Name: detection and recovery of palladium, gold and cobalt metals from the urban mine using novel sensors/adsorbents designated with nanoscale wagon-wheel-shaped pores
Uploaded: 2015-12-06T15:00:00.000+00:00
Duration: 10 min 31 s
Description: Watch this Scientific Journal Video about Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Po

这项工作是由教育，文化，体育，科学与技术部日本和环境部，政府的支持。

1.制造货车轮状，立方IA 3天介孔单片支架注意:控制立方几何（优先螺旋形IA三维对称）和孔整体支架采用三嵌段共聚物聚醚P123 [P123微米级颗粒表面;聚（环氧乙烷- 方框 -丙烯氧化物- 方框 -环氧乙烷）（EO 20的PEO 70 EO 20）]作为模板。 <ol><li> 2:在典型的条件下，以1.6的质量比添加P123，十五烷，和四甲基原硅酸盐（TMOS）在一个200毫升的圆底烧瓶中1.2到盐酸/ H 2 O（pH约1.0）;然后摇动混合物在45℃下，直至形成均匀的溶胶 - 凝胶。 </li><li>连接烧瓶到旋转蒸发器，并蒸发混合物，在45℃和1023帕斯卡的起始压力。在这些条件下，放热的水解和TMOS的缩合迅速发生。 </li><li>继续evaporati上10-20分钟该混合物，以获得绕连接烧瓶37-39的壁的光学凝胶状货车轮状整料。 </li><li>干燥含有同样制造的整体件的烧瓶在45℃下放置24小时以完成干燥过程。 </li><li>治疗用货车轮状的巨石在450 °下进行正常的大气条件下，8小时。 </li><li>研磨煅烧后的固体整料完全通过使用研钵和杵，并存储地面材料购买用作管理服务协定的制造的载体的平台。 </li></ol>材料2表征<ol><li>高分辨透射电子显微镜（HRTEM） <ol><li>分散1毫克样品在5毫升乙醇溶液使用超声清洁器，然后滴样品的两个小滴上的铜网格。 </li><li>真空干燥网格之前，在高分辨透射电子显微镜柱插入样品20分钟。 </li><li>使用连接到CCD照相机的透射电子显微镜的HRTEM执行。记录HRTEM显微照片以200千伏的加速电压，以获得0.1纳米的晶格分辨率。 </li></ol></li><li> N 2吸附-脱附等温线<ol><li>预治疗货车轮状样品在100 °℃下在真空下8小时，以平衡压力到10 -3乇。 </li><li>测量的 N 2吸附-脱附等温线在77K使用的表面积和孔径分析仪按照制造商的说明</li><li>通过使用非局部密度泛函理论确定从吸附等温线的孔径分布。通过使用从使用布鲁诺尔-埃米特-特勒（BET）理论的N 2吸附等温线的线性段点对多点吸附数据计算比表面积（S BET）。 </li></ol></li><li>小角度的粉末X射线衍射（XRD） <ol><li>测量X射线衍射图通过使用一个18千瓦的衍射仪和单色化CuKα线，按照制造商的＃39的说明。 </li><li>记录绕射通过同时使用石墨单色和GOBEL镜检测器与2θ角度在0.1和6.5°，对应于88.2和1.35纳米之间D-间距。 </li><li>研磨样品并传播该粉末上的样品架。确认的衍射峰，在2θ标准的重现性（±0.005°）分辨率。重复样品测量三次，以各种角度旋转（15°，30°，和45°）。 </li></ol></li></ol> 3.制备的Pd（II）的-MSA-1，金（Ⅲ）-MSA-2，和Co（Ⅱ）-MSA -3- <ol><li>钯的合成（II）的-MSA-1和Co（Ⅱ）-MSA -3- 注:使用压力辅助方法，通过1,5-二羧酸二苯基卡巴腙（L1）和2-亚硝基-1-萘酚以引导车皮轮状，立方IA三维整料的变形（L3）的配体（0.1M乙醇溶液）（Ⅱ）-MSA-1和Co（Ⅱ）-MSA-3，分别制作的Pd。 <ol><li>添加等hanolic -1,5-二羧酸二苯基卡巴腙（L1）或2-亚硝基-1-萘酚（L3）的解决方案，以固体车皮轮整料成圆形烧瓶中并混合下振荡1分钟。 </li><li>连接含有异质的EtOH-L1 /固体整料混合物以旋转蒸发器烧瓶中，并蒸发混合物，在45℃和1023帕斯卡的起始压力。 </li><li>连接含有异质的EtOH-L3 /固体整料混合物以旋转蒸发器另一个烧瓶中，并蒸发混合物，在50℃和1023百帕起始压力。除去从异构乙醇 - 配体/固体混合物整料真空下的EtOH溶液在环境温度下。 </li><li>澄清配体固体（MSA-1和MSA-3）的物理吸附的短程相互作用（ 即 ，范德华力和氢键相互作用）的货车轮的活性表面位点的丰富羟基之间形成的机理形支架和杂配体40,41。 </li><li>计算AMO固定化L1和L3的UNTS如下:Q E =（C 0 - 权证 ） 伏/米，其中 q e是吸附量，V为溶液体积（L），m为运营商（G）的质量， 和 C 0 和 C e为初始和上清探针浓度分别。固定化的L1和L3的量可以预计约为0.09毫摩尔/克。 </li></ol></li><li>金（III）的合成-MSA-2 注:适用积木协议来合成的Au（III）-MSA-2: <ol><li>固定40毫升dilauryldimethylammonium溴化物的0.1M乙醇溶液（DDAB）到0.5克的使用旋转蒸发器，以产生车皮轮状HOM-DDAB整料货车轮状HOM支架。 </li><li>溶解20毫克hydrophilic6羟基-5-（4- sulfonatophenylazo）-2-萘磺酸二钠盐（L2）的配位体在80ml去离子水。加入0.5克固体HOM-DDAB巨石。该ñ删除轰通过过滤2 O解决方案。 </li><li>洗HOM-DDAB-L2以去离子水，直到没有L2被洗脱;然后在65-70℃进行4小时干燥样品。注:毫摩尔L2的0.07每克HOM支架配体结合到HOM-DDAB 42。 </li><li>澄清（MSA-2）的基础上，L2-DDAB固耦合的形成机制。 </li></ol></li></ol> 4.批次研究用于检测钯（Ⅱ），金（III）和Co（II）离子<ol><li>浸入20毫克的车皮轮状的钯（Ⅱ），金（III）和Co（II）离子的混合物中的MSA-1，MSA-2，和MSA-3（离子浓度:2毫克/升） ;调整体积至20ml，pH值至2，7适当的pH值，和5.2，分别。 </li><li>在25机械地摇动混合物在温度控制的水浴 °℃45分钟，在300rpm的恒定搅拌速度。 </li><li>过滤器管理服务协议通过25毫米的滤纸;平衡后，用视觉色彩评估和反射光谱measurem已废除，以确定离子浓度。 </li><li>确定钯（Ⅱ），金（III）和Co（II）的目标离子浓度由在λ最大384，486比较MSA-1，MSA-2，和MSA-3的反射强度，和537纳米，分别在加入未知浓度目标样品与目标样品的标准浓度的。 </li><li>进行使用目标的Pd（II）的其他实验中，金（Ⅲ），和钴（II）离子浓度在2,7和5.2的最佳pH值，分别使用紫外可见光谱。每百万的部分（ppm时，毫克/升），十亿分之一（ppb的，微克/升），和摩尔（摩尔/升）单元被用来定义在溶液中的目标离子浓度。 </li></ol> 5.方法卸下钯（Ⅱ），金（III）和Co（II）离子<ol><li>沉浸在具体的Pd的混合物中每车皮轮状的MSA 40毫克（Ⅱ），金（III）和Co（II）离子浓度; pH调节的混合物，以具体的数值2,7，和5.2，分别在20μm的体积升，并搅拌混合物2小时，在室温。 </li><li>过滤固体医疗储蓄账户，并通过电感耦合等离子体质谱仪（ICP-MS）28-30分析滤液。 </li><li>计算根据下列方程式43 Langmuir等温: <img alt="式（1）" src="/files/ftp_upload/53044/53044eq1.jpg" /> 其中 C e的目标离子浓度，Q e是目标离子的平衡溶液量，Q 米 （毫克·g -1）以上为Pd（Ⅱ），金（III）或Co（II）离子除去的量形成所述单分子层覆盖， 和 K L是 Langmuir吸附平衡常数。例如， 第 q m个数据表示从具有高吸附效率（97％-98％）的含水介质的实际除去金属离子。 而且 ，k 的L值是与吸附/解吸速率一致，说明完全可逆的金属吸附测定法。 </li></o升&gt; 在货车轮状的医疗储蓄户口6.形成的金属 - 配体结合常数<ol><li>确定稳定性常数[PD-（L1）2]，[自动（L2）]和[CO-（L 3）2]配合物在pH 2,7和5.2，其可以预期到的（1o9氏多个）大约5.8，4.9，和7.9，分别为。 </li><li>根据下列等式28-32计算稳定性常数: 1o9氏S =（[ML] S / [L] S）×[M] 其中，[M]是自由钯（Ⅱ），金（Au）的浓度（Ⅲ），或Co（II）的溶液中的离子; [L]表示游离的L-浓度（即，L不是结合到钯（Ⅱ），金（III）或Co（II）离子）;和下标S指的是钯（Ⅱ）的总浓度，金（Ⅲ），或钴（II）在车皮轮状的MSA的固相离子。 </li><li>确定检测限管理服务协定（LOD）为钯（Ⅱ），金（III）和Co（II）离子，如下所示: LOD =3σ/Ψ 其中σ和Ψ是标准偏差和校正曲线40-42的斜率。 </li></ol> 7.选择性离子萃取实验系统注:确保专用性强的金属 - 配体结合，如下所示: <ol><li> pH调节提取液，以2,7，和5.2的钯（Ⅱ），金（III）和Co（II）离子。改变干扰金属离子≤5倍大于钯（Ⅱ）的浓度的浓度，金（III）和Co（II）的靶标离子。添加2ml的络合物形成剂（ 如 ，0.3-0.5柠檬酸/酒石酸）以在加入靶标离子的萃取溶液，以抑制主动反应的Cu（II）离子。 </li></ol>金属8.实时提取城市矿山<ol><li>溶解PCI板在强酸，以获得金属离子在溶液中。 </li><li>添加到管理服务协定包含Pd（Ⅱ），金（III）和Co（II）离子的溶液中提取这些离子进入固体医疗储蓄户口。 </li><li>过滤固体医疗储蓄户口和分析滤液用ICP-MS。 </li></ol>

