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...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.展开更多
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 applicatio...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.展开更多
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 nanoparticle...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.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-it...Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.展开更多
This study proposed an improved bio-carbonation of reactive magnesia cement(RMC)method for dredged sludge stabilization using the urea pre-hydrolysis strategy.Based on unconfined compression strength(UCS),pickling-dra...This study proposed an improved bio-carbonation of reactive magnesia cement(RMC)method for dredged sludge stabilization using the urea pre-hydrolysis strategy.Based on unconfined compression strength(UCS),pickling-drainage,and scanning electron microscopy(SEM)tests,the effects of prehydrolysis duration(T),urease activity(UA)and curing age(CA)on the mechanical properties and microstructural characteristics of bio-carbonized samples were systematically investigated and analyzed.The results demonstrated that the proposed method could significantly enhance urea hydrolysis and RMC bio-carbonation to achieve efficient stabilization of dredged sludge with 80%high water content.A significant strength increment of up to about 1063.36 kPa was obtained for the bio-carbonized samples after just 7 d of curing,which was 2.64 times higher than that of the 28-day cured ordinary Portland cement-reinforced samples.Both elevated T and UA could notably increase urea utilization ratio and carbonate ion yield,but the resulting surge in supersaturation also affected the precipitation patterns of hydrated magnesia carbonates(HMCs),which weakened the cementation effect of HMCs on soil particles and further inhibited strength enhancement of bio-carbonized samples.The optimum formula was determined to be the case of T?24 h and UA?10 U/mL for dredged sludge stabilization.A 7-day CA was enough for bio-carbonized samples to obtain stable strength,albeit slightly affected by UA.The benefits of high efficiency and water stability presented the potential of this method in achieving dredged sludge stabilization and resource utilization.This investigation provides informative ideas and valuable insights on implementing advanced bio-geotechnical techniques to achieve efficient stabilization of soft soil,such as dredged sludge.展开更多
Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently req...Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently required.Herein,utilizing the low boiling point of Zn,porous N-doped carbon was fabricated by carbonization of ZIF-8(Zn)at different temperature,and the microwave absorption performance was investigated.The porous N-doped carbon inherits the high porosity of ZIF-8 precursor.By increasing the carbonization temperature,the contents of Zn and N elements are decreased;the graphitization degree is improved;however,the specific surface area and porosity are increased first and then decreased.When the carbonization temperature is 1000°C,the porous N-doped carbon behaves enhanced microwave absorption.With an ultrathin thickness of 1.29 mm,the ideal RL reaches-50.57 dB at 16.95 GHz and the effective absorption bandwidth is 4.17 GHz.The mechanism of boosted microwave absorption is ascribed to the competition of graphitization and porosity as well as N dopants,resulting in high dielectric loss capacity and good impedance matching.The porous structure can prolong the pathways and raise the contact opportunity between microwaves and porous carbon,causing multiple scattering,interface polarization,and improved impedance matching.Besides,the N dopants can induce electron polarization and defect polarization.These results give a new insight to construct lightweight carbon-based microwave absorbents by regulating the graphitization and porosity.展开更多
N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial ...N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial Coulombic efficiency(ICE).In this study,high N-doped and low graphitic-N carbons(LGNCs)with enhanced ICE were synthesized by taking advantage of a denitrification strategy for graphitic carbon nitride(g-C_(3)N_(4)).In brief,more than 14.5 at%of N from g-C_(3)N_(4)(55.1 at%N)was retained by reacting graphitic-N with lithium,which was subsequently removed.As graphitic-N is largely responsible for the irreversible capacity,the anode's performance was significantly increased.Compared to general N-doped carbons with high graphitic-N proportion(>50%)and low N content(<15 at%),LGNCs delivered a low proportion of 10.8%-17.2% within the high N-doping content of 14.5-42.7 at%,leading to an enhanced specific capacity of 1499.9mAh g^(-1) at an ICE of 93.7% for the optimal sample of LGNC(4:1).This study provides a facile strategy to control the N content and speciation,achieving both high Li+storage capacity and high ICE,and thus promoting research and application of N-doped carbon materials.