Self-supporting nanoporous gold-palladium overlayer bifunctional catalysts toward oxygen reduction and evolution reactions
)
Download citation
586
Views
10
Downloads
40
Crossref
N/A
WoS
39
Scopus
6
CSCD
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial processes for energy conversion/storage systems, such as fuel cells, metal–air batteries, and water splitting. However, both reactions are severely restricted by their sluggish kinetics, thus requiring highly active, cost-effective, and durable electrocatalysts. Herein, we develop novel bifunctional nanocatalysts through surface nanoengineering of dealloying-driven nanoporous gold (NPG). Pd overlayers were precisely deposited onto the NPG ligament surface by epitaxial layer-by-layer growth. More importantly, the obtained NPG-Pd overlayer nanocatalysts exhibit remarkably enhanced electrocatalytic activities toward both the ORR and OER in alkaline media, benchmarked against a stateof- the-art Pt/C catalyst. The improved electrocatalytic performance is rationalized by the unique three-dimensional nanoarchitecture of NPG, enhanced Pd utilization efficiency from precise control of the Pd overlayers, and change in electronic structure, as revealed by density functional theory calculations.
menu
Self-supporting nanoporous gold-palladium overlayer bifunctional catalysts toward oxygen reduction and evolution reactions
)
Abstract
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial processes for energy conversion/storage systems, such as fuel cells, metal–air batteries, and water splitting. However, both reactions are severely restricted by their sluggish kinetics, thus requiring highly active, cost-effective, and durable electrocatalysts. Herein, we develop novel bifunctional nanocatalysts through surface nanoengineering of dealloying-driven nanoporous gold (NPG). Pd overlayers were precisely deposited onto the NPG ligament surface by epitaxial layer-by-layer growth. More importantly, the obtained NPG-Pd overlayer nanocatalysts exhibit remarkably enhanced electrocatalytic activities toward both the ORR and OER in alkaline media, benchmarked against a stateof- the-art Pt/C catalyst. The improved electrocatalytic performance is rationalized by the unique three-dimensional nanoarchitecture of NPG, enhanced Pd utilization efficiency from precise control of the Pd overlayers, and change in electronic structure, as revealed by density functional theory calculations.
References(42)
Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 2009, 1, 552–556.
Suntivich, J.; Gasteiger, H. A.; Yabuuchi, N.; Nakanishi, H.; Goodenough, J. B.; Shao-Horn, Y. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries. Nat. Chem. 2011, 3, 546–550.
Peng, Z. Q.; Freunberger, S. A.; Chen, Y. H.; Bruce, P. G. A reversible and higher-rate Li-O2 battery. Science 2012, 337, 563–566.
Cui, C. H.; Gan, L.; Heggen, M.; Rudi, S.; Strasser, P. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat. Mater. 2013, 12, 765–771.
Chen, C.; Kang, Y. J.; Huo, Z. Y.; Zhu, Z. W.; Huang, W. Y.; Xin, H. L.; Snyder, J. D.; Li, D. G.; Herron, J. A.; Mavrikakis, M. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 2014, 343, 1339–1343.
Zhang, L.; Roling, L. T.; Wang, X.; Vara, M.; Chi, M. F.; Liu, J. Y.; Choi, S. I.; Park, J.; Herron, J. A.; Xie, Z. X. et al. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 2015, 349, 412–416.
Huang, X. Q.; Zhao, Z. P.; Cao, L.; Chen, Y.; Zhu, E. B.; Lin, Z. Y.; Li, M. F.; Yan, A. M.; Zettl, A.; Wang, Y. M. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 2015, 348, 1230–1234.
Kanan, M. W.; Nocera, D. G. In situ formation of an oxygenevolving catalyst in neutral water containing phosphate and Co2+. Science 2008, 321, 1072–1075.
Yin, Q. S.; Tan, J. M.; Besson, C.; Geletii, Y. V.; Musaev, D. G.; Kuznetsov, A. E.; Luo, Z.; Hardcastle, K. I.; Hill, C. L. A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science 2010, 328, 342–345.
