Understanding Composition-Dependent Synergy of PtPd Alloy Nanoparticles in Electrocatalytic Oxygen Reduction Reaction

Wu, Jinfang; Shan, Shiyao; Cronk, Hannah; Chang, Fangfang; Kareem, Haval; Zhao, Yinguang; Luo, Jin; Petkov, Valeri; Zhong, Chuan-Jian

doi:10.1021/acs.jpcc.7b03043

Understanding Composition-Dependent Synergy of PtPd Alloy Nanoparticles in Electrocatalytic Oxygen Reduction Reaction

Journal Article · Thu Jun 22 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b03043· OSTI ID:1437488

Wu, Jinfang ^[1]; Shan, Shiyao ^[2]; Cronk, Hannah ^[2]; Chang, Fangfang ^[2]; Kareem, Haval ^[2]; Zhao, Yinguang ^[2]; Luo, Jin ^[2]; ^[3]; ^[2]

Inn Mongolia Univ., Hohhot (China); State Univ. of New York at Binghamton, NY (United States)
State Univ. of New York at Binghamton, NY (United States)
Central Michigan Univ., Mount Pleasant, MI (United States)

Gaining an insight into the relationship between the bimetallic composition and catalytic activity is essential for the design of nanoalloy catalysts for oxygen reduction reaction. This report describes findings of a study of the composition–activity relationship for PtPd nanoalloy catalysts in oxygen reduction reaction (ORR). Pt_nPd_100-n nanoalloys with different bimetallic compositions are synthesized by wet chemical method. While the size of the Pt₅₀Pd₅₀ nanoparticles is the largest among the nanoparticles with different compositions, the characterization of the nanoalloys using synchrotron high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis reveals that the nanoalloy with an atomic Pt:Pd ratio of 50:50 exhibits an intermediate lattice parameter. Electrochemical characterization of the nanoalloys shows a minimum ORR activity at Pt:Pd ratio close to 50:50, whereas a maximum activity is achieved at Pt:Pd ratio close to 10:90. The composition–activity correlation is assessed by theoretical modeling based on DFT calculation of nanoalloy clusters. In addition to showing an electron transfer from PtPd alloy to oxygen upon its adsorption on the nanoalloy, a relatively large energy difference between HOMO for nanoalloy and LUMO for oxygen is revealed for the nanoalloy with an atomic Pt:Pd ratio of 50:50. By analysis of the adsorption of OH species on PtPd (111) surfaces of different compositions, the strongest adsorption energy is observed for Pt₉₆Pd₁₀₅ (Pt:Pd ≈ 50:50) cluster, which is believed to be likely responsible for the reduced activity. Interestingly, the adsorption energy on Pt24Pd177 (Pt:Pd ≈ 10:90) cluster falls in between Pt₉₆Pd₁₀₅ and Pd₂₀₁ clusters, which is believed to be linked to the observation of the highest catalytic activity for the nanoalloy with an atomic Pt:Pd ratio of 10:90. Furthermore, these findings have implications for the design of composition-tunable nanoalloy catalysts for ORR.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; SC0006877

OSTI ID:: 1437488

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 26 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (40)

