这项研究是由能源，基础能源科学办公室，化学科学，地球科学和生物科学部的下奖DE-FG02-12ER16362美国能源部的支持。

1，合成家长财政部（溴YOMOF） <ol><li>称出50毫克的Zn（NO 3）2×6 H 2 O（0.17毫摩尔），37.8毫克DPNI（0.09毫摩尔）和64.5毫克1,4 -二溴2,3,5,6 -四（4 -羧基苯基基）苯（ 溴-TCPB，0.09毫摩尔）。将所有的固体成分中有4兰小瓶。 </li><li>加入10毫升DMF中有刻度的量筒，用固体组分的小瓶进行测量。然后，用9&#39;巴斯德移液管中，加浓盐酸1滴（0.05毫升）（注意！腐蚀眼睛，皮肤和粘膜。手柄带手套）。 </li><li>盖紧瓶盖小瓶调匀使用超声浴〜15分钟的成分。观察小瓶的内容物，因为它们形成悬浮液。 </li><li>放置在80ºC样品瓶在烘箱中两天。第1天，检查瓶，以确保其内容已完全溶解，形成了一个黄色的澄清溶液。第2天，观察黄耐撕裂墙壁上形结晶和小瓶的底部。以下的晶体的形成，除去从烘箱小瓶。 </li><li>使小瓶冷却至室温。然后用锅铲轻轻推动晶体关闭小瓶墙壁，所以他们都收集在小瓶中的地板上。让瓶中静置〜5分钟，以保证所有的晶体都落户在地板上。 </li><li>用9&#39;巴斯德移液管，温和地去除从管形瓶中的反应溶液中，同时避免吸干晶体进入吸管。留足够的溶液以使结晶完全覆盖，以防止框架干燥。 </li><li>加入〜5毫升新鲜的DMF与晶体的小瓶中。为了除去的酸性反应溶液，并截留在MOF毛孔任何未反应的原料浸泡在MOF晶体在新鲜的DMF中的至少一天。为获得最佳结果，定期更换新鲜批次的DMF（〜3倍以上的第一个小时的过程中，然后每6-12小时）。 </lI&gt; <li>储存在DMF中的溴YOMOF的晶体在室温直至进一步使用。 </li></ol> 2，表征粉末X射线衍射（PXRD） <ol><li>通过小心地切断的封闭端，使上3厘米的毛细管（用漏斗顶部）保持准备一个直径为0.7毫米的硼硅玻璃毛细管的实验。 </li><li>加热定期蜂蜡，直到它被熔化并浸在毛细管的窄（切断）端插入熔化的蜡。除去毛细管并让蜡固化如在毛细管底部的塞子。 </li><li>支持在少量模型粘土的毛细管。 </li><li>使用巴斯德吸管，吸取了晶体的几毫升溶液中。晶体和解决方案仔细地转移到毛细管虽然漏斗开口。用一张擦手纸或纸巾吸走多余的溶剂。避免溢出溶剂或结晶在毛细管的外表面。 </li><li>使晶体沉淀成一个小插件（大约2-5毫米的长度）。使用一小片橡皮泥，以密封所述毛细管的顶端（漏斗）端。 </li><li>取下测角头（铜针，磁架等 ）的任何安装装置，把你的毛细血管支持的橡皮泥上的测角仪头顶。 </li><li>中心在X射线束的毛细管，以确保晶体的插头不能进动其旋转。 注：结晶材料的体积将超过大多数标准实验室X射线源的电子束的尺寸。 </li><li>使用衍射仪的软件，准备了一系列的180°φ扫描，在2θ重叠的增量。例如，使用卡帕几何衍射仪配备有APEX2检测器设置在150毫米（DX），我们收集了一系列10秒，180°φ扫描的参数按表1。 </li><li>一旦框架已收集，使用衍射仪的软件对所有图像组合和集成在所得到的衍射图案。 </li></ol> 3，对溴YOMOF晶体表演溶剂辅助接头交换（销售） <ol><li>称取21毫克dped（0.095毫摩尔），溶于5毫升二甲基甲酰胺在2打兰小瓶超声波。 </li><li>使用6&#39;巴斯德吸管，收集溴YOMOF结晶和过滤他们在布氏漏斗。然后称出〜晶体30毫克;该晶体的其余部分返回到与溴YOMOF小瓶。 </li><li>分散的晶体，在预先制备的dped溶液。在烘箱中在100°C下24小时，将所得的混合物出售。 </li><li>第二天，检查通过1 H NMR的销售反应的进程。用抹刀或6&#39;巴斯德吸管，去除约2-5毫克的反应DMF溶液财政部晶体。通过浸没它们在少量清洁SOLV的冲洗这些晶体耳鼻喉科（溶剂如低沸点，如二氯甲烷，或相同的溶剂作为反应介质 - 在此情况下，二甲基甲酰胺）在一个1.5兰小瓶。 </li><li>添加〜1毫升氘代二甲基亚砜（D 6-DMSO）在一个单独的1.5-DRAM小瓶。滤出晶体，从清洗液和它们分散在D 6-DMSO。通过加入3滴氘代硫酸（D 2 SO 4）的混合物的晶体溶解。