Lignin‐derived carbon with pyridine N‐B doping and a nanosandwich structure for high and stable lithium storage

Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+) diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−) and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1) at 0.05 A g^(−1) and superior stability(96.5% retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+) and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+) migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Synthesis and Crystal Structure of Fe(aapo)_2Cl_3(aapo=2-Acetylamino Pyridine N-Oxide)

The complex Fe(aapo)2Cl3 with chemical formula C14H16Cl3FeN4O4 was obtained by the reaction of FeCl36H2O with apoHCl (apo = 2璦mino pyridine N璷xide) in acetonitrile. The result shows that CH3CN has been hydrolysised with the water from FeCl36H2O dissolving, and then the hydrolysised product condenses with apo to give aapo. A single-crystal X璻ay study of Fe(aapo)2Cl3 shows it belongs to the monoclinic system, space group C2/c with a = 15.873(3), b = 10.322(2), c = 11.987(2) ? b = 106.35(1), V = 1884.5(6) 3, Z = 4, Mr = 466.51, Dc = 1.644 g/cm3, m(MoKa) = 1.253 mm-1, F(000) = 948, R = 0.0377 and wR = 0.0749 for 1262 observed reflections with I > 2(I). Fe (Ⅲ) is coordinated by a trigonal bipyramidal geometry with three chlorine atoms lying on the equatorial plane and two oxygen atoms connected with the nitrogen atoms of pyridine rings occupying the axial positions, while the iron and Cl(1) atoms lie on the crystallographic 2-fold axis. The dihedral angle of two pyridine rings is 71.74(9). There exist N(2)H(2)…O(1)?hydrogen bonds in the crystal structure.

In-situ preparation of TiO_(2)/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO_(2) reduction performance

Photocatalytic CO_(2)conversion efficiency is hampered by the rapid recombination of photogenerated charge carriers.It is effective to suppress the recombination by constructing cocatalysts on photocatalysts with high-quality interfacial contact.Herein,we develop a novel strategy to in-situ grow ultrathin/V-doped graphene(NG)layer on TiO_(2) hollow spheres(HS) with large area and intimate interfacial contact via a chemical vapor deposition(CVD).The optimized TiO^(2)/NG HS nanocomposite achieves total CO_(2)conversion rates(the sum yield of CO,CH_(3)OH and CH_(4))of 18.11μmol·g^(-1)h^(-1),which is about 4.6 times higher than blank T1O_(2)HS.Experimental results demonstrate that intimate interfacial contact and abundant pyridinic N sites can effectively facilitate photogenerated charge carrier separation and transport,realizing enhanced photocatalytic CO_(2)reduction performance.In addition,this work provides an effective strategy for in-situ construction of graphene-based photocatalysts for highly efficient photocatalytic CO_(2)conversion.

Designing g-C_(3)N_(4)/N-Rich Carbon Fiber Composites for High-Performance Potassium-Ion Hybrid Capacitors

Potassium-based energy storage devices(PEDS)are considered as hopeful candidates for energy storage applications because of the abundant potassium resources in nature and high mobility in the electrolyte.although carbon materials show great potential for potassium-ion storage,poor rate performance,and unsatisfactory cycle lifespan in existing carbon-based PIBs anode,it also cannot match the dynamics and stability of the capacitor cathode.Nitrogen doping has been proven to be a effective modification strategy to improve the electrochemical performance of carbon materials.Hence,we prepare carbon nanofibers and g-C_(3)N_(4)composites with high nitrogen contents(19.78 at%);moreover,the sum of pyrrolic N and pyridinic N is up to 59.51%.It achieves high discharge capacity(391 m Ah g^(-1)at0.05 A g^(-1)),rate capacity(141 m Ah g^(-1)at 2 A g^(-1)),and long cycling performance(201 m Ah g^(-1)at 1 A g^(-1)over 3000 cycles)when as an anode for PIBs.Furthermore,it can deliver promising discharge capacity of132 m Ah g^(-1)at 0℃.Moreover,as battery anode for potassium-ion hybrid capacitors(PIHC)device with an active carbon cathode,it delivers energy/power density(62 and 2102 W kg^(-1))as well as high reversible capacity(106 m Ah g^(-1)at 1 A g^(-1)).

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.

