Di Giacomo Alessio, Myslovska Alina, De Roo Vic, Goeman Jan, Martins José C, Moreels Iwan
Department of Chemistry, Ghent University, 9000-Gent, Belgium.
Department of Organic and Macromolecular Chemistry, Ghent University, 9000-Gent, Belgium.
Nanoscale. 2024 Mar 21;16(12):6268-6277. doi: 10.1039/d3nr05157a.
Several established procedures are now available to prepare zinc blende CdSe nanoplatelets. While these protocols allow for detailed control over both thickness and lateral dimensions, the chemistry behind their formation is yet to be unraveled. In this work, we discuss the influence of the solvent on the synthesis of nanoplatelets. We confirmed that the presence of double bonds, as is the case for 1-octadecene, plays a key role in the evolution of nanoplatelets, through the isomerization of the alkene, as confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. Consequently, 1-octadecene can be replaced as a solvent (or solvent mixture), however, only by one that also contains α protons to CC double bonds. We confirm this synthesis of nanoplatelets in hexadecane spiked with a small amount of 1-octadecene, and in the aromatic solvent 1,2,3,4-tetrahydronaphthalene (tetralin). At the same time, the chemical reaction leading to the formation of nanoplatelets occurs to some extent in saturated solvents. A closer examination revealed that an alternative formation pathway is possible, through interaction of carboxylic acids, such as octanoic acid, with selenium. Next to shedding more light on the synthesis of CdSe nanoplatelets, fundamental understanding of the precursor chemistry paves the way to use optimized solvent admixtures as an additional handle to control the nanoplatelet synthesis, as well as to reduce potential self-polymerization hurdles observed with 1-octadecene.
现在有几种既定的方法可用于制备闪锌矿型CdSe纳米片。虽然这些方案可以对厚度和横向尺寸进行详细控制,但其形成背后的化学原理仍有待揭示。在这项工作中,我们讨论了溶剂对纳米片合成的影响。我们证实,如1-十八烯的情况,双键的存在通过烯烃的异构化在纳米片的演化中起关键作用,这已通过核磁共振光谱和质谱得到证实。因此,1-十八烯可以作为溶剂(或溶剂混合物)被替代,但只能被一种同样含有与CC双键相连的α质子的溶剂替代。我们在掺入少量1-十八烯的十六烷以及芳香族溶剂1,2,3,4-四氢萘(四氢化萘)中证实了这种纳米片的合成。同时,导致纳米片形成的化学反应在饱和溶剂中也会在一定程度上发生。进一步研究发现,通过辛酸等羧酸与硒的相互作用,可能存在另一种形成途径。除了更深入地了解CdSe纳米片的合成外,对前驱体化学的基本理解为使用优化的溶剂混合物作为控制纳米片合成的额外手段以及减少1-十八烯观察到的潜在自聚合障碍铺平了道路。