这项研究得到了科学和信息通信技术部资助的韩国国家研究基金会（NRF）（NRF-2022R1A2C1009706）的基础科学研究计划的支持。

制备MOF和配体所需的试剂列在 材料表中。
1. 建立合成后配体交换（PSE）过程
<ol><li>在真空下完全干燥预合成的UiO-66 MOF，以去除孔隙中任何未反应的金属盐和配体，以及残留的溶剂残留物过夜。 注：UiO-66 MOF的合成程序见 补充文件1 。</li>
	<li>制备功能化配体，H 2 BDC-三唑和H2BDC-四氮唑（制备过程见补充文件1;补充图1和补充图2用于表征）在隔离状态下并在真空下完全干燥过夜。</li>
	<li>通过将氢氧化钾溶解在去离子水中来制备4%氢氧化钾（KOH）水溶液。</li>
	<li>在带聚丙烯（PP）盖的20 mL闪烁瓶中进行PSE过程（参见 材料表）。</li>
	<li>测量H 2 BDC-三唑（23.3mg，0.1mmol）或H2BDC-四唑（23.4mg，0.1mmol）并放入闪烁瓶中。</li>
	<li>将H2BDC配体溶解在水溶液中。使用玻璃移液管将 1.0 mL 的 4% KOH 水溶液转移到含有 BDC-三唑或 BDC-四唑的闪烁瓶中。 注意：4%KOH水溶液是高度碱性的。避免任何形式的接触，并穿戴个人防护装备。</li>
	<li>超声处理混合物，直到所有固体完全溶解。</li>
	<li>将溶液中和至pH 7。使用玻璃移液管将1 M盐酸（HCl）水溶液搅拌转移到含有二羧酸的闪烁瓶中，直到达到pH 7。通过pH纸（及其颜色）或pH计测量pH值。 注意：在交换过程中保持pH值为7至关重要，因为MOF在碱性条件下（>pH 7）通常不稳定，并且BDC配体在酸性条件下（<pH 7）不溶。大约需要 1.5 mL 的 1 M HCl 水溶液来中和 BDC-三唑或含 BDC-四唑的溶液。</li>
	<li>将MOF加入二羧酸盐溶液中并孵育。将UiO-66 MOF（33mg，0.02mmol）加入含有pH 7溶液的闪烁瓶中。 注意：在pH 7时，UiO-66 MOF颗粒不溶于水，导致它们悬浮在水中。</li>
	<li>将含有MOF和配体的闪烁瓶在摇床中以120rpm和室温孵育24小时。 注意：搅拌可用作PSE工艺摇床孵育的替代方案。但是，应谨慎行事，因为磁力搅拌棒和MOF之间的物理接触会导致MOF颗粒破裂或断裂。</li>
</ol>2. 隔离交换的MOF和洗涤过程
<ol><li>孵育后，通过离心（1,166 x g ，5 分钟，室温）从混合物中分离固体 MOF。</li>
	<li>向获得的固体MOF中加入新鲜甲醇（10mL）并摇动混合物以形成非均相混合物以溶解剩余的未交换BDC配体。</li>
	<li>分离通过离心分离的固体（1,166 x g ，5分钟，室温）。</li>
	<li>再重复步骤2.2-2.3两次，总共三个洗涤周期。</li>
	<li>最后一次洗涤后，在真空下将交换的MOF固体完全干燥过夜。</li>
</ol>3. 粉末X射线衍射（PXRD）表征MOF的
<ol><li>将大约 10 mg 交换的 MOF 固体转移到 PXRD 样品架上（参见 材料表）。</li>
	<li>将样品架放入衍射仪中。</li>
	<li>收集 5° 至 30° 2θ 范围内的 PXRD 图型（图 2）。</li>
	<li>将获得的数据与父UiO-66 MOF和模拟模式进行比较。</li>
</ol>4. 消化后核磁共振（NMR）表征MOF
<ol><li>将大约 30 mg 交换的 MOF 固体转移到新鲜的 4 mL 小瓶中。</li>
	<li>使用微量移液器将 400 μL DMSO-d 6 转移到 MOF 样品中。</li>
	<li>使用微量移液器将 200 μL 4.14 M NH4F/D2O 溶液转移到 MOF 粉末的 DMSO-d 6 悬浮液中。 注意：可以使用大约 40% HF 的水溶液代替 NH4F/D2O 溶液。在这种情况下，在NMR中观察到一个显着的H2O峰。然而，在HF消解的情况下，可以更清晰的消化。 注意：HF对身体和中枢神经系统有剧毒。应避免所有形式的接触，应在通风橱中进行工作，并应穿戴个人防护设备。</li>
	<li>超声处理非均相混合物30分钟，直到MOF在消化后溶解在二甲基亚砜（DMSO）-D2O混合溶剂中。</li>
	<li>通过聚偏二氟乙烯（PVDF）注射器过滤器（Φ 13 mm，0.45 μm孔;参见 材料表）过滤溶液，同时将其从4 mL小瓶转移到NMR管中，从而去除任何剩余的不溶性固体。</li>
	<li>将核磁共振管放入核磁共振机器中。收集核磁共振数据（图3）。</li>
</ol>

