Department of Chemistry, Syracuse University , Syracuse, New York 13244, United States.
Center for Functional Nanomaterials, Brookhaven National Laboratory , Upton, New York 11973, United States.
ACS Nano. 2016 Jun 28;10(6):5864-72. doi: 10.1021/acsnano.6b00806. Epub 2016 May 17.
The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.
铯铅卤(CsPbX3;X = Cl(-),Br(-),I(-))钙钛矿纳米粒子(P-NPs)能够参与卤化物交换反应、催化 Finkelstein 有机卤化物取代反应,以及实时比色监测化学反应和检测阴离子的能力被描述出来。使用四辛基卤化物盐作为起点,通过与 P-NPs 进行卤化物交换来校准反应性、稳定性和离子交换程度。CsPbI3 与 Cl(-)或 Br(-)的交换会导致吸收和光致发光显著蓝移,而 I(-)与 CsPbBr3 的反应则会导致相似幅度的红移。考虑到高局部卤化物浓度和卤化物交换的易进行性,我们随后探索了 P-NPs 在类似于 Finkelstein 的反应中催化有机卤化物交换的能力。结果表明,P-NPs 是在非极性介质中取代有机卤化物的优异卤化物储库,不仅导致不同的有机卤化物产物,而且在反应过程中还会发生互补的颜色变化,可用于精确监测动力学。然后,将 P-NP 用作实时分析的光谱化学探针的优点扩展到可以与卤化物反应或导致独特的卤化物钙钛矿类别的其他阴离子。