Study Of Electric Catalytic Properties Of Biunclear IRON Pthalocyanine

Due to the large p-conjugated system in macrocycle, phthalocyanine compoundsnot only show good electrocatalytic activity, but also could be modified the structureof phthalocyanine molecule, This is by adjusting the central metal atom and peripheralsubstituent ground or the congregation morphology of the molecular to obtain therequired physical and chemical properties. The modifications of the structure makethem could be used in the fields of electrocatalytic activity widely in the future.Fuel cells is a kind of environmental friendly device that can convert chemicalenergy directly to electricity. Cathode oxygen reduction reaction (ORR) catalyst is thekey materials of Fuel Cells. Currently, Platinum and its alloys are good catalysts forORR used for fuel cell in low temperature condition, however, the high cost andshortage hinders its commercialization. In the effort to reduce the cost as well as toimprove the reliability of fuel cell catalysts, non-Pt (or non-noble metal) catalystshave attracted great attention over the last several decades. Among the non-noblemetal catalysts explored, transition metal-N4chelates such as metallophthalocyaninesand metalloporphyrins have shown great promise as candidates for fuel cell ORRcatalysts. Phthalocyanine compounds are considered as one of the most promisingcatalyst material to replace the noble metal.The stability of metallophthalocyanines is the main factor, which restrains thedevelopment of practicality as ORR catalysts. Being the ORR catalystsmetallphthalocyanine complexes will lead to the formation of a little amount of H₂O₂which will erode the Pc-ring and carrier badly, and then destroy the structure ofcatalysts. Thus how to improve the stability of metallophthalocyanines as the ORRcatalysts is all-important task in the fields of ORR electrocatalysts.In this study, we choose a planar binuclear iron phthalocyanine as ORR catalystand plan to improve the stability of ORR catalysts through its large p electronconjugated system. The main results and conclusions are as follows:Two binuclear metal phthalocyanine complexes are synthesized by solid routeUsing o-phthalic anhydride, pyromellitic dianhydride and metal salt as the rawmaterials at the present of urea and ammonium molybdate. The crude product waswashed with ammonia solution, hydrochloric acid, and water, followed by anextraction process with ethanol and tetrahydrofuran (THF) to purify the product. Afterthis extraction, the resultant dark blue solid was further purified by silica columnchromatography. The products have been characterized by IR, UV-Vis, HNMR,LDT-TOF-MS and elemental analysis respectively.The ORR catalytic activity of binuclear iron phthalocyanine (bi-FePc) has beeninvestigated using CV and RDE technique. The results show that this bi-FePc/Ccatalyst can catalyze a direct4-electron reduction of oxygen to water. The bi-FePc/C showed superior activity, has a about100mV higher ORR onset potential than theFePc/C catalyst. Chronoamperometry tests were conducted to examine the stability ofthe bi-FePc/C catalyst, and the results show that this bi-FePc/C electrocatalyst has abetter stability than the mononuclear FePc/C catalyst in acidic solution. This catalystalso has methanol tolerance, suggesting that it should be able to improve theperformance of a direct methanol fuel cell cathode.We successfully synthesized a planar binuclear iron phthalocyanine on carbonnanotube (bi-FePc/MWNT) catalyst for the oxygen reduction reaction by in situmethod for the first time. The electronic absorption spectra in a dimethyl sulfoxide(DMSO) solution of the products have been determined and indicated that bi-FePcwas successfully synthesized by this process. The influence of the reactants molarratio on the yield of bi-FePc/MWNT has been studied. The bi-FePc/MWNT catalystwas characterized by XRD, TEM and the results show that the bi-FePc was coateduniformly on the carbon nanotube. According to the high-resolution TEM image theclear lattice fringes can be observed.The effect of the time of the whole reaction process on the morphology of thebi-FePc/MWNT was discussed. The amount of molecules of bi-FePc coated on thecarbon nanotube was more and more as time prolonging.Using CV and RDE technique, it was confirmed that this bi-FePc/MWNT couldshow a nearly perfect ORR catalytic activity and stability in acidic solution. Thisnovel bi-FePc/MWNT catalyst can catalyze a direct4-electron reduction of oxygen towater. In comparison with a mononuclear FePc catalyst, this catalyst showed superioractivity and enhanced stability. This catalyst also has methanol tolerance, suggestingthat it should be able to improve the performance of a direct methanol fuel cellcathode.With dual-core iron phthalocyanine/carbon nanotube composites aselectrocatalysts chlorinated organics reduction of atrazine, by changing thetemperature, pH, electrolyte, the amount of catalyst, electrolytic cell structure, andelectrochemical reaction type of flow conditions set of conditions, such as removal ofthe influence factors and the relationship. Binuclear iron phthalocyanine/carbonnanotube composites can effectively degrade chlorinated organic compounds atrazine,48h after the degradation rate of up to98%. Using CA, the removal of the voltagesettings on the reaction to a certain extent, the voltage of0.55V is the best. Atrazine inthe dual-core power of iron phthalocyanine catalyst/carbon nanotube compositematerial under the action of hydroxyl dechlorination reaction, the product is2-hydroxy-4-amine base-6-isopropylamine-1,3,5-triazine, toxicity greatly reduced. Thisstudy not only the application of phthalocyanine opened up new areas of researchmore efficient degradation of endocrine disruptors atrazine new technologies for the treatment of pesticides resulting in contamination of water sources to provide a decentbasic research reference.This is the first time using dual-core iron phthalocyanine/carbon nanotubecomposite for electrocatalytic reduction of nitrate experiments; it has a certain natureof the electrocatalytic reduction of nitrate. The catalytic reduction of nitrate in waterhas been studied using bi-FePc loaded on multi-walled carbon nanotubes(bi-FePc/MWNT) as electrocatalyst. The results show that, bi-FePc/MWNT cancatalysis to remove nitrate in the water and shows a good selectivity towards nitrogen.The concentration of NO₃^--N was reduced from20mg·L^-1to13.7mg·L^-1in currentdensity of2.3mA/cm2, pH6.4and NO₃^--N of20mg·L^-1in the prstine water after20h. The removing rate of nitrate is up to31.5%. The catalytic activity and selectivitydepends on pH value, current density and catalyst amount.A small amount ofby-products are generated, but need to further improve the removal rate. But for thedenitrification study provide a new catalyst system, has made some contribution. Alsofor the application of phthalocyanine materials, provided broader space.