For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However...For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).展开更多
Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this ...Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.展开更多
CO_(2) electrolysis with solid oxide electrolytic cells(SOECs)using intermittently available renewable energy has potential applications for carbon neutrality and energy storage.In this study,a pulsed current strategy...CO_(2) electrolysis with solid oxide electrolytic cells(SOECs)using intermittently available renewable energy has potential applications for carbon neutrality and energy storage.In this study,a pulsed current strategy is used to replicate intermittent energy availability,and the stability and conversion rate of the cyclic operation by a large-scale flat-tube SOEC are studied.One hundred cycles under pulsed current ranging from -100 to -300 mA/cm^(2) with a total operating time of about 800 h were carried out.The results show that after 100 cycles,the cell voltage attenuates by 0.041%/cycle in the high current stage of−300 mA/cm^(2),indicating that the lifetime of the cell can reach up to about 500 cycles.The total CO_(2) conversion rate reached 52%,which is close to the theoretical value of 54.3% at -300 mA/cm^(2),and the calculated efficiency approached 98.2%,assuming heat recycling.This study illustrates the significant advantages of SOEC in efficient electrochemical energy conversion,carbon emission mitigation,and seasonal energy storage.展开更多
The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dea...The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.展开更多
CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,met...CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.展开更多
A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spe...A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3:1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.展开更多
A fast and simple method for determination of α, β, γ-hexachlorocyclohexanes (HCHs) in water using activated carbon fiber-solid phase microextraction(ACF-SPME) were studied. Results showed the performance of adsorp...A fast and simple method for determination of α, β, γ-hexachlorocyclohexanes (HCHs) in water using activated carbon fiber-solid phase microextraction(ACF-SPME) were studied. Results showed the performance of adsorption and desorption of three HCHs on ACF were excellent. A wide linear range from 10 to 100 μg/L and detection limits of the ng/L level were obtained using ACF-SPME with GC-MS in selected ion monitoring(SIM) acquisition mode. The proposed method was also successfully applied for determination of three HCHs in tap water. Compared to commercial fibers, ACF showed some advantages such as better resistance to solvents, higher thermal stability, longer lifetime and lower cost. The data demonstrated that GC-MS with ACF-SPME is well suitable for the analysis of HCHs in water.展开更多
Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all oth...Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.展开更多
The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out....The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out. High conversion (≥98%) and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.展开更多
The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared an...The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.展开更多
Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffra...Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.展开更多
A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water s...A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1–100 ng/mL (R(2) = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.展开更多
Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy eff...Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.展开更多
Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(...Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.展开更多
Direct synthesis of high-quality doped graphene on dielectric substrates without transfer is highly desired for simplified device processing in electronic applications.However,graphene synthesis directly on substrates...Direct synthesis of high-quality doped graphene on dielectric substrates without transfer is highly desired for simplified device processing in electronic applications.However,graphene synthesis directly on substrates suitable for device applications,though highly demanded,remains unattainable and challenging.Here,a simple and transfer-free synthesis of high-quality doped graphene on the dielectric substrate has been developed using a thin Cu layer as the top catalyst and polycyclic aromatic hydrocarbons as both carbon precursors and doping sources.N-doped and N,F-co-doped graphene have been achieved using TPB and F16Cu Pc as solid carbon sources,respectively.The growth conditions were systematically optimized and the as-grown doped graphene were well characterized.The growth strategy provides a controllable transfer-free route for high-quality doped graphene synthesis,which will facilitate the practical applications of graphene.展开更多
Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interph...Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.展开更多
Solid-phase-sintered Si C-based composites with short carbon fibers(Csf/SSi C) in concentrations ranging from 0 to 10wt% were prepared by pressureless sintering at 2100°C. The phase composition, microstructure,...Solid-phase-sintered Si C-based composites with short carbon fibers(Csf/SSi C) in concentrations ranging from 0 to 10wt% were prepared by pressureless sintering at 2100°C. The phase composition, microstructure, density, and flexural strength of the composites with different Csf contents were investigated. SEM micrographs showed that the Csf distributed in the SSi C matrix homogeneously with some gaps at the fiber/matrix interfaces. The densities of the composites decreased with increasing Csf content. However, the bending strength first increased and then decreased with increasing Csf content, reaching a maximum value of 390 MPa at a Csf content of 5wt%, which was 60 MPa higher than that of SSi C because of the pull-out strengthening mechanism. Notably, Csf was graphitized and damaged during the sintering process because of the high temperature and reaction with boron derived from the sintering additive B4C; this graphitization degraded the fiber strengthening effect.展开更多
Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.
