Name: generation of zerovalent metal core nanoparticles using n-(2-aminoethyl)-3-aminosilanetriol
Uploaded: 2016-02-11T13:00:00.000+00:00
Duration: 8 min 12 s
Description: Watch this Scientific Journal Video about Generation of Zerovalent Metal Core Nanoparticles Using n-2-aminoethyl-3-aminosilanetriol at JoVE.com

Dr. B.P.S. Chauhan would like to gratefully acknowledge William Paterson University for assigned release time (ART) award for part of the research described here and also for the research program in general.

注：さらに精製することなく、メーカーからのものであるように、すべての試薬が使用されています。反応は、完全な還元を確実にするために、UV-可視分光法を介して、最大1週間モニターしました。全ての反応は、通気フードの下で行われ、適切な安全服装は手袋、眼ゴーグル、及び白衣など、常時装着されます。 銀ナノ粒子の1の合成<ol><li>直接50ミリリットルの三角フラスコに硝酸銀の0.0169グラム（0.1ミリモル）を秤量。 </li><li> 20超純水の18.2MΩのミリリットルとマグネチックスターラーバーに追加します。蒸発を防ぐために、栓でフラスコをカバーしています。 </li><li>油浴に入れフラスコに攪拌機/ホットプレート上に位置し、その温度が60℃に維持されていることを確認します。 </li><li>ゆっくり精密マイクロピペットを用いて、2-ASTの144μL（0.2ミリモル）を追加します。すべてのシランを確保するため、溶液中のフラッシュピペットで数回溶液に移します。 </li><li>紫外可視分光測定値を取りますセクション5に記載されているプロトコルに従って。 </li><li> 6時間後、油浴からサンプルを削除し、ストレージ、TEM、FTIR、さらなる分析のために20ミリリットルのサンプルバイアルに移します。 注：金とパラジウムナノ粒子の合成は、216μL（0.3 mmol）の2-ASTを必要とする金ナノ粒子を除いて同じ方法および化学量論的な量に従います。反応は、最大2週間のナノ粒子を製造し続けることができるが、速度は初期速度と比較して有意ではありません。 </li></ol> 2.透過型電子顕微鏡（TEM）サンプル調製<ol><li>サンプルを室温まで冷却していることを確認してください。 </li><li>フィルター清潔なろ紙上に200カーボンメッシュホルムバール被覆銅グリッドを配置します。 </li><li> 1ミリリットルプラスチック製パスツールピペット、キャストドロップ直接グリッド上にナノ粒子サンプルの約60μLを使用しました。 </li><li>グリッドが撮影前に24時間乾燥することができます。 </li><li>以下の条件を用いて高解像度のTEM画像を取ります。10μAの電流および電圧22を加速 100 kVの。 </li></ol> 3.核磁気共鳴（NMR）試料の調製注：RTでNMRを実行します。高温では信号が得られたスペクトルの品質を劣化させる、合体することがあります。 <ol><li>きれいなNMRチューブに精密ピペット、ピペット重水素ガス（D 2 O）の50μLを使用しました。 </li><li>別のクリーン精密ピペットと、同じNMRチューブにピペットナノ粒子サンプルの400μLを。 <ol><li>サンプルはNMR管の内壁に付着することがあるように、ゆっくりとNMRチューブにソリューションを追加します。サンプルが付着しない場合は、チューブをキャップと底部への解決策を強制するために、チューブの上部を横に振ります。 </li></ol></li><li>揺れを繰り返しNMRチューブを反転させて、サンプルを混ぜます。 </li><li>製造元によって提供さNMRプロトコルによって設定された指示に従ってNMRに置き、試料管。千スキャンの上方には、適切な解像度のために必要があるかもしれません1 HプロトンNMRパルスプログラムでolution。 注：NMR管の壁はきれいでなければなりません。チューブの外壁は、スペクトルの明確化のために、分析前にマイクロファイバーや糸くずの出ない布で拭くことをお勧めします。 </li><li>終了時にサンプルを捨てます。親液にサンプルを返さないでください。 </li></ol> 4.フーリエ変換赤外（FTIR）分光法サンプル調製を変換します<ol><li>小さなガラス容器にナノ粒子サンプルの2ミリリットルを置きます。 3ミリリットル管や1ドラムガラスバイアルはうまく動作します。 </li><li>コックを装着した真空デシケーター中でガラス容器を配置することによって、サンプルを乾燥させます。 </li><li>真空ポンプ装置にデシケーターを取り付けます。サンプルの乾燥は真空の強さに応じて数時間かかる場合があります。コンテナ内の目に見える液体が存在しない後の試料を乾燥考えてみましょう。 </li><li>きれいなへらを使用してサンプルを下にこすり落とし、固体材料を集めます。 </li><li> ZnSe crystを装着ATR-FTIR分光器の上に固体材料を置き、らのダイオードレーザ。 </li><li> 4,000-500 cm -1で2.0のスペクトル分解能との間の32スキャンを統合するFTIRスペクトルを取得します。エアバックグラウンド23を使用してください。 </li></ol> 5.紫外可視分光法サンプル調製<ol><li>その飽和が分光計分析では発生しませんので、水にナノ粒子サンプルの1〜10個の希釈されているナノ粒子のサンプルに紫外可視分光法を実施します。 </li><li>反応は半時間間隔で実行されている間、UV-Visのためのナノ粒子のサンプルを削除してください。 </li><li>精密ピペットを用いて、ナノ粒子材料の100μlのを削除し、プラスチック製キュベットに配置します。 </li><li>同じキュベットに超純水の1ミリリットルを加え、ピペットを数回洗浄することにより十分に混合します。 </li><li> 250から800 nmの間の録音紫外可視吸収スペクトル。 </li><li>分析の後、反応にサンプルを返しません。適切な方法で分析物を処分。 </li></ol>

