咪唑啉缓蚀剂膜抑制腐蚀介质扩散行为的MD研究

采用分子动力学模拟的方法,对5种1-(2-氨乙基)-2-烷基-咪唑啉缓蚀剂[(NH2)C2H4-C3H4N2-CH2(CH2)nCH3,n=5,7,9,11,13]抑制CO2腐蚀的缓蚀机理进行了研究.计算了4种腐蚀介质粒子(H2O,H3O+,Cl-和HCO-3)在不同缓蚀剂膜中的扩散系数,并从自由体积分数、腐蚀介质粒子与缓蚀剂膜的相互作用、膜的自扩散性能等方面对缓蚀剂膜抑制腐蚀介质粒子扩散行为的微观机理进行了分析.扩散系数的计算结果表明:缓蚀剂膜能有效抑制腐蚀介质的迁移,削弱其腐蚀能力;与中性H2O分子对比,缓蚀剂膜对H3O+,Cl-和HCO-3带电离子的扩散具有更强的抑制效果;随烷基链长的增加,5种缓蚀剂膜对腐蚀粒子扩散的抑制能力呈增强趋势.综合分子动力学计算结果,5种缓蚀剂缓蚀性能随着烷基链长的增加逐渐增强,理论评价结论与实验结论相吻合.     

缓蚀剂膜抑制腐蚀介质扩散行为的分子动力学模拟

采用分子动力学模拟方法研究了4种腐蚀介质粒子(H₂O, H₃O⁺, HS^-和Cl^-)在6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂膜中的扩散行为. 计算了腐蚀介质粒子在不同缓蚀剂膜中的扩散系数、膜的自由体积分数、粒子与膜的相互作用能等, 并对缓蚀剂膜抑制腐蚀介质粒子扩散行为的微观机理进行了分析. 计算结果表明, 6种缓蚀剂膜均可有效阻碍腐蚀介质粒子向金属表面的扩散, 从而达到抑制或延缓腐蚀的目的; 随烷基链长的增加, 缓蚀剂膜对腐蚀介质粒子扩散行为的抑制能力逐渐增强; 同种缓蚀剂膜对正负离子H₃O⁺, HS^-和Cl^-比对中性的H₂O分子具有更强的扩散抑制能力.     

1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂缓蚀机理的理论研究

采用量子化学计算、分子动力学模拟和分子力学相结合的方法, 对6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂抑制H2S腐蚀的缓蚀机理进行研究, 并对其缓蚀性能进行评价. 前线轨道分布和Fukui指数表明, 6种缓蚀剂分子的反应活性区域均集中在分子的咪唑环上, 3个反应活性中心分别位于咪唑环上的N(4), N(7)和C(8)原子, 可使咪唑环在金属表面形成多中心吸附. 分子的反应活性及活性区域分布对烷基链长并不敏感. 单分子吸附能、膜的内聚能、吸附角和链间距的计算数据显示, 缓蚀剂膜的稳定性以及膜与金属基体的结合强度随链长的增加而增大; 当正构烷基碳链长度大于13时, 缓蚀剂可在金属表面形成一层高覆盖度、致密的疏水膜, 能有效阻碍溶液中的腐蚀介质向金属表面扩散, 从而达到阻碍或延缓腐蚀的目的.     

温度对半胱氨酸缓蚀性能影响的实验评价与机理研究

通过实验对不同温度条件下半胱氨酸抑制盐酸对碳钢腐蚀的性能进行评价, 并采用分子动力学模拟(Molecular Dynamics Simulation, 简称MD)方法, 从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行深入研究. 静态失重实验显示: 随温度的升高(25～65 ℃), 半胱氨酸缓蚀剂的缓蚀效率呈逐渐下降趋势, 其数值从88.36%降至61.64%. MD模拟发现: 随温度升高, 半胱氨酸缓蚀剂膜的自由体积逐渐增大, 且腐蚀粒子与缓蚀剂膜的相互作用也逐渐减弱, 更有利于腐蚀粒子在膜中的主动扩散; 同时膜内半胱氨酸分子的自扩散能力也随温度升高而增强, 腐蚀粒子在缓蚀剂膜携带下被动迁移的过程也随之加剧. 主动扩散和被动迁移两方面的变化表明, 腐蚀粒子在缓蚀剂膜中扩散能力随温度升高而增大; 也就是说, 随温度升高, 半胱氨酸缓蚀剂膜对腐蚀粒子的扩散抑制能力逐渐降低, 腐蚀粒子更易扩散运移至金属表面, 导致半胱氨酸缓蚀剂缓蚀效率的降低.     