充分超声处理带帽小瓶，得到均匀的溶液。 </li><li>所得到的NMR样品转移到NMR管中以巴斯德移液管和收集的NMR谱。进行64次扫描中，由于溶液是比较由于MOF晶体的溶解度低的稀释。 </li><li>解释频谱通过验证的所有DPNI已取代dped，并且该dped：BR-TCPB比为1：1。 注：如果DPNI仍然存在于晶体中，返回与小瓶将反应混合物于烘箱中，保持监测用1 H NMR对反应直至得到所需的产物。 </li><li>如果所有DPNI已取代dped，使反应停止通过倾析用9&#39;巴斯德移液管将反应溶液，并用新鲜的DMF代替。通过收集他们的PXRD图进行萨利姆-5晶体的额外特性;然后储存在​​DMF中结晶，直至进一步使用。 </li></ol> 4，激活SALEM-5晶体的超临界CO 2干燥<ol><li>在激活前，用乙醇交换所有的DMF来自MOF笼，它是相混溶的液态CO 2，并与超临界干燥机兼容。由来自MOF小瓶用9&#39;巴斯德吸管倾析DMF中，并用少量的乙醇代替它进行溶剂置换（足以完全浸没结晶）。 </li><li>继续溶剂交换3天，天天有新一批更换乙醇。确保所有的DMF中已经从晶体孔除去收集结晶的1 H NMR谱。 </li><li>检查一个具有足够的液体CO 2的水箱连接于超临界干燥。 </li><li>财政部晶体传送到使用6&#39;巴斯德吸管活化菜。然后尽可能多的乙醇，同时避免吸入晶体成吸管去除尽可能带出9个“”巴斯德吸管。 </li><li>拧下三个螺栓拆下活化室的盖，并检查是否有残留的MOF碎屑腔室（如果这些都存在时，擦拭室清洁用的Kimwipe）。用钳子，将激活菜财政部到室和螺丝盖放回原处。 </li><li>转动机上，打开CO 2罐。调节温度旋钮，实现0到10度之间的温度C.保持该温度范围在整个活化过程中保持CO 2在它的液体状态。 </li><li>一旦温度是在正确的范围内，调高“填充”旋钮缓慢。观察液态CO 2注入通过在腔室盖子的玻璃窗口的激活的菜。同时将压力读数上的轨距应增加，直到达到800磅。 </li><li>执行第一个“清除”，即激活溶剂的第一替换用新鲜批次。首先打开“填充”旋钮到，上面写着15，然后慢慢打开了“清洗”按钮，直到溶剂喷芽从管在仪器侧面的标记。让清洗去了〜5分钟;然后关闭“清除”按钮，打开“填充”按钮下来，上面写着5的标志。 </li><li>继续超临界干燥8小时，进行“清洗”，每2小时。 </li><li> 8小时后，TURN所有旋钮关闭，翻转的“热”开关。等到温度和压力超过临界点（31ºC和1,070磅）。 </li><li>流量计连接到管上的仪器的侧面和打开“渗色”旋钮。调节流量为1 毫升 /分钟;然后取出流量计，让二氧化碳从样本（通常发生的O / N）慢慢流血。 </li><li>第二天，检查压力已下降至0 PSI;若没有，打开了“流血”旋钮，直到达到预期的压降。关闭“流血”按钮，关闭“热”和电源开关仪器。 </li><li>除去从活化室中的样品。盖上激活盘紧密，敷在封口膜。存储激活SALEM-5在手套箱中备用。确保没有乙醇是存在于样品中收集的1 H NMR谱。 </li></ol> 5，收集N 2等温财政部获取其比表面积<ol><li>获得吸附管​​装有填料棒和密封料，准确地称量。权衡其至少两次，并确保两者平衡读数彼此一致在±0.01毫克。 </li><li>在预称重的管转移到手套箱中，并装入管内的活性SALEM-5样品。我们建议使用干净，干燥漏斗，如存储在手套箱激活MOF样品常常有静电电荷的和难以处理。从管中取出密封玻璃料和填料棒，用漏斗适应它;然后迅速反转在漏斗的激活盘，确保样品滑下的管。 </li><li>重新插入填充杆和密封釉料入装有SALEM-5管。填料棒缓慢且小心地滑入管，以避免溢出的样品和/或破管。从手套箱中取出试管。 </li><li>称量装入的管精确地，使用您用来装载空管相同的技术（以及相同的平衡）。 </li><li>放置的等温夹套在管中，加载上的吸附仪器的管和设置在吸着文件由进入空管的质量和与所述样品管中。调整文件撤离仪器上的样品的前向等温线的收集1小时。 </li><li>确保杜瓦用来存储液氮是通过注水，以使冰融化，然后擦拭干无冰和/或水。用液氮充满杜瓦到适当的标记，然后开始测量。在测量持续时间的任何位置的4至12小时，这取决于量和材料的孔隙率。 </li></ol>