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocataly...Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocatalysts, but it remains one challenge to finely engineer the active sites and porosity. Herein, we demonstrated that ionic porous polyamides were a kind of versatile precursors to prepare functional carbon materials in a one-step pyrolysis process. The polyamide precursors allowed the maintenance of abundant N species at high temperatures. The existence of ionic moieties and large specific surface area of the precursors promoted the formation of larger porosity carbon with a large specific surface area and sufficient active graphitic-N species by controlling the pyrolysis temperature. The catalyst was highly selective in the CO_(2) RR to produce CO with a maximum Faraday efficiency above 99%, attributable to the improved mass transfer in a large porosity system. This work shows that ionic polyamides are promising carbon precursors for the fabrication of metal-free electrocatalysts for CO_(2) RR.展开更多
Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especial...Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.展开更多
An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and ...An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and stirring at 70°C for 14 h.The morphology and structure of the rGO-like carbon were investigated by electron microscopies and Raman spectroscopy.The presence of C-N functional groups was analyzed by Fourier transform infrared and synchrotron X-ray photoemission spectroscopy,while the particle and the specific capacitance were measured by particle sizer and cyclic voltammetry.The highest specific capacitance of 72.78 F/g is achieved by the sample with 20%urea,having the smallest particles size and the largest surface area.The corresponding sample has shown to be constituted by the appropriate amount of C–N pyrrolic and pyridinic defects.展开更多
Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings th...Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.展开更多
Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated str...Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated strategy to anchor Co species on N-doped carbon nanorods for efficient ORR.Featuring ultrahigh N-doping(10.29 at.%),monodisperse Co nanocrystal decoration,and well-dispersed Co-N_(x)functionalization,the obtained Co-decorated N-doped carbon nanorods(Co@NCNR)exhibit a decent ORR performance comparable to commercial Pt/C in alkaline media.Aqueous ZABs have been assembled using Co@NCNR as the cathode catalyst.The assembled ZABs manifest high initial open-circuit voltage as well as high energy density.In addition,the Co@NCNR also demonstrates ideal ORR performance in quasi-solid-state ZABs.展开更多
In this study,hydrogels were prepared from municipal sludge to recycle and realize the value-added utilization of the carbon components in this abundant waste material.The carbon sources were extracted from the munici...In this study,hydrogels were prepared from municipal sludge to recycle and realize the value-added utilization of the carbon components in this abundant waste material.The carbon sources were extracted from the municipal sludge using synthesised nano CaO_(2)as an oxidant,and the carbon sources were graft copolymerised with acrylic acid monomer using N,N′-methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator.The factors influencing the hydrogel preparation were investigated by single-factor experiments.Based on the results of the single-factor experiments,a hydrogel with a swelling ratio of up to 19768.4%at 12 h was prepared with an oxidant dosage of 0.20 g,a monomer dosage of 5.8 g,a neutralisation degree of the monomer of 70%,an initiator dosage of 0.15 g,and a crosslinking agent dosage of 0.15 g.The hydrogel preparation conditions were optimized using the response surface method,and the interactions between the different reaction conditions were analysed to obtain the best preparation conditions.X-ray diffraction results showed that hydrogels were amorphous in structure.Scanning electron microscopy images showed that the SiO_(2)particles from the sludge acted as crosslinking points between different layers of hydrogel chains.The crosslinking polymerisation and crosslinking agent worked together to form hydrogels with an inorganic-organic double network structure,and this structure was highly stretchable,resulting in hydrogels with good swelling properties.展开更多
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...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.展开更多
Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water...Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.展开更多