温度对半胱氨酸缓蚀性能影晌的实验评价与机理研究

通过实验对不同温度条件下半胱氦酸抑制盐酸对碳钢腐蚀的性能进行评价,并采用分子动力学模拟(Molecular Dynamics Simulation,简称MD)方法,从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行深入研究.静态失重实验显示:随温度的升高(25～65℃),半胱氨睃缓蚀剂的缓蚀效率呈逐渐下降趋势,其数值从88.36%降至61.64%.MD模拟发现:随温度升高,半胱氨酸缓蚀剂膜的自由体积逐渐增大,且腐蚀粒子与缓蚀剂膜的相互作用也逐渐减弱,更有利于腐蚀粒子在膜中的主动扩散;同时膜内半胱氨酸分子的自扩散能力也随温度升高而增强,腐蚀粒子在缓蚀剂膜携带下被动迁移的过程也随之加剧.主动扩散和被动迁移两方面的变化表明,腐蚀粒子在缓蚀剂膜中扩散能力随温度升高而增大;也就是说,随温度升高,半胱氨酸缓蚀剂膜对腐蚀粒子的扩散抑制能力逐渐降低,腐蚀粒子更易扩散运移至金属表面,导致半胱氨酸缓蚀剂缓蚀效率的降低.     

咪唑啉缓蚀剂在Fe(001)表面吸附行为的分子动力学模拟

采用分子动力学模拟方法研究了5种不同烷基链长的咪唑啉类缓蚀剂在Fe(001)表面的吸附行为和成膜机制,并对其缓蚀机理进行了深入分析.研究结果表明:咪唑啉分子的极性头基会吸附在金属表面上,而烷基碳链则背离金属表面,并通过自身的扭转形变实现稳定吸附;随着烷基链长的增加,缓蚀剂与金属基体的结合强度逐渐增加,所形成缓蚀剂膜的致密性也逐渐增大;致密的缓蚀剂膜能有效地阻碍腐蚀介质向金属表面扩散,从而达到延缓金属腐蚀的目的.5种缓蚀剂缓蚀性能的理论评价结果与实验结果吻合.     

SDBS与HA缓蚀剂复配的实验与理论研究

通过静态失重法研究了十二烷基苯磺酸钠(SDBS)与六亚甲基四胺(HA)在盐酸溶液中对Q235钢的协同缓蚀效应, 并采用分子动力学模拟从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行分析. 结果显示: SDBS和HA单独使用时, 最高缓蚀效率分别为82.82%和79.46%, 复配后最高缓蚀效率可达到92.78%; 与两种缓蚀剂单独使用时相比, SDBS与HA复配后缓蚀剂膜体系中的自由空间明显下降, 削弱了膜内缓蚀剂分子的自扩散能力, 腐蚀粒子在缓蚀剂膜携带下的被动迁移也随之减弱; SDBS与HA复配能更有效抑制腐蚀粒子在缓蚀剂膜中的扩散, 也就是说复配后的缓蚀剂具有更好的缓蚀性能.     