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M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+and+synthesis+of+an+exceptionally+stable+and+highly+porous+metal-organic+framework.">Design and synthesis of an exceptionally stable and highly porous metal-organic framework.</a> Nature. 402, 276-279 (1999).</li><li>Ferey, G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chromium+Terephthalate-Based+Solid+with+Unusually+Large+Pore+Volumes+and+Surface+Area.">Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area.</a> Science. 309, 2040-2042 (2005).</li><li>Cavka, J. 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作者什么都没有透露。

MOF结晶是一个微妙的过程，可以通过在该描述的合成条件的多个参数的甚至轻微的变化被抑制。因此，需要特别注意的制备反应混合物时，应采取的。所述有机连接子的纯度应先于合成的发作1 H NMR证实，由于即使少量的杂质的存在是已知的完全防止结晶或导致的不希望的结晶产物的形成。极性，高沸点溶剂如DMF，N，N&#39;二甲基乙酰胺（DMA），N，N&#39;-diethylformamide（DEF）或?...

金属-有机骨架（MOFs）是一类由金属基节点（ 例如 ，锌离子 ，锌4 O 6 +，锆6 O 4（OH）4 12 +，3的Cr（H 2 O晶体配位聚合物的通过有机连接子连接）2 6+，锌2（COO）4）（ 例如 ，二，三，四和六羧酸盐，咪唑类1，dipyridyls; 见图1）2及其高度有序的（并且因此适合于。高水平的表征）的结构，并结合自身特殊的表面积（达7000 平方米 /克）3赋予他们的潜力，有吸引力的候选应用的转换，从储氢4和碳捕获5,6催化， 7,8感应9,10和捕光11毫不奇怪，MOFs材料已引起INTE了大量休息在科学和材料工程领域;在同行评审期刊MOFs材料出版物的数量已经成倍增加，在过去的十年中，与目前每年出版的1000-1500文章。 MOFs材料具有理想的性能的合成，但是，带来了一系列的挑战。吸引力，也就是其特殊的孔隙率，其实他们的主要点可能会出现，具体的MOFs材料，对他们的成功发展的最大障碍之一。这些材料的框架内的大空的空间存在有损于它们的热力学稳定性;作为一个结果，当MOFs材料都从头合成（ 即 ，由溶剂热反应的金属前体和有机连接子在一个步骤中），其构成积木常常倾向于聚集成更致密，少孔（和不太理想对于某些应用，如储气库）类似物12的程序后，再版oducibly获得期望的拓扑结构的框架已经形成，财政部的需要，以使其在需要的气体吸附过程的应用程序进行处理。