Ambient Synthesis of Au144(SR)60 Nanoclusters in Methanol
Ambient Synthesis of Au144(SR)60 Nanoclusters in Methanol
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DOI：
10.1021/cm200143s
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发表时间：
2011-04-26
影响因子：
8.6
通讯作者：
Jin, Rongchao
中科院分区：
文献类型：
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作者：
Qian, Huifeng;Jin, Rongchao
我们报告了一种在环境条件下合成原子单分散 Au-144(SR)(60) 纳米团簇的简便、一锅法。在此方法中，金盐前体首先与过量的硫醇和四辛基溴化铵 (TOABr) 在甲醇中混合，形成 Au(I)-SR 聚合物。然后，Au(I)-SR 被过量的 NaBH4（水溶液）还原形成纳米团簇。有趣的是，最初形成的多分散金纳米粒子在大约 5 小时内尺寸集中成两个单分散金纳米团簇：Au-144(SR)(60)（主要产物）和 Au-25(SR)(18)（副产物）。副产物 (Au-25(SR)(18)) 可以通过用丙酮洗涤产物轻松去除，从而产生纯 Au-144(SR)(60)。该方法适用于许多硫醇配体，包括 PhC2H4SH 和各种 CnH2n+1SH（其中 n = 4-8）。获得纯 Au-144(SR)(60) 的一些关键参数已确定，包括甲醇溶剂（与传统使用的甲苯相反）、较大的硫醇与 Au 比率 (>= 4)、O-2 和四辛基卤化铵 (TOAX，其中 X = Br、Cl) 的存在。简便的合成方法以及用该方法制备的产品将极大地有助于这种新型纳米材料的实际应用。
We report a facile, one-pot method for synthesizing atomically monodisperse Au-144(SR)(60) nanoclusters under ambient conditions. In this method, gold salt precursor is first mixed with excess thiol and tetraoctylammonium bromide (TOABr) in methanol to form Au(I)-SR polymers. Then, Au(I)-SR is reduced by excess NaBH4 (aqueous solution) to form nanoclusters. Interestingly, the initially formed, polydisperse Au nanoparticles are size-focused into two monodisperse gold nanoclusters: Au-144(SR)(60) (major product) and Au-25(SR)(18) (side product) over a similar to 5 h period. The side product (Au-25(SR)(18)) can be easily removed by washing the product with acetone, giving rise to pure Au-144(SR)(60). This method is applicable to a number of thiol ligands, including PhC2H4SH and various CnH2n+1SH (where n = 4-8). Some critical parameters to obtain pure Au-144(SR)(60) have been identified, including the methanol solvent (as opposed to toluene traditionally used), large thiol-to-Au ratios (>= 4), the presence of O-2 and tetraoctylammonium halide (TOAX, where X = Br, Cl). The facile synthetic method and the product made by this method should largely contribute to the practical application of this new type of nanomaterial.