Browse > Article
http://dx.doi.org/10.4491/KSEE.2016.38.5.242

Fundamental Mechanisms of Platinum Catalyst for Oxygen Reduction Reaction in Fuel Cell: Density Functional Theory Approach  

Kang, Seok Ho (Department of Environmental Engineering, Chungbuk National University)
Lee, Chang-Mi (Department of Environmental Engineering, Chungbuk National University)
Lim, Dong-Hee (Department of Environmental Engineering, Chungbuk National University)
Publication Information
Journal of Korean Society of Environmental Engineers / v.38, no.5, 2016 , pp. 242-248 More about this Journal
Abstract
The overall reaction rate of fuel cell is governed by oxygen reduction reaction (ORR) in the cathode due to its slowest reaction compared to the oxidation of hydrogen in the anode. The ORR efficiency can be readily evaluated by examining the adsorption strength of atomic oxygen on the surface of catalysts (i.e., known as a descriptor) and the adsorption energy can be controlled by transforming the surface geometry of catalysts. In the current study, the effect of the surface geometry of catalysts (i.e., strain effect) on the adsorption strength of atomic oxygen on platinum catalysts was analyzed by using density functional theory (DFT). The optimized lattice constant of Pt ($3.977{\AA}$) was increased and decreased by 1% to apply tensile and compressive strain to the Pt surface. Then the oxygen adsorption strengths on the modified Pt surfaces were compared and the electron charge density of the O-adsorbed Pt surfaces was analyzed. As the interatomic distance increased, the oxygen adsorption strength became stronger and the d-band center of the Pt surface atoms was shifted toward the Fermi level, implying that anti-bonding orbitals were shifted to the conduction band from the valence band (i.e., the anti-bonding between O and Pt was less likely formed). Consequently, enhanced ORR efficiency may be expected if the surface Pt-Pt distance can be reduced by approximately 2~4% compared to the pure Pt owing to the moderately controlled oxygen binding strength for improved ORR.
Keywords
Fuel Cell; Oxygen Reduction Reaction (ORR); Platinum (Pt) Catalysts; Density Functional Theory (DFT);
Citations & Related Records
연도 인용수 순위
  • Reference
1 Ahn, B. M., "OECD Factbook 2014," Korea Institute of S&T Evaluation and Planning(2014).
2 Srinivasan, S., Mosdale, R., Stevens, P. and Yang, C., "Fuel cells: Reaching the era of clean and efficient power generation in the twenty-first century," Annu. Rev. Environ. Resour., 24, 281-328(1999).
3 Ohayre, R. P., Cha, S. W., Colella, W. and Prinz, F. B., "Fuel Cell Fundamentals," John Wiley & Sons (Korean: Hanteemedia)(2008).
4 Behling, N. H., "Fuel Cells: Current Technology Challenges and Future Research Needs," Elsevier(2013).
5 He, C., Desai, S., Brown, G. and Bollepalli, S., "PEM Fuel Cell Catalysts: Cost, Performance, and Durability," Electrochem. Soc. Interface, Fall(2005).
6 Gasteiger, H. A., Kocha, S. S., Sompalli, B. and Wagner, F. T., "Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs," Appl. Catal. B, 56(1-2), 9-35(2005).   DOI
7 Greeley, J., Stephens, I. E. L., Bondarenko, A. S., Johansson, T. P., Hansen, H. A., Jaramillo, T. F., Rossmeisl, J., Chorkendorff, I. and Norskov, J. K., "Alloys of platinum and early transition metals as oxygen reduction electrocatalysts," Nat. Chem., 1(7), 552-556(2009).   DOI
8 Norskov, J. K., Rossmeisl, J., Logadottir, A., Lindqvist, L., Kitchin, J. R., Bligaard, T. and Jonsson, H., "Origin of the overpotential for oxygen reduction at a fuel-cell cathode," J. Phys. Chem. B, 108(46), 17886-17892(2004).   DOI
9 Ramaker, D. E., Korovina, A., Croze, V., Melke, J. and Roth, C., "Following ORR intermediates adsorbed on a Pt cathode catalyst during break-in of a PEM fuel cell by in operando X-ray absorption spectroscopy," Phys. Chem. Chem. Phys., 16(27), 13645-13653(2014).   DOI
10 Stamenkovic, V., Mun, B. S., Mayrhofer, K. J. J., Ross, P. N., Markovic, N. M., Rossmeisl, J., Greeley, J. and Norskov, J. K., "Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure," Angew. Chem. Int. Ed., 45(18), 2897-2901(2006).   DOI
11 Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J. J., Lucas, C. A., Wang, G., Ross, P. N. and Markovic, N. M., "Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces," Nat. Mater., 6(3), 241-247(2007).   DOI
12 Kohn, W. and Sham, L. J., "Self-Consistent Equations Including Exchange and Correlation Effects," Phys. Rev., 140 (4A), A1133-A1138(1965).   DOI
13 Kresse, G. and Hafner, J., "Ab initio molecular dynamics for liquid metals," Phys. Rev. B, 47(1), 558-561(1993).   DOI
14 Kresse, G. and Hafner, J., "Ab initio molecular-dynamics simulation of the liquid-metal amorphous-semiconductor transition in germanium," Phys. Rev. B, 49(20), 14251-14269(1994).   DOI
15 Kresse, G. and Joubert, D., "From ultrasoft pseudopotentials to the projector augmented-wave method," Phys. Rev. B, 59 (3), 1758-1775(1999).
16 Kresse, G. and Furthmuller, J., "Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set," Phys. Rev. B, 54(16), 11169-11186(1996).   DOI
17 Kresse, G. and Furthmuller, J., "Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set," Comput. Mater. Sci., 6(1), 15-50(1996).   DOI
18 Blochl, P. E., "Projector augmented-wave method," Phys. Rev. B, 50(24), 17953-17979(1994).   DOI
19 Perdew, J. P., Burke, K. and Ernzerhof, M., "Generalized gradient approximation made simple," Phys. Rev. Lett., 77 (18), 3865-3868(1996).   DOI
20 Monkhorst, H. J. and Pack, J. D., "Special points for Brillouinzone integrations," Phys. Rev. B, 13(12), 5188-5192(1976).   DOI
21 Callister, W. D. and Rethwisch, D. G., "Materials Science and Engineering: An Introduction, 9th Edition," Wiley(2014).
22 Michaelides, A. and Hu, P., "Hydrogenation of S to H2S on Pt(111): A first-principles study," J. Chem. Phys, 115(18), 8570-8574(2001).   DOI
23 Qi, L., Yu, J. and Li, J., "Coverage dependence and hydroperoxyl-mediated pathway of catalytic water formation on Pt (111) surface," J. Chem. Phys, 125(5), 054701(2006).   DOI