Name: preparation of hydrophobic metal-organic frameworks via plasma enhanced chemical vapor deposition of perfluoroalkanes for the removal of ammonia
Uploaded: 2013-10-10T22:00:00
Description: Watch this Scientific Journal Video about Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia at JoVE.com

作者感谢美国国防威胁降低局根据项目编号BA07PRO104资金，马丁·史密斯，CORRINE石和国防科学与技术实验室（DSTL）的科林·威利斯其在低压等离子技术的专业知识，和马修Browe和韦斯利戈登，埃奇伍德化学生物中心（ECBC）为microbreakthrough测试和接触角测量分别。

1。 Cu-BTC中的合成与制备<ol><li>搅拌12.5毫升的去离子水并在100毫升12.5毫升二甲基甲酰胺螺旋盖瓶为约5分钟。 </li><li>加0.87克（3.6毫摩尔）铜（II）三水合物接着0.50克均苯三酸（2.4毫摩尔）在罐中的溶液，并搅拌约5分钟。该解决方案将颜色变成蓝色。放置在预热的烘箱中加帽的瓶子在120℃下进行约24小时。 </li><li>从烤箱中取出瓶子里。一旦瓶子冷却至室温后，通过使用额定收回晶体大于或等于2.5...

<ol>
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Mater. Chem. , (2013).</li><li>K&#252;sgens, P., 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=Characterization+of+metal-organic+frameworks+by+water+adsorption.">Characterization of metal-organic frameworks by water adsorption.</a> Microporous and Mesoporous Mater. 120, 325-330 (2009).</li><li>Cavka, J. H., 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=A+New+Zirconium+Inorganic+Building+Brick+Forming+Metal+Organic+Frameworks+with+Exceptional+Stability.">A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability.</a> J. Am. Chem. Soc. 130, 13850-13851 (2008).</li><li>DeCoste, J. B., 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=Stability+and+degradation+mechanisms+of+metal-organic+frameworks+containing+the+Zr6O4(OH)4+secary+building+unit.">Stability and degradation mechanisms of metal-organic frameworks containing the Zr6O4(OH)4 secary building unit.</a> J. Mater. Chem. A. 1, 5642-5650 (2013).</li><li>Yang, S. J., Park, C. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+Highly+Moisture-Resistant+Black-Colored+Metal+Organic+Frameworks.">Preparation of Highly Moisture-Resistant Black-Colored Metal Organic Frameworks.</a> Adv. Mater. 24, 4010-4013 (2012).</li><li>Li, H., 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=Enhanced+Hydrostability+in+Ni-Doped+MOF-5.">Enhanced Hydrostability in Ni-Doped MOF-5.</a> Inorg. Chem. 51, 9200-9207 (2012).</li><li>Jasuja, H., Huang, Y. -. g., Walton, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Adjusting+the+Stability+of+Metal+-+Organic+Frameworks+under+Humid+Conditions+by+Ligand+Functionalization.">Adjusting the Stability of Metal - Organic Frameworks under Humid Conditions by Ligand Functionalization.</a> Langmuir. 28, 16874-16880 (2012).</li><li>Jasuja, H., Burtch, N. C., Huang, Y. -. g., Cai, Y., Walton, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+Water+Stability+of+an+Isostructural+Family+of+Zinc-Based+Pillared+Metal+-+Organic+Frameworks.">Kinetic Water Stability of an Isostructural Family of Zinc-Based Pillared Metal - Organic Frameworks.</a> Langmuir. 29, 633-642 (2012).</li><li>Decoste, J. B., Peterson, G. W., Smith, M. W., Stone, C. A., Willis, C. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+Stability+of+Cu-BTC+MOF+via+Perfluorohexane+Plasma-Enhanced+Chemical+Vapor+Deposition.">Enhanced Stability of Cu-BTC MOF via Perfluorohexane Plasma-Enhanced Chemical Vapor Deposition.</a> J. Am. Chem. Soc. 134, 1486-1489 (2012).</li><li>Bradley, R. H., Smith, M. W., Andreu, A., Falco, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+studies+of+novel+hydrophobic+active+carbons.">Surface studies of novel hydrophobic active carbons.</a> Appl. Surf. Sci. 257, 2912-2919 (2011).</li><li>Poire, E., 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=Modification+of+active+carbon+by+hydrophobic+plasma+plymers.">Modification of active carbon by hydrophobic plasma plymers.</a> Plasma Deposition of Polymeric Thin Films. 54, 185-196 (1994).</li><li>Hozumi, A., Takai, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+ultra+water-repellent+films+by+microwave+plasma-enhanced+CVD.">Preparation of ultra water-repellent films by microwave plasma-enhanced CVD.</a> Thin Solid Films. 303 (97), 222-225 (1997).</li><li>Dolbier, W. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Guide to Fluorine NMR for Organic Chemists. , (2009).</li><li>Maricq, M. M., Waugh, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=NMR+IN+ROTATING+SOLIDS.">NMR IN ROTATING SOLIDS.</a> J. Chem. Phys. 70, 3300-3316 (1979).</li><li>Kim, M., Cahill, J. F., Su, Y., Prather, K. A., Cohen, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Postsynthetic+ligand+exchange+as+a+route+to+functionalization+of+'inert'+metal-organic+frameworks.">Postsynthetic ligand exchange as a route to functionalization of 'inert' metal-organic frameworks.</a> Chem. Sci. 3, 126-130 (2012).</li><li>d'Agostino, R., 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=.">.</a> Advanced Plasma Technology. , (2008).</li><li>DeCoste, J. B., 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=+The+effect+of+water+adsorption+on+the+structure+of+the+carboxylate+containing+metal-organic+frameworks+Cu-BTC,+Mg-MOF-74,+and+UiO-66."> The effect of water adsorption on the structure of the carboxylate containing metal-organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66.</a> J. Mater. Chem. A. , (2013).</li></ol>

