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微米的滤纸真空过滤回收Cu-BTC中结晶。漂洗所得晶体，用二氯甲烷，最终将所述晶体在二氯甲烷中的新鲜溶液。 </li><li>更换溶剂，每24小时，用新鲜的二氯甲烷未来三天更换，协助从铜的毛孔去除溶剂挥发少的BTC。 </li><li>加热所述的Cu-BTC晶体至170℃的真空烘箱中或通过在Schlenk线，以从材料中除去任何残留的客体分子。全面启动Cu-BTC中应该是深蓝色到紫色的。 </li><li>确认分别通过粉末X-射线衍射和傅里叶变换红外光谱仪，其结构和化学组成的Cu-BTC的。 </li></ol> 2。氟烷烃在Cu-BTC 14的等离子体增强化学气相沉积<ol><li>每次实验前清洁等离子体反应器，也可以用在与空气等离子体在50瓦的等离子体处理至少30分钟任何玻璃器皿。这消除了可能的反应室或从先前实验的玻璃器皿的内表面上形成的任何全氟烷膜。 </li><li>把激活的Cu-BTC的已知量在250ml的Pyrex瓶中并扩散到整个瓶子在其侧面，以确保均匀的治疗。一种透明的布料应放在周围的颈瓶用橡皮筋，尽量减少样品是在施加真空损失的金额。 </li><li>将瓶子在等离子体腔室中。施加真空，直到室中达到的压力≤0.20毫巴至少30分钟，以除去可能已被吸附到样品上的任何水。 </li><li>接的全氟烷气体，并调整调节器的质量流量控制器的规格范围内的压力。 </li><li>调节质量流量控制器来填充该反应室与全氟烷气体的适当的量，以保持在实验的所需的压力。旋转的PECVD装置内的瓶创造一个更均匀的处理的粉末。 </li><li>用13.56 MHz射频发生器，并调整射频与LC匹配单元，以最大限度地提高功率，同时减少反射光的等离子体。整个治疗周期重新调整。 </li><li>一旦治疗不彻底，疏散任何室残留的全氟烷烃气体，然后放空至大气压。从PECVD装置中取出样品，并从瓶的两侧回收处理后的材料。抗静电设备应该被用来恢复材料的最大数据量。 </li><li>将处理后的材料在烘箱中于120℃以除去任何未反应的全氟烷烃气体。然后将处理后的材料在干燥器中，以防止吸附的水从大气中。 </li><li>冲洗残留在瓶中的残留物质，过滤，回收废物进行妥善处置。 </li><li>表征处理过的Cu-BTC与20女性魔角旋转核磁共振，傅里叶变换红外光谱和X-射线光电子能谱。 </li></ol> 3。 Cu-BTC中的下潮湿的环境下老化<ol><li>设定所需的温度和环境室的相对湿度，并允许它达到平衡。 </li><li>散布出样品的均匀一个开放的容器和地方​​的环境室中进行所需的时间量。 </li><li>用X-射线衍射和氮气吸附等温线特征的Cu-BTC中的样品在77 K来确定降解程度。 </li></ol> 4。氨Microbreakthrough实验2 <ol><li>先注入一个空的镇流器配210 ml的净氨准备氨的14.6 L镇流器在5000毫克/米3。然后填写镇流器零空气的15 psi的压力。连接所述镇流器与microbreakthrough装置线。 </li><li>运行管坯在microbreakthrough装置来确定供电信号。设置质量流量控制器为氨和干空气以8和12ml /分，分别创建毫升/分钟的20 2000毫克/米3的氨流量。运行一个程序的方法来控制气相色谱仪和光离子检测器，以确定在流出物中的氨的供给信号。湿气可以被添加到系统如果需要的话，通过一个温度控制的饱和器单元在必要的速率运行的稀释剂流的一部分，以达到所要求的相对湿度。 </li><li>将少量的在下面的标称内径4毫米的玻璃管中的玻璃料的玻璃棉。重约10-15毫克的材料进入管。所使用的质量应导致大约55 立方毫米的吸附剂量，导致约0.15秒的床的停留时间。 </li><li>通过玻璃管流动的干燥空气，因为它被加热到150℃保持1小时以除去任何吸附的水。再生后称取试样。 </li><li>将样品放置在线路和固定直立在水浴设定为25℃。 </li><li>设置质量流量控制器为氨和干空气以8和12ml /分，分别形成20毫升/分钟，在2000毫克/米3的氨流量而绕过样品的填充线与进料气体。 </li><li>通过样品流中的氨流和运行一个程序性的方法来控制气相色谱仪和光离子检测器来监测流出物中的氨的浓度。 </li><li>一旦排放浓度达到进料浓度，关掉氨流和样品允许截断气体是没有强烈地吸附到样品的任何氨。 </li><li>通过X-射线衍射和傅立叶变换红外分析从水浴接触后分析取出样品。 </li><li>集成的气相色谱仪的信号随时间变化的数据，以确定氨装载的样品。 </li></ol>

