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SYNTHESIS AND STRUCTURE OF PLATINUM (II) COMPLEXES WITH DECOMPOSITION PRODUCT OF DITHIODIETHYLAMINE βMERCAPTOETHYLAMINE 二硫代二乙胺-巯基乙胺分解产物铂配合物的合成与结构
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-1-21-28
G. Ajalova, Kh.I. Hasanov, A. N. Azizova, Sh.Q. Qasımov, K. K. Badalova
The interaction of dithiodiethylamine (cystamine) (L1 ) with Pt(II) in aqueous medium was studied and it showed that in aqueous solutions in an acidic medium, the disulfide bond L1 was cleaved, followed by coordination of platinum to form β-mercaptoethylamine (mercamine, LH). Depending upon the reaction conditions, binuclear complexes of composition µ(S)[Рt2(LН)2С14](I), µ(Cl)[Рt2(LН)2С14](II) with bridging chlorine or sulfur atoms were formed. At 70°С, a compound with a bridged position of sulfur atoms (complex I), and at lower temperatures (30-500 ) with a bridged position of chlorine atoms (complex II) were formed. X-ray structural analysis of the complex [Рt2(LН)2С14] (I) was carried out. Crystals I are rhombic, with 20°Са = 17.282(1), b = 9.986(1), с = 8.0188(9) Å;R = 0.029. Molecule I is a binuclear complex in which platinum atoms are linked by a pair of bridging thiolate ligands (-SСН2-СН2-МН3 + ). The Pt2S2 metallocycleis are bent along the sulfur-sulfur line, so that the dihedral angle between the coordination planes of platinum atoms is equal to 138°. The S–S distance, equal to 2.909(1) Å, is noticeably shorter than the doubled van der Waals radius of the sulfur atom (3.60 Å). The structure of the complexes was also confirmed by IR spectroscopy data.
研究了二硫代二乙胺(胱胺)(L1)与Pt(II)在水介质中的相互作用,结果表明,在酸性介质的水溶液中,二硫键L1被断裂,随后铂配位生成β-巯基乙胺(LH)。根据反应条件的不同,形成了由µ(S)[Рt2(LН)2С14](I)、µ(Cl)[Рt2(LН)2С14](II)和桥接氯或硫原子组成的双核配合物。在70°С时,形成了具有桥接位置的硫原子(配合物I)的化合物,在较低温度(30-500)下形成了具有桥接位置的氯原子(配合物II)的化合物。对配合物进行了x射线结构分析[Рt2(LН)2С14](1)。晶体I为菱形,20°Са = 17.282(1), b = 9.986(1), p = 8.0188(9) Å;R = 0.029。分子I是一个双核配合物,其中铂原子由一对桥接硫酸盐配体连接(-SСН2-СН2-МН3 +)。Pt2S2金属环沿硫-硫线弯曲,使得铂原子配位面之间的二面角为138°。S-S距离等于2.909(1)Å,明显短于硫原子的双范德华半径(3.60 Å)。红外光谱数据也证实了配合物的结构。
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引用次数: 0
THEORETICAL ASPECTS OF VIBRATIONAL SPECTROSCOPY OF CONDENSED SYSTEMS WITH IMPURITY PARTICLES 含杂质粒子凝聚体系振动光谱的理论研究
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-3-211-220
T. Marsagishvili, M. Machavariani
Some problems of vibrational spectroscopy of particles in condensed systems are considered in this work. One of the aspects of theoretical research is the study of the vibrational properties of individual particles in view of the nano-dimension of the molecules of the condensed system surrounding the particle. Using the apparatus of temperature, Green functions of the operators of polarization of condensed systems, two main mechanisms of influence on impurity particles from the medium, solvation and fluctuation, are distinguished. Theoretical results are obtained within the framework of these two mechanisms for calculating changes in the vibrational spectrum of individual particles. The theoretical results are used to analyze the experimental data on the vibrational spectra of the N2O molecule in polar solvents: methanol, ethyl alcohol, acetone, and 1,2-dichloroethane.
