In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

K, Niloofar Aligholizadeh; Alzate-Carvajal, Natalia; Nallayagari, Ashwini R.; Monyoncho, Evans A.; Zulevi, Barr; Serov, Alexey; Baranova, Elena A.

doi:10.1016/j.electacta.2024.145046

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

Journal Article · Wed Sep 11 00:00:00 EDT 2024 · Electrochimica Acta

DOI:https://doi.org/10.1016/j.electacta.2024.145046· OSTI ID:2440900

K, Niloofar Aligholizadeh ^[1]; Alzate-Carvajal, Natalia ^[1]; Nallayagari, Ashwini R. ^[1]; Monyoncho, Evans A. ^[1]; Zulevi, Barr ^[2]; ^[3]; Baranova, Elena A. ^[1]

Univ. of Ottawa, ON (Canada)
Pajarito Powder, LLC, Albuquerque, NM (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt. In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ~3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.

View Journal Article

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE

Grant/Contract Number:: AC05-00OR22725; AC36-08GO28308

OSTI ID:: 2440900

Alternate ID(s):: OSTI ID: 2474770

Journal Information:: Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 507; ISSN 0013-4686

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

Positive Impact of Acid-Heat Treatment on the Electrocatalytic Performance of Highly Active and Low Pt-Based Nanostructured Alloy Catalysts for Oxygen Reduction Reactions to Electrochemical Energy Conversion Devices Rahman, Md. Mijanur Energy Technology, Vol. 11, Issue 2, 2201026 https://doi.org/10.1002/ente.202201026	journal	November 2022
Green Chemistry: Advanced Electrocatalysts and System Design for Ammonia Oxidation Tian, Yunrui; Mao, Zixian; Wang, Liqun Small Structures, Vol. 4, Issue 6 https://doi.org/10.1002/sstr.202200266	journal	January 2023
Pt–Ru electrocatalysts for fuel cells: a representative review Petrii, Oleg A. Journal of Solid State Electrochemistry, Vol. 12, Issue 5 https://doi.org/10.1007/s10008-007-0500-4	journal	January 2008
Facile Preparation of Hollow Pt- and PtIr-Nanostructures with Spiky Surface for the Electro-Oxidation of Ammonia Kim, Haengsoo; Won, Dongsin; Nahm, Kee Suk Catalysis Letters, Vol. 144, Issue 3 https://doi.org/10.1007/s10562-013-1175-3	journal	December 2013
Investigation of cubic Pt alloys for ammonia oxidation reaction Chan, Yat Tung; Siddharth, Kumar; Shao, Minhua Nano Research, Vol. 13, Issue 7 https://doi.org/10.1007/s12274-020-2712-1	journal	February 2020
The Catalytic Activity of Pt:Ru Nanoparticles for Ethylene Glycol and Ethanol Electrooxidation in a Direct Alcohol Fuel Cell Silva, Júlio César M.; Ntais, Spyridon; Rajaraman, Vishwanathan Electrocatalysis, Vol. 10, 203-213 https://doi.org/10.1007/s12678-019-00515-8	journal	March 2019
DEMS-cyclic voltammetry investigation of the electrochemistry of nitrogen compounds in 0.5 M potassium hydroxide Wasmus, S.; Vasini, E. J.; Krausa, M. Electrochimica Acta, Vol. 39, Issue 1 https://doi.org/10.1016/0013-4686(94)85006-2	journal	January 1994
A method for measuring infrared reflection?Absorption spectra of molecules adsorbed on low-area surfaces at monolayer and submonolayer concentrations Golden, W. Journal of Catalysis, Vol. 71, Issue 2 https://doi.org/10.1016/0021-9517(81)90243-8	journal	October 1981
Untersuchungen Zur anodischen Oxidation von Ammoniak an Platin-Elektroden Gerischer, H.; Mauerer, A. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 25, Issue 3 https://doi.org/10.1016/S0022-0728(70)80103-6	journal	May 1970
Cyclic voltammetry as a technique for determining the surface area of RuO2 electrodes Burke, Laurence D.; Murphy, Oliver J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 96, Issue 1 https://doi.org/10.1016/S0022-0728(79)80299-5	journal	February 1979
Surface enhanced Raman spectra from silver electrodes in azide solution Kunz, R. E.; Gordon, J. G.; Philpott, M. R. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 112, Issue 2 https://doi.org/10.1016/S0022-0728(80)80422-0	journal	September 1980
Transition metal and nitrogen-doped mesoporous carbons as cathode catalysts for anion-exchange membrane fuel cells Lilloja, Jaana; Kibena-Põldsepp, Elo; Sarapuu, Ave Applied Catalysis B: Environmental, Vol. 306 https://doi.org/10.1016/j.apcatb.2022.121113	journal	June 2022
Ammonia electro-oxidation mechanism on the platinum (100) surface Wallace, Spencer W.; McCrum, Ian T.; Janik, Michael J. Catalysis Today, Vol. 371 https://doi.org/10.1016/j.cattod.2020.09.024	journal	July 2021
In-situ/operando Raman techniques for in-depth understanding on electrocatalysis Chen, Mingpeng; Liu, Di; Qiao, Lulu Chemical Engineering Journal, Vol. 461 https://doi.org/10.1016/j.cej.2023.141939	journal	April 2023
Evidence by SERS of azide anion participation in ammonia electrooxidation in alkaline medium on nanostructured Pt electrodes Vidal-Iglesias, F. J.; Solla-Gullón, J.; Pérez, J. M. Electrochemistry Communications, Vol. 8, Issue 1 https://doi.org/10.1016/j.elecom.2005.11.002	journal	January 2006