Nitrogen‐doped ordered mesoporous carbon (N‐OMC) catalysts were directly synthesized using SBA‐15 as a hard template and sucrose as a carbon source. Urea, which was used as the nitrogen source, was carbonized wit...Nitrogen‐doped ordered mesoporous carbon (N‐OMC) catalysts were directly synthesized using SBA‐15 as a hard template and sucrose as a carbon source. Urea, which was used as the nitrogen source, was carbonized with sucrose. A 3.6 wt% nitrogen doping of the carbon framework was achieved, with more than 70%of the nitrogen incorporated as quaternary nitrogen species. Only 0.2 wt% nitrogen doping, with only 32.7% quaternary nitrogen incorporation was obtained in an N‐OMC catalyst (N‐OMC‐T) prepared using a two‐step post‐synthesis method. The acetylene hy‐drochlorination activities of N‐OMC catalysts prepared via the one‐step method were higher than that of the N‐OMC‐T catalyst because of the higher nitrogen loadings.展开更多
Due to the advantages of high surface areas, large pore volumes and pore sizes, abundant nitrogen content that favored the metal-support interactions, N-doped ordered mesoporous carbons are regarded as a kind ...Due to the advantages of high surface areas, large pore volumes and pore sizes, abundant nitrogen content that favored the metal-support interactions, N-doped ordered mesoporous carbons are regarded as a kind of fascinating and potential support for the synthesis of effective supported cat-alysts. Here, a N-doped ordered mesoporous carbon with a high N content (9.58 wt%), high surface area (417 m^2/g), and three-dimensional cubic structure was synthesized successfully and used as an effective support for immobilizing Pt nanoparticles (NPs). The positive effects of nitrogen on the metal particle size enabled ultrasmall Pt NPs (about 1.0 ± 0.5 nm) to be obtained. Moreover, most of the Pt NPs are homogeneously dispersed in the mesoporous channels. However, using the ordered mesoporous carbon without nitrogen as support, the particles were larger (4.4 ± 1.7 nm) and many Pt NPs were distributed on the external surface, demonstrating the important role of the nitrogen species. The obtained N-doped ordered mesoporous material supported catalyst showed excellent catalytic activity (conversion 100%) and selectivity (〉99%) in the hydrogenation of halogenated nitrobenzenes under mild conditions. These values are much higher than those achieved using a commercial Pt/C catalyst (conversion 89% and selectivity 90%). This outstanding catalytic perfor-mance can be attributed to the synergetic effects of the mesoporous structure, N-functionalized support, and stabilized ultrasmall Pt NPs. Moreover, such supported catalyst also showed excellent catalytic performance in the hydrogenation of other halogenated nitrobenzenes and nitroarenes. In addition, the stability of the multifunctional catalyst was excellent and it could be reused more than 10 times without significant losses of activity and selectivity. Our results conclusively show that a N-doped carbon support enable the formation of ultrafine metal NPs and improve the reaction ac-tivity and selectivity.展开更多
Activated sludge process has been widely used to remove phosphorus and nitrogen from wastewater. However,the nitrogen and phosphorus removal is sometimes unsatisfactory due to the low influent COD.Another problem with...Activated sludge process has been widely used to remove phosphorus and nitrogen from wastewater. However,the nitrogen and phosphorus removal is sometimes unsatisfactory due to the low influent COD.Another problem with the activated sludge process is that large amount of waste activated sludge is produced,which needs further treatment.In this study,the waste activated sludge alkaline fermentation liquid was used as the main carbon source for phosphorus and nitrogen removal under anaerobic followed by alternating aerobic-anoxic conditions,and the results were compared with those using acetic acid as the carbon source.The use of alkaline fermentation liquid not only affected the transformations of phosphorus,nitrogen,intracellular polyhydroxyalkanoates and glycogen, but also led to higher removal efficiencies for phosphorus and nitrogen compared with acetic acid.It was observed that ammonium was completely removed with either alkaline fermentation liquid or acetic acid as the carbon source. However,the former resulted in higher removal efficiencies for phosphorus(95%)and nitrogen(82%),while the latter showed lower ones(87%and 74%,respectively).The presence of a large amount of propionic acid in the alkaline fermentation liquid was one possible reason for its higher phosphorus removal efficiency.Exogenous instead of endogenous denitrification was the main pathway for nitrogen removal with the alkaline fermentation liquid as the carbon source,which was responsible for its higher nitrogen removal efficiency.It seems that the alkaline fermentation liquid can replace acetic acid as the carbon source for phosphorus and nitrogen removal in anaerobic fol- lowed by alternating aerobic-anoxic sequencing batch reactor.展开更多
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...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.展开更多
基金support from the Natural Science Foundation of Jilin Province(Grant No.20200201073JC)the National Natural Science Foundation of China(Grant No.52130101)+1 种基金Interdisciplinary Integration and Innovation Project of JLU(Grant No.JLUXKJC2021ZY01)the Fundamental Research Funds for the Central Universities.
