氧化石墨烯固载四(对-羧基苯基)锰卟啉催化氧化甲苯
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摘要
为模拟细胞色素P-450酶催化活性空腔,提高昂贵金属卟啉的催化使用效率,采用改进的Hummers法制备氧化石墨烯,通过π-π非共价键以及配位作用制得氧化石墨烯固载四(对-羧基苯基)锰卟啉的仿生催化材料。采用红外可见光谱(FT-IR)、紫外可见光谱(UV-Vis)、热重分析(TG)、扫描电镜(SEM)、比表面积测试(BET)和X射线光电子能谱分析(XPS)等技术对此催化材料进行表征,并运用于催化氧化甲苯的性能研究。研究结果表明,在较优条件(170℃,0.8 MPa)下,用含0.5 mg四(对-羧基苯基)锰卟啉的催化材料催化氧气氧化甲苯可以重复使用4次,其催化氧化甲苯的平均转化率为12%,醇酮产率为5%,基本保持四(对-羧基苯基)锰卟啉对甲苯的催化活性。这表明氧化石墨烯对四(对-羧基苯基)锰卟啉的固载作用能提高金属卟啉的催化使用效率,降低金属卟啉核心催化剂的成本,具有较好的应用价值。
To simulate the catalytic cavity of Cytochrome P-450 enzyme,graphene oxide( GO) was prepared by modified Hummers method, and used for supportingmanganesetetrakis( pcarboxylphenyl) porphyrin( Mn TCPP Cl) by π-π and coordination interactions,forminggraphene oxide-supported metalloporphyrin. The catalytic material was characterized by FT-IR and UV-Vis spectra,Thermogravimetric Analysic( TG),Scaning Electron Microscope( SEM),BET surface area measurement( BET) and X-ray photoelectron spectroscopy( XPS). Mn TCPP Cl/GO was used tocatalyze methylbenzene oxidation with O2. Under optimum oxidation conditions( 170 ℃,0. 8 MPa),only 0. 5 mg of graphene oxide immobilized manganesetetrakis( p-carboxylphenyl) porphyrin were reused 4 times. On average,the methylbenzene conversion was 12% and the yields( ketone and alcohol) was 5%. These suggest that the catalytic material is better than the manganesetetrakis( pcarboxylphenyl) porphyrin.
To simulate the catalytic cavity of Cytochrome P-450 enzyme,graphene oxide( GO) was prepared by modified Hummers method, and used for supportingmanganesetetrakis( pcarboxylphenyl) porphyrin( Mn TCPP Cl) by π-π and coordination interactions,forminggraphene oxide-supported metalloporphyrin. The catalytic material was characterized by FT-IR and UV-Vis spectra,Thermogravimetric Analysic( TG),Scaning Electron Microscope( SEM),BET surface area measurement( BET) and X-ray photoelectron spectroscopy( XPS). Mn TCPP Cl/GO was used tocatalyze methylbenzene oxidation with O2. Under optimum oxidation conditions( 170 ℃,0. 8 MPa),only 0. 5 mg of graphene oxide immobilized manganesetetrakis( p-carboxylphenyl) porphyrin were reused 4 times. On average,the methylbenzene conversion was 12% and the yields( ketone and alcohol) was 5%. These suggest that the catalytic material is better than the manganesetetrakis( pcarboxylphenyl) porphyrin.
引文
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[17]ZHAO G,REN X,GAO X,et al.Removal of Pb(II)ions from aqueous solutions on few-layered graphene oxide nanosheets[J].Dalton Transactions,2011,40(41):10945-10952.
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[28]HUANG G,XIANG F,LI T M,et al.Selective oxidation of toluene over the new catalyst cobalt tetra(4-hydroxyl)phenylporphyrin supported on zinc oxide[J].Catalysis Communications,2011,12(10):886-889.
[29]HUANG G,LIU S Y,WANG A P,et al.Catalysis of structure-like macromolecules supported manganese tetraphenylporphyrin for cyclohexane oxidation[J].Catalysis Communications,2007,8(8):1183-1186.
[30]俞东军,李敏智,黄显著,等.壳聚糖修饰金属卟啉的制备及磁共振成像性能[J].光谱学与光谱分析,2013,33(10):2736-2739.
[31]STANKOVICH S,PINER R D,NGUYEN S B T,et al.Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets[J].Carbon,2006,44(15):3342-3347.
[32]SZABT,BERKESI O,DKNY I D.Study of deuterium-exchanged graphite oxide[J].Carbon,2005,43(15):3186-3189.
