R.E.M. thanks the Royal Society and the E.P.S.R.C. (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. J.C&#780;. acknowledges the Czech Science Foundation for the project of the Centre of Excellence (P106/12/G015) and the European Union Seventh Framework Programme (FP7/ 2007-&#173;-2013) under grant agreement n&#176;604307. The authors would like to thank P. Chlubn&#225;-Eli&#225;&#353;ov&#225;, W.J. Roth and P. Nachtigall for enlightening discussions.

注意:请查阅所有相关材料安全数据表（MSDS），并在使用前进行的所有过程进行风险评估。几个在该合成过程中使用的化学品是剧毒和致癌性。请这些程序包括工程控制（通风橱）和个人防护设备（安全眼镜，白大褂和适当的化学防护手套）存续期间全部使用适当的安全程序。 1.结构导向剂的制备UTL的合成<ol><li>溶解5.68克氢氧化钠140毫升蒸馏水。 30.66克1,4-二溴丁烷加入到该溶液并搅拌。 </li><li>加热该溶液至回流（油浴110℃）。 </li><li>添加逐滴（〜每秒1滴）16.07克（2R，6S）-2,6-二甲基哌啶并继续回流另外的12小时的。 </li><li>在冰浴中冷却至室温，然后寒意。 </li><li>溶解50克钠氢氧化物在75毫升的蒸馏水中，以制备40重量％的溶液。在冰上冷却。加70毫升冰水中冷却40重量％氢氧化钠溶液，以上述冷却溶液中。 </li><li>过滤白色沉淀物，并在最小的氯仿溶解。 </li><li>提取用氯仿含水残余物（3×200毫升）。结合的氯仿部，并使用约20克无水硫酸钠的干燥。 </li><li>使用滤纸过滤除去硫酸钠，并用氯仿（50毫升）洗涤。 </li><li>使用旋转蒸发直至白色沉淀开始形成部分汽化氯仿。从旋转蒸发器除去，加入乙醚，直到没有进一步沉淀是可见的。 </li><li>通过使用滤纸的漏斗过滤回收白色沉淀物，用乙醚（50毫升）洗涤。 </li><li>干燥白色沉淀在60℃CO / N，得到盐（6R，10S）-6,10 - 二甲基-5-氮鎓螺〔4,5〕癸烷溴化物。 </li><li>溶解25.0克的（6R，10S）-6,10 - 二甲基-5-氮鎓螺〔4,5〕癸烷溴化物在50毫升的蒸馏水。 </li><li>通过使用氢氧根离子交换树脂交换为氢氧根阴离子的溴化物的阴离子。 <ol><li> 25.0克氢氧根离子交换树脂加入到溴化物盐溶液，并搅拌12小时。 </li><li>过滤用滤纸将溶液，将滤液搅拌12小时下重新暴露至25.0克氢氧化离子交换树脂制成。重复暴露于氢氧化物离子交换树脂，直到硝酸银测试为卤素返回一个否定的结果。 注:硝酸银试验是溴离子非常敏感的测试。 <ol><li>酸化0.25毫升的产物溶液与2ml稀硝酸（1.0M）。添加的硝酸银溶液（0.05M）的产物溶液2-3滴。如果形成沉淀，然后重复暴露于氢氧化物离子交换树脂并重新测试，直到没有沉淀可以看到。 </li></ol></li></ol></li><li>确认氢氧化物的浓度e。通过用0.1M（这相当于0.1当量），使用酚酞溶液作为指示剂盐酸滴定。使用滴定管，慢慢的0.1M盐酸小等分添加到产品解决方案的已知体积的一小部分，直到酚酞指示剂只是改变颜色（ 即到达终点）。加入盐酸的总摩尔数等于在初始溶液氢氧化物的摩尔数。 </li><li>用蒸馏水稀释该溶液，得到0.625 M在氢氧化物的浓度。 </li></ol> 2.家长戈UTL分子筛的制备<ol><li>溶解1.08克二氧化锗分成15毫升结构导向剂的溶液（6R，10S）-6,10 - 二甲基-5-氮鎓螺[4,5]癸烷氢氧化物（0.625 1M浓度）。 </li><li>直至形成均匀的溶液分批1.246克热解法二氧化硅添加到上述溶液中，并搅拌另外的30分钟。 注意:将所得的凝胶具有0.8 的 SiO 2的摩尔组成:0.4的GeO 2:0.4 ROH:30 H 2 O，其中ROH为结构导向剂。 </li><li>转移凝胶到聚四氟乙烯内衬的高压釜（30毫升容量）。然后将在10天的烘箱，并加热到175℃。 </li><li> 10天之后，从烘箱中取出高压釜，并允许自然冷却至室温。通过过滤回收白色沸石产品。用大量的水（〜200毫升）洗涤。干燥在70℃CO / N的沸石。 </li><li> 1，之后冷却至RT，以2℃的速率前6小时，在550℃保持-通过以1℃min的速率加热沸石到550℃，除去从沸石的孔中的结构导向剂分钟- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:粉末X射线衍射图案应匹配给予n，用于在图2中UTL。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。 </li><li>存储煅烧沸石在干燥的惰性气氛中，以防止材料的水解。 </li></ol> 3.锗UTL的水解形成IPC-1P <ol><li> 1.0克煅烧沸石加至160毫升0.1M盐酸溶液。 </li><li>加热该混合物在95℃下18小时，冷却至RT，并用滤纸过滤回收固体。用大量的水（〜300毫升）中并在70℃CO / N干洗净。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以确认的IPC-1P的结构。 注意:粉末X射线衍射图案应匹配在图2 IPC-1P给出的干燥产物被指定。IPC-1P和被存储以进一步使用。 </li></ol> 4 IPC-4分子筛的制备<ol><li>放置0.5克IPC-1P的在陶瓷坩埚中并加热到575℃，在1℃min的加热速率- 1，保持在575℃下6小时之后冷却至RT在2℃min的速度前- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:粉末X射线衍射图案应匹配在图2中用于IPC-4给出。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。这会给锗多少保留在结构信息。 </li></ol> 5.准备IPC-2沸石<ol><li> 0.5克IPC-1P添加到10毫升1.0M的硝酸酸溶液。 </li><li> 0.1克diethoxydimethylsilane的（DEDMS）添加到该溶液中。 </li><li>在175℃下将溶液转移到聚四氟乙烯内衬的高压釜和热的烘箱中18小时。 </li><li>从烘箱中取出高压釜并使其自然冷却至室温。 </li><li>通过过滤回收白色产物，用大量的水（约100毫升），在70℃CO / N干洗净。 </li><li>获得的粉末X射线衍射光谱，证实结构。粉末X射线衍射图应与图2中用于IPC-2P给出。 </li><li>放置在陶瓷坩埚中并加热到575℃的产物在1℃min的加热速率- 1，保持在575℃下6小时之后冷却至RT在2℃min的速度前- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:衍射图案应符合Ť在图2 IPC-2中给出的帽子。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。 </li></ol>

