title: Synthesis of CuTCNQ/Au microrods by galvanic replacement of semiconducting phase I CuTCNQ with KAuBr4 in aqueous medium.
abstract: The spontaneous reaction between microrods of an organic semiconductor molecule, copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with [AuBr(4)](-) ions in an aqueous environment is reported. The reaction is found to be redox in nature which proceeds via a complex galvanic replacement mechanism, wherein the surface of the CuTCNQ microrods is replaced with metallic gold nanoparticles. Unlike previous reactions reported in acetonitrile, the galvanic replacement reaction in aqueous solution proceeds via an entirely different reaction mechanism, wherein a cyclical reaction mechanism involving continuous regeneration of CuTCNQ consumed during the galvanic replacement reaction occurs in parallel with the galvanic replacement reaction. This results in the driving force of the galvanic replacement reaction in aqueous medium being largely dependent on the availability of [AuBr(4)](-) ions during the reaction. Therefore, this study highlights the importance of the choice of an appropriate solvent during galvanic replacement reactions, which can significantly impact upon the reaction mechanism. The reaction progress with respect to different gold salt concentration was monitored using Fourier transform infrared (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS), as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were also investigated for their potential photocatalytic properties, wherein the destruction of the organic dye, Congo red, in a simulated solar light environment was found to be largely dependent on the degree of gold nanoparticle surface coverage. The approach reported here opens up new possibilities of decorating metal-organic charge transfer complexes with a host of metals, leading to potentially novel applications in catalysis and sensing.
authors.affiliation: School of Applied Sciences, RMIT University, GPO Box 2476 V, Melbourne, VIC 3001, Australia.
authors.forename: Andrew
authors.initials: A
authors.lastname: Pearson
authors.forename: Anthony P
authors.initials: AP
authors.lastname: O'Mullane
authors.forename: Suresh K
authors.initials: SK
authors.lastname: Bhargava
authors.forename: Vipul
authors.initials: V
authors.lastname: Bansal