This work is a part of the STW project "Integral solution for sustainable construction (IS2C, Fleur van Rossem for her support during the chip fabrication, Justyna Wiedemair for the chip design and Allison Bidulock for her support during the manuscript preparation.

1.芯片制造注意：该芯片包括一个银/氯化银工作电极（WE），一个银/氯化银的伪参考电极（伪RE）和一个玻璃芯片上的铂反电极。银金属沉积在玻璃芯片上，使用标准的洁净室处理16。它然后在0.1M的FeCl 3溶液氯化30秒，以形成在表面上的氯化银层。在银/氯化银WE（面积=9.812毫米2）位于中心，由银/氯化银的伪再生包围，如图1。 <ol><li>沉积在玻璃上的银金属，以形成一个平坦的银电极。在洁净室的一步一步芯片制造给出如下： <ol><li>光刻<ol><li>对于晶圆清洗，先浸泡玻璃晶片成浓。 HNO 3浴中以除去任何有机污染物，然后进入的1M KOH中以清洁表面。 </li><li>套用一个积极的光致抗蚀剂（200纳米厚）的晶片通过旋涂法进行预烘烤在95℃的抗蚀剂15分钟。 </li><li>通过玻璃掩膜暴露晶片于UV光，持续5秒。 </li><li>发展显影液光刻胶。这将暴露玻璃，其中电极会沉积和其余区域将未曝光的覆盖抗蚀剂的区域。 </li></ol></li><li>玻璃蚀刻<ol><li>浸入显影玻璃晶片中的KOH浴来蚀刻玻璃的露出面积。 </li></ol></li><li>金属沉积（溅射） <ol><li>在暴露的玻璃区域存款银色金属。 <ol><li>第一沉积20nm的钛（Ti）层（由溅射）作为用于玻璃的粘合层。 </li><li>然后70纳米钯（Pd）层（由溅射），为银和Ti之间的扩散阻挡层沉积。 </li><li>最后沉积金属银500纳米。这是在沉积的金属的厚度。该工作电极的面积为4mm 2。 </li><li>点选Remaining在丙酮浴通过剥离工艺抗拒。 </li></ol></li><li>骰子晶片到单个芯片的尺寸。该芯片是现在准备好被氯化，以形成一个片上的Ag / AgCl电极。 </li></ol></li></ol></li><li>放置芯片中一个内部设计的聚四氟乙烯芯片保持器， 如图1。保持器通过推销（或弹簧加载的销）提供了方便的电气连接，并包含一个电化学电池。 </li><li>氯化银电极，以形成芯片上的Ag / AgCl电极。对于这一点，倒0.1在单元M 氯化铁溶液中30秒。或至电极的银颜色变得灰暗。再浸泡并不重要，而更短的浸泡时间可导致没有沉积的Ag / AgCl的。 </li><li>用去离子水冲洗干净，其余的FeCl 3 .The芯片的芯片现在已准备好用于计时电位测量。 </li></ol>2.电解质准备注意：用不同浓度的氯化钾在0.5M KNO 3中制备的电解质。 <ol><li>制备50毫升50毫摩尔的KCl电解质原液（在50毫升溶液0.186克的KCl）。 </li><li>在相同的溶液中添加2.52克KNO 3，以形成0.5M的硝酸钾背景电解质。 </li><li>保持氯化物的起始浓度为零，KNO 3至0.5M换言之，在50毫升去离子水添加2.52克KNO 3。 </li><li>添加50毫摩尔的KCl，增加氯离子浓度（从1到6毫米）的电解质，系统地，如图以下步骤。 <ol><li>加入100μl的50毫米氯化钾成4.9毫升的0.5M KNO 3获得1毫米[CL]。 </li><li>添加104微升的50mM的KCl溶液加入到步骤2.4.1的溶液以获得2毫米[CL]。 </li><li>加入108.41微升50毫米氯化钾溶液中成S步2.4.2 olution拿到3毫米[CL]。 </li><li>加入113.19微升50毫米氯化钾溶液进入步2.4.3的解决方案，以获得4毫米[CL]。 </li><li>添加118.2微升的50mM的KCl溶液加入到步骤2.4.4的溶液以获得5mM的[CL]。 </li><li>添加123.3微升的50mM的KCl溶液加入到步骤2.4.5的溶液得到6毫[CL]。 </li></ol></li></ol> 3.实验装置注意：使用恒电位（生物科学仪器，法国）进行的测量。 <ol><li>放置在芯片保持器的芯片和连接电位的相应终端。 </li><li>连接电位到Ag / AgCl电极的工作电极端子。 </li><li>恒电位仪的参考电极端子连接到另一个Ag / AgCl电极。 </li><li>恒电位的相对电极终端连接到铂电极。 </li><li>放置补偿在一个法拉第笼勒特实验装置，以避免环境噪音。 </li></ol> 4.仪器操作设置注意：在电化学电池的操作参数通过恒电位仪的用户接口控制。在银/氯化银WE的施加电流脉冲期间的电位响应于不同浓度的氯离子的测量。 <ol><li>在恒电位仪程序，打开技术计时，并设置运行参数。 <ol><li>根据需要设置以下参数： <ol><li>电流（I S） </li><li>外加电流（T S）的时间</li></ol></li><li>通过单击电位节目的播放按钮，启动了这一技术。 注意：恒电位仪程序显示作为施加的电流脉冲下的时间的函数的电位应答。 </li></ol></li></ol> 5.测量和清单数据分析小号<ol><li>绘制的过渡时间与在电解质Cl离子浓度的校准曲线。 <ol><li>更改氯化钾电解质浓度氯，系统性。 <ol><li>用5毫升1mM的氯化钾与电化学电池的0.5M KNO 3背景电解质开始测量。 </li><li>通过使用恒电位开始计时电位实验和应用10毫安/厘米-2，10秒的电流和存储数据。 </li><li>集中系统地改变为6毫米1毫米的增量，并重复测量。 </li></ol></li><li>存储所测量的数据作为a.mpt文件和分析数据处理程序的数据文件。 <ol><li>用内部开发的数据处理程序来计算的潜在响应的一阶导数，并计算第一导数的峰值分析数据。第一导数的峰值为过渡时间。 注：完整的鳕鱼数据处理程序的ING在阿巴斯等人，2014年的补充信息中给出。 </li></ol></li><li>与每个1小时的间隔重复测量三次。 </li><li>打开所有的数据文件中的数据处理程序，并计算每个测量的过渡时间。过渡时间计算的细节的步骤给出如下： <ol><li>积与从计时电位测量的数据文件获得的时间的电位差。 </li><li>计算出的潜在响应的一阶导数。 </li><li>指示最大一阶导数的和它的时间。的最大一次导数的时间是过渡时间。 </li></ol></li><li>对于校准曲线，绘出的过渡时间的平方根相对于CL的离子的浓度。 </li><li>除了 ​​测量数据绘制基础上，沙方程25的理论曲线。计算back扩散coefficient从数据图。 <ol><li>在过渡时间之间的测量数据阴谋[CL]走线路上的任何点和记录的过渡时间和值[CL]。沙方程给定为： τ=（FC * / 2J（1 -叔氯 - ））2Dπ 这里，C *为散装Cl离子浓度，F为法拉第常数，J是电流密度，叔氯 -在传输数，D是扩散系数。忽视的T Cl -的 ，因为它的高背景电解质浓度接近于零。 </li><li>在扩散系数的砂方程中剩下的唯一变量;放的过渡时间，氯离子浓度和砂方程得到的扩散系数的值在所施加的电流的值。 </li></ol></li></ol></li><li>漂移测量<ol><li>倒入5毫升氯化钾1毫电化学电池。 </li><li>在恒电位，设定所施加的电流为10:00 -2和时间为10秒。 </li><li>测量为2周的每一天，测量间3小时的间隔三个测定的潜在响应。 </li><li>刷新电解质， 即1毫米氯化钾，执行测量前的每一天。 </li><li>绘制的过渡时间了两个多星期的测量。在每天的过渡时间的变化的过渡时间响应的漂移。 </li></ol></li><li>伪参考电极上的过渡时间测量作用 注意：各种伪引用诸如银/氯化银线，铂丝和钢丝进行测试，以测量过渡时间。 <ol><li>倾4毫米氯化钾电解质在电化学电池。 </li><li>使用银/氯化银作为伪参比电极和将其连接到恒电位仪的参考电极端子。由于阳极电流脉冲的Cl - ＃713;离子的银/氯化银工作电极附近耗尽。 </li><li>通过施加15上午-2的电流密度为10秒进行计时电位测量。 </li><li>重复测量结果与铂作为伪参考电极，并记录数据。 </li><li>重复与钢筋的测量值作为一个假参比电极，并记录数据。 </li><li>积为使用的各种伪参考电极测得的过渡时间。 </li><li>重复整套测量用KCl 5mM的，以及使用各种伪参考电极绘制的过渡时间。 </li></ol></li></ol>

