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。 注意: 并不是所有的 hdcat 都可以完全溶解在室温下, 但是当瓶子放在烤箱里的下一个步骤时, 它会很快溶解。</li>
	<li>在含 hdcat 的氯仿溶液中放置10毫克科大, 并将药瓶密封紧。</li>
	<li>把药瓶从手套箱里拿出来, 油脂实验在氯仿中悬浮, hdcat 几秒钟, 融汇溶液。 注: 不要将瓶子的内容暴露在周围空气中, 因为在反应介质中引入 O2可以推动邻苯二酚单元在溶液中的聚合, 而不是在晶体表面15。</li>
	<li>把瓶子放在烤箱里, 在70摄氏度的地方过夜。确保小瓶紧密密封, 以避免在反应期间的氯仿蒸发 (沸点 (CHCl3) = 61.2 °c)。 注意: 在某些情况下, 围绕螺钉盖的聚四氟乙烯带可能会有帮助。该协议要求预热烤箱在摄氏70摄氏度。温度不应高于摄氏70摄氏度, 否则非晶态产物即可获得。</li>
</ol>2。hdcat@HKUST 洗涤程序
<ol><li>在70摄氏度过夜后, 将瓶子取出烤箱, 并将其转移到手套盒, 连同15毫升离心管。</li>
	<li>用新鲜无水氯仿将瓶子的内容转移到手套箱内的离心管内。</li>
	<li>用离心 (3354 x g, 1 分钟) 将涂层材料 hdcat@HKUST。要确保离心管的密封紧密, 因为必须从手套箱取出, 以便离心材料。</li>
	<li>离心后在手套箱内快速引入离心管。</li>
	<li>使用吸管仔细提取上清, 并将其存放在干净的40毫升玻璃瓶中。</li>
	<li>将涂层材料悬浮在3毫升无水 CHCl3中, 以去除不附着在晶体表面的可能聚合的邻苯二酚单元。</li>
	<li>重复步骤 2.3-2.6 三次。</li>
	<li>将涂层材料悬浮在3毫升无水甲醇中。</li>
	<li>重复步骤 2.3-2.6 三次, 但使用无水甲醇, 以消除反应 hdcat 分子。 注: 不要扔掉 hdcat 解决方案, 因为该产品可以通过缓慢蒸发的解决方案在手套箱中回收和重用。</li>
	<li>用无水甲醇将洗涤过的 hdcat@HKUST 转移到玻璃瓶里, 等到涂层固体沉淀到瓶子的底部。</li>
	<li>取出上清液, 让粉末在室温下在手套盒中晾干。</li>
</ol>3。fdcat@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>介绍一个开放的4毫升玻璃瓶, 两个铲子和1毫升微到手套盒。</li>
	<li>在玻璃瓶内放置50毫克的 fdcat。 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 fdcat 的玻璃瓶中放置1毫升无水氯仿。 注: 并非所有的 fdcat 都可以完全溶解在室温下, 但当瓶子放在烤箱中的下一步时, 它会很快溶解。</li>
	<li>在含 fdcat 的氯仿溶液中放置10毫克科大, 并将药瓶密封紧。</li>
	<li>把药瓶从手套箱里拿出来, 油脂实验在氯仿中悬浮, fdcat 几秒钟, 融汇溶液。 注: 在任何情况下, 不要将瓶子的内容暴露在周围空气中, 因为在反应介质中引入 O2可以推动邻苯二酚单元在溶液中的聚合, 而不是在晶体15表面。</li>
	<li>把瓶子放在烤箱里, 在70摄氏度的地方过夜。确保小瓶紧密密封, 以避免在反应期间氯仿蒸发 (沸点 (CHCl3) = 61.2 °c)。 注意: 在某些情况下, 围绕螺钉盖的聚四氟乙烯带可能会有帮助。该协议要求预热烤箱在摄氏70摄氏度。温度不应高于摄氏70摄氏度, 否则非晶态产物即可获得。</li>
</ol>4. fdcat@HKUST 洗涤程序
<ol><li>在70摄氏度过夜后, 将瓶子取出烤箱, 并将其转移到手套盒, 连同15毫升离心管。</li>
	<li>用新鲜无水氯仿将瓶子的内容转移到手套箱内的离心管内。</li>
	<li>用离心 (3354 x g, 1 分钟) 将涂层材料 fdcat@HKUST。要确保离心管的密封紧密, 因为必须从手套箱取出, 以便离心材料。</li>
	<li>离心后将离心管迅速引入手套箱。</li>
	<li>使用吸管仔细提取上清, 并将其存放在干净的40毫升玻璃瓶中。</li>
	<li>将涂层材料悬浮在3毫升无水 CHCl3中, 以去除不附着在晶体表面的可能聚合的邻苯二酚单元。</li>
	<li>重复步骤 4.3-4.6 三次。</li>
	<li>将涂层材料悬浮在3毫升无水甲醇中。</li>
	<li>重复步骤 4.3-4.6 三次, 但使用无水甲醇, 以消除反应 fdcat 分子。 注: 不要扔掉 fdcat 解决方案, 因为该产品可以通过缓慢蒸发的解决方案在手套箱中回收和重用。</li>
	<li>用无水甲醇将洗涤过的 fdcat@HKUST 转移到玻璃瓶里, 等到涂层固体沉淀到瓶子的底部。</li>
	<li>取出上清液, 让粉末在室温下在手套盒中晾干。</li>
</ol>