三唑和四唑官能化 Zr-MOF 的合成和表征

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作者没有什么可透露的。

具有功能化BDC配体的PSE过程对Zr基UiO-66 MOF是一种简单而通用的获得带有化学标签的MOF的方法。PSE工艺最好在水性介质中进行，需要将配体溶解在水性介质中的初始步骤。当使用带有官能团的预合成BDC时，建议直接溶解在碱性溶剂中，例如4%KOH水溶液。或者，可以使用苯-1,4-二羧酸钠盐或钾盐。中和至pH 7对于使用功能化BDC的PSE工艺至关重要，因为MOFs在碱性条件下的低稳定性可能导致功效降低。建议?...

金属有机骨架（MOFs）是通过金属簇和多主题有机配体之间的配位键形成的三维多孔材料。MOF因其永久孔隙率、低密度以及结合有机和无机组分的能力而受到广泛关注，这使得多样化的应用成为可能1,2。此外，广泛的金属节点和支柱有机接头为MOF提供了理论上无限的结构组合。即使具有相同的框架结构，MOFs的物理和化学性质也可以通过配体功能化与化学标签来改变。这种改性过程为针对特定应用定制MOF的性质提供了一条有希望的途径3,4,5,6,7,8,9。
MOF合成前配体的预官能化和MOF的合成后修饰（PSM）都被用于引入和/或修饰MOF配体10,11中的官能团。特别是，共价PSMs已被广泛研究以引入新的官能团并产生一系列具有不同官能团的MOFs12,13,14。例如，UiO-66-NH2可以通过与适当的酰基卤（如乙酰氯或正己酰氯）的酰化反应转化为具有不同链长（从最短的乙酰胺到最长的正己基酰胺）的酰胺官能化UiO-66-AMs15,16。该方法证明了共价PSM将特定官能团引入MOF配体的多功能性，为广泛的应用铺平了道路。
除了共价PSM，合成后配体交换（PSE）是修饰MOF的一种有前途的策略（图1）。由于MOF由金属和配体（例如羧酸盐）之间的配位键组成，因此这些配位键可以用溶液中的外部配体代替。 将MOF暴露于含有具有化学标签的所需配体的溶液中可以通过PSE 17,18,19,20,21,22掺入MOF中。由于配位溶剂的存在加速了PSE过程，因此这种现象也称为溶剂辅助配体交换（SALE）23,24。该方法提供了一种灵活而简便的方法，用于使用广泛的外部配体功能化MOF，从而实现广泛的应用25,26,27,28,29。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65619/65619fig01.jpg"> 图 1：通过 PSE 合成三唑和四唑官能化的 H2BDC 配体以及制备三唑和四唑官能化的 UiO-66 MOF。 <a href="https://www.jove.com/files/ftp_upload/65619/65619fig01large.jpg" target="_blank">请点击此处查看此图的大图。</a>
PSE过程的进度可以通过调整配体比，交换温度和时间来控制。值得注意的是，室温PSE可以通过将溶液中的配体交换为MOF固体20来获得功能化的MOF。PSE策略对于将热不稳定官能团（如叠氮基团）和配位官能团（如苯酚基团）引入MOF结构特别有用18。此外，PSE策略已应用于具有金属和配位键变化的各种MOF。这种交换是MOFs 30,31,32化学中的通用过程。在这项研究中，我们提出了PSE从原始，非功能化MOF中获取功能化MOF的详细协议，并提供了一种表征策略来确认MOFs的成功功能化。该方法证明了PSE修饰不同官能团MOF的通用性和便利性。
合成含四唑的苯-1,4-二羧酸（H 2 BDC-四唑）33和含三唑的苯-1,4-二羧酸（H2BDC-三唑）作为靶配体，用于UiO-66 MOF的PSE，以获得新型、无配位的含三唑的MOF。三唑和四唑在其杂环上都具有酸性N-H质子，并且可以与金属阳离子配位，因此它们可用于构建MOFs 34,35。然而，关于将无配位的四唑类和三唑类药物纳入MOF和相关结构的研究有限。在三唑官能化Zr-MOFs的情况下，通过具有苯并三唑官能度的直接溶剂热合成研究了UiO-68型MOFs的光物理性质36。对于四唑功能化的Zr-MOFs，采用混合直接合成33。这些杂环功能化的MOFs可以在MOF孔中提供潜在的协调位点，用于催化，通过结合亲和力选择性分子摄取以及与能量相关的应用，例如燃料电池中的质子传导。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>2-Bromoterephthalic acid</td>
			<td>BLD Pharm</td>
			<td>BD5695</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Azidotrimethylsilane</td>
			<td>Simga Aldrich</td>
			<td>155071</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Bis(triphenylphosphine)palladium(II) dichloride</td>
			<td>TCI</td>
			<td>B1667</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Copper(I) cyanide</td>
			<td>Alfa-Aesar</td>
			<td>12135</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Copper(I) iodide</td>
			<td>Acros organics</td>
			<td>20150</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Digital Orbital Shaker</td>
