Synthesis Of One-dimensional Mirco/Nano Materials By Water-Soluble Template

In this dissertation, water-soluble templates of copper (Ⅱ) phenanthroline (phen) sulfate complexes including [Cu(phen)(H2O)2]·SO4and [Cu(phen)(OH)]2SO4·5H2O were prepared, and were used to synthesize one-dimensional (ID) micro/nano tubules of polypyrrole(PPy) and polyaniline (PANI). Their structures and properties were characterized by elemental analysis, X-ray powder diffraction (XRD), infrared spectroscopy (IR), photoluminescence spectrum, scanning electron microscopy (SEM), optical microscope, transmission electron microscopy (TEM), thermal analysis, etc. The effects of pH, temperature, concentration, ripening time, ultrasonication and surfactant on the morphologies, size and crystal structure of the as-prepared products were studied.Two water-soluble micro-nanometer materials of copper (Ⅱ) phenanthroline sulfate complexes including [Cu(phen)(H2O)2]·SO4and [Cu(phen)(OH)]2SO4·5H2O were synthesized by using copper sulfate and1,10-phenanthroline as raw materials. When pH of CUSO4solution equals to2.0and5.0, microscale flower-like and long belt-like morphologies of monoclinic [Cu(phen)(H2O)2]·SO4were obtained, respectively. Granular and belt-like products could be yielded with the change of the ratio of copper sulfate to phen. The size of [Cu(phen)(H2O)2]·SO4was found to be effected by the concentration of copper sulfate and deposition medium. When the initial pH was raised up to9.0and11.0, rod-like structures of [Cu(phen)(OH)]2SO4·5H2O were synthesized with average diameter of about172nm and253nm, respectively. With constant initial pH of9.0, the diameter of rod-like product can decrease with the reduction of the reaction temperature from60℃to4℃. As the ripening time was extended, the nanorod grew longer and wider. Ultrasonication had little influence on the final products. In addition, the photoluminescence spectrum of belt-like [Cu(phen)(H2O)2]·SO4showed a blue shift and enhanced emission compared with that of the nanorod-like complex of [Cu(phen)(OH)]2SO4·5H2O.Using the nanorod-like [Cu(phen)(OH)]2SO4·5H2O as a template and ammonium persulfate (APS) as an oxidant, PPy and PANI were prepared via chemical oxidation in ethanol-water solution. Corresponding micro-tubes were obtained easily after the elimination of those templates with deionized water. TEM images showed that the products had tubular structure, the PPy nanotubes were about72nm in internal diameter and17nm in wall thickness, while the PANI nanotubes were275nm and38nm respectively. Polymer with different diameter could be attained using different templates with corresponding diameter. The diameter of PPy decreased firstly and then increased when increasing the concentration of ammonia solution. The dispersion condition of PPy was improved as surfactant K30was added. The surface roughness of PANI nanotubes became worse with the increasing of oxidant concentration. Their diameter increased with reduction of template to monomer ratio and only irregular morphologies were obtained when the template to monomer ratio was too low due to the dissolution of templates.Using the belt-like [Cu(phen)(H2O)2]·SO4as a template; PPy nano-tubes were synthesized via chemical oxidation process and then this template was removed by deionized water. PPy nanotubes with less surface roughness were prepared using iron chlorides (FeCl3) as oxidants, due to their weak oxidative ability of FeCl3compared with APS, and the as-prepared products could be collapsed to form ribbon or sheet-like morphologies. With the rising of APS concentration, the decreasing of template concentration and volume ratio of ethanol to water, irregular morphologies of PPy were obtained.