The main problem in an efficient Zn(CH3COO)2/AC (AC-activated carbon) catalyst preparation is the achievement of uniform distribution of highly dispersed salt component on the activated carbon (AC) surface. The ...The main problem in an efficient Zn(CH3COO)2/AC (AC-activated carbon) catalyst preparation is the achievement of uniform distribution of highly dispersed salt component on the activated carbon (AC) surface. The solution of this problem is modification of the AC by hydrogen peroxide (H202) oxidation of the surface and treatment of AC with acetic acid as well as special methods of salt deposition and catalyst drying. The investigations of these ways of AC surface modification (treatment of AC with acetic acid and H2O2) have demonstrated the obtained AC to have both an increased adsorption capacity as to Zn(OAc)2 and optimum volumes of meso- and micro-pores as well as high catalyst activity in vinyl acetate (VA) synthesis. The characteristics of supports and catalysts were found out by benzene, water and acetic acid vapors adsorption. The distribution of the salt on the AC surface was studied by small-angle X-ray scattering (SAXS), by scanning electron microscopy (SEM) and X-ray micro-analysis (XMA). The catalysts were tested in vinyl acetate synthesis in flow-bed isothermal reactor by cyclic method at 175, 205 and 230℃.展开更多
Polyether and polyether/ester based TPU (thermoplastic polyurethanes) were investigated with wide-angle XRD (X-ray diffraction) and SAXS (small angle X-ray scattering). Furthermore, SAXS measurements were perfor...Polyether and polyether/ester based TPU (thermoplastic polyurethanes) were investigated with wide-angle XRD (X-ray diffraction) and SAXS (small angle X-ray scattering). Furthermore, SAXS measurements were performed in the temperature range of 30 ℃ to 130 ℃. Polyether based polymers exhibit only one broad diffraction signal in a region of 2 θ 15° to 25°. In case of polyurethanes with ether/ester modification, the broad diffraction signal arises with small sharp diffraction signals. SAXS measurements of polymers reveal the size and shape of the crystalline zones of the polymer. Between 30 ℃ and 130 ℃ the size of the crystalline zone changes significantly. The size decreases in most of investigated TPU. In the case of Desmopan 9365D an increase of the particle size was observed.展开更多
Different amounts of FCC slurry oil and HVGO were added to Tahe atmospheric residue respectively. The colloi- dal stability and asphaltene agglomeration of atmospheric residue and mixed oils were characterized by mean...Different amounts of FCC slurry oil and HVGO were added to Tahe atmospheric residue respectively. The colloi- dal stability and asphaltene agglomeration of atmospheric residue and mixed oils were characterized by means of the mass fraction normalized conductivity and the small-angle X-ray scattering technology (SAXS). The results indicated that the sta- bility of Tahe atmospheric residue decreased with an increasing amount of these oil fractions. It was found that the decline of the colloidal stability was attributed to the component polarity difference between oil fractions and the atmospheric resi- due. Though the aromaticity of FCC slurry oil was higher than that of HVGO, the polarity of aromatics and resins of FCC slurry oil was lower than those of HVGO. So the degree of the colloidal stability was more seriously destroyed by FCC slurry oil. The dispersion of asphaltenes in Tahe atmospheric residue was changed by adding FCC slurry oil and HVGO. The particle size of as-ohaltenes increased alon~ with the decline of the colloidal stability展开更多