<ol>
	<li>Corriu, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organosilicon+Chemistry+and+Nanoscience.">Organosilicon Chemistry and Nanoscience.</a> J Organomet Chem. 686, 32-41 (2003).</li><li>Chou, L. Y., Ming, K., Chan, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Strategies+for+the+intracellular+delivery+of+nanoparticles.">Strategies for the intracellular delivery of nanoparticles.</a> Chem. Soc. Rev. 40 (1), 233-245 (2011).</li><li>Richards, R., B&#246;nnemann, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthetic+Approaches+to+Metallic+Nanomaterials.">Synthetic Approaches to Metallic Nanomaterials.</a> Nanofabrication towards Biomedical Applications. , 4-9 (2005).</li><li>Bradley, J., Schmid, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chapter+6,+Unit+6.2.2,+The+Chemistry+of+Transition+Metal+Colloids:+Synthetic+Methods+for+the+Preparation+of+Colloidal+Transition+Metals.">Chapter 6, Unit 6.2.2, The Chemistry of Transition Metal Colloids: Synthetic Methods for the Preparation of Colloidal Transition Metals.</a> Clusters and Colloids. , 469-473 (1994).</li><li>Paterer, A., 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=Investigation+on+the+formation+of+copper+zinc+tin+sulphide+nanoparticles+from+metal+salts+and+dodecanethiol.">Investigation on the formation of copper zinc tin sulphide nanoparticles from metal salts and dodecanethiol.</a> Mater. Chem. Phys. 149-150, 94-98 (2015).</li><li>Yi, D. K., Lee, S. S., Ying, J. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Applications+of+Magnetic+Nanocomposite+Catalysts.">Synthesis and Applications of Magnetic Nanocomposite Catalysts.</a> Chem. Mater. 18, 2459-2461 (2006).</li><li>Piepenbrock, M. M., Lloyd, G. O., Clarke, N., Steed, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-+and+Anion-Binding+Supramolecular+Gels.">Metal- and Anion-Binding Supramolecular Gels.</a> Chem. Rev. 110, 1960-2004 (2010).</li><li>Wu, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+and+Structural+Characterization+of+Novel+Nanohybrids+by+Cationic+3D+Silica+Nanoparticles+Sandwiched+between+2D+Anionic+Montmorillonite+Clay+through+Electrostatic+Attraction.">Preparation and Structural Characterization of Novel Nanohybrids by Cationic 3D Silica Nanoparticles Sandwiched between 2D Anionic Montmorillonite Clay through Electrostatic Attraction.</a> J. Phys. Chem. C. 113 (30), 13036-13044 (2009).</li><li>Spitalsky, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Carbon+nanotube-polymer+composites:+Chemistry,+Processing,+Mechanical+and+Electrical+Properties.">Carbon nanotube-polymer composites: Chemistry, Processing, Mechanical and Electrical Properties.</a> Prog. Polym. Sci. 35, 357-401 (2010).</li><li>Link, S., El-Sayed, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spectral+Properties+and+Relaxation+Dynamics+of+Surface+Plasmon+Electronic+Oscillations+in+Gold+and+Silver+Nanodots+and+Nanorods.">Spectral Properties and Relaxation Dynamics of Surface Plasmon Electronic Oscillations in Gold and Silver Nanodots and Nanorods.</a> J. Phys. Chem. B. 103 (40), 8410-8426 (1999).</li><li>Fau, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Monitoring+the+Coordination+of+Amine+Ligands+on+Silver+Nanoparticles+Using+NMR+and+SERS.">Monitoring the Coordination of Amine Ligands on Silver Nanoparticles Using NMR and SERS.