Physics and Chemistry of Nanostructures, Ghent University, Belgium.
J Am Chem Soc. 2012 Dec 26;134(51):20705-12. doi: 10.1021/ja308861d. Epub 2012 Dec 12.
The effect of short-chain alcohols and acetonitrile on the ligand shell composition and the photoluminescence quantum yield of purified PbSe and CdSe quantum dots is analyzed by solution NMR and photoluminescence spectroscopy. We find that short-chain alcohols induce the release of X-type carboxylate ligands with a concurrent reduction of the photoluminescence quantum yield, while acetonitrile does not. We interpret this difference in terms of the protic or aprotic character of both nonsolvents, where only the protic alcohols can provide the protons needed to desorb carboxylate ligands. We find similar differences between short-chain alcohols and acetonitrile when used as nonsolvents during the purification of crude synthesis products, a result stressing the importance of using aprotic nonsolvents for nanocrystal purification or processing.
通过溶液 NMR 和光致发光光谱分析了短链醇和乙腈对纯化的 PbSe 和 CdSe 量子点配体壳层组成和光致发光量子产率的影响。我们发现,短链醇诱导 X 型羧酸配体的释放,同时光致发光量子产率降低,而乙腈则没有。我们根据两种非溶剂的质子性或非质子性特征来解释这种差异,只有质子性醇才能提供脱附羧酸配体所需的质子。当短链醇和乙腈用作粗合成产物纯化过程中的非溶剂时,我们发现它们之间存在类似的差异,这一结果强调了在纳米晶体纯化或加工过程中使用非质子性非溶剂的重要性。