Esswein, A. J.; Surendranath, Y.; Reece, S. Y.; Nocera, D. G. Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters. Energy Environ. Sci. 2011, 4, 499–504.
Suntivich, J.; May, K. J.; Gasteiger, H. A.; Goodenough, J. B.; Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 2011, 334, 1383–1385.
McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 2013, 135, 16977– 16987.
Luo, J. S.; Im, J. -H.; Mayer, M. T.; Schreier, M.; Nazeeruddin, M. K.; Park, N. -G.; Tilley, S. D.; Fan, H. J.; Grätzel, M. Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts. Science 2014, 345, 1593–1596.
Wu, J. B.; Zhang, J. L.; Peng, Z. M.; Yang, S. C.; Wagner, F. T.; Yang, H. Truncated octahedral Pt3Ni oxygen reduction reaction electrocatalysts. J. Am. Chem. Soc. 2010, 132, 4984–4985.
Calle-Vallejo, F.; Koper, M. T. M.; Bandarenka, A. S. Tailoring the catalytic activity of electrodes with monolayer amounts of foreign metals. Chem. Soc. Rev. 2013, 42, 5210–5230.
Shao, M.; Shoemaker, K.; Peles, A.; Kaneko, K.; Protsailo, L. Pt monolayer on porous Pd-Cu alloys as oxygen reduction electrocatalysts. J. Am. Chem. Soc. 2010, 132, 9253–9255.
Wang, R. Y.; Wang, C.; Cai, W. B.; Ding, Y. Ultralowplatinum- loading high-performance nanoporous electrocatalysts with nanoengineered surface structures. Adv. Mater. 2010, 22, 1845–1848.
Nørskov, J. K.; Bligaard, T.; Rossmeisl, J.; Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 2009, 1, 37–46.
Lang, X. Y.; Hirata, A.; Fujita, T.; Chen, M. W. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. Nat. Nanotechnol. 2011, 6, 232–236.
Meng, F. H.; Ding, Y. Sub-micrometer-thick all-solid-state supercapacitors with high power and energy densities. Adv. Mater. 2011, 23, 4098–4102.
Yu, Y.; Gu, L.; Lang, X. Y.; Zhu, C. B.; Fujita, T.; Chen, M. W.; Maier, J. Li storage in 3D nanoporous Au-supported nanocrystalline tin. Adv. Mater. 2011, 23, 2443–2447.
Liu, P.; Ge, X.; Wang, R.; Ma, H.; Ding, Y. Facile fabrication of ultrathin Pt overlayers onto nanoporous metal membranes via repeated Cu UPD and in situ redox replacement reaction. Langmuir 2009, 25, 561–567.
Brankovic, S. R.; Wang, J. X.; Adžic, R. R. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces. Surf. Sci. 2001, 474, L173–L179.
Henning, S.; Herranz, J.; Gasteiger, H. A. Bulk-palladium and palladium-on-gold electrocatalysts for the oxidation of hydrogen in alkaline electrolyte. J. Electrochem. Soc. 2015, 162, F178–F189.
Yan, X. J.; Xiong, H. Y.; Bai, Q. G.; Frenzel, J.; Si, C. H.; Chen, X. T.; Eggeler, G.; Zhang, Z. H. Atomic layer-bylayer construction of Pd on nanoporous gold via underpotential deposition and displacement reaction. RSC Adv. 2015, 5, 19409–19417.
Gokcen, D.; Bae, S. -E.; Brankovic, S. R. Stoichiometry of Pt submonolayer deposition via surface-limited redox replacement reaction. J. Electrochem. Soc. 2010, 157, D582–D587.
Fujita, T.; Guan, P. F.; McKenna, K.; Lang, X. Y.; Hirata, A.; Zhang, L.; Tokunaga, T.; Arai, S.; Yamamoto, Y.; Tanaka, N. et al. Atomic origins of the high catalytic activity of nanoporous gold. Nat. Mater. 2012, 11, 775–780.