The authors declare that they have no competing financial interests.

全球需求正在增长以准确和快速检测，选择性地识别和恢复钯（Ⅱ），金（III）中的一种手段，和Co（Ⅱ）从电子废料和LIB溶液离子。为了解决这个问题，车皮轮状，光管理服务协定进行化学检测/移除/提取和这些金属离子的回收被开发。 在设计事务协议，两个关键因素被认为如下:（1）受体和（2）的固定化/转导的支架。受体是负责管理服务协定的选择性的有机配体;支架是负责的稳定性，可重用性，以及管理服务协定的灵敏度。因为它们的高度均匀的通道，大的表面积，孔径分布，和可控车皮轮结构，其通常与立方双连续表面形态的[111]投影相关联（图1和2）中，基于MSA车皮的车轮IA 3天细微结构材料的支架设置在该检测/移除/提取和回收方法的潜在需求控制如下:配体嵌入HOM固体（即无浸出后洗涤所述配体），（2）感测的条件（1）的稳定性测定法，及（3）在再生/再利用循环化学处理条件 （即，后八个周期）;高配体表面覆盖和分散;机械强度;从城市矿山高效回收加工。 来制造稳定和健壮管理服务协定设计，车轮件内孔表面或连续夹杂物不同配体的monofunctionalization（即，L1，L2和L3; 图3-5）转换成可通过压力辅助来实现的HOM支架共缩合;使用L1和L3，高阶混合动力车MSA-1和MSA-3分别得到。 MSA-2控制的设计是基于微调表面图案Øf显示细观车轮支架结构。这是通过使用可分散的活性剂（DDAB），导致致密装饰车轮件孔腔内部L2信令中心完成的。与这些设计的MSA，金属离子可以与通过非共价键合（例如，氢键 ），金属配位，疏水力，范德华力，π-π相互作用和静电和/或电磁效应的有机部分（ 图3-5交互）。在感测测定中，纳米工程管理服务协定可以由一个靶的Pd（II）被触发，金（Ⅲ），或钴（II）离子种类和转导下协同pH，反应温度和接触时间（响应时间）的条件下测的光信号，使金属的结合成疏水性的或亲水性配体口袋被模仿。发达事务协议不仅除去钯（Ⅱ），金（III）和Co（Ⅱ）从复杂环境基质离子，但也提供了一个装置，用于一个简单的视觉金属离子浓度的比色估计;紫外-可见反射光谱灵敏量化金属离子浓度在宽范围的浓度（ 图3-6）。因此，管理服务协定提供一种简单和灵敏的比色为基础的解决方案，以检测在宽范围的金属离子浓度的变化以及对所述靶标离子敏感量化的装置，从而避免需要复杂的仪器。即使在超痕量浓度（≤0.19微克/升），在传感器的反射光谱的信号变化出现形成复合物（图1）中。 在批次传感/移除/提取系统中，货车轮状事务协议的主要优点是它们的选择性朝向目标离子，从而防止阻碍从干扰竞争的离子。 图6证实了选择性除去和有效地监测钯（Ⅱ），金（III）和Co（II）离子通过光学医疗储蓄账户。在竞争离子的存在下，管理服务协定的反射信号的微不足道的变化表明，弱螯合物竞争金属和L1，L2和L3之间形成，特别是在pH 2,7，和5.2，分别。该事务协议的选择性可以归因于高度稳定的八面体的形成[PD-（L1）2]，正方形平面[自动（L2）〕，和八面体[CO-（L 3）2]络合物。 用于判断的经过反复再生/再利用循环进行了调查车皮轮状事务协议的成本效益，可回收性和耐久性。 图8显示了事务协议保留了高效率的检测/移除/萃取钯（Ⅱ），金（Au）（ III）和Co（II）离子在重复再生/重用周期，虽然整体效率的第六再生/再利用循环后稍稍降低。立方IA三维细微结构和稳定性的L1，L2和L3的掺入或dered车皮轮形的孔隙（诱导强氢键和色散相互作用）中通过几个再生/再利用循环维持离子传感/捕获系统的功能发挥显著职能（参见图7）。 回收钯（Ⅱ），金（III）和Co（Ⅱ）从城市矿山离子可帮助限制与采矿这些金属相关，特别是相对于在陆地上和气候的影响对环境的破坏。使用真实城市矿山的样品，结果表明，本文所述的管理服务协定可以选择性回收钯，金从电子废物和Co从丢弃LIBS（ 表1图9），但实际的，可扩展的过程中仍然保持为未来适用性挑战从城市矿山金属回收率。 在所提出的管理协议的基础上，两个关键组件起到增强金属离子可访问性的重要作用，吸附能力，并在非均相过程恢复。首先，将大的表面-体积比和车轮件立方IA三维有序结构（MSAS）的开口的圆筒孔促进取向配体组件（如由钯（Ⅱ），金（III）和Co的柔性相互作用（II）与L1，L2和L3和金属-配体结合事件的高亲和力离子）（ 图3-5）。其次，选择性吸附/检测/提取过程主要取决于螯合剂的结构中，实验条件（特别是pH值），离子系统的组成中，金属离子浓度，和金属 - 配体结合事件。虽然该协议表示在质量显著进展，和的回收方法效率，还需要进一步的努力，使他们能够在环境废物其他苛刻的适用性被使用，在其中用高剂量的积极竞争性的金属如Cu富集（Ⅱ），铁（Ⅲ）的ð镍（II）离子。 总之，高效率，高性价比，货车轮状的医疗储蓄户口已经开发了用于恢复钯，金，钴金属从城市矿山。结果表明证据表明，医疗储蓄账户将提供一个路线金，钯，钴的可持续供应，以适应现代社会的需要，是有用的。

