Abstract
The strong drive to commercialize fuel cells for portable as well as transportation power sources has led to the tremendous growth in fundamental research aimed at elucidating the catalytic paths and kinetics that govern the electrode performance of proton exchange membrane (PEM) fuel cells. Advances in theory over the past decade coupled with the exponential increases in computational speed and memory have enabled theory to become an invaluable partner in elucidating the surface chemistry that controls different catalytic systems. Despite the significant advances in modeling vapor-phase catalytic systems, the widespread use of first principle theoretical calculations in the analysis of electrocatalytic systems has been rather limited due to the complex electrochemical environment. Herein, we describe the development and application of a first-principles-based approach termed the double reference method that can be used to simulate chemistry at an electrified interface. The simulations mimic the half-cell analysis that is currently used to evaluate electrochemical systems experimentally where the potential is set via an external potentiostat. We use this approach to simulate the potential dependence of elementary reaction energies and activation barriers for different electrocatalytic reactions important for the anode of the direct methanol fuel cell. More specifically we examine the potential-dependence for the activation of water and the oxidation of methanol and CO over model Pt and Pt alloy surfaces. The insights from these model systems are subsequently used to test alternative compositions for the development of improved catalytic materials for the anode of the direct methanol fuel cell.
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Donitz W (1998) Int J Hydrogen Energy 23:611
Wasmus S, Kuver A (1999) J Electroanal Chem 461:14
Haile SM (2003) Acta Materialia 51:5981
Bagotzky VS, Osetrova NV, Skundin AM (2003) Russ J Electrochem 39:919
Dillon R, Srinivasan S, Arico AS, Antonucci V (2004) J Power Sources 127:112
Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Appl Catal B 56:9
Jusys Z, Behm RJ (2001) J Phys Chem B 105:10874
Roth C, Benker N, Buhrmester T, Mazurek M, Loster M, Fuess H, Koningsberger DC, Ramaker DE (2005) J Am Chem Soc 127:14607
Gasteiger HA, Marković N, Ross PN Jr, Cairns EJ (1993) J Phys Chem 97:12020
Gasteiger HA, Marković N, Ross PN Jr, Cairns EJ (1994) J Phys Chem 98:617
Gasteiger HA, Marković NM, Ross PN Jr (1995) J Phys Chem 99:8290
Jusys Z, Kaiser J, Behm RJ (2002) Electrochim Acta 47:3693
de Mongeot FB, Scherer M, Gleich B, Kopatzki E, Behm RJ (1998) Surf Sci 411:249
Miki A, Ye S, Osawa M (2002) Chem Comm 1500
Waszczuk P, Lu G-Q, Wieckowski A, Lu C, Rice C, Masel RI (2002) Electrochim Acta 47:3637
Marcus RA (1956) J Chem Phys 24:966
Guidelli R, Schmickler W (2000) Electrochim Acta 45:2317
Anderson AB, Awad MK (1985) J Am Chem Soc 107:7854
Anderson AB, Ray NK (1982) J Phys Chem 86:488
Anderson AB (2003) Electrochim Acta 48:3743
Anderson AB, Cai Y, Sidik RA, Kang DB (2005) J Electroanal Chem 580:17
Rossmeisl J, Logadottir A, Nørskov JK (2005) Chem Phys 319:178
Nørskov JK, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin JR, Bligaard T, Jónsson H (2004) J Phys Chem B 108:17886
Rossmeisl J, Nørskov JK, Taylor CD, Janik MJ, Neurock M (2006) J Phys Chem B 110:21833
Okamoto Y, Sugino O, Mochizuki Y, Ikeshoji T, Morikawa Y (2003) Chem Phys Lett 377:236
Mattson TR, Paddison SJ (2003) Surf Sci 544:L697
Hartnig C, Spohr E (2005) Chem Phys 319:185
Kresse G, Furthmüller J (1996) Comput Mater Sci 6:15
Kresse G, Furthmüller J (1996) Phys Rev B 54:11169
Kresse G, Hafner J (1993) Phys Rev B 47:558
Vanderbilt D (1990) Phys Rev B 41:7892
Taylor CD, Kelly RG, Neurock M (2006) J Electrochem Soc 153:E207
Cao D, Lu G-Q, Wieckowski A, Wasileski SA, Neurock M (2005) J Phys Chem B 109:11622
Janik MJ, Neurock M (2007) Electrochim Acta 52:5517
Filhol JS, Neurock M (2006) Angew Chem Int Ed 45:402
Taylor CD, Wasileski SA, Filhol JS, Neurock M (2006) Phys Rev B 73:165402
Reiss H, Heller A (1985) J Phys Chem 89:4207
Taylor CD, Kelly RG, Neurock M (2007) J Electrochem Soc 154:F55
Henderson MA (2002) Surf Sci Rep 46:1
Marković NM, Ross PN Jr (2002) Surf Sci Rep 45:117
Desai SK, Pallassana V, Neurock M (2001) J Phys Chem B 105:9171
Desai SK, Neurock M (2003) Phys Rev B 68:075420
Doering DL, Madey TE (1982) Surf Sci 123:305
Taylor CD, Kelly RG, Neurock M (2007) Phys Rev B submitted
Suzuki T, Yamada T, Itaya K (1996) J Phys Chem 100:8954
Taylor CD, Janik MJ, Neurock M, Kelly RG (2007) Mol Sim 33:429
Janik MJ, Neurock M, in preparation
Henkelman G, Jónsson H (2000) J Chem Phys 113:9978
Henkelman G, Uberuaga BP, Jónsson H (2000) J Chem Phys 113:9901
Mills G, Jónsson H, Schenter GK (1995) Surf Sci 324:305
Liu P, Logadottir A, Nørskov JK (2003) Electrochim Acta 48:3731
Acknowledgements
This work was supported by the Army Research Office—MURI grant (DAAD19-03-1-0169) for fuel cell research. Computational resources at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory were used, in part, to complete this research as well as computing resources at the U.S. Army Research Laboratory Major Shared Resource Center. The authors thank Dr. Sally Wasileski, Dr. Jean-Sebastian Filhol, and Dr. Andrzej Wieckowski for their contributions to this research effort.
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Janik, M.J., Taylor, C.D. & Neurock, M. First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide. Top Catal 46, 306–319 (2007). https://doi.org/10.1007/s11244-007-9004-9
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DOI: https://doi.org/10.1007/s11244-007-9004-9