Name: electrophoretic crystallization of ultrathin high-performance metal-organic framework membranes
Uploaded: 2018-08-16T15:00:00
Description: Watch this Scientific Journal Video about Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes at JoVE.com

我们承认我们的家庭机构, 高等理工 Fédérale 洛桑 (EPFL), 为其慷慨的支持。该项目已从欧洲联盟2020《玛丽居里夫人-居里赠款协定》665667号下的研究和创新项目中获得资金。作者感谢帕斯卡亚历山大 Schouwink 为他的帮助与 XRD。

注意事项: 仔细阅读有关化学品的材料安全数据表 (MSDS)。实验中使用的一些化学物质是有毒的。本方法涉及纳米粒子的合成。因此, 采取适当的预防措施。整个合成过程必须在通风良好的油烟机中进行。
注:表 1列出了 MOF 薄膜合成中所涉及的仪器、化学品和材料的详细情况。
1. 制备金属盐溶液和前体溶胶的连接器溶液
注: ?...

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对于现有方法15的颁布方法的突出特点是, 颁布方法能够在广泛的多孔和型无孔基板上合成高共生矿、超薄的 MOF 薄膜。避免了任何衬底预处理, 使得这种方法对 MOF 薄膜的合成非常简单。虽然环保署的设备必须用于沉积核膜, 设备是由一个电源, 金属电极和烧杯, 这是相当简单和容易接近。我们认为, 这种简便的制定方法可以扩展到广泛的晶体薄膜的合成。
制?...

薄分子筛膜为分子分离提供了高能效, 可降低燃料的总成本, 共2捕获、净水、溶剂回收等1、2。MOFs 是一种有希望的材料, 用于合成分子筛膜, 因为它涉及 isoreticular 合成化学和相对直接的结晶3。迄今为止, 包括 ZIF-4、-7、-8、-9、-11、-67、90、93、UiO-66、HKUST-1 和 MIL-53 在内的各种晶体结构的 MOF 膜已报告4、5。这些膜是通过结晶高品质的多晶 MOF 薄膜上的一个孔的支持合成。通常, 为了获得较高的分离选择性, 有必要减少多晶 MOF 薄膜 (如针孔和晶界缺陷) 的缺陷。一种减少缺陷的简便方法是将厚膜结晶。毫不奇怪, 早些时候报告的 MOF 膜的一些是非常厚的 (超过5µm)。不幸的是, 厚膜导致一个长扩散路径, 这限制了膜渗透。因此, 在提高选择性的同时, 也牺牲了渗透。为了规避这种权衡, 必须开发方法来结晶超薄 (< 0.5 µm 厚), 无缺陷的 MOF 薄膜。
ZIF-8 是最密集的研究 MOF 为膜合成, 由于其特殊的化学和热稳定性和简单的结晶化学6,7。到目前为止, 所报道的超薄 ZIF-8 膜是通过改变底层多孔基底的表面化学或拓扑来实现的, 有利于 ZIF-8 的异质核, 这对于共生矿多晶硅薄膜是必不可少的。例如, 陈等。报道了1µm 厚 ZIF-8 膜的合成 (3-氨基丙基) triethoxysilane 改性2涂层聚偏氟乙烯 (PVDF) 中空纤维8。他们观察了高异质核密度并且归因于它对表面化学和纳米结构的同时修改。Peinemann 集团报告了一种金属螯合, polythiosemicarbazide (PTSC) 支持9的超薄 ZIF-8 膜。这种独特的金属螯合能力 PTSC 导致了锌离子的结合, 促进了 ZIF-8 的异质核, 进而导致高性能 ZIF-8 膜。一般而言, 调整基体化学和纳米结构有利于合成高性能 MOF 膜;然而, 这些方法相当复杂, 通常无法重新应用于从其他有吸引力的 mof 结构中合成 MOF 膜。
在这里, 我们报告的合成超薄, 高共生矿 ZIF-8 薄膜使用一个简单和多才多艺的结晶方法, 可以重新应用, 形成一个薄薄的共生矿薄膜的几个水晶材料10。我们展示了 ZIF-8 和 ZIF-7 膜的例子, 没有任何基体预处理, 这大大简化了制备过程。ZIF-8 薄膜是在广泛的基体 (陶瓷, 聚合物, 金属, 碳和石墨烯) 上制备的。500纳米厚的阳极氧化铝 (氧化铝) 的 ZIF-8 膜显示出具有吸引力的分离性能。高 H2 磁导 8.3 x 10-6摩尔 m-2 s-1 Pa-1和诱人的理想选择性 7.3 (h2/CO2), 15.5 (h 2/N2), 16.2 (h2/CH4), 和 2655 (h2/C3小时8) 实现。
实现上述壮举的结晶方法已经颁布。将 ZIF-8 原子核直接从晶体的前体溶胶沉积到基体上。该方法利用环保署的时间非常短 (1-4 分钟) 后的感应时间 (原子核出现在前体溶胶)。电场在带电的 MOF 原子核中的应用驱使它们朝着一个与外加电场强度成正比的电极, 胶体 (μ) 的电泳流动性, 以及浓度原子核 (Cn), 如等式1和2所示。
<img alt="Equation 1" src="/files/ftp_upload/58301/58301eq1.jpg"> (等式 1)
<img alt="Equation 2" src="/files/ftp_upload/58301/58301eq2.jpg"> (等式 2)
这里 v = 漂移速度, ζ原子核的泽塔电位, 真空 的介电常数, r = 介电常数和 η = 前体溶胶的粘度。
因此, 通过控制E和溶液 pH 值 (确定ζ), 可以控制原子核的填料密度。随后在前体溶胶中密集堆积的原子核的生长使得研究人员能够获得高共生矿的多晶薄膜。

