In order to solve the shortcomings of MoO_(3)/γ-Al_(2)O_(3)catalyst for sulfur-resistant methanation,a segmented plasma fluidized bed reactor was designed,where plasma discharge zone and the fluidization zone were se...In order to solve the shortcomings of MoO_(3)/γ-Al_(2)O_(3)catalyst for sulfur-resistant methanation,a segmented plasma fluidized bed reactor was designed,where plasma discharge zone and the fluidization zone were separated under higher discharge power.At the bed height of 30 mm,the gas velocity of 0.10 m·s^(-1)can provide a better fluidization state.The suitable discharge results can be achieved when the input power is 27 W and the discharge interval is 2.0 mm.With the extension of catalyst plasma treatment time,the conversion of CO decreases,but the selectivity of CH_(4)increases.Combined with N_(2)physical adsorption-desorption,XRD,TEM,Raman,TGA and TPR characterization,it was found that the active components of the catalyst are uniformly dispersed on the γ-Al_(2)O_(3)support.After plasma treatment,tetrahedral Mo species was used as the active center,and the interaction between Mo and the carrier was strengthened.It provides a novel approach for preparing catalyst with dielectric barrier discharge(DBD)fluidized bed reactor.展开更多
In this study, different methods were used to prepare MoO3/ZrO2 catalysts for sulfur resistant methanation reaction. It was found that MoO3/ZrO2 catalyst prepared by one-step co-precipitation method achieved high meth...In this study, different methods were used to prepare MoO3/ZrO2 catalysts for sulfur resistant methanation reaction. It was found that MoO3/ZrO2 catalyst prepared by one-step co-precipitation method achieved high methanation performance. CO conversion could reach up to 90% on 25 wt% MoO3/ZrO2 catalyst, much higher than that on the conventional 25 wt% MoO3/Al2O3 catalyst. The Mo-based catalysts were characterized by XRF, XRD, Raman, BET, TEM and H2-TPR etc. It was found that MoO3 particles were highly dispersed on ZrO2 support for 25 wt% MoO3/ZrO2 catalyst prepared at 65-85℃ because of its relatively larger pore size, which contributed to a high CO conversion. Meanwhile, when MoO3 loading exceeded the monolayer coverage, the formed crystalline MoO3 and ZrM020g might block the micropores of the catalyst and make the methanation activity declined. These results are useful for preparing highly efficient catalyst for CO methanation process.展开更多
The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium...The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.展开更多
All-solid-state lithium batteries(ASSLBs)are recognized as high energy density batteries system without safety issues within the next generation of batteries.The development of solid electrolytes is the crucial step o...All-solid-state lithium batteries(ASSLBs)are recognized as high energy density batteries system without safety issues within the next generation of batteries.The development of solid electrolytes is the crucial step of ASSLBs.The composite electrolyte has stable physical and electrochemical characteristics,and its comprehensive performance surpasses the individual solid electrolyte,bringing unique vitality to the solid electrolyte.However,their intrinsic weakness limits the development of composite electrolytes.In this review,we provide a comprehensive and in-depth understanding of the challenges and opportunities of composite electrolytes,with special focus on mechanisms of ion transport,nanostructure design towards high ionic conductivity,interfacial issues within electrolytes and electrodes.Furthermore,future development is prospected,which can shed light on researchers in this field and accelerate the industrial production of composite electrolytes.展开更多
A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study.The flue gas containing 200 mg·m^-3NO,1000-4000 mg·m^-3SO(2,)3%-9%O(2)and 10%-20%CO(2)was first oxidized ...A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study.The flue gas containing 200 mg·m^-3NO,1000-4000 mg·m^-3SO(2,)3%-9%O(2)and 10%-20%CO(2)was first oxidized b(y)O3 and then absorbed by ammonia in a bubbling reactor.Increasing the ammonia concentration or the SO2 content in flue gas can promote the absorption of NOx and extend the effective absorption time.On the contrary,both increasing the absorbent temperature or the O(2)content shorten the effective absorption time of NO((x.))The change of solution pH had substantial influence on NOx absorption.In the presence of CO(2)the NOx removal efficiency reached 89.2%when the absorbent temperature was raised to 60℃and the effective absorption time can be maintained for 8 h,which attribute to the buffering effect in the absorbent.Besides,both the addition of Na(2)S2 O3 and urea can promote the NOx removal efficiency when the absorbent temperature is 25℃and the addition of Na(2)S2 O3 had achieved better results.The advantage of adding Na(2)S2 O3 became less evident at higher absorbent temperature and coexistence of CO(2.)In all experiments,SO(2)removal efficiency was always above 99%,and it was basically not affected by the above factors.展开更多
