还原氧化石墨烯负载氧化钴杂化纳米催化剂的合成及其对一氧化碳氧化的催化性能（英文）
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摘要
采用沉淀和水热合成方法制备还原氧化石墨烯负载氧化钴纳米催化剂。采用XRD、Raman光源、SEM、TEM、氮气吸附、UV-Vis、XPS和H2-TPR等测试手段对所合成的催化剂进行表征。结果表明:颗粒尺寸均一的钴氧化物纳米颗粒均匀地分散在还原氧化石墨烯表面,所合成的材料具有较大的比表面积和均一的孔径分布。采用连续流动固定床微反-色谱装置对所合成的杂化催化剂对一氧化碳氧化的催化性能进行研究后发现,含还原氧化石墨烯质量分数为30%的催化剂具有最高的催化活性,能实现一氧化碳在100°C时的完全氧化。
The reduced graphene oxide(rGO) supported cobalt oxide nanocatalysts were prepared by the conventional precipitation and hydrothermal method. The as-prepared rGO-Co3 O4 was characterized by the XRD, Raman spectrum, SEM, TEM, N2-sorption, UV-Vis, XPS and H2-TPR measurements. The results show that the spinel cobalt oxide nanoparticles are highly fragmented on the r GO support and possess uniform particle size, and the as-prepared catalysts possess high specific surface area and narrow pore size distribution. The catalytic properties of the as-prepared rGO-Co3 O4 catalysts for CO oxidation were evaluated through a continuous-flow fixed-bed microreactor-gas chromatograph system. The catalyst with 30%(mass fraction) reduced graphene oxide exhibits the highest activity for CO complete oxidation at 100 °C.
The reduced graphene oxide(rGO) supported cobalt oxide nanocatalysts were prepared by the conventional precipitation and hydrothermal method. The as-prepared rGO-Co3 O4 was characterized by the XRD, Raman spectrum, SEM, TEM, N2-sorption, UV-Vis, XPS and H2-TPR measurements. The results show that the spinel cobalt oxide nanoparticles are highly fragmented on the r GO support and possess uniform particle size, and the as-prepared catalysts possess high specific surface area and narrow pore size distribution. The catalytic properties of the as-prepared rGO-Co3 O4 catalysts for CO oxidation were evaluated through a continuous-flow fixed-bed microreactor-gas chromatograph system. The catalyst with 30%(mass fraction) reduced graphene oxide exhibits the highest activity for CO complete oxidation at 100 °C.
引文
[1]HARUTAM,TSUBOTAS,KOBAYASHIT.Low-temperature oxidation of CO over gold supported on TiO2,α-Fe2O3, and Co3O4[J]. Journal of Catalysis, 1993, 144(1):175-192.
[2]AVGOUROPOULOSG,MANZOLIM,BOCCUZZIF.Catalytic performance and characterization of Au/doped-ceria catalysts for the preferentialCOoxidationreaction[J].JournalofCatalysis,2008,256(2):237-247.
[3]LI Ying-zhi, YU Yue, WANG Jian-guo, SONG Jie, LI Qiang, DONG Ming-dong, LIU Chang-jun. CO oxidation over graphene supported palladium catalyst[J]. Applied Catalysis B, 2012, 125:189-196.
[4]CHENShu-tang,SIRui,TAYLORE,JANZENJ,CHENJing-yi.SynthesisofPd/Fe3O4hybridnanocatalystswithcontrollable interface and enhanced catalytic activities for CO oxidation[J]. The Journal of Physical Chemistry C, 2012, 116(23):12969-12976.
[5]ENGEL T, ERTLG. Elementary steps in the catalytic oxidation of carbonmonoxideonplatinummetals[J].AdvancesinCatalysis,1979, 28:1-78.
[6]CHUAYPG,GUNASOORIYAGTKK.ControllingtheCO oxidationrateoverPt/TiO2catalystsbydefectengineeringofthe TiO2 support[J]. Journal of Catalysis, 2014, 311:306-313.
[7]CHEN H T. First-principles study of CO adsorption and oxidation on Ru-doped CeO2(111)surface[J]. The Journal of Physical Chemistry C, 2012, 116(10):6239-6246.
