PtRu合金催化剂电催化氧化甲醇的作用机理
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摘要
利用化学还原法合成了4种不同Pt/Ru原子比例的合金型PtRu/C、核壳型Ru@Pt/C及Pt/C直径相近的纳米金属催化剂。结果表明:Ru@Pt/C、PtRu/C催化剂纳米金属粒子的直径平均约为9~11nm,Ru@Pt/C呈核壳型结构;Ru@Pt/C电催化氧化甲醇机理较为符合电子效应机理,PtRu/C电催化氧化甲醇机理较为符合电子效应与双功能机理共同作用机理,催化机理的明确为新型催化剂的研发和改性提供了坚实的理论依据。
The alloyed PtRu/C,core-shell Ru@Pt/C and Pt/C nanocomposite catalysts in similar diameter with different Pt/Ru atomic ratios were synthesized by chemical reduction method.Physical characterization and electrochemical characterization results show that the diameter of Ru@Pt/C,PtRu/C nano-metal particles is about 9~11 nm,and Ru@Pt/C in core-shell structure.The mechanism of Ru@Pt/C electrocatalytic oxidation of methanol meets the electronic effect mechanism,the mechanism of PtRu/C is consistent with the electronic effect and the bifunctional mechanism.The clarification of the catalytic mechanism provides a solid theoretical basis for the development of new catalysts.
The alloyed PtRu/C,core-shell Ru@Pt/C and Pt/C nanocomposite catalysts in similar diameter with different Pt/Ru atomic ratios were synthesized by chemical reduction method.Physical characterization and electrochemical characterization results show that the diameter of Ru@Pt/C,PtRu/C nano-metal particles is about 9~11 nm,and Ru@Pt/C in core-shell structure.The mechanism of Ru@Pt/C electrocatalytic oxidation of methanol meets the electronic effect mechanism,the mechanism of PtRu/C is consistent with the electronic effect and the bifunctional mechanism.The clarification of the catalytic mechanism provides a solid theoretical basis for the development of new catalysts.
引文
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[2]SONG S,ZHOU W,LIANG Z,et al.The effect of methanol and ethanol cross-over on the performance of PtRu/C-based anode DAFCs[J].Applied Catalysis B Environmental,2005,55(1):65-72.
[3]MUNK J,CHRISTENSEN P A,HAMNETT A,et al.The electrochemical oxidation of methanol on platinum and platinum+ruthenium particulate electrodes studied by in-situ FTIR spectroscopy and electrochemical mass spectrometry[J].Journal of Electroanalytical Chemistry,1996,401(1/2):215-222.
[4]李伟,黄青丹,黄红良,等.DMFC阳极PtRu催化剂的研究进展[J].电池工业,2007,12(3):200-204.LI W,HUANG Q D,HUANG H L,et al.Research progress of PtRu catalysts for direct methanol fuel cells[J].Chinese Battery Industry,2007,12(3):200-204.
[5]IWASITA T,HOSTER H,JOHN-ANACKER A,et al.Methanol oxidation on PtRu electrodes.Influence of surface structure and Pt-Ru atom distribution[J].Langmuir,2000,16(2):522-529.
[6]LEE C H,LEE C W,KIM D I,et al.Characteristics of methanol oxidation on Pt-Ru catalysts supported by HOPG in sulfuric acid[J].International journal of hydrogen energy,2002,27(4):445-450.
[7]TING C C,LIU C H,TAI C Y,et al.The size effect of titania-supported Pt catalysts on the electrocatalytic activity towards methanol oxidation reaction primarily via the bifunctional mechanism[J].Journal of Power Sources,2015,280:166-172.
[8]WANTANABE M,UCHIDA M,MOTOO S.Preparation of highly dispersed Pt+Ru alloy clusters and the activity for the electro-oxidation of methanol[J].Journal of Electro-analytical Chemistry and Interfacial Electrochemistry,1987,229(1/2):395-406.
[9]PEREIRA L G S,PAGANIN V A,TICIANELLI E A.Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell[J].Electrochimica Acta,2009,54(7):1992-1998.
[10]TODA T,IGARASHI H,WATANABE M.Enhancement of the electrocatalytic O2reduction on Pt-Fe alloys[J].Journal of Electroanalytical Chemistry,1999,460(1):258-262.