对于蓬勃发展的使用铂族金属（PGM）的驱动力是其非凡的，有时独特的特性，这使它们在广泛的应用中重要组成部分。铂族金属可以在构建可持续发展的社会中发挥作用，而这些材料在各种现代的应用和产品应用于:化工过程催化，汽车排放控制，信息技术，消费电子产品，珠宝首饰，准备牙科材料，光伏发电的燃料电池和锂离子电池（LIB）1-10。在过去的一个世纪，世界经济的变化已经搭载了使用精确制导弹药。因为在清洁技术和高科技装备精确制导武器的重要性，使用精确制导弹药的急剧增加，在现代社会。由于急剧增加的使用铂族金属，特别是在生产电子设备，电子废弃物（电子废物）的累积导致了environmenta升挑战和问题。此外，最近商品价格飙升已经产生的电子废物1-4的挖掘新的兴趣。 电子废物含有这两种有害物质的和有价值的钯，金，钴金属。如果电子废物被弃置于堆填区或无害环境的方式不及时治疗，就可能造成环境破坏的高风险。钯，金中和电子废物钴金属是可持续的，这样的金属5-10"绿色"辅助资源。因此，高效的流程回收钯，金，钴 迫切需要从电子废物金属。 在许多技术领域未来的进步将需要初级金属资源的控制。由于钯，金，钴日益重要 在工业应用和解决环境问题11-13，开发吸附/萃取-金属ñ技术的认可和此类金属的回收已成为当务之急。 在电子产品中使用的主贵金属是银，金，钯，铂和少量铑4-8。回收钯和金，成为由于其独特的在广泛的工业应用，经济价值，和罕见的性能组合是至关重要的。市场机制已颇具影响力在增加收集和回收过时的电脑，电视，手机和其他电子设备的电路板的速度。批量生产的消费部件，如电脑主板，含有大约80克Pd和300克每吨电子垃圾金的;相应数额的移动电话手机130克Pd和200g金，每吨电子垃圾5-10。这个城市矿山拥有这些金属的巨量（相比之下，金以及钯存在于极低浓度的岩石（〜4纳克/克），土壤（1纳克/克），海水（0.05微克/升），和河水（0.2微克/升）14-16）。为了确保持续而可靠的钯，金，钴供应 金属未来的技术创新和新的电子设备，开发出一种高效，低成本的技术，回收贵金属的电子垃圾是非常重要的。这种技术可以作为对稀土矿，这些预测是供不应求，甚至耗尽，在100年的未来稀缺房源保险。 如钴的元素有一个必要的投入几乎所有的电化学储能电池等LIBS 17-19。由于信息技术的快速发展和库的范围广泛的利用，LIBS作为电子废物的释放探索出了一条新的环境挑战18-20。因此，通过回收这些资源，处理这些废弃物小心可能会打开了一个新的途径环境和工业应用。 几个强有力的和成熟的方法和分析技术已被用来鉴别和量化金（Ⅲ），钯（Ⅱ）及Co（Ⅱ）在天然矿石和工业废物，包括火焰和碳炉原子吸收分光光度法，紫外 - 可见（UV-VIS）光谱法，中子活化分析，和电感耦合等离子体质谱法14-16,21-27。尽管他们的通用性和日益普及，这些分析技术受到许多不足之处。例如，它们通常需要仔细规划和测试，涉及到许多样品制备步骤，以尽量减少样品基质干扰，需要精密的 ​​仪器和训练有素的人员，并且必须严格的实验条件17,21下进行。此外，所有这些分析技术包括预浓缩和分离步骤，例如溶剂分机raction，共沉淀，离子交换，和吸附，预浓缩从基质组分的靶金属离子之前，他们的判定20-27。此外，湿法冶金和火法冶炼技术通常用在工业19-22再循环链。因此，开发高效，具有成本效益和易于使用的分析方法来恢复钯，金，钴 由天然矿石和工业废金属都用于环境保护和工业部门的11-13重要。 新技术可以提供新的方法来化学分析，并从天然矿石和工业废金属的回收。最近的进展已经取得了降低成本，缩短制造光学化学纳米传感器/吸附剂的时间;然而，光学吸附剂仍用于特定现实世界传感，萃取，和恢复应用为各种金属28的-36。最近，研究集中在剪裁特定的固体中孔整料用作高灵敏度传感器的简单和同时肉眼检测和清除有毒和贵金属离子，如汞和金离子，来自水生样品28-32。这里，用于有选择地检测和有效地回收金的方法（Ⅲ）和Pd（II）从城市矿山报告;另外，该方法可应用于钴（II）离子从LIBS的恢复。回收金属通过该方法不仅应作为金（Ⅲ），钯（Ⅱ）的辅助源，和Co（II）离子也减少环境污染。的货车轮状事务协议的协议设计表明，在第一次，对钯的恢复控制的光学识别金（Ⅲ），钯（Ⅱ），和钴（II）离子，和一个高度选择性系统的证据（ II）离子（达〜95％）的矿石和工业废物。