因为MOFs材料在溶液中合成的，该笼和新生长的MOF晶体的通道通常是充分的高沸点溶剂用作反应介质;在除去溶剂而不诱导下的毛细力框架的崩溃需要一系列被称为“MOF激活”专门程序13最后，为了确保最终产品的纯度，并能对基本性质，MOFs材料确凿的研究需要进行严格的特征在于在它们的合成。鉴于MOFs材料是配位聚合物，这是在常规溶剂中高度不溶，这过程通常涉及用于这类材料特别开发了几种技术。许多这些技术依赖于X射线衍射（XRD），这是唯一的套房d，来提供这些结晶材料的高级别表征。 通常情况下，MOF合成在所谓从头方式采用金属前体（无机盐）和有机连接子之间一锅溶剂热反应。此方法存在多种限制，因为它们很少有控​​制权的MOF部件到框架的结构，将所得产物并不总是具有所需的拓扑结构。一个容易实施的方法，它允许绕过与从头 MOF合成相关联的问题是溶剂辅助链接交换（要买， 图2）。14-16此方法包括使容易获得的MOF晶体所需的连接物的浓溶液，直到女儿连接器完全取代那些家长。该反应进行中的单晶到单晶的方式 - 即，尽管在更换接头机智欣框架内，该材料保留了原始亲MOF的拓扑结构。销售基本上允许MOFs材料的合成与连接器拓扑的组合，很难获得新生 。到目前为止，这种方法已经成功地实施，以克服各种合成财政部的挑战，如控制连锁，17扩展财政部笼子，18,19合成高能量多晶20，催化活性材料20,21和现场隔离的开发保护反应的试剂。22 新合成的MOFs几乎总是有通道填充有它们的合成过程中使用的溶剂。此溶剂必须从框架移除，以便采取其气体吸附性能的优点。传统上，这是由实现）交换溶剂中的通道（通常喜欢为n的高沸点溶剂，N二甲基甲酰胺，二甲基甲酰胺）具有更多的挥发性溶剂像浸泡财政部晶体在所选择的溶剂中，b）加热MOF晶体在真空下以延长时间抽空溶剂，或c）一种这两种技术的组合，乙醇或二氯甲烷中。然而这些活化方法，不适合于许多高表面热力学上脆弱的MOFs可能遭受这样恶劣的条件下框架塌陷。的一种技术，它允许溶剂除去来自MOF的笼子，同时避免了大量的框架塌陷的发生，是激活通过超临界CO 2干燥23在此过程中，MOF结构内的溶剂置换成液态CO 2。的CO 2是随后加热加压超过其临界点，并最终允许从框架蒸发。由于超临界二氧化碳不具有毛细力，这个活化处理是强制少MOFs材料比传统的真空加热，并有启用访问大多数已发布至今超高布鲁诺尔-埃米特-泰勒（BET）表面积，包括财政部与冠军表面积。3,24,25 在本文中，我们描述了从头合成，作为一个很好的模板销售反应的代表性方便财政部-的柱，黑臭框架溴YOMOF 26日的长和比较弱结合N，N&#39; -二-4 -pyridylnaphthalenetetracarboxydiimide（DPNI）柱子可与内消旋 -1,2 -二（4 -吡啶基）-1,2 -乙二醇（dped），以产生一个同构MOF SALEM-5（图2）。18此外，我们的轮廓容易地交换要采取需要的步骤来激活SALEM-5超临界二氧化碳干燥，并成功收集其N 2等温线，并获得其比表面积。我们还描述了各种技术相关的MOF表征，如X射线晶体学和1 H-NMR波谱法（NMR）。