<ol>
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作者宣称，他们有没有竞争的财务权益。

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

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。

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 ...

preparation-hydrophobic-metal-organic-frameworks-via-plasma-enhanced

Research

JoVE Journal

Chemistry

15.4K 次观看.  Science Applications International Corporation (SAIC). 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。 

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

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 ...

科研

化学

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at &#60;60 &#176;C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

We present the synthesis of the organic-based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x, x~2) via low temperature chemical vapor deposition (CVD). This optimized recipe yields an increase in Curie temperature from 400 K to over 600 K and a dramatic improvement in magnetic resonance properties.

化学气相沉积的有机磁体，钒四氰

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in ...

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

对磷酸增强富集制备高度多孔配位聚合物涂层的孔聚合物石柱的

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

化学溶液沉积在硅外延大孔石英薄膜的制备

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

锗通过原子层沉积钙钛矿型钛酸锶的外延生长

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

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

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, their high cost production and/or incompatibility with microfabrication technologies, due to the use of pre-deposited catalyst-seeds and/or high processing temperatures exceeding 900 &#176;C, represent a drawback for a widespread use of these methods. Here, however, we report the synthesis of ZnO rods via a non-catalyzed vapor-solid mechanism enabled by using an aerosol-assisted chemical vapor deposition (CVD) method at 400 &#176;C with zinc chloride (ZnCl2) as the precursor and ethanol as the carrier solvent. This method provides both single-step formation of ZnO rods and the possibility of their direct integration with various substrate types, including silicon, silicon-based micromachined platforms, quartz, or high heat resistant polymers. This potentially facilitates the use of this method at a large-scale, due to its compatibility with state-of-the-art microfabrication processes for device manufacture. This report also describes the properties of these structures (e.g., morphology, crystalline phase, optical band gap, chemical composition, electrical resistance) and validates its gas sensing functionality towards carbon monoxide.

Columnar zinc oxide structures in the form of rods are synthesized via aerosol-assisted chemical vapor deposition without the use of pre-deposited catalyst-seed particles. This method is scalable and compatible with various substrates based on either silicon, quartz or polymers.

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

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.

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

摘要

探索更多视频

此视频中的章节

功能化的合成与表征金属 - 有机骨架

化学气相沉积的有机磁体，钒四氰

对磷酸增强富集制备高度多孔配位聚合物涂层的孔聚合物石柱的

化学溶液沉积在硅外延大孔石英薄膜的制备

锗通过原子层沉积钙钛矿型钛酸锶的外延生长

金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

金属-有机框架的表面功能化改善防潮性能

使用气性金属-有机框架（MoF）开发异构异构选择性催化剂

单晶核壳金属有机骨架的合成

对金属有机骨架进行光谱测量的技术指南

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

摘要

探索更多视频

此视频中的章节

功能化的合成与表征金属 - 有机骨架

化学气相沉积的有机磁体，钒四氰

对磷酸增强富集制备高度多孔配位聚合物涂层的孔聚合物石柱的

化学溶液沉积在硅外延大孔石英薄膜的制备

锗通过原子层沉积钙钛矿型钛酸锶的外延生长

金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

金属-有机框架的表面功能化改善防潮性能

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

单晶核壳金属有机骨架的合成

对金属有机骨架进行光谱测量的技术指南

使用气性金属-有机框架（MoF）开发异构异构选择性催化剂