磁场作用下铁电极的不均匀阳极溶解

采用电化学方法以及扫描电镜形貌观察研究了磁场对铁在硫酸溶液中的阳极溶解的影响 .恒电位极化测试结果表明 ,随外加阳极电位的增加 ,磁场的存在将加速阳极溶解 ,使振荡态或钝态变为活性溶解态 ,维持钝态 .于特定电位下与重力方向平行的电极表面两侧将因局部溶解加速而出现凹陷 .由于电极周边浓度梯度场的特殊性以及磁场的作用方向导致了铁的不均匀阳极溶解     

硫酸根离子对铁在弱碱性溶液中阳极溶解和钝化行为的影响

采用浸泡实验, 电化学测试和表面分析技术研究了硫酸根离子浓度对铁在稀碳酸氢钠溶液中开路状态和阳极极化行为的影响. 在无硫酸根离子及含有少量硫酸根离子的碳酸氢钠溶液中, 铁的开路电位约为(-0.225±0.005) V, 并呈现钝化状态, 其电化学阻抗很大, 腐蚀速率较低. 在含有较高浓度硫酸根离子的碳酸氢钠溶液中, 铁的开路电位为(-0.790±0.010) V并呈现活性溶解状态, 其电化学阻抗较小, 腐蚀速率较高, 同时阳极极化曲线上能观察到活化-钝化转变现象. 由于铁在含有较高浓度硫酸根离子的碳酸氢钠溶液中处于活化状态, 阳极极化曲线上存在数个电流峰. 足够高的硫酸根离子浓度会导致铁表面预先形成或转变而成的氧化膜失效. 相比于自然曝氧状态, 在除氧条件下较低的硫酸根离子浓度即可引起铁在碳酸氢钠溶液中由钝态向活性溶解态的转变.     

基于CdS:Mn敏化TiO_2纳米管的光电化学传感器用于硫酸盐还原菌的检测

本文以钛片为原料,采用阳极氧化法制备二氧化钛纳米管(TiO_2-NTs)材料,以壳聚糖(CS)作为交联剂,通过连续离子层吸附与反应(SILAR)法制备了TiO_2-NTs/CdS∶Mn光电化学(PEC)传感器,用于检测硫酸盐还原菌(SRB)。传感器中的Cd~(2+)和Mn~(2+)与SRB的代谢产物H_2S结合产生的CdS∶Mn纳米晶掺杂结构,有效降低了电子-空穴复合率,导致光电流明显增强,可实现对SRB的实时检测。在1.0×10~2～1.0×10~8 CFU/mL范围内,SRB浓度的对数与传感器检测的电流值呈良好的线性关系,检出限为28 CFU/mL。该传感器为SRB的快速检测提供新策略。     

元素掺杂碳基材料在锂硫电池中的应用

可移动电子设备、电动汽车及站式储能的蓬勃发展对具有高能量密度和长循环寿命的储能体系的开发提出了迫切需求。锂硫电池由于活性物质硫成本低廉并具有高理论能量密度(2600 Wh·kg^-1),成为最具希望的下一代可充电电池。但是,硫及其放电产物导电性差以及多硫化物溶解穿梭导致的一系列严重问题制约了锂硫电池的实际应用。碳基材料通常被用作硫载体以改善正极的导电性,然而,非极性碳材料与极性多硫化物的相互作用较弱,对于多硫化物仅起到有限的物理吸附和阻挡作用,穿梭效应所导致的电池容量严重衰减问题难以得到有效改善。通过杂原子如N、S、Co、B等的掺杂可在碳材料上引入极性或化学吸附位点,大大增强了碳材料对于多硫化物的吸附能力,有效改善了电池的循环稳定性,并且由于掺杂改变了碳材料的电子结构,甚至可以提升碳材料的电子导电性,从而提高了活性物质的利用率。本文对锂硫电池中多孔碳、碳纳米管以及石墨烯等碳基材料常用的元素掺杂进行了介绍,其中包括单元素掺杂、双元素掺杂和多元素掺杂,分析了不同掺杂元素对碳基材料性能的影响,并对元素掺杂碳基材料在锂硫电池中的发展前景进行了展望。     