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The authors have nothing to disclose.

该ADOR过程的实际机制的完整描述超出了本文的范围，但可以在发表的论文中找到引用。3，5，8然而，这是值得推广的过程中的潜在重要性。沸石制剂的ADOR方法从在以何种方式制备最终材料沸石合成的传统方法有很大不同。这方面最重要的结果是，使用该ADOR方法制备的材料具有的潜力是从传统上的沸石根本不同的。特别是有范围使用ADOR法制备是大力独特的材料。这背后的理论在参考文献8中描述。 以上的孔隙率的控制是另一个领域，所述ADOR方法显示不同的性质，以传统的方法。13特别是，它是可能的编写，J再一个全系列沸石与连续可调的孔隙率，这已不是迄今为止可能利用沸石水热合成制得。使系列的变形是在上述方法的步骤3。通过改变从0.1M的使用的酸的浓度一路多达6 M（甚至超越）一种可以根据最终材料的性质。如何可以做到这一点的全部细节在参考文献13给出这既是一个很好的机会和风险。有时，如果所用的酸的浓度，温度和时间留给反应不是最佳所得材料显示的衍射图案，其中最强峰的位置不匹配在图2中所示的那些，但是，在这样的情况这可以通过从与那些在参考文献13中描述的实验比较的粉末X​​射线图案进行识别。 在协议中的关键步骤，以确保一个成功的OUtcome实现是那些与操作。首先，它是重要的，在与该层叠体的中间体接触的任何解决方案不是碱性的，因为这促进了二氧化硅的溶解，特别是在高温下。其次，ADOR过程的不可逆最后步骤是关键因素，因此该材料的适当的组织（步骤3.2和5.2）是用于该过程的成功是至关重要的。如上所述，时间和酸度是在这个过程中都重要的变量，因此确保这些步骤是优化是非常重要的。 如所描述的上面有父沸石是与位于该结构的特定位置的锗一锗的要求。这将限制可被用作母体沸石的数量。沸石UTL是已经显著探索作为父的唯一材料。不过，也有早期迹象表明，其他家长可能会成功AP合股的过程，但进一步的工作是在这方面的需要。 为了确保ADOR方法工作，极大必须小心在操作拆卸步骤之后，以确保中间IPC-1P的层不会溶解或经受显著重排。同样重要的是要获得的权利，以优化最终产品的反应条件的酸度，时间和温度。过度反应条件等精细控制，可在一审相当混乱，是我们的心愿背后的主要驱动力有过程的视频描述。 总之，本过程描述如何沸石合成的ADOR方法可应用于与UTL框架结构的锗以形成两个不同的沸石，IPC-2（OKO）和IPC-4（PCR）。

沸石是一类由角共享四面体的三维开放装置，其中在所述四面体的中心的金属阳离子（传统的硅和铝）由4氧化物阴离子包围的固体。这些角共享四面体导致可以具有各种各样的细孔结构的不同的沸石框架不同的安排。这些孔结构能够容纳的小分子，从而导致他们的应用程序石化，核和医学领域内，等等。需要注意的是沸石拓扑结构和材料，因为识别其拓扑结构（如UTL）或实际材料（ 例如，IPC-2）码-有关更多信息，请参阅国际分子筛协会的网站上，www.iza-online.org 。 沸石的重要特征是它们的孔隙率，其由管辖的量和accessibil定义它们的效用其中，最重要的化学发生的内表面面积的性。这又决定了材料的化学活性和选择性。沸石科学（事实上在所有多孔材料科学）的主要目标是控制孔隙度。 沸石是由水热法，1，2，它几乎没有变化在过去的50年传统的合成。事实上，在过去的重大进展出现在1961年引进季铵盐作为结构导向剂1，并在1982年的磷可以代替硅引起的铝族材料的发现。3鉴于极大效用沸石，有必要制订新的路线，新材料的极大兴趣。这样的路线是最近开发的战略ADOR 4 - 7其中父沸石组装，然后Disassembl编和以这样的方式组织以允许最后重新组装成一个新的固体所得物种。这使得使用已经内置到它的框架，我们可以利用固有的不稳定性事先准备好的沸石。8这个可怜的稳定性从水解不稳定锗掺入了优先位于D4R（双四环）单元中的茎绑定相邻二氧化硅层次丰富起来（ 图1）。这些D4R单元可以使用相对温和的处理从而可以在中间层状材料进行进一步化学处理被选择性地除去。4 传统的水热合成和ADOR之间的主要区别是框架形成的最终方法​​。在水热合成法，这是一个可逆的过程，允许最终结构是结晶的。在ADOR过程，然而，最终的框架形成阶段（重组）是一种不可逆共在高温下的各层的ndensation。以获得高度结晶的最终材料的关键是则组织步骤，其中所述分层的中间体被布置在正确的相对位置，以允许在不可逆凝结成新的框架，以作为最佳的是可能发生的。 在下面的例子中，我们显示如何母体沸石，用UTL沸石拓扑，9一锗，10可以使用预先准备好的有机阳离子作为结构导向剂（SDA）制备（大会工序）。此协议的成功的关键是在沸石，这使得亲GE- UTL到被拆卸和有组织，利用水解在酸以产生层状中间称为IPC-1P特定场所锗的位置。该中间体然后可以在两种不同的方式进行处理。在高温下IPC-1P材料直接重组联TOA沸石与IPC-4的结构，其拓扑是由国际沸石协会（IZA）给出的代码的PCR。然而，在IPC-1P可以不同地通过层之间的含硅种类物质的插层组织。我们称这种操作的IPC-2P的结果。此插和有组织的IPC-2P材料的高温处理导致称为IPC-2新沸石，其拓扑给出IZA代码OKO。所述OKO（IPC-2）和PCR（IPC-4）拓扑结构之间的区别在于，IPC-2包含UTL之间二氧化硅亚基（单个四圈，S4R）样层而IPC-4具有无S4R单元。 沸石是由X射线衍射，N 2吸附和能量色散X射线分析使用扫描电子显微镜表征。