Asphaltene is one of the most heavy components, asphaltene adsorption is a serious problem in oil production and processing. In this paper, the progress in the investigation of asphaltene adsorption from the aspects o...Asphaltene is one of the most heavy components, asphaltene adsorption is a serious problem in oil production and processing. In this paper, the progress in the investigation of asphaltene adsorption from the aspects of adsorption model and adsorption behavior is reviewed. Asphaltene of adsorption model include the Langmuir, Freundlich, Langmuir-Freundlich, Rcdlich-Pctcrson, BET adsorption isothcrm. The adsorption behavior of asphaltene was characterized by a variety of structure-probing methods such as N:-adsorption, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS) measurements, and FT-IR spectroscopy. To understand better the adsorption progress of petroleum, asphaltene must understand the whole adsorption behavior of asphaltene.展开更多
The phase behaviors of the complex formed by didodecyldimethylammonium bromide(DDAB)and cetyltrimethylammonium bromide(CTAB)interacting with three different types of DNAs,salmon testes DNA(~2000 bp),21-bp double...The phase behaviors of the complex formed by didodecyldimethylammonium bromide(DDAB)and cetyltrimethylammonium bromide(CTAB)interacting with three different types of DNAs,salmon testes DNA(~2000 bp),21-bp double-stranded oligonucleotides(oligo-ds DNA),and 21-nt single-stranded oligonucleotides(oligo-ss DNA)were studied by synchrotron small-angle X-ray scattering.It was found that the DNA length and flexibility,together with the positive/negative charge ratio,determined the final structure.At higher charge ratios,the DNA length exhibited negligible effect.Both oligo-ds DNA and salmon DNA formed inverted hexagonal packing of cylinders with CTAB,as well as bilayered lamella with DDAB.However,at lower charge ratios,oligo-ds DNA formed a distorted hexagonal phase with CTAB and a new structure with DDAB,which was different from the behaviors of salmon DNA.The flexible oligo-ss DNA formed rich structures that were subject to environmental disturbance.Kinetic study also indicated that the structures of the complex formed by oligo-ss DNA took much longer to mature than the structures formed by oligo-ds DNA.We attributed this result to the conformational adjustment of oligo-ss DNA in the complex.展开更多
Pore structure of Chinese coals with heating and pressurization treatments was studied using small angle X-ray scattering (SAXS), N2 adsorption/desorption isotherms and scanning electron microscope (SEM). SAXS was...Pore structure of Chinese coals with heating and pressurization treatments was studied using small angle X-ray scattering (SAXS), N2 adsorption/desorption isotherms and scanning electron microscope (SEM). SAXS was performed for some sam- ples after heat treatment at seven elevated temperatures from 25 to 250℃ at 0 MPa and for other samples with hydrostatic pressure treatment at 0, 5, 10, 15 and 20 MPa at the room temperature. The results show that N2 adsorption isotherm together with SAXS could be a comprehensive method to evaluate the pore shape and the pore size distribution: the pore shapes are generally spherical for low rank coal and they are mainly ellipsoidal for high rank coal. All these measurements were then interpreted using the fractal theory to reveal relationship between surface fractals and coal rank, and the evolution of surface fractals under heating and pressurization treatments. The results show that surface fractal dimension (Ds) changes with different treating temperature and pressure and maximum vitrinite reflectance (Ro,m). Especially in the bituminous stage, Ds shows an increasing trend with Ro,m under varied temperatures. Moreover, Ds shows an increasing trend with increasing temperature before 200℃, and a decreasing trend after 200℃. Furthermore, the results show that Ds has a more complex relationship with Ro.m under varied treating temperature than that under varied treating pressure.展开更多