Cu-BTC中的合成中，如在大多数MOFs材料，可以在很大程度上依赖于所用反应物的比例和合成进行的温度。改变在合成中使用的温度或溶剂已被证明能产生MOF结构20的不同的形态。因此它具有很强的重要性跟随阐述在文献中对于任何MOF所合成的过程。此外，应该在选择容器中进行的合成考虑了反应物，溶剂和合成条件。 MOFs材料尺寸范围可以从一种材料到下一个，但Cu-BTC中具有非常细的晶体?...

金属-有机骨架（MOFs）已成为有毒气体去除1-3多孔材料的领先级。 MOFs材料具有前所未有的能力来定制功能进行有针对性的化学作用。的Cu-BTC（也称为科-1或Cu 3（BTC）2）以前已经发现有异常高的氨负荷，但是，这是在该材料的结构稳定性4成本。在Cu-BTC进一步的研究表明，湿气本身是能够降解的MOF的结构，使之失效的许多潜在的应用5,6,21。含MOFs材料在水的液体或高湿度存在一定的羧酸盐的结构不稳定性一直是一个很大的威慑力在商业或工业应用7使用。 这将是最为理想的用于化学去除具有内在的稳定性湿度的存在MOFs材料。然而，许多莫FS具有超强的稳定性，如UIO-66，拥有化学去除能力较差，而许多MOFs材料与金属的开放等网站MOF-74和Cu-BTC中具有优越的耐化学去除能力2,4,8,9。在MOF-74和Cu-BTC的开口的金属部位提高有毒气体，如氨的吸收，但这些位点也容易结合水，中毒的活性位点，并在许多情况下导致结构损坏。为了保存的水财政部不稳定的化学性质，各种尝试，以提高MOFs材料的水稳定性而制定的。 MOF-5的已被证明具有增强的后热处理耐湿性，通过创建围绕MOF的碳质层，但是，增加的疏水性是在表面积为代价，并最终功能10。 MOF-5也已经显示出具有其水稳定性通过掺杂Ni 2 +的离子11增加。此外，1,4 - 二氮杂双环[2.2.2]辛烷包含ING MOFs材料（也称为DMOFs）已被用于通过各种侧基的1,4 -苯二羧酸连接器12,13掺入展现水稳定性的调整。 缺乏某些MOFs材料的水稳定性，特别那些具有高毒性气体吸收，导致全氟烷烃的使用等离子体增强化学气相沉积（PECVD）向MOF的表面上创建氟化基团，以增加其疏水性14。这种技术提供了独特的益处，它可用于改变包含芳香族氢，以及MOFs材料的内表面上的其它潜在的官能团的任何MOF。然而，该技术可以是难以控制由于高度反应性自由基的等离子体的形成。的基团，不仅与芳香族的氢原子发生反应，也可与CF 的X基团已经反应到MOF表面。小心控制的程序是必要的，以确保孔径BLOckage不会发生，渲染财政部无效的。这一技术已被用于其他改变碳材料的润湿性能，但是，就我们所知，它以前从未被用来提高微孔材料的水稳定性15,16。

