Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of hig...Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.展开更多
The ZnO molecule plays an important role in the industry due to it special features, anti-corrosion anti-bacterial properties, as well as due to its low electrical conductivity and heat resistance. In these experiment...The ZnO molecule plays an important role in the industry due to it special features, anti-corrosion anti-bacterial properties, as well as due to its low electrical conductivity and heat resistance. In these experimental researches, the sol-gel method was chosen, which enables control of nucleation, aging and growth of particles in the solution. ZnO synthesis was prepared utilizing chemical method with Zinc acetate dyhidrate and NaOH with the appropriate methanol solvent and heating (60˚C). The methods used in identification and characterization are FTIR, UV/VIS, OPTICAL MICROSCOPY, SEM and XRD. The FTIR spectra of synthesized ZnO with corresponding ones show characteristic bands at the corresponding wavelengths, which confirm the presence of ZnO nanoparticles. SEM characterization of ZnO shows the morphology of needle-shaped nanoparticles. XRD spectar in this research by chemical method indicates the particle size of 17.76 nm.展开更多
With the recent advancement in nanotechnology,nanoparticles(NPs)offer an ample variety of smart functions than conventional materials in various aspects.As compared to larger particles,NPs possess unique characteristi...With the recent advancement in nanotechnology,nanoparticles(NPs)offer an ample variety of smart functions than conventional materials in various aspects.As compared to larger particles,NPs possess unique characteristics and excellent abilities,such as low toxicity,chemical stability,surface functionality,and biocompatibility.These advantageous properties allow them to be widely utilized in many applications,including biomedical applications,energy applications,IT applications,and industrial applications.In order to fulfill the increasing demands of NP applications,existing NP synthesis methods need to be improved based on the requirements of different applications to further their usage.A comprehensive understanding of the relationships between synthesis parameters and properties of NPs can help us better fine-tune them with designed properties and minimal toxicity.This review paper will discuss the commonly used synthesis methods of functionalized NPs,as well as future directions and challenges to develop various synthesis methods further.展开更多
Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have ...Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.展开更多
A brief review of the works of the author and his co-authors on the application of nonlinear analysis, numerical and analytical methods for solving the nonlinear inverse problems (synthesis problems) for optimizing th...A brief review of the works of the author and his co-authors on the application of nonlinear analysis, numerical and analytical methods for solving the nonlinear inverse problems (synthesis problems) for optimizing the different types of radiating systems, is presented in the paper. The synthesis problems are formulated in variational statements and further they are reduced to research and numerical solution of nonlinear integral equations of Hammerstein type. The existence theorems are proof, the investigation methods of nonuniqueness problem of solutions and numerical algorithms of finding the optimal solutions are proved.展开更多
Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) o...In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) or N-methyl- 2-pyrrolidone(NMP) on solvothermal synthesis of [Zn4O(BDC)3]8 were investigated through a combined DFT and experimental study. XRD and SEM showed that the absorbability of NMP in the pore of [Zn4O(BDC)3]8 was weaker than that of DMF. The thermal decomposition temperature of [Zn4O(BDC)3]8 synthesized in DMF was higher than that in NMP according to TG and FT-IR. In addition, the nitrogen sorption isotherms indicated that NMP improved gas sorption property of [Zn4O(BDC)3]8. The COSMO optimized calculations indicated that the total energy of Zn4O(BDC)3 in NMP was higher than that in DMF, and compared with non-solvent system, the charge of zinc atoms decreased and the charge value was the smallest in NMP. Furthermore, the interaction of DMF, NMP or DEF in [Zn4O(BDC)3]8 crystal model was calculated by DFT method. The results suggested that NMP should be easier to be removed from pore of materials than DMF from the point of view of energy state. It can be concluded that NMP was a favorable solvent to synthesize [Zn4O(BDC)3]8 and the microscopic mechanism was that the binding force between Zn4O(BDC)3 and NMP molecule was weaker than DMF.展开更多