碳纳米管复合微球修饰L-色氨酸及其对LDL的吸附性能

本文以多孔碳纳米管/活性炭复合微球为载体, 以L-色氨酸为配基, 采用环氧氯丙烷偶联法, 制得修饰L-色氨酸的碳纳米管/活性炭复合微球(L-CNTs/AC)。采用扫描电镜、氮气吸附、傅立叶红外光谱、热分析、X射线光电子能谱等对复合微球进行表征;通过体外静态吸附法对其低密度脂蛋白(LDL)吸附能力进行初步研究。结果表明:环氧氯丙烷偶联法可接枝上L-色氨酸。复合微球中碳纳米管加入量越多, 对LDL的吸附能力越强;当碳纳米管加入量为45wt%时, 对LDL的吸附量达4.623 mg·g^-1, 是未添加碳纳米管的2.3倍多。这是因为碳纳米管不仅可促进复合微球中20~100 nm孔的形成, 而且还可促进复合微球配基修饰量的增多, 从而大大增强了复合微球对LDL的吸附能力。此复合微球可望开发成一种新型的血液灌流LDL吸附剂。     

碳钢在生物膜和硫化物膜下的电化学腐蚀行为

应用丝束电极技术比较了SRB生物膜以及硫化物膜对Q2 35碳钢腐蚀过程的影响机制 ,采用电位、电流扫描技术测试了生物膜和FeS膜下的碳钢腐蚀不均匀性特征 ,发现由于膜的导电性致使表面电位扫描已不能作为膜下局部腐蚀的判据 .动电位扫描表明无氧近中性溶液中 ,硫化物膜对碳钢具有一定保护作用 .电化学阻抗谱显示 ,硫化物膜电容增加缓慢 ,其极化电阻Rp 随时间呈先增后降的趋势 .与硫化物膜相比 ,生物膜表现出极大的电容 (10 4 ～ 10 5μF/cm2 ) ,且膜电容随时间呈S型增加 ,而极化电阻Rp 则呈指数下降 ,由此可知生物膜加速了腐蚀     

添加CaO对煤热解过程中砷和硫迁移转化的影响

利用高频炉反应器在800-1 200℃对添加质量分数10%CaO的云南镇雄煤(YNZX)进行了快速热解实验,采用连续化学提取、X射线衍射(XRD)、扫描电子显微镜-能谱(SEM-EDX)和X射线光电子能谱(XPS)等分析手段,考察了CaO添加对煤快速热解过程中砷和硫迁移转化的影响。结果表明,CaO能显著抑制砷与硫的释放。CaO对砷释放的抑制率在800℃时最高达41.19%,对硫释放的抑制率在1 000℃时最高,为39.89%;两者的抑制率呈负相关。As-Ca复合物和CaS的形成是砷与硫释放率降低的主要原因;添加CaO后,As-Ca复合物的生成使残渣态砷含量增加,CaS的形成使硫化物结合态砷含量减少。热解后硫元素在CaO表面富集,占据更多的吸附活性位,对砷的固定产生抑制作用;添加CaO后焦中硫仍主要以硫化物的形式存在,亚硫酸盐的含量有所增加。     

用丝束电极研究模拟碳化混凝土孔隙液中缓蚀剂对碳钢局部腐蚀的抑制行为

应用丝束电极(WBE)的电位/电流扫描技术, 研究了含Cl-的模拟碳化混凝土孔隙液中, Q345B碳钢局部腐蚀在空间和时间上的发生和发展特征, 同时比较了四乙烯五胺(TEPA)和亚硝酸钠缓蚀剂对局部腐蚀抑制能力的差异. 结果表明NO-2离子能快速渗透腐蚀产物层, 并抑制锈层下的碳钢活性溶解, 而乙烯胺由于在锈蚀层内的扩散速率低, 初期反而会促进锈层下的局部腐蚀, 随着烯胺分子扩散并吸附于锈蚀层/金属界面处, 碳钢活性溶解才受到抑制. 电化学阻抗谱(EIS)可反映局部腐蚀的萌发, 但难以表征缓蚀剂在碳钢表面的不均匀吸附特征. 基于丝束电极表面电位/电流分布所提出的局部腐蚀因子(LF), 可定量表征腐蚀的不均匀特征以及缓蚀剂对局部腐蚀的修复能力.     