</a> Langmuir. 31 (4), 1362-1367 (2015).</li><li>Patil, H. B., Borse, S. V., Patil, D. R., Patil, U. K., Patil, H. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+silver+nanoparticles+by+microbial+method+and+their+characterization.">Synthesis of silver nanoparticles by microbial method and their characterization.</a> Arch. Phys. Res. 2 (3), 153-158 (2011).</li><li>Ghosh, S., Sarma, N., Mandal, M., Kundu, S., Esumi, K., Pal, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evolution+of+gold+nanoparticles+in+micelle+by+UV-irradiation:+A+conductometric+study.">Evolution of gold nanoparticles in micelle by UV-irradiation: A conductometric study.</a> Curr. Sci. 84 (6), 791-795 (2003).</li><li>Paul, B., Bhuyan, B., Purkayastha, D. D., Dey, M., Dhar, S. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Green+synthesis+of+gold+nanoparticles+using+Pogestemon+benghalensis+(B)+O.+Ktz+leaf+extract+and+studies+of+their+photocatalytic+activity+in+degradation+of+methylene.">Green synthesis of gold nanoparticles using Pogestemon benghalensis (B) O. Ktz leaf extract and studies of their photocatalytic activity in degradation of methylene.</a> Mater. Lett. 148, 37-40 (2015).</li><li>Chauhan, B. P. S., Rathore, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Regioselective+Synthesis+of+Multifunctional+Hybrid+Polysiloxanes+Achieved+by+Pt-Nanocluster+Catalysis.">Regioselective Synthesis of Multifunctional Hybrid Polysiloxanes Achieved by Pt-Nanocluster Catalysis.</a> J. Am. Chem. Soc. 127, 5790-5791 (2005).</li><li>Chauhan, B. P. S., Rathore, S., Bandoo, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=&#34;Polysiloxane-Pd&#34;+Nanocomposites+as+Recyclable+Chemoselective+Hydrogenation+Catalysts.">&#34;Polysiloxane-Pd&#34; Nanocomposites as Recyclable Chemoselective Hydrogenation Catalysts.</a> J. Am. Chem. Soc. 126, 8493-8500 (2004).</li><li>Chauhan, B. P. S., Rathore, S., Chauhan, M., Krawicz, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Polysiloxane+Stabilized+Palladium+Colloids+and+Evidence+of+Their+Participation+in+Silaesterification+Reactions.">Synthesis of Polysiloxane Stabilized Palladium Colloids and Evidence of Their Participation in Silaesterification Reactions.</a> J. Am. Chem. Soc. 125, 2876-2877 (2003).</li><li>Chauhan, B. P. S., Sardar, R., Tewari, P., Sharma, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> , 23-25 (2003).</li><li>Pouchert, C. J., Pouchert, C. .. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Non-Aromatic+Amines.">Non-Aromatic Amines.</a> The Aldrich Library of Infrared Spectra. , (1983).</li><li>Arkles, 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=Infrared+Analysis+of+Organosilicon+Compounds:+Spectra-Structure+Correlations.">Infrared Analysis of Organosilicon Compounds: Spectra-Structure Correlations.</a> Silicon Compounds Register and Review. , (1987).</li><li>Corriu, R. J. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hypervalent+Species+of+Silicon-structure+and+Reactivity.">Hypervalent Species of Silicon-structure and Reactivity.</a> J. Organomet. Chem. 400, 81-106 (1990).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Basic Instruction Manual: Hitachi HT7700 TEM. , 1-28 (2014).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> OMNIC User's Guide Version 7.3: Thermo Electron Corporation. , 151-216 (2006).</li></ol>

