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表面活性剂辅助合成法制备的沸石咪唑酯骨架结构-8纳米晶体的ζ电位及粒径分析

Zeta Potential and Size Analysis of Zeolitic Imidazolate Framework-8 Nanocrystals Prepared by Surfactant-Assisted Synthesis.

作者信息

Jongert Tristan K, Slowinski Ian A, Dao Benjamin, Cortez Victor H, Gredig Thomas, Plascencia Nestor D, Tian Fangyuan

机构信息

Department of Chemistry & Biochemistry, California State University Long Beach, Long Beach, California 90840, United States.

Department of Physics & Astronomy, California State University Long Beach, Long Beach, California 90840, United States.

出版信息

Langmuir. 2024 Mar 26;40(12):6138-6148. doi: 10.1021/acs.langmuir.3c03193. Epub 2024 Mar 15.

Abstract

The crystal nucleation and growth mechanism of monodispersed metal-organic framework nanoparticles were studied using time-resolved light dynamic, electrokinetic, and powder X-ray diffraction methods. We confirmed that zeolitic imidazolate framework-8 (ZIF-8) nanocrystals follow a nonclassical crystal growth pathway, where a fast nucleation occurs with dense liquid clusters or nanocrystals forming spontaneously when two precursors are mixed. We also explored the zeta potential and solvodynamic size changes of ZIF-8 prepared by a surfactant-assisted synthesis. Three modulators, including 1-methylimidazole (1-mIm), tris(hydroxymethyl)aminomethane (THAM), and (1-hexadecyl)trimethylammonium bromide (CTAB), were studied. We found that 1-mIm dramatically increases the rate of nucleation of ZIF-8. With an increasing amount of 1-mIm, which functions as a coordination modulator, the size increases, and the zeta potential of ZIF-8 decreases. Whereas THAM, as both a coordination and a deprotonation modulator, increases the size and zeta potential of ZIF-8 simultaneously, CTAB, as a long alkyl cationic surfactant, mainly adsorbs on the surface of ZIF-8, and the zeta potential of the formed ZIF-8 is controlled by the amount of CTAB in solution compared with its critical micelle concentration. Overall, we reveal that the modulator type and concentration can be used to control the size and zeta potential of the dispersed ZIF-8 nanocrystals in a colloid system. The experiments also enable identification of the nucleation and crystal growth processes of ZIF-8. The findings will be applicable to other nanocrystals in colloid systems, which are used for heterogeneous catalysis and guest molecular loadings.

摘要

采用时间分辨光动力学、电动动力学和粉末X射线衍射方法研究了单分散金属有机框架纳米颗粒的晶体成核和生长机制。我们证实,沸石咪唑酯骨架-8(ZIF-8)纳米晶体遵循非经典晶体生长途径,即当两种前驱体混合时,会快速成核,同时形成致密的液体团簇或纳米晶体。我们还研究了通过表面活性剂辅助合成制备的ZIF-8的zeta电位和溶剂动力学尺寸变化。研究了三种调节剂,包括1-甲基咪唑(1-mIm)、三(羟甲基)氨基甲烷(THAM)和十六烷基三甲基溴化铵(CTAB)。我们发现1-mIm显著提高了ZIF-8的成核速率。随着作为配位调节剂的1-mIm用量增加,ZIF-8的尺寸增大,zeta电位降低。而THAM作为配位和去质子化调节剂,同时增加了ZIF-8的尺寸和zeta电位,CTAB作为长链烷基阳离子表面活性剂,主要吸附在ZIF-8表面,与临界胶束浓度相比,溶液中CTAB的量控制着所形成ZIF-8的zeta电位。总体而言,我们揭示了调节剂的类型和浓度可用于控制胶体体系中分散的ZIF-8纳米晶体的尺寸和zeta电位。这些实验还能够确定ZIF-8的成核和晶体生长过程。这些发现将适用于胶体体系中的其他纳米晶体,这些纳米晶体用于多相催化和客体分子负载。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6d51/10976884/60a4123611ad/la3c03193_0001.jpg

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