Tuning Oxygen Reduction Reaction Activity via Controllable Dealloying: A Model Study of Ordered Cu3Pt/C Intermetallic Nanocatalysts

被引:296
作者
Wang, Deli [1 ]
Yu, Yingchao [1 ]
Xin, Huolin L. [2 ]
Hovden, Robert [5 ]
Ercius, Peter [3 ]
Mundy, Julia A. [5 ]
Chen, Hao [1 ]
Richard, Jonah H. [4 ]
Muller, David A. [5 ,6 ]
DiSalvo, Francis J. [1 ]
Abruna, Hector D. [1 ]
机构
[1] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
[2] Cornell Univ, Dept Phys, Ithaca, NY 14853 USA
[3] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Natl Ctr Electron Microscopy, Berkeley, CA 94720 USA
[4] Bard Coll, Dept Phys, Annandale On Hudson, NY 12504 USA
[5] Cornell Univ, Sch Appl & Engn Phys, Ithaca, NY 14853 USA
[6] Cornell Univ, Kavli Inst, Ithaca, NY 14853 USA
基金
美国国家科学基金会;
关键词
Fuel cell; ORR; electrocatalyst; ordered intermetallic nanoparticle; dealloying; PT-M M; ELECTROCATALYTIC ACTIVITY; CO; CATALYSTS; NANOPARTICLES; NI; MICROSCOPY; STABILITY; SURFACES; ALLOYS;
D O I
10.1021/nl302404g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A promising electrocatalyst prototype of low Pt mole fraction, intermetallic nanoparticles of Cu3Pt, has been prepared using a simple impregnation-reduction method, followed by a post heat-treatment. Two dealloying methods (electrochemical and chemical) were implemented to control the atomic-level morphology and improve performance for the oxygen reduction reaction (ORR). The morphology and elemental composition of the dealloyed nanoparticles were characterized at angstrom resolution using an aberration-corrected scanning transmission electron microscope equipped with an electron energy loss spectrometer. We found that the electrochemical dealloying method led to the formation of a thin Pt skin of ca. 1 nm in thickness with an ordered Cu3Pt core structure, while chemical leaching gave rise to a "spongy" structure with no ordered structure being preserved. A three-dimensional tomographic reconstruction indicated that numerous voids were formed in the chemically dealloyed nanoparticles. Both dealloying methods yielded enhanced specific and mass activities toward the ORR and higher stability relative to Pt/C. The spongy nanoparticles exhibited better mass activity with a slightly lower specific activity than the electrochemically dealloyed nanoparticles after 50 potential cycles. In both cases, the mass activity was still enhanced after 5000 potential cycles.
引用
收藏
页码:5230 / 5238
页数:9
相关论文
共 42 条
[1]   Platinum monolayer fuel cell electrocatalysts [J].
Adzic, R. R. ;
Zhang, J. ;
Sasaki, K. ;
Vukmirovic, M. B. ;
Shao, M. ;
Wang, J. X. ;
Nilekar, A. U. ;
Mavrikakis, M. ;
Valerio, J. A. ;
Uribe, F. .
TOPICS IN CATALYSIS, 2007, 46 (3-4) :249-262
[2]   Electrocatalysis of oxygen reduction on a carbon supported platinum-vanadium alloy in polymer electrolyte fuel cells [J].
Antolini, E ;
Passos, RR ;
Ticianelli, EA .
ELECTROCHIMICA ACTA, 2002, 48 (03) :263-270
[3]   The stability of Pt-M (M = first row transition metal) alloy catalysts and its effect on the activity in low temperature fuel cells - A literature review and tests on a Pt-Co catalyst [J].
Antolini, Ermete ;
Salgado, Jose R. C. ;
Gonzalez, Ernesto R. .
JOURNAL OF POWER SOURCES, 2006, 160 (02) :957-968
[4]   Oxygen electroreduction at catalysts PtM (M = Co, Ni, or Cr) [J].
Bogdanovskaya, V. A. ;
Tarasevich, M. R. ;
Kuznetsova, L. N. ;
Zhutaeva, G. V. ;
Lozovaya, O. V. .
RUSSIAN JOURNAL OF ELECTROCHEMISTRY, 2010, 46 (08) :925-933
[5]   Sub-Nanometer-Resolution Elemental Mapping of "Pt3Co" Nanoparticle Catalyst Degradation in Proton-Exchange Membrane Fuel Cells [J].
Carlton, Christopher E. ;
Chen, Shuo ;
Ferreira, Paulo J. ;
Allard, Lawrence F. ;
Shao-Horn, Yang .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2012, 3 (02) :161-166
[6]   Electrocatalytic activity of ordered intermetallic phases for fuel cell applications [J].
Casado-Rivera, E ;
Volpe, DJ ;
Alden, L ;
Lind, C ;
Downie, C ;
Vázquez-Alvarez, T ;
Angelo, ACD ;
DiSalvo, FJ ;
Abruña, HD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (12) :4043-4049
[7]   Hollow platinum spheres with nano-channels: Synthesis and enhanced catalysis for oxygen reduction [J].
Chen, Hao Ming ;
Liu, Ru-Shi ;
Lo, Man-Yin ;
Chang, Sung-Chun ;
Tsai, Li-Duan ;
Peng, Yu-Min ;
Lee, Jyh-Fu .
JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (20) :7522-7526
[8]   The potential of zero total charge of Pt nanoparticles and polycrystalline electrodes with different surface structure The role of anion adsorption in fundamental electrocatalysis [J].
Chen, Qing-Song ;
Solla-Gullon, Jose ;
Sun, Shi-Gang ;
Feliu, Juan M. .
ELECTROCHIMICA ACTA, 2010, 55 (27) :7982-7994
[9]   VISIBILITY OF SINGLE ATOMS [J].
CREWE, AV ;
WALL, J ;
LANGMORE, J .
SCIENCE, 1970, 168 (3937) :1338-&
[10]   Data Processing for Atomic Resolution Electron Energy Loss Spectroscopy [J].
Cueva, Paul ;
Hovden, Robert ;
Mundy, Julia A. ;
Xin, Huolin L. ;
Muller, David A. .
MICROSCOPY AND MICROANALYSIS, 2012, 18 (04) :667-675