<table><tbody><tr><td>Tetramethylorthosilicate (TMOS)</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 681-84-5</td><td>Molecular Weight 152.22; Linear Formula Si(OCH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;; 218472-500G</td></tr><tr><td>Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), PEG-PPG-PEG, Pluronic&amp;reg; P-123</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 9003-11-6</td><td>average Mn ~5,800</td></tr><tr><td>Sodium citrate tribasic dehydrate</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 6132-04-3</td><td>Linear Formula HOC(COONa)(CH&lt;sub&gt;2&lt;/sub&gt;COONa)&lt;sub&gt;2&lt;/sub&gt; &amp;middot; 2H&lt;sub&gt;2&lt;/sub&gt;O; Molecular Weight 294.10; S4641-500G</td></tr><tr><td>Pentadecane, C15</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 629-62-9</td><td>Linear Formula CH&lt;sub&gt;3&lt;/sub&gt;(CH&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;13&lt;/sub&gt;CH&lt;sub&gt;3&lt;/sub&gt;; Molecular Weight 212.41</td></tr><tr><td>&lt;em&gt;N&lt;/em&gt;-cyclohexyl-3-aminopropane sulfonic acid (CAPS)</td><td>Dojindo Chemicals (Japan)</td><td>343-00484, Lot.DE132</td><td>Linear Formula C&lt;sub&gt;9&lt;/sub&gt;H&lt;sub&gt;19&lt;/sub&gt;NO&lt;sub&gt;3&lt;/sub&gt;S, M1254-250G, Molecular Weight 221.32</td></tr><tr><td>2-Nitroso-1-naphthol (NN)</td><td>Tokyo Chemical Industry Con, LTD (TCI)</td><td>Product Number N0267</td><td>Linear Formula ONC&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;6&lt;/sub&gt;OH, M1254-250G, Molecular Weight 173.17</td></tr><tr><td>Sunset Yellow FCF</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 2783-94-0</td><td>Empirical Formula (Hill Notation) C&lt;sub&gt;16&lt;/sub&gt;H&lt;sub&gt;10&lt;/sub&gt;N&lt;sub&gt;2&lt;/sub&gt;Na&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;7&lt;/sub&gt;S&lt;sub&gt;2&lt;/sub&gt;, Molecular Weight 452.37, 465224-25G</td></tr><tr><td>Diphenylthiocarbazone</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 60-10-6</td><td>Linear Formula C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;NHNHCSN=NC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;, Molecular Weight 256.33, 194832-10G</td></tr><tr><td>4-hydrazinobenzoic acid</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 619-67-0</td><td>Linear Formula H&lt;sub&gt;2&lt;/sub&gt;NNHC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;CO&lt;sub&gt;2&lt;/sub&gt;H, Molecular Weight 152.15, 246395-25G</td></tr><tr><td>Carbon disulfide</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 75-15-0</td><td>Empirical Formula (Hill Notation) CS&lt;sub&gt;2&lt;/sub&gt;, Molecular Molecular Weight 76.14, 335266-100ML</td></tr><tr><td>Ethanol absolute</td><td>Sigma&amp;ndash;Aldrich Company Ltd. (USA)</td><td>CAS Number 64-17-5</td><td>Linear Formula CH&lt;sub&gt;3&lt;/sub&gt;CH&lt;sub&gt;2&lt;/sub&gt;OH, Molecular Weight 46.07, 24102-1L-R</td></tr><tr><td>Small angle powder X-ray diffraction (XRD)&amp;nbsp;</td><td>Bruker D8 Advance</td><td></td><td>Small angle powder X-ray diffraction (XRD) patterns were measured by using a 18 kW diffractometer (Bruker D8 Advance) with monochromated CuK&amp;alpha; radiation and with scattering reflections recorded for 2&amp;theta; angles between 0.1&amp;#176; and 6.5&amp;#176; corresponding to d-spacing between 88.2 and 1.35 nm. First, the powder samples were ground and spread on a sample holder. The samples were scanned in the range from 2&amp;theta; = 0.1&amp;#176;&amp;ndash;6.5&amp;#176; with step size of 0.02&amp;#176;. To confirm the resolution of the diffraction peaks with standard reproducibility in 2&amp;theta; (&amp;plusmn;0.005), the sample measurement was recorded by using both graphite monochromator and G&amp;ouml;bel mirror detectors. Both detectors were used to generate focusing beam geometry and parallel primary beam. The sample measurement was repeated three times under rotating at various degrees (15&amp;#176;, 30&amp;#176; and 45&amp;#176;).</td></tr><tr><td>N&lt;sub&gt;2&lt;/sub&gt; adsorption&amp;ndash;desorption isotherms&amp;nbsp;</td><td>BELSORP MIN-II analyzer (JP. BEL Co. Ltd)</td><td></td><td>N&lt;sub&gt;2&lt;/sub&gt; adsorption&amp;ndash;desorption isotherms were measured using a BELSORP MIN-II analyzer (JP. BEL Co. Ltd) at 77 K. The pore size distribution was determined from the adsorption isotherms by using nonlocal density functional theory (NLDFT). Specific surface area (SBET) was calculated using multi-point adsorption data from a linear segment of the N&lt;sub&gt;2&lt;/sub&gt; adsorption isotherms using Brunauer&amp;ndash;Emmett&amp;ndash;Teller (BET) theory. Before the N&lt;sub&gt;2&lt;/sub&gt; isothermal analysis, all prepared samples were pre-treated at 100 &amp;#176;C for 8 hr under vacuum until the pressure was equilibrated to 10&lt;sup&gt;&amp;minus;3&lt;/sup&gt; Torr.</td></tr><tr><td>High-resolution transmission electron microscopy (HRTEM)&amp;nbsp;</td><td>JEOL JEM model 2100F microscope</td><td></td><td>High-resolution transmission electron microscopy (HRTEM) was performed using a JEOL JEM model 2100F microscope. HRTEM was conducted at an acceleration voltage of 200 kV to obtain a lattice resolution of 0.1 nm. The HRTEM images were recorded using a CCD camera. In the HRTEM characterization, the sample was dispersed in ethanol solution using an ultrasonic cleaner, and then dropped on a copper grid. Prior to inserting the samples in the HRTEM column, the grid was vacuum dried for 20 min. Energy Dispersive X-ray micro-analyzers (EDX) were recorded by employing Horiba EDS-130S, which directly connected with Hitachi FE-SEM S-4300. Elemental mapping of all samples was carried out with the energy dispersive X-ray micro-analyzers with an acceleration voltage of 30 kV. Ten distinct spots were analyzed per sample, which resulted in 99% confidence bounds of &amp;plusmn;0.01 in the molar fraction of each cation (with their sum normalized to unity).&amp;nbsp;</td></tr><tr><td>UV-Vis-NIR spectrophotometer</td><td>Shimadzu 3700</td><td></td><td>The absorbance spectrum of the nano-collectors material was measured by UV-Vis-NIR spectrophotometer (Shimadzu 3700).</td></tr><tr><td>Inductively coupled plasma mass spectrometry (ICP-MS)</td><td>Perkin Elmer Elan-6000 ICP-MS</td><td></td><td>In selective removal, metal ion concentrations were determined by ICP-AES. The instrument was calibrated using four standard solutions containing 0, 0.5, 1.0 and 2.0 mg/L (for each element) and the correlation coefficient of calibration curve was higher than 0.9999.</td></tr><tr><td>inductively coupled plasma atomic emission spectrometry (ICP-AES)</td><td>PerkinElmer Elan-6000&amp;nbsp;</td><td></td><td></td></tr></tbody></table>

detection and recovery of palladium, gold and cobalt metals from the urban mine using novel sensors/adsorbents designated with nanoscale wagon-wheel-shaped pores

开发低成本，高效的流程回收和再利用钯，金，从城市矿山钴金属仍处于工业化国家显著的挑战。这里，光学mesosensors /吸附剂的开发（MSAS），用于高效的识别和Pd（II）中的选择性恢复，金（Ⅲ），和Co（Ⅱ）从城市矿山达到了。准备基于使用高阶介孔单片支架医疗储蓄账户的简单，一般方法描述。分层立方IA 3天车皮轮状事务协议被锚固螯合剂（着色剂）制成三维孔穴和中孔的单片支架的微米级颗粒表面。研究结果表明，在第一次，控制光学识别钯（Ⅱ），金（Au）的证据（Ⅲ），和Co（II）离子和钯的恢复高度选择性系统（II）离子（达〜95％）在矿石和工业废物。此外，控制评估过程中描述了她EIN涉及内在特性（ 如视觉信号的变化，长期稳定，吸附效率，超凡的灵敏度，选择性和可重用性）的评价;因此，昂贵的，精密的仪器是不需要的。结果表明证据表明，医疗储蓄户口将吸引全世界的关注，回收和循环再造钯，金，钴一个有前途的技术手段 金属。