Membranes with high ion conductivity and selectivity are important for vanadium redox flow batteries.Herein, densely quaternized anion exchange membranes based on quaternary ammonium functionalized octa-benzylmethyl-c...Membranes with high ion conductivity and selectivity are important for vanadium redox flow batteries.Herein, densely quaternized anion exchange membranes based on quaternary ammonium functionalized octa-benzylmethyl-containing poly(fluorenyl ether ketone)s(QA-OMPFEKs) were prepared from the(i) condensation polymerization of a newly developed octa-benzylmethyl-containing bisphenol monomer via Ullmann coupling,(ii) bromination at the benzylmethyl sites using N-bromosuccinimide, and(iii)quaternization of the bromomethyl groups using trimethylamine. The QA-OMPFEK-20 with an ion exchange capacity(IEC) of 1.66 mmolg^-1 exhibited a higher SO42-conductivity(9.62mScm^-1) than that of the QA-TMPFEK-40(4.82mScm^-1) at room temperature, which had a slightly higher IEC of 1.73 mmolg-1but much lower QA density.The enhanced SO42-conductivity of QA-OMPFEK-20 was attributed to the ion-segregated structure arising from the densely anchored QA groups, which was validated by SAXS observation. Furthermore, the QA-OMPFEK-20 showed much lower VO2+permeability(1.24×10^-14m^2s^-1) than QA-TMPFEK-40(5.40×10^-13m^2s^-1) and Nafion N212(5.36×10^-12m^2s^-1), leading to improved Coulombic and energy efficiencies in Vanadium redox flow batteries(VRFBs). Therefore, the Ullmann coupling extension is a valuable approach for the development of high performance anion exchange membranes for VRFBs.展开更多
Flow-induced preordering or precursor(FIP) has been studied in a series of lightly cross-linked high-density polyethylene with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray ...Flow-induced preordering or precursor(FIP) has been studied in a series of lightly cross-linked high-density polyethylene with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray scattering(SAXS) and wide-angle X-ray diffraction(WAXD) measurements. Based on the incipient strains of SAXS and WAXD signals during extension in a large temperature range, strain-temperature diagrams for flow-induced preordering and nucleation were constructed and revealed that flow-induced crystallization(FIC) undergoes two stages: melt-precursor transition(MPT) and precursor-nuclei transition(PNT). At different temperatures, FIP with different inner structures and morphologies can be induced by strain; these embryos have shape and structure that are related to those of the corresponding critical nuclei. With the strain-temperature diagrams, the thermodynamic properties of FIP are deduced, which shows that compared with the relative nuclei the FIP always has a lower bulk free energy(?H) and a much lower surface free energy(?e). In extreme cases(high temperature), the ?e of FIP can be negligible. The quantitative estimation of the thermodynamic parameters suggests the existence of variant FIPs, which plays a vital role for the subsequent progress of PNT and the whole process of FIC.展开更多
文摘通过小角X-射线散射与结构预测的方法研究人乳β-酪蛋白的3级结构,并分析其生理功能。通过使用DEAE Sepharose FAST Flow琼脂糖凝胶获得纯度大于90%的β-酪蛋白纯品,并对其溶液进行小角X-射线散射(0.2 mol磷酸盐缓冲溶液,10 mmol DTT,p H 6.7),将获得的人乳β-酪蛋白的结构信息与通过折叠识别及从头预测构建的预测模型进行比较,筛选出在试验条件下与试验结果最相符的人乳β-酪蛋白3级结构模型,该模型结构松散,含有较少的α-螺旋和β-折叠。同时结合模型对人乳β-酪蛋白磷酸化、糖基化及脂质化等蛋白质功能位点进行了分析,认为人乳β-酪蛋白含有12个可以与乳糖或葡萄糖结合的糖基化位点,7个脂质化位点,其磷酸化位点与已知的5个磷酸化位点相符。
文摘The main problem in an efficient Zn(CH3COO)2/AC (AC-activated carbon) catalyst preparation is the achievement of uniform distribution of highly dispersed salt component on the activated carbon (AC) surface. The solution of this problem is modification of the AC by hydrogen peroxide (H202) oxidation of the surface and treatment of AC with acetic acid as well as special methods of salt deposition and catalyst drying. The investigations of these ways of AC surface modification (treatment of AC with acetic acid and H2O2) have demonstrated the obtained AC to have both an increased adsorption capacity as to Zn(OAc)2 and optimum volumes of meso- and micro-pores as well as high catalyst activity in vinyl acetate (VA) synthesis. The characteristics of supports and catalysts were found out by benzene, water and acetic acid vapors adsorption. The distribution of the salt on the AC surface was studied by small-angle X-ray scattering (SAXS), by scanning electron microscopy (SEM) and X-ray micro-analysis (XMA). The catalysts were tested in vinyl acetate synthesis in flow-bed isothermal reactor by cyclic method at 175, 205 and 230℃.