<table border="0" cellpadding="0" cellspacing="0" width="352">
	<tbody>
		<tr height="64">
			<td height="64" style="height:64px;width:88px;">Name of Material/ Equipment</td>
			<td style="width:88px;">Company</td>
			<td style="width:88px;">Catalog number</td>
			<td style="width:88px;">Comments/Description</td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">6&#8217;&#8217; Pasteur pipet</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">14673-010</td>
			<td style="width:88px;">For transferring MOF crystals</td>
		</tr>
		<tr height="127">
			<td height="127" style="height:127px;width:88px;">9&#8217;&#8217; Pasteur pipet</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">14673-043</td>
			<td style="width:88px;">For separating liquid solution from MOF crystals</td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">1-dram vials</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;"></td>
			<td style="width:88px;">For preparation of NMR samples</td>
		</tr>
		<tr height="64">
			<td height="64" style="height:64px;width:88px;">2-dram vials</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">66011-088</td>
			<td style="width:88px;">For small-scale SALE reactions</td>
		</tr>
		<tr height="106">
			<td height="106" style="height:106px;width:88px;">4-dram vials</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">66011-121</td>
			<td style="width:88px;">For de novo pillared-paddlewheel MOF synthesis</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">NMR tube Grade 7</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">897235-0000</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">NMR instrument Avance III 500 MHz</td>
			<td style="width:88px;">Bruker</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">Oven</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">414004-566</td>
			<td style="width:88px;">For solvothermal MOF reactions</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:88px;">Sonicator</td>
			<td style="width:88px;">Branson</td>
			<td style="width:88px;">3510-DTH</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">Balance</td>
			<td style="width:88px;">Mettler-Toledo</td>
			<td style="width:88px;">XS104</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="78">
			<td height="100" rowspan="2" style="height:101px;width:88px;">Superctitical CO2 dryer</td>
			<td rowspan="2" style="width:88px;">Tousimis&#8482; Samdri&#174;</td>
			<td rowspan="2" style="width:88px;">8755B</td>
			<td rowspan="2" style="width:88px;">For activation of pillared-paddlewheel MOFs</td>
		</tr>
		<tr height="22">
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">Activation dish</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="148">
			<td height="148" style="height:148px;width:88px;">Tristar II 3020</td>
			<td style="width:88px;">Micromeritics</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">For collection of gas isotherms/measurement of BET surface area</td>
		</tr>
		<tr height="211">
			<td height="211" style="height:211px;width:88px;">X-ray diffractometer</td>
			<td style="width:88px;">Bruker</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">Kappa geometry goniometer, CuK&#945; radiation and Powder-diffraction data collection plugin.</td>
		</tr>
		<tr height="106">
			<td height="106" style="height:106px;width:88px;">Capillary tubes</td>
			<td style="width:88px;">Charles-Supper</td>
			<td style="width:88px;">Boron-Rich BG07&#160;</td>
			<td style="width:88px;">Thin walled Boron Rich capillary 0.7mm diameter</td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">Beeswax</td>
			<td style="width:88px;">Huber</td>
			<td style="width:88px;">WAX</td>
			<td style="width:88px;">sticky wax for specimen fixation</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">Modeling Clay</td>
			<td style="width:88px;">Van Aken</td>
			<td style="width:88px;">Plastalina</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;width:88px;">CO2 (l)</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;width:88px;">N2 (l)</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;width:88px;">N2 (g)</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;">N/A</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="64">
			<td height="64" style="height:64px;width:88px;">DMF</td>
			<td style="width:88px;">VWR</td>
			<td style="width:88px;">MK492908</td>
			<td style="width:88px;">For MOF reactions and storage</td>
		</tr>
		<tr height="106">
			<td height="106" style="height:106px;width:88px;">Ethanol</td>
			<td style="width:88px;">Sigma-Aldrich</td>
			<td style="width:88px;">459844</td>
			<td style="width:88px;">For solvent exchange before supercritical drying</td>
		</tr>
		<tr height="51">
			<td height="51" style="height:51px;width:88px;">Zn(NO3)2 &#215; 6 H2O</td>
			<td style="width:88px;">Fluka</td>
			<td style="width:88px;">96482</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:88px;">dped</td>
			<td style="width:88px;">TCI</td>
			<td style="width:88px;">D0936</td>
			<td style="width:88px;"></td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">dpni</td>
			<td style="width:88px;"></td>
			<td style="width:88px;"></td>
			<td style="width:88px;">Synthesized according to a published procedure</td>
		</tr>
		<tr height="85">
			<td height="85" style="height:85px;width:88px;">Br-tcpb</td>
			<td style="width:88px;"></td>
			<td style="width:88px;"></td>
			<td style="width:88px;">Synthesized according to a published procedure</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">D2SO4</td>
			<td style="width:88px;">Cambridge Isotopes</td>
			<td style="width:88px;">DLM-33-50</td>
			<td style="width:88px;">For MOF NMR</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:88px;">d6-DMSO</td>
			<td style="width:88px;">Cambridge Isotopes</td>
			<td style="width:88px;">DLM-10-100</td>
			<td style="width:88px;">For MOF NMR</td>
		</tr>
	</tbody>
</table>

