Interaction of tetradecyltrimethylammonium bromide with bovine serum albumin in different compositions: Effect of temperatures and electrolytes/urea

Herein, the interaction of a protein, bovine serum albumin (BSA), with tetradecyltrimethylammonium bromide (TTAB, a cationic surfactant), has been investigated using the conductivity measurement technique in pure water and some sodium salts (NaCl, Na₂SO₄, Na₂CO₃, and Na₃PO₄) solutions at temperature range of 295.15-320.15 K. Results reveal that, in the plot of specific conductivity versus the concentration of TTAB, only a single critical micelle concentration (cmc) was found for the TTAB + BSA mixed system in all solvents media studied. The addition of BSA in aqueous TTAB solution, the value of cmc undergoes a change from its pure form, which indicates the presence of strong interaction operating between the BSA and TTAB molecules. In aqueous system, the cmc values of the TTAB + BSA mixtures are obtained higher compared to the values found for single TTAB surfactant. However, the addition of salt decreases the cmc value of mixed TTAB + BSA system. The values of cmc of the BSA + TTAB mixed system at 310.15 K and 1.00 mmol·kg^-1 ionic strength of salt followed the order: cmc_Na2CO3 > cmc_Na3PO4 > cmc_NaCl > cmc_Na2SO4. The cmc values of TTAB + BSA mixture were found to be lowered in urea solution within the concentrations studied. The values of degree of dissociation (α) and fraction of counter ion binding (β) were found to be dependent on additives and temperature. The free energy of micellization (△G_m^o) is negative for all the systems, which manifests that the micellization phenomenon is energetically spontaneous. The enhancement of the negative value of △G_m^o in aqueous salt solutions reveals an increase of spontaneity of the TTAB + BSA micellization process. The values of △G_m^o also reveal that the spontaneity of micelle formation is enhanced at higher temperatures in all media studied. The values of free energy of transfer (△G_{m, t}^o) were also determined for numerous solvent media used in the present study and described with appropriate reasoning.     

Kinetics of the reduction of Mn at the dropping mercury electrode in aqueous-dioxan mixtures

Reduction of Mn²⁺ has been studied in aqueous dioxan mixtures at a dropping mercury electrode. The reduction has been found to be quasi-reversible and hence kinetic parameters (K_s and ) have been calculated by Gellings' method. The K_s values are found to be in the order of 10⁻³ cm/s. The effect of halide ions has also been studied in aqueous dioxan solvent mixtures using sodium chloride and sodium bromide as base electrolytes in place of sodium perchlorate. The effect of temperature has also been studied.     

Ce1-xNixOy氧载体在化学链甲烷重整耦合CO2还原中的应用

化学链甲烷重整耦合CO₂还原技术既能生产合成气还可以还原CO₂生成CO。采用共沉淀法制备不同Ce/Ni摩尔比的系列Ce_1-xNi_xO_{y（x = 0,0.2,0.4,0.6,0.8,1）氧载体。通过XRD、BET、XPS及CH4-TPR等表征对氧载体的理化性质进行了研究。系统考察了Ce1-xNixOy氧载体在化学链甲烷重整耦合CO2还原反应中的反应性能。与单一金属氧化物NiO和CeO2相比,Ce1-xNixOy复合氧载体在该反应中具有更高的活性和热稳定性。在甲烷部分氧化阶段,Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体具有较高的CH4转化率。经历了20次redox循环实验,Ce0.2Ni0.8Oy氧载体的CO2转化率几乎保持不变,表明Ce0.2Ni0.8Oy氧载体具有较高的热稳定性。}     

温度对氨基酸同系物在盐酸二甲双胍水溶液中体积和黏度特性的影响(英文)

Density(ρ)and viscosity(η)are measured for glycine,DL-α-alanine DL-α-valine,and DL-α-leucine in 0.05,0.10,0.15 and 0.20 mol·L-1aqueous metformin hydrochloride at 308.15,313.15 and 318.15 K.The measured values are used to estimate some important parameters,such as partial molal volume Vφ,standard partial molal volume0Vφ,transfer volume 0 ΔVφ,hydration number nH,the second derivative of infinite dilution of partial molal volume with respect to temperature,viz.,2 0 2 Vφ /T,viscosity B-coefficient,variation of B with temperature,viz., dB/dT,free energy of activation per mole of solvent0 * 1 Δμand solute 0* 2 Δμof the amino acids.These parameters are interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.In addition,0Vφ, 0 ΔVφ,viscosity B-coefficient,ΔB and 0* 2 Δμare split into group contributions(3NH COO +-)and CH2 of the amino acids using their linear correlation and their behavior is discussed.     

