这项工作是由欧洲燃料电池和Hydruogen联合执行下的合作项目BOR4STORE（批准号：303428协定）和基础设施项目H2FC（赠款协​​议号FP7-284522）的支持。

1.仪器<ol><li>使用由通过高压气体配管连接的四个主要部件的基本超临界干燥（SCD）装置：气体供应，真空系统，传感器（温度和压力），和样品环境（其可在浴中浸没）。确保建设优质不锈钢阀门，管件和管道，额定压力为至少10兆帕80-300 K之间的温度范围内 注意：示意图示于图1。 </li><li>对于氮理学博士（NSCD）处理，确保气源的纯度研究装有0-10兆帕之间的出口压力控制压力调节器（&gt; 99.999％）的氮气。附加一个50升瓶（20兆帕）的装置，并在使用前冲洗系统用纯氮气多次。 </li><li>保证真空系统能够实现真空压力下降到&lt;0.1帕的并且被连接到该装置与一精细控制针阀。优选地，使用无油粗抽泵和一个分子拖动涡轮泵，串联放置。 </li><li>使用至少两个压力传感器对压力的精确测量期间理学治疗：真空测量和高压力传感器的低压压力传感器来实现0.1-10 7帕之间的总测的压力范 ​​围。 </li><li>使用至少两个温度传感器，用于必要的最小的精度来执行典型理学治疗：与样品和77-300 K的主要气体计量歧管用于精确测量内的传感器热接触的传感器（ 例如 ，K型热电偶） 。 </li><li>检查该样本保持器必须包含必要的样品用于治疗的量的适当的内部容积，并且由不锈钢制成。 注：加长的圆柱形设计有助于同浴热接触。 </li><li>确保封闭该样本容器的嵌合是appropr黄昏时分的高压和重复使用（ 例如 ，世伟洛克VCR）。通过管道的适当长度（汲取管），用于样品支架的完全浸没入熔池连接样本容器容积的阀从外部环境隔离。 </li></ol><img alt="图1" src="/files/ftp_upload/52817/52817fig1.jpg" /> 在环境温度和（B）（A）中，在浴中的试样浸入后： 图1.超临界氮气干燥（NSCD）一种用于在典型的实验室使用简化NSCD装置的示意图。气体供应在这项工作中所描述的方法是氮，但是这一般装置推广到其他理学流体与一个临界点躺着的温度和压力，如CO 2的实用范围内。组件被标记为与第一致Ë这里所描述的协议。 <a href="https://www.jove.com/files/ftp_upload/52817/52817fig1highres.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 2.准备工作<ol><li>负载0.2-0.5克样品（γ-Mg系（BH 4）2，粉末形式，以下湿式化学合成和标准的干燥方法）到样本保持在适当条件下，通常在惰性气氛如氩气手套箱，在环境温度下或更低。关闭样品保持器（嵌合F2）与过滤器垫圈，然后关闭阀（阀V4）。样品架传送到装置和连接（嵌合F1）。 </li><li>打开计量歧管通过V2真空和撤离。打开V3和疏散。由V1用氮气净化的装置和经由V2撤离。开放V4和撤离样品在RT达24小时，以达到系统（&lt;0.1帕）的最小压力。 </li><li>安装示例浴（见<strong&gt;的图2）的样品架周围。通过提高浴到位上剪叉式升降机，或类似的机制执行此。 </li><li>设定加热到所需未来液体温度（T L，见步骤3.1）的110 K，并继续撤离设备直至温度达到平衡。 </li></ol><img alt="图2" src="/files/ftp_upload/52817/52817fig2.jpg" /> 图2.低温炉样品浴一个示意图（左）和一个cryostatic热浴环境照片（右）相应于含有NSCD处理期间的样品架，允许测量和77-298 K之间的样品温度控制<a href="https://www.jove.com/files/ftp_upload/52817/52817fig2highres.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 3.超临界氮曝光<ol&gt; <li>对于γ-Mg系（BH 4）2，（示范的在这个协议中的主题）的NSCD处理选择的110 K的液体温度（T L）这对应于一个中等的液体溶剂密度（〜0.6克毫升-1） ;在必要时获得本协议的其他NSCD治疗过程中的应用调整（见下面的注释）。 </li><li>通过关闭V2封闭该系统至真空。油门开V1慢，使压力提高到相图的液相区。平衡系统在2兆帕和T L。 </li><li>浸泡试样在液体N 2 4小时。 </li><li>与斜坡≤2，K MIN -1设置加热器150开。允许的压力增加不高于该装置的最大额定压力（此{P MAX应≥10兆帕）;如果必要的话，仔细地发泄过剩的压力，通过V2真空。平衡系统以P max和150 K. </li><li>泡在SUP样本ercritical N 2 1小时。 </li></ol><img alt="图3" src="/files/ftp_upload/52817/52817fig3.jpg" /> 图3.氮相图氮，这里的流体密度（如图线性灰度）详细的相图使用REFPROP（状态的修正韦伯-笃-鲁宾公式）计算。41多种线密度不变的示紫色。固相边界和沸腾过渡线被显示为红色。蓝线表示的相图是有关使用N 2干燥或提取加工的区域的边界。 <a href="https://www.jove.com/files/ftp_upload/52817/52817fig3highres.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 注意：对于此协议的其他材料的应用，建立适当的治疗NSCD舍姆Ë通过选择所需的目标物种的有效溶解的条件。指的是N 2的相图，在图3中所示，为了实现高的流体密度在液相（ 例如，0.8-1克·毫升-1），选择80-90 K.一件T l对于中等的液体密度（ 例如，0.6-0.8克·毫升-1），选择90-115 K的试错法一个T L可能是必要的。 4.超临界氮素释放<ol><li>仔细节流V2，使压力尽可能慢减少破解系统至真空。反复破解系统根据需要实现12-24小时的大致时间跨度逐渐下降到高真空（&lt;0.1 ​​Pa）的高真空率。 </li><li>取下样品浴缸和全开V2完全撤离样品。平衡在室温和高真空（&lt;0.1帕）。 </li><li>脱气样品在RT和&lt;0.1帕为1-24小时，为desired。 </li></ol> 5.后处理<ol><li>关闭阀门V3和V4，和从（嵌合F1），该装置移动样品支架。 </li><li>样品架传送到惰性环境进行处理，如在氩气填充的手套箱中。在密封容器中在环境温度下或低于除去从样品保持器（嵌合F2），并存储该样本。 </li></ol>