周期性螺旋形立方IA 3天单片支架和货车轮状医疗储蓄户口的大圆柱开放孔（直径可达10纳米）采用压力辅助的直接模板与P123共聚物微乳体系制造。该事务协议的TEM显微照片表明组织大域尺寸和不同取向的几何形状在螺旋形双连续立方IA三维有序结构车皮轮状通道（ 图1）。虽然在L1，L2和L3探针直接物理吸附到单片支架（〜80毫克每克支架的探针），该事务协议提供控制电位浸出洗涤时的配位体的，感测条件测定法，以及在化学处理再生/再利用循环。 货车车轮形状毛孔功能的医疗储蓄户口的立方IA三维结构，就证明了TEM照片（ 图1）。该沿主导小面的[111]方向记录，HRTEM显微照片表明立方体双连续表面形态37-39的形成。六倍对称信道与在货车车轮形状的孔不同的纳米尺寸的互连分别特性管理服务协定的立方Ia3d晶格结构（图1，中心）44。此外，该协议在晶胞晶格由TEM显微照片（22.5纳米）与小角X射线衍射（ 一个= D 211√6）确定的晶胞参数决定表示立方Ia3d MSA形态的形成。 各种几何形状的孔在每个车轮图案围绕这个六重取向的外观是可控的Pd（II），金（III）和Co（II）离子的扩散，吸附，和恢复。 图2B的关键特征表明均匀形孔的几何形状和立体的结构特性<e1.03孔体积（V p）的 0.98，和;米&gt; IA 三维 MSA-1，MSA-2，和MSA-3被保留（表面面积 （S BET）的560，520，和570米2 /克1.09的厘米3 /克;和孔径（D / 纳米）的8.2，8.1，和8.2纳米，分别作为自N 2等温线的结果证明）。此保留的立方IA 3天的MSA结构完整性用于合理设计的管理服务协定的，为此，钯（Ⅱ），金（III）和Co检测到具有快速响应时间（II）离子，甚至在纳摩尔浓度（ 图3-5）。与潜在的功能活性位点的有机部分，有相当大数量的强烈锚定到经由氢键车轮件孔表面，并与保持立方IA三维几何的分散的相互作用，如由布拉格反射面（HKL）（图2A ）。的稳定的有机 - 无机混合事务协议与合适的形成住宿L1，L2和L3进入货车车轮孔可能导致配位体的过程中的金属离子传感/捕获/去除测定法和可重用性/恢复过程没有浸出。 特异性和货车轮状管理服务协定的灵敏度为目标钯（Ⅱ），金（III）和Co（II）离子是由调节pH至2，图7，和5.2，分别控制。这些特定的pH值是为选择性的，敏感的，高效的监视和删除使用事务协议（图6A）的金属离子的最适合的。用于感测所述量化过程/捕获钯（Ⅱ），金（III）和Co（II）离子与MSA-1，MSA-2，和MSA-3涉及检测在色的响应时间的变化的颜色强度（R t）的 2，3和5分钟，分别。为了评估管理服务协定的敏感性，在反射光谱颜色过渡，可以被人眼检测到被仔细监测在宽范围的金属离子浓度的（0-5,000微克/升）。 图中的MSA-1的颜色和反射率强度6B-D显示的变化，MSA-2，和MSA-3在λ最大384，486，和537纳米，分别。八面体的形成[PD-（L1）2]，正方形平面[自动（L2）〕，和八面体[CO-（L 3）2]配合物（稳定期间这些变化表明金属到配体的结合事件这些配合物的常数比竞争离子复合物的更高; 图7）.The反射的事务协议的光谱响应表示的有效检测/识别金属。此外， 图6F显示了事务协议是非常有效地除去和监测钯（Ⅱ），金（III）和Co（Ⅱ）从城市矿山离子和LIB解决方案在很宽的浓度范围内（从微克/升，以毫克/升），甚至在0.19，0.6低浓度的限制，和0.51微克/升，分别。 佤族的离子感应/离子去除率坤轮状事务协议朝向钯（Ⅱ），金（III）和Co（Ⅱ）在缺乏和存在干扰离子的存在下的离子进行了评价（图7）。显著变化是可见的颜色图案和反射光谱是显而易见的，在大多数情况下，在加入1〜18竞争离子[即，K（Ⅰ），钠（Ⅰ），李（Ⅰ），钙（Ⅱ的（G1） ），铁（Ⅲ），和铜（II）;镉（G2）（Ⅱ），铅（II），汞（Ⅱ），镍（Ⅱ），锰（II），铝（Ⅲ）;和（G3）的Bi（III），锌（Ⅱ），镝（III），铒（Ⅲ），何（Ⅲ），和La（Ⅲ）]将钯（Ⅱ），金（III）和Co的（二）离子系统，确认选择的去除，高效的监控目标（T）离子。低浓度的镍（Ⅱ），铜（II）和Fe（Ⅲ）离子的干扰，但干扰通过使用0.3-0.5柠檬酸/酒石酸溶液作为抑制剂消除;在可见的彩色图案无显着变化，并重新FL ecta​​nce光谱在加入高浓度的各种阳离子的最佳离子感应/捕获条件发生（P的H 2，7，和5.2，40毫克的管理服务协定，将20ml体积，25℃）（图7）。这些结果表明在很宽的范围内含有高浓度的竞争离子45,46的实际样品的选择性识别和靶标离子捕获。 货车轮状事务协议的可重用性是通过检查目标离子传感/捕获测定的反射光谱并测定吸收效率（E％），为再生/重用周期的函数进行评估。回收过程如下进行汽提的钯（Ⅱ），金（III）和Co（Ⅱ）从MSA表面的离子（ 即 ，解络合）。解络合处理经钯完成（Ⅱ） - ，金（Ⅲ） - ，和Co（Ⅱ）-MSAs用0.1M的HClO 4，0.1M硫脲在1％浓HCl，和的2M HCl，分别。该解络合处理进行反复彻底删除钯（II），金（III）和Co（Ⅱ）由MSA表面离子。紫外可见spectros复制和ICP-MS被用来确认在MSA表面是游离金属（ 图8）。摄取效率为MSA-1，MSA-2，和MSA-3计算为％（℃ 的 A / C 0），其中C A是由固体管理服务协定目标离子浓度摄取和 C 0是初始目标离子的浓度。结果表明，货车车轮形医疗储蓄账户的功能均保持超过八再生/再利用循环46,47。 加入Pd（II）和Au中回收（Ⅲ）从电子废料（即，PCI板）和Co（Ⅱ）从库进行几个阶段: 第一阶段是研磨PCI板组件的机械分离。 第二级包括一个预处理湿法冶金工艺，其中，所述PCI板的芯片（电子废物源）的沥滤以2 MH 2 SO 4的一个的混合物次0.2 MH 2 O 2在90℃下进行6小时，以溶解碱金属（铜，铁，镍，铝，锂，锰，钴和锌）和部分溶解的塑料和Pd（II）和金（Ⅲ中的悬浮液）离子8。未溶解的塑料过滤后，浸出残渣用HCl的组合的酸和HNO 3（3:1）在70℃下3小时，以形成钯的可溶性溶液（Ⅱ），金（Ⅲ），银（Ⅰ ），铁（III），锡（IV）和Al（III）离子。铁（Ⅲ），锡（IV）和Al（III）离子沉淀用2 M氢氧化钠和滤出提高pH值溶液高达4.5。使用氯化钠氯化银沉淀并滤出（图9）。此外，LIBS废物组分与HNO 3处理 ，导致钴的混合物（II），镍（Ⅱ），锰（Ⅱ），李（Ⅰ），铁（Ⅲ），和Al（Ⅲ）离子。 第三阶段涉及一系列的在受控的实验条件下进行间歇实验。在这些实验中，浸出溶液进行纯化，钯（Ⅱ）和Au（III）的离子从使用MSA-1和MSA-2的电子废料溶液中回收（ 参见图9），和钴（II），从使用MSA-3（表1）的LIB溶液的主要产品回收。除去后，将滤液用ICP-MS进行分析。 在第四阶段中，加入Pd（II）和金（Ⅲ）的由MSA-1和MSA-2的比例摄取来自实际城市矿山复合混合物[0.119毫克/升钯（Ⅱ），0.35毫克/升的Au（Ⅲ ），0.23毫克/升银（Ⅰ），7.05毫克/升的Cu（Ⅱ），5.78毫克/升的Ni（Ⅱ），13.35毫克/升的Fe（III），7.09毫克/升的Al（Ⅲ）〕进行测定。 MSA-3被用来估计Co的恢复（Ⅱ）从一个真实的LIB复合混合物离子[1.75毫克/升的Co（Ⅱ），420毫克/升的Ni（II），350毫克/升的Mn（Ⅱ），370 mg / L的李（I）中，7毫克/升的Fe（III），1毫克/升的Al（Ⅲ）〕。钯的摄取效率（Ⅱ），金（III）和Co（Ⅱ）如下计算由MSA-1，MSA-2，和MSA-3离子:电子（％）= C A / C E = C 0 - 权证 / C <suB&gt; 0，其中C A是由固体管理服务协定目标离子浓度摄取， 和 C e和C 0是目标离子浓度在平衡和初始解。 表1列出的结果为钯的提取的真实样本研究（Ⅱ），金（III）和Co（II）中使用的管理服务协定;钯的比例摄取（Ⅱ），金（III）和Co（Ⅱ）分别为约79％，68％和66％之间。 使用剥离剂（图3-5）的第五阶段涉及回收实验释放钯（Ⅱ），金（III）和Co（II）的与该车轮状的MSA表面离子。回收效率（R％），计算如下 :R（％）= C R / C A，其中C R是由汽提剂中释放在溶液中的目标离子浓度。 ICP-MS分析所收集的溶液表明&gt;&gt; 98％的金属离子的我们重新发布了简单的化学剥皮（ 表1）。这一结果表明，钯（Ⅱ），金（III）和Co的超痕量水平（II）离子是从城市矿山由管理服务协定萃取。 <img alt="图1" src="/files/ftp_upload/53044/53044fig1.jpg" /> 图1.调查货车轮状的几何结构。在医疗储蓄户口的立方IA三维结构的车轮图案的高分辨的显微照片。中心:晶体形状。 <img alt="图2" src="/files/ftp_upload/53044/53044fig2.jpg" /> 图2.确定的货车车轮形的孔隙介孔晶格和表面的参数。XRD图谱（A）和N 2吸附 /货车轮状，立方IA 3天的医疗储蓄户口脱附等温线（B）。 在MSA-1。制备的Pd（II）的通过-MSA-1和Co（Ⅱ）-MSA-3中的压力辅助法的图3的系统的工程 。 <img alt="图4" src="/files/ftp_upload/53044/53044fig4.jpg" /> 通过压力辅助法在MSA-3。制备的Co（Ⅱ）-MSA-3 的图4的系统的工程 。 <img alt="图5" src="/files/ftp_upload/53044/53044fig5.jpg" /> 在MSA-2。制作金（III） 的 -MSA-2通过积木协议图5.系统工程 。 <img alt="图6" src="/files/ftp_upload/53044/53044fig6.jpg" /> 图6.受控pH依赖性钯（Ⅱ），金（III）和Co（II）离子- S的ensing系统。 （A）的pH值-响应曲线货车轮状期间目标钯（Ⅱ），金（Au）的感测和去除测定MSA-1，MSA-2，和MSA-3（Ⅲ），和Co（II）离子。反射光谱的效率监测pH值在λ 最大= 384，486的分别的功能，并且537纳米。 （ 乙 - D）的目标离子浓度如MSA-1的反射光谱的函数，MSA-2，和MSA-3。对于事务协议（E）的颜色映射添加了2 ppm的钯（Ⅱ），金（III）和Co（II）。 （F）的校准曲线的（R - R o）相对于 [M 的n +]为MSA-1，MSA-2，和MSA-3。注意:R和R 0代表事务协议的反射率与和不加入靶标离子，分别。 <img alt="图7" src="/files/ftp_upload/53044/53044fig7.jpg" /> 图7.研究的钯（Ⅱ）的，金（Ⅲ），和钴（II）离子选择性系统（A - C）的选择性车皮轮状MSA-1，MSA-2，和MSA-3朝向钯（II）（2毫克/升），金（Ⅲ）（1毫克/升），和钴（II）（2毫克/升）离子传感和离子去除率测定。 （D）的顺序颜色响应ofMSA-1，MSA-2，和MSA-3（空白，即，不含金属的测定）朝向目标钯（Ⅱ），金（III），以及在加入的干扰的钴（II）离子离子在单一的，二元的，和离子（G1-G3）基团。 <img alt="图8" src="/files/ftp_upload/53044/53044fig8.jpg" /> 图8.复用性的车皮轮状事务协议（A）的评价货车轮状，光学感测/除去目标离子的后8再生/再循环测定的（目标离子浓度:2毫克/升; pH值和了MSA-1，MSA-2，和MSA-3信号的响应时间的值:pH值= 2，7，一个ð5.2，R T = 2，3，5分钟; T = 25 C）。 （二）吸收效率与再生循环次数。 <img alt="图9" src="/files/ftp_upload/53044/53044fig9.jpg" /> 加入Pd（II）和金（Au）图9实恢复（III）离子从电子废料的解决方案。湿法冶金处理的PCI板和Pd（II）和Au中恢复（Ⅲ）从电子废料溶液离子 。 <table fo:keep-together.within-page="1"><tbody><tr><td fo:width="0.45in" width="45"> 目标离子 </td><td fo:width="0.8in" width="120"> 目标离子测定 </td><td> 靶标离子（毫克/升） </td><td fo:width="4in" width="300"> 共存的金属离子（毫克/升） </td><td fo:width="0.3in" width="30"> E＆ </td><td fo:width="0.2in" width="20"> R％了 </td></TR&gt; <tr><td rowspan="3">钯（II）的</td><td> C 0 </td><td> 0.119 </td><td>银（I）中:0.23，金（Ⅲ）:0.35，铝（Ⅲ）:7.09，镍（Ⅱ）:5.78，铁（Ⅲ）:13.35，铜（II）:7.05 </td><td rowspan="3"> 79 </td><td rowspan="3"> 97 </td></tr><tr><td> 权证 </td><td> 0.025 </td><td>银（I）中:0.225，金（Ⅲ）:0.351，铝（Ⅲ）:7.11，镍（Ⅱ）:5.77，铁（Ⅲ）:13.32，铜（II）:6.95 </td></tr><tr><td> C R </td><td> 0.0913 </td><td>银（I）中:0.00，金（Ⅲ）:0.001，铝（Ⅲ）:0.00，镍（Ⅱ）:0.002，铁（Ⅲ）:0.005，铜（II）:0.009 </td></tr><tr><td rowspan="3">金（III）的</td><td> C 0 </td><td> 0.35 </td><td>银（I）中:0.23，钯（Ⅱ）:0.119，铝（Ⅲ）:7.09，镍（Ⅱ）:5.78，铁（Ⅲ）:13.35，铜（II）:7.05 </td><td rowspan="3"> 68 </td><td rowspan="3"> 98 </td></tr><tr><td> 权证 </td><td> 0.11 </td><td>银（I）中:0.231，钯（Ⅱ）:0.118，铝（Ⅲ）:7.00，镍（Ⅱ）:5.66，铁（Ⅲ）:13.29，铜（II）:6.92 </td></tr><tr><td> C R </td><td> 0.235 </td><td>银（I）中:0.00，钯（Ⅲ）:0.002，铝（Ⅲ）:0.00，镍（Ⅱ）:0.004，铁（Ⅲ）:0.003，铜（II）:0.01 </td></tr><tr><td rowspan="3">钴（II） </td><td> C 0 </td><td> 1.75 </td><td>的Ni（II）420，锰（II）:350，李（Ⅰ）:370，铁（Ⅲ）:2.00，铝（Ⅲ）:0.40 </td><td rowspan="3"> 66.3 </td><td rowspan="3"> 95 </td></tr><tr><td> 权证 </td><td> 0.59 </td><td>的Ni（Ⅱ）:419.34，锰（II）:350.06，李（Ⅰ）:370，铁（Ⅲ）:1.91，铝（Ⅲ）:0.05 </td></tr><tr><td> C R </td><td> 1.15 </td><td>的Ni（II）:0.85，锰（Ⅱ）:0.00，李（Ⅰ）:0.00，铁（Ⅲ）:0.05，铝（Ⅲ）:0.02 </td></tr></tbody></table> 实际样品在表1中的定量测定金属离子。对于钯的恢复的ICP-MS分析数据（Ⅱ），金（III）和Co（Ⅱ）在电子废料和LIB溶液离子 。