Spinel ferrites NiFeOsupported Ru catalysts have been prepared via a simple sol–gel route and applied for converting biomass-derived furfural to 2-methylfuran. The as-prepared catalysts were characterized by thermogr...Spinel ferrites NiFeOsupported Ru catalysts have been prepared via a simple sol–gel route and applied for converting biomass-derived furfural to 2-methylfuran. The as-prepared catalysts were characterized by thermogravimetric analysis（TG）, Nadsorption–desorption, X-ray diffraction（XRD）, scanning electronic microscopy（SEM）, and X-ray photoelectron spectroscopy（XPS）. Results showed that the catalysts had well-dispersed Ru active sites and large surface area for calcination temperature ranging from 300 to 500 ℃. The conversion of biomass-derived furfural into 2-methylfuran was conducted over Ru/NiFeOthrough catalytic transfer hydrogenation in liquid-phase with 2-propanol as the hydrogen source. A significantly enhanced activity and increased 2-methylfuran yield have been achieved in this study. Under mild conditions（180 ℃ and 2.1 MPa N）, the conversion of furfural exceeds 97% and 2-methylfuran yield was up to 83% over the catalyst containing 8 wt% Ru. After five repeated uses, the catalytic activity and the corresponding product yield remained almost unchanged. The excellent catalytic activity and recycling performance provide a broad prospects for various practical applications.展开更多
Sodium-ion batteries(SIBs) have gained more scientists’ interest, owing to some facts such as the natural abundance of Na, the similarities of physicochemical characteristics between Li and Na. The irreversible Na+io...Sodium-ion batteries(SIBs) have gained more scientists’ interest, owing to some facts such as the natural abundance of Na, the similarities of physicochemical characteristics between Li and Na. The irreversible Na+ions consumption during the first cycle of charge/discharge process(due to the formation of the solid electrolyte interface(SEI) on the electrode surface and other irreversible reactions) is the factor that determines high performance SIBs and largely reduces the capacity of the full cell SIBs. Thus, the initial coulombic efficiency(ICE) of SIBs for both anode and cathode materials, is a key parameter for high performance SIBs, and the point is to increase the transport rate of the Na+ions. Therefore, developing SIBs with high ICE and rate performance becomes vital to boost the commercialization of SIBs. Here we provide a review on the methods to improve the ICE and the rate performance, by summarizing some methods of improving the ICE and rate performance of the anode and cathode materials for SIBs, and end by a conclusion with some perspectives and recommendations.展开更多
We reported a coaxial,micro-dielectric barrier discharge(micro-DBD)reactor and a conventional DBD reactor for the direct conversion of methane into higher hydrocarbons at atmospheric pressure.The effects of input powe...We reported a coaxial,micro-dielectric barrier discharge(micro-DBD)reactor and a conventional DBD reactor for the direct conversion of methane into higher hydrocarbons at atmospheric pressure.The effects of input power,residence time,discharge gap and external electrode length were investigated for methane conversion and product selectivity.We found the conversion of methane in a micro-DBD reactor was higher than that in a conventional DBD reactor.And at an input power of 25.0 W,the conversion of methane and the total C2+C3 selectivity reached 25.10% and 80.27%,respectively,with a micro-DBD reactor of 0.4 mm discharge gap.Finally,a nonlinear multiple regression model was used to study the correlations between both methane conversion and product selectivity and various system variables.The calculated data were obtained using SPSS 12.0 software.The regression analysis illustrated the correlations between system variables and both methane conversion and product selectivity.展开更多
The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method a...The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.展开更多
High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretic...High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.展开更多