<ol>
	<li>Page, C., Treadaway, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Aspects+of+the+electrochemistry+of+steel+in+concrete.">Aspects of the electrochemistry of steel in concrete.</a> Nature. 297, 109-115 (1982).</li><li>Koleva, D. A., Hu, J., van Breugel, K., Boshkov, N., de Wit, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conventional+and+pulse+cathodic+protection+of+reinforced+concrete:+electrochemical+approach+and+microstructural+investigations.">Conventional and pulse cathodic protection of reinforced concrete: electrochemical approach and microstructural investigations.</a> ECS Transactions. 1, 287-298 (2006).</li><li>Montemor, M., Simoes, A., Ferreira, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chloride-induced+corrosion+on+reinforcing+steel:+from+the+fundamentals+to+the+monitoring+techniques.">Chloride-induced corrosion on reinforcing steel: from the fundamentals to the monitoring techniques.</a> Cement and Concrete Composites. 25, 491-502 (2003).</li><li>Wegen, G., Polder, R. B., Breugel, K. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Guideline+for+service+life+design+of+structural+concrete:+A+performance+based+approach+with+regard+to+chloride+induced+corrosion.">Guideline for service life design of structural concrete: A performance based approach with regard to chloride induced corrosion.</a> Heron. 57 (3), (2012).</li><li>Yoon, I., Koenders, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Theoretical+time+evolution+of+critical+chloride+content+in+concrete.">Theoretical time evolution of critical chloride content in concrete.</a> Structural Durability &amp; Health Monitoring. 5, 275-294 (2010).</li><li>Du, R. G., Hu, R. G., Huang, R. S., Lin, C. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+measurement+of+Cl-concentrations+and+pH+at+the+reinforcing+steel/concrete+interface+by+combination+sensors.">In situ measurement of Cl-concentrations and pH at the reinforcing steel/concrete interface by combination sensors.</a> Analytical Chemistry. 78, 3179-3185 (2006).</li><li>Angst, U., Elsener, B., Larsen, C. K., Vennesland, &. #. 2. 1. 6. ;. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Potentiometric+determination+of+the+chloride+ion+activity+in+cement+based+materials.">Potentiometric determination of the chloride ion activity in cement based materials.</a> Journal of Applied Electrochemistry. 40, 561-573 (2010).</li><li>Laferri&#232;re, F., Inaudi, D., Kronenberg, P., Smith, I. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+new+system+for+early+chloride+detection+in+concrete.">A new system for early chloride detection in concrete.</a> Smart Materials and Structures. 17, 045017 (2008).</li><li>Tang, J. L., Wang, J. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Measurement+of+chloride-ion+concentration+with+long-period+grating+technology.">Measurement of chloride-ion concentration with long-period grating technology.</a> Smart Materials and Structures. 16, 665 (2007).</li><li>Kohri, M., Ueda, T., Mizuguchi, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+a+near-infrared+spectroscopic+technique+to+estimate+the+chloride+ion+content+in+mortar+deteriorated+by+chloride+attack+and+carbonation.">Application of a near-infrared spectroscopic technique to estimate the chloride ion content in mortar deteriorated by chloride attack and carbonation.</a> Journal of Advanced Concrete Technology. 8, 15-25 (2010).</li><li>Tripathi, S. R., Inoue, H., Hasegawa, T., Kawase, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Non-destructive+Inspection+of+Chloride+Ion+in+Concrete+Structures+Using+Attenuated+Total+Reflection+of+Millimeter+Waves.">Non-destructive Inspection of Chloride Ion in Concrete Structures Using Attenuated Total Reflection of Millimeter Waves.</a> Journal of Infrared, Millimeter, and Terahertz Waves. 34, 181-186 (2013).</li><li>Abbas, Y., Olthuis, W., van den Berg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+chronopotentiometric+approach+for+measuring+chloride+ion+concentration.">A chronopotentiometric approach for measuring chloride ion concentration.</a> Sensors and Actuators B: Chemical. 188, 433-439 (2013).</li><li>Climent-Llorca, M. A., Viqueira-P&#233;rez, E., L&#242;pez-Atalaya, M. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Embeddable+Ag/AgCl+sensors+for+in-situ+monitoring+chloride+contents+in+concrete.">Embeddable Ag/AgCl sensors for in-situ monitoring chloride contents in concrete.</a> Cement and Concrete Research. 26, 1157-1161 (1996).</li><li>Myrdal, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> The electrochemistry and characteristics of embeddable reference electrodes for concrete. , (2014).</li><li>Angst, U., Vennesland, &. #. 2. 1. 6. ;., Myrdal, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Diffusion+potentials+as+source+of+error+in+electrochemical+measurements+in+concrete.">Diffusion potentials as source of error in electrochemical measurements in concrete.</a> Materials and Structures. 42, 365-375 (2009).</li><li>Abbas, Y., de Graaf, D. B., Olthuis, W., van den Berg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=No+more+conventional+reference+electrode:+Transition+time+for+determining+chloride+ion+concentration.">No more conventional reference electrode: Transition time for determining chloride ion concentration.</a> Analytica Chimica Acta. 821, 81-88 (2014).</li><li>Meyer, R. E., Posey, F. A., Lantz, P. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chronopotentiometry+of+the+Ag&#8722;+AgCl+system+and+analysis+for+the+chloride+ion.">Chronopotentiometry of the Ag&#8722; AgCl system and analysis for the chloride ion.</a> Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 19, 99-109 (1968).</li><li>Olthuis, W., Langereis, G., Bergveld, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+metrits+of+differential+measuring+in+time+and+space.">The metrits of differential measuring in time and space.</a> Biocybernetics and Biomedical Engineering. 21, 5-26 (2001).</li><li>Bakker, E., Bhakthavatsalam, V., Gemene, K. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Beyond+potentiometry:+robust+electrochemical+ion+sensor+concepts+in+view+of+remote+chemical+sensing.">Beyond potentiometry: robust electrochemical ion sensor concepts in view of remote chemical sensing.</a> Talanta. 75, 629-635 (2008).</li><li>Olthuis, W., Bomer, J., Bergveld, P., Bos, M., Van der Linden, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Iridium+oxide+as+actuator+material+for+the+ISFET-based+sensor-actuator+system.">Iridium oxide as actuator material for the ISFET-based sensor-actuator system.</a> Sensors and Actuators B: Chemical. 5, 47-52 (1991).</li><li>Bergveld, P., Eijkel, J., Olthuis, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Detection+of+protein+concentrations+with+chronopotentiometry.">Detection of protein concentrations with chronopotentiometry.</a> Biosensors and Bioelectronics. 12, 905-916 (1997).</li><li>Iwamoto, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Derivative+chronopotentiometry.">Derivative chronopotentiometry.</a> Analytical Chemistry. 31, 1062-1065 (1959).</li><li>Olthuis, W., Bergveld, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simplified+design+of+the+coulometric+sensor-actuator+system+by+the+application+of+a+time-dependent+actuator+current.">Simplified design of the coulometric sensor-actuator system by the application of a time-dependent actuator current.</a> Sensors and Actuators B: Chemical. 7, 479-483 (1992).</li><li>Olthuis, W., Bergveld, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Integrated+coulometric+sensor-actuator+devices.">Integrated coulometric sensor-actuator devices.</a> Microchimica Acta. 121, 191-223 (1995).</li><li>Bard, A. J., Faulkner, L. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrochemical methods: fundamentals and applications. , (2001).</li><li>Bakker, E., B&#252;hlmann, P., Pretsch, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymer+Membrane+Ion-Selective+Electrodes-What+are+the+Limits?+.">Polymer Membrane Ion-Selective Electrodes-What are the Limits? .</a> Electroanalysis. 11, 915-933 (1999).</li></ol>