<table><tbody><tr><td>Sodium hydroxide</td><td>Fisher Chemical</td><td>S/4920/53</td><td>99%</td></tr><tr><td>1,4-dibromobutane</td><td>Aldrich</td><td>140805-500G</td><td>99%</td></tr><tr><td>(2R,6S)-2,6-dimethylpiperidine&amp;nbsp;</td><td>Aldrich</td><td>41470-100ML</td><td>&gt;99%</td></tr><tr><td>Paraffin oil</td><td>Fisher Chemical</td><td>P/0320/17</td><td></td></tr><tr><td>Chloroform</td><td>Fisher Chemical</td><td>C/4920/17</td><td>&gt;99%</td></tr><tr><td>Sodium sulfate (anhydrous)</td><td>Fisher Chemical</td><td>S/6600/60</td><td>&gt;99%</td></tr><tr><td>Diethyl ether</td><td>Sigma Aldrich</td><td>24002-2.5L</td><td>&gt;99.5%</td></tr><tr><td>Ambersep 900-OH</td><td>Acros Organics</td><td>301340025</td><td></td></tr><tr><td>Hydrochloric acid, 0.1 N</td><td>Fluka</td><td>318965-500ML</td><td></td></tr><tr><td>Phenolphthalein</td><td>Sigma Aldrich</td><td>105945-50G</td><td>ACS Reagent</td></tr><tr><td>Silver nitrate</td><td>Ames Goldsmith</td><td></td><td></td></tr><tr><td>Germanium dioxide</td><td>Alfa Aesar</td><td>11155</td><td>100.00%</td></tr><tr><td>fumed silica (Cab-o-sil M-5)</td><td>Acros Organics</td><td>403731500</td><td></td></tr></tbody></table>

synthesis of zeolites using the ador (assembly-disassembly-organization-reassembly) route

Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on their framework topology. For new applications or improvements to existing ones, new zeolites with novel pore systems are desirable. We demonstrate a method for the synthesis of novel zeolites using the ADOR route. ADOR is an acronym for Assembly, Disassembly, Organization and Reassembly. This synthetic route takes advantage of the assembly of a relatively poorly stable that which can be selectively disassembled into a layered material. The resulting layered intermediate can then be organized in different manners by careful chemical manipulation and then reassembled into zeolites with new topologies. By carefully controlling the organization step of the synthetic pathway, new zeolites with never before seen topologies are capable of being synthesized. The structures of these new zeolites are confirmed using powder X-ray diffraction and further characterized by nitrogen adsorption and scanning electron microscopy. This new synthetic pathway for zeolites demonstrates its capability to produce novel frameworks that have never been prepared by traditional zeolite synthesis techniques.