β-榄香烯聚乙二醇衍生物的合成及体外抗癌活性

以中草药有效成分β-榄香烯为起始原料, 在碱性条件下与氨基化的聚乙二醇(PEG)反应合成了一系列β-榄香烯单取代PEG衍生物, 利用IR, ¹H NMR及¹³C NMR对其结构进行了表征. 并采用WST-1法观察其对人宫颈癌细胞(Hela)、人白血病细胞(K562)的抑制作用, 探讨其体外抗肿瘤活性. 细胞实验结果表明经PEG修饰的β-榄香烯的抗癌活性有不同程度的增强.     

锂硫电池中的硫正极电催化认识

以单质硫为正极的锂硫电池表现出极高的放电比容量(1672 mAh·g^-1),是极具潜力的下一代二次动力电池。然而,充放电过程中溶解的高阶多硫化锂(Li₂S_n,4≤n≤8)的穿梭效应,以及硫物种缓慢的氧化还原动力学过程是锂硫电池商业应用前需要解决的关键问题。而电化学催化的引入是解决上述问题行之有效的策略。本文从电化学催化角度出发,重新讨论认识多硫化物的存在形式,并从吸附-催化、活性中间体两个方面,根据不同的反应机理、路径分析多硫化物转化机制,总结定量评价催化性能方法,以期为锂硫电池高效电催化剂的设计提供思路。     

Effect of absorbed hydrogen on the iron dissolution

The rate of the anodic dissolution of iron in acid sulfate electrolytes is reduced by hydrogen absorbed in the metal. The dependence of the degree of retardation of the anodic process on the concentration of hydrogen atoms in the near-surface layer of the metal is obtained. The difference in the effect the adsorbed and absorbed forms of hydrogen exert on the iron dissolution rate is noted. At a certain content of absorbed hydrogen, the current efficiency for dissolved iron exceeds 100%, and the weight loss of the hydrogen-charged metal is maximum under the conditions of its anodic polarization. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

H~2S对硫酸溶液中铁腐蚀作用的CNDO/2研究

动电位扫描得出工业纯铁在含H~2S的H~2SO~4溶液中腐蚀的电化学行为。应用CNDO/2法确定了阴、阳极电位下H~2S,HS^-在金属Fe晶面上的稳定吸附取向与最佳吸附间距,通过对吸附物总能量、结合能、净电荷分布的计算,得出H~2S体系阴、阳极反应被加速的微观机制。阳极电位下,大量HS^-为S原子的平行吸附方式,HS^-负电荷大部分向Fe转移,促进铁的溶解。阴极电位下,少量H~2S则为H原子的平行吸附方式,Fe表面负电荷向H~2S分子中与Fe作用的H转移,促进析氢。在CNDO/2法计算的基础上,圆满地解释了实验结果。     

Effect of Cl~-ion on Anodic Iron Dissolution in H_2S-Containing Sulfuric Acid Solutions

ResearchershavestudiedtheeffectofCI-onthestructureandpropertiesofthecorrosionproductsinchloridesolutionscontainingH,S"'.IthasbeenfoundthattherearenocorrosioneffectsonironsurfaceswhicharesubmergedinconcentratedacidicchloridesolutionswithlowHZSlevel.Inthepast,theinteractionbetweentheCI-ionandFehasnotbeenstudiedcompletelyandintensively.TheanodicreactionofironinacidicsolutionscontainingHZSwastheironoxidationcatalyzedbyHS-3.WhenCI-ispresentinHZS-containingacidicsolutions,theeffectofCI-onir…     

Microbial reduction of SO2 as a means of byproduct recovery from regenerable,dry scrubbing processes for flue gas desulfurization

A project is under way at the University of Tulsa to investigate the reduction of SO₂ to H₂S by sulfate reducing bacteria (SRB) in co-culture with mixed fermentative heterotrophs. We have previously demonstrated that SO₂ is completely reduced to H₂S (contact times of 1–2 s) in cultures in which no redox poising agents were required and glucose served as the ultimate source of carbon energy. We have proposed that such a microbial process could be coupled with a Claus reactor to recover elemental sulfur as a byproduct of regenerable, dry scrubbing processes for flue gas desulfurization. The development of this process concept has continued with a study of the use of molasses as a source of carbon and reduced nitrogen, identification of important non-SRB heterotrophs in process cultures, and the identification of the end products of carbohydrate fermentation that serve as carbon and energy sources for the SRB and identification of the end products of SRB metabolism.     