CuY zeolite is a promising catalyst in the field of manufacturing dimethyl carbonate(DMC) through oxidative carbonylation of methanol. Cu^+ exchanged with Br?nsted acid sites are supposed to be active for this reactio...CuY zeolite is a promising catalyst in the field of manufacturing dimethyl carbonate(DMC) through oxidative carbonylation of methanol. Cu^+ exchanged with Br?nsted acid sites are supposed to be active for this reaction. However, the location of Cu^+ in small cages can not interact with reactants because of steric hindrance, which lead to a waste of Cu species. In this work, NH_4F solution was used to modify the pore structure of zeolite Y by etching the framework T atoms. Physical and chemical adsorption of probe molecules with different size are used to determine the changes of porosity as well as the accessibility of Cu^+ sites. At an optimized etching time, the small cages were opened with maintained zeolitic framework. As a result, more Cu^+ species located in small cages become accessible to reactants, which contributes to the enhanced activity in this reaction.展开更多
In this paper, Ce_(0.2)Zr_(0.8)O_2 composite supports were prepared by different Ce-addition methods including impregnation of cerium(CeZr-imp), impregnation of citric acid and cerium(CeZr-CA) simultaneously and depos...In this paper, Ce_(0.2)Zr_(0.8)O_2 composite supports were prepared by different Ce-addition methods including impregnation of cerium(CeZr-imp), impregnation of citric acid and cerium(CeZr-CA) simultaneously and deposition precipitation method(CeZr-DP), respectively. The as-prepared supports were applied to prepare 10 wt% MoO_3/Ce_(0.2)Zr_(0.8)O_2 catalysts for sulfur-resistant methanation. The N_2 adsorption/desorption,X-ray diffraction(XRD), Raman spectroscopy(RS), X-ray photoelectron(XPS), temperature-programmed reduction by hydrogen(H_2-TPR) were undertaken to get textural properties, morphological information and structures of the catalysts. The results showed that Mo O_3 was highly dispersed on the surface of these three supports and Ce was mostly of coexisted in Ce^(4+)/Ce^(3+) redox pairs. Compared with Mo/CeZrimp, the CO conversion increased by 10% and 15% for Mo/CeZr-CA and Mo/CeZr-DP, respectively. This was mainly attributed to the larger specific surface area, Ce^(3+) concentration and content of active MoS_2 on the surface of catalysts.展开更多
Barrier coverage of wireless sensor networks is an important issue in the detection of intruders who are attempting to cross a region of interest.However,in certain applications,barrier coverage cannot be satisfied af...Barrier coverage of wireless sensor networks is an important issue in the detection of intruders who are attempting to cross a region of interest.However,in certain applications,barrier coverage cannot be satisfied after random deployment.In this paper,we study how mobile sensors can be efficiently relocated to achieve k-barrier coverage.In particular,two problems are studied:relocation of sensors with minimum number of mobile sensors and formation of k-barrier coverage with minimum energy cost.These two problems were formulated as 0–1 integer linear programming(ILP).The formulation is computationally intractable because of integrality and complicated constraints.Therefore,we relax the integrality and complicated constraints of the formulation and construct a special model known as RELAX-RSMN with a totally unimodular constraint coefficient matrix to solve the relaxed 0–1 ILP rapidly through linear programming.Theoretical analysis and simulation were performed to verify the effectiveness of our approach.展开更多
Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,featur...Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.展开更多
This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and ...This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.展开更多
Direct conversion of methane into C2 hydrocarbons through alternating current electric field enhanced plasma was studied under room temperature, atmospheric pressure and low power conditions. The distribution of elect...Direct conversion of methane into C2 hydrocarbons through alternating current electric field enhanced plasma was studied under room temperature, atmospheric pressure and low power conditions. The distribution of electrical field intensity and distribution of energy were calculated with software that was developed by us according to the charge simulation method. The results indicated that the energy of tip of electrode was 0.36 J/mm^3 and it was higher than the methane dissociation energy （0.0553 J/mm^3）. The methane located at this area can be activated easily. The higher-energy particles produced by dissociation collided with molecules around them and initiated consecutive reactions between free radicals and molecules. The method was proved to be valided and could be taken as a basis for the electrical field study concerned.展开更多