文摘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.
文摘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.
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘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.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
基金supported by the National Natural Science Foundation of China (21878340)supported in part by the High-Performance Computing Center of Central South University
文摘Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.41925012 and 42230710)the Key Laboratory Cooperation Special Project of Western Cross Team of Western Light,CAS(Grant No.xbzg-zdsys-202107).
文摘This study proposed an improved bio-carbonation of reactive magnesia cement(RMC)method for dredged sludge stabilization using the urea pre-hydrolysis strategy.Based on unconfined compression strength(UCS),pickling-drainage,and scanning electron microscopy(SEM)tests,the effects of prehydrolysis duration(T),urease activity(UA)and curing age(CA)on the mechanical properties and microstructural characteristics of bio-carbonized samples were systematically investigated and analyzed.The results demonstrated that the proposed method could significantly enhance urea hydrolysis and RMC bio-carbonation to achieve efficient stabilization of dredged sludge with 80%high water content.A significant strength increment of up to about 1063.36 kPa was obtained for the bio-carbonized samples after just 7 d of curing,which was 2.64 times higher than that of the 28-day cured ordinary Portland cement-reinforced samples.Both elevated T and UA could notably increase urea utilization ratio and carbonate ion yield,but the resulting surge in supersaturation also affected the precipitation patterns of hydrated magnesia carbonates(HMCs),which weakened the cementation effect of HMCs on soil particles and further inhibited strength enhancement of bio-carbonized samples.The optimum formula was determined to be the case of T?24 h and UA?10 U/mL for dredged sludge stabilization.A 7-day CA was enough for bio-carbonized samples to obtain stable strength,albeit slightly affected by UA.The benefits of high efficiency and water stability presented the potential of this method in achieving dredged sludge stabilization and resource utilization.This investigation provides informative ideas and valuable insights on implementing advanced bio-geotechnical techniques to achieve efficient stabilization of soft soil,such as dredged sludge.
基金financially supported by National Natural Science Foundation of China(Nos.51572218 and 11504293)Natural Science Foundation of Shaanxi Province(No.2019JM-138)+1 种基金Natural Science Foundation from Department of Science and Technology of Shaanxi Province(Nos.2021JQ-431,2021JM-304,and 2021JQ-427)Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0946)。
文摘Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently required.Herein,utilizing the low boiling point of Zn,porous N-doped carbon was fabricated by carbonization of ZIF-8(Zn)at different temperature,and the microwave absorption performance was investigated.The porous N-doped carbon inherits the high porosity of ZIF-8 precursor.By increasing the carbonization temperature,the contents of Zn and N elements are decreased;the graphitization degree is improved;however,the specific surface area and porosity are increased first and then decreased.When the carbonization temperature is 1000°C,the porous N-doped carbon behaves enhanced microwave absorption.With an ultrathin thickness of 1.29 mm,the ideal RL reaches-50.57 dB at 16.95 GHz and the effective absorption bandwidth is 4.17 GHz.The mechanism of boosted microwave absorption is ascribed to the competition of graphitization and porosity as well as N dopants,resulting in high dielectric loss capacity and good impedance matching.The porous structure can prolong the pathways and raise the contact opportunity between microwaves and porous carbon,causing multiple scattering,interface polarization,and improved impedance matching.Besides,the N dopants can induce electron polarization and defect polarization.These results give a new insight to construct lightweight carbon-based microwave absorbents by regulating the graphitization and porosity.