碳钢在N-甲基二乙醇胺介质中的电化学阻抗谱研究

应用电化学阻抗谱(EIS)研究碳钢在N-甲基二乙醇胺(MDEA)介质中的腐蚀行为.实验表明,未经预阴极活化处理的碳钢表面存在氧化膜,溶解氧促使它腐蚀速率增大,经活化处理去除氧化膜后则相反.在不含热稳定性盐(HSS)的MDEA溶液中,碳钢的腐蚀性随MDEA浓度的增加呈先上升后下降趋势;而在HSS高含量的溶液中,其腐蚀性则随MDEA浓度的增加而单调下降.在含有HSS模拟溶液中,碳钢的阳极极化EIS随极化电位由低到高分别出现感抗、负阻抗以及Warburg阻抗响应等特征,对应于孔蚀、活化状态向钝化状态过渡以及进入钝化的趋势,腐蚀反应的阴极过程表现为电化学反应和扩散传质混合控制,阳极过程为电化学反应控制.     

Electrochemical interferometry of a carbon steel in 5–20 ppm KGR-134 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and with seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, an electromagnetic method, and by the electrochemical impedance spectroscopy (EIS), an electronic method. So, the abrupt rate change in the number of the fringe evolutions during corrosion test, EIS, of the carbon steel is called electrochemical interferometry. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of KGR-134 corrosion inhibitor using the EIS method, at room temperature. The electrochemical interferograms of the carbon steel in different solutions represent a detail picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data which were obtained from the EIS tests. Consequently, holographic interferometry is found to be very useful as an electrochemical interferometer for monitoring the anodic dissolution behaviors of metals in aqueous solutions, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

Investigation of carbon steel anodic dissolution in ammonium chloride solutions using electrochemical impedance spectroscopy

The anodic dissolution of carbon steel in ammonium chloride (NH₄Cl) solutions (5, 10, and 20 wt%) is investigated via various electrochemical techniques and other complementary techniques. The polarization measurements reveals that the carbon steel is susceptible to general corrosion. The impedance data taken at various overpotentials shows multiple loops, corresponding to capacitance, inductance, and negative capacitance, and the number of time constants observed is also not the same for various NH₄Cl concentrations. From reaction mechanism analysis, a multi-step reaction mechanism with three adsorbed intermediates and three dissolution paths (one chemical path and two electrochemical paths) is proposed to describe the observed patterns in impedance measurements. The surface coverage of intermediate species and the contribution of chemical reaction and electrochemical reaction to the overall corrosion rate are also estimated from the proposed model. The results obtained from field emission scanning electron microscopy and Raman spectroscopy measurements are also reported.     

Inexpensive and robust iron-based electrode substrates for water electrolysis and energy storage

The instability of iron under anodic conditions makes iron-based electrode substrates unsuitable for alkaline electrolyzers and rechargeable alkaline batteries. Therefore, significantly more expensive substrates such as nickel foam or sintered nickel are used. Nickel adds a significant cost to electrolysis and energy storage systems. We show that iron substrates can be stabilized using a unique protective thermal coating. These coatings can also yield some of the most electrocatalytically active electrodes in addition to showing no notable change in performance even after 1500 h of anodic polarization. Besides sintered iron, low-carbon steel mesh can be stabilized similarly. Low-carbon steel protected by a thin layer of lithium-doped cobalt spinel was found to be an excellent current collector for positive nickel hydroxide electrodes in alkaline batteries. Thus, surface-modified iron substrates, 40 times less expensive than nickel, are promising for lowering the material costs of alkaline water electrolyzers and rechargeable alkaline batteries.