School of Applied Sciences, RMIT University, GPO Box 2476 V, Melbourne, Australia.
Inorg Chem. 2011 Mar 7;50(5):1705-12. doi: 10.1021/ic1021752. Epub 2011 Jan 19.
In this study, the reaction of semiconductor microrods of phase I copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with KAuBr(4) in acetonitrile is reported. It was found that the reaction is redox in nature and proceeds via a galvanic replacement mechanism in which the surface of CuTCNQ is replaced with metallic gold nanoparticles. Given the slight solubility of CuTCNQ in acetonitrile, two competing reactions, namely CuTCNQ dissolution and the redox reaction with KAuBr(4), were found to operate in parallel. An increase in the surface coverage of CuTCNQ microrods with gold nanoparticles occurred with an increased KAuBr(4) concentration in acetonitrile, which also inhibited CuTCNQ dissolution. The reaction progress with time was monitored using UV-visible, FT-IR, and Raman spectroscopy as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were investigated for their photocatalytic properties, wherein the destruction of Congo red, an organic dye, by simulated solar light was found dependent on the surface coverage of gold nanoparticles on the CuTCNQ microrods. This method of decorating CuTCNQ may open the possibility of modifying this and other metal-TCNQ charge transfer complexes with a host of other metals which may have significant applications.
在这项研究中，报道了 I 相铜 7,7,8,8-四氰基对醌二甲烷（CuTCNQ）半导体微棒与 KAuBr(4)在乙腈中的反应。研究发现，该反应本质上是氧化还原反应，通过原电池置换机制进行，其中 CuTCNQ 的表面被金属金纳米粒子取代。由于 CuTCNQ 在乙腈中的溶解度较小，发现两种竞争性反应，即 CuTCNQ 溶解和与 KAuBr(4)的氧化还原反应，同时进行。随着乙腈中 KAuBr(4)浓度的增加，CuTCNQ 微棒表面的金纳米粒子覆盖率增加，同时抑制了 CuTCNQ 的溶解。使用紫外-可见、FT-IR 和拉曼光谱以及 XRD 和 EDX 分析和 SEM 成像监测反应随时间的进展。研究了 CuTCNQ/Au 纳米复合材料的光催化性能，发现刚果红（一种有机染料）的破坏程度取决于 CuTCNQ 微棒上金纳米粒子的表面覆盖率。这种用金纳米粒子修饰 CuTCNQ 的方法可能为修饰这种和其他金属-TCNQ 电荷转移配合物提供可能性，与许多其他金属结合，可能具有重要的应用。
