和频振动光谱研究多晶金电极/溶液界面乙腈分子取向的flip-flop行为  

The Flip-Flop Behavior of Acetonitrile at Au Electrode Surface Investigated by Sum Frequency Generation Vibrational Spectroscopy

作　　者：黄芝[1] 唐鑫[1] 邓罡华[1] 周恩财 王鸿飞 郭源[1] 

机构地区：[1]中国科学院化学研究所分子反应动力学国家重点实验室,北京100190 [2]天津艾达恒晟科技发展有限公司,天津300200 [3]Division of Scientific Resource Environmental Molecular Science Laboratory,Pacific Northwest National Laboratory,Washington,USA

出　　处：《电化学》2011年第2期134-138,共5页Journal of Electrochemistry

基　　金：国家自然科学基金(20773143);973(2007CB815205)资助

摘　　要：应用和频振动光谱研究乙腈/金电极界面吸附,观测到乙腈的甲基振动峰强度随电极电势而变化.当电极电势越过零电荷电势(pzc)时,甲基振动峰符号发生反转,这意味着该基团取向发生反转(flip-flop).由此而推断乙腈分子在金电极界面的吸附构型.即在零电荷电势下,电极界面吸附的乙腈分子构型为甲基靠近电极表面而腈基远离电极表面;高于零电荷电势,则变为腈基靠近电极表面而甲基远离电极表面.The electrochemical interface between liquid acetonitrile and polycrystal gold electrode is investigated by in situ infrared visible sum frequency generation spectroscopy（SFG-VS）.The structure of acetonitrile adsorbed at polycrystal gold electrode surface is studied as a function of electrode potential.The SFG spectra of CH3 group indicate acetonitrile orients in response to the electrode potential.The SFG signal of CH3 group turns lower as the electrode potential changes from-700 mV to 300 mV,and vanishes around the 300 mV（pzc）,then becomes a negative signal above 500 mV,which indicates that the orientation is predominately with the CH3 group toward the metal between-700 and 300 mV and with the CN group toward the metal above 300 mV.It is the first time to observe the flip-flop behavior of acetonitrile dipole at the polycrystal gold electrode surface,which might become a common phenomenon.

关 键 词：和频振动光谱 取向反转 金电极 乙腈 

分 类 号：O621.25[理学—有机化学]