以KMnO_4改性炭黑为载体Pd-Ni催化剂的制备和性能
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摘要
以不同浓度的KMnO_4溶液预处理的炭黑为载体,通过沉淀共还原法合成了3种Pd_1Ni_1/AC_x(x=3、5、7)催化剂。采用XPS、ICP、XRD和TEM对催化剂进行了表征。结果表明:Pd_1Ni_1/AC_5的Pd负载量(质量分数,下同)最大(3.66%),Pd晶粒的平均粒径最小(4.71 nm),且均匀地分布在KMn O_4氧化处理后的碳载体上,活性位点较多;XRD显示,3种Pd_1Ni_1/AC_x催化剂中大部分的Ni均以无定形形式存在。电化学性能测试结果表明:3种催化剂均表现出比商业Pd/C更好的电化学稳定性和存活率;其中,Pd_1Ni_1/AC_5电化学活性表面积达62.21 m~2/g_(Pd),且乙醇催化氧化活性为1797.85 A/g_(Pd)。
Three kinds of Pd_1Ni_1/AC_x(x=3,5,7)catalysts were synthesized by precipitation co-reduction method with carbon black pretreated with different concentrations of potassium permanganate solution as supports.These catalysts were characterized by XPS,ICP,XRD and TEM.The results showed that catalyst Pd_1Ni_1/AC_5 had the largest Pd loading(3.66%,mass fraction,the same below),the average particle size(4.71 nm)of Pd grains was the smallest.In addition,Pd particles were evenly dispersed on carbon black supports,which resulted in more active sites.XRD results indicated that most of Ni components exhibited an amorphous form in all three Pd_1Ni_1/AC_x catalysts.Electrochemical tests demonstrated that all three catalysts showed better electrochemical stability and survival ratio than commercial Pd/C catalyst.Especially,the electrochemical active surface area of Pd_1Ni_1/AC_5 reached 62.21 m~2/g_(Pd),and the ethanol catalytic activity was 1797.85 A/g_(Pd).
Three kinds of Pd_1Ni_1/AC_x(x=3,5,7)catalysts were synthesized by precipitation co-reduction method with carbon black pretreated with different concentrations of potassium permanganate solution as supports.These catalysts were characterized by XPS,ICP,XRD and TEM.The results showed that catalyst Pd_1Ni_1/AC_5 had the largest Pd loading(3.66%,mass fraction,the same below),the average particle size(4.71 nm)of Pd grains was the smallest.In addition,Pd particles were evenly dispersed on carbon black supports,which resulted in more active sites.XRD results indicated that most of Ni components exhibited an amorphous form in all three Pd_1Ni_1/AC_x catalysts.Electrochemical tests demonstrated that all three catalysts showed better electrochemical stability and survival ratio than commercial Pd/C catalyst.Especially,the electrochemical active surface area of Pd_1Ni_1/AC_5 reached 62.21 m~2/g_(Pd),and the ethanol catalytic activity was 1797.85 A/g_(Pd).
引文
[1]Zhang N,Feng Y,Zhu X,et al.Superior bifunctional liquid fuel oxidation and oxygen reduction electrocatalysis enabled by ptnipd core-shell nanowires[J].Adv Mater,2017,29(7):1603774.
[2]Zhang K,Xu H,Yan B,et al.Superior ethylene glycol oxidation electrocatalysis enabled by hollow PdNi nanospheres[J].Electrochim Acta,2018,268:383-391.
[3]Wang F,Tang S,Yu Y,et al.Preparation of palladium nanoparticle catalyst in ionic liquid and its catalytic properties for Heck-Mizoroki reaction[J].Chinese Journal of Catalysis,2014,35(12):1921-1926.
[4]Zhao Shihuai(赵世怀),Zhang Cuicui(张翠翠),Yang Zibo(杨紫博),et al.Research Progress of Alkaline Fuel Cell Anode Catalysts[J].Fine Chemicals(精细化工),2017,35(8):1261-1266.
[5]Wang X,Tang Y,Gao Y,et al.Carbon-supported Pd-Ir catalyst as anodic catalyst in direct formic acid fuel cell[J].J Power Sources,2008,175(2):784-788.
[6]Sim?es M,Baranton S,Coutanceau C.Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration[J].Appl Catal B:Environmental,2010,93(3/4):354-362.
[7]Modibedi R M,Ozoemena K I,Mathe M K.Palladium-based nanocatalysts for alcohol electrooxidation in alkaline media[M]//Electrocatalysis in Fuel Cells.London:Springer,2013:129-156.