本文研究了凝聚体系中粒子振动光谱的一些问题。理论研究的一个方面是研究单个粒子的振动特性,考虑到粒子周围凝聚体系的分子的纳米尺度。利用温度仪、凝聚体系极化算子的格林函数,区分了介质对杂质粒子的两种主要影响机制:溶剂化和波动。在这两种机制的框架内得到了计算单个粒子振动谱变化的理论结果。利用理论结果分析了N2O分子在甲醇、乙醇、丙酮和1,2-二氯乙烷等极性溶剂中的振动谱实验数据。
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引用次数: 0
COMPARATIVE ANALYSIS OF NEW MONOMER AND GEMINI SURFACTANTS SYNTHESIZED ON THE BASIS OF DODECANOIC ACID AND ETHANE-1,2- DIAMINE DEPENDING ON THEIR MOLAR RATIO 十二烷酸与乙烷-1,2-二胺按摩尔比合成的新型单体表面活性剂与Gemini表面活性剂的比较分析
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-2-178-187
I. Zarbaliyeva, H. Nabiyeva, Amina Alimova, S. Zargarova
This article includes thorough information on the synthesis process and physicochemical properties of the products generated from the reaction of dodecanoic acid and ethane-1,2-diamine IR spectroscopy was used to confirm the structure and composition of the reaction products. Several parameters of the obtained surfactants were distinguished, including surface tension, electrical conductivity, and petro-dispersing parameters. Comparative analysis has been given based on the properties of the mono and gemini surfactant. At last, final suggestions were made, taking into account the salts' applicable qualities.
本文全面介绍了十二烷酸与乙烷-1,2-二胺反应产物的合成过程和理化性质,并利用红外光谱对反应产物的结构和组成进行了确定。对所得表面活性剂的几个参数进行了区分,包括表面张力、电导率和石油分散参数。对单、双表面活性剂的性能进行了比较分析。最后,根据盐类的适用特性,提出了建议。
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引用次数: 0
EQUILIBRIUM CONDITIONS, ADSORPTION KINETICS OF THE GeO2-Cu(II)-NaCl SYSTEM ON DIAION CRBO2 ANIONITE AND DESORPTION MODE FROM SPENT COLUMNS GeO2-Cu(II)-NaCl体系在阳离子CRBO2阴离子上的平衡条件、吸附动力学及废柱解吸模式
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-1-64-71
M. Jafarli, A. Abbasov
The IR spectrum of DIAION CRBO2 anionite synthesized on the basis of a chelating agent, a styrene macromolecule with a glucamine functional group, has been studied. Sorption properties of anionite with respect to the germanium(IV)-copper(II)-Cl-system have been studied.. It is shown that the interaction of hydroxyl and amino groups of anionite with germanate and copper(II) ions is based on the formation of corresponding complexes. Various variants of sorption isotherms are constructed, calculation equations are proposed, which are followed by isotherms, the role of external, mixed and internal diffusion on the basis of the kinetic mechanism of processes is clarified.The desorption mode of the studied components from the treated anionite column was determined.