粉末X射线衍射图（ 图2）被收集用于生产的所有材料，包括中间层阶段的IPC-1P和IPC-2P。粉末X射线衍射是用于确定存在的沸石相的性质的主要技术。注意，IPC-1P和IPC-2P的晶体结构没有完全表征，为材料总有点无序。然而，每个粉末衍射图案可作为感兴趣的相位的"指纹"。寻找最重要的特征是在图案，这给对晶胞尺寸信息的峰值的位置。每个沸石（和中间体）的具有不同的单位单元尺寸等在每个收集的衍射图案的峰值位置是诊断该特定相的存在，并应与图2所示的参考图案的位置，在汉邦丘拉尔最强峰的位置是看的第一件事。如果该主峰的位置的位置相匹配的参考模式则还要查看是否其它峰也匹配。如果所使用的衍射仪完全一致，并保持那么这场比赛应该是比较好的。存在于样品的X射线衍射图案中不存在在图2的各个图案额外的峰表明，准备好的样品是不相纯的。中的衍射图案的峰的强度是不适合的相位识别程序重要的是，它们可以由于在仪器的不同样本和参考图案之间的不同，以便可以被忽略。在完成全面的结构研究时，得到原子的位置，这是没有必要在这项研究中的信息只强度变得重要。 而X射线衍射是主甲基结构分析，氮吸附等温线（ 图3）的外径，也可用于表征产物沸石。此实验方法首先要求存在于该通道的孔的任何分子（通常是水）通过加热样品，通常是在真空下除去。然后将样品冷却，一般到77 K和氮气的少量施用给系统，要么重量或体积测量用于确定多少氮气已吸附的样品。氮吸附量作图气体的压力，得到在图3所示的等温线，一个成功的合成将显示类似的形状的等温线，以在图1中的那些节目。在总吸附量将成为最大的最佳情况父UTL样品与用于IPC-2和最低量是低级用于IPC-4。这种匹配的孔隙尺寸的变化。由此数据，也可以得到使用BET方程式（ 表1）的表面区域11中元素分析是可以用来确定哪个锗已经从产物中除去的程度的另一种技术。任何适当的化学分析技术可被使用，但我们已经使用能量色散X射线分析（EDX）的扫描型电子显微镜，以确定父锗UTL沸石的组成和最终沸石的IPC-2和-4（ 表1）。 <img alt="图4" src="/files/ftp_upload/53463/53463fig1.jpg" /> 图 1. 拟议机制的原理，从父沸石UTL到最终沸石IPC-2父UTL的-4。D4R单元以红色突出显示。 <a href="https://www.jove.com/files/ftp_upload/53463/53463fig1large.jpg" target="_blank">P</a>租赁点击此处查看该图的放大版本。 <img alt="图4" src="/files/ftp_upload/53463/53463fig2.jpg" /> 图 2. 粉末父&#39;作为造"和煅烧UTL沸石（左）和中间体和最终沸石（右）的X射线衍射图案。的IPC-2P是与现有DEMDA嵌入层状IPC-1P的产物煅烧。 <a href="https://www.jove.com/files/ftp_upload/53463/53463fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图4" src="/files/ftp_upload/53463/53463fig3.jpg" /> 图 3。在77K记录UTL（黑）的氮吸附等温线，IPC-2（蓝色）和IPC-4（红色）。吸附等温线显示为未填充的形状和desorpti在等温线填充形状。这个数字是由亲切自然出版集团的许可基准4.转载<a href="https://www.jove.com/files/ftp_upload/53463/53463fig3large.jpg" target="_blank">请点击这里查看该图的放大版本。</a> <table><tbody><tr><td> 沸石 </td><td> 比表面积（米2 /克） </td><td> SI:比戈 </td></tr><tr><td> GE-UTL </td><td> 541.3±1.1 </td><td> 5.8 </td></tr><tr><td> IPC-2 </td><td> 334±1.0 </td><td> &gt; 500 </td></tr><tr><td> IPC-4 </td><td> 236±0.7 </td><td> 90 </td></tr></tbody></table> 表 1。孔隙度值和沸石的元素组成。

Watch this Scientific Journal Video about Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route at JoVE.com

Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route

一个由ADOR准备新沸石的协议（A ssembly-ðisassembly-Ørganization- - [R eassembly）合成路线介绍。

沸石使用ADOR（汇编拆卸组织-重组）路线的合成

Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on ...

synthesis-zeolites-using-ador-assembly-disassembly-organization

Research

JoVE Journal

Chemistry

Synthesis of Zeolites Using the ADOR (Assembly-Disassembly-Organization-Reassembly) Route

13.2K 次观看.  The University of St Andrews. 一个由ADOR准备新沸石的协议（A ssembly-ðisassembly-Ørganization- - [R eassembly）合成路线介绍。 

视频: Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 &#176;C in the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 &#176;C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control.
Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity.

A protocol for the diastereoselective one-pot preparation of cis-N-Ts-iodoaziridines is described. The generation of diiodomethyllithium, addition to N-Ts aldimines and cyclization of the amino gem-diiodide intermediate to iodoaziridines is demonstrated. Also included is a protocol to rapidly and quantitatively assess the most appropriate stationary phase for purification by chromatography.

合成和Iodoaziridines纯化涉及定量选择最优固定相的色谱

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. ...

科研

化学

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

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 and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

合成与盘状磷酸盐锆剥落获取胶体液晶

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 &#176;C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 &#176;C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 &#176;C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 &#176;C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

A protocol for high-temperature and high-pressure gas adsorption measurements on zeolite H-ZSM-5 using an adsorption measurement device based on a langatate crystal microbalance is presented. Prior to the adsorption measurements, the synthesis of zeolite H-ZSM-5 on the langatate crystal microbalance sensor by the steam-assisted crystallization (SAC) method is demonstrated.

基于一个Langatate体微天平的高温高压气体吸附在分子筛吸附器H-ZSM-5

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate ...

工程学

Nanostructured Ag-zeolite Composites as Luminescence-based Humidity Sensors

Small silver clusters confined inside zeolite matrices have recently emerged as a novel type of highly luminescent materials. Their emission has high external quantum efficiencies (EQE) and spans the whole visible spectrum. It has been recently reported that the UV excited luminescence of partially Li-exchanged sodium Linde type A zeolites [LTA(Na)] containing luminescent silver clusters can be controlled by adjusting the water content of the zeolite. These samples showed a dynamic change in their emission color from blue to green and yellow upon an increase of the hydration level of the zeolite, showing the great potential that these materials can have as luminescence-based humidity sensors at the macro and micro scale. Here, we describe the detailed procedure to fabricate a humidity sensor prototype using silver-exchanged zeolite composites. The sensor is produced by suspending the luminescent Ag-zeolites in an aqueous solution of polyethylenimine (PEI) to subsequently deposit a film of the material onto a quartz plate. The coated plate is subjected to several hydration/dehydration cycles to show the functionality of the sensing film.

A protocol for the synthesis of moisture-responsive luminescent Ag-zeolite composites is described in this report.

纳米银沸石复合材料作为基于发光的湿度传感器

Small silver clusters confined inside zeolite matrices have recently emerged as a novel type of highly luminescent materials. Their emission has high ...

Two-way Valorization of Blast Furnace Slag: Synthesis of Precipitated Calcium Carbonate and Zeolitic Heavy Metal Adsorbent

The aim of this work is to present a zero-waste process for storing CO2 in a stable and benign mineral form while producing zeolitic minerals with sufficient heavy metal adsorption capacity. To this end, blast furnace slag, a residue from iron-making, is utilized as the starting material. Calcium is selectively extracted from the slag by leaching with acetic acid (2 M CH3COOH) as the extraction agent. The filtered leachate is subsequently physico-chemically purified and then carbonated to form precipitated calcium carbonate (PCC) of high purity (&lt;2 wt% non-calcium impurities, according to ICP-MS analysis). Sodium hydroxide is added to neutralize the regenerated acetate. The morphological properties of the resulting calcitic PCC are tuned for its potential application as a filler in papermaking. In parallel, the residual solids from the extraction stage are subjected to hydrothermal conversion in a caustic solution (2 M NaOH) that leads to the predominant formation of a particular zeolitic mineral phase (detected by XRD), namely analcime (NaAlSi2O6&#8729;H2O). Based on its ability to adsorb Ni2+, as reported from batch adsorption experiments and ICP-OES analysis, this product can potentially be used in wastewater treatment or for environmental remediation applications.