[8]Jin C,Wang Z,Huo Q,et al.Different behaviors of PdAu/C catalysts in electrooxidation of propane-1,3-diol and propane-1,2-diol[J].Ionics,2015,21(3):841-847.
[9]Jian S,Li Y.Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction[J].Chinese Journal of Catalysis,2016,37(1):91-97.
[10]Liu Bing(刘冰),Ma Ronghua(马荣华),Liu Chuntao(刘春涛).Characterization and Cr(Ⅵ)adsorption capability of activated carbon modified with KMnO4[J].Chemial Reagents(化学试剂),2016,38(9):819-823.
[11]Han Zhen(韩真),Liu Lianying(刘莲英),Yang Wantai(杨万泰).Oxidation modification of carbon black surface and its water dispersibility[J].Journal of Beijing University of Chemical Technology(北京化工大学学报),2010,37(1):78-84.
[12]Ding Chunsheng(丁春生),Zhu Qianfen(诸钱芬),Lu Jingke(卢敬科),et al.Preparation and characterization of activated carbon modified by KMnO4 and its Pb2+adsorption capability[J].Urban Environment&Urban Ecology(城市环境与城市生态),2011(1):42-46.
[13]Dash S,Munichandraiah N.Nanoflowers of PdRu on PEDOT for electrooxidation of glycerol and its analysis[J].Electrochim Acta,2015,180:339-352.
[14]Yang S,Zhang X,Mi H,et al.Pd nanoparticles supported on functionalized multi-walled carbon nanotubes(MWCNTs)and electrooxidation for formic acid[J].J Power Sources,2008,175(1):26-32.
[15]Shen S Y,Zhao T S,Xu J B,et al.Synthesis of PdNi catalysts for the oxidation of ethanol in alkaline direct ethanol fuel cells[J].J Power Sources,2010,195(4):1001-1006.
[16]Sim?es M,Baranton S,Coutanceau C.Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration[J].Appl Catal B:Environmental,2010,93(3/4):354-362.
[17]Zhang Z,Xin L,Sun K,et al.Pd-Ni electrocatalysts for efficient ethanol oxidation reaction in alkaline electrolyte[J].Int J Hydrogen Energy,2011,36(20):12686-12697.
[18]Hafez I H,Berber M R,Fujigaya T,et al.Enhancement of platinum mass activity on the surface of polymer-wrapped carbon nanotube-based fuel cell electrocatalysts[J].Sci rep,2014,4:6295.
[19]Zhang H,Liu G,Shi L,et al.Single-atom catalysts:Emerging multifunctional materials in heterogeneous catalysis[J].Adv Energy Mater,2018,8(1):1701343.
[20]Feng Y,Bin D,Yan B,et al.Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation[J].JColloid and Int Science,2017,493:190-197.
[21]Qin Y H,Yang H H,Zhang X S,et al.Electrophoretic deposition of network-like carbon nanofibers as a palladium catalyst support for ethanol oxidation in alkaline media[J].Carbon,2010,48(12):3323-3329.
[22]Hu F P,Wang Z,Li Y,et al.Improved performance of Pd electrocatalyst supported on ultrahigh surface area hollow carbon spheres for direct alcohol fuel cells[J].J Power Sources,2008,177(1):61-66.
[23]Huang L,Han Y,Zhang X,et al.One-step synthesis of ultrathin Pt x Pb nerve-like nanowires as robust catalysts for enhanced methanol electrooxidation[J].Nanoscale,2017,9(1):201-207.
[24]Xu H,Yan B,Zhang K,et al.Self-supported worm-like PdAg nanoflowers as efficient electrocatalysts towards ethylene glycol oxidation[J].ChemElectroChem,2017,4(10):2527-2534.
[25]Zhang K,Bin D,Yang B,et al.Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation[J].Nanoscale,2015,7(29):12445-12451.
[2]Zhang K,Xu H,Yan B,et al.Superior ethylene glycol oxidation electrocatalysis enabled by hollow PdNi nanospheres[J].Electrochim Acta,2018,268:383-391.
[3]Wang F,Tang S,Yu Y,et al.Preparation of palladium nanoparticle catalyst in ionic liquid and its catalytic properties for Heck-Mizoroki reaction[J].Chinese Journal of Catalysis,2014,35(12):1921-1926.
[4]Zhao Shihuai(赵世怀),Zhang Cuicui(张翠翠),Yang Zibo(杨紫博),et al.Research Progress of Alkaline Fuel Cell Anode Catalysts[J].Fine Chemicals(精细化工),2017,35(8):1261-1266.
