Batch and Flow Nanomanufacturing of Large Quantities of Colloidal Silver and Gold Nanocrystals Using Deep Eutectic Solvents
Batch and Flow Nanomanufacturing of Large Quantities of Colloidal Silver and Gold Nanocrystals Using Deep Eutectic Solvents
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DOI：
10.1021/acssuschemeng.0c04244
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发表时间：
2020-10-05
影响因子：
8.4
通讯作者：
Baker, Gary A.
中科院分区：
文献类型：
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作者：
Adhikari, Laxmi;Larm, Nathaniel E.;Baker, Gary A.
为了满足工业应用的需求，需要显着强化纳米粒子合成的工艺。不幸的是，由于试剂、溶剂、人员和时间利用效率低下，传统的纳米颗粒合成方法（即使用传统溶剂的方法）在很大程度上是不可持续的。作为一种可能的前进方向，我们展示了硝酸二甲铵-多元醇低共熔溶剂 (DES) 系统与油胺配对的优势，可快速、轻松地生产大量可分散在疏水性有机溶剂（如甲苯）中的高质量银和金纳米颗粒。我们研究了三种潜在的多元醇作为 DES 的氢键供体（即三甘醇、乙二醇、甘油），提供温度半优化，并使用间歇式和连续流反应形式研究产品质量。这些 DES 具有非凡的金属溶解性能，能够以相当高的浓度（即银和金含量分别为 1000 和 400 mM）生产单分散的造币金属胶体，且产量基本上是定量的。作为这种高金属浓度的结果的例证，使用 1000 mM AgNO3 的 1 mL 反应在几分钟内产生 107 mg 银纳米粒子，比使用相同反应体积进行的传统水合成高出约 1000 至 4000 倍。同样，在相同金属负载量下，以 0.24 mL min(-1) 的中等流速转化为连续流动微流体合成，每分钟可产生 26 mg 银纳米粒子。这相当于每天 37.4 克可分离的纳米颗粒，这是一个可观的产量，可以通过并行操作多个连续流反应器进一步放大。最后，我们通过使用 11-巯基十一烷酸进行配体交换表面反应，证明了油胺稳定的金纳米颗粒从非极性溶剂（甲苯）到水溶液中的有效相转移，并完全保留了纳米颗粒的尺寸、形态、单分散性（8.8% RSD）和胶体稳定性。这项研究指出了 DES 作为可扩展、可持续和流动过程中的高性能流体的特殊未来，以加强纳米制造工作。
Significant process intensification of nanoparticle synthesis is required to meet the demands of industrial applications. Unfortunately, conventional nanoparticle synthetic methods (i.e., those using traditional solvents) are largely unsustainable long term due to inefficient reagent, solvent, personnel, and time utilization. As one possible path forward, we demonstrate the benefits of a dimethylammonium nitrate-polyol deep eutectic solvent (DES) system paired with oleylamine for the rapid and facile production of significant quantities of high-quality silver and gold nanoparticles dispersible in hydrophobic organic solvents such as toluene. We investigate three potential polyols as the hydrogen bond donor of the DES (i.e., triethylene glycol, ethylene glycol, glycerol), provide a temperature semioptimization, and investigate product quality using both batch and continuous flow reaction formats. These DESs possess extraordinary metal dissolution properties and are capable of producing monodispersed coinage metal colloids at remarkably high concentrations (i.e., 1000 and 400 mM silver and gold content, respectively) in essentially a quantitative yield. As an illustration of the consequence of this high metal concentration, a 1 mL reaction employing 1000 mM AgNO3 produces 107 mg of silver nanoparticles within minutes, some 1000- to 4000-fold higher than a conventional aqueous synthesis performed using the same reaction volume. Likewise, translation to continuous flow millifluidic synthesis at a moderate flow rate of 0.24 mL min(-1) at the same metal loading yields 26 mg of silver nanoparticles per minute. This amounts to 37.4 g of isolable nanoparticles daily, a substantial output, which can be amplified further by operating multiple continuous flow reactors in parallel. Finally, we demonstrate the efficient phase transfer of the oleylamine-stabilized gold nanoparticles from nonpolar solvent (toluene) into aqueous solution by applying a ligand-exchange surface reaction using 11-mercaptoundecanoic acid with full preservation of nanoparticle size, morphology, monodispersity (8.8% RSD), and colloidal stability. This research points to an exceptional future for DESs as high-performance fluids in scalable, sustainable, and flow processes toward the intensification of nanomanufacturing efforts.