研究了以具有氨基葡萄糖官能团的苯乙烯大分子为螯合剂合成的DIAION CRBO2阴离子的红外光谱。研究了阴离子对锗(IV)-铜(II)- cl -体系的吸附性能。结果表明,阴离子的羟基和氨基与锗酸盐和铜(II)离子的相互作用是以形成相应的配合物为基础的。构造了吸附等温线的各种变体,给出了等温线的计算方程,并在动力学机理的基础上阐明了外扩散、混合扩散和内扩散的作用。测定了所研究组分在处理后的阴离子柱上的解吸模式。
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引用次数: 0
SYNTHESIS OF AMINOMETHYL DERIVATIVES OF 3-MERCAPTO-2- HYDROXYPROPYL-1-ISOBUTYL ETHER AND THEIR STUDY AS PROTECTIVE ADDITIVES TO LUBRICANT OILS 3-巯基-2-羟丙基-1-异丁基醚胺甲基衍生物的合成及其作为润滑油保护添加剂的研究
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-1-48-56
V. Farzaliyev, Sh.R. Aliyev, R. Babai, R. Mammadova, G. Guliyeva, A. Mammadov, G.Sh. Eivazova
The electrochemical corrosion prevention of engines and mechanisms is a task of great national, economic and defense importance. Lubricating oils commonly used in engineering do not have sufficient protective properties and are unable to effectively protect it from corrosion, both during operation and during short-term and long-term inactivity. One of the simplest and most rational ways to solve this problem is the use of lubricants containing effective protective (conservation) additives, which, without worsening the normal working properties of oils provide them conservation properties. By the action of 3-mercapto-2- hydroxypropyl-1-isobutyl ether, taken as a synthon, with secondary aliphatic and heterocyclic amines under the conditions of the Mannich reaction, a number of aminomethyl derivatives were synthesized. Aminomethyl derivatives of 3-mercapto-2-hydroxypropyl-1-isobutyl ether are dissolved well in oils and are stable during storage. The protective properties of the synthesized compounds were studied in M-12 oil. The best test results were obtained with 3-piperidinomethilthio-2-hydroxypropyl-1-isobutyl ether - at a concentration of 1% to the lubricating oil M-12, the corrosion of a steel plate in a humid chamber is 3%, in sea water after 24 hours – 5%, the corrosion of a steel plate under the action of a 0.1% acid solution HBr – 3,5%. These results are higher than those of the standard - industrial additive urea succinimide. (SIM).
发动机及机械的电化学防腐是一项具有重大国家、经济和国防意义的任务。工程上常用的润滑油,无论是在运行过程中,还是在短期和长期不活动的情况下,都没有足够的防护性能,不能有效地保护其免受腐蚀。解决这一问题的最简单和最合理的方法之一是使用含有有效保护(养护)添加剂的润滑油,这些添加剂在不恶化油的正常工作性能的情况下提供了它们的养护性能。以3-巯基-2-羟丙基-1-异丁基醚为合成物,在曼尼希反应条件下与仲脂肪胺和杂环胺反应,合成了许多氨基甲基衍生物。3-巯基-2-羟丙基-1-异丁基醚的氨基甲基衍生物在油中溶解良好,储存稳定。对合成的化合物在M-12油中的保护性能进行了研究。试验结果表明,3-哌替啶甲基硫代-2-羟丙基-1-异丁基醚-在润滑油M-12中浓度为1%时,钢板在潮湿室内的腐蚀率为3%,在海水中24小时后腐蚀率为5%,在0.1%的酸溶液HBr - 3,5%的作用下腐蚀钢板。这些结果高于标准工业添加剂琥珀酰亚胺脲。(SIM)。
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引用次数: 0
SYNTHESIS AND CHARACTERISTICS OF SULFATED CHITOSAN BASED ON CHITIN/CHITOSAN FROM ARTEMIA PARTHENOGENETICA CYSTS 单性蒿壳聚糖/壳聚糖硫酸盐酸化壳聚糖的合成及性能研究
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-3-242-250
B.P. Karlybaeva, G. Berdimbetova, A. Boymirzaev
This article presents for the first-time the sulfated chitosan (SCS), synthesized on the basis of chitin/chitosan obtained from cysts of the Karakalpak population of Artemia parthenogenetica of the Aral Sea, and some of its physicochemical characteristics. Structural studies of chitin/chitosan and SCS were carried out by infrared spectroscopy. The IR spectrum data showed amide I (C=O-NHR) bands characteristic of chitin at 1640 cm-1 , and for chitosan absorption bands of the amino group (-NH2) at 1588 cm -1 . Signals at 870 and 614 cm-1 and 1125-1388 cm-1 in SCS comply with C-O-S and S=O bonds, which indicates the inclusion of sulfate groups in chitosan. The degree of substitution (DS) established by the gravimetric method, is in line with 1.32. The molecular weights of chitosan and SCS were calculated using size exclusion chromatography (SEC). According to the calculation of SEC for chitosan, an average molecular weight (MW) complies with 16 kDa, and for SCS - 1-3 kDa.
