著者はの低圧プラズマ技術における専門知識のためのプロジェクト数BA07PRO104、マーティン·スミス、コリーヌ·ストーン、防衛科学技術研究所（DSTL）のコリン·ウィリスの下での資金調達のための国防脅威削減局に感謝し、そしてマシューBroweとウェズリー·ゴードンそれぞれmicrobreakthroughテストと接触角測定用のエッジウッド化学生物学センター（ECBC）。

1。 CU-BTCの合成と準備<ol><li>約5分間のキャップジャースクリューの脱イオン水12.5ミリリットルと100ミリリットル中のジメチルホルムアミド12.5ミリリットルをかき混ぜる。 </li><li> 0.87グラム（3.6ミリモル）瓶中の溶液にトリメシン酸0.50gの（2.4ミリモル）、続いて銅（II）六水和物を添加し、約5分間撹拌する。解決策は、色が青色に変わります。約24時間、120℃で予熱したオーブンで栓をしたジャーを配置します。 </li><li>オーブンからjarファイルを削除します。ジャーを室温に冷却したら、より大きい又は2.5ミクロンに等しい結晶を回収し、評価濾紙を用いて真空ろ過を介したCu-BTCの結晶を回収する。最終的にはジクロロメタンの新鮮な溶液中の結晶を配置し、ジクロロメタンで得られた結晶を洗浄します。 </li><li>溶剤を24時間毎に交換およびCu-の細孔から低揮発性溶剤の除去を支援するために、次の3日間、新鮮なジクロロメタンで置き換えるBTC。 </li><li>材料から残留ゲスト分子を除去するために真空オーブンで、またはシュレンク·ラインを介して170°CまでのCu-BTC結晶を加熱する。完全に活性化のCu-BTCの色は紫色に青深いなければならない。 </li><li>粉末X線回折ビア構造およびCu-BTCの化学的構成を確認し、各々、赤外分光法フーリエ変換。 </li></ol> 2。のCu-BTC 14ペルフルオロアルカンのプラズマ化学気相成長法<ol><li>各実験の前にプラズマ反応器と、少なくとも30分間、50 Wでの空気プラズマでプラズマ処理に使用される任意のガラス器具を清浄。これは、反応室または前の実験からのガラス製品の内面に形成された可能性のあるペルフルオロアルカン膜を除去する。 </li><li> 250ミリリットルパイレックスボトルで活性化のCu-BTCの既知量を置き、均質な治療を確保するために、その側面にボトル全体に広がる。透過性の布の周りに配置する必要があります真空を適用する際に失われたサンプルの量を最小にするためにゴムバンドを有するボトルのネック。 </li><li>プラズマチャンバ内でボトルを置きます。チャンバーは、試料に吸着している可能性のある水を除去するために、少なくとも30分間0.20ミリバール≤圧力になるまで真空を適用します。 </li><li>パーフルオロアルカンガスを接続し、マスフローコントローラの仕様内の圧力レギュレータを調整します。 </li><li>実験の所望の圧力を維持するためにパーフルオロアルカンガス適量の反応チャンバを充填するためにマスフローコントローラを調整する。粉末のより均一な治療を作成するためにPECVD装置内でボトルを回転させます。 </li><li> 13.56MHzのRF発生器と、反射率を最小にしながらパワーを最大化するためにLCマッチング部と同調無線周波数を用いてプラズマを照らす。治療を通して定期的に再調整。 </li><li>処置が完了すると、任意のチャンバを排気残留パーフルオロアルカンガス、次いで大気圧にベント。 PECVD装置からサンプルを取り出して、ボトルの側面から処理された材料を回収する。帯電防止デバイスは、材料の最大量を回復するために使用されるべきである。 </li><li>未反応のパーフルオロアルカンガスを除去するために120℃のオーブンで処理された材料を配置します。その後、大気中の水分の吸着を防止するために、デシケーター中で処理された材料を置く。 </li><li>瓶の中に残って残留物質を洗浄し、適正処理のための廃棄物を回収するためにフィルタリングします。 </li><li>核磁気共鳴スピニング20 Fマジック角で処理したCu-BTCを特徴付ける、赤外分光法、およびX線光電子分光法フーリエ変換。 </li></ol> 3。湿潤条件下のCu-BTCの高齢化<ol><li>環境室の所望の温度と相対湿度を設定し、それを平衡化させる。 </li><li>中に均一にサンプルを広げる所望の時間のための環境室で開かれた容器と場所。 </li><li>劣化の程度を決定するために77 KでのX線回折および窒素等温線でのCu-BTCサンプルを特徴付ける。 </li></ol> 4。アンモニアMicrobreakthrough実験2 <ol><li>最初のきちんとしたアンモニアの210ミリリットルで、空のバラストを注入することにより、5000ミリグラム/ m 3でのアンモニアの14.6 Lバラストを準備します。その後、15 psiの圧力にゼロ空気で安定器を埋める。 microbreakthrough装置に沿った安定器を接続します。 </li><li>フィード信号を決定するmicrobreakthrough装置で素管を実行します。 20ml /分ミリグラム/ m 3でアンモニア2,000の流れを作成するために、それぞれ、8および12 ml /分にアンモニア及び乾燥空気用のマスフローコントローラを設定する。流出液中のアンモニアの供給信号を決定するために、ガスクロマトグラフおよび光イオン化検出器を制御するためのプログラム化された方法を実行する。水分がシステムに追加することができ必要な相対湿度を達成するの​​に必要な速度で温度制御された飽和器セルを介して希釈剤流の一部を実行して、所望の場合。 </li><li>公称4mmの内径をガラス管中のガラスフリット以下グラスウールの少量を置く。チューブに材料の約10〜15 mgの重量を量る。使用される質量は、約0.15秒のベッドの滞留時間が得られる、約55 mm 3の体積の収着剤をもたらすはずである。 </li><li>それは、任意の吸着水を除去するために1時間150℃に加熱し、ガラス管を通して乾燥空気を流す。再生後、試料を秤量する。 </li><li>ラインでサンプルを置き、25℃に設定した水浴中で直立確保</li><li>供給ガスで充填ラインにサンプルを迂回して2,000ミリグラム/ m 3のアンモニアで20 ml /分の流れを作成するために、それぞれ、8および12 ml /分にアンモニア及び乾燥空気用のマスフローコントローラを設定する。 </li><li>試料を通過したアンモニアの流れをフローとプログラムさを実行します。流出液中のアンモニア濃度を監視するためにガスクロマトグラフおよび光イオン化検出器を制御する方法。 </li><li>排出濃度は、供給濃度に達すると、アンモニア流のスイッチを切り、試料に強く吸着されないオフガス任意アンモニアに試料を可能にする。 </li><li> X線回折を介して、露光後の分析のために水浴からサンプルを取り出して、赤外線分析フーリエ変換。 </li><li>サンプル用のアンモニア負荷を決定するために、時間データ対ガスクロマトグラフ信号を統合します。 </li></ol>