Many methods are proposed to deal with the type synthesis of parallel kinematic mechanisms(PKMs), but most of them are less intuitive to some extent. Thus, to propose a concise and intuitive type synthesis method fo...Many methods are proposed to deal with the type synthesis of parallel kinematic mechanisms(PKMs), but most of them are less intuitive to some extent. Thus, to propose a concise and intuitive type synthesis method for engineering application is a very challenging issue, which should be further studied in the field. Grassmann line geometry, which can investigate the dimensions of spatial line-clusters in a concise way, is taken as the mathematic foundation. Atlas method is introduced to visually describe the degrees of freedom(DOFs) and constraints of a mechanism, and the dual rule is brought in to realize the mutual conversion of the freedom-space and constraint-space. Consequently, a systematic method based on Grassmann line geometry and Atlas method is generated and the entire type synthesis process is presented. Three type 4-DOF PKMs, i.e., 1T3R, 2T2R and 3T1R(T: translational DOF; R: rotational DOF), are classified according to the different combinations of the translational DOFs and rotational DOFs. The type synthesis of 4-DOF PKMs is carried out and the possible configurations are thoroughly investigated. Some new PKMs with useful functions are generated during this procedure. The type synthesis method based on Grassmann line geometry and Atlas method is intuitive and concise, and can reduce the complexity of the PKMs' type synthesis. Moreover, this method can provide theoretical guidance for other PKMs' type synthesis and engineering application. A novel type synthesis method is proposed, which solves the existing methods' problems in terms of complicated, not intuitive and unsuitable for practical application.展开更多
Nanosize cerium-zirconium solid solution(CZO)with a special fluorite structure has received an increasing research interest due to their remarkable advantages such as excellent oxygen storage capacity and great flexib...Nanosize cerium-zirconium solid solution(CZO)with a special fluorite structure has received an increasing research interest due to their remarkable advantages such as excellent oxygen storage capacity and great flexibility in their composition and structure.By partial metal(including rare earth,transition,alkaline earth or other metal)doping into CZO,the physicochemical properties of these catalytic materials can be controllable adjusted for the study of specific reactions.To date,nanosize CZO has been prepared by co-precipitation,sol-gel,surfactant-assisted approach,solution combustion,micro-emulsion,high energy mechanical milling,etc.The advent of these methodologies has prompted researchers to construct well-defined networks with customized micromorphology and functionalities.In this review,we describe not only the basic structure and synthetic strategies of CZO,but also their relevant applications in environmental catalysis,such as the purification for CO,nitrogen oxides(NOx),volatile organic compounds(VOC),soot,hydrocarbon(HC),CO2 and solid particulate matters(PM),and some reaction mechanisms are also summarized.展开更多
High purity Y_2O_3 nano-powders was synthesized directly from solution ofindustrial YCl_3 by method of oxalate precipitation through super-micro-reactors made by complexnon-ionic surfactant. The purity and diameter of...High purity Y_2O_3 nano-powders was synthesized directly from solution ofindustrial YCl_3 by method of oxalate precipitation through super-micro-reactors made by complexnon-ionic surfactant. The purity and diameter of Y_2O_3 particles were controlled by such processingparameters as concentration of YCl_3 and oxalic acid and complex non-ionic surfactant etc. TEMphotomicrographs show that Y_2O_3 particles are spherical in shape, with an average diameter of lessthan 30 nm. Test results certify that the purity and particle diameter as well as the dispersion ofY_2O_3 nano-powder depend on the concentrations of YCl_3, oxalic acid and complex non-ionicsurfactant. The optimum ranges of the concentrations for YCl_3 and complex non-ionic surfactant whenthe diameter of Y_2O_3 particles is smaller than 100 nm are 0.43 ~1.4 mol ? L^(-1) and0.031~0.112 mol·L^(-1) respectively, while the mass fraction range of oxalic acid is 10% ~18% .The purity of Y_2O_3 nano-powder tested by ICP-AES analysis is 99.99% .展开更多
LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4(M=Co,Ni,Mn) by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction(...LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4(M=Co,Ni,Mn) by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS).The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.展开更多