競合する金融利害関係はありません。

本論文で報告された塩は、その金属で試験された唯一の塩です。その結果、この反応戦略は、金属のすべての塩、特に金で動作するであろうことが不確実です。水中のこれらの塩の溶解度は、反応時間、形態、及び収率の観点から、反応の結果に影響を及ぼし得ます。全ての反応においては、シランは、既に溶解した金属塩溶液に添加しました。 注意がこれらの反応は?...

デザイナーのナノ材料は増加の需要やアプリケーションなど、そのように合成する種々の方法を実行します。例えば、レーザアブレーションまたは化学エッチングのような「トップダウン」方法は、その優れた制御性および信頼性サブミクロンレベルまで材料を解決する能力のために使用されてきました。これらの方法は、所望のナノ構造のサイズが減少するにつれて、典型的には製造コストを増大させる細かい部品に加工するバルク材料に依存しています。これまで合成の別の方法は、分子レベルでの合成を制御し、所望のナノ構造に構築「ボトムアップ」アプローチです。これは、これらのナノ構造材料1の世代において所望の自己組織化、機能性、受動性、および安定性上のコントロールのかなりの程度を与えます。分子レベルで仕事をすることで、ハイブリッドナノ複合材料は、同じstructu内の両方の材料の利点を提供する生成することができます再。 ナノ材料は、ボトムアップ戦略を介して合成されるように、方法は、粒子サイズ、形状、質感、疎水性、多孔性、電荷、および機能2を制御するために使用される必要があります。金属コアナノ粒子​​合成では、最初の金属塩は、今度は他の粒子の核生成を指示するゼロ価の粒子を生成するために、自己触媒過程で還元されます。これは、クラスタリングにつながり、最終的にナノ粒子の生産3。作成されたナノ粒子のサイズを制御し、溶液から沈殿するのを防止するために、そのようなリガンド、界面活性剤、イオン電荷、大きなポリマーなどの安定剤をさらに凝集4-10からナノ粒子をブロックするそれらの能力のために利用されます。これらの材料は、立体障害による貫通嵩高い基の存在のために、またはクーロン反発3のいずれかによって、ナノ粒子のファンデルワールス力を阻害します。 トンで彼の作品、容易な、ワンポット、シランを用いた各種金属コアナノ粒子の生成のための合成戦略、N-（2-アミノエチル）-3- aminosilanetriol（2- AST）は（ 図1）に提示されています。この化合物の配位子は、金属前駆体を還元し、比較的高い効率を有する金属ナノ粒子を安定化することが可能です。存在する3つのシラノール部分はまた、架橋することができ、これは、マトリックス内のナノ粒子（ 図2）を含浸させたオルガノシランポリマーの相互接続ネットワークを形成します。容易に水の存在下で加水分解を受けるほとんどのシランとは異なり、この化合物は、疎水性のために、安定性、及び制御のために有益である、水中で安定化されます。