基金National Natural Science Foundation of China,Grant/Award Number:51777138Deutsche Forschungsgemeinschaft(DFG,German Research Foundation),Grant/Award Number:491183248Open Access Publishing Fund of the University of Bayreuth。
文摘N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial Coulombic efficiency(ICE).In this study,high N-doped and low graphitic-N carbons(LGNCs)with enhanced ICE were synthesized by taking advantage of a denitrification strategy for graphitic carbon nitride(g-C_(3)N_(4)).In brief,more than 14.5 at%of N from g-C_(3)N_(4)(55.1 at%N)was retained by reacting graphitic-N with lithium,which was subsequently removed.As graphitic-N is largely responsible for the irreversible capacity,the anode's performance was significantly increased.Compared to general N-doped carbons with high graphitic-N proportion(>50%)and low N content(<15 at%),LGNCs delivered a low proportion of 10.8%-17.2% within the high N-doping content of 14.5-42.7 at%,leading to an enhanced specific capacity of 1499.9mAh g^(-1) at an ICE of 93.7% for the optimal sample of LGNC(4:1).This study provides a facile strategy to control the N content and speciation,achieving both high Li+storage capacity and high ICE,and thus promoting research and application of N-doped carbon materials.
基金support from the National Natural Science Foundation of China ( 22072065, 22178162, U1662107, and 21476109)Six talent peaks project in Jiangsu Province (JNHB-035)+1 种基金State Key Laboratory of Materials-Oriented Chemical Engineering (KL18-09)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocatalysts, but it remains one challenge to finely engineer the active sites and porosity. Herein, we demonstrated that ionic porous polyamides were a kind of versatile precursors to prepare functional carbon materials in a one-step pyrolysis process. The polyamide precursors allowed the maintenance of abundant N species at high temperatures. The existence of ionic moieties and large specific surface area of the precursors promoted the formation of larger porosity carbon with a large specific surface area and sufficient active graphitic-N species by controlling the pyrolysis temperature. The catalyst was highly selective in the CO_(2) RR to produce CO with a maximum Faraday efficiency above 99%, attributable to the improved mass transfer in a large porosity system. This work shows that ionic polyamides are promising carbon precursors for the fabrication of metal-free electrocatalysts for CO_(2) RR.
基金supported by National Natural Science Foundation of China(Nos.U20A20246,51872108)the Fundamental Research Funds for the Central Universities(Nos.30106200463 and CCNU20TS006)Graduate Education Innovation Grant from Central China Normal University(No.2020CXZZ101).
文摘Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.
基金supported by“Hibah Penelitian Dasar Kompetitif Nasional”,Ministry of Education,Culture,Research and Technology,Indonesia,2021–2022(D).The use of the synchrotron XPES facility at SLRI(Public Organization),Thailand,and some experimental facilities at UNIMAP and UPM,Malaysia,would also be appreciated.
文摘An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and stirring at 70°C for 14 h.The morphology and structure of the rGO-like carbon were investigated by electron microscopies and Raman spectroscopy.The presence of C-N functional groups was analyzed by Fourier transform infrared and synchrotron X-ray photoemission spectroscopy,while the particle and the specific capacitance were measured by particle sizer and cyclic voltammetry.The highest specific capacitance of 72.78 F/g is achieved by the sample with 20%urea,having the smallest particles size and the largest surface area.The corresponding sample has shown to be constituted by the appropriate amount of C–N pyrrolic and pyridinic defects.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51803151,51973152,51773147,52173078,52130303,51973158)the State Key Program of National Natural Science Foundation of China(No.51633007)the Seed Foundation of Tianjin University(No.2105018).
文摘Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.
基金supported by the National Natural Science Foundation of China(52072283)the National Key Research and Development Program of China(2020YFA0715000)+1 种基金Shenzhen Fundamental Research Program(JCYJ20190809114409397)supported by the Fundamental Research Funds for the Central Universities(WUT:2021III016GX).