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作者没有什么可透露的。

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><tbody><tr><td>Basolite C-300</td><td>Sigma-Aldrich</td><td>688614</td><td>Commercial HKUST</td></tr><tr><td>Anhydrous Methanol (99.8%)</td><td>Sigma-Aldrich</td><td>322415</td><td></td></tr><tr><td>Anhydrous Chloroform (&gt;99%)</td><td>Sigma-Aldrich</td><td>288306</td><td></td></tr><tr><td>Mettler Toledo TGA/SDTA 851</td><td>Mettler Toledo</td><td></td><td>Thermogravimetric Analyser</td></tr><tr><td>Agilent Cary 630 FTIR</td><td>Agilent</td><td></td><td>FT-IR Spectrophotometer, ATR Module</td></tr><tr><td>PANalytical X&amp;rsquo;Pert Pro</td><td>PANalytical</td><td></td><td>Powder XRD Diffractometer</td></tr><tr><td>AUTOSORB-6 apparatus</td><td>Quantachrome</td><td></td><td>Nitrogen Isotherms were carried out with this equipment. Activation of the samples was carried out under dynamic vacuum at 170 &amp;deg;C. Performed by the technical service of Universitat d&#039;Alacant.</td></tr><tr><td>K-Alpha X-ray photoelectron spectrometer system</td><td>Thermo-Scientific</td><td></td><td>Analysis were performed at the X-Ray unit of the Universitat d&#039;Alacant</td></tr><tr><td>FEI Quanta 650 FEG scanning electron microscope</td><td>Fisher Scientific</td><td></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。

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. ...

surface-functionalization-metal-organic-frameworks-for-improved

Research

JoVE Journal

Chemistry

16.0K 次观看.  Universitat de València. 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。

视频: Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

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

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

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 ...

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 ...

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 ...

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

溶剂热合成 MIL-96 和 UiO-66-NH2在纤维垫上原子层沉积金属氧化物涂层上的合成

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

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

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

超薄高性能金属-有机骨架膜的电泳结晶

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...

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.

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 ...

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. ...

金属-有机框架的表面功能化改善防潮性能

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此视频中的章节

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

功能化的合成与表征金属 - 有机骨架

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

溶剂热合成 MIL-96 和 UiO-66-NH₂在纤维垫上原子层沉积金属氧化物涂层上的合成

超薄高性能金属-有机骨架膜的电泳结晶

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

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

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

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