文摘Polyether and polyether/ester based TPU (thermoplastic polyurethanes) were investigated with wide-angle XRD (X-ray diffraction) and SAXS (small angle X-ray scattering). Furthermore, SAXS measurements were performed in the temperature range of 30 ℃ to 130 ℃. Polyether based polymers exhibit only one broad diffraction signal in a region of 2 θ 15° to 25°. In case of polyurethanes with ether/ester modification, the broad diffraction signal arises with small sharp diffraction signals. SAXS measurements of polymers reveal the size and shape of the crystalline zones of the polymer. Between 30 ℃ and 130 ℃ the size of the crystalline zone changes significantly. The size decreases in most of investigated TPU. In the case of Desmopan 9365D an increase of the particle size was observed.
基金Financial support was provided by the Ministry of Science and Technology of China through the National Basic Research Program (Grant No. 2010CB217807)
文摘Different amounts of FCC slurry oil and HVGO were added to Tahe atmospheric residue respectively. The colloi- dal stability and asphaltene agglomeration of atmospheric residue and mixed oils were characterized by means of the mass fraction normalized conductivity and the small-angle X-ray scattering technology (SAXS). The results indicated that the sta- bility of Tahe atmospheric residue decreased with an increasing amount of these oil fractions. It was found that the decline of the colloidal stability was attributed to the component polarity difference between oil fractions and the atmospheric resi- due. Though the aromaticity of FCC slurry oil was higher than that of HVGO, the polarity of aromatics and resins of FCC slurry oil was lower than those of HVGO. So the degree of the colloidal stability was more seriously destroyed by FCC slurry oil. The dispersion of asphaltenes in Tahe atmospheric residue was changed by adding FCC slurry oil and HVGO. The particle size of as-ohaltenes increased alon~ with the decline of the colloidal stability
文摘Asphaltene is one of the most heavy components, asphaltene adsorption is a serious problem in oil production and processing. In this paper, the progress in the investigation of asphaltene adsorption from the aspects of adsorption model and adsorption behavior is reviewed. Asphaltene of adsorption model include the Langmuir, Freundlich, Langmuir-Freundlich, Rcdlich-Pctcrson, BET adsorption isothcrm. The adsorption behavior of asphaltene was characterized by a variety of structure-probing methods such as N:-adsorption, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS) measurements, and FT-IR spectroscopy. To understand better the adsorption progress of petroleum, asphaltene must understand the whole adsorption behavior of asphaltene.
基金financially supported by the National Natural Science Foundation of China(21174007)the National Basic Research Program of China(2012CB821500)
文摘The phase behaviors of the complex formed by didodecyldimethylammonium bromide(DDAB)and cetyltrimethylammonium bromide(CTAB)interacting with three different types of DNAs,salmon testes DNA(~2000 bp),21-bp double-stranded oligonucleotides(oligo-ds DNA),and 21-nt single-stranded oligonucleotides(oligo-ss DNA)were studied by synchrotron small-angle X-ray scattering.It was found that the DNA length and flexibility,together with the positive/negative charge ratio,determined the final structure.At higher charge ratios,the DNA length exhibited negligible effect.Both oligo-ds DNA and salmon DNA formed inverted hexagonal packing of cylinders with CTAB,as well as bilayered lamella with DDAB.However,at lower charge ratios,oligo-ds DNA formed a distorted hexagonal phase with CTAB and a new structure with DDAB,which was different from the behaviors of salmon DNA.The flexible oligo-ss DNA formed rich structures that were subject to environmental disturbance.Kinetic study also indicated that the structures of the complex formed by oligo-ss DNA took much longer to mature than the structures formed by oligo-ds DNA.We attributed this result to the conformational adjustment of oligo-ss DNA in the complex.