The authors have nothing to disclose.

的过渡时间是拐点的时刻;它在理论上是独立基准电位即参考电极。因此，任何金属线可以用作过渡时间测量的伪参考电极。在对比中混凝土氯离子的现有电位测量这种方法能够长期和校准免费测量。此外，灵敏度和浓度的检测范围可以通过调节所施加的电流脉冲来调节。对于更高的CL浓度，这是在混凝土的情况下，较高的电流脉冲，应适用于保持6秒内的过渡时间。 虽?...

基于Ag / AgCl电极的过渡时间测定中氯离子传感器呈现。这样做的目的是在长期连续监测在电解液中的氯离子的过程中，避免固有漂移。计时电位测量，这是一种动态测量方法中，Ag / AgCl电极的用于此目的。这里的Ag / AgCl电极的电势的变化率的刺激（恒电流脉冲）期间进行测量。这种方法的优点是通过躲避液体结参考电极，而是使用任何金属线作为一个假参比电极，因此允许CL离子浓度为长期（岁）的检测和原位应用中，如证明混凝土结构内部的测量。 在混凝土结构中的氯离子是降解1,2的主要原因之一。它启动了钢筋点蚀第二结果在结构3的最终失败。因此，在具体测量CL离子不可避免地要预测的结构4,5的使用寿命和维护周期。不同感测原理已经报道为氯离子的测量在混凝土如电化学6,7，光学8,9和电磁10,11。然而，光学和电磁方法具有笨重的设置，是难以集成作为一个独立的系统，并与选择性12的问题。在电化学技术，一个Ag / AgCl电极的电位测量是本领域的方法6,7,13的状态。尽管有希望的结果，这种方法仅限于实验室规模的测量，因为在有缺陷的数据14,15在参考电势和扩散势降导致的漂移。基于动态电化学测量（DEM）的过渡时间的方法可以缓解这个问题由于潜在漂流16。 在DEM，一个系统的所施加的刺激反应测定17-19。这种系统的例子是计时。这里所施加的电流脉冲被用作刺激消耗电极表面附近的离子和相应的电势响应被测量。在一个Ag / AgCl电极的阳极电流启动一个法拉第反应（位于Ag + CL <img alt="图1" src="/files/ftp_upload/53312/arrow.jpg" />氯化银+ E），导致氯离子接近电极表面耗尽。的电势变化是所施加的电流的函数，并且在电解质12,20中（选择性）离子的浓度。这些离子完全消耗电极附近的时刻表面电位升高的变化率迅速，给人拐点21。潜在的时间响应曲线（测时电位）上的拐点表示的过渡时间，并且可以从被确定最大的潜在响应22的第一导数的。的过渡时间是离子浓度的特性。这种方法已被用来确定不同的离子浓度17和电解质23,24的pH。在一个Ag / AgCl电极作为工作电极的情况下（向其中电流被施加）的耗尽离子将是氯离子17。因此，测量其过渡时间将决定它的浓度。