synthesis and characterization of functionalized metal-organic frameworks

金属 - 有机框架已经引起了研究关注数量惊人，因为他们是有吸引力的候选人，许多工业和技术的应用。他们的签名属性是其超高的孔隙率，但是它赋予了一系列的挑战，当涉及到双方构建他们，与他们一起工作。确保通过连接器/节点组装所需财政部的化学和物理功能到可以选择造成困难的高度多孔框架，少孔和热力学更稳定的同族元素（ 例如 ，其他多晶型，链中的类似物）往往优先采用常规的合成方法获得。一旦获得了期望的产物，其表征通常需要地址的并发症而产生，例如，旅客分子损失或微晶的择优取向是可能的专门技术。最后，访问MOFs材料里面大的空隙中使用APPL涉及气体ications可能会产生问题，因为框架可能会受到除去溶剂分子（溶剂热合成的残余）的过程中坍塌。在本文中，我们描述了在我们的实验室无论是解决或避免这些问题经常使用的合成与表征方法。该方法包括溶剂辅助的接头交换，在毛细管中的粉末X射线衍射，并用超临界CO 2的干燥材料活化（空腔抽真空）。最后，我们提供了一个协议，用于确定用于将所述的Brunauer-埃米特 - 特勒分析氮吸附等温线的合适的压力区域，从而估计MOFs材料以良好的精度的表面积。

盐酸中的MOF合成使用往往有利于高质量MOF晶体的生长。因为它减慢了羧酸盐的脱质子化（与连接子与金属中心结合），它促进了较大的晶体的生长，并防止形成无定形和晶相，其可以形成，如果该反应允许进行更迅速的。事实上，因为这可以在图3中可以看出，被该反应过程中产生的柱，水车MOFs材料形成的足够质量的单晶数据集很大，黄色晶体。此外，在具有高沸点的结合使用的HCl，...

Watch this Scientific Journal Video about Synthesis and Characterization of Functionalized Metal-organic Frameworks at JoVE.com

Synthesis and Characterization of Functionalized Metal-organic Frameworks

合成的有意设计的金属 - 有机骨架材料，激活和表征是具有挑战性的，尤其是当构建块是不相容的或不需要的多晶型物都在期望的形式热力学上有利的。我们描述了如何通过超临界CO 2的干燥溶剂辅助的接头交换，粉末X射线衍射中的毛细血管和激活的应用程序，可以解决这些挑战。

功能化的合成与表征金属 - 有机骨架

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

synthesis-characterization-functionalized-metal-organic

Research

JoVE Journal

Chemistry

47.7K 次观看.  Northwestern University. 合成的有意设计的金属 - 有机骨架材料，激活和表征是具有挑战性的，尤其是当构建块是不相容的或不需要的多晶型物都在期望的形式热力学上有利的。我们描述了如何通过超临界CO 2的干燥溶剂辅助的接头交换，粉末X射线衍射中的毛细血管和激活的应用程序，可以解决这些挑战。 

视频: Synthesis and Characterization of Functionalized Metal-organic Frameworks

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

增强型氟烷烃的化学气相沉积等离子通过疏水金属 - 有机骨架的制备氨的去除

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

科研

化学

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

Synthesis of a Water-soluble Metal&amp;#8211;Organic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

金属-有机框架的表面功能化改善防潮性能

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of the reaction site in metal-organic framework (MOF)&#8211;based catalysts in an enantioselective catalytic reaction system. Therefore, a method of validating the reaction site of MOF-based catalysts is necessary to investigate this issue. Substrate size discrimination by pore size was accomplished by comparing the substrate size versus the reaction rate in two different types of carbonyl-ene reactions with two kinds of MOFs. The MOF catalysts were used to compare the performance of the two reaction types (Zn-mediated stoichiometric and Ti-catalyzed carbonyl-ene reactions) in two different media. Using the proposed method, it was observed that the entire MOF crystal participated in the reaction, and the interior of the crystal pore played an important role in exerting chiral control when the reaction was stoichiometric. Homogeneity of the chiral environment of MOF catalysts was established by the size control method for a particle used in the Zn-mediated stoichiometric reaction system. The protocol proposed for the catalytic reaction revealed that the reaction mainly occurred on the catalyst surface regardless of the substrate size, which reveals the actual reaction sites in MOF-based heterogeneous catalysts. This method for reaction site validation of MOF catalysts suggests various considerations for developing heterogeneous enantioselective MOF catalysts.

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

Here, we present a protocol for active site validation of metal-organic framework catalysts by comparing stoichiometric and catalytic carbonyl-ene reactions to find out whether a reaction takes place on the inner or outer surface of metal-organic frameworks.