Using cetyltrimethylammonium bromide (CTAB) as the template agent, cerium nitrate as the cerium resource, yttrium nitrate as the yttrium resource, and ammonium carbonate as the precipitating agent, mesoporous CeO2 p...Using cetyltrimethylammonium bromide (CTAB) as the template agent, cerium nitrate as the cerium resource, yttrium nitrate as the yttrium resource, and ammonium carbonate as the precipitating agent, mesoporous CeO2 powders doped with different yttrium contents were successfully synthesized using a chemical precipitation method, under an alkalescent condition. Properties of the obtained samples were characterized and analyzed with X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX), transmission electron microscopy (TEM), infrared (IR) absorbance, and the BET method. For the prepared samples with 20% (molar ratio) Y-doped content, a BET specific surface area of 106. 6 m^2 · g^- 1, with an average pore size of3~27 nm were obtained. XRD patterns showed that the doped samples were with a cubic fluorite structure. TEM micrographs revealed that the doped samples showed a spherical morphology with a diameter ranging from 20 to 30 nm and a round pore shape. IR results indicated that the Ce-O-Ce vibration intensity decreased as the Y-doped content increased. N2 adsorption-desorption isotherms showed that the samples possessed typical mesopore characteristics. The average pore size of the samples decreased alter mesoporous CeO2 was doped with yttrium, and the average pore size decreased largely as the Y-doped content increased.展开更多
The mechanism of self-propagating high-temperature synthesis (SHS) of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scannin...The mechanism of self-propagating high-temperature synthesis (SHS) of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scanning electron microscope (SEM) with energy dispersive X-ray (EDX) spectrometry, and the combustion temperature was measured. The results showed that the combustion reaction started with local formation of Ti-Cu melt and could be described with the dissolution-precipitation mechanism, namely, Ti, Cu, and C particles dissolved into the Ti-Cu solution and TiC particles precipitated in the saturated Ti-Cu-C liquid solution. The local formation of Ti-Cu melt resulted from the solid diffusion between Ti and Cu particles.展开更多
Gold nanoparticles with different shapes and sizes were prepared by adding gold precursor (HAuC14) to an electrolyzed aqueous solution of poly(N-vinylpyrrolidone) (PVP) and KN03, which indicates the good reducin...Gold nanoparticles with different shapes and sizes were prepared by adding gold precursor (HAuC14) to an electrolyzed aqueous solution of poly(N-vinylpyrrolidone) (PVP) and KN03, which indicates the good reducing capacity of the PVP-containing solution after being treated by electrolysis. Using a catholyte and an anolyte as the reducing agents for HAuC14,' respectively, most gold nanoparticles were spherical particles in the former case but plate-like particles in the latter case. The change in the pH value of electrolytes caused by the electrolysis of water would be the origin of the differences in shape and morphology of gold nanoparticles. A hypothesis of the H+ or OH- catalyzed PVP degradation mechanism was proposed to interpret why the pH value played a key role in determining the shape or morphology of gold nanoparticles. These experiments open up a new method for effectively controlling the shape and morphology of metal nanoparticles by using electrochemical methods.展开更多
High quality potassium hexatitanate whiskers were hydrothermally synthesized in one step under moderate temperature and pressure conditions. Effects of the titanium source and reaction conditions on the hydrothermal r...High quality potassium hexatitanate whiskers were hydrothermally synthesized in one step under moderate temperature and pressure conditions. Effects of the titanium source and reaction conditions on the hydrothermal reaction rate, product phase component, and morphology of whiskers were investigated. The results show that the reactivity of hydrated titania, anatase TiO2, and rutile TiO2 with KOH decreases in turn, and with hydrated titania as titanium source, it is difficult to obtain potassium hexatitanate whiskers with good morphology. In contrast, uniform potassium hexatitanate whiskers with a length of 10-20 μm and a diameter of 200-700 nm were obtained using anatase TiO2 as titanium source. The investigation demonstrates that the initial KOH concentration, annealing temperature and time, molar ratio of K2O/TiO2, etc. significantly affect the morphology of the as-synthesized whiskers. The optimized synthesis condition is as follows: anatase as a titanium source 10 wt.% KOH solution; annealing temperature and time of 300℃ and 5 h, respectively; K2O/TiO2 molar ratio of 5, etc. A rhombic potassium hexatitanate was prepared under the optimum condition and the whisker grew along the [110] direction. The reaction mechanism was discussed.展开更多
In order to investigate the mechanism of combustion synthesis of TiC-Ti cermet, a mixture of Ti and C was used for a combustion front quenching test, and the microstructural evolution in the quenched sample was analyz...In order to investigate the mechanism of combustion synthesis of TiC-Ti cermet, a mixture of Ti and C was used for a combustion front quenching test, and the microstructural evolution in the quenched sample was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). Also, a temperature-time profile of the combustion reaction was measured. Based on the experimental results, a reaction-dissolution-precipitation mechanism of the combustion synthesis of TiC-Ti was proposed.展开更多