Watch this Scientific Journal Video about Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Po

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

由于重视和广泛使用的钯，金，钴 在高科技设备的金属，它们的回收和再利用是一个重要的工业挑战。本文所述的金属回收系统是一个简单的，低成本的用于将有效的检测，除去和回收这些金属的来自城市矿山。

检测和钯的回收，从城市矿山黄金和钴金属使用标有纳米货车车轮形的孔隙新型传感器/吸附剂

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in ...

detection-recovery-palladium-gold-cobalt-metals-from-urban-mine-using

Universidad San Sebastian

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JoVE Journal

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28.0K 次观看.  National Institute for Materials Science, Japan. 由于重视和广泛使用的钯，金，钴 在高科技设备的金属，它们的回收和再利用是一个重要的工业挑战。本文所述的金属回收系统是一个简单的，低成本的用于将有效的检测，除去和回收这些金属的来自城市矿山。 

视频: Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

Regeneration of Arrayed Gold Microelectrodes Equipped for a Real-Time Cell Analyzer

The label-free cell-based assay is advantageous for biochemical study because of it does not require the use of experimental animals. Due to its ability to provide more dynamic information about cells under physiological conditions than classical biochemical assays, this label-free real-time cell assay based on the electric impedance principle is attracting more attention during the past decade. However, its practical utilization may be limited due to the relatively expensive cost of measurement, in which costly consumable disposable gold microchips are used for the cell analyzer. In this protocol, we have developed a general strategy to regenerate arrayed gold microelectrodes equipped for a commercial label-free cell analyzer. The regeneration process includes trypsin digestion, rinsing with ethanol and water, and a spinning step. The proposed method has been tested and shown to be effective for the regeneration and repeated usage of commercial electronic plates at least three times, which will help researchers save on the high running cost of real-time cell assays.

