Synthesis and characterization of polymer/inorganic intercalation compounds.

摘要

Poly(ethylene-oxide), poly(vinylpyrrolidone), poly(propylene-oxide) and methyl-cellulose have been intercalated in {dollar}rm Vsb2Osb5{dollar}{dollar}{lcub}cdot n{rcub}rm Hsb2O{dollar} xerogel by mixing aqueous polymer solutions with aqueous {dollar}rm Vsb2Osb5{dollar} gels followed by slow drying. Various phases of the polymer/{dollar}rm Vsb2Osb5{dollar} materials were prepared by changing the stoichiometric conditions. Irradiation with UV or visible dramatically changes the electronic structure of {dollar}rm Vsb2Osb5{dollar} framework and results in enhanced electrical conductivity. The conductivity decreases as the polymer content increases. The thermopower data are consistent with a n-type semiconductor.; The reaction of {dollar}rm Vsb2Osb5{dollar} xerogel with {dollar}rm Csb6Hsb5NHsb3I{dollar} in a 1:4 molar ratio in {dollar}rm CHsb2Clsb2{dollar} for 2 days yielded (anilinium){dollar}sb{lcub}0.4{rcub}rm Vsb2Osb5cdot0.4Hsb2O{dollar} 1. Exposure to air resulted in an intra-lamellar polymerization to form {dollar}{lcub}{dollar}1/n(-C{dollar}rmsb6Hsb4NH{dollar}-){dollar}rmsb n{rcub}sb{lcub}0.4{rcub}Vsb2Osb5cdot0.4Hsb2O{dollar} 2. Magnetic susceptibility measurements showed a {dollar}rmmusb{lcub}eff{rcub}{dollar} of 1.3 BM for 1 and 0.87 BM for 2. The electrical conductivity of 2 (10{dollar}sp{lcub}-3{rcub}{dollar} S/cm) is higher than that of 1 (10{dollar}sp{lcub}-5{rcub}{dollar} S/cm) while the thermopower of 2 ({dollar}-{dollar}100 {dollar}mu{dollar}V/K) is smaller than that of 1 ({dollar}-{dollar}20 {dollar}mu{dollar}V/K).; {dollar}rm Asb xV{dollar}{dollar}sb2Osb5cdot nrm Hsb2O{dollar} xerogels (A = K and Cs, 0.05 {dollar}<{dollar} x {dollar}<{dollar} 0.6) were synthesized by reacting {dollar}rm Vsb2Osb5{dollar} xerogel with various amounts of KI and CsI in acetone under N{dollar}sb2{dollar} for 3 days. X-ray diffraction and FT-IR indicated that the pristine {dollar}rm Vsb2Osb5{dollar} framework is preserved. The magnetic behavior of the {dollar}rm Asb xV{dollar}{dollar}sb2Osb5cdot nrm Hsb2O{dollar} phases is best described as Curie-Weiss type coupled with temperature independent paramagnetism (TIP). The Curie constant and EPR peak-width of the {dollar}rm Asb xV{dollar}{dollar}sb2Osb5cdot nrm Hsb2O{dollar} materials show a maximum value at x {dollar}sim{dollar} 0.3. Charge transport studies indicate a thermally activated semiconductor. Optical diffuse reflectance spectra are reported.; Aniline and N-phenyl-1,4-phenylenediamine (PPDA) were intercalated in {dollar}rm HUOsb2PO{lcub}sb4cdot4{rcub}Hsb2O{dollar} (HUP), {dollar}alpha{dollar}-Ti(HOPO{dollar}rmsb3){lcub}sb2cdot H{rcub}sb2O{dollar} (TiP) and {dollar}alpha{dollar}-Zr(HOPO{dollar}rmsb3){lcub}sb2cdot H{rcub}sb2O{dollar} (ZrP) to form precursors for polymerization. Thermal treatment at 130{dollar}spcirc{dollar}C in air resulted in an intralamellar polymerzation of aniline and PPDA to polyaniline. The formation of polyaniline was confirmed by spectroscopy, EPR and magnetic susceptibility. X-ray diffraction data indicated a monolayer of polyaniline in HUP and TiP, and a bilayer of polyaniline in ZrP. All materials are insulators. The MW of the polyaniline was estimated by gel permeation chromatography.