离子液体[Bmim]Cl在H2SO4中对Q235钢的缓蚀实验和理论分析

探究1-丁基-3-甲基-咪唑氯盐([Bmim]Cl)在H_2SO_4介质中对Q235钢的缓蚀性能,解决酸性环境在金属表面造成的腐蚀危害。采用静态缓蚀失重法、电化学法分析了不同浓度[Bmim]Cl对Q235钢的缓蚀性能。Q235钢表面形貌特征以及吸附行为分别采用了扫描电子显微镜(SEM)及吸附等温模型进行了分析。采用理论模拟计算分析了缓蚀剂分子在碳钢表面的缓蚀机理。结果表明,[Bmim]Cl为阴极主导的混合型缓蚀剂,随[Bmim]Cl浓度的增加,缓蚀效果越好,当[Bmim]Cl浓度为0.6 mol·L~(-1)时,缓蚀效率可达91%以上,等温吸附模型证明缓蚀剂分子可自发吸附在金属表面,符合Langmuir等温线。[Bmim]Cl通过化学键与Q235钢表面结合形成了以咪唑杂环为吸附中心、稳定化学吸附的单分子吸附层,且[Bmim]~+平行吸附于表面达到防腐蚀效果。[Bmim]Cl是一种性能优异的防腐蚀剂,能有效预防Q235钢在H_2SO_4介质中的腐蚀。     

吡哌酸、左氧氟沙星及环丙沙星在 0.5mol/L H2SO4中对碳钢的缓蚀性能与机理研究

利用失重实验、动电位极化曲线测试、交流阻抗测试(EIS)及扫描电子显微镜(SEM)方法对吡哌酸(8-乙基-5-氧代-5,8-二氢-2-(1-哌嗪基)吡啶并[2,3-d]嘧啶-6-羧酸)、左氧氟沙星[(±)-9-氟-2,3-二氢-3-甲基-10-(4-甲基-1-哌嗪基)-7-氧代-7H-吡啶并[1,2,3-de][1,4]苯并恶嗪-6-羧酸]及环丙沙星[1-环丙基-6-氟-1,4-二氧-4-氧代-7-(1-哌嗪基)-3-喹啉羧酸]在303 K时0.5 mol/L H2SO4 中对碳钢的缓蚀性能、作用机理进行研究.失重实验得出,303 K 时试样浸泡在0.5 mol/L H2SO4 溶液中的腐蚀速度随缓蚀剂的浓度增大而减小,同时三种缓蚀剂的缓蚀效率显著增大.电化学测试表明缓蚀剂分子对阴阳极反应均有抑制作用,但对阴极的抑制作用更加明显,其抑制作用与缓蚀剂在金属表面的覆盖有关.303 K 时缓蚀剂在金属表面的吸附行为符合 Langmuir 等温线,且作用过程物理、化学吸附兼有.扫描电子显微镜观察结果表明,添加三种缓蚀剂对碳钢表面的腐蚀起到了显著的保护作用.同种条件下的测试结果表明,环丙沙星缓蚀性能最强.     

一种新型酸化缓蚀剂的制备及性能研究

曼尼希碱是一种性能优良的缓蚀剂,在油气井的酸化作业中被大量应用.本文以甲醛、苯乙酮、乙二胺和对二甲氨基苯甲醛为原料,十二烷基苯磺酸钠为两相催化剂,在乙醇中同时发生曼尼希和西佛碱反应,合成了一种新型的曼尼希碱缓蚀剂,并通过正交试验优化得出最佳合成条件.采用静态挂片失重法测定其缓蚀性能,结果表明,该酸化缓蚀剂在温度90℃、腐蚀时间4 h、12%HCl+3%HF的土酸介质中、缓蚀剂加量为1%的条件下,N80钢片的腐蚀速率为2.06 g·m~(-2)·h~(-1),具有良好的缓蚀性能,并达到行业标准中的一级指标.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

Preparation, properties, and reactions of metal-containing heterocycles: Part CV. Synthesis and structure of polyoxadiphosphaplatinaferrocenophanes

A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂]PtCl₂ (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂ (n=1–3) (3a–c) and (PhCN)₂PtCl₂ under high dilution conditions in CH₂Cl₂. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂OH)₂ (n=1–3) (1a–c) with: (i) CH₃SO₂Cl in CH₂Cl₂ and (ii) LiPPh₂ in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg²⁺, or NH₄⁺ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na⁺ or K⁺ leads to an insignificant effect.     

