Wang Feifan, Zou Feixue, Yu Xinxin, Feng Zhenyu, Du Na, Zhong Yaohua, Huang Xirong
Key Laboratory of Colloid and Interface Chemistry of the Education Ministry of China, Shandong University, Jinan 250100, China.
Phys Chem Chem Phys. 2016 Apr 21;18(15):9999-10004. doi: 10.1039/c6cp00800c. Epub 2016 Mar 23.
A non-aqueous solution of tetra-n-butylammonium fluoride (TBAF) in ethylene glycol has been tried for the first time as a supporting electrolyte for the electropolymerization of 3-aminophenylboronic acid (APBA). Unlike the traditional acidic aqueous solution, the present medium needs no exogenous protons; moreover, the presence of CF3COOH is found to be unfavorable for the polymerization. The protons are in situ generated by the reaction between the boronic acid group on APBA and 1,2-dihydroxyl on ethylene glycol. So, ethylene glycol serves as not only the solvent but also the proton source. As a part of the supporting electrolyte, F(-) is found to be involved in the electrochemical synthesis of poly(3-aminophenylboronic acid) (PAPBA), but it is not indispensable. Studies on the electropolymerization process indicate that the size of the ions in the electrolyte affects the rate of the doping/dedoping process. The smaller the cation, the easier the doping/dedoping process, and the better the stability of the grown film. As demonstrated by Fourier transform infrared spectra, UV-vis spectra, and scanning electron microscopy, the obtained PAPBA is a cross-linked nanoporous polymer membrane that has a good adherence to the glassy carbon electrode.
首次尝试将四丁基氟化铵（TBAF）在乙二醇中的非水溶液用作3-氨基苯硼酸（APBA）电聚合的支持电解质。与传统的酸性水溶液不同，本介质不需要外源质子；此外，发现CF3COOH的存在对聚合不利。质子由APBA上的硼酸基团与乙二醇上的1,2-二羟基之间的反应原位产生。因此，乙二醇不仅用作溶剂，还用作质子源。作为支持电解质的一部分，发现F(-)参与聚（3-氨基苯硼酸）（PAPBA）的电化学合成，但它不是必不可少的。对电聚合过程的研究表明，电解质中离子的大小影响掺杂/脱掺杂过程的速率。阳离子越小，掺杂/脱掺杂过程越容易，生长膜的稳定性越好。傅里叶变换红外光谱、紫外可见光谱和扫描电子显微镜表明，所获得的PAPBA是一种交联的纳米多孔聚合物膜，对玻碳电极具有良好的附着力。
