Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

Zhao, Yinguang; Maswadeh, Yazan; Shan, Shiyao; Cronk, Hannah; Skeete, Zakiya; Prasai, Binay; Luo, Jin; Petkov, Valeri; Zhong, Chuan-Jian

doi:10.1021/acs.jpcc.7b03901

Title: Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

Journal Article · Thu Aug 03 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b03901· OSTI ID:1437478

Zhao, Yinguang ^[1]; Maswadeh, Yazan ^[2]; Shan, Shiyao ^[1]; Cronk, Hannah ^[1]; Skeete, Zakiya ^[1]; Prasai, Binay ^[2]; Luo, Jin ^[1];

^[2];

^[1]

State Univ. of New York, Binghamton, NY (United States)
Central Michigan Univ., Mt. Pleasant, MI (United States)

Understanding the evolution of the composition and atomic structure of nanoalloy catalysts in the ethanol oxidation reaction (EOR) is essential for the design of active and robust catalysts for direct ethanol fuel cells. This article describes a study of carbon-supported platinum–ruthenium electrocatalysts (PtRu/C) with different bimetallic compositions and their activities in the EOR, an important anode reaction in direct ethanol fuel cells (DEFCs). The study focused on establishing the relationship between the catalyst’s composition, atomic structure, and catalytic activity for the EOR. Ex situ and in situ synchrotron high-energy X-ray diffraction (HE-XRD) experiments coupled with atomic pair distribution function (PDF) analysis and in situ energy-dispersive X-ray (EDX) analysis were employed to probe the composition and structural evolution of the catalysts during the in situ EOR inside a membrane electrode assembly (MEA) in the fuel cell. The results revealed an intriguing composition–structure–activity relationship for the PtRu electrocatalysts under EOR experimental conditions. In particular, the alloy with a Pt/Ru ratio of ~50:50 was found to exhibit a maximum EOR activity as a function of the bimetallic composition. This composition–activity relationship coincides with the relationship between the Pt interatomic distances and coordination numbers and the bimetallic composition. Notably, the catalytic activities of the PtRu electrocatalysts showed a significant improvement during the EOR, which can be related to atomic-level structural changes in the nanoalloys occurring during the EOR, as indicated by in situ HE-XRD/PDF/EDX data. Here, the findings shed some new light on the mechanism of the ethanol oxidation reaction over bimetallic alloy nanocatalysts, which is important for the rational design and synthesis of active nanoalloy catalysts for DEFCs.

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

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

Grant/Contract Number:: AC02-06CH11357; SC0006877; CHE 1566283

OSTI ID:: 1437478

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 32; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 14 works

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References (45)

