Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

Wang, Deli; Liu, Sufen; Wang, Jie; Lin, Ruoqian; Kawasaki, Masahiro; Rus, Eric; Silberstein, Katharine E.; Lowe, Michael A.; Lin, Feng; Nordlund, Dennis; Liu, Hongfang; Muller, David A.; Xin, Huolin L.; Abruña, Héctor D.

doi:10.1038/ncomms11941

Title: Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

Journal Article · Thu Jun 23 00:00:00 EDT 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms11941· OSTI ID:1280818

Wang, Deli ^[1]; Liu, Sufen ^[1]; Wang, Jie ^[1]; Lin, Ruoqian ^[2];

^[3]; Rus, Eric ^[4]; Silberstein, Katharine E. ^[4]; Lowe, Michael A. ^[4]; Lin, Feng ^[5];

^[6]; Liu, Hongfang ^[1];

^[4];

^[2]; Abruña, Héctor D. ^[4]

Huazhong Univ. of Science and Technology
Brookhaven National Lab. (BNL), Upton, NY (United States)
JEOL USA, Inc., Peabody, MA (United States)
Cornell Univ., Ithaca, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here in this paper, we show that by incorporating trace amounts of gold in palladium-based ternary (Pd₆CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. The uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. In conclusion, this work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0012704; SC0001086

OSTI ID:: 1280818

Alternate ID(s):: OSTI ID: 1336047

Report Number(s):: BNL-112299-2016-JA; ncomms11941

Journal Information:: Nature Communications, Vol. 7; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 61 works

Citation information provided by
Web of Science

References (40)

Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli Nature Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/nchem.623	journal	April 2010
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S. Nature Chemistry, Vol. 1, Issue 7, p. 552-556 https://doi.org/10.1038/nchem.367	journal	September 2009
Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis Cui, Chunhua; Gan, Lin; Heggen, Marc Nature Materials, Vol. 12, Issue 8 https://doi.org/10.1038/nmat3668	journal	June 2013
Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Arenz, Matthias Nature Materials, Vol. 6, Issue 3, p. 241-247 https://doi.org/10.1038/nmat1840	journal	February 2007
Improved Oxygen Reduction Activity on Pt₃Ni(111) via Increased Surface Site Availability Stamenkovic, V. R.; Fowler, B.; Mun, B. S. Science, Vol. 315, Issue 5811, p. 493-497 https://doi.org/10.1126/science.1135941	journal	January 2007
Electrocatalytic oxygen reduction on single-walled carbon nanotubes supported Pt alloys nanoparticles in acidic and alkaline conditions Golikand, Ahmad Nozad; Asgari, Mehdi; Lohrasbi, Elaheh Journal of Applied Electrochemistry, Vol. 39, Issue 8 https://doi.org/10.1007/s10800-009-9812-7	journal	February 2009
Oxygen Reduction Reaction on Carbon Supported Pt and Pd in Alkaline Solutions Jiang, L.; Hsu, A.; Chu, D. Journal of The Electrochemical Society, Vol. 156, Issue 3 https://doi.org/10.1149/1.3058586	journal	January 2009
Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts Wang, Deli; Xin, Huolin L.; Hovden, Robert Nature Materials, Vol. 12, Issue 1, p. 81-87 https://doi.org/10.1038/nmat3458	journal	October 2012
Highly Uniform Platinum Icosahedra Made by Hot Injection-Assisted GRAILS Method Zhou, Wei; Wu, Jianbo; Yang, Hong Nano Letters, Vol. 13, Issue 6 https://doi.org/10.1021/nl401214d	journal	May 2013
Platinum Concave Nanocubes with High-Index Facets and Their Enhanced Activity for Oxygen Reduction Reaction Yu, Taekyung; Kim, Do Youb; Zhang, Hui Angewandte Chemie International Edition, Vol. 50, Issue 12 https://doi.org/10.1002/anie.201007859	journal	February 2011
Tuning Oxygen Reduction Reaction Activity via Controllable Dealloying A Model Study of Ordered Cu₃Pt/C Intermetallic Nanocatalysts Wang, Deli; Yu, Yingchao; Xin, Huolin L. Nano Letters, Vol. 12, Issue 10, p. 5230-5238 https://doi.org/10.1021/nl302404g	journal	September 2012
Size-Dependent Morphology of Dealloyed Bimetallic Catalysts: Linking the Nano to the Macro Scale Oezaslan, Mehtap; Heggen, Marc; Strasser, Peter Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja2088162	journal	December 2011
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces Chen, C.; Kang, Y.; Huo, Z. Science, Vol. 343, Issue 6177 https://doi.org/10.1126/science.1249061	journal	February 2014
Pt-Decorated PdCo@Pd/C Core−Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction Wang, Deli; Xin, Huolin L.; Yu, Yingchao Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja107874u	journal	December 2010
Improving Electrocatalysts for O ₂ Reduction by Fine-Tuning the Pt−Support Interaction: Pt Monolayer on the Surfaces of a Pd ₃ Fe(111) Single-Crystal Alloy Zhou, Wei-Ping; Yang, Xiaofang; Vukmirovic, Miomir B. Journal of the American Chemical Society, Vol. 131, Issue 35 https://doi.org/10.1021/ja9039746	journal	September 2009
Manageable N-doped Graphene for High Performance Oxygen Reduction Reaction Zhang, Yuewei; Ge, Jun; Wang, Lu Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02771	journal	September 2013
Facile Synthesis of Surfactant-Free Au Cluster/Graphene Hybrids for High-Performance Oxygen Reduction Reaction Yin, Huajie; Tang, Hongjie; Wang, Dan ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn302984x	journal	August 2012
Palladium Monolayer and Palladium Alloy Electrocatalysts for Oxygen Reduction ^† Shao, M. H.; Huang, T.; Liu, P. Langmuir, Vol. 22, Issue 25 https://doi.org/10.1021/la0610553	journal	December 2006
Non-precious Ir–V bimetallic nanoclusters assembled on reduced graphene nanosheets as catalysts for the oxygen reduction reaction Zhang, Ruizhong; Chen, Wei Journal of Materials Chemistry A, Vol. 1, Issue 37, p. 11457-11464 https://doi.org/10.1039/c3ta12067h	journal	January 2013
An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes Li, Yanguang; Zhou, Wu; Wang, Hailiang Nature Nanotechnology, Vol. 7, Issue 6 https://doi.org/10.1038/nnano.2012.72	journal	May 2012
Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction Liang, Yongye; Li, Yanguang; Wang, Hailiang Nature Materials, Vol. 10, Issue 10, p. 780-786 https://doi.org/10.1038/nmat3087	journal	August 2011
A class of non-precious metal composite catalysts for fuel cells Bashyam, Rajesh; Zelenay, Piotr Nature, Vol. 443, Issue 7107 https://doi.org/10.1038/nature05118	journal	September 2006
Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts Cheng, Fangyi; Shen, Jian; Peng, Bo Nature Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/nchem.931	journal	December 2010
Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction Gong, K.; Du, F.; Xia, Z. Science, Vol. 323, Issue 5915, p. 760-764 https://doi.org/10.1126/science.1168049	journal	February 2009
Pd−Fe Nanoparticles as Electrocatalysts for Oxygen Reduction Shao, Min-Hua; Sasaki, Kotaro; Adzic, Radoslav R. Journal of the American Chemical Society, Vol. 128, Issue 11 https://doi.org/10.1021/ja060167d	journal	March 2006
Oxygen reduction reaction on carbon supported Palladium–Nickel alloys in alkaline media Li, Bing; Prakash, Jai Electrochemistry Communications, Vol. 11, Issue 6 https://doi.org/10.1016/j.elecom.2009.03.037	journal	June 2009
Pt Monolayer on Porous Pd−Cu Alloys as Oxygen Reduction Electrocatalysts ^† Shao, Minhua; Shoemaker, Krista; Peles, Amra Journal of the American Chemical Society, Vol. 132, Issue 27 https://doi.org/10.1021/ja101966a	journal	July 2010
Pd−Ti and Pd−Co−Au Electrocatalysts as a Replacement for Platinum for Oxygen Reduction in Proton Exchange Membrane Fuel Cells Fernández, José L.; Raghuveer, Vadari; Manthiram, Arumugam Journal of the American Chemical Society, Vol. 127, Issue 38 https://doi.org/10.1021/ja0534710	journal	September 2005
Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction Sasaki, Kotaro; Naohara, Hideo; Choi, YongMan Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2124	journal	January 2012
Facile Synthesis of Carbon-Supported Pd–Co Core–Shell Nanoparticles as Oxygen Reduction Electrocatalysts and Their Enhanced Activity and Stability with Monolayer Pt Decoration Wang, Deli; Xin, Huolin L.; Wang, Hongsen Chemistry of Materials, Vol. 24, Issue 12, p. 2274-2281 https://doi.org/10.1021/cm203863d	journal	June 2012
Surface segregation energies in transition-metal alloys Ruban, A. V.; Skriver, H. L.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 24 https://doi.org/10.1103/PhysRevB.59.15990	journal	June 1999
Predicted Trends of Core−Shell Preferences for 132 Late Transition-Metal Binary-Alloy Nanoparticles Wang, Lin-Lin; Johnson, Duane D. Journal of the American Chemical Society, Vol. 131, Issue 39 https://doi.org/10.1021/ja903247x	journal	October 2009
Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect Yin, Y. Science, Vol. 304, Issue 5671 https://doi.org/10.1126/science.1096566	journal	April 2004
Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters Zhang, J.; Sasaki, K.; Sutter, E. Science, Vol. 315, Issue 5809, p. 220-222 https://doi.org/10.1126/science.1134569	journal	January 2007
Multimetallic Core/Interlayer/Shell Nanostructures as Advanced Electrocatalysts Kang, Yijin; Snyder, Joshua; Chi, Miaofang Nano Letters, Vol. 14, Issue 11 https://doi.org/10.1021/nl5028205	journal	October 2014
Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong Nature Communications, Vol. 5, Article No. 5185 https://doi.org/10.1038/ncomms6185	journal	November 2014
Tuning the electronic behavior of Au nanoparticles with capping molecules Zhang, P.; Sham, T. K. Applied Physics Letters, Vol. 81, Issue 4 https://doi.org/10.1063/1.1494120	journal	July 2002
Organosulfur-Functionalized Au, Pd, and Au−Pd Nanoparticles on 1D Silicon Nanowire Substrates: Preparation and XAFS Studies Zhang, Peng; Zhou, Xingtai; Tang, Yuanhong Langmuir, Vol. 21, Issue 18 https://doi.org/10.1021/la0501031	journal	August 2005
Charge redistribution and electronic behavior in a series of Au-Cu alloys Kuhn, M.; Sham, T. K. Physical Review B, Vol. 49, Issue 3 https://doi.org/10.1103/PhysRevB.49.1647	journal	January 1994
Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for Oxygen Reduction Reaction Wang, Deli; Xin, Huolin L.; Yu, Yingchao arXiv https://doi.org/10.48550/arxiv.1011.4721	text	January 2010