[8]CAO Jian-liang, WANG Yan, YU Xiu-ling, WANG Shu-rong, WU Shi-hua,YUANZhong-yong.MesoporousCuO-Fe2O3composite catalystsforlow-temperaturecarbonmonoxideoxidation[J].Applied Catalysis B, 2008, 79(1):26-34.
[9]LUO Meng-fei, MA Jing-meng, LU Ji-qing, SONG Yu-peng, WANG Yue-juan.High-surfaceareaCuO-CeO2catalystspreparedbya surfactant-templatedmethodforlow-temperatureCOoxidation[J].Journal of Catalysis, 2007, 246(1):52-59.
[10]HU Lin-hua, SUN Ke-qiang, PENG Qing, XU Bo-qing, LI Ya-dong.Surface active sites on Co3O4 nanobelt and nanocube model catalysts for CO oxidation[J]. Nano Research, 2010, 3(5):363-368.
[11]JIA Ming-jun, ZHANG Wen-xiang, TAO Yu-guo, WANG Gui-ying,CUIXiang-hao,ZHANGChun-lei,WUTong-hao,DONG Guo-qiang.Preparation,characterizationandCOoxidationof nanometerCo3O4[J].ChemicalResearchinChineseUniversity,1999, 4:637-639.
[12]XIAOJun-wu,WANLian,WANGXue,KUANGQin,DONG Shuang,XIAOFei,WANGShuai.MesoporousMn3O4-CoO core–shellsphereswrappedbycarbonnanotubes:Ahigh performancecatalystfortheoxygenreductionreactionandCO oxidation[J]. Journal of Materials Chemistry A, 2014, 2:3794-3800.
[13]CAOJian-liang,YANZhao-li,WANGYan,SUNGuang,WANG Xiao-dong,BALAHari,ZHANGZhan-ying.CTAB-assisted synthesisofmesoporousCoFe2O4withhighcarbonmonoxide oxidation activity[J]. Materials Letters, 2013, 106:322-325.
[14]ZHANGYan,WANGQin,YEWei-chun,LIJia-jia,WANG Chun-ming.Pdmicro-nanoparticleselectrodepositedongraphene/polyimide membrane for electrocatalytic oxidation of formic acid[J].TransactionsofNonferrousMetalsSocietyofChina,2015,25(9):2986-2993.
[15]YOO E J, OKATA T, AKITA T, KOHYAMA M,NAKAMURA J,HONMA I. Enhanced electrocatalytic activity of Pt subnanoclusters ongraphenenanosheetsurface[J].NanoLetters,2009,9:2255-2259.
[16]WANGYi,GUOChun-xian,LIUJie-hua,CHENTao,YANG Hong-bin,LIChang-ming.Ce O2nanoparticles/graphenenanocomposite-basedhighperformancesupercapacitor[J].Dalton Transactions, 2011, 40:6388-6391.
[17]PERERASD,MARIANORG,VUK,NOURN,SEITZO,CHABALY,BALKUSKJ.Hydrothermalsynthesisof grapheneTiO2 nanotube composites with enhanced photocatalytic activity[J].ACS Catalysis, 2012, 2(6):949-956.
[18]HE Yong-min, CHEN Wan-jun, LI Xiao-dong, ZHANG Zhen-xing,FUJie-cai,ZHAOChang-hui,XIEEr-qing.Freestanding three-dimensional graphene/MnO2 composite networks asultralight andflexiblesupercapacitorelectrodes[J].ACSNano,2013,7(1):174-182.
[19]LIFeng-yu,ZHAOJi-jun,CHENZhong-fang.Fe-anchored grapheneoxide:Alow-costandeasilyaccessiblecatalystfor low-temperatureCOoxidation[J].TheJournalofPhysical Chemistry C, 2012, 116(3):2507-2514.
[20]HUMMERS W S, OFFEMAN R E. Preparation of graphitic oxide[J].Journal of the American Chemical Society, 1958, 80(6):1339-1339.
[21]KIM H, SEO D H, KIM S W, KIM J, KANG K. Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries[J].Carbon, 2011, 49(1):326-332.
