3 41 6 2010 11 JOU RNAL OF TA IYUAN UN IV ERSIT Y OF TECHNOLO GY Vol. 41 No. 6 Nov. 2010 :100729432 (2010) 0620728205 Ni Pt2Ru / C 1, 1, 2, 1, 1, 1 (11, 030024 ;21, 116023) : 5 Pt2Ru2Ni/ C, X ( XRD) X ( XPS),, Ni Pt2Ru/ C,Ni Pt2Ru2Ni, Pt 52Ru42Ni0. 7/ C, 1. 0 mol/ L NaO H + 1. 0 mol/ L CH3 O H 842. 2 ma/ mg, Pt 52Ru5/ C 0. 16 V,, 0. 58 : ; ; ; :O646 :A (DMFC),, ( PEM2DMFC), : ;, O2, PEM2 DMFC, DMFC, ( A EM2DMFC),,, ;,O H -, [1 ], (A EM2DMFC) [1,2 ], Pt [ 327 ],,CO Hads COads Pt, O Hads CO2,CH3 O Hads COads COads, CH3 O H,,, O Hads, O Hads [2 ], Trip kovic Pt Ru Pt2Ru, Pt [8 ] Ru O H -, O Hads, Ru, O H -, O Hads, Ru,Ni, O H - H2 O, O Hads [9 ], Ni Pt2 Ru, Ni Pt2Ru2Ni/ C, Pt2Ru2Ni/ C,,, X ( XRD),X ( XPS), Ni 3 :2009212215 :(20676088) ; (863 ) (2006AA05Z139) ; (20091402110009) : (1979 - ),,, :,,, ( Tel) 15035138531, ( E2mail) sbliu @tyut. edu. cn
6 :Ni Pt2Ru/ C 729, Ni Pt2Ru2Ni/ C 1 111 Pt2Ru2Ni/ C [10 ] Pt 52 Ru42Ni0. 7 / C( Pt,Ru,Ni 5 4 0. 7, ), 5. 500 g ( 20 %) 41. 5 ml (0. 25 mol/ L, ), 0. 2075 mol/ L ( T HF ) 6615 mg PtCl2 4115 mgrucl3 4. 5 mgnicl2, 51011 mg, 40 5. 4 ml,, 4 h, 6 ml, 1 h 106. 5 mg ( 60 %), 12 h,, 4 h,,, 100,,NiCl2 1. 2 ( 4 mm), Al2 O3,, 7. 5 mg 2. 5 ml,, 6. 3 L,, Na2 fion ( 5 %),80, 60 g/ cm 2 1. 3,, Hg/ Hg2 SO4 ( MSE),,NaO H ( 0. 1, 0. 5,1. 0,2. 0 mol/ L ) + CH3 O H ( 0. 1, 0. 5,1. 0,2. 0 mol/ L ) 20 min,, 20 mv/ s, (30 + 1) VMP2 ( PA R ) MSE 1. 4 XRD, D/ max22500 ( Rigaku), Cu K, 40 kv, 100 ma, 8 / min, 2 30 85 ; V G Scientific ESCALab250i2XL (XPS), Al K X, 300 W 2 2. 1 1 Ni Pt2Ru2Ni/ C XRD, 5 Pt [111 ],[ 200 ],[220 ],[ 311 ], 39. 7,46. 4,68. 1,81. 6 ;, Pt [ 111 ],Pt [ 220 ], c,d,e,pt [ 111 ] [ 220 ] a,pt 52Ru5/ C ;b,pt 52Ru4/ C ;c,pt 52Ru42Ni0. 3/ C ; d,pt52ru42ni0. 7/ C ;e,pt52ru42ni1. 5/ C 1 XRD a,b, Ru Ni, Pt (fcc), Pt [ 111 ] ; Ni, Pt Ru, Pt2Ru/ C Ni Scherrer [ 11 ] : d = 0194 / B (2 ) cos. : d ; ( = 0. 154 2 nm),b (2 ) ; Pt [ 220 ], [9 ] : Pt52Ru5 / C 3. 9 nm, Pt 52Ru4 / C 3. 7 nm, Pt 52Ru42Ni0. 3 / C 2. 4 nm, Pt 52Ru42 Ni0. 7 2. 9 nm,pt 52Ru42Ni1. 5 / C 2. 7 nm 212 XPS 2 Pt 52Ru42Ni0. 7 / C XPS 22a Pt Pt4f 7/ 2, 71. 5 ev Pt 0 Pt4f 7/ 2,72. 6 ev Pt 2 + Pt4f7/ 2 22b Ru Ru3p 3/ 2
730 41, 461. 9 ev Ru 0 Ru3p3/ 2, 464. 1 ev RuO2 Ru3p3/ 2 [12 ] 22 c Ni Ni2p 3/ 2 ;, 854. 0,855. 6,857. 6 ev NiO,Ni (O H) 2,NiOO H Ni2p3/ 2 XPS, Pt 52Ru42Ni0. 7 / C,Pt 0,Pt 2 + Pt 56 %,44 % ; Pt 52Ru4 / C, Pt52Ru42Ni0. 3 / C, Pt 52Ru42Ni1. 5 / C,Pt 0 47 %,53 %,61 % Ni, Pt ; Pt 52Ru42Ni0. 7 / C, Ru 0 RuO2 Ru 41 % 59 % ;Ni NiO Ni (O H) 2 NiOO H, 12 %,78 %,10 %, Pt 52Ru42Ni1. 5 / C Ni 5 %,23 %,72 %, Ni 0, Pt,Ru,Ni, 0,,, 2. 