<table border="0" cellpadding="0" cellspacing="0" width="1009">
	<tbody>
		<tr height="25">
			<td height="25" style="height:25px;width:373px;">Platinum wire (&#8805;99.99% trace metals)</td>
			<td style="width:292px;">Sigma Aldrich, the Netherlands</td>
			<td style="width:172px;">EP1330-1EA</td>
			<td style="width:172px;"></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Potassium chloride (BioXtra, &#8805;99.0%)</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>P9333-500G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Potassium hydroxide (90% pure reagent grade)</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>484016-1KG</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Ferric chloride&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>451649-1G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">potassium nitrate (&#62; 99% reagent grade)&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>P6083-500G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Ag/AgCl liquid junction reference electrode&#160;</td>
			<td>BASi, USA</td>
			<td>model MF-2079</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">VSP potentiostat</td>
			<td>Biologic Science Instruments, France</td>
			<td>VSP 300</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Steel wire</td>
			<td>Microlab TU Delft</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Silver wire&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

dynamic electrochemical measurement of chloride ions

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver chloride electrode is used extensively for potentiometric measurement of chloride ions concentration in electrolyte. In this measurement, long-term and continuous monitoring is limited due to the inherent drift and the requirement of a stable reference electrode. We utilized the chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode. A galvanostatic pulse is applied to an Ag/AgCl electrode which initiates a faradic reaction depleting the Cl&#713; ions near the electrode surface. The transition time, which is the time to completely deplete the ions near the electrode surface, is a function of the ion concentration, given by the Nernst equation. The square root of the transition time is in linear relation to the chloride ion concentration. Drift of the response over two weeks is negligible (59 &#181;M/day) when measuring 1 mM [Cl&#713;]using a current pulse of 10 Am-2. This is a dynamic measurement where the moment of transition time determines the response and thus is independent of the absolute potential. Any metal wire can be used as a pseudo-reference electrode, making this approach feasible for long-term measurement inside concrete structures.

该Ag / AgCl电极被制造使用标准洁净室处理的玻璃芯片（图1）上。使用了计时电位测量装置（图2），并使用电位测定响应。观察Cl离子浓度对过渡时间的效果，含有4,5和6的Cl毫离子的0.5M的KNO 3背景溶液进行测量（图3）。的过渡时间与Cl离子浓度的平方根的校准曲线与理论曲线（图4）沿着作图。过渡时间的响应，测?...

Watch this Scientific Journal Video about Dynamic Electrochemical Measurement of Chloride Ions at JoVE.com

Dynamic Electrochemical Measurement of Chloride Ions

Dynamic measurement of chloride ions is presented. Transition time of an Ag/AgCl electrode, during a chronopotentiometric technique, can give the concentration of chloride ions in electrolyte. This method does not require a stable conventional reference electrode.

氯离子的动态电化学测试

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver ...

dynamic-electrochemical-measurement-of-chloride-ions

Research

Education

JoVE Core

JoVE Journal

Analytical Chemistry

Chemistry

Unit 1

Electrochemical Analyses and Redox Titration

SCIENTISTS IN ACTION

11.3K 次观看.  University of Twente. Dynamic measurement of chloride ions is presented. Transition time of an Ag/AgCl electrode, during a chronopotentiometric technique, can give the concentration of chloride ions in electrolyte. This method does not require a stable conventional reference electrode.