MnO x -ZSM-5脱硝催化剂制备的溶剂效应研究

MnO _x -ZSM-5脱硝催化剂具有较好的低温氨选择性催化还原反应（NH₃-SCR）活性,因其原料成本低、脱硝效率高等优点成为研究热点。详细叙述了采用蒸干溶剂法、通过调变制备过程中溶剂组成（乙醇和水或其混合溶液）制备系列MnO _x -ZSM-5催化剂,并首次研究了“溶剂效应”对催化剂脱硝性能产生影响的原因。利用X射线衍射（XRD）、光电子能谱仪（XPS）、程序升温氨吸附法（NH₃-TPD）、N₂物理吸附、氢气程序升温还原（H₂-TPR）以及扫描电子显微镜（SEM）等表征手段分析了催化剂物化性质、锰存在状态与催化性能之间的相互关系。结果发现,随着溶剂中水分占比的提高,MnO _x -ZSM-5脱硝催化剂的比表面积降低,具有高催化活性的Mn⁴⁺物种比例迅速下降,这些原因均导致催化剂的脱硝活性逐步降低。说明溶剂组成会影响催化剂的脱硝性能,因此在制备MnO _x -ZSM-5脱硝催化剂时选取合适的溶剂是至关重要的,这为如何制备高活性的MnO _x -ZSM-5脱硝催化剂提供了重要信息。     

脱硝协同汞氧化聚苯硫醚四元催化滤料制备方法及理化特性

采用原位氧化法（ISM）、浸渍煅烧法（ICM）和涂覆法（CM）制备聚苯硫醚（PPS）双效催化滤料,在模拟烟气固定床系统中考察了滤料低温NO_x催化协同Hg⁰氧化性能,深入分析了原位氧化滤料表面形貌、元素分布、晶态结构和Hg及NO_x赋存形态。结果表明：在相同条件下,3种制备方法对应滤料催化活性大小顺序为Mn-Ce-Fe-Co-O_x/PPS@ISM＞Mn-Ce-Fe-Co-O_x/PPS@ICM＞Mn-Ce-Fe-Co-O_x/PPS@CM。ISM对应PPS单层饱和负载量约为0.9,活性反应温度窗口为110~210℃,其中170℃时Mn-Ce-Fe-Co-O_x/PPS@ISM的非均相NO氧化、NO_x还原和Hg⁰氧化效率最高分别达到8.6%、84.6%和93.2%。程序升温脱附实验结果表明：(0.9)Mn-Ce-Fe-Co-O_x/PPS@ ISM表面NO_x吸附活性位点中弱碱位数量占优,而中碱位化学吸附NO主要以NO_y（y=2或3）结构存在,歧化态NO₂次之。同时,Hg与NO在氧气条件下以非均相反应途径转化为HgO和Hg(NO₃)₂/Hg₂(NO₃)₂。表征结果表明：ISM制备的MnO_x、CeO_x、CoO_x和Fe₂O₃复合氧化物呈弱晶相、高度分散团絮状结构赋存于PPS@ISM纤维。     

PC-88A为载体的大块液膜体系Cu(II)传输动力学

采用以2-乙基己基膦酸-2-乙基己基单酯(PC-88A)为载体、CHCl3为膜溶剂的大块液膜分离体系,研究了搅拌速度、载体浓度、体系温度对铜离子迁移的影响. 获得了不同反应温度下的表观反应速率常数,萃取与反萃取表观反应活化能分别为41.97和8.59 kJ/mol. 铜离子的迁移过程可用2个串联的准一级不可逆过程描述,萃取过程化学反应为控速步骤,反萃取过程扩散为控速步骤.     

面向烟气NOx净化与回收的新型吸附工艺

合理高效的吸附工艺是决定吸附法净化和回收烟气中NO_x工业可行性的关键工艺环节。提出一种通过外部补充气体实现固定床循环体空间内多次循环解吸NO_x的新型吸附工艺（GVTSA）。基于该工艺,采用Na-ZSM-5分子筛作为吸附剂,以某钢厂烧结机脱硫后烟气为原料（组分）进行了NO_x吸附回收实验研究。结果表明,GVTSA工艺相较传统吸附工艺（TSA工艺、VSA工艺）可获取更高的NO_x回收量,在优选条件下（220℃,-50 kPa）,NO_x回收率达到90%,解吸气中NO₂浓度由原料气的36 mg·m^-3提升到2%以上,NO_x循环吸附量可达0.10 mmol·g^-1,16次吸脱附循环稳定。研究结果可为烟气NO_x治理与资源化工业应用提供参考。     