Chaining watermark is an effective way to verify the integrity of streaming data in wireless network environment,especially in resource-constrained sensor networks,such as the perception layer of Internet of Things ap...Chaining watermark is an effective way to verify the integrity of streaming data in wireless network environment,especially in resource-constrained sensor networks,such as the perception layer of Internet of Things applications.However,in all existing single chaining watermark schemes,how to ensure the synchronization between the data sender and the receiver is still an unsolved problem.Once the synchronization points are attacked by the adversary,existing data integrity authentication schemes are difficult to work properly,and the false negative rate might be up to 50 percent.And the additional fixed group delimiters not only increase the data size,but are also easily detected by adversaries.In this paper,we propose an effective dual-chaining watermark scheme,called DCW,for data integrity protection in smart campus IoT applications.The proposed DCW scheme has the following three characteristics:(1)In order to authenticate the integrity of the data,fragile watermarks are generated and embedded into the data in a chaining way using dynamic grouping;(2)Instead of additional fixed group delimiters,chained watermark delimiters are proposed to synchronize the both transmission sides in case of the synchronization points are tampered;(3)To achieve lossless integrity authentication,a reversible watermarking technique is applied.The experimental results and security analysis can prove that the proposed DCW scheme is able to effectively authenticate the integrity of the data with free distortion at low cost in our smart meteorological Internet of Things system.展开更多
A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method...A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method.The combination of plasma and the Mn/γ-Al2O3 catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone,with the 10% Mn/γ-Al2O3 catalyst exhibiting the best tetracycline hydrochloride degradation efficiency.A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W,with only 69.7% by a single plasma process.The highest energy yield of the plasma-catalytic process is 91.7 g kWh-1.Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.展开更多
CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resis...CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeOsupport prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N-adsorption–desorption, temperature-programmed reduction（TPR）, X-ray diffraction（XRD）, Raman spectroscopy（RS） and scanning electron microscope（SEM）. The results indicated that the saturated monolayer loading MoOon Ce-3 support was lower than 5% and there were some crystalline MoOparticles on the surface of the Mo/Ce-3. The preparation method of CeOhad a big influence on the specific surface area, the crystalline of CeO, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.展开更多
Digital watermarking technology is adequate for copyright protection and content authentication.There needs to be more research on the watermarking algorithm after printing and scanning.Aiming at the problem that exis...Digital watermarking technology is adequate for copyright protection and content authentication.There needs to be more research on the watermarking algorithm after printing and scanning.Aiming at the problem that existing anti-print scanning text image watermarking algorithms cannot take into account the invisibility and robustness of the watermark,an anti-print scanning watermarking algorithm suitable for text images is proposed.This algorithm first performs a series of image enhancement preprocessing operations on the printed scanned image to eliminate the interference of incorrect bit information on watermark embedding and then uses a combination of Discrete Wavelet Transform(DWT)-Singular Value Decomposition(SVD)to embed the watermark.Experiments show that the average Normalized Correlation(NC)of the watermark extracted by this algorithm against attacks such as Joint Photographic Experts Group(JPEG)compression,JPEG2000 compression,and print scanning is above 0.93.Especially,the average NC of the watermark extracted after print scanning attacks is greater than 0.964,and the average Bit Error Ratio(BER)is 5.15%.This indicates that this algorithm has strong resistance to various attacks and print scanning attacks and can better take into account the invisibility of the watermark.展开更多
基金supported by the National Natural Science Foundation of China(22178255).