[5]Wang X,Tang Y,Gao Y,et al.Carbon-supported Pd-Ir catalyst as anodic catalyst in direct formic acid fuel cell[J].J Power Sources,2008,175(2):784-788.
[6]Sim?es M,Baranton S,Coutanceau C.Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration[J].Appl Catal B:Environmental,2010,93(3/4):354-362.
[7]Modibedi R M,Ozoemena K I,Mathe M K.Palladium-based nanocatalysts for alcohol electrooxidation in alkaline media[M]//Electrocatalysis in Fuel Cells.London:Springer,2013:129-156.
[8]Jin C,Wang Z,Huo Q,et al.Different behaviors of PdAu/C catalysts in electrooxidation of propane-1,3-diol and propane-1,2-diol[J].Ionics,2015,21(3):841-847.
[9]Jian S,Li Y.Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction[J].Chinese Journal of Catalysis,2016,37(1):91-97.
[10]Liu Bing(刘冰),Ma Ronghua(马荣华),Liu Chuntao(刘春涛).Characterization and Cr(Ⅵ)adsorption capability of activated carbon modified with KMnO4[J].Chemial Reagents(化学试剂),2016,38(9):819-823.
[11]Han Zhen(韩真),Liu Lianying(刘莲英),Yang Wantai(杨万泰).Oxidation modification of carbon black surface and its water dispersibility[J].Journal of Beijing University of Chemical Technology(北京化工大学学报),2010,37(1):78-84.
[12]Ding Chunsheng(丁春生),Zhu Qianfen(诸钱芬),Lu Jingke(卢敬科),et al.Preparation and characterization of activated carbon modified by KMnO4 and its Pb2+adsorption capability[J].Urban Environment&Urban Ecology(城市环境与城市生态),2011(1):42-46.
[13]Dash S,Munichandraiah N.Nanoflowers of PdRu on PEDOT for electrooxidation of glycerol and its analysis[J].Electrochim Acta,2015,180:339-352.
[14]Yang S,Zhang X,Mi H,et al.Pd nanoparticles supported on functionalized multi-walled carbon nanotubes(MWCNTs)and electrooxidation for formic acid[J].J Power Sources,2008,175(1):26-32.
[15]Shen S Y,Zhao T S,Xu J B,et al.Synthesis of PdNi catalysts for the oxidation of ethanol in alkaline direct ethanol fuel cells[J].J Power Sources,2010,195(4):1001-1006.
[16]Sim?es M,Baranton S,Coutanceau C.Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration[J].Appl Catal B:Environmental,2010,93(3/4):354-362.
[17]Zhang Z,Xin L,Sun K,et al.Pd-Ni electrocatalysts for efficient ethanol oxidation reaction in alkaline electrolyte[J].Int J Hydrogen Energy,2011,36(20):12686-12697.
[18]Hafez I H,Berber M R,Fujigaya T,et al.Enhancement of platinum mass activity on the surface of polymer-wrapped carbon nanotube-based fuel cell electrocatalysts[J].Sci rep,2014,4:6295.
[19]Zhang H,Liu G,Shi L,et al.Single-atom catalysts:Emerging multifunctional materials in heterogeneous catalysis[J].Adv Energy Mater,2018,8(1):1701343.
[20]Feng Y,Bin D,Yan B,et al.Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation[J].JColloid and Int Science,2017,493:190-197.
[21]Qin Y H,Yang H H,Zhang X S,et al.Electrophoretic deposition of network-like carbon nanofibers as a palladium catalyst support for ethanol oxidation in alkaline media[J].Carbon,2010,48(12):3323-3329.
[22]Hu F P,Wang Z,Li Y,et al.Improved performance of Pd electrocatalyst supported on ultrahigh surface area hollow carbon spheres for direct alcohol fuel cells[J].J Power Sources,2008,177(1):61-66.
[23]Huang L,Han Y,Zhang X,et al.One-step synthesis of ultrathin Pt x Pb nerve-like nanowires as robust catalysts for enhanced methanol electrooxidation[J].Nanoscale,2017,9(1):201-207.
[24]Xu H,Yan B,Zhang K,et al.Self-supported worm-like PdAg nanoflowers as efficient electrocatalysts towards ethylene glycol oxidation[J].ChemElectroChem,2017,4(10):2527-2534.
[25]Zhang K,Bin D,Yang B,et al.Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation[J].Nanoscale,2015,7(29):12445-12451.