Name: surface functionalization of metal-organic frameworks for improved moisture resistance
Uploaded: 2018-09-05T15:30:00
Description: Watch this Scientific Journal Video about Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance at JoVE.com

这项工作得到欧盟 (紧急救济 Stg 化学-财政司司长-MOF 445 714122)、西班牙 MINECO (杰出 MDM-2015-0538 单位) 和加泰罗尼亚自治区 Valenciana 447 (赠款 GV/2016/137) 的支持。沙菲·萨米湾还有。感谢西班牙 448 MINECO 为拉蒙 y Cajal 奖学金和外国证券投资基金 449 (CTQ2014-59209-P), 分别。N.M.P. 感谢军政府 450 P10-FQM-6050 的博士后奖学金。梅森·麦克法兰和 451 D.R.M. 还感谢西班牙政府452项目 MAT2015-70615-R 提供的ﬁnancial 支助和453菲德基金的支持。ICN2 由 CERCA 方案/加泰罗尼亚自治区加泰罗尼亚提供资金, 并得到西班牙经济、工业和竞争力部 Severo 奥乔亚方案的支持 (MINECO, 不批准。SEV-2013-0295)。

1。hdcat@HKUST 的合成工艺
注: 整个过程必须在手套箱内进行, 以避免接触周围的湿气。因此, 所有使用的试剂和溶剂必须是干燥和储存在手套盒。
<ol><li>带一个开放的4毫升玻璃瓶, 两个铲子和1毫升微到手套箱。</li>
	<li>将50毫克的 hdcat 转移到玻璃瓶中。 注: 在某些情况下, 为了避免静电的不良影响, 可能需要防静电枪。</li>
	<li>在含有 hdcat 的玻璃瓶中放置1毫升无水氯仿。 ?...

<ol>
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本文所报道的方法为在温和条件下与合成儿茶酚类化合物直接反应的 MOF 晶体表面改性提供了一种简单有效的方法, 无论链的功能如何。与传统的生产 polydopamine 涂层的方法不同, 这条路线可以在无水和无氧条件下进行, 而且没有任何可能危及 MOF 稳定性的基础加法。甲醇和氯仿最初选择的基础上的工作14,20和由于在这些溶剂中的邻苯二酚分子的高溶解度。...

金属-有机框架是由无机金属部件 (通常称为二级建筑单元) 建立的一类晶体多孔材料, 由一类有机配体通过协调键 s 总线在一起。这些 s 总线的自组装与有机连接器, 使3D 多孔结构的形成与非常高的表面区域和有希望的应用在气体存贮和分离领域1,2, 催化和传感3。然而, 其适用性的主要限制因素是它们在水中的稳定性较差4,5, 因为它们中的大多数结合了价金属在其结构中产生的不稳定的协调键, 如在古典材料如 MOF-56或科大7。
解决这一问题的常用方法一方面是通过使用高电荷金属 (如锆或 Ti (IV))、基本的n-捐助者配体7、8或配以酸的结合物来建立更强的协调键。和基本网站9。但是, 这种方法仅限于新材料, 不允许提高 MOFs 的稳定性。另一方面, 提高已经已知材料的稳定性的方法使用后综合修改方法在空空间引入疏水性基团, 通过对链接器10,11 的后综合修改.或化学气相沉积 (CVD)12。不幸的是, 这些方法的稳定性是以大幅度减少材料的孔隙度和使用尖端仪器为代价的。最近使用的改性膦酸, 如 12-dioleoyl 锡-磷脂酰3磷酸 (多巴)13或n-octadecylphosphonic 酸 (中)14, 以传授憎水性的已知锆 (IV) MOFs 也应强调。
邻苯二酚类化合物, 如多巴胺, 已广泛用于 functionalize 广泛的材料, 通过形成 polydopamine15。然而, 这些涂层的形成仅限于使用含水缓冲溶液的微基本溶液, 不适合 MOFs 与不稳定的债券。Bortoluzzi等人最近报告说, polydopamine 可以在溶液中产生的双核酞铜 (II) 复合物, 以铜2(µ O) 为催化16中心, 它显示 catecholase 样的催化活动, 令人联想到自然酶, 如邻苯二酚氧化酶17和酪氨酸酶18。最近, 我们已经展示了如何一个基于铜 (II) 桨轮 s 总线连接通过 trimesate 连接器, 称为科大, 可以防止水解降解的功能性儿茶酚类化合物聚合, 如 4-hepatdecyl-邻苯二酚 (hdcat)或 fluorinated-4-undecylcatechol (fdcat), 在水晶的表面19。这种简单的方法证明了如何在温和的条件下合成有效的功能涂层, 而不管邻苯二酚的功能如何, 如果不使用缓冲液来破坏框架的稳定性, 由于仿生铜 (II) 单位的催化活性。我们认为, 这种新方法可以使功能涂层的形成, 除了防止水解降解, 可能会使选择性吸附的手性分子或挥发性有机化合物。