文摘Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated strategy to anchor Co species on N-doped carbon nanorods for efficient ORR.Featuring ultrahigh N-doping(10.29 at.%),monodisperse Co nanocrystal decoration,and well-dispersed Co-N_(x)functionalization,the obtained Co-decorated N-doped carbon nanorods(Co@NCNR)exhibit a decent ORR performance comparable to commercial Pt/C in alkaline media.Aqueous ZABs have been assembled using Co@NCNR as the cathode catalyst.The assembled ZABs manifest high initial open-circuit voltage as well as high energy density.In addition,the Co@NCNR also demonstrates ideal ORR performance in quasi-solid-state ZABs.
基金support from the National Visiting Scholar Program for Key Young Teachers of Central and Western Universities,the Ministry of Education(19042)the Key Science and Technology Project of Henan Province(212102310064)the National Innovation and the Entrepreneurship Training Program for College Students,Ministry of Education(202111517002).
文摘In this study,hydrogels were prepared from municipal sludge to recycle and realize the value-added utilization of the carbon components in this abundant waste material.The carbon sources were extracted from the municipal sludge using synthesised nano CaO_(2)as an oxidant,and the carbon sources were graft copolymerised with acrylic acid monomer using N,N′-methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator.The factors influencing the hydrogel preparation were investigated by single-factor experiments.Based on the results of the single-factor experiments,a hydrogel with a swelling ratio of up to 19768.4%at 12 h was prepared with an oxidant dosage of 0.20 g,a monomer dosage of 5.8 g,a neutralisation degree of the monomer of 70%,an initiator dosage of 0.15 g,and a crosslinking agent dosage of 0.15 g.The hydrogel preparation conditions were optimized using the response surface method,and the interactions between the different reaction conditions were analysed to obtain the best preparation conditions.X-ray diffraction results showed that hydrogels were amorphous in structure.Scanning electron microscopy images showed that the SiO_(2)particles from the sludge acted as crosslinking points between different layers of hydrogel chains.The crosslinking polymerisation and crosslinking agent worked together to form hydrogels with an inorganic-organic double network structure,and this structure was highly stretchable,resulting in hydrogels with good swelling properties.
基金supported by the National Science Foundation of China(21805235)the Opening Foundation of Creative Platform of the Key Laboratory of the Education Department of Hunan Province(20K131)the Construct Program of the Key Discipline in Hunan Province。
文摘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.
基金the National Natural Science Foundation of China(Nos.52072151,52171211,52102253,52271218,U22A20145)the Jinan Independent Innovative Team(2020GXRC015)+1 种基金the Major Program of Shandong Province Natural Science Foundation(ZR2021ZD05)the Science and Technology Program of University of Jinan(XKY2119).
文摘Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.
基金supported by the National Natural Science Foundation of China (20803064)the Natural Science Foundation of Zhejiang Province (Y4090348)~~
文摘Nitrogen‐doped ordered mesoporous carbon (N‐OMC) catalysts were directly synthesized using SBA‐15 as a hard template and sucrose as a carbon source. Urea, which was used as the nitrogen source, was carbonized with sucrose. A 3.6 wt% nitrogen doping of the carbon framework was achieved, with more than 70%of the nitrogen incorporated as quaternary nitrogen species. Only 0.2 wt% nitrogen doping, with only 32.7% quaternary nitrogen incorporation was obtained in an N‐OMC catalyst (N‐OMC‐T) prepared using a two‐step post‐synthesis method. The acetylene hy‐drochlorination activities of N‐OMC catalysts prepared via the one‐step method were higher than that of the N‐OMC‐T catalyst because of the higher nitrogen loadings.