本文首次介绍了以咸海单性蒿(Artemia parthenogenetica) Karakalpak种群包囊中提取的几丁质/壳聚糖为原料合成的硫酸化壳聚糖(SCS)及其理化特性。利用红外光谱对甲壳素/壳聚糖和SCS进行了结构研究。红外光谱数据显示甲壳素的酰胺I (C=O-NHR)吸收带在1640 cm-1处,壳聚糖的氨基(-NH2)吸收带在1588 cm-1处。SCS中870和614 cm-1和1125-1388 cm-1处的信号符合C-O-S和S=O键,表明壳聚糖中包含硫酸盐基团。用重量法确定的取代度(DS)符合1.32。采用粒径排斥色谱法(SEC)计算壳聚糖和SCS的分子量。经SEC计算,壳聚糖的平均分子量(MW)为16 kDa, SCS - 1-3 kDa。
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引用次数: 0
PHASE EQUILIBRA IN THE Ag2Se–Ag8GeSe6–Ag8SiSe6 SYSTEM AND CHARACTERIZATION Of the Ag8Si1-xGexSe6 SOLID SOLUTIONS Ag2Se-Ag8GeSe6-Ag8SiSe6体系的相平衡及Ag8Si1-xGexSe6固溶体的表征
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-3-229-241
G. Ashirov, K. N. Babanly, L. Mashadiyeva, Y. Yusibov, M. Babanly
Phase equilibria in the Ag2Se–Ag8SiSe6–Ag8GeSe6 system were studied by differential thermal analysis and X-ray diffraction thechnique. Based on the experimental results and literature data, the projection of the liquidus surface of the Ag2Se–Ag8SiSe6–Ag8GeSe6 system, the isothermal section at 300 K and some polythermal sections of the phase diagram were constructed. It was determined that continuous series of solid solution are formed based on high-temperature cubic modification and limited solid solution areas are formed based on low-temperature modification of initial compounds on the Ag8SiSe6–Ag8GeSe6 side of concentration triangle. The formation of solid solutions leads to a sharp decreasing of polymorphic transition temperatures of ternary compounds and stabilization of high-temperature phases at room temperature. The liquidus surface of the Ag2Se–Ag8SiSe6–Ag8GeSe6 system consists of 2 areas reflecting the initial crystallization of α'-phase based on HT-Ag2Se and HT-Ag8Si1-xGexSe6 solid solutions. The obtained new phases are of interest as environmentally safe materials with thermoelectric properties and mixed ion-electron conductivity.
采用差热分析和x射线衍射技术研究了Ag2Se-Ag8SiSe6-Ag8GeSe6体系的相平衡。根据实验结果和文献数据,构建了Ag2Se-Ag8SiSe6-Ag8GeSe6体系的液相面投影、300 K等温截面和部分相图的多热截面。结果表明,在浓度三角形的Ag8SiSe6-Ag8GeSe6侧,高温立方改性可形成连续系列的固溶体,低温改性初始化合物可形成有限的固溶体区域。固溶体的形成导致三元化合物的多晶转变温度急剧降低,高温相在室温下稳定。ag2se - ag8sie6 - ag8gese6体系的液相表面由2个区域组成,反映了HT-Ag2Se和HT-Ag8Si1-xGexSe6固溶体的α′相初始结晶。所获得的新相是具有热电性能和混合离子-电子导电性的环保安全材料。
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引用次数: 0
STUDY OF REACTION OF NICKEL (II) WITH 2.4-TYAZOLIDINDYON COMPLEX AND ITS DERIVATIVES 镍(ii)与2.4-噻唑烷酮配合物及其衍生物的反应研究
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-2-168-177
A. Zalov, K. A. Kuliyev, K. Aliyeva
Spectrophotometric methods are used to study the reaction of the nickel complex with 2.4- tyazolidindico (L) and its derivatives {5- (gasilysiliden) -2,4-tyazolidindio (L1), 5- (2-chlorbenzyliden) -2,4- tyazolidindion (L2), 5-(2-hydroxybenzylide) -2,4-tiazoleader (L3), 5- (4-hydroxybenzylide)-2,4- tyazolidindion(L4),5-(2-Brom-5-methoxybenzyiliden)-2,4-tiazolyidinedion (L5). With a single extraction, the chloroform is extracted by 97.8-98.4 % of the nickel. The study of the dependence of complexation on pH showed that the optimal range of acidity, at which the optical density is maximum and constant, is at pH 2.3- 8.0. The optimal condition for the formation and extraction of the nickel complex of these compounds is (2.0- 2.5) × 10-4 M concentration L. Nickel complexes with L are stable in water and organic solvents and do not decompose for three days, and after extraction for more than a month. The maximum optical density is achieved within 5 minutes. The maximum analytical signal during the complex of nickel L is observed at 470-482 nm/ molar absorption coefficients (1.37-1.61)×104 . The comprehensive form of nickel is Ni2+while the number of protons supplanted by it from one molecule L turned out to be equal to 1. Nickel and its complexes in the organic phase are not polymerized and are in a monomeric form (γ = 1.01-1.07). The proposed method under already established optimal conditions is used to determine Ni (II) in wastewater, bottom deposits, as well as in oil and oil products.
