光谱学与光谱分析
光譜學與光譜分析
광보학여광보분석
SPECTROSCOPY AND SPECTRAL ANALYSIS
2014年
12期
3345-3349
,共5页
刘文涵%袁荣辉%滕渊洁
劉文涵%袁榮輝%滕淵潔
류문함%원영휘%등연길
表面增强拉曼光谱%紫外光谱%2,3-二巯基丁二酸镍配合物%金电极%修饰膜
錶麵增彊拉曼光譜%紫外光譜%2,3-二巰基丁二痠鎳配閤物%金電極%脩飾膜
표면증강랍만광보%자외광보%2,3-이구기정이산얼배합물%금전겁%수식막
SERS%UV spectra%Nickel(Ⅱ) complexes of 2,3-Dimercaptosuccinate%Gold electrode%Modified film
采用非现场表面增强拉曼光谱(ex-situ SERS)与电还原等方法,对2,3-二巯基丁二酸(DMSA)及与Ni(Ⅱ)所形成的配位化合物DMSA-Ni(Ⅱ),在活性Au电极表面的修饰膜进行了研究。先由紫外吸收光谱测算了DMSA与Ni2+形成的配合物参数,其配位比为1∶2,稳定常数为4.716×107,可知形成的配合物较稳定。研究表明,DMSA与活性Au发生了吸附作用,DMSA-Ni(Ⅱ)形成的是S—Ni—O配位键,DMSA-Ni (Ⅱ)在Au电极上电还原时出现了两个还原峰,认为:负扫出现的第1个还原峰是由DMSA-Ni(Ⅱ)配合物动态平衡中的DMSA与Au吸附键合的RS—Au基团产生,而第2个还原峰与配合物中的Ni2+有关。通过Au表面DMSA-Ni(Ⅱ)修饰膜覆盖度的测定、分子面积的比对表明,DMSA-Ni(Ⅱ)在活性Au表面的分子排布状态可能是分散的或局部连接的单分子层,而非聚集在一起的致密层或分子间重叠的多层形式。
採用非現場錶麵增彊拉曼光譜(ex-situ SERS)與電還原等方法,對2,3-二巰基丁二痠(DMSA)及與Ni(Ⅱ)所形成的配位化閤物DMSA-Ni(Ⅱ),在活性Au電極錶麵的脩飾膜進行瞭研究。先由紫外吸收光譜測算瞭DMSA與Ni2+形成的配閤物參數,其配位比為1∶2,穩定常數為4.716×107,可知形成的配閤物較穩定。研究錶明,DMSA與活性Au髮生瞭吸附作用,DMSA-Ni(Ⅱ)形成的是S—Ni—O配位鍵,DMSA-Ni (Ⅱ)在Au電極上電還原時齣現瞭兩箇還原峰,認為:負掃齣現的第1箇還原峰是由DMSA-Ni(Ⅱ)配閤物動態平衡中的DMSA與Au吸附鍵閤的RS—Au基糰產生,而第2箇還原峰與配閤物中的Ni2+有關。通過Au錶麵DMSA-Ni(Ⅱ)脩飾膜覆蓋度的測定、分子麵積的比對錶明,DMSA-Ni(Ⅱ)在活性Au錶麵的分子排佈狀態可能是分散的或跼部連接的單分子層,而非聚集在一起的緻密層或分子間重疊的多層形式。
채용비현장표면증강랍만광보(ex-situ SERS)여전환원등방법,대2,3-이구기정이산(DMSA)급여Ni(Ⅱ)소형성적배위화합물DMSA-Ni(Ⅱ),재활성Au전겁표면적수식막진행료연구。선유자외흡수광보측산료DMSA여Ni2+형성적배합물삼수,기배위비위1∶2,은정상수위4.716×107,가지형성적배합물교은정。연구표명,DMSA여활성Au발생료흡부작용,DMSA-Ni(Ⅱ)형성적시S—Ni—O배위건,DMSA-Ni (Ⅱ)재Au전겁상전환원시출현료량개환원봉,인위:부소출현적제1개환원봉시유DMSA-Ni(Ⅱ)배합물동태평형중적DMSA여Au흡부건합적RS—Au기단산생,이제2개환원봉여배합물중적Ni2+유관。통과Au표면DMSA-Ni(Ⅱ)수식막복개도적측정、분자면적적비대표명,DMSA-Ni(Ⅱ)재활성Au표면적분자배포상태가능시분산적혹국부련접적단분자층,이비취집재일기적치밀층혹분자간중첩적다층형식。
2 ,3-Dimercaptosuccinic acid (DMSA) and its complex Nickel(Ⅱ) 2 ,3-Dimercaptosuccinate (DMSA-Ni(Ⅱ)) were as-sembled on the electrochemically activated Au electrode and the modified films were investigated by ex-situ SERS ,SEM and elec-tro-reduction .The coordination ratio (1∶2) and stability constant (4.716 × 107 ) of DMSA and Nickel(Ⅱ ) were firstly con-firmed by UV .Then ,the SERS spectra showed that DMSA was absorbed on the surface of activated Au and the coordinate bond of DMSA-Ni(Ⅱ) was existed as S—Ni—O .Meanwhile ,two reduction peaks of DMSA-Ni(Ⅱ) on Au electrode were presented at negative potential .The first peak (from positive to negative values) was related to the RS—Au group which was produced by the mutual absorption of DMSA and Au .The second reduction peak was related to Nickel (Ⅱ) .Finally ,it was further confirmed by calculating the surface coverage and comparison of molecular area .And it was found that the molecular arrangement of DM-SA-Ni(Ⅱ) on Au electrode generated as monolayer which was dispersed or connected partly instead of concentrated or over-lapped .