[22]CAOJian-liang,LIGao-jie,WANGYan.Oilshaleashsupported CuOnanocatalysts:Preparation,characterizationandcatalytic activityforCOoxidation[J].JournalofEnvironmentalChemical Engineering, 2015, 3(3):1725-1730.
[23]PARKS,ANJH,PINERRD,JUNGI,YANGDX,VELAMAKANNIA,NGUYENST,RUOFFRS.Aqueous suspensionandcharacterizationofchemicallymodifiedgraphene sheets[J]. Chemistry of Materials, 2008, 20(21):6592-6594.
[24]TUINSTRA F, KOENIG J L. Raman spectrum of graphite[J]. The Journal of Physical Chemistry C, 1970, 53:1126-1130.
[25]JIANGJing,LILiang-chao.Synthesisofsphere-likeCo3O4nanocrystals via a simple polyol route[J]. Materials Letters, 2007,61(27):4894-4896.
[26]YUAN Zhong-yong, REN Tie-zhen, VANTOMME A, SU Bao-lian.Facileandgeneralizedpreparationofhierarchicallymesoporousmacroporousbinarymetaloxidematerials[J].Chemistryof Materials, 2004, 16(24):5096-5106.
[27]YAOYun-jin,YANGZe-heng,SUNHong-qi,WANGShao-bin.HydrothermalsynthesisofCo3O4-grapheneforheterogeneous activationofperoxymonosulfatefordecompositionofphenol[J].Industrial&EngineeringChemistryResearch,2012,51(46):14958-14965.
[28]LOU Y, MA J, CAO X M, WANG L, DAI Q G, ZHAO Z Y, CAI Y F,ZHAN W C, GUO Y L, HU P, LU G Z, GUO Y. Promoting effects of In2O3onCo3O4forCOoxidation:TuningO2 activationandCO Adsorption Strength Simultaneously[J]. ACS Catalysis, 2014, 4(11):4143-4152.
[29]WUZhong-shuai,RENWen-cai,WENLei,GAOLi-bo,ZHAO Jin-ping,CHENZong-ping,ZHOUGuang-min,LIFeng,CHENG Hui-ming. Graphene anchored with Co3O4 nanoparticles as anode of lithiumionbatterieswithenhancedreversiblecapacityandcyclic performance[J]. ACS Nano, 2010, 4(6):3187-3194.
[30]GAO Li-na, YUE Wen-bo, TAO Shan-shan, FAN Lou-zhen. Novel strategyforpreparationofgraphene-Pd,Ptcomposite,andits enhanced electrocatalytic activity for alcohol oxidation[J]. Langmuir,2013, 29(3):957-964.
[31]KANGM,SONGMW,KIMKL.Catalyticoxidationofcarbon monoxideoverCoOx/CeO2catalysts[J].ReactionKinetics,Mechanisms and Catalysis, 2003, 79(1):3-10.
[32]TANGCW,KUOMC,LINCJ,WANGCB,CHIENSH.Evaluation of carbon monoxide oxidation over CeO2/Co3O4 catalysts:Effect of ceria loading[J]. Catalysis Today, 2008, 131:520-525.
[33]KANGM,SONGMW,LEECH.Catalyticcarbonmonoxide oxidation over CoOx/CeO2 composite catalysts[J]. Applied Catalysis A, 2003, 251:143-156.
[34]LUO Jin-yong, MENG Ming, LI Xiang, LI Xin-gang, ZHA Yu-qing,HU Tian-dou, XIE Ya-ning, ZHANG Jing. Mesoporous Co3O4-Ce O2andPd/Co3O4-Ce O2catalysts:Synthesis,characterizationand mechanisticstudyoftheircatalyticpropertiesforlow-temperature CO oxidation[J]. Journal of Catalysis, 2008, 254(2):310-324.
[35]WANG C B, TANG C W, TSAI H C, CHIEN S H. Characterization andcatalyticoxidationofcarbonmonoxideoversupportedcobalt catalysts[J]. Catalysis Letters, 2006, 107(3-4):223-230.