[33]POURSABERI T,GANJALI M R,HASSANISADI M.A novel fluoride-selective electrode based on metalloporphyrin grafted-grapheneoxide[J].Talanta,2012,101(22):128-134.
[34]毕纯.卟啉—石墨烯非共价复合材料的制备及性质测定[D].南京:南京大学,2012.
[35]JAHAN M,BAO Q,LOH K P.Electrocatalytically active graphene-porphyrin MOF composite for oxygen reduction reaction[J].Journal of the American Chemical Society,2012,134(15):6707-6713.
[36]ZHENG L,YE D,XIONG L,et al.Preparation of cobalt-tetraphenylporphyrin/reduced graphene oxide nanocomposite and its application on hydrogen peroxide biosensor[J].Analytica Chimica Acta,2013,768(1):69-75.
[37]AND M K,JARONIEC M.Gas Adsorption Characterization of Ordered Organic-Inorganic Nanocomposite Materials[J].Chemistry of Materials,2001,13(10):3169-3183.
[38]RASALINGAM S,MAHONEY L,WU C M,et al.Aging dependent phase transformation of mesostructured titanium dioxide nanomaterials prepared by evaporation-induced self-assembly process:Implications for solar hydrogen production[J].Materials Science,2015,2(3):230-242.
[39]苏海亮.氧化石墨烯负载席夫碱金属配合物的制备、表征及其环氧化催化性能研究[D].长春:吉林大学,2015.
[40]CHANG H,QIN J,XIAO P,et al.Highly reversible and recyclable absorption under both hydrophobic and hydrophilic conditions using a reduced bulk graphene oxide material[J].Advanced Materials,2016,28(18):3504-3509.
[41]HUANG J W,LIU Z L,GAO X R,et al.Hydroxylation of cyclohexane catalyzed by iron(III)-metal-free porphyrin dimer with molecular oxygen:The effect of the steric hindrance and the intramolecular interaction between the two porphyrin rings[J].Crystengcomm,2016,18(12):2203-2209.
[42]PARK S,AN J,POTTS J R,et al.Hydrazine-reduction of graphite-and graphene oxide[J].Carbon,2011,49(9):3019-3023.
[43]FURTOS G,NAGHIU M A,DECLERCQ H,et al.Nano forsterite biocomposites for medical applications:Mechanical properties and bioactivity[J].Journal of Biomedical Materials Research Part B Applied Biomaterials,2015,104(7):1290-1301.
[44]YOU J M,HAN H S,LEE H K,et al.Enhancedelectrocatalytic activity of oxygen reduction by cobalt-porphyrin functionalized withgraphene oxide in an alkaline solution[J].International Journal of Hydrogen Energy,2014,39(10):4803-4811.
[45]GE R,LI X,KANG S Z,et al.Highly efficient graphene oxide/porphyrin photocatalysts for hydrogen evolution and the interfacial electron transfer[J].Applied Catalysis B Environmental,2016,187:67-74.
[46]MORADI S E.Efficient photocatalytic hydrogen evolution by iron platinum loaded reduced graphene oxide[J].Chemical and Biochemical Engineering Quarterly,2016,30(1):1-7.
[47]李拥虎.氧化石墨烯/壳聚糖复合材料的制备及其载药性能研究[D].成都:西南交通大学,2013.
[48]HUANG G,MO L Q,CAI J L,et al.Environmentally friendly and efficient catalysis of cyclohexane oxidation by iron meso-tetrakis(pentafluorophenyl)porphyrin immobilized on zinc oxide[J].Applied Catalysis B Environmental,2015,162(10):364-371.
[2]杨洋洋,刘懿,朱明乔.甲苯液相催化氧化制苯甲醛绿色工艺研究进展[J].精细化工中间体,2011,28(5):66-70.
[3]葛欣.甲苯气相选择性氧化制苯甲醛的研究进展[J].石油化工,2009,38(8):903-910.
[4]SRIVASTAVA K,DEVRA V,RANI A.Fly ash supported vanadia catalyst:An efficient catalyst for vapor phase partial oxidation of toluene in a micro-reactor[J].Fuel Processing Technology,2014,121(121):1-8.
[5]金少瑾.甲苯液相氧化反应催化剂及其催化性能研究[D].杭州:浙江大学,2012.
[6]KANTHAM M L,SREEKANTH P,RAO K K,et al.Selective liquid phase air oxidation of toluene catalysed by composite catalytic system:US,US6743952[P].2004-06-01.