3 21311 Ni Pt2Ru/ C 3 Ni Pt2Ru2Ni/ C 1 mol/ L NaO H + 1 mol/ L CH3 O H 2 Pt 52Ru42Ni017/ C XPS Pt52Ru5 / C,, Ni Ru Pt52Ru4 4 1 mol/ L NaO H + 1 mol/ L CH3 O H Tafel,5 Tafel b 3 Pt Ru Ni,4 Ni, Pt52Ru4/ C, Pt52Ru42Ni0. 3 / C, Pt52Ru42Ni0. 7 / C, Pt52Ru42Ni1. 5 / C : - 0. 95, - 0. 97, - 1. 1, - 1. 1 V, 317. 6,382. 8,842. 2,229. 5 ma/ mg ; Ni,, Pt52Ru42Ni0. 7 / C,Pt52Ru5/ C 1. 34, 110 mv Pt52Ru4 / C Ru,Pt52Ru42Ni0. 7 / C 4 Tafel, Ni ( b ) ; a,,ni (Ni Pt 017 5),, Pt52 Ru4 / C,,,Pt52Ru42Ni0. 7 / C Pt52Ru5/ C,,, 0. 342 ma/ mg,, Pt52Ru4 / C, 0. 034 9 ma/ mg
6 :Ni Pt2Ru/ C 731 2. 3. 2 5 Pt 52Ru42Ni0. 7 / C 1 mol/ L NaO H + n mol/ L CH3 O H, 1 mol/ L,,,, 0. 62 ;, 1 2 mol/ L,,,, 0. 53 2 mol/ L CH3 O H, 1 123. 5 ma/ mg 5 Pt 52Ru42Ni0. 7/ C 6 Pt 52Ru42Ni0. 7 / C 1 mol/ L CH3 O H + n mol/ L NaO H, 1 mol/ L,,,, ; 1 2 mol/ L,,,, 2 mol/ L NaO H, - 0. 59 V, 1 mol/ L NaO H 0. 40 V,, 801 ma/ mg, 1 mol/ L NaO H 815 ma/ mg, 0. 16, Ru XPS, Ni Ni ( O H ) 2 NiOO H,,Ni (O H) 2 Ni (O H) 2 Ni 2 + + 2O Hads + 2e - O Hads, CO Hads COads CH3 O Hads ;, Ni 2 + Ni 2 + + 2O H - Ni (O H) 2 COads CO Hads [2 ], O Hads,, Ni O H -,Ni, Ni,Ni Ni, Ni,Ni, Pt,, Ni, Pt 5 Ru42Ni0. 7 / C NaO H 1 mol/ L O H -, Pt Ni 5d 9 6s 1 3d 8 4s 2, Pt, d s Pt,, d Pt Ni d, Ni Pt s,, Pt, Pt Ni, Pt 0 Pt Ni, Pt d, Pt CH3 O H,, CO Hads COads,CO Hads COads, [3 ],Ni, 3 6 Pt 52Ru42Ni0. 7/ C, Ni Pt 52 Ru4 / C, 1) Ni Pt2Ru,Ni Pt2Ru2Ni, Ni,Ni Ni, Ni,Ni,,, Pt 52Ru42Ni0. 7 / C
732 41 2) Pt 52Ru4 Ni Ru ;Ni O H - 3) 1 mol/ L, 0. 62 ; NaO H 0. 5 2. 0 mol/ L, O H - 0. 16 : [ 1 ] Yu E H, Scott K. Development of direct met hanol alkaline fuel cells using anion exchange membranes[j ]. J Power Sources, 2004, 137 (2) : 248. [ 2 ] Yu E H, Scott K, Reeve R W. A study of t he anodic oxidation of met hanol on Pt in alkaline solutions[j ]. J Electroanal Chem, 2003, 547 (1) :17224. [ 3 ],,,. Ru, Sn Co Pt/ C [J ]., 2006, 27 (9) :7872792. [ 4 ] Manoharan R, Prabhuram J. Possibilities of prevention of formation of poisoning species on direct met hanol fuel cell anodes [J ]. J Power Sources, 2001, 96 :2202225. [ 5 ] Assiongbon K A, Roy D. Electro2oxidation of met hanol on gold in alkaline media : Adsorption characteristics of reaction in2 termediates studied using time resolved electro2chemical impedance and surface plasmon resonance techniques[j ]. J Surface Science, 2005, 594 :992119. [ 6 ] Orozco G, Perez M C, Rincon A, et al. Electro2oxidation of met hanol on silver in alkaline medium[j ]. J Electroanal Chem, 2000, 495 :71278. [ 7 ] Heli H, Jafarian M, Mahjani M G., et al. Electro2oxidation of met hanol on copper in alkaline solution[j ]. Electrochem Ac2 ta, 2004, 