以重氮树脂与4-甲酰基苯甲酸为底层构筑三联吡啶-钌离子层-层自组装超薄功能膜  

FABRICATION AND OPTOELECTRONIC CONVERSION OF LAYER-BY-LAYERSELF-ASSEMBLY FILMS BASED ON TERPYRIDINES AND METAL IONS ON SURFACE OF SUBSTRATE MODIFIED BY DIAZORESIN AND 4-FORMYLBENZOIC ACID

作　　者：潘月秀[1] 佟斌[1] 赵玮[1] 申进波[1] 石建兵[1] 支俊格[2] 董宇平[1] 

机构地区：[1]北京理工大学材料科学与工程学院,北京100081 [2]北京理工大学理学院,北京100081

出　　处：《高分子学报》2009年第12期1301-1306,共6页Acta Polymerica Sinica

基　　金：高等学校博士学科点专项科研基金(项目号20050007018);国家自然科学基金(基金号50573008;20634020)资助项目

摘　　要：在呈负电性的基底表面依次使用重氮树脂(DR)、4-甲酰基苯甲酸(FBA)和4-′(4-氨基苯基)-2,2′:6′,2″-三联吡啶(Atpy)进行修饰,在先后经过离子键转变为共价键和希夫碱反应后,实现了2,2′:6′,2″-三联吡啶基团在基片表面的锚定;然后基于配位作用,由1,4-二(2,2′:6′,2″-三联吡啶-4′-基)苯(Bi-tpy)与RuCl3在其表面构筑具有纳米尺寸的金属-有机超分子超薄膜.紫外-可见光谱、AFM均证明了这种层层自组装超薄膜的成功形成.光电转换显示其具有良好的光电转换性能和光化学稳定性,其转换效率与膜的厚度呈现较好的线性关系.To enhance the stability of the layer-by-layer （LBL） self-assembled films fabricated from terpyridines and ruthenium ions, a new method of introducing mono-terpyridinyl groups onto the surface of substrates was designed in this paper. First, diazoresin （DR） and sodium salt of 4-formylbenzoic acid （FBA） were successively deposited on the surface of substrate by self-assembly （SA） technique. Following decomposition of the diazonium group in DR under UV irradiation, the ionic bonds between substrate, DR and FBA were synchronously converted to the covalent bonds. Furthermore, the terpyridinyl groups were introduced onto the outmost surface through the Schiff base reaction between 4＇- （4-amino-phenyl）-2,2＇ ： 6＇, 2-terpyridine （Atpy） and formyl groups in DR-FBA. So that, the DR-FBA-Atpy monolayer film anchored on substrate was formed and very stable, which achieved the modification to substrates and provided active sites to coordinatively react with ruthenium ions. Consequently, diffluent 1,4- bis （ 2,2＇ ： 6＇, 2-terpyridine-4-yl） benzene （ Bi- tpy） and RuCl3 muhilayer films were formed on the DR- FBA-Atpy mouolayer through coordination bonds based on LBL self-assembled technique. The UV-Vis analysis results indicated that the LBL Bi-tpy/RuC13 self-assembled muhilayer films were successfully fabricated and the progressive assembly ran regularly with almost equal amounts of deposition in each cycle. The AFM images of the 4- bilayer Bi-tpy/RuCl3 film on silicon wafer showed round-shaped small domains with size of 25 nm. Under illumination, the self-assembled film on ITO showed effective photoinduced charge transfer. A linear relationship between conversion efficiency and the number of bilayers was discussed.

关 键 词：重氮树脂 希夫碱反应 三联吡啶 配位自组装 光电转换 

分 类 号：TB383.2[一般工业技术—材料科学与工程]