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. However, the synthesis of single-crystalline core-shell MOFs is very challenging, and thus a limited number of examples have been reported. Here, we suggest a method of synthesizing single-crystalline HKUST-1@MOF-5 core-shells, which is HKUST-1 at the center of MOF-5. Through the computational algorithm, this pair of MOFs was predicted to have the matched lattice parameters and chemical connection points at the interface. To construct the core-shell structure, we prepared the octahedral- and cubic-shaped HKUST-1 crystals as a core MOF, in which the (111) and (001) facets were mainly exposed, respectively. Via the sequential reaction, the MOF-5 shell was well-grown on the exposed surface, showing a seamless connect interface, which resulted in the successful synthesis of single-crystalline HKUST-1@MOF-5. Their pure phase formation was proved by optical microscopic images and powder X-ray diffraction (PXRD) patterns. This method presents the potential of and insights into the single-crystalline core-shell synthesis with different kinds of MOFs.

Here, we demonstrate a protocol for the two-step synthesis of single-crystalline core-shells using a non-isostructural metal-organic framework (MOF) pair, HKUST-1 and MOF-5, which have well-matched crystal lattices.

单晶核壳金属有机骨架的合成

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. ...

A Technical Guide for Performing Spectroscopic Measurements on Metal-Organic Frameworks

Metal-organic frameworks (MOFs) offer a unique platform to understand light-driven processes in solid-state materials, given their high structural tunability. However, the progression of MOF-based photochemistry has been hindered by the difficulty in spectrally characterizing these materials. Given that MOFs are typically larger than 100 nm in size, they are prone to excessive light scatter, thereby rendering data from valuable analytical tools like transient absorption and emission spectroscopy nearly uninterpretable. To gain meaningful insights of MOF-based photo-chemical and physical processes, special consideration must be taken toward properly preparing MOFs for spectroscopic measurements, as well as the experimental setups that garner higher quality data. With these considerations in mind, the present guide provides a general approach and set of guidelines for the spectroscopic investigation of MOFs. The guide addresses the following key topics: (1) sample preparation methods, (2) spectroscopic techniques/measurements with MOFs, (3) experimental setups, (3) control experiments, and (4) post-run stability characterization. With appropriate sample preparation and experimental approaches, pioneering advancements toward the fundamental understanding of light-MOF interactions are significantly more attainable.

Here, we use a polymer stabilizer to prepare metal-organic framework (MOF) suspensions that exhibit markedly decreased scatter in their ground-state and transient absorption spectra. With these MOF suspensions, the protocol provides various guidelines to characterize the MOFs spectroscopically to yield interpretable data.

对金属有机骨架进行光谱测量的技术指南

Metal-organic frameworks (MOFs) offer a unique platform to understand light-driven processes in solid-state materials, given their high structural ...

从多主题膦接头合成低价 MOF

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

作者聚焦：从多主题膦接头合成低价金属有机框架的实验方法  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

多位膦接头合成低价金属有机骨架的实验方法

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...

氧化还原活性 MOF 固态电化学的磁力表征

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs show outstanding performance in terms of gravimetric or areal capacitance and cyclic stability, unfortunately their electrochemical mechanisms are not well understood in most cases. Traditional spectroscopic techniques, such as X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), have only provided vague and qualitative information about valence changes of certain elements, and the mechanisms proposed based on such information are often highly disputable. In this article, we report a series of standardized methods, including the fabrication of solid-state electrochemical cells, electrochemistry measurements, the disassembly of cells, the collection of MOF electrochemical intermediates, and physical measurements of the intermediates under the protection of inert gases. By using these methods for quantitatively clarifying the electronic and spin state evolution within a single electrochemical step of redox-active MOFs, one can provide clear insight into the nature of electrochemical energy storage mechanisms not only for MOFs, but also for all other materials with strongly correlated electronic structures.

作者聚焦：氧化还原活性金属有机框架固态电化学中中间体的磁力表征  

Ex situ magnetic surveys can directly provide bulk and local information on a magnetic electrode to reveal its charge storage mechanism step by step. Herein, electron spin resonance (ESR) and magnetic susceptibility are demonstrated to monitor the evaluation of paramagnetic species and their concentration in a redox-active metal-organic framework (MOF).

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...