Postsynthetic Thiol-Induced Reshaping of Copper Sulfide Nanoparticles
Postsynthetic Thiol-Induced Reshaping of Copper Sulfide Nanoparticles
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DOI：
10.1021/acs.chemmater.2c03049
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发表时间：
2022-12
影响因子：
8.6
通讯作者：
Haley L. Young;Connor R. McCormick;Auston G. Butterfield;Enrique D. Gomez;R. Schaak
中科院分区：
文献类型：
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作者：
Haley L. Young;Connor R. McCormick;Auston G. Butterfield;Enrique D. Gomez;R. Schaak
硫化铜的纳米颗粒，包括铁锰矿Cu1.8S，是许多应用的重要材料，并且它们还作为阳离子交换反应的通用模板，将它们转化为衍生的金属硫化物化合物和复杂的异质结构。在合成过程中确定的尺寸和形状的奈米菱铁矿，其形态保留在合成后的修改，如阳离子交换。在这里，我们展示了在90至160 °C的温度范围内，用1-十二烷乙烷（1-DDT）和叔十二烷乙烷（t-DDT）处理合成后的罗辉石纳米颗粒的形态修饰。这些硫醇通常用作纳米颗粒合成中的配体和/或硫试剂，诱导形态重塑，同时保持组成、晶体结构和颗粒体积。例如，在130 °C下，在1-DDT的存在下，56 nm × 21 nm的roxbyite纳米棒转变为32 nm的球形颗粒。纳米棒的长度逐渐减小，宽度逐渐增加，在中间时间点形成一系列具有可调纵横比的椭圆体。对照实验指出了一个单晶到单晶的途径，涉及材料的扩散和迁移，这可以通过增加纳米颗粒中阳离子空位的密度来加速。由于这一途径，硫醇诱导的形态变化是选择性的硫化铜区域的异质结构的纳米棒含有roxbyite和ZnS，Co 9 S8，或CuInS 2使用部分阳离子交换反应，提供访问的衍生物纳米粒子的库，否则无法访问的形态。
Nanoparticles of copper sulfide, including roxbyite Cu1.8S, are important materials for many applications, and they also serve as versatile templates for cation exchange reactions that transform them into derivative metal sulfide compounds and complex heterostructures. The sizes and shapes of roxbyite nanoparticles are generally determined during synthesis, and their morphologies are retained during postsynthetic modifications such as cation exchange. Here, we demonstrate postsynthetic morphological modification of roxbyite nanoparticles by treating them with 1-dodecanethiol (1-DDT) andtert-dodecanethiol (t-DDT) at temperatures ranging from 90 to 160 °C. These thiols, which are typically used as ligands and/or sulfur reagents in nanoparticle synthesis, induce morphological reshaping while maintaining composition, crystal structure, and particle volume. For example, 56 nm × 21 nm roxbyite nanorods transform to 32 nm spherical particles in the presence of 1-DDT at 130 °C for two or more hours. The nanorods progressively decrease in length and increase in width, forming a series of ellipsoids having tunable aspect ratios at intermediate time points. Control experiments point to a single-crystal-to-single-crystal pathway that involves material diffusion and migration, which can be accelerated by increasing the density of cation vacancies in the nanoparticles. Because of this pathway, the thiol-induced morphology changes are selective to the copper sulfide regions of heterostructured nanorods containing roxbyite and ZnS, Co9S8, or CuInS2made using partial cation exchange reactions, providing access to a library of derivative nanoparticles having otherwise inaccessible morphologies.