			<td>Daihan Scientific</td>
			<td>SHO-1D</td>
			<td>PSE</td>
		</tr>
		<tr>
			<td>Formic Acid</td>
			<td>Daejung chemical</td>
			<td>F0195</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Hybrid LC/Q-TOF system</td>
			<td>Bruker BioSciences</td>
			<td>maXis 4G</td>
			<td>HR-MS</td>
		</tr>
		<tr>
			<td>Lithum hydroxide monohydrate</td>
			<td>Daejung chemical</td>
			<td>5087-4405</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Magnesium sulfate</td>
			<td>Samchun chemical</td>
			<td>M1807</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Methyl alcohol</td>
			<td>Daejung chemical</td>
			<td>M0584</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>N,N-Dimethylformamide</td>
			<td>Daejung chemical</td>
			<td>D0552</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Nuclear Magnetic Resonance Spectrometer-500 MHz</td>
			<td>Bruker</td>
			<td>AVANCE 500MHz</td>
			<td>NMR</td>
		</tr>
		<tr>
			<td>Polypropylene cap (22 mm, Cork-Backed Foil Lined)</td>
			<td>Sungho Korea</td>
			<td>22-200</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Potassium cyanide</td>
			<td>Alfa-Aesar</td>
			<td>L13273</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>PVDF Synringe filter (13 mm, 0.45 &#181;m)</td>
			<td>LK Lab Korea</td>
			<td>F14-61-363</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Scintillation vial (20 mL, borosilicate glass)</td>
			<td>Sungho Korea</td>
			<td>74504-20</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Sodium azide&#160;</td>
			<td>TCI</td>
			<td>S0489</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Sodium bicarbonate</td>
			<td>Samchun chemical</td>
			<td>S0343</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Tetrabutylammonium fluoride (1 M THF solution)</td>
			<td>Acros organics</td>
			<td>20195</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine</td>
			<td>TCI</td>
			<td>T0424</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine hydrochloride</td>
			<td>Daejung chemical</td>
			<td>8628-4405</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Trimethylsilyl-acetylene</td>
			<td>Alfa-Aesar</td>
			<td>A12856</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triphenylphosphine</td>
			<td>TCI</td>
			<td>T0519</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>X RAY DIFFRACTOMETER SYSTEM</td>
			<td>Rigaku</td>
			<td>MiniFlex 600</td>
			<td>PXRD</td>
		</tr>
		<tr>
			<td>Zirconium(IV) chloride</td>
			<td>Alfa-Aesar</td>
			<td>12104</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
	</tbody>
</table>