To fabricate electronic packaging shell of coppermatrix composite with characteristics of high ther mal conductivity and low thermal expansion coefficient, semisolid forming technology, and powder metallurgy was combi...To fabricate electronic packaging shell of coppermatrix composite with characteristics of high ther mal conductivity and low thermal expansion coefficient, semisolid forming technology, and powder metallurgy was combined. Conventional mechanical mixing of Cu and SiC could have insufficient wettability, and a new method of semisolid processing was introduced for billets preparation. The SiC/Cu composites were first prepared by PM, and then, semisolid reheating was performed for the successive semisolid forging. Composite billets with SiC 35 % vol ume fraction were compacted and sintered pressurelessly, microstructure analysis showed that the composites pre pared by PM had high density, and the combination between SiC particles and Cualloy was good. Semisolid reheating was the crucial factor in determining the micro structure and thixotropic property of the billet. An opti mised reheating strategy was proposed: temperature 1,025 ℃and holding time 5 min.展开更多
Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures. The experiments were done moderately a...Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures. The experiments were done moderately at mild condition and high yields in suitable times were obtained.展开更多
基金National Key R&D Program of China,Grant/Award Number:2022YFB4000120Fundamental Research Funds for the Central Universities,Grant/Award Number:2022ZYGXZR101。
文摘For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).
基金supported by the National Natural Science Foundation of China(grant nos.21975026 and 22005033)the National Postdoctoral Program of China(no.BX20180037)+1 种基金China Postdoctoral Science Foundation(no.2018M640077)the Beijing Institute of Technology Research Fund Program for Young Scholars(no.XSQD-202108005).
文摘Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.
基金National Key Research&Development Project,Grant/Award Number:2017YFE0129300Ningbo Science and Technology Innovation 2025 Major Project,Grant/Award Numbers:2019B10046,2020Z107+2 种基金Zhejiang Provincial Key R&D Program,Grant/Award Number:2021C01101National Natural Science Foundation of China,Grant/Award Numbers:U20A20251,11932005The from 0 to 1 Innovative Program of CAS,Grant/Award Number:ZDBS-LY-JSC021。
文摘CO_(2) electrolysis with solid oxide electrolytic cells(SOECs)using intermittently available renewable energy has potential applications for carbon neutrality and energy storage.In this study,a pulsed current strategy is used to replicate intermittent energy availability,and the stability and conversion rate of the cyclic operation by a large-scale flat-tube SOEC are studied.One hundred cycles under pulsed current ranging from -100 to -300 mA/cm^(2) with a total operating time of about 800 h were carried out.The results show that after 100 cycles,the cell voltage attenuates by 0.041%/cycle in the high current stage of−300 mA/cm^(2),indicating that the lifetime of the cell can reach up to about 500 cycles.The total CO_(2) conversion rate reached 52%,which is close to the theoretical value of 54.3% at -300 mA/cm^(2),and the calculated efficiency approached 98.2%,assuming heat recycling.This study illustrates the significant advantages of SOEC in efficient electrochemical energy conversion,carbon emission mitigation,and seasonal energy storage.
基金supported by the National Key Research and Development Program of China(2021YFB2400200)the National Natural Science Foundation of China(52104313,22172117,52072298)the Scientific Research Program of Shaanxi Provincial Education Department(21JK0808)。
文摘The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.22072110 and 21872107)the Key Research and Development Projects of Hubei Province,China(2022BAA083)。
文摘CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.
基金supported by the National Natural Science Foundation of China(2123600121176056)+1 种基金the Programme for 100 Excellent Talents in Universities of Hebei Province(II)(BR2-208)the Natural Science Foundation of Hebei Province(B2015202228)~~
文摘A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3:1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.
文摘A fast and simple method for determination of α, β, γ-hexachlorocyclohexanes (HCHs) in water using activated carbon fiber-solid phase microextraction(ACF-SPME) were studied. Results showed the performance of adsorption and desorption of three HCHs on ACF were excellent. A wide linear range from 10 to 100 μg/L and detection limits of the ng/L level were obtained using ACF-SPME with GC-MS in selected ion monitoring(SIM) acquisition mode. The proposed method was also successfully applied for determination of three HCHs in tap water. Compared to commercial fibers, ACF showed some advantages such as better resistance to solvents, higher thermal stability, longer lifetime and lower cost. The data demonstrated that GC-MS with ACF-SPME is well suitable for the analysis of HCHs in water.