The controllable synthesis of tantalate K1.9Na0.1Ta2O6·2H2O has been successfully achieved by a two-step technique,namely,the molten salt and hydrothermal methods,at a low temperature. By simply varying the KOH c...The controllable synthesis of tantalate K1.9Na0.1Ta2O6·2H2O has been successfully achieved by a two-step technique,namely,the molten salt and hydrothermal methods,at a low temperature. By simply varying the KOH concentration in the hydrothermal process,K1.9Na0.1Ta2O6·2H2O particles with spherical,cuboctahedral,and durian-like morphologies were synthesized. The photocatalytic activity of the obtained samples for the degradation of rhodamine B was studied under ultraviolet light,which indicates that the photocatalytic properties of the samples are highly dependent on their morphologies. The K1.9Na0.1Ta2O6·2H2O nanospheres,with rough surfaces and the highest specific surface area,exhibit the best performance. The present work provides a unique approach for the controlled synthesis of tantalate photocatalysts,which are difficult to achieve through other synthetic approaches.展开更多
Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate therm...Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate thermodynamic data provide basic thermodynamic quantities for the actual chemical engineering process and are useful in analyzing product distribution because FTS demonstrates many features of an equilibrium-controlled system. Our results show that the number of thermodynamically allowed products to increase when lowering temperature, raising pressure, and raising H2/CO ratio. At low temperature, high pressure and high H2/CO ratio, many products are thermodynamically allowed and the selectivity of product has to be controlled by kinetic factors. On the other hand, high selectivity of lighter products can be realized in thermodynamics by raising temperature and lowering pressure. We found that the equilibrium product yield will reach a maximum and remain unchanged when lowering temperature, raising pressure, and raising H2/CO ratio to some limits, implying that optimizing reaction conditions has no effect on equilibrium product yields beyond these limits. The thermodynamic analysis is also useful in designing and evaluating FTS reaction mechanisms. We found that reaction pathways through formaldehyde should be discarded because of its extremely low equilibrium yield. Recently, in the FTS process using metal-oxide-zeolite catalysts for the highly selective production of C2-C4 olefins and aromatic hydrocarbons, there are several guesses on the possible reaction intermediates entering the zeolite channel. Our results show that ketene, methanol, and dimethyl ether are three possible reaction intermediates.展开更多
基金supported by Basic Frontier Scientific Research of the Chinese Academy of Sciences(ZDBS-LY-JSC041)the National Natural Science Foundation of China(22178348)+1 种基金the open research fund of the State Key Laboratory of Mesoscience and Engineering(MESO-23-D06)the Youth Innovation Promotion Association CAS(292021000085)。
文摘Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.
文摘The ZnO molecule plays an important role in the industry due to it special features, anti-corrosion anti-bacterial properties, as well as due to its low electrical conductivity and heat resistance. In these experimental researches, the sol-gel method was chosen, which enables control of nucleation, aging and growth of particles in the solution. ZnO synthesis was prepared utilizing chemical method with Zinc acetate dyhidrate and NaOH with the appropriate methanol solvent and heating (60˚C). The methods used in identification and characterization are FTIR, UV/VIS, OPTICAL MICROSCOPY, SEM and XRD. The FTIR spectra of synthesized ZnO with corresponding ones show characteristic bands at the corresponding wavelengths, which confirm the presence of ZnO nanoparticles. SEM characterization of ZnO shows the morphology of needle-shaped nanoparticles. XRD spectar in this research by chemical method indicates the particle size of 17.76 nm.
文摘With the recent advancement in nanotechnology,nanoparticles(NPs)offer an ample variety of smart functions than conventional materials in various aspects.As compared to larger particles,NPs possess unique characteristics and excellent abilities,such as low toxicity,chemical stability,surface functionality,and biocompatibility.These advantageous properties allow them to be widely utilized in many applications,including biomedical applications,energy applications,IT applications,and industrial applications.In order to fulfill the increasing demands of NP applications,existing NP synthesis methods need to be improved based on the requirements of different applications to further their usage.A comprehensive understanding of the relationships between synthesis parameters and properties of NPs can help us better fine-tune them with designed properties and minimal toxicity.This review paper will discuss the commonly used synthesis methods of functionalized NPs,as well as future directions and challenges to develop various synthesis methods further.