[7]JOHNSTONE A,ROWBOTTOM K T,SANDERSON W R,et al.Oxidation of alkylaromatics:US,US5473101[P].1995-12-05.
[8]SUN Z,LI G,ZHANG Y,et al.Ag-Cu-BTC prepared by postsynthetic exchange as effective catalyst for selective oxidation of toluene to benzaldehyde[J].Catalysis Communications,2015,59(59):92-96.
[9]WU X,DENG Z,YAN J,et al.Effect of acetic anhydride on the oxidation of toluene to benzaldehyde with metal/bromide catalysts[J].Industrial&Engineering Chemistry Research,2014,53(38):14601-14606.
[10]张文明,雷福琼.金属卟啉催化空气氧化甲苯制取苯甲醛及苯甲醇的新工艺[J].浙江化工,2014,45(3):29-33.
[11]REBELO S H,SIMES M Q,NEVES M G M S,et al.Oxidation ofΔ4-andΔ5-steroids with hydrogen peroxide catalyzed by porphyrin complexes of MnIIIand FeⅢ[J].European Journal of Organic Chemistry,2004,2004(2004):4778-4787.
[12]RANI V R,KISHAN M R,KULKARNI S J,et al.Immobilization of metalloporphyrin complexes in molecular sieves and their catalytic activity[J].Catalysis Communications,2005,6(8):531-538.
[13]HUANG G,WANG P,SHEN L,et al.Porous chitosan-supported metal tetra(4-carboxyphenyl)porphyrin as a practical model for the hydrophobic pocket/cavity of cytochrome P-450 enzyme.[J].Materials Science&Engineering C,2015,49:844-850.
[14]KAWAMURA Y,MITSUHASHI M,TANIBE H,et al.Adsorption of Metal Ions on Polyaminated Highly Porous Chitosan Chelating Resin[J].Industrial&Engineering Chemistry Research,2002,32(2):386-391.
[15]沈万慈.石墨产业的现代化与天然石墨的精细加工[J].中国非金属矿工业导刊,2005(6):3-7.
[16]LIANG X,WANG S,LIU S,et al.A novel octadecylsilane functionalized graphene oxide/silica composite stationary phase for high performance liquid chromatography[J].Journal of Separation Science,2012,35(16):2003-2009.
[17]ZHAO G,REN X,GAO X,et al.Removal of Pb(II)ions from aqueous solutions on few-layered graphene oxide nanosheets[J].Dalton Transactions,2011,40(41):10945-10952.
[18]JOHNSON J A,PETERSEN B M,KORMOS A,et al.A New approach to non-coordinating anions:Lewis acid enhancement of porphyrin metal centers in a zwitterionic metal-organic framework[J].Journal of the American Chemical Society,2017,138(32):10293-10298.
[19]GE R,WANG X,ZHANG C,et al.The influence of combination mode on the structure and properties of porphyrin-graphene oxide composites[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2015,483:45-52.
[20]HUANG G,RUXUN YUAN,PENG Y,et al.Oxygen oxidation of ethylbenzene over manganese porphyrin is promoted by the axial nitrogen coordination in powdered chitosan[J].Rsc Advances,2016,6(54):48571-48579.
[21]ACIK M,LEE G,MATTEVI C,et al.Unusual infrared-absorption mechanism in thermally reduced graphene oxide.[J].Nature Materials,2010,9(10):840-845.
[22]梅光泉,袁晓玲,曾锦萍.5,10,15,20-四(4-羧基苯基)卟啉及其钯(Ⅱ)配合物的合成与表征[J].化学试剂,2008,30(11):809-812.
[23]AHMADI E,RAMAZANI A,HAMDI Z,et al.5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin covalently bound to nanosilica surface:Preparation,characterization and chemosensor application to detect TNT[J].Silicon,2015,7(4):323-332.
[24]MIN Y H,JO Y D,LEE J H,et al.Remarkable solvent,porphyrin ligand,and substrate effects on participation of multiple active oxidants in manganese(III)porphyrin catalyzed oxidation reactions[J].Chemistry,2013,19(5):1810-1818.
[25]HUMMERS W S,OFFEMAN R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1339.
[26]JOSHI C,KUMAR P,BEHERA B,et al.A graphene/hemin hybrid material as an efficient green catalyst for stereoselective olefination of aldehydes[J].Rsc Advances,2015,5(121):100011-100017.
[27]曾凯,黄冠,原汝迅,等.纳米孔壳聚糖接枝四(对-羧基苯基)锰卟啉催化氧化乙苯[J].广西大学学报(自然科学版),2015,40(3):505-513.