This protocol describes a general strategy to regenerate commercial arrayed gold microelectrodes equipped for a label-free cell analyzer aimed at saving on the high running costs ofmicrochip-based assays. The regeneration process includes trypsin digestion, rinsing with ethanol and water, and a spinning step, which enables repeated usage of microchips.

用于实时细胞分析仪的阵列金电极再生

The label-free cell-based assay is advantageous for biochemical study because of it does not require the use of experimental animals. Due to its ability ...

科研

生物化学

Microfabrication of Nanoporous Gold Patterns for Cell-material Interaction Studies

Nanostructured materials with feature sizes in tens of nanometers have enhanced the performance of several technologies, including fuel cells, biosensors, biomedical device coatings, and drug delivery tools. Nanoporous gold (np-Au), produced by a nano-scale self-assembly process, is a relatively new material that exhibits large effective surface area, high electrical conductivity, and catalytic activity. These properties have made np-Au an attractive material to scientific community. Most studies on np-Au employ macro-scale specimens and focus on fundamental science of the material and its catalytic and sensor applications. The macro-scale specimens limit np-Au's potential in miniaturized systems, including biomedical devices. In order to address these issues, we initially describe two different methods to micropattern np-Au thin films on rigid substrates. The first method employs manually-produced stencil masks for creating millimeter-scale np-Au patterns, while the second method uses lift-off photolithography to pattern sub-millimeter-scale patterns. As the np-Au thin films are obtained by sputter-deposition process, they are compatible with conventional microfabrication techniques, thereby amenable to facile integration into microsystems. These systems include electrically-addressable biosensor platforms that benefit from high effective surface area, electrical conductivity, and gold-thiol-based surface bioconjugation. We describe cell culture, immunostaining, and image processing techniques to quantify np-Au's interaction with mammalian cells, which is an important performance parameter for some biosensors. We expect that the techniques illustrated here will assist the integration of np-Au in platforms at various length-scales and in numerous applications, including biosensors, energy storage systems, and catalysts.

We report on techniques to micropattern nanoporous gold thin films via stencil printing and photolithography, as well as methods to culture cells on the microfabricated patterns. In addition, we describe image analysis methods to characterize morphology of the material and the cultured cells using scanning electron and fluorescence microscopy techniques.

细胞物质相互作用研究微细的纳米多孔金模式

Nanostructured materials with feature sizes in tens of nanometers have enhanced the performance of several technologies, including fuel cells, biosensors, ...

生物工程

In Situ Detection and Single Cell Quantification of Metal Oxide Nanoparticles Using Nuclear Microprobe Analysis

Micro-analytical techniques based on chemical element imaging enable the localization and quantification of chemical composition at the cellular level. They offer new possibilities for the characterization of living systems and are particularly appropriate for detecting, localizing and quantifying the presence of metal oxide nanoparticles both in biological specimens and the environment. Indeed, these techniques all meet relevant requirements in terms of (i) sensitivity (from 1 up to 10 &#181;g.g-1 of dry mass), (ii) micrometer range spatial resolution, and (iii) multi-element detection. Given these characteristics, microbeam chemical element imaging can powerfully complement routine imaging techniques such as optical and fluorescence microscopy. This protocol describes how to perform a nuclear microprobe analysis on cultured cells (U2OS) exposed to titanium dioxide nanoparticles. Cells must grow on and be exposed directly in a specially designed sample holder used on the optical microscope and in the nuclear microprobe analysis stages. Plunge-freeze cryogenic fixation of the samples preserves both the cellular organization and the chemical element distribution. Simultaneous nuclear microprobe analysis (scanning transmission ion microscopy, Rutherford backscattering spectrometry and particle induced X-ray emission) performed on the sample provides information about the cellular density, the local distribution of the chemical elements, as well as the cellular content of nanoparticles. There is a growing need for such analytical tools within biology, especially in the emerging context of Nanotoxicology and Nanomedicine for which our comprehension of the interactions between nanoparticles and biological samples must be deepened. In particular, as nuclear microprobe analysis does not require nanoparticles to be labelled, nanoparticle abundances are quantifiable down to the individual cell level in a cell population, independently of their surface state.

In Situ Detection and Single Cell Quantification of Metal Oxide Nanoparticles Using Nuclear Microprobe Analysis

We describe a procedure for the detection of chemical elements present in situ in human cells as well as their in vitro quantification. The method is well-suited to any cell type and is particularly useful for quantitative chemical analyses in single cells following in vitro metal oxide nanoparticles exposure.

原位金属氧化物纳米粒子的核探针检测与单细胞定量研究

Micro-analytical techniques based on chemical element imaging enable the localization and quantification of chemical composition at the cellular level. ...

化学

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity and convenient colorimetric readout. However, high densities of nanoparticles are typically needed for detection. The available synthesis-based enhancement protocols are either limited to gold and silver nanoparticles or rely on precise enzymatic control and optimization. Here, we present a protocol to enhance the colorimetric readout of gold, silver, silica, and iron oxide nanoprobes. It was observed that the colorimetric signal can be improved by up to a 10000-fold factor. The basis for such signal enhancement strategies is the chemical reduction of Au3+ to Au0. There are several chemical reactions that enable the reduction of Au3+ to Au0. In the protocol, Good&#39;s buffers and H2O2 are used and it is possible to favor the deposition of Au0 onto the surface of existing nanoprobes, in detriment of the formation of new gold nanoparticles. The protocol consists of the incubation of the microarray with a solution consisting of chloroauric acid and H2O2 in 2-(N-morpholino)ethanesulfonic acid pH 6 buffer following the nanoprobe-based detection assay. The enhancement solution can be applied to paper and glass-based sensors. Moreover, it can be used in commercially available immunoassays as demonstrated by the application of the method to a commercial allergen microarray. The signal development requires less than 5 min of incubation with the enhancement solution and the readout can be assessed by naked eye or low-end image acquisition devices such as a table-top scanner or a digital camera.

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

In this work, a protocol for signal enhancement of nanoprobe-based biosensing is presented. The protocol is based on the reduction of chloroauric acid onto the surface of existing nanoprobes that consist of gold, silver, silica or iron-oxide nanoparticles.

原位金纳米粒子合成快速 Nanoprobe 信号增强

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity ...

High Resolution Physical Characterization of Single Metallic Nanoparticles

Individual molecules can be detected and characterized by measuring the degree by which they reduce the ionic current flowing through a single nanometer-scale pore. The signal is characteristic of the molecule&#39;s physicochemical properties and its interactions with the pore. We demonstrate that the nanopore formed by the bacterial protein exotoxin Staphylococcus aureus alpha hemolysin (&#945;HL) can detect polyoxometalates (POMs, anionic metal oxygen clusters), at the single molecule limit. Moreover, multiple degradation products of 12-phosphotungstic acid POM (PTA, H3PW12O40) in solution are simultaneously measured. The single molecule sensitivity of the nanopore method allows for POMs to be characterized at significantly lower concentrations than required for nuclear magnetic resonance (NMR) spectroscopy. This technique could serve as a new tool for chemists to study the molecular properties of polyoxometalates or other metallic clusters, to better understand POM synthetic processes, and possibly improve their yield. Hypothetically, the location of a given atom, or the rotation of a fragment in the molecule, and the metal oxidation state could be investigated with this method. In addition, this new technique has the advantage of allowing the real-time monitoring of molecules in solution.&#160;

Here, we present a protocol to detect discrete metal oxygen clusters, polyoxometalates (POMs), at the single molecule limit using a biological nanopore-based electronic platform. The method provides a complementary approach to traditional analytical chemistry tools used in the study of these molecules.

单金属纳米粒子的高分辨率物理特性

Individual molecules can be detected and characterized by measuring the degree by which they reduce the ionic current flowing through a single ...