文摘In order to solve the shortcomings of MoO_(3)/γ-Al_(2)O_(3)catalyst for sulfur-resistant methanation,a segmented plasma fluidized bed reactor was designed,where plasma discharge zone and the fluidization zone were separated under higher discharge power.At the bed height of 30 mm,the gas velocity of 0.10 m·s^(-1)can provide a better fluidization state.The suitable discharge results can be achieved when the input power is 27 W and the discharge interval is 2.0 mm.With the extension of catalyst plasma treatment time,the conversion of CO decreases,but the selectivity of CH_(4)increases.Combined with N_(2)physical adsorption-desorption,XRD,TEM,Raman,TGA and TPR characterization,it was found that the active components of the catalyst are uniformly dispersed on the γ-Al_(2)O_(3)support.After plasma treatment,tetrahedral Mo species was used as the active center,and the interaction between Mo and the carrier was strengthened.It provides a novel approach for preparing catalyst with dielectric barrier discharge(DBD)fluidized bed reactor.
基金supported by the Tianjin Municipal Science and Technology Commission(14JCZDJC37500)
文摘In this study, different methods were used to prepare MoO3/ZrO2 catalysts for sulfur resistant methanation reaction. It was found that MoO3/ZrO2 catalyst prepared by one-step co-precipitation method achieved high methanation performance. CO conversion could reach up to 90% on 25 wt% MoO3/ZrO2 catalyst, much higher than that on the conventional 25 wt% MoO3/Al2O3 catalyst. The Mo-based catalysts were characterized by XRF, XRD, Raman, BET, TEM and H2-TPR etc. It was found that MoO3 particles were highly dispersed on ZrO2 support for 25 wt% MoO3/ZrO2 catalyst prepared at 65-85℃ because of its relatively larger pore size, which contributed to a high CO conversion. Meanwhile, when MoO3 loading exceeded the monolayer coverage, the formed crystalline MoO3 and ZrM020g might block the micropores of the catalyst and make the methanation activity declined. These results are useful for preparing highly efficient catalyst for CO methanation process.
基金financially supported by National Key Research and Development Program of China(2018YFC1901605)the National Postdoctoral Program for Innovative Talents(BX201600192)+1 种基金Hunan Provincial Science and Technology Plan(2017TP1001)Innovation Mover Program of Central South University(GCX20190893Y)。
文摘The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.
基金financially supported by the National Natural Science Foundation of China(52074359,51904342,U19A2019)the Hunan Provincial Science and Technology Plan(2020JJ3048)+2 种基金the Science and Technology Innovation Program of Hunan Province(2020RC4005,2019RS1004)the science and technology plan key project of Hunan Province(2020GK2100)the Innovation Mover Program of Central South University(2020CX007)。
文摘All-solid-state lithium batteries(ASSLBs)are recognized as high energy density batteries system without safety issues within the next generation of batteries.The development of solid electrolytes is the crucial step of ASSLBs.The composite electrolyte has stable physical and electrochemical characteristics,and its comprehensive performance surpasses the individual solid electrolyte,bringing unique vitality to the solid electrolyte.However,their intrinsic weakness limits the development of composite electrolytes.In this review,we provide a comprehensive and in-depth understanding of the challenges and opportunities of composite electrolytes,with special focus on mechanisms of ion transport,nanostructure design towards high ionic conductivity,interfacial issues within electrolytes and electrodes.Furthermore,future development is prospected,which can shed light on researchers in this field and accelerate the industrial production of composite electrolytes.
基金financially supported by the National Key Research and Development Program of China(2016YFB0600701)。
文摘A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study.The flue gas containing 200 mg·m^-3NO,1000-4000 mg·m^-3SO(2,)3%-9%O(2)and 10%-20%CO(2)was first oxidized b(y)O3 and then absorbed by ammonia in a bubbling reactor.Increasing the ammonia concentration or the SO2 content in flue gas can promote the absorption of NOx and extend the effective absorption time.On the contrary,both increasing the absorbent temperature or the O(2)content shorten the effective absorption time of NO((x.))The change of solution pH had substantial influence on NOx absorption.In the presence of CO(2)the NOx removal efficiency reached 89.2%when the absorbent temperature was raised to 60℃and the effective absorption time can be maintained for 8 h,which attribute to the buffering effect in the absorbent.Besides,both the addition of Na(2)S2 O3 and urea can promote the NOx removal efficiency when the absorbent temperature is 25℃and the addition of Na(2)S2 O3 had achieved better results.The advantage of adding Na(2)S2 O3 became less evident at higher absorbent temperature and coexistence of CO(2.)In all experiments,SO(2)removal efficiency was always above 99%,and it was basically not affected by the above factors.
