通过浊度测量评估锆金属有机框架的结晶动力学,以指导快速微波辅助合成。

Assessing Crystallisation Kinetics of Zr Metal-Organic Frameworks through Turbidity Measurements to Inform Rapid Microwave-Assisted Synthesis.

作者信息

Griffin Sarah L, Briuglia Maria L, Ter Horst Joop H, Forgan Ross S

机构信息

WestCHEM School of Chemistry, University of Glasgow, Glasgow, UK.

EPSRC Centre for Innovative Manufacturing in, Continuous Manufacturing and Crystallisation (CMAC), Strathclyde Institute of Pharmacy and Biomedical Sciences, Technology and Innovation Centre, University of Strathclyde, 99 George Street, Glasgow, UK.

出版信息

Chemistry. 2020 May 26;26(30):6910-6918. doi: 10.1002/chem.202000993. Epub 2020 May 11.

Abstract

Controlling the crystallisation of metal-organic frameworks (MOFs), network solids of metal ions or clusters connected by organic ligands, is often hindered by the significant number of synthetic variables inherent to their synthesis. Coordination modulation, the addition of monotopic competing ligands to solvothermal syntheses, can allow tuning of physical properties (particle size, porosity, surface chemistry), enhance crystallinity, and select desired phases, by modifying the kinetics of self-assembly, but its mechanism(s) are poorly understood. Herein, turbidity measurements were used to assess the effects of modulation on the solvothermal synthesis of the prototypical Zr terephthalate MOF UiO-66 and the knowledge gained was applied to its rapid microwave synthesis. The studied experimental parameters-temperature, reagent concentration, reagent aging, metal precursor, water content, and modulator addition-all influence the time taken for onset of nucleation, and subsequently allow microwave synthesis of UiO-66 in as little as one minute. The simple, low cost turbidity measurements align closely with previously reported in situ synchrotron X-ray diffraction studies, proving their simplicity and utility for probing the nucleation of complex materials while offering significant insights to the synthetic chemist.

摘要

控制金属有机框架(MOF)的结晶过程颇具挑战,MOF是由金属离子或簇与有机配体连接而成的网络固体,其合成过程中存在大量固有的合成变量。配位调制,即在溶剂热合成中添加单齿竞争配体,可以通过改变自组装动力学来调节物理性质(粒径、孔隙率、表面化学性质),提高结晶度并选择所需的相,但其作用机制尚不清楚。在此,通过浊度测量来评估调制对典型的锆对苯二甲酸MOF UiO-66溶剂热合成的影响,并将所获得的知识应用于其快速微波合成。所研究的实验参数——温度、试剂浓度、试剂老化、金属前驱体、含水量和调制器添加量——都会影响成核开始所需的时间,进而能够在短短一分钟内实现UiO-66的微波合成。简单、低成本的浊度测量结果与先前报道的原位同步加速器X射线衍射研究结果密切吻合,证明了其在探测复杂材料成核方面的简单性和实用性,同时为合成化学家提供了重要的见解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/64bc/7318326/4d281b55ece6/CHEM-26-6910-g001.jpg

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