基金Scientific and Technological Research and Development Foundation of Shenzhen City(JC201005280504A)Shenzhen Key Laboratory of Functional Polymer Foundation(FP20110008)
基金National Major Research Program for Science and Technology of China (Grant No. 2011ZX05034-01)
文摘Pore structure of Chinese coals with heating and pressurization treatments was studied using small angle X-ray scattering (SAXS), N2 adsorption/desorption isotherms and scanning electron microscope (SEM). SAXS was performed for some sam- ples after heat treatment at seven elevated temperatures from 25 to 250℃ at 0 MPa and for other samples with hydrostatic pressure treatment at 0, 5, 10, 15 and 20 MPa at the room temperature. The results show that N2 adsorption isotherm together with SAXS could be a comprehensive method to evaluate the pore shape and the pore size distribution: the pore shapes are generally spherical for low rank coal and they are mainly ellipsoidal for high rank coal. All these measurements were then interpreted using the fractal theory to reveal relationship between surface fractals and coal rank, and the evolution of surface fractals under heating and pressurization treatments. The results show that surface fractal dimension (Ds) changes with different treating temperature and pressure and maximum vitrinite reflectance (Ro,m). Especially in the bituminous stage, Ds shows an increasing trend with Ro,m under varied temperatures. Moreover, Ds shows an increasing trend with increasing temperature before 200℃, and a decreasing trend after 200℃. Furthermore, the results show that Ds has a more complex relationship with Ro.m under varied treating temperature than that under varied treating pressure.
基金supported by the National Natural Science Foundation of China (51503038)
文摘Membranes with high ion conductivity and selectivity are important for vanadium redox flow batteries.Herein, densely quaternized anion exchange membranes based on quaternary ammonium functionalized octa-benzylmethyl-containing poly(fluorenyl ether ketone)s(QA-OMPFEKs) were prepared from the(i) condensation polymerization of a newly developed octa-benzylmethyl-containing bisphenol monomer via Ullmann coupling,(ii) bromination at the benzylmethyl sites using N-bromosuccinimide, and(iii)quaternization of the bromomethyl groups using trimethylamine. The QA-OMPFEK-20 with an ion exchange capacity(IEC) of 1.66 mmolg^-1 exhibited a higher SO42-conductivity(9.62mScm^-1) than that of the QA-TMPFEK-40(4.82mScm^-1) at room temperature, which had a slightly higher IEC of 1.73 mmolg-1but much lower QA density.The enhanced SO42-conductivity of QA-OMPFEK-20 was attributed to the ion-segregated structure arising from the densely anchored QA groups, which was validated by SAXS observation. Furthermore, the QA-OMPFEK-20 showed much lower VO2+permeability(1.24×10^-14m^2s^-1) than QA-TMPFEK-40(5.40×10^-13m^2s^-1) and Nafion N212(5.36×10^-12m^2s^-1), leading to improved Coulombic and energy efficiencies in Vanadium redox flow batteries(VRFBs). Therefore, the Ullmann coupling extension is a valuable approach for the development of high performance anion exchange membranes for VRFBs.
基金supported by the National Natural Science Foundation of China(51325301,51033004,51120135002,51227801)the Joint Fund of the National Natural Science Foundation of China and the China Academy of Engineering Physics(U1330202)+1 种基金Project 2013BB05 supported by the Key Laboratory of Neutron Physics,China Academy of Engineering Physicsin part supported by"Ludo Frevel Crystallography Scholarships"from the International Centre for Diffraction Data
文摘Flow-induced preordering or precursor(FIP) has been studied in a series of lightly cross-linked high-density polyethylene with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray scattering(SAXS) and wide-angle X-ray diffraction(WAXD) measurements. Based on the incipient strains of SAXS and WAXD signals during extension in a large temperature range, strain-temperature diagrams for flow-induced preordering and nucleation were constructed and revealed that flow-induced crystallization(FIC) undergoes two stages: melt-precursor transition(MPT) and precursor-nuclei transition(PNT). At different temperatures, FIP with different inner structures and morphologies can be induced by strain; these embryos have shape and structure that are related to those of the corresponding critical nuclei. With the strain-temperature diagrams, the thermodynamic properties of FIP are deduced, which shows that compared with the relative nuclei the FIP always has a lower bulk free energy(?H) and a much lower surface free energy(?e). In extreme cases(high temperature), the ?e of FIP can be negligible. The quantitative estimation of the thermodynamic parameters suggests the existence of variant FIPs, which plays a vital role for the subsequent progress of PNT and the whole process of FIC.