Ambient synthesis of nanomaterials by in situ heterogeneous metal/ligand reactions

• Published in: Nanoscale 2019-08, Vol.11 (29), p.14060-14069
• Main Authors: Chang, Boyce S, Thomas, Brijith, Chen, Jiahao, Tevis, Ian D, Karanja, Paul, Çınar, Simge, Venkatesh, Amrit, Rossini, Aaron J, Thuo, Martin M
• Format: Article
• Language: English
• Subjects: Carboxylic acids; Chemical synthesis; Coordination polymers; Crystal structure; Etchants; High aspect ratio; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ligands; Metal particles; Morphology; Nanomaterials; NANOSCIENCE AND NANOTECHNOLOGY; Polymers; Stoichiometry
• ISSN: 2040-3364; 2040-3372
• DOI: 10.1039/c9nr05448k

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.