Peroxymonosulfate activation by Fe-N-S co-doped tremella-like carbocatalyst for degradation of bisphenol A: Synergistic effect of pyridine N, Fe-Nx, thiophene S

Bisphenol A(BPA)has received increasing attention due to its long-term industrial application and persistence in environmental pollution.Iron-based carbon catalyst activation of peroxymonosulfate(PMS)shows a good prospect for effective elimination of recalcitrant contaminants in water.Herein,considering the problem about the leaching of iron ions and the optimization of heteroatoms doping,the iron,nitrogen and sulfur co-doped tremellalike carbon catalyst(Fe-NS@C)was rationally designed using very little iron,S-C_(3)N_(4) and low-cost chitosan(CS)via the impregnation-calcination method.The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA(20 mg/L)by activating PMS with the high kinetic constant(1.492 min^(−1))in 15 min.Besides,the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference,but also maintained an excellent degradation efficiency on different pollutants.Impressively,increased S-C_(3)N_(4) doping amount modulated the contents of different N species in Fe-NS@C,and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing SC_(3)N_(4) contents,verifying pyridine N and Fe-Nx as main active sites in the system.Meanwhile,thiophene sulfur(C-S-C)as active sites played an auxiliary role.Furthermore,quenching experiment,EPR analysis and electrochemical test proved that surface-bound radicals(·OH and SO_(4)^(·−))and non-radical pathways worked in the BPA degradation(the former played a dominant role).Finally,possible BPA degradation route were proposed.This work provided a promising way to synthesize the novel Fe,N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.

New insight into the synergy of nitrogen-related sites on biochar surface for sulfamethoxazole adsorption from water

In-depth exploration of the relationship among different adsorption sites is conducive to design of efficient adsorbents for target pollutants removal from water.In this study,the experiments,multivariate non-linear regression and density functional theory calculations are applied to explore the possible synergistic effects of three nitrogen(N)-containing sites on cow dung biochar surface for sulfamethoxazole(SMX)adsorption.Notably,a strong synergistic effect between pyridinic N and pyrrolic N sites was found for sulfamethoxazole adsorption.The adsorption energies of SMX on four pyrrolic N-coupled pyridinic N structures were-1.02,-0.41,-0.49 and-0.72 e V,much higher than the sum of adsorption energies(-0.31 e V)on pyrrolic N and pyridinic N.Besides,the alteration of Mulliken charge revealed that the simultaneous presence of pyridinic N and pyrrolic N improved the electron transfer remarkably from-0.459 e and 0.094 e to-0.649 e and 0.186 e,benefiting for SMX adsorption.This work firstly explored the possible synergies of adsorption sites on biochar surface for organic contaminants removal from water,which shed new lights on the adsorption mechanism and provided valuable information to design efficient adsorbents in the field of water treatment.

NH_(4)Cl-assisted preparation of single Ni sites anchored carbon nanosheet catalysts for highly efficient carbon dioxide electroreduction

Single-atomic transition metal-nitrogen codoped carbon(M-N-C)are efficient substitute catalysts for noble metals to catalyze the electrochemical CO_(2) reduction reaction(CO_(2)RR).However,the uncontrolled aggregations of metal and serious loss of nitrogen species constituting the M-N_(x) active sites are frequently observed in the commonly used pyrolysis procedure.Herein,single-atomic nickel(Ni)-based sheet-like electrocatalysts with abundant Ni-N_(4) active sites were created by using a novel ammonium chloride(NH_(4)Cl)-assited pyrolysis method.Spherical aberration correction electron microscopy and X-ray absorption fine structure analysis clearly revealed that Ni species are atomically dispersed and anchored by N in Ni-N_(4) structure.The addition of NH_(4)Cl optimized the mesopore size to 7-10 nm and increased the concentrations of pyridinic N(3.54 wt%)and Ni-N_(4)(3.33 wt%)species.The synergistic catalytic effect derived from Ni-N_(4) active sites and pyridinic N species achieved an outstanding CO_(2) RR performance,presenting a high CO Faradaic efficiency(FE_(CO))up to 98% and a large CO partial current density of 8.5 mA cm^(-2) at a low potential of-0.62 V vs.RHE.Particularly,the FE_(CO) maintains above 80% within a large potential range from -0.43 to -0.73 V vs.RHE.This work provides a practical and feasible approach to building highly active single-atomic catalysts for CO_(2) conversion systems.

Activating multisite high-entropy alloy nanocrystals via enriching M–pyridinic N–C bonds for superior electrocatalytic hydrogen evolution

The activation of multisite high-entropy alloy(HEA)electrocatalysts is helpful for improving the atomic utilization of each metal in water electrolysis catalysis.Herein,well-dispersed HEA nanocrystals on Nrich graphene with abundant M–pyridinic N–C bonds were synthesized through an ultrasonic-assisted confinement synthesis method.Operando Raman analysis and density functional theory calculations revealed that the electrocatalysts presented the optimal electronic rearrangement with fast ratedetermined H_(2)O dissociation kinetics and favorable H^(*)adsorption behavior that greatly enhanced hydrogen generation in alkaline electrolyte.A small overpotential of only 138.6 mV was required to obtain the current density of 100 mA cm^(-2) and the Tafel slope of as low as 33.0 mV dec^(-1),which was considerably smaller than the overpotentials of the counterpart with poor M–pyridinic N–C bonds(290.4 mV)and commercial Pt/C electrocatalysts(168.6 mV).The atomic structure,coordination environment,and electronic structure were clarified.This work provides a new avenue toward activating HEA as advanced electrocatalysts and promotes the research on HEA for energy-related electrolysis.