Xu, C. X.; Su, J. X.; Xu, X. H.; Liu, P. P.; Zhao, H. J.; Tian, F.; Ding, Y. Low temperature CO oxidation over unsupported nanoporous gold. J. Am. Chem. Soc. 2007, 129, 42–43.
Zhang, J. T.; Liu, P. P.; Ma, H. Y.; Ding, Y. Nanostructured porous gold for methanol electro-oxidation. J. Phys. Chem. C 2007, 111, 10382–10388.
Fujita, T.; Qian, L. -H.; Inoke, K.; Erlebacher, J.; Chen, M. -W. Three-dimensional morphology of nanoporous gold. Appl. Phys. Lett. 2008, 92, 251902.
Grden, M.; Lukaszewski, M.; Jerkiewicz, G.; Czerwinski, A. Electrochemical behaviour of palladium electrode: Oxidation, electrodissolution and ionic adsorption. Electrochim. Acta 2008, 53, 7583–7598.
Stephens, I. E. L.; Bondarenko, A. S.; Grønbjerg, U.; Rossmeisl, J.; Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ. Sci. 2012, 5, 6744–6762.
Wang, R. Y.; Liu, J. G.; Liu, P.; Bi, X. X.; Yan, X. L.; Wang, W. X.; Meng, Y. F.; Ge, X. B.; Chen, M. W.; Ding, Y. Ultra-thin layer structured anodes for highly durable low-Pt direct formic acid fuel cells. Nano Res. 2014, 7, 1569–1580.
Wang, C.; Waje, M.; Wang, X.; Tang, J. M.; Haddon, R. C.; Yan, Y. S. Proton exchange membrane fuel cells with carbon nanotube based electrodes. Nano Lett. 2004, 4, 345–348.
Bandarenka, A. S.; Varela, A. S.; Karamad, M.; Calle-Vallejo, F.; Bech, L.; Perez-Alonso, F. J.; Rossmeisl, J.; Stephens, I. E.; Chorkendorff, I. Design of an active site towards optimal electrocatalysis: Overlayers, surface alloys and near-surface alloys of Cu/Pt(111). Angew. Chem., Int. Ed. 2012, 51, 11845–11848.
Stamenkovic, V.; Mun, B. S.; Mayrhofer, K. J. J.; Ross, P. N.; Markovic, N. M.; Rossmeisl, J.; Greeley, J.; Nørskov, J. K. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew. Chem. 2006, 118, 2963–2967.
Hammer, B.; Nørskov, J. K. Theoretical surface science and catalysis—Calculations and concepts. Adv. Catal. 2000, 45, 71–129.
Mavrikakis, M.; Hammer, B.; Nørskov, J. K. Effect of strain on the reactivity of metal surfaces. Phys. Rev. Lett. 1998, 81, 2819.
Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.; Chen, J. G. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals. J. Chem. Phys. 2004, 120, 10240–10246.
Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.; Chen, J. G. Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. Phys. Rev. Lett. 2004, 93, 156801.
Strasser, P.; Koh, S.; Anniyev, T.; Greeley, J.; More, K.; Yu, C. F.; Liu, Z. C.; Kaya, S.; Nordlund, D.; Ogasawara, H. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2010, 2, 454–460.
Sun, J. Z.; Shi, J.; Xu, J. L.; Chen, X. T.; Zhang, Z. H.; Peng, Z. Q. Enhanced methanol electro-oxidation and oxygen reduction reaction performance of ultrafine nanoporous platinum–copper alloy: Experiment and density functional theory calculation. J. Power Sources 2015, 279, 334–344.
Publication history
Copyright
Acknowledgements
The authors gratefully acknowledge financial support by the National Basic Research Program of China (No. 2012CB932800), National Natural Science Foundation of China (Nos. 51371106 and 51222202), and Young Tip-top Talent Support Project (the Organization Department of the Central Committee of the CPC). The Institute of Materials of Ruhr University Bochum (Germany) is acknowledged for the support of SEM and TEM characterization. This work also made use of the resources of the Center of Electron Microscopy of Zhejiang University.
FEEDBACK 
TOP