<table border="0" cellpadding="0" cellspacing="0" style="width:572px;" width="573">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Basolite C-300</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td align="right" style="width:119px;">688614</td>
			<td style="width:167px;">Commercial HKUST</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Anhydrous Methanol (99.8%)</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td align="right">322415</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Anhydrous Chloroform (&#62;99%)</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td align="right">288306</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Mettler Toledo TGA/SDTA 851</td>
			<td style="width:71px;">Mettler Toledo</td>
			<td style="width:119px;"></td>
			<td>Thermogravimetric Analyser</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Agilent Cary 630 FTIR</td>
			<td style="width:71px;">Agilent</td>
			<td style="width:119px;"></td>
			<td>FT-IR Spectrophotometer, ATR Module</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">PANalytical X&#8217;Pert Pro</td>
			<td style="width:71px;">PANalytical</td>
			<td style="width:119px;"></td>
			<td>Powder XRD Diffractometer</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">AUTOSORB-6 apparatus</td>
			<td style="width:71px;">Quantachrome</td>
			<td style="width:119px;"></td>
			<td>Nitrogen Isotherms were carried out with this equipment. Activation of the samples was carried out under dynamic vacuum at 170 &#176;C. Performed by the technical service of Universitat d&#39;Alacant.</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">K-Alpha X-ray photoelectron spectrometer system</td>
			<td style="width:71px;">Thermo-Scientific</td>
			<td style="width:119px;"></td>
			<td>Analysis were performed at the X-Ray unit of the Universitat d&#39;Alacant</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">FEI Quanta 650 FEG scanning electron microscope</td>
			<td style="width:71px;">Fisher Scientific</td>
			<td style="width:119px;"></td>
			<td>Used to observe partcle morphologies and dimensions</td>
		</tr>
	</tbody>
</table>

surface functionalization of metal-organic frameworks for improved moisture resistance

金属-有机框架 (MOFs) 是一类多孔无机材料, 具有良好的储气、分离、催化和传感性能。然而, 限制其适用性的主要问题是它们在潮湿条件下的稳定性较差。解决这一问题的常用方法是通过使用高电荷金属来形成坚固的金属连接器键, 这仅限于一些结构, 通过合成后的修改 (PSM) 将 alkylic 群引入到框架中, 或化学气相沉积 (CVD) 增强了整个骨架的疏水性。最后两个通常会激起物质的孔隙度的急剧减少。这些战略不允许利用已经存在的 MOF 的属性, 而且必须找到新的方法来提高水中 MOFs 的稳定性, 同时保持其性能完好无损。在这里, 我们报告了一种新的方法, 以提高 MOF 晶体的水稳定性, 其中铜2(O2C)4桨轮单位, 如科大 (科大代表香港科学 & 科技大学), 与儿茶酚类化合物具有烷基和氟烷基链功能。通过利用铜 II. 离子的非饱和金属点和催化 catecholase 活性, 我们能够通过氧化和随后聚合的邻苯二酚单元的表面, 形成鲁棒疏水性涂层。晶体在无氧和无水条件下不破坏框架的底层结构。这种方法不仅提供了改善水稳定性的材料, 而且还对保护涂层的功能进行了控制, 从而能够开发出用于吸附和分离挥发性有机化合物的功能涂层。.我们相信, 这种方法也可以扩展到其他不稳定的 MOFs 的开放金属网站。

所有的试剂和材料都储存在手套箱中, 并作为收到没有任何进一步的净化, 除非另有说明。整个过程是在一个手套箱中进行, 以避免接触湿气, 可能会降低未涂布的材料。
为了确保实验的重现性, 在商业上可用的科大的平均粒度接近40-50 µm (图 1), 作为以前的研究表明, 粒子是重要的可重现表面密度功能化<sup...

Watch this Scientific Journal Video about Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance at JoVE.com

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

在厌氧条件下, 以科大为原料, 采用合成儿茶酚类化合物的材料直接反应, 对邻苯二酚具有良好的功能。整个晶体周围的均匀涂层的形成归因于铜 (II) 脂肪酸在晶体外表面的仿生催化活性。

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

Preparation of the Metal&#45;Organic Framework &#40;MOF&#41; Sample for Nitrogen Porosimetry

Preparation of the Metal-Organic Framework (MOF) Sample for Nitrogen Porosimetry (Video) | JoVE 

用于氮气孔隙法的金属有机框架（MOF）样品的制备