视频: Dynamic Electrochemical Measurement of Chloride Ions

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

The chemical and physical effects of ultrasound arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species and to the emission of light, named sonoluminescence. In this manuscript, we describe the techniques allowing study of extreme intrabubble conditions and chemical reactivity of acoustic cavitation in solutions. The analysis of sonoluminescence spectra of water sparged with noble gases provides evidence for nonequilibrium plasma formation. The photons and the "hot" particles generated by cavitation bubbles enable to excite the non-volatile species in solutions increasing their chemical reactivity. For example the mechanism of ultrabright sonoluminescence of uranyl ions in acidic solutions varies with uranium concentration: sonophotoluminescence dominates in diluted solutions, and collisional excitation contributes at higher uranium concentration. Secondary sonochemical products may arise from chemically active species that are formed inside the bubble, but then diffuse into the liquid phase and react with solution precursors to form a variety of products. For instance, the sonochemical reduction of Pt(IV) in pure water provides an innovative synthetic route for monodispersed nanoparticles of metallic platinum without any templates or capping agents. Many studies reveal the advantages of ultrasound to activate the divided solids. In general, the mechanical effects of ultrasound strongly contribute in heterogeneous systems in addition to chemical effects. In particular, the sonolysis of PuO2 powder in pure water yields stable colloids of plutonium due to both effects.

Acoustic cavitation in liquids submitted to power ultrasound creates transient extreme conditions inside the collapsing bubbles, which are the origin of unusual chemical reactivity and light emission, known as sonoluminescence. In the presence of noble gases, nonequilibrium plasma is formed. The "hot" particles and the photons generated by collapsing bubbles are able to excite species in solution.

活化分子，离子和固体颗粒与声空化

The chemical and physical effects of ultrasound arise not from a direct interaction of molecules with sound waves, but rather from the acoustic ...

科研

化学

Measurement of Particle Size Distribution in Turbid Solutions by Dynamic Light Scattering Microscopy

A protocol for measuring polydispersity of concentrated polymer solutions using dynamic light scattering is described. Dynamic light scattering is a technique used to measure the size distribution of polymer solutions or colloidal particles. Although this technique is widely used for the assessment of polymer solutions, it is difficult to measure the particle size in concentrated solutions due to the multiple scattering effect or strong light absorption. Therefore, the concentrated solutions should be diluted before measurement. Implementation of the confocal optical component in a dynamic light scattering microscope1 helps to overcome this barrier. Using such a microscopic system, both transparent and turbid systems can be analyzed under the same experimental setup without a dilution. As a representative example, a size distribution measurement of a temperature-responsive polymer solution was performed. The sizes of the polymer chains in an aqueous solution were several tens of nanometers at a temperature below the lower critical solution temperature (LCST). In contrast, the sizes increased to more than 1.0 &#181;m when above the LCST. This result is consistent with the observation that the solution turned turbid above the LCST.

A protocol for the direct measurement of particle size distribution in concentrated solutions using dynamic light scattering microscopy is presented.

通过动态光散射显微镜混浊解决方案粒度分布的测定

A protocol for measuring polydispersity of concentrated polymer solutions using dynamic light scattering is described. Dynamic light scattering is a ...

Fabrication and Testing of Photonic Thermometers

In recent years, a push for developing novel silicon photonic devices for telecommunications has generated a vast knowledge base that is now being leveraged for developing sophisticated photonic sensors. Silicon photonic sensors seek to exploit the strong confinement of light in nano-waveguides to transduce changes in physical state to changes in resonance frequency. In the case of thermometry, the thermo-optic coefficient, i.e., changes in refractive index due to temperature, causes the resonant frequency of the photonic device such as a Bragg grating to drift with temperature. We are developing a suite of photonic devices that leverage recent advances in telecom compatible light sources to fabricate cost-effective photonic temperature sensors, which can be deployed in a wide variety of settings ranging from controlled laboratory conditions, to the noisy environment of a factory floor or a residence. In this manuscript, we detail our protocol for the fabrication and testing of photonic thermometers.

We describe the process of fabrication and testing of photonic thermometers.

光子温度计的制作与测试

In recent years, a push for developing novel silicon photonic devices for telecommunications has generated a vast knowledge base that is now being ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

电化学阻抗谱作为电化学速率常数估计的一种工具

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the aziridine ring. The utility of bicyclic aziridinium ions, specifically 1-azoniabicyclo[3.1.0]hexane and 1-azoniabicyclo[4.1.0]heptane tosylate highlighted in the aziridine ring openings by the nucleophile with the release of the ring strain to yield the corresponding ring-expanded azaheterocycles such as pyrrolidine, piperidine and azepane with diverse substituents on the ring in regio- and stereospecific manner. Herein, we report a simple and convenient method for the preparation of the stable 1-azabicyclo[4.1.0]heptane tosylate followed by selective ring opening via a nucleophilic attack either at the bridge or at the bridgehead carbon to yield piperidine and azepane rings, respectively. This synthetic strategy allowed us to prepare biologically active natural products containing piperidine and azepane motif including sedamine, allosedamine, fagomine and balanol in highly efficient manner.

