Chang Boyce S, Thomas Brijith, Chen Jiahao, Tevis Ian D, Karanja Paul, Çınar Simge, Venkatesh Amrit, Rossini Aaron J, Thuo Martin M
Department of Materials Science and Engineering, Iowa State University, 2220 Hoover Hall, Ames, IA 50011, USA.
US DOE Ames Laboratory, Ames, Iowa, USA50011.
Nanoscale. 2019 Aug 7;11(29):14060-14069. doi: 10.1039/c9nr05448k. Epub 2019 Jul 17.
Coordination polymers are ideal synthons in creating high aspect ratio nanostructures, however, conventional synthetic methods are often restricted to batch-wise and costly processes. Herein, we demonstrate a non-traditional, frugal approach to synthesize 1D coordination polymers by in situ etching of zerovalent metal particle precursors. This procedure is denoted as the heterogeneous metal/ligand reaction and was demonstrated on Group 13 metals as a proof of concept. Simple carboxylic acids supply the etchant protons and ligands for metal ions (conjugate base) in a 1 : 1 ratio. This scalable reaction produces a 1D polymer that assembles into high-aspect ratio 'nanobeams'. We demonstrate control over crystal structure and morphology by tuning the: (i) metal center, (ii) stoichiometry and (iii) structure of the ligands. This work presents a general scalable method for continuous, heat free and water-based coordination polymer synthesis.
配位聚合物是构建高长径比纳米结构的理想合成子，然而，传统的合成方法往往局限于分批且成本高昂的过程。在此，我们展示了一种非传统的、节俭的方法，通过对零价金属颗粒前驱体进行原位蚀刻来合成一维配位聚合物。该过程被称为非均相金属/配体反应，并以第13族金属为例进行了概念验证。简单的羧酸以1:1的比例为金属离子（共轭碱）提供蚀刻剂质子和配体。这种可扩展的反应产生一种一维聚合物，其组装成高长径比的“纳米束”。我们通过调节：（i）金属中心、（ii）化学计量比和（iii）配体结构来展示对晶体结构和形态的控制。这项工作提出了一种通用的可扩展方法，用于连续、无热且基于水的配位聚合物合成。