<table border="1">
	<tbody>
		<tr>
			<td>Name of Material/ Equipment</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments/Description</td>
		</tr>
		<tr>
			<td>Copper (II) Nitrate Trihydrate</td>
			<td>Sigma-Aldrich</td>
			<td>61194</td>
			<td></td>
		</tr>
		<tr>
			<td>Trimesic acid</td>
			<td>Sigma-Aldrich</td>
			<td>482749</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Sigma-Aldrich</td>
			<td>130147</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethyl Formamide</td>
			<td>Sigma-Aldrich</td>
			<td>319937</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Sigma-Aldrich</td>
			<td>187332</td>
			<td></td>
		</tr>
		<tr>
			<td>Hexafluoroethane</td>
			<td>Synquest Labs</td>
			<td>1100-2-05</td>
			<td></td>
		</tr>
		<tr>
			<td>Femto-Plasma System</td>
			<td>Diener Electronic</td>
			<td>Basic unit type B</td>
			<td></td>
		</tr>
		<tr>
			<td>Plasma Generator</td>
			<td>Diener Electronic</td>
			<td>Type D</td>
			<td>0-100 W at 13.56 MHz</td>
		</tr>
		<tr>
			<td>Rotary Vane Pump for Plasma System</td>
			<td>Leybold</td>
			<td>D16BCS PFPE</td>
			<td>Appropriate for corrosive gases</td>
		</tr>
		<tr>
			<td>Powder Treatment Device</td>
			<td>Diener Electronic</td>
			<td>Option 5.9</td>
			<td>Glass bottle and rotating devise within plasma system</td>
		</tr>
		<tr>
			<td>Environmental Chamber</td>
			<td>Associated Environmental Systems</td>
			<td>HD-205</td>
			<td></td>
		</tr>
		<tr>
			<td>Gas Chromatograph</td>
			<td>Hewlet Packard</td>
			<td>HP5890 Series II</td>
			<td></td>
		</tr>
		<tr>
			<td>Photoionization Detector</td>
			<td>O-I Analytical</td>
			<td>4430/5890</td>
			<td></td>
		</tr>
		<tr>
			<td>Photoionization Detector Lamp</td>
			<td>Excilitis</td>
			<td>FK-794U</td>
			<td></td>
		</tr>
		<tr>
			<td>Water bath</td>
			<td>NESLAB</td>
			<td>RTE-111</td>
			<td></td>
		</tr>
		<tr>
			<td>Fritted glass tubes</td>
			<td>CDA Analytical</td>
			<td>MX062101</td>
			<td>Dynatherm sampling tubes</td>
		</tr>
	</tbody>
</table>

preparation of hydrophobic metal-organic frameworks via plasma enhanced chemical vapor deposition of perfluoroalkanes for the removal of ammonia

等离子体增强化学汽相全氟烷烃的沉积（PECVD）一直被研究用于调谐表面的润湿性能。对于高比表面积微孔材料，如金属 - 有机骨架（MOFs），独特的挑战提出自己的PECVD治疗。在此协议为财政部这是以前不稳定，在潮湿条件下的发展呈现。该协议描述的Cu-BTC（也称为科-1），Cu-BTC中的治疗用PECVD全氟烷烃的，潮湿的条件下材料的老化，并在微孔材料的毫克量的后续氨microbreakthrough实验的合成。 Cu-BTC中具有非常高的表面积（〜1800米2 / g）的比较时大多数材料或表面是先前已经通过PECVD方法治疗。如腔室压力和处理时间的参数是非常重要的，以确保全氟烷血浆渗入和反应s的内MOF表面。此外，可用于各种试验气体和微孔材料的协议，用于阐述在这里氨microbreakthrough实验。

<html>内的有代表性的结果，作者选择了要显示的Cu-BTC的4小时在0.30毫巴的压力，并具有处理过的50瓦金属有机骨架的等离子体功率处理用六氟乙烷（C 2 F 6），0.50克样品的特性在适当的条件下全氟离子应显示增强的疏水性。这可以通过将粉末上的液态水顶部和如果样品浮筒或测量接触角水对压片如图1中看到的确定来证明。对于Cu-BTC中和的C 2 F 6等离子处?...

Watch this Scientific Journal Video about Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia at JoVE.com

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

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

本文中的程序，在微孔材料，如金属 - 有机骨架，以提高它们的稳定性和疏水性的全氟烃的等离子体增强化学气相沉积进行了描述。此外，样品的毫克量的突破试验进行详细说明。

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

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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 ...

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Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

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Aerosol-assisted Chemical Vapor Deposition of Metal Oxide Structures: Zinc Oxide Rods

金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

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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)

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

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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. ...

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

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 ...

Synthesis of Low-Valent MOFs from Multitopic Phosphine Linkers

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

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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, ...

Magnetometric Characterization of Redox-Active MOFs Solid-State Electrochemistry

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

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks (Video) | JoVE 

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 ...