Corresponding Author

Gao-ren LI(ligaoren@mail.sysu.edu.cn)


The development of non-Pt anode electrocatalysts with high activity and long-term durability at low cost for fuel cells still remains enormous challenge. Here we report the Pd nanoparticles supported on Ni foams etched by the mixed acids (HNO3+H2SO4+H3PO4+CH3COOH) (Pd/ME-NF) that are designed and fabricated as high-performance electrocatalysts for ethanol oxidation in alkaline media. Because of the advantages of large open space, fast electrolyte penetration/diffusion and rapid electron transfer process, the Pd/ME-NF catalysts exhibited significantly improved electrocatalytic activity and durability compared with the commercial Pd/C catalysts.

Graphical Abstract


Pd nanoparticle, Ni foam, mixed acids etching, electrocatalyst, ethanol oxidation

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[1] Wang D, Xin H L, Hovden R, et al. Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts[J]. Nature Materials, 2012, 12(1): 81-87.
[2] Jia Y Y, Jiang Y Q, Zhang J W, et al. Unique excavated rhombic dodecahedral PtCu3 alloy nanocrystals constructed with ultrathin nanosheets of high-energy {110} facets[J]. Journal of the American chemical society, 2014, 136(10): 3748-3751.
[3] Yang H. Platinum-based electrocatalysts with core-shell nanostructures[J]. Angewandte Chemie International Edition, 2011, 50(12): 2674-2676.
[4] Liu W, Herrmann A K, Geiger D, et al. High-performance electrocatalysis on palladium aerogels[J]. Angewandte Chemie International Edition, 2012, 51(23): 5743-5747.
[5] Kloke A, Stetten F V, Zengerle R, et al. Strategies for the fabrication of porous platinum electrodes[J]. Advanced Materials, 2011, 23(43): 4976-5008.
[6] Wang D, Chou H L, Lin Y C, et al. Simple replacement reaction for the preparation of ternary Fe1-xPtRux nanocrystals with superior catalytic activity in methanol oxidation reaction[J]. Journal of the American chemical society, 2012, 134: 10011-10020.
[7] Strmcnik D, Escudero-Escribano M, Kodama K, et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide[J]. Nature Chemistry, 2010, 2(10): 880-885.
[8] Debe M. Electrocatalyst approaches and challenges for automotive fuel cells[J]. Nature, 2012, 486(7401): 43-51.
[9] Xia B, Wu H B, Wang X, et al. One-pot synthesis of cubic PtCu3 nanocages with enhanced electrocatalytic activity for the methanol oxidation reaction[J]. Journal of the American Chemical Society, 2012, 134: 13934-13937.
[10] Huang X Q, Zhang H H, Guo C Y et al. Simplifying the creation of hollow metallic nanostructures: one-pot synthesis of hollow palladium/platinum single-crystalline nanocubes[J]. Angewandte Chemie International Edition, 2009, 48(26): 4808-4906.
[11] Wen Z H, Cui S M, Pu H H, et al. Metal nitride/graphene nanohybrids: general synthesis and multifunctional titanium nitride/graphene electrocatalyst[J]. Advanced Materials, 2011, 23(45): 5445-5450.
[12] Sanabria-Chinchilla J, Asazawa K, Sakamoto T, et al. Noble metal-free hydrazine fuel cell catalysts: EPOC cffect in competing chemical and electrochemical reaction pathways[J]. Journal of the American Chemical Society, 2011, 133(14): 5425-5431.
[13] Wang S Y, Iyyamperumal E, Roy A, et al. Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction: a synergetic effect by Co-doping with boron and nitrogen[J]. Angewandte Chemie International Edition, 2011, 50(49): 11756-11760.
[14] Wu J B, Qi L, You H J, et al. Icosahedral platinum alloy nanocrystals with enhanced electrocatalytic activities[J]. Journal of the American Chemical Society, 2012, 134(29): 11880-11883.