49 :499925006. [ 8 ] Tripkovic A V, Popovic K D, Grgur B N, et al. Met hanol electrooxidation on supported Pt and Pt Ru catalyst s in acid and al2 kaline solutions[j ]. J Electrochim Acta, 2002, 47 (22223) :370723714. [ 9 ] Mart nez H M V, Rojas S. Effect of Ni addition over Pt Ru/ C based electrocatalyst s for fuel cell applications[j ]. Appl Catal B Environ, 2006, 69 :75284. [ 10 ] Gotz M, Wendt H. Binary and ternary anode catalyst formulations including t he element s W, Sn and Mo for PEMFCs oper2 ated on methanol or reformate gas[j ]. Electrochim Acta, 1998, 43 (24) :363723644. [ 11 ] Radmilovic V, Gasterger H A, Ross P N. Structure and chemical composition of a supported Pt2Ru electrocatalyst for methanol oxidation[j ]. J Catal, 1995, 154 (1) :982106. [ 12 ] Prabhuram J, Zhao T S, Liang Z X,et al. A simple met hod for t he synt hesis of Pt Ru nanoparticles on t he multi2walled car2 bon nanotube for t he anode of a DMFC[J ]. Electrochim Acta, 2007, 52 (7) :264922656. Effect of Doping with Ni on the Performance of Pt2Ru / C f or Methanol Electro2Catalytic Oxidation in Alkaline Media ZHANG Tao 1, L IU Shi2bin 1, YANG Shao2hua 2, L I Yi2bing 1, ZHANG Zhong2lin 1, HAO Xiao2gang 1 (11 I nstitute of Clean Technique f or Chemical Engineering, Tai y uan Universit y of Technology, Tai y uan 030024, China; 21 Dalian I nstitute of Chemical Physics, Chinese A cadem y of S ciences, Dalian 116023, China) Abstract :The catalyst s of Pt2Ru2Ni/ C wit h different ato m ratio were p repared by colloidal met hod. The surface composition and crystal pattern of nano2particle supported by carbon black were characterized by X2ray diff ractio n and energy dispersive X2ray spect ro scop y. The catalyst ac2 tivity in different met hanol and NaO H concentration electrolytes was measured by cyclic voltam2 metry. The result s show t hat, the performance of Pt2Ru/ C for met hanol electro2oxidation was improved mark2edly by doping wit h Ni, and t he relation between the activity of Pt2Ru2Ni/ C and Ni atom ratio in alloy nano particles appeared volcanic. The Pt5 Ru4 Ni0. 7 / C gave t he best perform2 ance among t he five catalyst s wit h different Ni atom ratio, and t he peak current density on Pt 52 Ru42Ni0. 7 / C reached 842. 2 ma/ mg and t he onset potential of met hanol electro2oxidation was 0. 16 V lower t han t hat of Pt 52Ru5 / C in 1. 0 mol/ L NaO H + 1. 0 mol/ L CH3 O H. In the electrolyte wit h low met hanol concentration, t he met hanol reaction order was 0. 58. Key words :platinum nano2alloy ; elect ro2catalyst ; met hanol elect ro2o xidatio n ; alkaline media ( : )