Discussion of Thermally Activated Approaches to Glass Fracture

A review of the Charles and Hillig approach to thermally activated crack growth mechanisms indicates that this theory may be applicable to cracking in vacuum at high temperatures but not to stress-corrosion cracking in aqueous solutions. For stress-corrosion mechanisms, the ramifications are 2-fold: (1) Thermal activation analysis shows that the true activation energy in soda-lime glasses is closer to 0.55 × 10⁵ J/mol (13.2 kcal/mol) than to the 1.2×10⁵ J/mol (29 kcal/mol) obtained using the Charles and Hillig approach; and (2) other models for slow crack growth controlled by bulk diffusion of H₂, OH^-, or Na⁺-H⁺ are suggested and shown to be consistent with much of the observed phenomena.     

低温脱硝催化剂研究进展

在传统选择性催化还原技术（SCR）催化剂的基础上,分别以钒-钛系催化剂、固溶体催化剂和新型MnO _x 催化剂为重点介绍了近些年低温SCR催化剂的研究进展,综述了不同活性组分的复合型催化剂的制备方法、元素掺杂、反应机理和抗性等,并通过分析不同复合型催化剂的表征总结了催化剂的性能状况以及低温脱硝效率,着重阐述了新型MnO _x 催化剂所具有的优异脱硝特性,认为通过改性提高新型MnO _x 的抗水抗硫性将会成为该领域未来的发展方向和研究热点,最后介绍了不同负载体对新型MnO _x 催化剂的催化效率的影响规律,发现二氧化钛负载体具有良好的抗水性,三氧化二铝负载体能显著增强催化活性,二氧化铈负载体的热稳定性较好。     

镧掺杂PMN-PT陶瓷在准同型相界处的相组成调控

采用两步预烧工艺制备Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_1-zTi_zO₃(z=0.28、0.29、0.30、0.31)陶瓷,其准同型相界(MPB)的化学组成位于PbTiO₃含量为0.29 mol和0.30 mol附近。选取准同型相界两侧的化学组成,制备四方晶相Pb(Mg_1/3Nb_2/3)_0.66Ti_0.34O₃和三方晶相Pb_1-1.5xLa_x(Mg_1/3Nb_2/3)_1-yTi_yO₃(x=0.083 3~0.041 7,y=0.206 7~0.273 3)陶瓷粉体。将两种晶相粉体按照设计比例(三方晶相摩尔分数w=0.3、0.4、0.5、0.6)混合,干压成型,烧结成化学组成相同、晶相占比不同的Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃陶瓷。研究了晶相组成对陶瓷压电性能、介电性能、铁电性能的影响。结果表明,高温烧结后,陶瓷中的三方晶相和四方晶相占比与配料比基本一致。当w=0.5时,1 250 ℃烧结陶瓷中三方晶相与四方晶相含量占比分别为0.47、0.53,晶粒平均尺寸为(5.24±0.23) μm,相对密度为96.76%。陶瓷的压电应变常数d₃₃、径向机电转换系数k_p、厚度机电转换系数k_t、相对介电常数ε_r、剩余极化强度P_r和场致应变系数S(1 Hz、3.5 kV/mm)分别为1 014 pC/N、0.67、0.64、10 955、24 μC/cm²和0.21%。该方法可人为调控化学组成位于准同型相界的陶瓷的晶相占比。     

废CeO x -MnO x 基SCR脱硝催化剂还原酸浸综合回收铈锰

废选择性催化还原（SCR）脱硝催化剂中含有大量的有价金属,直接废弃易造成资源浪费及环境污染。以废CeO _x -MnO _x 基SCR脱硝催化剂为原料,采用热力学分析结合湿法冶金实验方法,研究了浸出条件对Ce、Mn元素浸出率的影响。结果表明,废催化剂直接酸浸Ce、Mn元素浸出率低,还原-酸浸Ce、Mn元素热力学条件上可行,抗坏血酸对Ce、Mn高价氧化物有明显的还原作用。当抗坏血酸质量分数为30%、硫酸浓度2mol/L、液固比6∶1、搅拌速度350r/min、80℃恒温反应5h时,Ce、Mn的浸出率分别达到92.09%、95.51%。加入抗坏血酸后,部分Ce⁴⁺和Mn⁴⁺还原为Ce³⁺和Mn²⁺,Ce⁴⁺/Ce的比值由75.82%降低到71.62%,Mn⁴⁺/Mn的比值由29.39%降低到27.17%,同时削弱了高价Ce辅助低价Mn向高价Mn转化的作用,使得Ce、Mn高效浸出,为CeO _x -MnO _x 基废催化剂中Ce、Mn资源化利用奠定了基础。     