Cited By (10)

Hyperporous-Carbon-Supported Nonprecious Metal Electrocatalysts for the Oxygen Reduction Reaction Zhai, Tian-Long; Xuan, Cuijuan; Xu, Jincheng Chemistry - An Asian Journal, Vol. 13, Issue 18 https://doi.org/10.1002/asia.201800747	journal	August 2018
Enhanced Oxygen Reduction Activity on Carbon Supported Pd Nanoparticles Via SiO ₂ Bao, Zhikang; Zhou, Hu; Song, Xin ChemCatChem, Vol. 11, Issue 4 https://doi.org/10.1002/cctc.201801511	journal	January 2019
High‐Performance Ordered PdCuFe/C Intermetallic Catalyst for Electrochemical Oxygen Reduction in Proton Exchange Membrane Fuel Cells Ji, Xiangdong; Gao, Peng; Zhang, Libo ChemElectroChem, Vol. 6, Issue 12 https://doi.org/10.1002/celc.201900390	journal	May 2019
Solvent-mediated length tuning of ultrathin platinum–cobalt nanowires for efficient electrocatalysis Xu, Hui; Wei, Jingjing; Zhang, Min Journal of Materials Chemistry A, Vol. 6, Issue 47 https://doi.org/10.1039/c8ta08251k	journal	January 2018
Deposition and morphological evolution of nanostructured palladium during potential cycling: a liquid-cell TEM study Yang, Jie; Prabhudev, Sagar; Andrei, Carmen M. Chemical Communications, Vol. 55, Issue 62 https://doi.org/10.1039/c9cc02885d	journal	January 2019
Solid-solution alloy nanoparticles of a combination of immiscible Au and Ru with a large gap of reduction potential and their enhanced oxygen evolution reaction performance Zhang, Quan; Kusada, Kohei; Wu, Dongshuang Chemical Science, Vol. 10, Issue 19 https://doi.org/10.1039/c9sc00496c	journal	January 2019
Highly stable Pt ₃ Ni nanowires tailored with trace Au for the oxygen reduction reaction Wu, Zhifu; Su, Ya-Qiong; Hensen, Emiel J. M. Journal of Materials Chemistry A, Vol. 7, Issue 46 https://doi.org/10.1039/c9ta08682j	journal	January 2019
Recent Progress in Nitrogen-Doped Metal-Free Electrocatalysts for Oxygen Reduction Reaction Wu, Zexing; Song, Min; Wang, Jie Catalysts, Vol. 8, Issue 5 https://doi.org/10.3390/catal8050196	journal	May 2018
Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials Gunji, Takao; Matsumoto, Futoshi Inorganics, Vol. 7, Issue 3 https://doi.org/10.3390/inorganics7030036	journal	March 2019
Active Sites Derived from Heteroatom Doping in Carbon Materials for Oxygen Reduction Reaction Duo Wu, Winston; Xu, Dan Electrocatalysts for Fuel Cells and Hydrogen Evolution - Theory to Design https://doi.org/10.5772/intechopen.77048	book	December 2018

Similar Records

Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

Patent · Tue Dec 21 00:00:00 EST 2010 · OSTI ID:1280818

Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; +1 more

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

Journal Article · Tue Apr 26 00:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1280818

Zhang, Lulu; Su, Dong; Zhu, Shangqian; +4 more

Platinum-monolayer Electrocatalysts: Palladium Interlayer on IrCo Alloy Core Improves Activity in Oxygen-reduction Reaction

Journal Article · Mon Nov 15 00:00:00 EST 2010 · Journal of Electroanalytical Chemistry · OSTI ID:1280818

Gong, K; Chen, W -F; Sasaki, K; +8 more

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
Oxygen Reduction Reaction
Fuel Cell
Center for Functional Nanomaterials

Title: Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

Citation Formats

References (40)

Cited By (10)

Similar Records

Related Subjects