A protocol for the parallel production of precipitated calcium carbonate and zeolitic material from blast furnace slag via mineral carbonation and alkaline hydrothermal conversion, respectively, is presented. The performance of the zeolitic material towards nickel adsorption is tested.

高炉矿渣的双向稳定物价:沉淀碳酸钙和沸石重金属吸附剂的合成

The aim of this work is to present a zero-waste process for storing CO2 in a stable and benign mineral form while producing zeolitic minerals with ...

High Temperature Fabrication of Nanostructured Yttria-Stabilized-Zirconia (YSZ) Scaffolds by In Situ Carbon Templating Xerogels

We demonstrate a method for the high temperature fabrication of porous, nanostructured yttria-stabilized-zirconia (YSZ, 8 mol% yttria - 92 mol% zirconia) scaffolds with tunable specific surface areas up to 80 m2&#183;g-1. An aqueous solution of a zirconium salt, yttrium salt, and glucose is mixed with propylene oxide (PO) to form a gel. The gel is dried under ambient conditions to form a xerogel. The xerogel is pressed into pellets and then sintered in an argon atmosphere. During sintering, a YSZ ceramic phase forms and the organic components decompose, leaving behind amorphous carbon. The carbon formed in situ serves as a hard template, preserving a high surface area YSZ nanomorphology at sintering temperature. The carbon is subsequently removed by oxidation in air at low temperature, resulting in a porous, nanostructured YSZ scaffold. The concentration of the carbon template and the final scaffold surface area can be systematically tuned by varying the glucose concentration in the gel synthesis. The carbon template concentration was quantified using thermogravimetric analysis (TGA), the surface area and pore size distribution was determined by physical adsorption measurements, and the morphology was characterized using scanning electron microscopy (SEM). Phase purity and crystallite size was determined using X-ray diffraction (XRD). This fabrication approach provides a novel, flexible platform for realizing unprecedented scaffold surface areas and nanomorphologies for ceramic-based electrochemical energy conversion applications, e.g. solid oxide fuel cell (SOFC) electrodes.

High Temperature Fabrication of Nanostructured Yttria-Stabilized-Zirconia YSZ Scaffolds by In Situ Carbon Templating Xerogels

A protocol for fabricating porous, nanostructured yttria-stabilized-zirconia (YSZ) scaffolds at temperatures between 1,000 &#176;C and 1,400 &#176;C is presented.

通过纳米氧化钇稳定的二氧化锆（YSZ）的支架的高温加工<em&gt;原位</em&gt;碳模板干凝胶

We demonstrate a method for the high temperature fabrication of porous, nanostructured yttria-stabilized-zirconia (YSZ, 8 mol% yttria - 92 mol% zirconia) ...

Resource Recycling of Red Soil to Synthesize Fe2O3/FAU-type Zeolite Composite Material for Heavy Metal Removal

Heavy metal-polluted water is of great concern to human health and the eco-environment. In situ water remediation techniques enabled by highly efficient adsorption materials are of great importance in these circumstances. Among all the materials used in water remediation, iron-based nanomaterials and porous materials are of great interest, benefiting from their rich redox reactivity and adsorption function. Here, we developed a facile protocol to directly convert the widely spread red soil in south China to fabricate the Fe2O3/faujasite (FAU)-type zeolite composite material. 
The detailed synthesis procedure and synthesis parameters, such as reaction temperature, reaction time, and the Si/Al ratio in the raw materials, have been carefully tuned. The as-synthesized composite materials show good adsorption capacity for typical heavy metal(loid) ions. With 0.001 g/mL Fe2O3/FAU-type zeolite composite material added to different heavy metal(loid)-polluted aqueous solutions (single type of heavy metal(loid) concentration: 1,000 mg/L [ppm]), the adsorption capacity was shown to be 172, 45, 170, 40, 429, 693, 94, and 133 mg/g for Cu (II), Cr (III), Cr (VI), As (III), Cd (II), Pb (II), Zn (II), and Ni (II) removal, respectively, which can be further expanded for heavy metal-polluted water and soil remediation.