Systematic study of H2 production from catalytic photoreforming of cellulose over Pt catalysts supported on TiO2

Hydrogen (H₂) production from photocatalytic reforming of cellulose is a promising way for sustainable H₂ to be generated. Herein, we report a systematic study of the photocatalytic reforming of cellulose over Pt/m-TiO₂ (i.e. mixed TiO₂, 80% of anatase and 20% of rutile) catalysts in water. The optimum operation condition was established by studying the effect of Pt loading, catalyst concentration, cellulose concentration and reaction temperature on the gas production rate of H₂ (r_H2) and CO₂ (r_CO2), suggesting an optimum operation condition at 40 ℃ with 1.0 g·L^-1 of cellulose and 0.75 g·L^-1 of 0.16-Pt/m-TiO₂ catalyst (with 0.16 wt% Pt loadting) to achieve a relatively sound photocatalytic performance with rH₂ = 9.95 μmol·h^-1. It is also shown that although the photoreforming of cellulose was operated at a relatively mild condition (i.e. with an UV-A lamp irradiation at 40 ℃ in the aqueous system), a low loading of Pt at ~0.16 wt% on m-TiO₂ could promote the H₂ production effectively. Additionally, by comparing the reaction order expressed from both r_H2 (a₁) and rCO₂ (a₂) with respect to cellulose and water, the possible mechanism of H₂ production was proposed.     

无定形MnOx/SiO2催化剂的合成及低温催化氧化甲醛机理

甲醛因其污染范围广、持续时间长、危害性大等特性被视为室内有害物质的头号“杀手”。本文采用自组装法于SiO₂表面原位生长MnO_x（MnO_x/SiO₂催化剂）并用于低温催化氧化甲醛的研究,XRD、SEM-EDS、TEM和BET表征显示,MnO_x以无定形态均匀地分布在SiO₂载体表面,同时考察了MnO_x的负载量以及煅烧温度对甲醛催化活性的影响。实验结果表明,优选的质量分数13% MnO_x/SiO₂无定形催化剂具有较大的比表面积（高达164.85m²/g）和丰富的活性位点（Mn³⁺,75.6%）,而较大的比表面积有利于更多的甲醛分子吸附在催化剂表面并进行活化反应。对甲醛进行连续性动态检测,结果显示催化剂在连续催化6h后仍保持80%以上的去除效率,表明无定形催化剂具有良好的低温催化效果。随着温度的升高,催化甲醛过程中间产物（甲酸根）被进一步分解,有利于催化剂的再生使用,当温度达到90℃时,甲醛的去除效果可达90%。     

Kinetic Study of an Effective Pb(II) Transport through a Bulk Liquid Membrane Containing Calix[6]arene Hexaester Derivative as a Carrier

The article describes transport of Pb(II) through bulk liquid membrane (BLM) containing calix[6]arene hexaester derivative (1) as a carrier. The effect of various parameters such as temperature, carrier concentration, stirring speed and type of solvent on the Pb(II) transport efficiency of the carrier through BLM was evaluated. The activation energy values for the extraction and re-extraction were found as 56.33 kJ mol^?1 and 14.79 kJ mol^?1, respectively. These values demonstrate that the process is diffusionally controlled by Pb(II). Observations indicate that the membrane entrance and exit rate constants (k₁, k₂) increase with increasing stirring speed as well as carrier concentration and decrease with increasing temperature. The effect of solvent on k₁ and k₂ was found to be in the order of CH₂Cl₂ > CHCl₃ > CCl₄.     

Highly efficient and selective membrane transport of silver(I) using hexathia-18-crown-6 as a specific ion carrier

Hexathia-18-crown-6 (HT18C6) was used as a specific ion carrier for the transport of silver ion through a chloroform bulk liquid membrane. In the presence of thiosulfate ion as a suitable stripping agent in the receiving phase, the amount of silver transported across the liquid membrane after 60 min is 99.5±1.0%. The selectivity of Ag⁺ transport from the aqueous solutions containing other Mⁿ⁺ cations such as Tl⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Hg²⁺, and Cr³⁺ ions was investigated. Except with Hg²⁺ ion, non of the cations used interfere the silver transport, even at a Mⁿ⁺/Ag⁺ molar ratio of 500. The interfering effect of Hg²⁺ ion was successfully eliminated in the presence of EDTA at pH 5.     