Protonated ethanol and its neutral counterparts

Collisionally activated dissociation and neutralization-reionization experiments reveal that protonation of ethanol leads to two distinct isomers, the classical ion CH₃CH₂OH⁺₂ and the proton-bound complex C₂H₄…H⁺…OH₂. The neutral counterpart of the latter is unstable, whereas that of the former can be produced in a bound state if the CH₃CH₂OH⁺₂ precursor ion is formed under low ion source pressure conditions and, thus, with higher internal energies. This suggests that there are substantial differences in the geometries of CH₃CH₂OH⁺₂ and the hypervalent CH₃CH₂OH₂ ·. This provides only a partial explanation for unusual isotope effects; C₂H₅OD₂ ·, CH₃CD₂OD₂ ·, and CD₃CH₂OD₂ · are substantially more stable than C₂D₅OD₂ · and C₂H₅OH₂ ·.     

Syntheses and structural characterization of trivalent lanthanide complexes of p-sulfonatothiacalix[4]arene

The X-ray crystallographic studies are reported for the water-soluble trivalent lanthanide complexes of the macrocyclic p-sulfonatothiacalix[4]arene [Gd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·H₃O⁺·5H₂O (1) and Na[Nd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·3H₂O (2). The complexes are isostructural and belong to monoclinic system, C2/m space group. The Ln³⁺ metal ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a dimethyl sulfoxide (DMSO) molecule that occupies the cavity of the thiacalixarene and six aqua ligands. The thiacalixarenes are linked by the coordinated water molecules through hydrogen bonding to form a 2D polymer. The p-sulfonatothiacalixarenes maintain the clay-like bi-layer structure in the coordination network.     

Reaction of silylpentacarbonylmanganese with hydride-transfer reagents: reduction of carbonyl ligands accompanied with Si---C and C---C coupling

Treatment of Mn(CO)₅SiTol^p₂H (2) with an excess of LiAlH₄, NaBH₄, or NaBH₃(CN) in THF at room temperature gave hydrosilane H---SiTol^p₂H in high yield together with Mn₂(CO)₁₀. No reduction of CO ligands was observed. On the other hand, treatment of 2 with an excess of Red-Al (=Na[(CH₃OCH₂CH₂O)₂AlH₂]) in toluene and subsequent addition of aqueous acidic solution afforded alkylsilanols (CH₃)SiTol^p₂(OH) and (C₂H₅)SiTol^p₂(OH). Treatment of the reaction mixture of 2 and Red-Al with LiAlH₄ in diethyl ether instead of hydrolysis gave alkylhydrosilanes (CH₃)SiTol^p₂H and (C₂H₅)SiTol^p₂H. The methyl and ethyl groups on silicon originate from the CO ligands in 2. These products clearly demonstrate that not only the Si---C coupling, but also C---C coupling occurs efficiently in this reaction.     

The coupling effect of the thermodynamic swelling process in pervaporation

In order to analyze the coupling effect in thermodynamic swelling process, the relationship between the activity and volume fraction of each component within membrane was defined as ^m_i=γ^m_iφ^m_i. The concept of reference state in thermodynamic swelling process which only considered the interaction between individual component and membrane matrix was also set up. The difference of activity coefficient of each component within the membrane from reference state reflected the contribution of coupling effect to thermodynamic swelling process. For chitosan and H₂SO₄ crosslinking chitosan membrane the influence of coupling effect on selectivity of H₂O in thermodynamic swelling process could be described from distribution coefficients and competition distribution coefficients of H₂O and EtOH successfully. The interaction between H₂O and the membrane matrix dominated the activity coefficient of H₂O within the membrane, and the coupling effect between H₂O and EtOH within the membrane only had a little influence on the activity coefficient of H₂O. However, the activity coefficient of EtOH was dominated strongly by the coupling effect between H₂O and EtOH within the membrane. This was attributed to the large amount of H₂O present in the membrane. The distribution coefficient of EtOH, k^m₂ and competition distribution coefficient of membrane k^m₁₂ directly determined the selectivity of H₂O in thermodynamic swelling process and the coupling effect between H₂O and EtOH within the membrane had a negative influence on the selectivity of H₂O within the membrane.     