[36]CAOJian-liang,LIGao-jie,WANGYan,SUNGuang,WANG Xiao-dong, HARI Bala, ZHANG Zhan-ying. Mesoporous Co-Fe-O nanocatalysts:Preparation,characterizationandcatalyticcarbon monoxideoxidation[J].JournalofEnvironmentalChemical Engineering, 2014, 2:477-483.
[37]SCHUMACHERB,PLZAKV,KINNEM,BEHMRJ.Highly activeAu/TiO2catalystsforlow-temperatureCOoxidation:Preparation,conditioningandstability[J].CatalysisLetters,2003,89(1-2):109-114.
[38]BROQVISTP,PANASI,PERSSONH.ADFTstudyonCO oxidationoverCo3O4[J].JournalofCatalysis,2002,201(2):198-206.
[39]POLLARDMJ,WEINSTOCKBA,BITTERWOLFTE,GRIFFITHS P R, NEWBERY A P, PAINE J B. A mechanistic study ofthelow-temperatureconversionofcarbonmonoxidetocarbon dioxide over a cobalt oxide catalyst[J]. Journal of Catalysis, 2008,254(2):218-225.
[40]SEDMAKG,HO?EVARS,LEVECJ.KineticsofselectiveCO oxidationinexcessofH2overthenanostructuredCu0.1Ce0.9O2-ycatalyst[J]. Journal of Catalysis, 2003, 213(2):135-150.
[2]AVGOUROPOULOSG,MANZOLIM,BOCCUZZIF.Catalytic performance and characterization of Au/doped-ceria catalysts for the preferentialCOoxidationreaction[J].JournalofCatalysis,2008,256(2):237-247.
[3]LI Ying-zhi, YU Yue, WANG Jian-guo, SONG Jie, LI Qiang, DONG Ming-dong, LIU Chang-jun. CO oxidation over graphene supported palladium catalyst[J]. Applied Catalysis B, 2012, 125:189-196.
[4]CHENShu-tang,SIRui,TAYLORE,JANZENJ,CHENJing-yi.SynthesisofPd/Fe3O4hybridnanocatalystswithcontrollable interface and enhanced catalytic activities for CO oxidation[J]. The Journal of Physical Chemistry C, 2012, 116(23):12969-12976.
[5]ENGEL T, ERTLG. Elementary steps in the catalytic oxidation of carbonmonoxideonplatinummetals[J].AdvancesinCatalysis,1979, 28:1-78.
[6]CHUAYPG,GUNASOORIYAGTKK.ControllingtheCO oxidationrateoverPt/TiO2catalystsbydefectengineeringofthe TiO2 support[J]. Journal of Catalysis, 2014, 311:306-313.
[7]CHEN H T. First-principles study of CO adsorption and oxidation on Ru-doped CeO2(111)surface[J]. The Journal of Physical Chemistry C, 2012, 116(10):6239-6246.
[8]CAO Jian-liang, WANG Yan, YU Xiu-ling, WANG Shu-rong, WU Shi-hua,YUANZhong-yong.MesoporousCuO-Fe2O3composite catalystsforlow-temperaturecarbonmonoxideoxidation[J].Applied Catalysis B, 2008, 79(1):26-34.
[9]LUO Meng-fei, MA Jing-meng, LU Ji-qing, SONG Yu-peng, WANG Yue-juan.High-surfaceareaCuO-CeO2catalystspreparedbya surfactant-templatedmethodforlow-temperatureCOoxidation[J].Journal of Catalysis, 2007, 246(1):52-59.
[10]HU Lin-hua, SUN Ke-qiang, PENG Qing, XU Bo-qing, LI Ya-dong.Surface active sites on Co3O4 nanobelt and nanocube model catalysts for CO oxidation[J]. Nano Research, 2010, 3(5):363-368.
[11]JIA Ming-jun, ZHANG Wen-xiang, TAO Yu-guo, WANG Gui-ying,CUIXiang-hao,ZHANGChun-lei,WUTong-hao,DONG Guo-qiang.Preparation,characterizationandCOoxidationof nanometerCo3O4[J].ChemicalResearchinChineseUniversity,1999, 4:637-639.