基金supported by the National Natural Science Foundation of China (Nos. 21822407 and 22074154)Youth Innovation Promotion Association CAS (2021420)the Foundation for Sci & Tech Research Project of Gansu Province (20JR10RA045 and 20JR5RA573)。
文摘Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.
文摘A brief review of the works of the author and his co-authors on the application of nonlinear analysis, numerical and analytical methods for solving the nonlinear inverse problems (synthesis problems) for optimizing the different types of radiating systems, is presented in the paper. The synthesis problems are formulated in variational statements and further they are reduced to research and numerical solution of nonlinear integral equations of Hammerstein type. The existence theorems are proof, the investigation methods of nonuniqueness problem of solutions and numerical algorithms of finding the optimal solutions are proved.
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
基金Project(51104185)supported by the National Natural Science Foundation of ChinaProject(2010QZZD003)supported by the Key Project of Central South University of Fundamental Research Funds for the Central Universities of China
文摘In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) or N-methyl- 2-pyrrolidone(NMP) on solvothermal synthesis of [Zn4O(BDC)3]8 were investigated through a combined DFT and experimental study. XRD and SEM showed that the absorbability of NMP in the pore of [Zn4O(BDC)3]8 was weaker than that of DMF. The thermal decomposition temperature of [Zn4O(BDC)3]8 synthesized in DMF was higher than that in NMP according to TG and FT-IR. In addition, the nitrogen sorption isotherms indicated that NMP improved gas sorption property of [Zn4O(BDC)3]8. The COSMO optimized calculations indicated that the total energy of Zn4O(BDC)3 in NMP was higher than that in DMF, and compared with non-solvent system, the charge of zinc atoms decreased and the charge value was the smallest in NMP. Furthermore, the interaction of DMF, NMP or DEF in [Zn4O(BDC)3]8 crystal model was calculated by DFT method. The results suggested that NMP should be easier to be removed from pore of materials than DMF from the point of view of energy state. It can be concluded that NMP was a favorable solvent to synthesize [Zn4O(BDC)3]8 and the microscopic mechanism was that the binding force between Zn4O(BDC)3 and NMP molecule was weaker than DMF.
基金supported by National Natural Science Foundation of China(Grant No.51135008)National Basic Research Program of China(973 Program,Grant No.2013CB035400)China Postdoctoral Science Foundation(Grant Nos.2012M520256,2013T60107)
文摘Many methods are proposed to deal with the type synthesis of parallel kinematic mechanisms(PKMs), but most of them are less intuitive to some extent. Thus, to propose a concise and intuitive type synthesis method for engineering application is a very challenging issue, which should be further studied in the field. Grassmann line geometry, which can investigate the dimensions of spatial line-clusters in a concise way, is taken as the mathematic foundation. Atlas method is introduced to visually describe the degrees of freedom(DOFs) and constraints of a mechanism, and the dual rule is brought in to realize the mutual conversion of the freedom-space and constraint-space. Consequently, a systematic method based on Grassmann line geometry and Atlas method is generated and the entire type synthesis process is presented. Three type 4-DOF PKMs, i.e., 1T3R, 2T2R and 3T1R(T: translational DOF; R: rotational DOF), are classified according to the different combinations of the translational DOFs and rotational DOFs. The type synthesis of 4-DOF PKMs is carried out and the possible configurations are thoroughly investigated. Some new PKMs with useful functions are generated during this procedure. The type synthesis method based on Grassmann line geometry and Atlas method is intuitive and concise, and can reduce the complexity of the PKMs' type synthesis. Moreover, this method can provide theoretical guidance for other PKMs' type synthesis and engineering application. A novel type synthesis method is proposed, which solves the existing methods' problems in terms of complicated, not intuitive and unsuitable for practical application.
基金financially supported by the National Natural Science Foundation of China (21673290, U1662103)~~
文摘Nanosize cerium-zirconium solid solution(CZO)with a special fluorite structure has received an increasing research interest due to their remarkable advantages such as excellent oxygen storage capacity and great flexibility in their composition and structure.By partial metal(including rare earth,transition,alkaline earth or other metal)doping into CZO,the physicochemical properties of these catalytic materials can be controllable adjusted for the study of specific reactions.To date,nanosize CZO has been prepared by co-precipitation,sol-gel,surfactant-assisted approach,solution combustion,micro-emulsion,high energy mechanical milling,etc.The advent of these methodologies has prompted researchers to construct well-defined networks with customized micromorphology and functionalities.In this review,we describe not only the basic structure and synthetic strategies of CZO,but also their relevant applications in environmental catalysis,such as the purification for CO,nitrogen oxides(NOx),volatile organic compounds(VOC),soot,hydrocarbon(HC),CO2 and solid particulate matters(PM),and some reaction mechanisms are also summarized.