基金supported by the National Natural Science Foundation of China(201573136,U1510105)the Scientific Research Start-up Funds of Shanxi University(RSC723)~~
文摘Due to the advantages of high surface areas, large pore volumes and pore sizes, abundant nitrogen content that favored the metal-support interactions, N-doped ordered mesoporous carbons are regarded as a kind of fascinating and potential support for the synthesis of effective supported cat-alysts. Here, a N-doped ordered mesoporous carbon with a high N content (9.58 wt%), high surface area (417 m^2/g), and three-dimensional cubic structure was synthesized successfully and used as an effective support for immobilizing Pt nanoparticles (NPs). The positive effects of nitrogen on the metal particle size enabled ultrasmall Pt NPs (about 1.0 ± 0.5 nm) to be obtained. Moreover, most of the Pt NPs are homogeneously dispersed in the mesoporous channels. However, using the ordered mesoporous carbon without nitrogen as support, the particles were larger (4.4 ± 1.7 nm) and many Pt NPs were distributed on the external surface, demonstrating the important role of the nitrogen species. The obtained N-doped ordered mesoporous material supported catalyst showed excellent catalytic activity (conversion 100%) and selectivity (〉99%) in the hydrogenation of halogenated nitrobenzenes under mild conditions. These values are much higher than those achieved using a commercial Pt/C catalyst (conversion 89% and selectivity 90%). This outstanding catalytic perfor-mance can be attributed to the synergetic effects of the mesoporous structure, N-functionalized support, and stabilized ultrasmall Pt NPs. Moreover, such supported catalyst also showed excellent catalytic performance in the hydrogenation of other halogenated nitrobenzenes and nitroarenes. In addition, the stability of the multifunctional catalyst was excellent and it could be reused more than 10 times without significant losses of activity and selectivity. Our results conclusively show that a N-doped carbon support enable the formation of ultrafine metal NPs and improve the reaction ac-tivity and selectivity.
基金Supported by the National High Technology Research and Development Program of China(2007AA06Z326)the Programfor New Century Excellent Talents(06-0373)in University
文摘Activated sludge process has been widely used to remove phosphorus and nitrogen from wastewater. However,the nitrogen and phosphorus removal is sometimes unsatisfactory due to the low influent COD.Another problem with the activated sludge process is that large amount of waste activated sludge is produced,which needs further treatment.In this study,the waste activated sludge alkaline fermentation liquid was used as the main carbon source for phosphorus and nitrogen removal under anaerobic followed by alternating aerobic-anoxic conditions,and the results were compared with those using acetic acid as the carbon source.The use of alkaline fermentation liquid not only affected the transformations of phosphorus,nitrogen,intracellular polyhydroxyalkanoates and glycogen, but also led to higher removal efficiencies for phosphorus and nitrogen compared with acetic acid.It was observed that ammonium was completely removed with either alkaline fermentation liquid or acetic acid as the carbon source. However,the former resulted in higher removal efficiencies for phosphorus(95%)and nitrogen(82%),while the latter showed lower ones(87%and 74%,respectively).The presence of a large amount of propionic acid in the alkaline fermentation liquid was one possible reason for its higher phosphorus removal efficiency.Exogenous instead of endogenous denitrification was the main pathway for nitrogen removal with the alkaline fermentation liquid as the carbon source,which was responsible for its higher nitrogen removal efficiency.It seems that the alkaline fermentation liquid can replace acetic acid as the carbon source for phosphorus and nitrogen removal in anaerobic fol- lowed by alternating aerobic-anoxic sequencing batch reactor.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21965034,21703185,U1903217,51901013,and 21666037)the Xinjiang Autonomous Region Major Projects(2017A02004)+4 种基金the Leading Project Foundation of Science Department of Fujian Province(Grant No.2018H0034)the Resource Sharing Platform Construction Project of Xinjiang Province(PT1909)the Nature Science Foundation of Xinjiang Province(2017D01C074)the Opening Project of National Joint Engineering Research Center for Abrasion Control and Molding of Metal Materials,Henan University of Science and Technology(No.HKDNM201906)the Young Scholar Science Foundation of Xinjiang Educational Institutions(XJEDU2016S030)。
文摘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.