Facile Exchange of Tightly Bonded L-Type Oleylamine and Diphenylphosphine Ligands on Copper Indium Diselenide Nanocrystals Mediated by Molecular Iodine
Facile Exchange of Tightly Bonded L-Type Oleylamine and Diphenylphosphine Ligands on Copper Indium Diselenide Nanocrystals Mediated by Molecular Iodine
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DOI：
10.1021/acs.chemmater.8b04016
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发表时间：
2018-11
影响因子：
8.6
通讯作者：
D. Houck;B. Korgel
中科院分区：
文献类型：
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作者：
D. Houck;B. Korgel
二硒化铜铟（CuInSe 2）纳米晶体是典型的I-III-VI族半导体量子点材料，通常在油胺（OLAm）作为溶剂和封端配体中合成，通常添加二苯基膦（DPP）以提高反应产率。利用1H核磁共振谱，我们研究了在CuInSe 2纳米晶体上的OLAm和DPP的缔合，发现它们都表现为紧密键合的L型配体。当将甲苯-d8分散体加热至100 °C时，没有可观察到的OLAm或DPP的解吸，并且当纳米晶体暴露于其他L型物质如三辛基膦（TOP）或十八烷基乙撑（ODT）时，没有发生配体交换，所述其他L型物质可以X型或L型结合。然而，分子碘（I2）被发现很容易取代的OLAm和DPP从表面和促进有效和完全的配体交换与TOP或ODT，并表现为一个刘易斯酸Z型配体。我们还发现，X型配体，硬脂酸…
Copper indium diselenide (CuInSe2) nanocrystals are a prototypical I–III–VI semiconductor quantum dot material, typically synthesized in oleylamine (OLAm) as a solvent and capping ligand, often with the addition of diphenylphosphine (DPP) to improve the reaction yield. Using 1H nuclear magnetic resonance spectroscopy, we study the association of OLAm and DPP on CuInSe2 nanocrystals and find that they both behave as tightly bonded L-type ligands. There is no observable desorption of OLAm or DPP when a toluene-d8 dispersion is heated to 100 °C, and no ligand exchange occurs when the nanocrystals are exposed to other L-type species like trioctylphosphine (TOP) or octadecanethiol (ODT), which can bind as either X-type or L-type. Molecular iodine (I2), however, is found to readily displace both OLAm and DPP from the nanocrystal surface and facilitate efficient and complete ligand exchange with either TOP or ODT and appears to behave as a Lewis acid Z-type ligand. We also find that the X-type ligand, stearic ac...