Hybrid CuTCNQ/AgTCNQ Metal‐Organic Charge Transfer Complexes via Galvanic Replacement vs Corrosion‐Recrystallization
Hybrid CuTCNQ/AgTCNQ Metal‐Organic Charge Transfer Complexes via Galvanic Replacement vs Corrosion‐Recrystallization
复制标题
DOI：
10.1002/adfm.201402320
复制
发表时间：
2014-12
影响因子：
19
通讯作者：
A. Pearson;R. Ramanathan;A. O’Mullane;V. Bansal
中科院分区：
文献类型：
--
作者：
A. Pearson;R. Ramanathan;A. O’Mullane;V. Bansal
这项研究报道了两种基于7，7，8，8-四氰基喹二甲烷(TCNQ)的有机电荷转移络合物的金属-有机半导体的混合。结果表明，在水溶液和乙腈中，CuTCNQ半导体微棒与Ag+离子自发反应生成CuTCNQ/AgTCNQ杂化产物，尽管反应机理完全不同。在水环境中，反应通过复杂的电偶置换(GR)机理进行，其中除了AgTCNQ纳米线外，Ag0纳米颗粒和Cu(OH)2晶体修饰了CuTCNQ微棒的表面。相反，在乙腈中，GR机制在热力学上是不利的，而腐蚀-再结晶机制导致CuTCNQ微棒被AgTCNQ纳米片修饰，从而得到纯的CuTCNQ/AgTCNQ杂化金属-有机电荷转移络合物。虽然经常报道两种不同无机半导体的杂化，但这份报告开创了两种金属-有机半导体杂化的先河，这将扩大基于TCNQ的电荷转移络合物的范围，用于改进催化、传感、电子和生物应用。
This study reports a hybrid of two metal‐organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8‐tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion‐recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal‐organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal‐organic semiconductors that will expand the scope of TCNQ‐based charge transfer complexes for improved catalysis, sensing, electronics, and biological applications.