl-NDC//LiFePO_(4)full cell shows its great potential in practical application.

The synergistic catalysis on Co nanoparticles and CoNx sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF

An efficient sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons(Co@NCs) via pyrolysis of aniline-modified ZIFs,has been demonstrated.Aniline can coordinate and absorb on the surface of ZIF(ZIF-CoZn3-PhA),accelerate the precipitation of ZIFs,thus resulting in smaller ZIF particle size.Meanwhile,the aniline on the surface of ZIF-CoZn3-PhA promotes the formation of the protective carbon shell and smaller Co nanoparticles,and increases nitrogen content of the catalyst.Because of these prope rties of Co@NC-PhA-3,the oxidative esterification of 5-hydroxymethylfurfural can be carried out under ambient conditions.According to our experimental and computational results,a synergistic catalytic effect between CoNx sites and Co nanoparticles has been established,in which both Co nanoparticles and CoNx can activate O2 while Co nanoparticles bind and oxidize HMF.Moreover,the formation and release of active oxygen species in CoNx sites are reinfo rced by the electronic interaction between Co nanoparticles and CoNx.