<ol>
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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>

著者は、彼らが競合する経済的利益を持っていないことを宣言します。

のCu-BTCの合成は、ほとんどのMOFのように、使用される反応物の比および合成で実施される温度に大きく依存することができる。合成に使用される温度又は溶媒をMOF構造20の別の形態を産生することが示されている変える。したがって、任意のMOF合成されるために、文献に記載された手順に従うことが強く重要である。合成を実施するには、容器を選択する際に、さらに、1は、反応物?...

有機金属構造体（MOF）は、有毒ガス除去1-3多孔質材料のリーディングクラスとなっている。 MOFは、標的化学的相互作用のための機能を調整する前例のない能力を有する。以前に例外的に高いアンモニア負荷を有することが見出されている（また、2 HKUST-1またはCu 3（BTC）としても知られる）のCu-BTCであるが、これは、材料の構造的安定性4のコストである。のCu-BTCに関するさらなる研究は、水分自体は、多くの潜在的な用途のために無効5,6,21それをレンダリングする、MOF構造を分解することができることを示している。液体の水や高湿度の存在下でのMOFを含む特定のカルボン酸の構造的な不安定性は、商業や工業用途7で使用する主要な抑止力となっている。 これは、湿度の存在下での固有の安定性を有するように化学的除去に用いられるのMOFのための最も理想的である。しかし、多くのMOMOF-74とCu-BTCのようなオープン金属部位を持つ多くのMOFは、優れた化学的除去能力2,4,8,9を持っている間、このようなUIO-66のような優れた安定性とFSは、、、貧しい化学的除去能力を持っている。 MOF-74とCu-BTCで開か金属部位は、アンモニアなどの有毒ガスの取り込みを強化するが、これらのサイトには、活性部位を汚染し、構造的な故障につながる多くの場合、水と結合しやすい。水に不安定なMOFの化学的性質を維持するために、MOFは、水安定性を高めるために様々な試みがなされている。 MOF-5は、MOFの周りに炭素層を形成することにより、熱処理の際に耐湿性の向上を有することが示されているが、疎水性の増加は、表面積および最終的に10の機能を犠牲にしてである。 MOF-5はまた、そのhydrostabilityは、Ni 2 +イオン11を用いてドーピングによって増加有することが示されている。さらに、1,4 - ジアザビシクロ[2.2.2]オクタン含有（またDMOFsとしても知られる）ING MOFは、1,4 -ベンゼンジカルボキシレートリンカー12,13上の種々のペンダント基を組み込むことによって水安定性の同調を示すために使用されてきた。 MOFは、特定のhydrostabilityの不足、高い有毒ガスが吸収され、具体的なものは、その疎水性を増加させるために14 MOFの表面にフッ素化されたグループを作成するためにペルフルオロアルカンのプラズマ強化化学蒸着（PECVD）の使用につながった。この技術は、芳香族水素、並びにのMOFの内面上の他の潜在的な官能基を含有する任意のMOFを変更するために使用することができることをユニークな利点を提供する。しかしながら、この技術は、プラズマ中の高反応性ラジカルの形成を制御することは困難であることができる。ラジカルは芳香族の水素原子と反応するだけでなく、CF X基で既にMOF表面にのみ反応していない。手順の注意深い制御は、細孔BLOを確保する必要があるckageは財務省が無効レンダリング、発生しません。この技術は、炭素材料の濡れ特性を変化させるために他のユーザーによって使用されてきたが、我々の知る限り、それは、以前は微孔質材料のhydrostabilityを高めるために使用されていなかった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