[15] Wang H J, Ishihara S, Ariga K, et al. All-metal layer-by-layer films: bimetallic alternate layers with accessible mesopores for enhanced electrocatalysis[J]. Journal of the American Chemical Society, 2012, 134(26): 10819-10821.
[16] Wang A L, Xu H, Fen J X, et al. Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation[J]. Journal of the American chemical society, 2013, 135(29): 10703-10709.
[17] Wang G W, Huang B, Xiao L, et al. Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells[J]. Journal of the American Chemical Society, 2014, 136(27): 9643-9649.
[18] Gao M R, Gao Q, Jiang J, et al. A methanol-tolerant Pt/CoSe2 nanobelt cathode catalyst for direct methanol fuel cells[J]. Angewandte Chemie International Edition, 2011, 50(21): 4905-5010.
[19] Hong J W, Kim D, Lee Y W, et at. Atomic-distribution-dependent electrocatalytic activity of Au-Pd bimetallic nanocrystals[J]. Angewandte Chemie International Edition, 2011, 50(38): 8876-9042.
[20] Wu H X, Li H J, Zhai Y J, et al. Facile synthesis of free-standing Pd-based nanomembranes with enhanced catalytic performance for methanol/ethanol oxidation[J]. Advanced Materials, 2012, 24(12): 1594-1597.
[21] Mazumder V, Chi M F, Mankin M N, et al. A facile synthesis of MPd (M = Co, Cu) nanoparticles and their catalysis for formic acid oxidation[J]. Nano Letters, 2012, 12(2): 1102-1106.
[22] Zhu C Z, Guo S J, Dong S J. PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules[J]. Advanced Materials, 2012, 24(17): 2326-2331.
[23] Han B H, Carlton E C, Kongkanand A, et. al. Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells[J]. Energy Environmental Science, 2014, 8(1): 258-266.
[24] Mayrhofer K J J, Hartl K, Juhart V, et al. Degradation of carbon-supported Pt bimetallic nanoparticles by surface segregation[J]. Journal of the American Chemical Society, 2009, 131(45): 16348-16349.
[25] Wang D L, Yu Y C, Xin H L, et at. Tuning oxygen reduction reaction activity via controllable dealloying: a model study of ordered Cu3Pt/C intermetallic nanocatalysts[J]. Nano Letters, 2012, 12(10): 5230-5238.
[26] Kang Y J, Murray C B. Synthesis and electrocatalytic properties of cubic Mn-Pt nanocrystals (nanocubes)[J]. Journal of the American Chemical Society, 2010, 132(22): 7568-7569.
[27] Wanjala B N, Fang B, Luo J, et al. Correlation between atomic coordination structure and enhanced electrocatalytic activity for trimetallic alloy catalysts[J]. Journal of the American Chemical Society, 2011, 133(32): 12714-12727.
[28] Yang G W, Xu C L, Li H L. Electrodeposited nickel hydroxide on nickel foam with ultrahigh capacitance[J]. Chemical Communications, 2008, 48: 6537-6539.
[29] Long J, Dunn B, Rolison D R, et al. Three-dimensional battery architectures[J]. Chemical Reviews, 2004, 104(10): 4463-4492.
[30] Chang Y H, Lin C T, Chen T Y, et al. Highly efficient electrocatalytic hydrogen production by MoSx grown on graphene-protected 3D Ni foams[J]. Advanced Materials, 2013, 25(5): 756-760.
[31] Grdeń M, Alsabet M, Jerkiewicz G. Surface science and electrochemical analysis of nickel foams[J]. ACS Applied Materials Interfaces, 2012, 4(6): 3012-3021.
[32] Chierchie T, Mayer C, Lorenz W J. Structural changes of surface oxide layers on palladium[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1982, 135(2), 211-220.
[33] Poon K C, Tan D C L, Vo D T T, et al. Newly developed stepwise electroless deposition enables a remarkably facile synthesis of highly active and stable amorphous Pd nanoparticle electrocatalysts for oxygen reduction reaction[J]. Journal of the American Chemical Society, 2014, 136(14): 5217-5220.



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