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作者什么都没有透露。

这可能是由于其相对较低的临界温度（126 K），N 2 -历来被忽视作为有效理学溶剂。在早先的报告，3,17,42,43它仅被暗示在等于或高于室温，在那里它显示只有少量的溶剂化功率加工温度的范围内，由于其低的流体密度在其相图的这个区域（除在极高的压力，43）。在实现的N 2的实际效用作为超临界溶剂的关键步骤是在维持处理温度在临界点附近，那里的密度（因此?...

超临界流体萃取（SFE）和干燥（SCD）方法被很好地建立在广泛的实际应用，特别是在食品工业和石油工业，也可在化学合成，分析和材料的加工。1-6使用干燥或提取介质在高于其临界点条件往往是更快，更清洁和更有效的比传统的（液体）的技术，并具有可通过操作条件稍作调整相对于高度可调的流体的溶剂化功率的额外优点3,7一种简单的方法理学包括三个基本步骤。第一步是露出其包含在其液体中的目标杂质化合物来适当选择理学流体的固体（或者液体）的原料（或接近液体超临界相），在那里它的高密度对应于高（也许选择性7）溶剂功率相对于所述靶物种。 Ť他第二步骤加热和压缩上述所选理学流体的临界点，系统中的封闭容器，以使流体和其溶解靶物种不通过相界这可能导致分离。最后一步是缓慢降低理学流体的真空压力在高于临界温度的温度下，使含有目标物种逃脱，再次没有遇到一个相界或沿途的任何有害的表面张力作用的流体溶液。 起始原料为左耗尽目标物种的，并且可以进行迭代处理，如果有必要的。在超临界流体萃取的情况下，目标溶质种类是所需产物，并从供进一步使用的解决方案。8,9-收集在其他情况下，将干燥的或纯化的起始材料是期望的产物，并将所提取的杂质被丢弃。这后一种情况下，这里所指作为理学方法，被发现是一种有效的策略，高表面积，微孔材料，如金属 - 有机骨架（MOFs），其中，在真空下传统的热处理方法在许多情况下，在清除孔不充分的预处理所有的不速之客，或导致孔隙坍塌。10二氧化碳理学博士（CSCD）处理现在是一个常规的后期合成的过程MOFs材料，11导致增加氮可接触的表面面积比高达1000％未经处理的材料12其他的改进，如在催化活性。13其他值得注意的超临界流体的应用是作为一种广泛可调谐介质进行化学反应，14-16超临界流体色谱（SCFC）6,17,18和合成气凝胶和先进复合材料。19- 22 对于干燥应用，理学博士流体是基于两个标准来选择：一）接近它的临界点到环境的条件（为方便起见，并降低能源成本或处理复杂性）和b）其溶剂化功率相对于所述靶物种。二氧化碳（CO 2）已被证明是在许多应用中方便理学流体，因为它是无毒的，不可燃的，并且价格便宜，并且可以进行调节，以表现出高的溶剂化功率朝向一些普通的有机靶物种在其近液体的状态（在&lt;10兆帕的压力和温度273-323 K）1-3,7-9其他常见的超临界溶剂（或共溶剂）包括水（跨越一个显着的其环境和超临界状态之间溶剂性能范围23），丙酮，乙烯，甲醇，乙醇，和乙烷，覆盖从极性（质子和非质子传递）到非极性的，并具有对环境条件相对临界点附近的频谱。 二氧化碳是迄今为止最常用理学流体。在建立CSCD方法中，反应性的原料不是抑制因子，因为二氧化碳是只有非常弱的温度接近它的临界点的反应。然而，由于其在水或CO 2存在强的反应，除了在加热下其（可能故意量身定做）不稳定某些类的材料，如所谓的复合氢化物（ 例如 ，铝氢化物和硼氢化物）在处理本独特的挑战24-26此外，还有在这样的材料如高密度的储氢化合物，27-30极大国际兴趣，因此，可以在纳米结构和/或多孔的品种31-33。对于这样的反应性的，不稳定的，纳米结构材料的有效的净化，理学的方法是有前途的策略。34所述理学流体必须使用具有适用于穿入窄空腔分子直径小并且还具有高的溶剂化功率朝向目标杂质，WHI勒剩余朝向起始材料本身不反应。这里，利用超临界氮气（N 2）作为用于这种提取和特别干燥应用提供有效的流体呈现。具体超临界氮气干燥（NSCD）方法是下面描述的γ相镁硼氢化其中目标种类包括二硼烷和正丁基的化合物（类似但不专门识别为正丁烷）的纯化。下面的协议可以很容易地修改一般扩展到其他超临界氮气干燥或提取过程。