ペルフルオロアルカンのプラズマ強化化学蒸着（PECVD）は、長い表面の濡れ性を調整するために研究されている。このような有機金属構造体（MOF）のような高表面積のマイクロポーラス材料については、固有の課題は、PECVDトリートメントには自分自身を提示。ここに条件多湿以前に不安定であったMOFの開発のためのプロトコルが提示されている。プロトコルは、（また、香港科技大学-1とも呼ばれる）のCu-BTC、ペルフルオロアルカンのPECVD、多湿条件下での材料の経年変化、および微孔性材料のミリグラム量でのその後のアンモニアmicrobreakthrough実験のCu-BTCの治療の合成を記載している。以前にPECVD法によって処理されている大部分の材料又は表面と比較した場合のCu-BTCは、極めて高い表面積（〜1800メートル2 / g）を有する。例えば、チャンバ圧力、処理時間などのパラメータは、パーフルオロアルカンプラズマが確実に浸透することが極めて重要であり、反応インナーMOF面とS。さらに、実験はここに記載のmicrobreakthroughアンモニアのプロトコルは、テストガスおよび微孔性材料、様々に利用することができる。

<html>代表的な結果の中に著者は、4 0.30ミリバールの圧力でHRとで処理された50 W.のMOFのプラズマ出力のために、（C 2 F 6）、ヘキサフルオロエタンで処理されたのCu-BTCの0.50グラムサンプルの特性を表示することにしました適切な条件の下でパーフルオロアルカンプラズマが強化された疎水性を表示する必要があります。これは、液体の水の上に粉末を配置し、 図1?...

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

本明細書にそれらの安定性および疎水性を高めるために、このような金属 - 有機骨格としての微孔性材料上にペルフルオロアルカンのプラズマ化学気相堆積のための手順が記載されている。さらに、サンプルのミリグラム量の破過試験は詳細に記載されている。

プラズマを介した疎水性有機金属フレームワークの製造は、アンモニアの除去のためにペルフルオロアルカンの化学的気相成長法を強化

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 ビュー.  Science Applications International Corporation (SAIC). 本明細書にそれらの安定性および疎水性を高めるために、このような金属 - 有機骨格としての微孔性材料上にペルフルオロアルカンのプラズマ化学気相堆積のための手順が記載されている。さらに、サンプルのミリグラム量の破過試験は詳細に記載されている。 

ビデオ: 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.

官能化有機金属構造体の合成とキャラクタリゼーション

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

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.

有機マグネットの化学気相堆積、バナジウムテトラ

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

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.

原子層堆積法を介してゲルマニウム上のペロブスカイト型チタン酸ストロンチウムのエピタキシャル成長

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.

エアロゾルによる金属酸化物の構造の化学蒸着: 酸化亜鉛棒

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.

金属有機性フレームワークの耐湿性を向上のための表面機能化

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.

キラル金属有機フレームワーク(MRF)を用いた不均一なエナンチオ選択的触媒の開発

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.

単結晶コアシェル金属有機構造体の合成

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.

金属有機フレームワークの分光測定を行うための技術ガイド

Metal-organic frameworks (MOFs) offer a unique platform to understand light-driven processes in solid-state materials, given their high structural ...

マルチトピックホスフィンリンカーからの低原子価MOFの合成

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

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

著者スポットライト:マルチトピックホスフィンリンカーからの低原子価金属有機フレームワークの合成のための実験的アプローチ  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

多位ホスフィンリンカーからの低原子価金属-有機構造体の合成のための実験的アプローチ

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...