采用分光光度法研究了镍配合物与2.4-噻唑基茚二酮(L)及其衍生物{5-(气化硅基)-2,4-噻唑基茚二酮(L1)、5-(2-氯苄基)-2,4-噻唑基茚二酮(L2)、5-(2-羟基苄基)-2,4-噻唑烯二酮(L3)、5-(4-羟基苄基)-2,4-噻唑烯二酮(L4)、5-(2-溴-5-甲氧基苄基)-2,4-噻唑烯二酮(L5)的反应。一次提取,氯仿的镍提取率为97.8% ~ 98.4%。络合作用对pH的依赖性研究表明,pH 2.3 ~ 8.0是光密度最大且恒定的最佳酸度范围。这些化合物的镍配合物形成和萃取的最佳条件为(2.0 ~ 2.5)× 10-4 M浓度L,含L的镍配合物在水和有机溶剂中稳定,萃取3天不分解,萃取1个月以上。5分钟内达到最大光密度。在470 ~ 482 nm/摩尔吸收系数(1.37 ~ 1.61)×104处观察到镍L络合物的最大分析信号。镍的综合形式是Ni2+,而它从一个分子L中取代的质子数等于1。镍及其配合物在有机相中不聚合,以单体形式存在(γ = 1.01-1.07)。在已建立的最佳条件下,所提出的方法可用于测定废水、底部沉积物以及石油和石油产品中的Ni (II)。
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引用次数: 0
HYROGEN BOND IN CRYSTAL STRUCTURE OF SALTS OF SYMMETRIC POLYMETHYLFERRICINIUM CATİONS (SYM.[(CH3)mC5H5–m]2Fe+X – , m=3,4,5 or МеnFc+X – , n = 6, 8, 10; X– = PF6 – , BF4 – , Br3 – )
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-3-203-210
N. Ibrahimova, S.M. Rustemova, G. М. Jafarov, I. U. Lyatifov
The article explains reasons of elongation (0.019 Å) of the bond between iron–cyclopentadienyl ring in the 1,2,4,1,2,4-hexamethylferricinium (sym. Ме6Fc+ ) cation formed due to the one-electron oxidation of iron atom of sym.1,2,4,1,2,4-hexamethylferrocene (sym. Ме6Fc) molecule which is 2-2.5 times smaller (0.04–0.05 Å) than that observed in pairs of ferrocene/ferricinium (Fc/Fc+ ), sym. octamethylferrocene/sym.octamethylferricinium (Ме8Fc/Me8Fc+ ) and decamethylferrocene/decamethylferricinium (Ме10Fc/Ме10Fc+ ). For this purpose, X-ray structural parameters characterizing the interaction between cation and anion in the sym.Ме6Fc+PF6 – complex was compared with appropriate parameters in Ме8Fc+BF4 – , Ме10Fc+Br3 and Ме10Fc+PF6 – complexes; and it was mooted that there is an F …H type hydrogen bond in this complex taking into account the length of the non-valent F…H contact (bond) in the sym. Ме6Fc+PF6 – complex. The lengths of Р–F bonds and F–P–F angles of the PF6 – anion in the listed 4 sandwich complexes were compared with appropriate parameters in the РF6 – anion of the LiРF6 crystal. It has been unequivocally proved that F…H hydrogen bonds exist in the sym.Ме6Fc+PF6 – complex.