基金supported by the National Natural Science Foundation of China(21573031 and 21428301)the Fundamental Research Funds for the Central Universities(DUT15ZD106)
文摘Spinel ferrites NiFeOsupported Ru catalysts have been prepared via a simple sol–gel route and applied for converting biomass-derived furfural to 2-methylfuran. The as-prepared catalysts were characterized by thermogravimetric analysis（TG）, Nadsorption–desorption, X-ray diffraction（XRD）, scanning electronic microscopy（SEM）, and X-ray photoelectron spectroscopy（XPS）. Results showed that the catalysts had well-dispersed Ru active sites and large surface area for calcination temperature ranging from 300 to 500 ℃. The conversion of biomass-derived furfural into 2-methylfuran was conducted over Ru/NiFeOthrough catalytic transfer hydrogenation in liquid-phase with 2-propanol as the hydrogen source. A significantly enhanced activity and increased 2-methylfuran yield have been achieved in this study. Under mild conditions（180 ℃ and 2.1 MPa N）, the conversion of furfural exceeds 97% and 2-methylfuran yield was up to 83% over the catalyst containing 8 wt% Ru. After five repeated uses, the catalytic activity and the corresponding product yield remained almost unchanged. The excellent catalytic activity and recycling performance provide a broad prospects for various practical applications.
基金financially supported by National Key Research and Development Program of China (No.2019YFC1907805)National Natural Science Foundation of China (No.52004338)+1 种基金Hunan Provincial Natural Science Foundation of China (No.2020JJ5696)Guangdong Provincial Department of Natural Resources (No.2020-011)。
文摘Sodium-ion batteries(SIBs) have gained more scientists’ interest, owing to some facts such as the natural abundance of Na, the similarities of physicochemical characteristics between Li and Na. The irreversible Na+ions consumption during the first cycle of charge/discharge process(due to the formation of the solid electrolyte interface(SEI) on the electrode surface and other irreversible reactions) is the factor that determines high performance SIBs and largely reduces the capacity of the full cell SIBs. Thus, the initial coulombic efficiency(ICE) of SIBs for both anode and cathode materials, is a key parameter for high performance SIBs, and the point is to increase the transport rate of the Na+ions. Therefore, developing SIBs with high ICE and rate performance becomes vital to boost the commercialization of SIBs. Here we provide a review on the methods to improve the ICE and the rate performance, by summarizing some methods of improving the ICE and rate performance of the anode and cathode materials for SIBs, and end by a conclusion with some perspectives and recommendations.
基金supported by the National Natural Science Foundation of China (NSFC) under the grant of No.21176175 and No.20606023
文摘We reported a coaxial,micro-dielectric barrier discharge(micro-DBD)reactor and a conventional DBD reactor for the direct conversion of methane into higher hydrocarbons at atmospheric pressure.The effects of input power,residence time,discharge gap and external electrode length were investigated for methane conversion and product selectivity.We found the conversion of methane in a micro-DBD reactor was higher than that in a conventional DBD reactor.And at an input power of 25.0 W,the conversion of methane and the total C2+C3 selectivity reached 25.10% and 80.27%,respectively,with a micro-DBD reactor of 0.4 mm discharge gap.Finally,a nonlinear multiple regression model was used to study the correlations between both methane conversion and product selectivity and various system variables.The calculated data were obtained using SPSS 12.0 software.The regression analysis illustrated the correlations between system variables and both methane conversion and product selectivity.
文摘The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.
基金financially supported by the National Key Research and Development Program of China (2018YFC1901605)the National Natural Science Foundation of China (52004338)+2 种基金the Hunan Provincial Natural Science Foundation of China (2020JJ5696)the Guangdong Provincial Department of Natural Resources (2020-011)the Fundamental Research Funds for the Central Universities of Central South University (2020zzts058)。
文摘High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.