文摘High purity Y_2O_3 nano-powders was synthesized directly from solution ofindustrial YCl_3 by method of oxalate precipitation through super-micro-reactors made by complexnon-ionic surfactant. The purity and diameter of Y_2O_3 particles were controlled by such processingparameters as concentration of YCl_3 and oxalic acid and complex non-ionic surfactant etc. TEMphotomicrographs show that Y_2O_3 particles are spherical in shape, with an average diameter of lessthan 30 nm. Test results certify that the purity and particle diameter as well as the dispersion ofY_2O_3 nano-powder depend on the concentrations of YCl_3, oxalic acid and complex non-ionicsurfactant. The optimum ranges of the concentrations for YCl_3 and complex non-ionic surfactant whenthe diameter of Y_2O_3 particles is smaller than 100 nm are 0.43 ~1.4 mol ? L^(-1) and0.031~0.112 mol·L^(-1) respectively, while the mass fraction range of oxalic acid is 10% ~18% .The purity of Y_2O_3 nano-powder tested by ICP-AES analysis is 99.99% .
基金financially supported by the National High-Tech Research and Development(863) Program of China(No.2006AA11A160)the National Natural Science Foundation of China(No.50604018)
文摘LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4(M=Co,Ni,Mn) by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS).The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.
基金Project supported by the International Cooperation of Science and Technology Ministry PRC (2005DFBA028)the National Natural Science Foundation of China (59925412)
文摘Using cetyltrimethylammonium bromide (CTAB) as the template agent, cerium nitrate as the cerium resource, yttrium nitrate as the yttrium resource, and ammonium carbonate as the precipitating agent, mesoporous CeO2 powders doped with different yttrium contents were successfully synthesized using a chemical precipitation method, under an alkalescent condition. Properties of the obtained samples were characterized and analyzed with X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX), transmission electron microscopy (TEM), infrared (IR) absorbance, and the BET method. For the prepared samples with 20% (molar ratio) Y-doped content, a BET specific surface area of 106. 6 m^2 · g^- 1, with an average pore size of3~27 nm were obtained. XRD patterns showed that the doped samples were with a cubic fluorite structure. TEM micrographs revealed that the doped samples showed a spherical morphology with a diameter ranging from 20 to 30 nm and a round pore shape. IR results indicated that the Ce-O-Ce vibration intensity decreased as the Y-doped content increased. N2 adsorption-desorption isotherms showed that the samples possessed typical mesopore characteristics. The average pore size of the samples decreased alter mesoporous CeO2 was doped with yttrium, and the average pore size decreased largely as the Y-doped content increased.
基金This work was financially supported by the Natural Science Foundation of Shaanxi Province, China (No.2004E107)
文摘The mechanism of self-propagating high-temperature synthesis (SHS) of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scanning electron microscope (SEM) with energy dispersive X-ray (EDX) spectrometry, and the combustion temperature was measured. The results showed that the combustion reaction started with local formation of Ti-Cu melt and could be described with the dissolution-precipitation mechanism, namely, Ti, Cu, and C particles dissolved into the Ti-Cu solution and TiC particles precipitated in the saturated Ti-Cu-C liquid solution. The local formation of Ti-Cu melt resulted from the solid diffusion between Ti and Cu particles.
基金supported by the National Natural Science Foundation of China(No.21073111)the Natural Science Foundation of Shandong Province,China(No.ZR2010BQ029)
文摘Gold nanoparticles with different shapes and sizes were prepared by adding gold precursor (HAuC14) to an electrolyzed aqueous solution of poly(N-vinylpyrrolidone) (PVP) and KN03, which indicates the good reducing capacity of the PVP-containing solution after being treated by electrolysis. Using a catholyte and an anolyte as the reducing agents for HAuC14,' respectively, most gold nanoparticles were spherical particles in the former case but plate-like particles in the latter case. The change in the pH value of electrolytes caused by the electrolysis of water would be the origin of the differences in shape and morphology of gold nanoparticles. A hypothesis of the H+ or OH- catalyzed PVP degradation mechanism was proposed to interpret why the pH value played a key role in determining the shape or morphology of gold nanoparticles. These experiments open up a new method for effectively controlling the shape and morphology of metal nanoparticles by using electrochemical methods.