氨分解制氢棒状La x Ce1-x O y 负载Ru催化剂

氨分解得到的H₂不含CO _x 、SO _x 、NO _x 等有害物质,是其他所有含碳资源为原料制氢所不能比拟的。本文采用无模板水热法制备了一系列棒状载体,并采用沉积沉淀法制备了Ru/La _x Ce_1-x O _y 催化剂,考察了制备方法、催化剂组成对性能的影响,并通过扫描电镜（SEM）、X射线衍射（XRD）、BET、H₂-程序升温还原（TPR）和CO₂-程序升温脱附（TPD）进行了表征。结果表明,La₂O₃掺杂量为40%的Ru/La_0.4Ce_0.6O_1.8催化剂在常压、7800h^-1、450℃下氨分解转化率为98%。该催化剂活性高归因于部分还原的CeO_2-x 对Ru的供电子性能和Ru/La_0.4Ce_0.6O_1.8催化剂表面的强碱性增加了对Ru活性位的给电子能力。同时考察了K₂O含量的影响,最优的催化剂为Ru-2%K/La_0.4Ce_0.6O_1.8,在400℃、7800h^-1氨气转化率可以达到93%。结果表明Ru-2%K/La_0.4Ce_0.6O_1.8可以作为一种新型高效氨分解催化剂,为工业化应用提供了可能,具有良好的发展前景。     

磷化法制备Ni x P y 及其复合材料光解水性能

磷化镍具有Ni₃P、Ni₁₂P₅、Ni₂P、Ni₅P₄等多种晶相,深入研究各个晶相的制备规律和稳定存在条件对开发磷化镍基催化材料至关重要。本文系统考察了磷化时间、磷化温度、Ni/P摩尔比、磷化气速和磷源种类对制备晶相的影响。结果发现,以Ni₃P为前体、红磷为磷源时,可以得到Ni₅P₄、Ni₂P、Ni₁₂P₅三种晶相;以次磷酸盐为磷源时只能得到Ni₂P和Ni₁₂P₅晶相。当以红磷为磷源时,反应温度是影响晶相的主要因素,磷化温度为500℃、600℃和800℃时分别得到Ni₅P₄、Ni₂P和Ni₁₂P₅晶相。将制备的Ni₃P、Ni₂P、Ni₁₂P₅和Ni₅P₄作为助剂,与CdS复合制备光催化复合材料,得到的4种Ni _x P _y /CdS复合材料均表现出良好的光解水制氢性能,Ni₅P₄/CdS表现出最优的产氢能力,为CdS的5.4倍。表征结果证明,引入Ni _x P _y 能够有效抑制反应过程中CdS的载流子复合,提升其光解水反应活性。     

高铁酸钾强化铁锰氧化膜过滤去除水中有机物

前期研究发现铁锰氧化膜(MeO_x)对水中氨氮、铁、锰等污染物具有较高的去除率,但对水中有机物(以COD_Mn计)的去除效果较差。为了提高MeO_x对COD_Mn的去除率,本研究采用高铁酸钾强化MeO_x的催化氧化过程,探究其对水中COD_Mn的有效去除及相关影响因素。实验结果表明：仅投加0.1mg/L的高铁酸钾强化MeO_x过滤,对于进水中20mg/L的COD_Mn,去除率可达到约92.5%;滤速对其具有一定的影响,去除率随着滤速的提高呈下降的趋势,在6～10m/h出水滤速中的COD_Mn均能达到3.0mg/L以下,当滤速达到11m/h时去除率下降到81.65%;较低的p H(约6.51)具有一定的不利影响,COD_Mn的去除率随着p H的降低而逐渐下降;进水中NH₄⁺也会影响COD_Mn的去除,NH₄...     

Effect of carrier type on coupled transport kinetics of thiocyanate ions through liquid membranes

Coupled transport of thiocyanate ions through a liquid membrane containing quaternary ammonium chloride salts in chloroform was examined. The influences of the carrier type in the membrane phase on the coupled transport of thiocyanate ions were investigated. The kinetics of the coupled transport were analyzed in the formalism of two consecutive irreversible first-order reactions and the kinetic parameters (k_1d, k_2m, k_2a, R_m^max, t_max, J_d^max, J_amax) were also calculated. For the coupled transport of thiocyanate ions, quaternary ammonium chloride salts having different carbon atom numbers (C_n) used as carriers were found to increase thiocyanate ions transport efficiency with increasing carbon atom numbers. Tetradecyl trimethylammonium chloride (TDTMACl), hexadecyl trimethylammonium chloride (HDTMACl), and tetraoctyl ammonium chloride (TOACl) were found to be the most effective carrier types for transport of thiocyanate ions when C_n is greater than 16. The activation energies for maximum membrane entrance and exit fluxes were calculated as 32.45 kJ/mol and 34.75 kJ/mol, respectively. The values of the activation energy indicate that the process is controlled by species diffusion.