• 专利标题:   Method for preparing graphene-porphyrin modified electrode, involves mixing flake graphite, potassium persulfate and phosphorus pentoxide, and adding composite material graphene oxide and porphyrin and modified glassy carbon electrode.
  • 专利号:   CN103852505-A, CN103852505-B
  • 发明人:   CHEN L, GUO B, GUO X, WANG F
  • 专利权人:   HARBIN INST TECHNOLOGY
  • 国际专利分类:   G01N027/30
  • 专利详细信息:   CN103852505-A 11 Jun 2014 G01N-027/30 201455 Pages: 10 Chinese
  • 申请详细信息:   CN103852505-A CN10120552 28 Mar 2014
  • 优先权号:   CN10120552

▎ 摘  要

NOVELTY - A graphene-porphyrin modified electrode preparing method involves mixing natural crystalline flake graphite, potassium persulfate and phosphorus pentoxide to obtain graphene oxide dispersion solution. The obtained 5-(4-phenyl)-10, 15, 20-triphenyl porphyrin is added to hydrochloric acid followed by subjecting the mixture to column chromatography, extracting 5-(4-amidogen) phenyl-10, 15, 20-tri-phenyl manganese porphyrin, mixing triethylamine and purified manganese porphyrin complex and adding mixtures into modified glassy carbon electrode to obtain graphene-porphyrin modified electrode. USE - Method for preparing graphene-porphyrin modified electrode. ADVANTAGE - The Method enables preparing graphene-porphyrin modified electrode with good anti-interference performance and stability. DETAILED DESCRIPTION - A graphene-porphyrin modified electrode preparing method involves mixing 6 g natural crystalline flake graphite, 5 g potassium persulfate and 5 g phosphorus pentoxide and adding 24 ml sulfuric acid, stirring the mixture at 80 degrees C for 4.5 hours in oil bath to obtain pre-graphite oxide. The 23 ml of mixture is allowed in ice water bath and 98% concentrated sulfuric acid is added followed by cooling the mixture at 3.5-5 degrees C, adding 1 g pre-graphite oxide, stirring the mixture, adding 3.5 g potassium permanganate into mixture, maintaining the water bath at 4-6 degrees C, stirring the mixture in water bath at 35 degrees C for 2 hours, adding 90 ml distilled water, stirring the mixture at 98 degrees C for 15 minutes, diluting the mixture using 75 ml of distilled water, adding 10 ml hydrogen peroxide into mixture, centrifuging the obtained mixture to obtain graphene oxide dispersion solution, drying the solution to oxidized graphite alkene solid, adding 30 mg obtained graphene oxide to 20 ml thionyl chloride solution, adding 0.5ml dimethylformamide (DMF) solution and maintaining the mixture at 70 degrees C for 24 hours to obtain acyl chloride graphene. The 9.85 ml benzaldehyde is added in 200 ml propionic acid solution to heat and refluxed. The 6.75 ml pyrrole is added into refluxed solution to react for 80-l00 minutes and 200 ml anhydrous ethanol is added. The temperature is maintained to 20 degrees C for 10-12 hours, filtered and obtained solid is dissolved in dichloromethane. The dissolved mixture is subjected to column chromatography to obtain porphyrin. The porphyrin is added to 75 ml chloroform and mixture is stirred at 0-5 degrees C. The 75 ml chloroform solution is added into 27 mmol nitric acid and allowed for 1.5 hours to react. The obtained mixture is added with ink green and subjected to column chromatography to obtain 5-(4-phenyl)-10, 15, 20-triphenyl porphyrin. The 0.6 g 5-(4-phenyl)-10, 15, 20-triphenyl porphyrin is added to 40 ml of 25% concentrated hydrochloric acid and 3 g chloride is added followed by stirring the mixture at 65 degrees C for 1.2 hours, cooling the mixture at room temperature, filtering, subjecting the mixture to column chromatography to obtain 5-(4-amidogen) phenyl-10,15,20-triphenyl porphyrin, adding 30 ml DMF solution into 60 mg 5-(4-amidogen) phenyl-10,15,20-triphenyl porphyrin, adding 1 g anhydrous manganese (II) chloride into mixture, stirring the mixture for 150 degrees C, refluxing the mixture for 2 hours, washing and extracting 5-(4-amidogen) phenyl-10, 15, 20-tri-phenyl manganese porphyrin, purifying by column chromatography to obtain pure manganese porphyrin complex, adding graphene acyl chloride into DMF solution, adding 0.5 ml triethylamine and 30 mg purified manganese porphyrin complex, refluxing the mixture at 130 degrees C for 72 hours, cooling the mixture at room temperature, adding 300 ml ether into mixture, collecting the precipitate, filtering, washing to obtain functional composite material of graphene oxide and porphyrin, subjecting the obtained product to ultrasonication using DMF solution, adding functional composite material of graphene oxide and porphyrin into 5 mu l modified glassy carbon electrode and maintaining the temperature at 4 degrees C for 10-12 hours to obtain graphene-porphyrin modified electrode.