synthesis of triazole and tetrazole-functionalized zr-based metal-organic frameworks through post-synthetic ligand exchange

金属有机骨架（MOF）是通过金属簇和有机配体之间的配位键形成的一类多孔材料。鉴于它们的配位性质，有机配体和支柱框架可以很容易地从MOF中去除和/或与其他配位分子交换。通过将靶配体引入含MOF的溶液中，可以通过称为合成后配体交换（PSE）的过程 获得 具有新化学标签的功能化MOF。PSE是一种简单实用的方法，可通过固溶平衡过程 制备 具有新化学标签的各种MOF。此外，PSE可以在室温下进行，允许将热不稳定的配体掺入MOF中。在这项工作中，我们通过使用含杂环三唑和四唑的配体来官能化基于Zr的MOF（UiO-66;UiO = 奥斯陆大学）。消解后，通过粉末X射线衍射和核磁共振波谱等多种技术 对 功能化的MOF进行表征。

交换的UiO-66 MOF、UiO-66-三唑和UiO-66-四氮唑的成功合成产生了无色微晶固体。H 2 BDC-三唑和H2BDC-四唑配体也表现出无色固态。用于确定交换成功的标准方法包括测量PXRD图案并将样品的结晶度与原始UiO-66 MOF进行比较。图2显示了交换的UiO-66-三唑和UiO-66-四唑的PXRD模式，以及原始UiO-66和模拟数据。模拟的PXRD图谱是根据所报道的目标MOF的晶体结构生成的。由于配体交...

Watch this Scientific Journal Video about Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange at JoVE.com

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 

合成后配体交换（PSE）是一种多功能且功能强大的工具，用于将官能团安装到金属有机框架（MOF）中。将MOF暴露于含有三唑和四唑官能化配体的溶液中，可以通过PSE工艺将这些杂环部分掺入Zr-MOF中。

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. ...

我们的主要研究课题是通过各种技术将具有有趣官能团的多孔金属有机框架MOFs功能化。本研究的重点是MOF中的杂轮安装。PSE，合成后配体交换是这项工作的主要技术。在整个固溶体交换过程中，具有目标官能团的配体可以安装在预合成的MOFS中。特别是， 一些不稳定的配体和具有配位基团的配体可以通过PSE技术有效地掺入MOFs中.三唑和四唑官能团都具有多个配位氮槽。因此，金属羧酸盐与金属三唑酸盐或四唑酸盐之间存在协调竞争。在PSE过程中，靶配体的掺入比例很容易控制，并且通过这种方法可以在单个MOF中安装多个靶标。

synthesis-triazole-tetrazole-functionalized-zr-based-metal-organic

Research

JoVE Journal

Chemistry

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

2.6K 次观看.  Chungbuk National University. 我们的主要研究课题是通过各种技术将具有有趣官能团的多孔金属有机框架MOFs功能化。本研究的重点是MOF中的杂轮安装。PSE，合成后配体交换是这项工作的主要技术。在整个固溶体交换过程中，具有目标官能团的配体可以安装在预合成的MOFS中。特别是， 一些不稳定的配体和具有配位基团的配体可以通过PSE技术有效地掺入MOFs中.三唑和四唑官能团都具有多个配位氮槽。

视频: 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 

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 ...