基金financial supports from the National Natural Science Foundation of China NSFC, Nos. U1510203, 21406120, 21325626
文摘CuY zeolite is a promising catalyst in the field of manufacturing dimethyl carbonate(DMC) through oxidative carbonylation of methanol. Cu^+ exchanged with Br?nsted acid sites are supposed to be active for this reaction. However, the location of Cu^+ in small cages can not interact with reactants because of steric hindrance, which lead to a waste of Cu species. In this work, NH_4F solution was used to modify the pore structure of zeolite Y by etching the framework T atoms. Physical and chemical adsorption of probe molecules with different size are used to determine the changes of porosity as well as the accessibility of Cu^+ sites. At an optimized etching time, the small cages were opened with maintained zeolitic framework. As a result, more Cu^+ species located in small cages become accessible to reactants, which contributes to the enhanced activity in this reaction.
基金Financial supports from the National High Technology Research and Development Program of China (863 Project) (2015AA050504)the National Natural Science Foundation of China (21576203)
文摘In this paper, Ce_(0.2)Zr_(0.8)O_2 composite supports were prepared by different Ce-addition methods including impregnation of cerium(CeZr-imp), impregnation of citric acid and cerium(CeZr-CA) simultaneously and deposition precipitation method(CeZr-DP), respectively. The as-prepared supports were applied to prepare 10 wt% MoO_3/Ce_(0.2)Zr_(0.8)O_2 catalysts for sulfur-resistant methanation. The N_2 adsorption/desorption,X-ray diffraction(XRD), Raman spectroscopy(RS), X-ray photoelectron(XPS), temperature-programmed reduction by hydrogen(H_2-TPR) were undertaken to get textural properties, morphological information and structures of the catalysts. The results showed that Mo O_3 was highly dispersed on the surface of these three supports and Ce was mostly of coexisted in Ce^(4+)/Ce^(3+) redox pairs. Compared with Mo/CeZrimp, the CO conversion increased by 10% and 15% for Mo/CeZr-CA and Mo/CeZr-DP, respectively. This was mainly attributed to the larger specific surface area, Ce^(3+) concentration and content of active MoS_2 on the surface of catalysts.
基金supported by the NSFC(U1536206,61232016,U1405254,61373133,61502242,71401176)BK20150925the PAPD fund
文摘Barrier coverage of wireless sensor networks is an important issue in the detection of intruders who are attempting to cross a region of interest.However,in certain applications,barrier coverage cannot be satisfied after random deployment.In this paper,we study how mobile sensors can be efficiently relocated to achieve k-barrier coverage.In particular,two problems are studied:relocation of sensors with minimum number of mobile sensors and formation of k-barrier coverage with minimum energy cost.These two problems were formulated as 0–1 integer linear programming(ILP).The formulation is computationally intractable because of integrality and complicated constraints.Therefore,we relax the integrality and complicated constraints of the formulation and construct a special model known as RELAX-RSMN with a totally unimodular constraint coefficient matrix to solve the relaxed 0–1 ILP rapidly through linear programming.Theoretical analysis and simulation were performed to verify the effectiveness of our approach.
基金financially supported by Science and Technology Foundation of Guizhou Province(QKHZC[2020]2Y037)the Science and Technology Innovation Program of Hunan Province(2020RC4005,2019RS1004)+2 种基金Research start-up funding from Central South University(202044019)Innovation Mover Program of Central South University(2020CX007)National Natural Science Foundation of China(U21A20284)
文摘Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.
文摘This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.
文摘Direct conversion of methane into C2 hydrocarbons through alternating current electric field enhanced plasma was studied under room temperature, atmospheric pressure and low power conditions. The distribution of electrical field intensity and distribution of energy were calculated with software that was developed by us according to the charge simulation method. The results indicated that the energy of tip of electrode was 0.36 J/mm^3 and it was higher than the methane dissociation energy （0.0553 J/mm^3）. The methane located at this area can be activated easily. The higher-energy particles produced by dissociation collided with molecules around them and initiated consecutive reactions between free radicals and molecules. The method was proved to be valided and could be taken as a basis for the electrical field study concerned.