Performance comparison of low-temperature direct alcohol fuel cells with different anode catalysts Zhou, W. J.; Zhou, B.; Li, W. Z. Journal of Power Sources, Vol. 126, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.08.009	journal	February 2004
Direct Ethanol Fuel Cell Using Hydrotalcite Clay as a Hydroxide Ion Conductive Electrolyte Tadanaga, Kiyoharu; Furukawa, Yoshihiro; Hayashi, Akitoshi Advanced Materials, Vol. 22, Issue 39 https://doi.org/10.1002/adma.201001766	journal	August 2010
“In situ” analysis by infrared reflectance spectroscopy of the adsorbed species resulting from the electrosorption of ethanol on platinum in acid medium Beden, B.; Morin, M. -C.; Hahn, F. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 229, Issue 1-2 https://doi.org/10.1016/0022-0728(87)85152-5	journal	August 1987
Electrooxidation pathways of simple alcohols at platinum in pure nonaqueous and concentrated aqueous environments as studied by real-time ftir spectroscopy Gao, Ping; Chang, Si-Chung; Zhou, Zhihua Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 272, Issue 1-2 https://doi.org/10.1016/0022-0728(89)87077-9	journal	November 1989
“In situ” infrared reflectance spectroscopic study of the early stages of ethanol adsorption at a platinum electrode in acid medium Perez, J. M.; Beden, B.; Hahn, F. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 262, Issue 1-2 https://doi.org/10.1016/0022-0728(89)80026-9	journal	April 1989
A sniftirs study of ethanol oxidation on platinum Iwasita, T.; Rasch, B.; Cattaneo, E. Electrochimica Acta, Vol. 34, Issue 8 https://doi.org/10.1016/0013-4686(89)87139-7	journal	August 1989
A dems and FTir spectroscopic investigation of adsorbed ethanol on polycrystalline platinum Iwasita, Teresa; Pastor, Elena Electrochimica Acta, Vol. 39, Issue 4 https://doi.org/10.1016/0013-4686(94)80097-9	journal	March 1994
A kinetic analysis of the electro-oxidation of ethanol at a platinum electrode in acid medium Hitmi, H.; Belgsir, E. M.; Léger, J. -M. Electrochimica Acta, Vol. 39, Issue 3 https://doi.org/10.1016/0013-4686(94)80080-4	journal	February 1994
Elementary steps in the oxidation and dissociative chemisorption of ethanol on smooth and stepped surface planes of platinum electrodes Shin, Jungwon; Tornquist, Wade J.; Korzeniewski, Carol Surface Science, Vol. 364, Issue 2 https://doi.org/10.1016/0039-6028(96)00615-2	journal	August 1996
Progress in the study of electrocatalytic reactions of organic species Iwasita, T.; Dalbeck, R.; Pastor, E. Electrochimica Acta, Vol. 39, Issue 11-12 https://doi.org/10.1016/0013-4686(94)85170-0	journal	August 1994
Early stages in the oxidation of ethanol at low index single crystal platinum electrodes Xia, X. H.; Liess, H. -D.; Iwasita, T. Journal of Electroanalytical Chemistry, Vol. 437, Issue 1-2 https://doi.org/10.1016/S0022-0728(97)00404-X	journal	November 1997
Ethanol oxidation on PtRu electrodes studied by differential electrochemical mass spectrometry Fujiwara, N.; Friedrich, K. A.; Stimming, U. Journal of Electroanalytical Chemistry, Vol. 472, Issue 2 https://doi.org/10.1016/S0022-0728(99)00282-X	journal	August 1999
Direct ethanol PEM fuel cells: The case of platinum based anodes Song, S.; Zhou, W.; Zhou, Z. International Journal of Hydrogen Energy, Vol. 30, Issue 9 https://doi.org/10.1016/j.ijhydene.2004.11.006	journal	August 2005
Bi- and tri-metallic Pt-based anode catalysts for direct ethanol fuel cells Zhou, W. J.; Li, W. Z.; Song, S. Q. Journal of Power Sources, Vol. 131, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.12.040	journal	May 2004
A comparative study on ethanol oxidation behavior at Pt and PtRh electrodeposits Sen Gupta, Sagar; Datta, Jayati Journal of Electroanalytical Chemistry, Vol. 594, Issue 1 https://doi.org/10.1016/j.jelechem.2006.05.022	journal	August 2006
Ternary Pt/Rh/SnO₂ electrocatalysts for oxidizing ethanol to CO₂ Kowal, A.; Li, M.; Shao, M. Nature Materials, Vol. 8, Issue 4, p. 325-330 https://doi.org/10.1038/nmat2359	journal	January 2009
Catalytic and Electrocatalytic Oxidation of Ethanol over Palladium-Based Nanoalloy Catalysts Yin, Jun; Shan, Shiyao; Ng, Mei Shan Langmuir, Vol. 29, Issue 29 https://doi.org/10.1021/la401839m	journal	July 2013
Electrochemical Reactivity of Ethanol on Porous Pt and PtRu: Oxidation/Reduction Reactions in 1 M HClO ₄ Schmidt, Volkmar M.; Ianniello, Remo; Pastor, Elena The Journal of Physical Chemistry, Vol. 100, Issue 45 https://doi.org/10.1021/jp9617027	journal	January 1996
Catalysis of ethanol electrooxidation by PtRu: the influence of catalyst composition Camara, G. A.; de Lima, R. B.; Iwasita, T. Electrochemistry Communications, Vol. 6, Issue 8 https://doi.org/10.1016/j.elecom.2004.06.001	journal	August 2004
Ethanol electro-oxidation on carbon-supported Pt, PtRu and Pt3Sn catalysts: A quantitative DEMS study Wang, H.; Jusys, Z.; Behm, R. J. Journal of Power Sources, Vol. 154, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.10.034	journal	March 2006
Electro-oxidation of ethanol using PtRu/C electrocatalysts prepared by alcohol-reduction process Spinacé, Estevam V.; Neto, Almir Oliveira; Vasconcelos, Teonas R. R. Journal of Power Sources, Vol. 137, Issue 1 https://doi.org/10.1016/j.jpowsour.2004.05.030	journal	October 2004
Effect of the degree of alloying of PtRu/C (1:1) catalysts on ethanol oxidation Pires, Felipe I.; Corradini, Patricia G.; Paganin, Valdecir A. Ionics, Vol. 19, Issue 7 https://doi.org/10.1007/s11581-012-0822-9	journal	November 2012