An Efficient Method for Selective Desalination of Radioactive Iodine Anions by Using Gold Nanoparticles-Embedded Membrane Filter

Here, we demonstrate a detail protocol for the preparation of nanomaterials-embedded composite membranes and its application to the efficient and ion-selective removal of radioactive iodines. By using citrate-stabilized gold nanoparticles (mean diameter: 13 nm) and cellulose acetate membranes, gold nanoparticle-embedded cellulose acetate membranes (Au-CAM) have easily been fabricated. The nano-adsorbents on Au-CAM were highly stable in the presence of high concentration of inorganic salts and organic molecules. The iodide ions in aqueous solutions could rapidly be captured by this engineered membrane. Through a filtration process using an Au-CAM containing filter unit, excellent removal efficiency (&gt;99%) as well as ion-selective desalination result was achieved in a short time. Moreover, Au-CAM provided good reusability without significant decrease of its performances. These results suggested that the present technology using the engineered hybrid membrane will be a promising process for the large-scale decontamination of radioactive iodine from liquid wastes.

An efficient method for the rapid and ion-selective desalination of radioactive iodine in several aqueous solutions is described by using gold nanoparticles-immobilized cellulose acetate membrane filters.

用金纳米粒子-嵌入式膜过滤法选择性脱盐放射性碘阴离子的有效方法

Here, we demonstrate a detail protocol for the preparation of nanomaterials-embedded composite membranes and its application to the efficient and ...

工程学

A Closed-Type Wireless Nanopore Electrode for Analyzing Single Nanoparticles

Measuring the intrinsic features of single nanoparticles by nanoelectrochemistry holds deep fundamental importance and has potential impacts in nanoscience. However, electrochemically analyzing single nanoparticles is challenging, as the sensing nanointerface is uncontrollable. To address this challenge, we describe here the fabrication and characterization of a closed-type wireless nanopore electrode (WNE) that exhibits a highly controllable morphology and outstanding reproducibility. The facile fabrication of WNE enables the preparation of well-defined nanoelectrodes in a general chemistry laboratory without the use of a clean room and expensive equipment. One application of a 30 nm closed-type WNE in analysis of single gold nanoparticles in the mixture is also highlighted, which shows a high current resolution of 0.6 pA and high temporal resolution of 0.01 ms. Accompanied by their excellent morphology and small diameters, more potential applications of closed-type WNEs can be expanded from nanoparticle characterization to single molecule/ion detection and single-cell probing.

Here, we present a protocol for fabrication of a closed-type wireless nanopore electrode and subsequent electrochemical measurement of single nanoparticle collisions.

一种用于分析单纳米粒子的闭式无线纳米粒子电极

Measuring the intrinsic features of single nanoparticles by nanoelectrochemistry holds deep fundamental importance and has potential impacts in ...

Gold Nanoparticle Modified Carbon Fiber Microelectrodes for Enhanced Neurochemical Detection

For over 30 years, carbon-fiber microelectrodes (CFMEs) have been the standard for neurotransmitter detection. Generally, carbon fibers are aspirated into glass capillaries, pulled to a fine taper, and then sealed using an epoxy to create electrode materials that are used for fast scan cyclic voltammetry testing. The use of bare CFMEs has several limitations, though. First and foremost, the carbon fiber contains mostly basal plane carbon, which has a relatively low surface area and yields lower sensitivities than other nanomaterials. Furthermore, the graphitic carbon is limited by its temporal resolution, and its relatively low conductivity. Lastly, neurochemicals and macromolecules have been known to foul at the surface of carbon electrodes where they form non-conductive polymers that block further neurotransmitter adsorption. For this study, we modify CFMEs with gold nanoparticles to enhance neurochemical testing with fast scan cyclic voltammetry. Au3+ was electrodeposited or dipcoated from a colloidal solution onto the surface of CFMEs. Since gold is a stable and relatively inert metal, it is an ideal electrode material for analytical measurements of neurochemicals. Gold nanoparticle modified (AuNP-CFMEs) had a stability to dopamine response for over 4 h. Moreover, AuNP-CFMEs exhibit an increased sensitivity (higher peak oxidative current of the cyclic voltammograms) and faster electron transfer kinetics (lower &#916;EP or peak separation) than bare unmodified CFMEs. The development of AuNP-CFMEs provides the creation of novel electrochemical sensors for detecting fast changes in dopamine concentration and other neurochemicals at lower limits of detection. This work has vast applications for the enhancement of neurochemical measurements. The generation of gold nanoparticle modified CFMEs will be vitally important for the development of novel electrode sensors to detect neurotransmitters in vivo in rodent and other models to study neurochemical effects of drug abuse, depression, stroke, ischemia, and other behavioral and disease states.

In this study, we modify carbon-fiber microelectrodes with gold nanoparticles to enhance the sensitivity of neurotransmitter detection.

用于增强神经化学检测的金纳米粒子改性碳纤维微电极

For over 30 years, carbon-fiber microelectrodes (CFMEs) have been the standard for neurotransmitter detection. Generally, carbon fibers are aspirated into ...

Quantitative SERS Detection of Uric Acid via Formation of Precise Plasmonic Nanojunctions within Aggregates of Gold Nanoparticles and Cucurbit[n]uril

This work describes a rapid and highly sensitive method for the quantitative detection of an important biomarker, uric acid (UA), via surface-enhanced Raman spectroscopy (SERS) with a low detection limit of ~0.2 &#956;M for multiple characteristic peaks in the fingerprint region, using a modular spectrometer. This biosensing scheme is mediated by the host-guest complexation between a macrocycle, cucurbit[7]uril (CB7), and UA, and the subsequent formation of precise plasmonic nanojunctions within the self-assembled Au NP: CB7 nanoaggregates. A facile Au NP synthesis of desirable sizes for SERS substrates has also been performed based on the classical citrate-reduction approach with an option to be facilitated using a lab-built automated synthesizer. This protocol can be readily extended to multiplexed detection of biomarkers in body fluids for clinical applications.

Quantitative SERS Detection of Uric Acid via Formation of Precise Plasmonic Nanojunctions within Aggregates of Gold Nanoparticles and Cucurbit[n]uril

A host-guest complex of cucurbit[7]uril and uric acid was formed in an aqueous solution before adding a small amount into Au NP solution for quantitative surface-enhanced Raman spectroscopy (SERS) sensing using a modular spectrometer.

通过在金纳米颗粒和葫芦的聚集体中形成精确的等离子体纳米结来定量检测尿酸

This work describes a rapid and highly sensitive method for the quantitative detection of an important biomarker, uric acid (UA), via surface-enhanced ...

Versatile Technique to Produce a Hierarchical Design in Nanoporous Gold

The potential to generate variable pore sizes, simplistic surface modification, and a breadth of commercial uses in the fields of biosensors, actuators, drug loading and release, and the development of catalysts have unquestionably accelerated the usage of nanoporous gold (NPG)-based nanomaterials in research and development. This article describes the process of the generation of hierarchical bimodal nanoporous gold (hb-NPG) by employing a step-wise procedure involving electrochemical alloying, chemical dealloying techniques, and annealing to create both macro- and mesopores. This is done to improve the utility of NPG by creating a bicontinuous solid/void morphology. The area available for surface modification is enhanced by smaller pores, while molecular transport benefits from the network of larger pores. The bimodal architecture, which is the result of a series of fabrication steps, is visualized using scanning electron microscopy (SEM) as a network of pores that are less than 100 nm in size and connected by ligaments to larger pores that are several hundred nanometers in size. The electrochemically active surface area of the hb-NPG is assessed using cyclic voltammetry (CV), with a focus on the critical roles that both dealloying and annealing play in creating the necessary structure. The adsorption of different proteins is measured by solution depletion technique, revealing the better performance of hb-NPG in terms of protein loading. By changing the surface area to volume ratio, the created hb-NPG electrode offers tremendous potential for biosensor development. The manuscript discusses a scalable method to create hb-NPG surface structures, as they offer a large surface area for the immobilization of small molecules and improved transport pathways for faster reactions.

Nanoporous gold with a hierarchical and bimodal pore size distribution can be produced by combining electrochemical and chemical dealloying. The composition of the alloy can be monitored via EDS-SEM examination as the dealloying process advances. The material's loading capacity can be determined by studying protein adsorption onto the material.

在纳米多孔金中产生分层设计的多功能技术

The potential to generate variable pore sizes, simplistic surface modification, and a breadth of commercial uses in the fields of biosensors, actuators, ...