Bicyclic aziridinium ions such as 1-azoniabicyclo[4.1.0]heptane tosylate were generated from 2-[4-tolenesulfonyloxybutyl]aziridine, which was utilized for the preparation of substituted piperidines and azepanes via regio- and stereospecific ring-expansion with various nucleophiles. This highly efficient protocol allowed us to prepare diverse azaheterocycles including natural products such as fagomine, febrifugine analogue and balanol.

稳定笼 Aziridinium 离子的制备及其开环 Azaheterocycles 的合成

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the ...

Disentangling High Strength Copolymer Aramid Fibers to Enable the Determination of Their Mechanical Properties

Traditionally, soft body armor has been made from poly(p-phenylene terephthalamide) (PPTA) and ultra-high molecular weight polyethylene. However, to diversify the fiber choices in the United States body armor market, copolymer fibers based on the combination of 5-amino-2-(p-aminophenyl) benzimidazole (PBIA) and the more conventional PPTA were introduced. Little is known regarding the long-term stability of these fibers, but as condensation polymers, they are expected to have potential sensitivity to moisture and humidity. Therefore, characterizing the strength of the materials and understanding their vulnerability to environmental conditions is important for evaluating their use lifetime in safety applications. Ballistic resistance and other critical structural properties of these fibers are predicated on their strength. To accurately determine the strength of the individual fibers, it is necessary to disentangle them from the yarn without introducing any damage. Three aramid-based copolymer fibers were selected for the study. The fibers were washed with acetone followed by methanol to remove an organic coating that held the individual fibers in each yarn bundle together. This coating makes it difficult to separate single fibers from the yarn bundle for mechanical testing without damaging the fibers and affecting their strength. After washing, fourier transform infrared (FTIR) spectroscopy was performed on both washed and unwashed samples and the results were compared. This experiment has shown that there are no significant variations in the spectra of poly(p-phenylene-benzimidazole-terephthalamide-co-p-phenylene terephthalamide) (PBIA-co-PPTA1) and PBIA-co-PPTA3 after washing, and only a small variation in intensity for PBIA. This indicates that the acetone and methanol rinses are not adversely affecting the fibers and causing chemical degradation. Additionally, single fiber tensile testing was performed on the washed fibers to characterize their initial tensile strength and strain to failure, and compare those to other reported values. Iterative procedural development was necessary to find a successful method for performing tensile testing on these fibers.

The primary goal of the study is to develop a protocol to prepare consistent specimens for accurate mechanical testing of high strength copolymer aramid fibers, by removing a coating and disentangling the individual fiber strands without introducing significant chemical or physical degradation.

解析高强共聚物芳纶纤维使其力学性能的测定

Traditionally, soft body armor has been made from poly(p-phenylene terephthalamide) (PPTA) and ultra-high molecular weight polyethylene. However, to ...

Electrochemical Roughening of Thin-Film Platinum Macro and Microelectrodes

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries of the metal. Using this method, a crack free, thin-film macroelectrode surface with up to 40 times increase in active surface area was obtained. The roughening is easy to do in a standard electrochemical characterization laboratory and incudes the application of voltage pulses followed by extended application of a reductive voltage in a perchloric acid solution. The protocol includes the chemical and electrochemical preparation of both a macroscale (1.2 mm diameter) and microscale (20 &#181;m diameter) platinum disc electrode surface, roughening the electrode surface and characterizing the effects of surface roughening on electrode active surface area. This electrochemical characterization includes cyclic voltammetry and impedance spectroscopy and is demonstrated for both the macroelectrodes and the microelectrodes. Roughening increases electrode active surface area, decreases electrode impedance, increases platinum charge injection limits to those of titanium nitride electrodes of same geometry and improves substrates for adhesion of electrochemically deposited films.

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries. The electrochemical techniques of cyclic voltammetry and impedance spectroscopy are demonstrated to characterize these electrode surfaces.

薄膜铂金宏观和微电极的电化学粗加工

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries ...