Enhancing ethanol oxidation rate at PtRu electro-catalysts using metal-oxide additives Zignani, S. C.; Baglio, V.; Sebastián, D. Electrochimica Acta, Vol. 191 https://doi.org/10.1016/j.electacta.2016.01.085	journal	February 2016
Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells Sebastián, D.; Serov, A.; Matanovic, I. Nano Energy, Vol. 34 https://doi.org/10.1016/j.nanoen.2017.02.039	journal	April 2017
Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt–Ru nanoalloy catalysts Prasai, Binay; Ren, Yang; Shan, Shiyao Nanoscale, Vol. 7, Issue 17 https://doi.org/10.1039/C5NR00800J	journal	January 2015
Rational Design of Supported PdAu Nanoparticle Catalysts from Structured Nanoparticle Precursors Dash, Priyabrat; Bond, Toby; Fowler, Candace The Journal of Physical Chemistry C, Vol. 113, Issue 29 https://doi.org/10.1021/jp9037182	journal	June 2009
Synthesis of PdNi catalysts for the oxidation of ethanol in alkaline direct ethanol fuel cells Shen, S. Y.; Zhao, T. S.; Xu, J. B. Journal of Power Sources, Vol. 195, Issue 4 https://doi.org/10.1016/j.jpowsour.2009.08.079	journal	February 2010
Structural dynamics and activity of nanocatalysts inside fuel cells by in operando atomic pair distribution studies Petkov, Valeri; Prasai, Binay; Shan, Shiyao Nanoscale, Vol. 8, Issue 20 https://doi.org/10.1039/C6NR01112H	journal	January 2016
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
Solving the nanostructure problem: exemplified on metallic alloy nanoparticles Petkov, Valeri; Prasai, Binay; Ren, Yang Nanoscale, Vol. 6, Issue 17 https://doi.org/10.1039/C4NR01633E	journal	January 2014
Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen Alayoglu, Selim; Nilekar, Anand U.; Mavrikakis, Manos Nature Materials, Vol. 7, Issue 4, p. 333-338 https://doi.org/10.1038/nmat2156	journal	March 2008
Single-step synthesis of PtRu/N-doped graphene for methanol electrocatalytic oxidation Xu, Xiao; Zhou, Yingke; Lu, Jiming Electrochimica Acta, Vol. 120 https://doi.org/10.1016/j.electacta.2013.12.062	journal	February 2014
Rapid synthesis of a PtRu nano-sponge with different surface compositions and performance evaluation for methanol electrooxidation Xiao, Meiling; Feng, Ligang; Zhu, Jianbing Nanoscale, Vol. 7, Issue 21 https://doi.org/10.1039/C5NR00639B	journal	January 2015
Facile synthesis of platinum–ruthenium nanodendrites supported on reduced graphene oxide with enhanced electrocatalytic properties Zheng, Jie-Ning; Li, Shan-Shan; Chen, Fang-Yi Journal of Power Sources, Vol. 266 https://doi.org/10.1016/j.jpowsour.2014.04.128	journal	November 2014
Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation Li, Huanqiao; Sun, Gongquan; Cao, Lei Electrochimica Acta, Vol. 52, Issue 24 https://doi.org/10.1016/j.electacta.2007.04.056	journal	August 2007
Preparation and characterization of Pt/C and PtRu/C electrocatalysts for direct ethanol fuel cells Liu, Zhaolin; Ling, Xing Yi; Su, Xiaodi Journal of Power Sources, Vol. 149 https://doi.org/10.1016/j.jpowsour.2005.02.009	journal	September 2005
The influence of PtRu atomic composition on the yields of ethanol oxidation: A study by in situ FTIR spectroscopy Camara, G. A.; de Lima, R. B.; Iwasita, T. Journal of Electroanalytical Chemistry, Vol. 585, Issue 1 https://doi.org/10.1016/j.jelechem.2005.08.004	journal	November 2005
In-Situ Monitoring of Particle Growth at PEMFC Cathode under Accelerated Cycling Conditions Redmond, Erin L.; Setzler, Brian P.; Juhas, Pavol Electrochemical and Solid-State Letters, Vol. 15, Issue 5 https://doi.org/10.1149/2.004206esl	journal	January 2012
Anode structure design for generating high stable power output for direct ethanol fuel cells Ekdharmasuit, Panuwat; Therdthianwong, Apichai; Therdthianwong, Supaporn Fuel, Vol. 113 https://doi.org/10.1016/j.fuel.2013.05.046	journal	November 2013
The role of an anode microporous layer in direct ethanol fuel cells at different ethanol concentrations Ekdharmasuit, Panuwat; Therdthianwong, Apichai; Therdthianwong, Supaporn International Journal of Hydrogen Energy, Vol. 39, Issue 4 https://doi.org/10.1016/j.ijhydene.2013.11.051	journal	January 2014
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
Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher Phys. Chem. Chem. Phys., Vol. 16, Issue 26 https://doi.org/10.1039/C4CP00737A	journal	January 2014
Electro-oxidation of small organic molecules on well-characterized PtRu alloys Gasteiger, Hubert A.; Marković, Nenad; Ross, Philip N. Electrochimica Acta, Vol. 39, Issue 11-12 https://doi.org/10.1016/0013-4686(94)85171-9	journal	August 1994
Recent advances in the development of direct alcohol fuel cells (DAFC) Lamy, Claude; Lima, Alexandre; LeRhun, Véronique Journal of Power Sources, Vol. 105, Issue 2 https://doi.org/10.1016/S0378-7753(01)00954-5	journal	March 2002
Effect of PtRu alloy composition on high-temperature methanol electro-oxidation Aricò, A. S.; Antonucci, P. L.; Modica, E. Electrochimica Acta, Vol. 47, Issue 22-23 https://doi.org/10.1016/S0013-4686(02)00342-0	journal	August 2002

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
platinum
bioethanol
catalysts
catalytic activity
fuel cells

Title: Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

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