Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles.
Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles.
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DOI：
10.1038/ncomms13008
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发表时间：
2016-10-13
影响因子：
16.6
通讯作者：
Williams, Charlotte K.
中科院分区：
文献类型：
--
作者：
Pike, Sebastian D.;White, Edward R.;Shaffer, Milo S. P.;Williams, Charlotte K.
由分子前驱体自下而上合成配体稳定的功能纳米粒子应用广泛，但难以从机理上进行研究。在这里，我们使用31P核磁共振波谱跟踪亚膦配体在合成一系列连接的锌氧簇合物过程中的轨迹，这些簇合物包含4，6和11个锌原子。利用有机金属途径，团簇在溶液中快速相互转化和自组装，基于热力学平衡而不是成核动力学。这些团簇也在合成亚膦酸氧化锌纳米颗粒的过程中被原位识别。出乎意料的是，在大多数合成过程中，配体被隔离到稳定的锌原子簇上，只有在最后一步才会配位到纳米颗粒表面。除了一条通向(可选掺杂的)锌簇合物的通用和可访问的路线外，这些发现还有助于理解明确定义的分子前体在合成小的(2-4 nm)纳米颗粒过程中所起的作用。配体和表面活性剂在由分子前驱体合成纳米颗粒的过程中起着重要作用，尽管它们的确切作用尚不清楚。在这里，作者分离了一系列中等大小的锌原子簇，并能够通过光谱探测自组装和配体效应。
The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2–4 nm) nanoparticles. Ligands and surfactants play an important part in the synthesis of nanoparticles from molecular precursors although their exact roles are poorly understood. Here, the authors isolate a range of intermediate sized zinc clusters and are able to spectroscopically probe the self-assembly and ligand effects.
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