Resource Recycling of Red Soil to Synthesize Fe2O3/FAU-type Zeolite Composite Material for Heavy Metal Removal

This article presents a novel and convenient route to synthesize Fe2O3/faujasite (FAU)-type zeolite composite material from red soil. The detailed synthesis parameters have been finely tuned. The obtained composite material can be used for efficient heavy metal-contaminated water remediation, indicating its potential applications in environmental engineering.

红壤资源化循环利用合成Fe2O3/FAU型重金属去除用分子筛复合材料

Heavy metal-polluted water is of great concern to human health and the eco-environment. In situ water remediation techniques enabled by highly efficient ...

环境科学

Organic Structure-directing Agent-free Synthesis for *BEA-type Zeolite Membrane

Membrane separation has drawn attention as a novel-energy saving separation process. Zeolite membranes have great potential for hydrocarbon separation in petroleum and petrochemical fields because of their high thermal, chemical, and mechanical strength. A *BEA-type zeolite is an interesting membrane material because of its large pore size and wide Si/Al range. This manuscript presents a protocol for *BEA membrane preparation by a secondary growth method that does not use an organic structure-directing agent (OSDA). The preparation protocol consists of four steps: pretreatment of support, seed preparation, dip-coating, and membrane crystallization. First, the *BEA seed crystal is prepared by conventional hydrothermal synthesis using OSDA. The synthesized seed crystal is loaded on the outer surface of a 3 cm long tubular &#945;-Al2O3 support by a dip-coating method. The loaded seed layer is prepared with the secondary growth method using a hydrothermal treatment at 393 K for 7 days without using OSDA. A *BEA membrane having very few defects is successfully obtained. The seed preparation and dip-coating steps strongly affect the membrane quality.

A *BEA seed crystal was loaded on a porous &#945;-Al2O3 support by the dip-coating method, and hydrothermally grown without using an organic structure-directing agent. A *BEA-type zeolite membrane having very few defects was successfully prepared by the secondary growth method.

有机结构定向无代理合成，用于_BEA型沸石膜

Membrane separation has drawn attention as a novel-energy saving separation process. Zeolite membranes have great potential for hydrocarbon separation in ...

三唑和四唑官能化 Zr-MOF 的合成和表征

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. Given their coordinative nature, the organic ligands and strut framework can be readily removed from the MOF and/or exchanged with other coordinative molecules. By introducing target ligands to MOF-containing solutions, functionalized MOFs can be obtained with new chemical tags via a process called post-synthetic ligand exchange (PSE). PSE is a straightforward and practical approach that enables the preparation of a wide range of MOFs with new chemical tags via a solid-solution equilibrium process. Furthermore, PSE can be performed at room temperature, allowing the incorporation of thermally unstable ligands into MOFs. In this work, we demonstrate the practicality of PSE by using heterocyclic triazole- and tetrazole-containing ligands to functionalize a Zr-based MOF (UiO-66; UiO = University of Oslo). After digestion, the functionalized MOFs are characterized via various techniques, including powder X-ray diffraction and nuclear magnetic resonance spectroscopy.

作者聚焦：金属有机框架功能化：合成后配体交换的进步、挑战和力量 

Post-synthetic ligand exchange (PSE) is a versatile and powerful tool for installing functional groups into metal-organic frameworks (MOFs). Exposing MOFs to solutions containing triazole- and tetrazole-functionalized ligands can incorporate these heterocyclic moieties into Zr-MOFs through PSE processes.

通过合成后配体交换合成三唑和四唑功能化Zr基金属有机骨架

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. ...