基金financially supported by the National Natural Science Foundation of China(Grant nos.21376001,21576028 and 21506012)。
文摘Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.
基金the National Key Project ofScientific and Technical SupportingPrograms Funded by the Ministry of Science & Technology of China (No.2006BAE03B06)the Shanghai International Cooperation of Science and Technology Project (No.06SR07101).
文摘The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out. High conversion (≥98%) and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.
文摘The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.
基金supported by the Natural Science Foundation of Shanxi Province(201601D102006)the Key Science and Technology Program of Shanxi Province,China(MD2014-09,MD2014-10)~~
文摘Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.
文摘A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1–100 ng/mL (R(2) = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.
基金This study was financially supported by the National Key R&D Research Program of China(Grant No.2018YFB0905400)National Natural Science Foundationof China(Grant Nos.,51925207,U1910210,51972067,51802044,and 51872277)+2 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)Fundamental Research Funds for the Central Universities of China(Grant No.WK2060140026)the DNL Cooperation Fund,CAS(Grant No.DNL180310).
文摘Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.
基金financial support from the National Natural Science Foundation of China(grant No.21706085)Subsidized Project for Postgraduates’Innovative Fund in Scientific Research of Huaqiao Universitythe Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education/Shandong Province of China(grant No.KF201804)。
文摘Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.
基金supported by Natural Science Foundation of China(NSFC)(Grant No.91333112U1432249)+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutionssupported by Collaborative Innovation Center of Suzhou Nano Science&Technology and sponsored by Qing Lan Project
文摘Direct synthesis of high-quality doped graphene on dielectric substrates without transfer is highly desired for simplified device processing in electronic applications.However,graphene synthesis directly on substrates suitable for device applications,though highly demanded,remains unattainable and challenging.Here,a simple and transfer-free synthesis of high-quality doped graphene on the dielectric substrate has been developed using a thin Cu layer as the top catalyst and polycyclic aromatic hydrocarbons as both carbon precursors and doping sources.N-doped and N,F-co-doped graphene have been achieved using TPB and F16Cu Pc as solid carbon sources,respectively.The growth conditions were systematically optimized and the as-grown doped graphene were well characterized.The growth strategy provides a controllable transfer-free route for high-quality doped graphene synthesis,which will facilitate the practical applications of graphene.
基金Project supported by the State Grid Technology Project,China(Grant No.DG71-17-010)。
文摘Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.
基金financially supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20110006110025)the National Natural Science Foundation of China(No.U1134102)
文摘Solid-phase-sintered Si C-based composites with short carbon fibers(Csf/SSi C) in concentrations ranging from 0 to 10wt% were prepared by pressureless sintering at 2100°C. The phase composition, microstructure, density, and flexural strength of the composites with different Csf contents were investigated. SEM micrographs showed that the Csf distributed in the SSi C matrix homogeneously with some gaps at the fiber/matrix interfaces. The densities of the composites decreased with increasing Csf content. However, the bending strength first increased and then decreased with increasing Csf content, reaching a maximum value of 390 MPa at a Csf content of 5wt%, which was 60 MPa higher than that of SSi C because of the pull-out strengthening mechanism. Notably, Csf was graphitized and damaged during the sintering process because of the high temperature and reaction with boron derived from the sintering additive B4C; this graphitization degraded the fiber strengthening effect.
文摘Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.
基金supported by the National Natural Science Foundation of China(No.51174028)the Beijing Natural Science Foundation(No.2102029)
文摘To fabricate electronic packaging shell of coppermatrix composite with characteristics of high ther mal conductivity and low thermal expansion coefficient, semisolid forming technology, and powder metallurgy was combined. Conventional mechanical mixing of Cu and SiC could have insufficient wettability, and a new method of semisolid processing was introduced for billets preparation. The SiC/Cu composites were first prepared by PM, and then, semisolid reheating was performed for the successive semisolid forging. Composite billets with SiC 35 % vol ume fraction were compacted and sintered pressurelessly, microstructure analysis showed that the composites pre pared by PM had high density, and the combination between SiC particles and Cualloy was good. Semisolid reheating was the crucial factor in determining the micro structure and thixotropic property of the billet. An opti mised reheating strategy was proposed: temperature 1,025 ℃and holding time 5 min.
文摘Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures. The experiments were done moderately at mild condition and high yields in suitable times were obtained.