伸长的文章解释了原因(0.019)之间的债券iron-cyclopentadienyl环的1、2、4、124-hexamethylferricinium(信谊。Ме6 Fc +)阳离子形成由于sym.1铁原子的单电子氧化,2、4、124-hexamethylferrocene(信谊。Ме6 Fc)小分子2 - 2.5倍(0.04 -0.05)比观察双二茂铁/ ferricinium (Fc / Fc +), sym. octamethylferrocene /信谊。八甲基铁(Ме8Fc/Me8Fc+)和十甲基二茂铁/十甲基铁(Ме10Fc/Ме10Fc+)。为此,将表征sym.Ме6Fc+PF6 -配合物中正阴离子相互作用的x射线结构参数与Ме8Fc+BF4 -、Ме10Fc+Br3和Ме10Fc+PF6 -配合物中的适当参数进行了比较;考虑到系统Ме6Fc+PF6 -配合物中非价F…H键(键)的长度,提出该配合物中存在F…H型氢键。将列出的4种夹层配合物中PF6 -阴离子的Р-F键长度和F-P-F角与LiРF6晶体中РF6 -阴离子的适当参数进行了比较。已经明确地证明了sym.Ме6Fc+PF6 -配合物中存在F…H氢键。
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引用次数: 0
RESEARCH INTO THE EFFECT OF ETCHING PROCESS OF POROUS TITANIUM CURRENT COLLECTORS IN HYDROCHLORIC ACID ON THE PERFORMANCE OF WATER ELECTROLYZERS WITH A PROTON EXCHANGE MEMBRANE 研究了多孔钛集流器在盐酸中蚀刻工艺对质子交换膜水电解槽性能的影响
Pub Date : 2023-01-01 DOI: 10.32737/2221-8688-2023-1-7-20
G.R. Kiselev, V. Fateev, I. Baranov
Based on the modern methods of SEM, voltammetry, and gravimetric analysis, samples of current collectors used in electrolyzers with a solid polymer electrolyte, made of porous titanium with various degrees of etching in concentrated hydrochloric acid, were studied. A gravimetric study of the etching process of samples of various sizes from porous titanium showed that throughout the process there is a loss of mass of the sample, with the exception of two short intervals, presumably due to the formation of hydrides (60-80 sec) and oxides (4-5 min), and the samples of smaller volumes were more sensitive to weight loss and weight growth. The use of the SEM method made it possible to reveal that etching over different time intervals changes the structure of porous titanium, reducing the average particle size and increasing their porosity .In this case, the surface inhomogeneity increases due to the formation of cavities in titanium and deterioration of the contact of the current collector surface with the catalytic layer. The consequence of this is the difference in the current-voltage characteristics of electrolysis cells with different duration of etching of the current collectors: there is a decrease in the productivity of electrolysis with an increase in the duration of etching of the current collectors by ~8% for etching more than 1 minute and ~18% for etching more than 4 minutes as compared to the simultaneous immersion of the sample in acid to clean the surface.
采用扫描电子显微镜(SEM)、伏安法(volammetry)和重量法(重量法)等现代分析方法,对多孔钛制成的固体聚合物电解质在浓盐酸中不同程度蚀刻的集流器样品进行了研究。对不同尺寸多孔钛样品的刻蚀过程进行的重量研究表明,在整个刻蚀过程中,除了两个短间隔外,样品的质量都有损失,这可能是由于氢化物(60-80秒)和氧化物(4-5分钟)的形成,体积较小的样品对重量损失和重量增长更敏感。利用扫描电镜方法可以发现,不同时间间隔的蚀刻改变了多孔钛的结构,降低了平均粒径,增加了孔隙率,在这种情况下,由于钛中形成空腔和集电极表面与催化层的接触恶化,表面不均匀性增加。这样做的结果是,随着集流器蚀刻时间的不同,电解电池的电流电压特性也不同:与同时将样品浸泡在酸中清洁表面相比,当集流器蚀刻时间超过1分钟时,电解电池的生产率会下降~8%,而当集流器蚀刻时间超过4分钟时,电解电池的生产率会下降~18%。
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引用次数: 0
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