<table>
	<tbody>
		<tr>
			<td>Zinc nitrate hexahydrate</td>
			<td>Sigma-Aldrich</td>
			<td>96482-500G</td>
			<td>98% purity</td>
		</tr>
		<tr>
			<td>2-Methylimidazole</td>
			<td>Sigma-Aldrich</td>
			<td>M50850-500G</td>
			<td>99% purity</td>
		</tr>
		<tr>
			<td>Benzimidazole</td>
			<td>TCI</td>
			<td>B0054-500G</td>
			<td>98% purity</td>
		</tr>
		<tr>
			<td>Tape</td>
			<td>DuPont</td>
			<td>KPT-1/8</td>
			<td></td>
		</tr>
		<tr>
			<td>Epoxy</td>
			<td>GC Electronics</td>
			<td>19-823</td>
			<td></td>
		</tr>
		<tr>
			<td>Copper foil</td>
			<td>Alfa Aesar</td>
			<td>13380.CV</td>
			<td>99.9% purity</td>
		</tr>
		<tr>
			<td>Power source for EPD</td>
			<td>Gamry Instruments</td>
			<td>Interface 1000E Potentiostat</td>
			<td></td>
		</tr>
		<tr>
			<td>Ultrasonic cleaner</td>
			<td>MTI corporation</td>
			<td>VGT-1860QTD</td>
			<td></td>
		</tr>
		<tr>
			<td>AAO</td>
			<td>GE Healthcare Life Sciences&#8206;</td>
			<td>6809-7013</td>
			<td></td>
		</tr>
		<tr>
			<td>PAN</td>
			<td>Shandong MegaVision</td>
			<td></td>
			<td>The molecular weight cut-off is 100 kDa</td>
		</tr>
	</tbody>
</table>

electrophoretic crystallization of ultrathin high-performance metal-organic framework membranes

我们报告的合成薄, 高共生矿, 多晶金属-有机框架 (MOF) 膜上广泛的未经修改的孔隙和非孔隙的支持 (聚合物, 陶瓷, 金属, 碳和石墨烯)。我们开发了一种新的结晶技术, 它被称为制定的方法: 电泳核组装为结晶的高共生矿薄膜 (颁布)。这种方法允许通过电泳沉积 (环保署) 直接从前体溶胶的 MOFs 在选择的基体上的异质核的高密度。包装良好的 mof 原子核的生长导致了一个高度共生矿的多晶 mof 薄膜。我们表明, 这种简单的方法可以用于合成薄, 共生矿沸石咪唑框架 (ZIF)-7 和 ZIF-8 薄膜。由此产生的 500 nm 厚的 ZIF-8 膜显示一个相当高的 H2渗透 (8.3 x 10-6摩尔 m-2 s-1 Pa-1) 和理想气体选择性 (7.3 为 h2/CO2, 15.5 为 h2/N2,16.2 为 h2/CH4, 2655 为 h2/C3H8)。c3h6/C3h8分离的一个吸引人的性能也实现了 (c3h6的磁导 9.9 x 10 摩尔 m-8 s-2 Pa-1和 C-1h6/C3H8理想选择性31.6 在25°c)。总体而言, 由于其简单性, 制定过程可以推广到合成共生矿薄膜的多种纳米孔晶体材料。

一个自制的环保署的设置被用来合成 MOF 电影 (图 1)。扫描电镜 (SEM) 图像和 X 射线衍射 (XRD) 模式收集的 ZIF-8 核膜 (图 2)。扫描电镜用于对氧化铝支架、ZIF-8/AAO 膜、PAN 支撑、ZIF-8/PAN 膜、ZIF-8/graphene 膜、ZIF-7/AAO 膜的表面和断面形貌进行图像处理 (图 3)。在温度控制的膜模块中测量了 ZIF-8 膜的气体磁导 (<strong...

Watch this Scientific Journal Video about Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes at JoVE.com

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

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