| 摘要: | This thesis is focused on electrochemical syntheses of bis(terpyridine)metal complex polymers with network and wire structures on carbon electrode and their applications. This thesis involves five chapters. Chapter 1 is an introduction of research background and research direction. In Chapter 2, the electrochemical synthesis of bis(terpyridine)iron network complex on glassy carbon and its application in electric energy storage are described. In Chapter 3, the preparation of bis(terpyridine)iron network-carbon nanotube hybridized material and its energy storage application are included. In Chapter 4, the electrochemical synthesis of ultra-long bis(terpyridine)metal molecular wire and their characterizations are explained. Chapter 5 is the conclusion of this thesis.
In chapter 1, the research background is introduced. First, the chemical properties, synthetic methods and various applications of bis(terpyridine)metal complexes, such as molecular electronics, light harvesting units and sensors, are explained. Second, several surface modification methods and their characteristics are introduced. Third, the distinguishing feature of supercapacitors and their preparations are described. Forth, molecular electronics and their operation theory are introduced. Finally, the aim of this thesis, using electrochemical polymerization methods to prepare functional complex polymers on carbon, is explained.
In Chapter 2, a bis(terpyridine)iron network complex was synthesized via electrochemical polymerization on a glassy carbon electrode. This network complex shows high capacity retention at high scan rates. When scan rate increases to 10 Vs-1, the capacity only decreases by 24% compared with scan rate of 0.025 Vs-1. Moreover, it can be charged to 80% in 0.08 s, 90% in 0.16 s and 95% in 0.35 s. On the other hand, the charged material can be discharged to 80% in 0.08 s, 90% in 0.16 s and 95% in 0.62 s. Finally the network complex is highly stable for continuous charging and discharging process. After 3000 cycles, the capacity of this network only decreases 5%.
In Chapter 3, the bis(terpyridine)iron network complex was successfully immobilized on a carbon nanotube porous electrode. This complex network-carbon nanotube hybridized material also can be charged and discharged at high scan rates and shows good stability under continuous operation. Moreover, as the carbon nanotube electrode provides much higher effective surface area, the areal capacitance of this hybridized material increases dramatically comparing with only the network complex on glassy carbon.
In Chapter 4, ultra-long bis(terpyridine)metal complex wires arrays on carbon electrodes were synthesized by electrochemical polymerization. Their chemical structures were characterized to be a linear rigid wire with azobenzene bridging by Raman spectroscopy. From AFM measurements, the molecular wire arrays show uniform length structure on electrode surface. On the other hand, this electrochemical method also can produce very long molecular wire. The longest one is found to be 7410 layers and corresponds to 14.82 μm, which is the longest bis(terpyridin)metal complex wire known. Moreover, according to electrochemical measurements, electrons in this wire can move freely, although it is longer than 14 μm. Finally, this electrochemical method also can synthesize hetero metal wires on carbon electrodes, which show unique diode properties. In short, this electrochemical method can not only efficiently generate long molecular wires, but can also be used to link different molecule components to form a molecular device.
In Chapter 5, the researches of this thesis are concluded. |