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Compressed Nitrogen Gas</td>
			<td>Messer Schweiz AG</td>
			<td></td>
			<td>50 L bottle, purity &#62; 99.999%, &#60;3 ppmv H2O</td>
		</tr>
		<tr>
			<td>Liquid Nitrogen</td>
			<td>Pan Gas AG</td>
			<td></td>
			<td>Bulk storage, on site</td>
		</tr>
		<tr>
			<td>Custom Supercritical Drying Apparatus</td>
			<td>Empa</td>
			<td></td>
			<td>Swagelok (compression fitting and VCR) components</td>
		</tr>
		<tr>
			<td>Custom Cryogenic Furnace Bath</td>
			<td>Empa</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Custom Labview Interface</td>
			<td>Empa</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

supercritical nitrogen processing for the purification of reactive porous materials

Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. Herein, nitrogen is presented as a novel supercritical drying fluid for specialized applications such as in the processing of reactive porous materials, where carbon dioxide and other fluids are not appropriate due to their higher chemical reactivity. Nitrogen exhibits similar physical properties in the near-critical region of its phase diagram as compared to carbon dioxide: a widely tunable density up to ~1 g ml-1, modest critical pressure (3.4 MPa), and small molecular diameter of ~3.6 &#197;. The key to achieving a high solvation power of nitrogen is to apply a processing temperature in the range of 80-150 K, where the density of nitrogen is an order of magnitude higher than at similar pressures near ambient temperature. The detailed solvation properties of nitrogen, and especially its selectivity, across a wide range of common target species of extraction still require further investigation. Herein we describe a protocol for the supercritical nitrogen processing of porous magnesium borohydride.

碱金属和碱土金属硼氢化物是潜在的储氢材料，其在分解。27,29其他分解产物递送气态氢的含量大，如乙硼烷也有时被解吸的气体中检测到，但其来源没有先验明确;有可能它们是纯相的分解产品，但也可以是杂质的杂质反应或产物剩从化学合成。35镁硼氢化的多孔相（γ-Mg系（BH 4）2）表现出既具有高比表面积（&gt; 1,000米2 g -1）以上和氢。36及其脱?...

Watch this Scientific Journal Video about Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials at JoVE.com

Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials

氮气是用于萃取或干燥过程的有效的超临界流体，由于其小的分子尺寸，高密度在近液体超临界状态，和化学惰性。我们提出了一个超临界氮气干燥协议用于净化处理的反应性的，多孔的材料。

超临界氮处理的活性多孔材料的净化

Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. ...

supercritical-nitrogen-processing-for-purification-reactive-porous

Research

JoVE Journal

Chemistry

14.6K 次观看.  Empa, Swiss Federal Laboratories for Materials Science and Technology. 氮气是用于萃取或干燥过程的有效的超临界流体，由于其小的分子尺寸，高密度在近液体超临界状态，和化学惰性。我们提出了一个超临界氮气干燥协议用于净化处理的反应性的，多孔的材料。 