Characteristics of a zirconia composite membrane fabricated by a laser firing method

By a method of laser firing, a high zirconia containing (70%) composite membrane on porous ceramic tubing was successfully fabricated. The laser sintered composite membrane was characterized by gas separation/permeation experiments. In the separation experiment of a CO₂---CH₄ gaseous mixture, it was found that the separation factor of CH₄ over CO₂ was 1.15. In the pure gases permeation experiment, it was found that Knudsen diffusion is considered to be predominant in the permeation mechanism for pure gases H₂, He, CH₄, N₂, O₂, and CO₂, and the permeation mechanism of H₂O at lower temperature depends mainly on surface diffusion and on Knudsen diffusion at higher temperature.     

Effect of high coverages on proton transfer in the zeolite/water system

The density functional theory and Hartree–Fock methods were used to investigate the proton transfer reaction for a series of model clusters of zeolite/(H₂O)_n; n=1,2,3, and 4. Without promoted water, the hydrogen-bonded dimer of the water/zeolite system exists as a simple hydrogen-bonded complex, ZOH.(H₂O)₂, and no proton transfer occurs from zeolite to water. The third promoted water, ZOH(H₂O)₂H₂O, was found to induce a pathway for proton transfer, but at least addition two promoted molecules, ZO(H₃O⁺)H₂O(H₂O)₂, must be involved for complete proton transfer from zeolite to H₂O. The results show that the hydronium ion in water cluster adsorbed on zeolite, ZO(H₃O⁺)(H₂O)₃, can considerably affect the structure and bonding of the hydrogen-bonded dimer of water. The OO distance is contracted from 2.818 Å found in the neutral complex, ZOH(H₂O)₄, to 2.777 Å for ion-pair complex, ZO(H₃O⁺)(H₂O)₃. The distance between the oxygen of the hydronium ion and the zeolitic acid site oxygen is predicted to be 2.480 Å which is in good agreement with the experimentally observed value of 2.510 Å. The corresponding density functional adsorption energy of the high coverages of adsorbing molecules on zeolite is calculated to be −9.14 kcal/mol per molecule at B3LYP/6-311+G(d,p) level of theory and compares well with the experimental observation of −8.20 kcal/mol.     

Spacer molecules in peptide sequences: incorporation into analogues of atrial natriuretic factor

The spacer reagents FmocHN(CH₂CH₂CH₂)₃CH₂COOPfp (1b) and FmocHN(CH₂CH₂O)₃CH₂COOPfp (2d) have been prepared and used to substitute for tetra-residue sequences in the cyclic portion of Atrial Natriuretic Factor (ANF) by solid phase peptide assembly.     

基于萘酰亚胺-苯并咪唑鎓的荧光传感器对H2PO-4的高选择性识别

设计合成了基于萘酰亚胺-咪唑鎓的受体分子1和2,通过荧光发射光谱研究了受体分子1和2对阴离子F^-、Cl^-、Br^-、I^-、AcO^-、HSO^-₄、H₂PO^-₄、NO^-₃、ClO^-₄的识别性能。 研究发现,在受体分子1和2的乙腈溶液(5.0×10^-6 mol/L)中加入10倍化学计量的H₂PO^-₄时,受体分子1的荧光猝灭率高达98%,受体分子2的荧光猝灭率仅为24%。 表明具有多重识别位点的受体分子1在构型上与H₂PO^-₄更匹配,可作为H₂PO^-₄的荧光关闭型(turn-off)探针。 受体分子1与H₂PO^-₄的结合比为1∶1,结合常数为(1.25±0.11)×10⁵ L/mol,检出限为6.90×10^-6 mol/L。