The significance of bromide in the Brust-Schiffrin synthesis of thiol protected gold nanoparticles.

The significance of bromide in the Brust-Schiffrin synthesis of thiol protected gold nanoparticles.
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DOI:
10.1039/c7sc03266h
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发表时间:
2017-12-01
期刊:
影响因子:
8.4
通讯作者:
Dryfe RAW
Dryfe RAW
中科院分区:
化学1区
文献类型:
--
作者:
Booth SG;Uehara A;Chang SY;La Fontaine C;Fujii T;Okamoto Y;Imai T;Schroeder SLM;Dryfe RAW

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烷硫醇保护的金属纳米粒子的两相 Brust-Schiffrin 合成机制已被证明对前体物质和反应物条件高度敏感。烷硫醇保护的金属纳米粒子的两相 Brust-Schiffrin 合成机制已知对前体物质和反应物条件高度敏感。在这项工作中,X 射线吸收光谱与液/液电化学结合使用,以强调 Br– 在反应机理中的重要性。 [AuBr4]– 物质被证明是 Brust-Schiffrin 方法中的首选前体,因为它比 [AuCl4]– 更能抵抗 Au(i) 硫醇盐物质的形成。先前的文献已经证明,避免使用 Au(i) 硫醇盐对于实现纳米颗粒的良好产率至关重要,因为 [Au(i)X2]– 物质更容易被 NaBH4 还原。我们认为本文描述的 [AuBr4]-物种的观察到的行为解释了迄今为止文献中报告的行为的差异。这种新的机理理解应该能够以更高的产率合成纳米粒子并降低粒径多分散性。
The mechanism of the two-phase Brust–Schiffrin synthesis of alkane thiol protected metal nanoparticles has been shown to be highly sensitive to the precursor species and reactant conditions. The mechanism of the two-phase Brust–Schiffrin synthesis of alkane thiol protected metal nanoparticles is known to be highly sensitive to the precursor species and reactant conditions. In this work X-ray absorption spectroscopy is used in conjunction with liquid/liquid electrochemistry to highlight the significance of Br– in the reaction mechanism. The species [AuBr4]– is shown to be a preferable precursor in the Brust–Schiffrin method as it is more resistant to the formation of Au(i) thiolate species than [AuCl4]–. Previous literature has demonstrated that avoidance of the Au(i) thiolate is critical to achieving a good yield of nanoparticles, as [Au(i)X2]– species are more readily reduced by NaBH4. We propose that the observed behavior of [AuBr4]– species described herein explains the discrepancies in reported behavior present in the literature to date. This new mechanistic understanding should enable nanoparticle synthesis with a higher yield and reduce particle size polydispersity.
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