[12]XIAOJun-wu,WANLian,WANGXue,KUANGQin,DONG Shuang,XIAOFei,WANGShuai.MesoporousMn3O4-CoO core–shellsphereswrappedbycarbonnanotubes:Ahigh performancecatalystfortheoxygenreductionreactionandCO oxidation[J]. Journal of Materials Chemistry A, 2014, 2:3794-3800.
[13]CAOJian-liang,YANZhao-li,WANGYan,SUNGuang,WANG Xiao-dong,BALAHari,ZHANGZhan-ying.CTAB-assisted synthesisofmesoporousCoFe2O4withhighcarbonmonoxide oxidation activity[J]. Materials Letters, 2013, 106:322-325.
[14]ZHANGYan,WANGQin,YEWei-chun,LIJia-jia,WANG Chun-ming.Pdmicro-nanoparticleselectrodepositedongraphene/polyimide membrane for electrocatalytic oxidation of formic acid[J].TransactionsofNonferrousMetalsSocietyofChina,2015,25(9):2986-2993.
[15]YOO E J, OKATA T, AKITA T, KOHYAMA M,NAKAMURA J,HONMA I. Enhanced electrocatalytic activity of Pt subnanoclusters ongraphenenanosheetsurface[J].NanoLetters,2009,9:2255-2259.
[16]WANGYi,GUOChun-xian,LIUJie-hua,CHENTao,YANG Hong-bin,LIChang-ming.Ce O2nanoparticles/graphenenanocomposite-basedhighperformancesupercapacitor[J].Dalton Transactions, 2011, 40:6388-6391.
[17]PERERASD,MARIANORG,VUK,NOURN,SEITZO,CHABALY,BALKUSKJ.Hydrothermalsynthesisof grapheneTiO2 nanotube composites with enhanced photocatalytic activity[J].ACS Catalysis, 2012, 2(6):949-956.
[18]HE Yong-min, CHEN Wan-jun, LI Xiao-dong, ZHANG Zhen-xing,FUJie-cai,ZHAOChang-hui,XIEEr-qing.Freestanding three-dimensional graphene/MnO2 composite networks asultralight andflexiblesupercapacitorelectrodes[J].ACSNano,2013,7(1):174-182.
[19]LIFeng-yu,ZHAOJi-jun,CHENZhong-fang.Fe-anchored grapheneoxide:Alow-costandeasilyaccessiblecatalystfor low-temperatureCOoxidation[J].TheJournalofPhysical Chemistry C, 2012, 116(3):2507-2514.
[20]HUMMERS W S, OFFEMAN R E. Preparation of graphitic oxide[J].Journal of the American Chemical Society, 1958, 80(6):1339-1339.
[21]KIM H, SEO D H, KIM S W, KIM J, KANG K. Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries[J].Carbon, 2011, 49(1):326-332.
[22]CAOJian-liang,LIGao-jie,WANGYan.Oilshaleashsupported CuOnanocatalysts:Preparation,characterizationandcatalytic activityforCOoxidation[J].JournalofEnvironmentalChemical Engineering, 2015, 3(3):1725-1730.
[23]PARKS,ANJH,PINERRD,JUNGI,YANGDX,VELAMAKANNIA,NGUYENST,RUOFFRS.Aqueous suspensionandcharacterizationofchemicallymodifiedgraphene sheets[J]. Chemistry of Materials, 2008, 20(21):6592-6594.
[24]TUINSTRA F, KOENIG J L. Raman spectrum of graphite[J]. The Journal of Physical Chemistry C, 1970, 53:1126-1130.
[25]JIANGJing,LILiang-chao.Synthesisofsphere-likeCo3O4nanocrystals via a simple polyol route[J]. Materials Letters, 2007,61(27):4894-4896.
[26]YUAN Zhong-yong, REN Tie-zhen, VANTOMME A, SU Bao-lian.Facileandgeneralizedpreparationofhierarchicallymesoporousmacroporousbinarymetaloxidematerials[J].Chemistryof Materials, 2004, 16(24):5096-5106.