Asymmetric Thermoelectrochemical Cell for Harvesting Low-grade Heat under Isothermal Operation

Low-grade heat is abundantly available in the environment as waste heat. The efficient conversion of low-grade heat into electricity is very difficult. We developed an asymmetric thermoelectrochemical cell (aTEC) for heat-to-electricity conversion under isothermal operation in the charging and discharging processes without exploiting the thermal gradient or the thermal cycle. The aTEC is composed of a graphene oxide (GO) cathode, a polyaniline (PANI) anode, and 1M KCl as the electrolyte. The cell generates a voltage due to the pseudocapacitive reaction of GO when heating from room temperature (RT) to a high temperature (TH, ~40-90 &#176;C), and then current is successively produced by oxidizing PANI when an external electrical load is connected. The aTEC demonstrates a remarkable temperature coefficient of 4.1 mV/K and a high heat-to-electricity conversion efficiency of 3.32%, working at a TH = 70 &#176;C with a Carnot efficiency of 25.3%, unveiling a new promising thermoelectrochemical technology for low-grade heat recovery.

Low-grade heat is abundant, but its efficient recovery is still a great challenge. We report an asymmetric thermoelectrochemical cell using graphene oxide as a cathode and polyaniline as an anode with KCl as the electrolyte. This cell works under isothermal heating, exhibiting a high heat-to-electricity conversion efficiency in low-temperature regions.

用于在等温操作下收集低档热量的不对称热电化学电池

Low-grade heat is abundantly available in the environment as waste heat. The efficient conversion of low-grade heat into electricity is very difficult. We ...

Fabrication of Thin Film Silver/Silver Chloride Electrodes with Finely Controlled Single Layer Silver Chloride

This paper aims to present a protocol to form smooth and well-controlled films of silver/silver chloride (Ag/AgCl) with designated coverage on top of thin film silver electrodes. Thin film silver electrodes sized 80 &#181;m x 80 &#181;m and 160 &#181;m x 160 &#181;m were sputtered on quartz wafers with a chromium/gold (Cr/Au) layer for adhesion. After passivation, polishing and cathodic cleaning processes, the electrodes underwent galvanostatic oxidation with consideration of Faraday&#39;s Law of Electrolysis to form smooth layers of AgCl with a designated degree of coverage on top of the silver electrode. This protocol is validated by inspection of scanning electron microscope (SEM) images of the surface of the fabricated Ag/AgCl thin film electrodes, which highlights the functionality and performance of the protocol. Sub-optimally fabricated electrodes are fabricated as well for comparison. This protocol can be widely used to fabricate Ag/AgCl electrodes with specific impedance requirements (e.g., probing electrodes for impedance sensing applications like impedance flow cytometry and interdigitated electrode arrays).

This paper aims to present a method to form smooth and well-controlled films of silver chloride (AgCl) with designated coverage on top of thin film silver electrodes.

薄膜银/银氯化银电极的制造，具有精细控制的单层氯化银

This paper aims to present a protocol to form smooth and well-controlled films of silver/silver chloride (Ag/AgCl) with designated coverage on top of thin ...

Probing Surface Electrochemical Activity of Nanomaterials using a Hybrid Atomic Force Microscope-Scanning Electrochemical Microscope (AFM-SECM)

Scanning electrochemical microscopy (SECM) is used to measure the local electrochemical behavior of liquid/solid, liquid/gas and liquid/liquid interfaces. Atomic force microscopy (AFM) is a versatile tool to characterize micro- and nanostructure in terms of topography and mechanical properties. However, conventional SECM or AFM provides limited laterally resolved information on electrical or electrochemical properties at nanoscale. For instance, the activity of a nanomaterial surface at crystal facet levels is difficult to resolve by conventional electrochemistry methods. This paper reports the application of a combination of AFM and SECM, namely, AFM-SECM, to probe nanoscale surface electrochemical activity while acquiring high-resolution topographical data. Such measurements are critical to understanding the relationship between nanostructure and reaction activity, which is relevant to a wide range of applications in material science, life science and chemical processes. The versatility of the combined AFM-SECM is demonstrated by mapping topographical and electrochemical properties of faceted nanoparticles (NPs) and nanobubbles (NBs), respectively. Compared to previously reported SECM imaging of nanostructures, this AFM-SECM enables quantitative assessment of local surface activity or reactivity with higher resolution of surface mapping.

Probing Surface Electrochemical Activity of Nanomaterials using a Hybrid Atomic Force Microscope-Scanning Electrochemical Microscope AFM-SECM

Atomic force microscopy (AFM) combined with scanning electrochemical microscopy (SECM), namely, AFM-SECM, can be used to simultaneously acquire high-resolution topographical and electrochemical information on material surfaces at nanoscale. Such information is critical to understanding heterogeneous properties (e.g., reactivity, defects, and reaction sites) on local surfaces of nanomaterials, electrodes and biomaterials.

使用混合原子力显微镜扫描电化学显微镜（AFM-SECM）探测纳米材料的表面电化学活性

Scanning electrochemical microscopy (SECM) is used to measure the local electrochemical behavior of liquid/solid, liquid/gas and liquid/liquid interfaces. ...