<table><tbody><tr><td>n-(2-aminoethyl)-3-aminosilanetriol (2-AST)</td><td>Gelest</td><td>SIA0590.0</td><td>25% in H&lt;sub&gt;2&lt;/sub&gt;O</td></tr><tr><td>Silver nitrate</td><td>Sigma Aldrich</td><td>S6506</td><td></td></tr><tr><td>Gold(III) chloride trihydrate</td><td>Sigma Aldrich</td><td>520918</td><td></td></tr><tr><td>Palladium(II) Nitrate</td><td>Alfa Aesar</td><td>11035</td><td></td></tr><tr><td>Deuterium Dioxide</td><td>Cambridge Isotope Laboratories</td><td>DLM-4-100</td><td></td></tr></tbody></table>

generation of zerovalent metal core nanoparticles using n-(2-aminoethyl)-3-aminosilanetriol

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of n-(2-aminoethyl)-3-aminosilanetriol is presented. This compound can be used to effectively reduce and complex metal salts into metal core nanoparticles coated with the compound. By controlling the concentrations of salt and silane one is able to control reaction rates, particle size, and nanoparticle coating. The effects of these changes were characterized through transmission electron microscopy (TEM), UV-Vis spectrometry (UV-Vis), Nuclear Magnetic Resonance spectroscopy (NMR) and Fourier Transform Infrared spectroscopy (FTIR). A unique aspect to this reaction is that usually silanes hydrolyze and cross-link in water; however, in this system the silane is water-soluble and stable. It is known that silicon and amino moieties can form complexes with metal salts. The silicon is known to extend its coordination sphere to form penta- or hexa-coordinated species. Furthermore, the silanol group can undergo hydrolysis to form a Si-O-Si silica network, thereby transforming the metal nanoparticles into a functionalized nanocomposites.

ナノ粒子形成は、個々の金属ナノ粒子のための特徴的なピークを生成しなければならないような反応は、紫外 - 可視分光法を介して監視しました。合成された材料の最終的な分析は、TEMおよびFTIRを介して達成されました。 FTIRスペクトルは、サンプルの乾燥粉末から得られました。粒子サイズ分析は、TEM平均化結果を介して得られた画像から、ナノ粒子の直径を測定?...

Watch this Scientific Journal Video about Generation of Zerovalent Metal Core Nanoparticles Using n-2-aminoethyl-3-aminosilanetriol at JoVE.com

Generation of Zerovalent Metal Core Nanoparticles Using n-2-aminoethyl-3-aminosilanetriol

A novel method for metal core nanoparticle synthesis using a water stable silanol is described.

ゼロ価金属コアのナノ粒子の生成は、N-使用（2-アミノエチル）-3- aminosilanetriol

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of ...

generation-zerovalent-metal-core-nanoparticles-using-n-2-aminoethyl-3

Research

JoVE Journal

Chemistry

Generation of Zerovalent Metal Core Nanoparticles Using n-(2-aminoethyl)-3-aminosilanetriol

7.6K ビュー.  William Paterson University. A novel method for metal core nanoparticle synthesis using a water stable silanol is described.

ビデオ: Generation of Zerovalent Metal Core Nanoparticles Using n-2-aminoethyl-3-aminosilanetriol

Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are encapsulated in polystyrene-block-poly(acrylic acid) (PSPAA) shells and then used as monomers for their self-assembly. Spherical PSPAA micelles upon acid treatment are known to assemble into cylindrical micelles. Exploiting this tendency, the core-shell nanoparticles are induced to aggregate, coalesce, and then transform into long chains. When more than one type of nanoparticles are used, random and block &#8220;copolymers&#8221; of nanoparticles can be obtained. Detailed procedures are reported for the PSPAA encapsulation of nanoparticles, homo- and co-polymerization of the core-shell nanoparticles, separation and purification of the resulting nanoparticle chains. Transformations of single-line chains into double- and triple-line chains are also presented. The synergy between the polymer shell and the embedded nanoparticles leads to an unusual chain-growth polymerization mode, giving long nanoparticle chains that are distinct from the products of the traditional step-growth aggregation process.

Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We report protocols for &#8220;polymerizing&#8221; various types of polymer-encapsulated metal nanoparticles into long chains of &#8220;homo-&#8220; and &#8220;co-polymers&#8221;.

ポリスチレンを使用しました<em&gt;ブロック</em&gt; - ポリ（アクリル酸）は、それらのホモポリマーおよび共重合用単量体として金属ナノ粒子をコーティングを採用

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are ...

化学

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The silica-encapsulated metal oxide nanoparticles are then carburized in a methane/hydrogen atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal carbide nanoparticles. During the carburization process, the silica shells prevent the sintering of adjacent carbide nanoparticles while also preventing the deposition of excess surface carbon. Alternatively, the silica-encapsulated metal oxide nanoparticles can be nitridized in an ammonia atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal nitride nanoparticles. By adjusting the reverse microemulsion parameters, the thickness of the silica shells, and the carburization/nitridation conditions, the transition metal carbide or nitride nanoparticles can be tuned to various sizes, compositions, and crystal phases. After carburization or nitridation, the silica shells are then removed using either a room-temperature aqueous ammonium bifluoride solution or a 0.1 to 0.5 M NaOH solution at 40-60 &#176;C. While the silica shells are dissolving, a high surface area support, such as carbon black, can be added to these solutions to obtain supported early transition metal carbide or nitride nanoparticles. If no high surface area support is added, then the nanoparticles can be stored as a nanodispersion or centrifuged to obtain a nanopowder.

A &#8220;removable ceramic coating method&#8221; is presented in visual format for the synthesis of non-sintered and metal-terminated monometallic and bimetallic early transition metal carbide and nitride nanoparticles with tunable sizes and crystal structures.

モノとバイメタル早期遷移金属炭化物と窒化物ナノ粒子の逆マイクロエマルジョン媒介合成

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The ...

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.

The synthesis of uniform gold nanoparticles coated with semiconductor shells of CdS or ZnS is performed. The semiconductor coating is conducted by first depositing a silver sulfide shell and exchanging the silver cations for zinc or cadmium cations.

合成、キャラクタリゼーション、およびハイブリッドのAu / CdSのとAu / ZnSのコア/シェルナノ粒子の機能化

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

超分子コロイドの合成とキャラクタリゼーション

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

A rapid, direct solution-based reduction synthesis method to obtain Au, Pd, and Pt aerogels is presented.

Au、Pd、およびソリューションに基づく還元を介して Pt エアロゲルの迅速合成法

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various ...

Synthesis of Bimetallic Pt/Sn-based Nanoparticles in Ionic Liquids

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular physico-chemical properties of ionic liquids (ILs) are exploited to control both nucleation and growth processes. The nanoparticles form colloidal sols of very high colloidal stability in the IL, which is particularly interesting in view of their use as quasi-homogeneous catalysts. Procedures for both nanoparticle extraction in conventional solvents and for nanoparticle precipitation are presented. The size, structure and composition of the synthesized nanocrystals are confirmed using inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDX). By this, we show that the nanocrystals are random-type alloy and of small (2-3 nm) size. The catalytic activity and selectivity in the hydrogenation of &#945;,&#946;-unsaturated aldehydes is tested in a semi-continuous batch-type reactor. In this context, the bimetallic Pt/Sn-based nanoparticles reveal a high selectivity towards the unsaturated alcohol.

A protocol for the synthesis of bimetallic nanoparticles in ionic liquids and the procedure of their catalytic testing in the selective hydrogenation of unsaturated aldehydes are described.