[27]YAOYun-jin,YANGZe-heng,SUNHong-qi,WANGShao-bin.HydrothermalsynthesisofCo3O4-grapheneforheterogeneous activationofperoxymonosulfatefordecompositionofphenol[J].Industrial&EngineeringChemistryResearch,2012,51(46):14958-14965.
[28]LOU Y, MA J, CAO X M, WANG L, DAI Q G, ZHAO Z Y, CAI Y F,ZHAN W C, GUO Y L, HU P, LU G Z, GUO Y. Promoting effects of In2O3onCo3O4forCOoxidation:TuningO2 activationandCO Adsorption Strength Simultaneously[J]. ACS Catalysis, 2014, 4(11):4143-4152.
[29]WUZhong-shuai,RENWen-cai,WENLei,GAOLi-bo,ZHAO Jin-ping,CHENZong-ping,ZHOUGuang-min,LIFeng,CHENG Hui-ming. Graphene anchored with Co3O4 nanoparticles as anode of lithiumionbatterieswithenhancedreversiblecapacityandcyclic performance[J]. ACS Nano, 2010, 4(6):3187-3194.
[30]GAO Li-na, YUE Wen-bo, TAO Shan-shan, FAN Lou-zhen. Novel strategyforpreparationofgraphene-Pd,Ptcomposite,andits enhanced electrocatalytic activity for alcohol oxidation[J]. Langmuir,2013, 29(3):957-964.
[31]KANGM,SONGMW,KIMKL.Catalyticoxidationofcarbon monoxideoverCoOx/CeO2catalysts[J].ReactionKinetics,Mechanisms and Catalysis, 2003, 79(1):3-10.
[32]TANGCW,KUOMC,LINCJ,WANGCB,CHIENSH.Evaluation of carbon monoxide oxidation over CeO2/Co3O4 catalysts:Effect of ceria loading[J]. Catalysis Today, 2008, 131:520-525.
[33]KANGM,SONGMW,LEECH.Catalyticcarbonmonoxide oxidation over CoOx/CeO2 composite catalysts[J]. Applied Catalysis A, 2003, 251:143-156.
[34]LUO Jin-yong, MENG Ming, LI Xiang, LI Xin-gang, ZHA Yu-qing,HU Tian-dou, XIE Ya-ning, ZHANG Jing. Mesoporous Co3O4-Ce O2andPd/Co3O4-Ce O2catalysts:Synthesis,characterizationand mechanisticstudyoftheircatalyticpropertiesforlow-temperature CO oxidation[J]. Journal of Catalysis, 2008, 254(2):310-324.
[35]WANG C B, TANG C W, TSAI H C, CHIEN S H. Characterization andcatalyticoxidationofcarbonmonoxideoversupportedcobalt catalysts[J]. Catalysis Letters, 2006, 107(3-4):223-230.
[36]CAOJian-liang,LIGao-jie,WANGYan,SUNGuang,WANG Xiao-dong, HARI Bala, ZHANG Zhan-ying. Mesoporous Co-Fe-O nanocatalysts:Preparation,characterizationandcatalyticcarbon monoxideoxidation[J].JournalofEnvironmentalChemical Engineering, 2014, 2:477-483.
[37]SCHUMACHERB,PLZAKV,KINNEM,BEHMRJ.Highly activeAu/TiO2catalystsforlow-temperatureCOoxidation:Preparation,conditioningandstability[J].CatalysisLetters,2003,89(1-2):109-114.
[38]BROQVISTP,PANASI,PERSSONH.ADFTstudyonCO oxidationoverCo3O4[J].JournalofCatalysis,2002,201(2):198-206.
[39]POLLARDMJ,WEINSTOCKBA,BITTERWOLFTE,GRIFFITHS P R, NEWBERY A P, PAINE J B. A mechanistic study ofthelow-temperatureconversionofcarbonmonoxidetocarbon dioxide over a cobalt oxide catalyst[J]. Journal of Catalysis, 2008,254(2):218-225.
[40]SEDMAKG,HO?EVARS,LEVECJ.KineticsofselectiveCO oxidationinexcessofH2overthenanostructuredCu0.1Ce0.9O2-ycatalyst[J]. Journal of Catalysis, 2003, 213(2):135-150.