A Highly Durable Platinum Nanocatalyst for Proton Exchange Membrane Fuel Cells: Multiarmed Starlike Nanowire Single Crystal Sun, Shuhui; Zhang, Gaixia; Geng, Dongsheng Angewandte Chemie, Vol. 123, Issue 2 https://doi.org/10.1002/ange.201004631	journal	November 2010
Enhancement of oxygen reduction activity by sequential impregnation of Pt and Pd on carbon support Jung, Dohwa; Beak, Sangchul; Nahm, Kee Suk Korean Journal of Chemical Engineering, Vol. 27, Issue 6 https://doi.org/10.1007/s11814-010-0292-6	journal	September 2010
Theoretical investigations of the catalytic role of water in propene epoxidation on gold nanoclusters: A hydroperoxyl-mediated pathway Chang, Chun-Ran; Wang, Yang-Gang; Li, Jun Nano Research, Vol. 4, Issue 1 https://doi.org/10.1007/s12274-010-0083-8	journal	December 2010
Underneath the Bragg Peaks Egami, T.; Billinge, S. J. L. Materials Today, Vol. 6, Issue 6 https://doi.org/10.1016/S1369-7021(03)00635-7	journal	June 2003
Nanostructure by high-energy X-ray diffraction Petkov, Valeri Materials Today, Vol. 11, Issue 11 https://doi.org/10.1016/S1369-7021(08)70236-0	journal	November 2008
DFT studies on Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh) clusters for CO oxidation Lian, Xin; Guo, Wenlong; Liu, Feila Computational Materials Science, Vol. 96 https://doi.org/10.1016/j.commatsci.2014.09.025	journal	January 2015
Insights into surface–adsorbate interactions in corrosion inhibition processes at the molecular level Özcan, Muzaffer; Toffoli, Daniele; Üstünel, Hande Corrosion Science, Vol. 80 https://doi.org/10.1016/j.corsci.2013.11.062	journal	March 2014
PdPt alloy nanocubes as electrocatalysts for oxygen reduction reaction in acid media Jukk, Kristel; Kongi, Nadezda; Tammeveski, Kaido Electrochemistry Communications, Vol. 56 https://doi.org/10.1016/j.elecom.2015.04.001	journal	July 2015
Study of O2 and OH adsorption energies on Pd–Cu alloys surface with a quantum chemistry approach Fouda-Onana, F.; Savadogo, O. Electrochimica Acta, Vol. 54, Issue 6 https://doi.org/10.1016/j.electacta.2008.10.026	journal	February 2009
Electrochemical preparation and characterization of PdPt nanocages with improved electrocatalytic activity toward oxygen reduction reaction Zhang, Geng; Shao, Zhi-Gang; Lu, Wangting Electrochimica Acta, Vol. 103 https://doi.org/10.1016/j.electacta.2013.04.045	journal	July 2013
Nanoporous PtPd Alloy Electrocatalysts with High Activity and Stability toward Oxygen Reduction Reaction Duan, Huimei; Xu, Caixia Electrochimica Acta, Vol. 152 https://doi.org/10.1016/j.electacta.2014.11.160	journal	January 2015
Optimization of Pt-Pd alloy catalyst and supporting materials for oxygen reduction in air-cathode Microbial Fuel Cells Quan, Xiangchun; Mei, Ying; Xu, Hengduo Electrochimica Acta, Vol. 165 https://doi.org/10.1016/j.electacta.2015.02.235	journal	May 2015
A simple one-pot strategy to platinum–palladium@palladium core–shell nanostructures with high electrocatalytic activity Lv, Jing-Jing; Zheng, Jie-Ning; Wang, Ying-Ying Journal of Power Sources, Vol. 265 https://doi.org/10.1016/j.jpowsour.2014.04.108	journal	November 2014
Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2 Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F. Journal of Power Sources, Vol. 276 https://doi.org/10.1016/j.jpowsour.2014.11.086	journal	February 2015
Iron-embedded boron nitride nanosheet as a promising electrocatalyst for the oxygen reduction reaction (ORR): A density functional theory (DFT) study Feng, Li-yan; Liu, Yue-jie; Zhao, Jing-xiang Journal of Power Sources, Vol. 287 https://doi.org/10.1016/j.jpowsour.2015.04.094	journal	August 2015
A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites Wang, Qin; Li, Yingjun; Liu, Baocang Journal of Power Sources, Vol. 297 https://doi.org/10.1016/j.jpowsour.2015.07.099	journal	November 2015
PtPd porous nanorods with enhanced electrocatalytic activity and durability for oxygen reduction reaction Lu, Yizhong; Jiang, Yuanyuan; Chen, Wei Nano Energy, Vol. 2, Issue 5 https://doi.org/10.1016/j.nanoen.2013.02.006	journal	September 2013
Effect of Pt: Pd atomic ratio in Pt–Pd/C electrocatalyst-coated membrane on the electrocatalytic activity of ORR in PEM fuel cells Thanasilp, Sarawalee; Hunsom, Mali Renewable Energy, Vol. 36, Issue 6 https://doi.org/10.1016/j.renene.2010.10.024	journal	June 2011
The adsorption and dissociation of H2S on Cu(100) surface: A DTF study Chen, Shenghui; Sun, Shuangqing; Lian, Bingjie Surface Science, Vol. 620 https://doi.org/10.1016/j.susc.2013.10.014	journal	February 2014
PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy Wu, Jinfang; Shan, Shiyao; Luo, Jin ACS Applied Materials & Interfaces, Vol. 7, Issue 46 https://doi.org/10.1021/acsami.5b08478	journal	November 2015
Composition–Structure–Activity Relationships for Palladium-Alloyed Nanocatalysts in Oxygen Reduction Reaction: An Ex-Situ/In-Situ High Energy X-ray Diffraction Study Wu, Jinfang; Shan, Shiyao; Petkov, Valeri ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01608	journal	August 2015