文摘High quality potassium hexatitanate whiskers were hydrothermally synthesized in one step under moderate temperature and pressure conditions. Effects of the titanium source and reaction conditions on the hydrothermal reaction rate, product phase component, and morphology of whiskers were investigated. The results show that the reactivity of hydrated titania, anatase TiO2, and rutile TiO2 with KOH decreases in turn, and with hydrated titania as titanium source, it is difficult to obtain potassium hexatitanate whiskers with good morphology. In contrast, uniform potassium hexatitanate whiskers with a length of 10-20 μm and a diameter of 200-700 nm were obtained using anatase TiO2 as titanium source. The investigation demonstrates that the initial KOH concentration, annealing temperature and time, molar ratio of K2O/TiO2, etc. significantly affect the morphology of the as-synthesized whiskers. The optimized synthesis condition is as follows: anatase as a titanium source 10 wt.% KOH solution; annealing temperature and time of 300℃ and 5 h, respectively; K2O/TiO2 molar ratio of 5, etc. A rhombic potassium hexatitanate was prepared under the optimum condition and the whisker grew along the [110] direction. The reaction mechanism was discussed.
文摘In order to investigate the mechanism of combustion synthesis of TiC-Ti cermet, a mixture of Ti and C was used for a combustion front quenching test, and the microstructural evolution in the quenched sample was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). Also, a temperature-time profile of the combustion reaction was measured. Based on the experimental results, a reaction-dissolution-precipitation mechanism of the combustion synthesis of TiC-Ti was proposed.
基金supported by the National Natural Science Foundation of China(U140319321473261+3 种基金41305112)the Excellent Youth Foundation of Xinjiang Uygur Autonomous Region(2013711004)the CAS "Light of West China" Program(YB201303)the CAS/SAFEA International Partnership Program for Creative Research Teams~~
文摘The controllable synthesis of tantalate K1.9Na0.1Ta2O6·2H2O has been successfully achieved by a two-step technique,namely,the molten salt and hydrothermal methods,at a low temperature. By simply varying the KOH concentration in the hydrothermal process,K1.9Na0.1Ta2O6·2H2O particles with spherical,cuboctahedral,and durian-like morphologies were synthesized. The photocatalytic activity of the obtained samples for the degradation of rhodamine B was studied under ultraviolet light,which indicates that the photocatalytic properties of the samples are highly dependent on their morphologies. The K1.9Na0.1Ta2O6·2H2O nanospheres,with rough surfaces and the highest specific surface area,exhibit the best performance. The present work provides a unique approach for the controlled synthesis of tantalate photocatalysts,which are difficult to achieve through other synthetic approaches.
基金the National Natural Science Foundation of China (No.91645201, No.21873019 and No.21573044).
文摘Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate thermodynamic data provide basic thermodynamic quantities for the actual chemical engineering process and are useful in analyzing product distribution because FTS demonstrates many features of an equilibrium-controlled system. Our results show that the number of thermodynamically allowed products to increase when lowering temperature, raising pressure, and raising H2/CO ratio. At low temperature, high pressure and high H2/CO ratio, many products are thermodynamically allowed and the selectivity of product has to be controlled by kinetic factors. On the other hand, high selectivity of lighter products can be realized in thermodynamics by raising temperature and lowering pressure. We found that the equilibrium product yield will reach a maximum and remain unchanged when lowering temperature, raising pressure, and raising H2/CO ratio to some limits, implying that optimizing reaction conditions has no effect on equilibrium product yields beyond these limits. The thermodynamic analysis is also useful in designing and evaluating FTS reaction mechanisms. We found that reaction pathways through formaldehyde should be discarded because of its extremely low equilibrium yield. Recently, in the FTS process using metal-oxide-zeolite catalysts for the highly selective production of C2-C4 olefins and aromatic hydrocarbons, there are several guesses on the possible reaction intermediates entering the zeolite channel. Our results show that ketene, methanol, and dimethyl ether are three possible reaction intermediates.