[28]HUANG G,XIANG F,LI T M,et al.Selective oxidation of toluene over the new catalyst cobalt tetra(4-hydroxyl)phenylporphyrin supported on zinc oxide[J].Catalysis Communications,2011,12(10):886-889.
[29]HUANG G,LIU S Y,WANG A P,et al.Catalysis of structure-like macromolecules supported manganese tetraphenylporphyrin for cyclohexane oxidation[J].Catalysis Communications,2007,8(8):1183-1186.
[30]俞东军,李敏智,黄显著,等.壳聚糖修饰金属卟啉的制备及磁共振成像性能[J].光谱学与光谱分析,2013,33(10):2736-2739.
[31]STANKOVICH S,PINER R D,NGUYEN S B T,et al.Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets[J].Carbon,2006,44(15):3342-3347.
[32]SZABT,BERKESI O,DKNY I D.Study of deuterium-exchanged graphite oxide[J].Carbon,2005,43(15):3186-3189.
[33]POURSABERI T,GANJALI M R,HASSANISADI M.A novel fluoride-selective electrode based on metalloporphyrin grafted-grapheneoxide[J].Talanta,2012,101(22):128-134.
[34]毕纯.卟啉—石墨烯非共价复合材料的制备及性质测定[D].南京:南京大学,2012.
[35]JAHAN M,BAO Q,LOH K P.Electrocatalytically active graphene-porphyrin MOF composite for oxygen reduction reaction[J].Journal of the American Chemical Society,2012,134(15):6707-6713.
[36]ZHENG L,YE D,XIONG L,et al.Preparation of cobalt-tetraphenylporphyrin/reduced graphene oxide nanocomposite and its application on hydrogen peroxide biosensor[J].Analytica Chimica Acta,2013,768(1):69-75.
[37]AND M K,JARONIEC M.Gas Adsorption Characterization of Ordered Organic-Inorganic Nanocomposite Materials[J].Chemistry of Materials,2001,13(10):3169-3183.
[38]RASALINGAM S,MAHONEY L,WU C M,et al.Aging dependent phase transformation of mesostructured titanium dioxide nanomaterials prepared by evaporation-induced self-assembly process:Implications for solar hydrogen production[J].Materials Science,2015,2(3):230-242.
[39]苏海亮.氧化石墨烯负载席夫碱金属配合物的制备、表征及其环氧化催化性能研究[D].长春:吉林大学,2015.
[40]CHANG H,QIN J,XIAO P,et al.Highly reversible and recyclable absorption under both hydrophobic and hydrophilic conditions using a reduced bulk graphene oxide material[J].Advanced Materials,2016,28(18):3504-3509.
[41]HUANG J W,LIU Z L,GAO X R,et al.Hydroxylation of cyclohexane catalyzed by iron(III)-metal-free porphyrin dimer with molecular oxygen:The effect of the steric hindrance and the intramolecular interaction between the two porphyrin rings[J].Crystengcomm,2016,18(12):2203-2209.
[42]PARK S,AN J,POTTS J R,et al.Hydrazine-reduction of graphite-and graphene oxide[J].Carbon,2011,49(9):3019-3023.
[43]FURTOS G,NAGHIU M A,DECLERCQ H,et al.Nano forsterite biocomposites for medical applications:Mechanical properties and bioactivity[J].Journal of Biomedical Materials Research Part B Applied Biomaterials,2015,104(7):1290-1301.
[44]YOU J M,HAN H S,LEE H K,et al.Enhancedelectrocatalytic activity of oxygen reduction by cobalt-porphyrin functionalized withgraphene oxide in an alkaline solution[J].International Journal of Hydrogen Energy,2014,39(10):4803-4811.
[45]GE R,LI X,KANG S Z,et al.Highly efficient graphene oxide/porphyrin photocatalysts for hydrogen evolution and the interfacial electron transfer[J].Applied Catalysis B Environmental,2016,187:67-74.
[46]MORADI S E.Efficient photocatalytic hydrogen evolution by iron platinum loaded reduced graphene oxide[J].Chemical and Biochemical Engineering Quarterly,2016,30(1):1-7.
[47]李拥虎.氧化石墨烯/壳聚糖复合材料的制备及其载药性能研究[D].成都:西南交通大学,2013.
[48]HUANG G,MO L Q,CAI J L,et al.Environmentally friendly and efficient catalysis of cyclohexane oxidation by iron meso-tetrakis(pentafluorophenyl)porphyrin immobilized on zinc oxide[J].Applied Catalysis B Environmental,2015,162(10):364-371.