Highly Stable and Active Pt−Cu Oxygen Reduction Electrocatalysts Based on Mesoporous Graphitic Carbon Supports Gupta, Gaurav; Slanac, Daniel A.; Kumar, Pavan Chemistry of Materials, Vol. 21, Issue 19 https://doi.org/10.1021/cm901203n	journal	October 2009
Oxophilicity and Structural Integrity in Maneuvering Surface Oxygenated Species on Nanoalloys for CO Oxidation Shan, Shiyao; Petkov, Valeri; Yang, Lefu ACS Catalysis, Vol. 3, Issue 12 https://doi.org/10.1021/cs400700r	journal	November 2013
DFT Prediction of Oxygen Reduction Reaction on Palladium–Copper Alloy Surfaces Sha, Yao; Yu, Ted H.; Merinov, Boris V. ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs4009623	journal	March 2014
Enhanced Electrocatalytic Performance of Processed, Ultrathin, Supported Pd–Pt Core–Shell Nanowire Catalysts for the Oxygen Reduction Reaction Koenigsmann, Christopher; Santulli, Alexander C.; Gong, Kuanping Journal of the American Chemical Society, Vol. 133, Issue 25 https://doi.org/10.1021/ja111130t	journal	June 2011
Structure and Activity of Carbon-Supported Pt−Co Electrocatalysts for Oxygen Reduction Salgado, José R. C.; Antolini, Ermete; Gonzalez, Ernesto R. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp0486649	journal	November 2004
Design and Preparation of Highly Active Pt−Pd/C Catalyst for the Oxygen Reduction Reaction Li, Huanqiao; Sun, Gongquan; Li, Na The Journal of Physical Chemistry C, Vol. 111, Issue 15 https://doi.org/10.1021/jp067755y	journal	April 2007
Carbon-Supported Pd−Pt Nanoalloy with Low Pt Content and Superior Catalysis for Formic Acid Electro-oxidation Zhang, Han-Xuan; Wang, Chao; Wang, Jin-Yi The Journal of Physical Chemistry C, Vol. 114, Issue 14 https://doi.org/10.1021/jp100835b	journal	March 2010
Study of Supported PtCu and PdAu Bimetallic Nanoparticles Using In-Situ X-ray Tools Oxford, Sean M.; Lee, Peter L.; Chupas, Peter J. The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp103675n	journal	June 2010
Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt ₃ M (M = Pt, Ru, Sn, Re, Rh, and Pd) Xu, Zhen-Feng; Wang, Yixuan The Journal of Physical Chemistry C, Vol. 115, Issue 42 https://doi.org/10.1021/jp206051k	journal	September 2011
Anchoring Effect of Exfoliated-Montmorillonite-Supported Pd Catalyst for the Oxygen Reduction Reaction Xia, Meirong; Ding, Wei; Xiong, Kun The Journal of Physical Chemistry C, Vol. 117, Issue 20 https://doi.org/10.1021/jp402367g	journal	May 2013
Catalytic Activity of Pd/Cu Random Alloy Nanoparticles for Oxygen Reduction Tang, Wenjie; Zhang, Liang; Henkelman, Graeme The Journal of Physical Chemistry Letters, Vol. 2, Issue 11 https://doi.org/10.1021/jz2004717	journal	May 2011
Experimental and theoretical studies of triisopropanolamine as an inhibitor for aluminum alloy in 3% NaCl solution Ren, Xiaolei; Xu, Shenying; Chen, Siyi RSC Advances, Vol. 5, Issue 123 https://doi.org/10.1039/C5RA21050J	journal	January 2015
Ultralong Pt-on-Pd bimetallic nanowires with nanoporous surface: nanodendritic structure for enhanced electrocatalytic activity Guo, Shaojun; Dong, Shaojun; Wang, Erkang Chemical Communications, Vol. 46, Issue 11 https://doi.org/10.1039/b922148d	journal	January 2010
Tailoring of Pd–Pt bimetallic clusters with high stability for oxygen reduction reaction Cheng, Daojian; Wang, Wenchuan Nanoscale, Vol. 4, Issue 7 https://doi.org/10.1039/c2nr12097f	journal	January 2012
Stability issues in Pd-based catalysts: the role of surface Pt in improving the stability and oxygen reduction reaction (ORR) activity Singh, R. K.; Rahul, R.; Neergat, M. Physical Chemistry Chemical Physics, Vol. 15, Issue 31 https://doi.org/10.1039/c3cp50697e	journal	January 2013
PdCu alloy nanoparticle-decorated copper nanotubes as enhanced electrocatalysts: DFT prediction validated by experiment Wu, Dengfeng; Xu, Haoxiang; Cao, Dapeng Nanotechnology, Vol. 27, Issue 49 https://doi.org/10.1088/0957-4484/27/49/495403	journal	November 2016
DFT study of Pt7-x Rux (x = 0, 1, 2, 3) clusters and their interactions with CO Lian, Xin; Tian, Wei Quan; Guo, Wenlong The European Physical Journal D, Vol. 68, Issue 3 https://doi.org/10.1140/epjd/e2014-40609-6	journal	March 2014
Effect of Atomic Ordering on the Catalytic Activity of Carbon Supported PtM (M=Fe, Co, Ni, and Cu) Alloys for Oxygen Reduction in PEMFCs Xiong, L.; Manthiram, A. Journal of The Electrochemical Society, Vol. 152, Issue 4 https://doi.org/10.1149/1.1862256	journal	January 2005
Simple Preparation of Pd Core Nanoparticles for Pd Core/Pt Shell Catalyst and Evaluation of Activity and Durability for Oxygen Reduction Reaction Inoue, Hiroshi; Sakai, Ryotaro; Kuwahara, Taiki Catalysts, Vol. 5, Issue 3 https://doi.org/10.3390/catal5031375	journal	July 2015

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Application of differential resonant high-energy X-ray diffraction to three-dimensional structure studies of nanosized materials: A case study of Pt–Pd nanoalloy catalysts Petkov, Valeri; Shastri, Sarvjit; Kim, Jong-Woo Acta Crystallographica Section A Foundations and Advances, Vol. 74, Issue 5 https://doi.org/10.1107/s2053273318009282	journal	September 2018

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