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature solvents. These coordinating ligands help solubilize and stabilize the nanoparticles while in solution, and can influence the resulting size and reactivity of the nanoparticles during their formation. Despite the ubiquity of using ligands during synthesis, the presence of aliphatic ligands on the nanoparticle surface can result in a number of problems during the end use of the nanoparticles, necessitating further ligand stripping or ligand exchange procedures. We have developed a way to synthesize cadmium sulfide (CdS) nanoparticles using a unique sulfur copolymer. This sulfur copolymer is primarily composed of elemental sulfur, which is a cheap and abundant material. The sulfur copolymer has the advantages of operating both as a high temperature solvent and as a sulfur source, which can react with a cadmium precursor during nanoparticle synthesis, resulting in the generation of ligand free CdS. During the reaction, only some of the copolymer is consumed to produce CdS, while the rest remains in the polymeric state, thereby producing a nanocomposite material. Once the reaction is finished, the copolymer stabilizes the nanoparticles within a solid polymeric matrix. The copolymer can then be removed before the nanoparticles are used, which produces nanoparticles that do not have organic coordinating ligands. This nascent synthesis technique presents a method to produce metal-sulfide nanoparticles for a wide variety of applications where the presence of organic ligands is not desired.

Herein we present a method to synthesize ligand-free cadmium sulfide (CdS) nanoparticles based on a unique sulfur copolymer. The sulfur copolymer operates as a high temperature solvent and a sulfur source during the nanoparticle synthesis and stabilizes the nanoparticles after the reaction.

a硫磺共聚物基质内的免费配体硫化镉纳米粒子的合成

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

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. ...

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 ...

Facile Synthesis of Colloidal Lead Halide Perovskite Nanoplatelets via Ligand-Assisted Reprecipitation

In this work, we demonstrate a facile method for colloidal lead halide perovskite nanoplatelet synthesis (Chemical formula: L2[ABX3]n-1BX4, L: butylammonium and octylammonium, A: methylammonium or formamidinium, B: lead, X: bromide and iodide, n: number of [BX6]4- octahedral layers in the direction of nanoplatelet thickness) via ligand-assisted reprecipitation. Individual perovskite precursor solutions are prepared by dissolving each nanoplatelet constituent salt in N,N-dimethylformamide (DMF), which is a polar organic solvent, and then mixing in specific ratios for targeted nanoplatelet thickness and composition. Once the mixed precursor solution is dropped into nonpolar toluene, the abrupt change in the solubility induces the instantaneous crystallization of nanoplatelets with surface-bound alkylammonium halide ligands providing colloidal stability. Photoluminescence and absorption spectra reveal emissive and strongly quantum-confined features. X-ray diffraction and transmission electron microscopy confirm the two-dimensional structure of the nanoplatelets. Furthermore, we demonstrate that the band gap of perovskite nanoplatelets can be continuously tuned in the visible range by varying the stoichiometry of the halide ion(s). Lastly, we demonstrate the flexibility of the ligand-assisted reprecipitation method by introducing multiple species as surface-capping ligands. This methodology represents a simple procedure for preparing dispersions of emissive 2D colloidal semiconductors.

This work demonstrates facile room-temperature synthesis of colloidal quantum-confined lead halide perovskite nanoplatelets by ligand-assisted reprecipitation method. Synthesized nanoplatelets show spectrally narrow optical features and continuous spectral tunability throughout the visible range by varying the composition and thicknesses.

通过配体辅助再沉淀对胶体铅卤化物的可理解合成

In this work, we demonstrate a facile method for colloidal lead halide perovskite nanoplatelet synthesis (Chemical formula: L2[ABX3]n-1BX4, L: ...

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.