イオン液体のバイメタルの Pt/Sn ベースのナノ粒子の合成

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

表面有機金属化学の方法論を用いてシリカ支持触媒によるイミンメタセシス

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

Presented here is a protocol for the synthesis of silver-palladium (Ag-Pd) alloy nanoparticles (NPs) supported on ZrO2 (Ag-Pd/ZrO2). This system allows for harvesting energy from visible light irradiation to accelerate and control molecular transformations. This is illustrated by nitrobenzene reduction under light irradiation catalyzed by Ag-Pd/ZrO2 NPs.

可視光照明下におけるプラスモニック触媒のための銀パラジウム合金ナノ粒子の調製

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular ...

Gold Nanoparticle Synthesis

Gold nanoparticles (Au nanoparticles) that are ~12 nm in diameter were synthesized by rapidly injecting a solution of 150 mg (0.15 mmol) of tetrachloroauric acid in 3.0 g (3.7 mmol, 3.6 mL) of oleylamine (technical grade) and 3.0 mL of toluene into a boiling solution of 5.1 g (6.4 mmol, 8.7 mL) of oleylamine in 147 mL of toluene. While boiling and mixing the reaction solution for 2 hours, the color of the reaction mixture changed from clear, to light yellow, to light pink, and then slowly to dark red. The heat was then turned off, and the solution was allowed to gradually cool down to room temperature for 1 hour. The gold nanoparticles were then collected and separated from the solution using a centrifuge and washed three times; by vortexing and dispersing the gold nanoparticles in 10 mL portions of toluene, and then precipitating the gold nanoparticles by adding 40 mL portions of methanol and spinning them in a centrifuge. The solution was then decanted to remove any remaining byproducts and unreacted starting materials. Drying the gold nanoparticles in a vacuum environment produced a solid black pellet; which could be stored for long periods of time (up to one year) for later use, and then redissolved in organic solvents such as toluene.

A protocol for synthesizing ~12 nm diameter gold nanoparticles (Au nanoparticles) in an organic solvent is presented. The gold nanoparticles are capped with oleylamine ligands to prevent agglomeration. The gold nanoparticles are soluble in organic solvents such as toluene.

ゴールドナノ粒子合成

Gold nanoparticles (Au nanoparticles) that are ~12 nm in diameter were synthesized by rapidly injecting a solution of 150 mg (0.15 mmol) of ...

Triplet Fusion Upconversion Nanocapsule Synthesis

Triplet fusion upconversion (UC) allows for the generation of one high energy photon from two low energy input photons. This well-studied process has significant implications for producing high energy light beyond a material's surface. However, the deployment of UC materials has been stymied due to poor material solubility, high concentration requirements, and oxygen sensitivity, ultimately resulting in reduced light output. Toward this end, nanoencapsulation has been a popular motif to circumvent these challenges, but durability has remained elusive in organic solvents. Recently, a nanoencapsulation technique was engineered to tackle each of these challenges, whereupon an oleic acid nanodroplet containing upconversion materials was encapsulated with a silica shell. Ultimately, these nanocapsules (NCs) were durable enough to enable triplet fusion upconversion-facilitated volumetric three-dimensional (3D) printing. By encapsulating upconversion materials with silica and dispersing them in a 3D printing resin, photopatterning beyond the surface of the printing vat was made possible. Here, video protocols for the synthesis of upconversion NCs are presented for both small-scale and large-scale batches. The outlined protocols serve as a starting point for adapting this encapsulation scheme to multiple upconversion schemes for use in volumetric 3D printing applications.

This protocol details the synthesis of upconversion nanocapsules for subsequent use in photopolymerizable resins for triplet fusion upconversion-facilitated volumetric 3D printing.

トリプレット融合アップコンバージョンナノカプセル合成

Triplet fusion upconversion (UC) allows for the generation of one high energy photon from two low energy input photons. This well-studied process has ...