基金This work is supported by the Major Program of the National Social Science Fund of China under Grant No.17ZDA092by the Electronic Information and Control of Fujian University Engineering Research Center Fund under Grant No.EIC1704+3 种基金by the National Key R&D Program of China under grant 2018YFB1003205by the National Natural Science Foundation of China under grant 61173136,U1836208,U1536206,U1836110,61602253,61672294by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)fundby the Collaborative Innovation Center of Atmospheric Environment and Equipment Technology(CICAEET)fund,China.
文摘Chaining watermark is an effective way to verify the integrity of streaming data in wireless network environment,especially in resource-constrained sensor networks,such as the perception layer of Internet of Things applications.However,in all existing single chaining watermark schemes,how to ensure the synchronization between the data sender and the receiver is still an unsolved problem.Once the synchronization points are attacked by the adversary,existing data integrity authentication schemes are difficult to work properly,and the false negative rate might be up to 50 percent.And the additional fixed group delimiters not only increase the data size,but are also easily detected by adversaries.In this paper,we propose an effective dual-chaining watermark scheme,called DCW,for data integrity protection in smart campus IoT applications.The proposed DCW scheme has the following three characteristics:(1)In order to authenticate the integrity of the data,fragile watermarks are generated and embedded into the data in a chaining way using dynamic grouping;(2)Instead of additional fixed group delimiters,chained watermark delimiters are proposed to synchronize the both transmission sides in case of the synchronization points are tampered;(3)To achieve lossless integrity authentication,a reversible watermarking technique is applied.The experimental results and security analysis can prove that the proposed DCW scheme is able to effectively authenticate the integrity of the data with free distortion at low cost in our smart meteorological Internet of Things system.
文摘A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method.The combination of plasma and the Mn/γ-Al2O3 catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone,with the 10% Mn/γ-Al2O3 catalyst exhibiting the best tetracycline hydrochloride degradation efficiency.A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W,with only 69.7% by a single plasma process.The highest energy yield of the plasma-catalytic process is 91.7 g kWh-1.Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.
基金Financial supports from the National High Technology Research and Development Program of China(863 Project)(2015AA050504)the National Natural Science Foundation of China(21576203)
文摘CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeOsupport prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N-adsorption–desorption, temperature-programmed reduction（TPR）, X-ray diffraction（XRD）, Raman spectroscopy（RS） and scanning electron microscope（SEM）. The results indicated that the saturated monolayer loading MoOon Ce-3 support was lower than 5% and there were some crystalline MoOparticles on the surface of the Mo/Ce-3. The preparation method of CeOhad a big influence on the specific surface area, the crystalline of CeO, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.
基金sponsored by the National Natural Science Foundation of China under Grants 61972207,U1836208,U1836110,61672290,and the Project was through the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institution.
文摘Digital watermarking technology is adequate for copyright protection and content authentication.There needs to be more research on the watermarking algorithm after printing and scanning.Aiming at the problem that existing anti-print scanning text image watermarking algorithms cannot take into account the invisibility and robustness of the watermark,an anti-print scanning watermarking algorithm suitable for text images is proposed.This algorithm first performs a series of image enhancement preprocessing operations on the printed scanned image to eliminate the interference of incorrect bit information on watermark embedding and then uses a combination of Discrete Wavelet Transform(DWT)-Singular Value Decomposition(SVD)to embed the watermark.Experiments show that the average Normalized Correlation(NC)of the watermark extracted by this algorithm against attacks such as Joint Photographic Experts Group(JPEG)compression,JPEG2000 compression,and print scanning is above 0.93.Especially,the average NC of the watermark extracted after print scanning attacks is greater than 0.964,and the average Bit Error Ratio(BER)is 5.15%.This indicates that this algorithm has strong resistance to various attacks and print scanning attacks and can better take into account the invisibility of the watermark.