[11]LIU J,ZOU S,XIAO L,et al.Well-dispersed bimetallic catalysts confined in mesoporous metal oxides and their optimized catalytic activity for nitrobenzene hydrogenation[J].Catalysis Science&Technology,2014,4(2):441-446.
[12]YANG J,LEE J Y,CHEN L X,et al.A phase-transfer identification of core-shell structures in Ag-Pt catalysts[J].The Journal of Physical Chemistry B,2005,109(12):5468-5472.
[13]RAMIREZ-CABALLERO G E,MA Y,CALLEJAS-TOVAR R,et al.Surface segregation and stability of core-shell alloy catalysts for oxygen reduction in acid medium[J].Physical Chemistry Chemical Physics,2010,12(9):2209-2218.
[14]赵硕,段东红,卫国强,等.核壳型Ru@Pt在甲醇电催化氧化反应中的电子效应研究[J].太原理工大学学报,2016,47(4):471-477.ZHAO S,DUAN D H,WEI G Q,et al.Electronic effect of core-shell Ru@Pt nano-particle catalysts in methanol electro-oxidation[J].Journal of Taiyuan University of Technology,2016,47(4):471-477.
[15]陈煜,唐亚文,李钢,等.一种制备碳载高合金化Pt-Ru催化剂的方法[J].无机化学学报,2006,22(1):59-64.CHEN Y,TANG Y W,LI G,et al.Preparation of carbon supported high alloying Pt-Ru catalyst[J].Chinese Journal of Inorganic Chemistry,2006,22(1):59-64.
[16]KAPLAN D,BURSTEIN L,ROSENBERG Y,et al.Comparison of methanol and ethylene glycol oxidation by alloy and coreshell platinum based catalysts[J].Journal of Power Sources,2011,196(20):8286-8292.
[17]ZHANG J M,ZHU F F,ZHANG K H,et al.Pt-Ru catalysts prepared by a modified polyol process for direct methanol fuel cells[J].Precious Metals,2012(s1):222-226.
[18]CAMARA G A,GIZ M J,PAGANIN V A,et al.Correlation of electrochemical and physical properties of PtRu alloy electrocatalysts for PEM fuel cells[J].Journal of Electroanalytical Chemistry,2002,537(1):21-29.
[19]LIU S B,MA Y H,WEI G Q,et al.Methanol electro-oxidation kinetics on Ni@Pt nanoparticles coated by amorphous metal(In Chinese)[J].Journal of Taiyuan University of Technology,2012,43(3):300-304.
[20]BECKER E D,FARRAR T C.Fourier transform spectroscopy[J].Science,1972,178(4059):361-368.
[21]MUTHUSWAMY N,DE LA Fuente J L G,TRAN D T,et al.Ru@Pt core-shell catalysts for methanol fuel cell catalyst:Control and effects of shell composition[J].International Journal of Hydrogen Energy,2013,38(36):16631-16641.
[22]WANG J J,LIU Y T,CHEN I L,et al.Near-monolayer platinum shell on core-shell nanocatalysts for high-performance direct methanol fuel cell[J].The Journal of Physical Chemistry C,2014,118(5):2253-2262.
[23]KRAUSA M,VIELSTICH W.Study of the electrocatalytic influence of Pt/Ru and Ru on the oxidation of residues of small organic molecules[J].Journal of Electroanalytical Chemistry,1994,379(1/2):307-314.
[24]LIN S D,HSIAO T C,CHANG J R,et al.Morphology of carbon supported Pt-Ru electrocatalyst and the CO tolerance of anodes for PEM fuel cells[J].The Journal of Physical Chemistry B,1999,103(1):97-103.
[25]WATANABE M,MOTOO S.Electrocatalysis by ad-atoms:Part III.Enhancement of the oxidation of carbon monoxide on platinum by ruthenium ad-atoms[J].Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,1975,60(3):275-283.
[26]HOLSTEIN W L,ROSENFELD H D.In-situ X-ray absorption spectroscopy study of Pt and Ru chemistry during methanol electrooxidation[J].The Journal of Physical Chemistry B,2005,109(6):2176-2186.