NO -induced deactivation of Pt electrocatalysis towards the ammonia oxidation reaction Kim, Haesol; Chung, Min Wook; Choi, Chang Hyuck Electrochemistry Communications, Vol. 94 https://doi.org/10.1016/j.elecom.2018.08.001	journal	September 2018
Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M=Ir, Pd, SnOx) nanoparticles Lomocso, Thegy L.; Baranova, Elena A. Electrochimica Acta, Vol. 56, Issue 24 https://doi.org/10.1016/j.electacta.2011.07.041	journal	October 2011
Ammonia electro-oxidation on alloyed PtIr nanoparticles of well-defined size Allagui, Anis; Oudah, Mohamed; Tuaev, Xenia International Journal of Hydrogen Energy, Vol. 38, Issue 5 https://doi.org/10.1016/j.ijhydene.2012.11.079	journal	February 2013
Direct ammonia fuel cell performance using PtIr/C as anode electrocatalysts Assumpção, Mônica H. M. T.; da Silva, Sirlane G.; de Souza, Rodrigo F. B. International Journal of Hydrogen Energy, Vol. 39, Issue 10 https://doi.org/10.1016/j.ijhydene.2014.01.053	journal	March 2014
Evaluation of carbon supported platinum-úruthenium nanoparticles for ammonia electro-oxidation: Combined fuel cell and electrochemical approach Silva, Julio Cesar M.; Ntais, Spyridon; Teixeira-Neto, Erico International Journal of Hydrogen Energy, Vol. 42, Issue 1, 193-201 https://doi.org/10.1016/j.ijhydene.2016.09.135	journal	November 2016
Improvement in stability of PtRu electrocatalyst by carbonization of in-situ polymerized polyaniline Zhang, Quan; Yang, Zehui; Ling, Ying International Journal of Hydrogen Energy, Vol. 43, Issue 28, 12730-12738 https://doi.org/10.1016/j.ijhydene.2018.03.160	journal	April 2018
Towards continuous ammonia electro-oxidation reaction on Pt catalysts with weakened adsorption of atomic nitrogen Wang, Yuanhui; Yang, Zehui; Yang, Jun International Journal of Hydrogen Energy, Vol. 45, Issue 41, 21816-21824 https://doi.org/10.1016/j.ijhydene.2020.05.180	journal	June 2020
Ternary PtPdCo mesoporous nanospheres with superior electrocatalytic performance towards methanol oxidation reaction Li, Weicong; Bhuvanendran, Narayanamoorthy; Liu, Huiyuan Journal of Alloys and Compounds, Vol. 933 https://doi.org/10.1016/j.jallcom.2022.167706	journal	February 2023
Pt-Sn-Co nanocubes as highly active catalysts for ethanol electro-oxidation Rizo, Ruben; Bergmann, Arno; Timoshenko, Janis Journal of Catalysis, Vol. 393, 247-258 https://doi.org/10.1016/j.jcat.2020.11.017	journal	November 2020
Creating metal-carbide interactions to boost ammonia oxidation activity for low-temperature direct ammonia fuel cells Fang, Huihuang; Liao, Chen; Ying, Yiran Journal of Catalysis, Vol. 417, 129-139 https://doi.org/10.1016/j.jcat.2022.11.028	journal	November 2022
Enhanced electrocatalytic activity of PtRu/nitrogen and sulphur co-doped crumbled graphene in acid and alkaline media Pang, Liuqing; Miao, Yuanyuan; Bhange, Siddheshwar N. Journal of Colloid and Interface Science, Vol. 590, 154-163 https://doi.org/10.1016/j.jcis.2021.01.049	journal	January 2021
Ammonia as an alternative fuel for vehicular applications: Paving the way for adsorbed ammonia and direct ammonia fuel cells Sonker, Muskan; Tiwary, Saurabh Kr; Shreyash, Nehil Journal of Cleaner Production, Vol. 376 https://doi.org/10.1016/j.jclepro.2022.133960	journal	November 2022
Ammonia electrooxidation on dendritic Pt nanostructures in alkaline solutions investigated by in-situ FTIR spectroscopy and online electrochemical mass spectroscopy Ye, Jin-Yu; Lin, Jian-Long; Zhou, Zhi-You Journal of Electroanalytical Chemistry, Vol. 819 https://doi.org/10.1016/j.jelechem.2017.12.062	journal	June 2018
Platinum nanoparticles loaded on pristine and boron oxide modified carbon nano-onions for enhanced ammonia electrooxidation in alkaline direct ammonia fuel cells Sikeyi, Ludwe L.; Ntuli, Themba D.; Mongwe, Thomas H. Journal of Electroanalytical Chemistry, Vol. 917 https://doi.org/10.1016/j.jelechem.2022.116411	journal	July 2022
On the use of ammonia electrolysis for hydrogen production Vitse, Frédéric; Cooper, Matt; Botte, Gerardine G. Journal of Power Sources, Vol. 142, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2004.09.043	journal	March 2005
Screening of electrocatalysts for direct ammonia fuel cell: Ammonia oxidation on PtMe (Me: Ir, Rh, Pd, Ru) and preferentially oriented Pt(100) nanoparticles Vidal-Iglesias, F. J.; Solla-Gullón, J.; Montiel, V. Journal of Power Sources, Vol. 171, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.015	journal	September 2007
Effect of pore diameter of wormholelike mesoporous carbon supports on the activity of Pt nanoparticles towards hydrogen electrooxidation Song, Shuqin; Yin, Shibin; Li, Zhenghui Journal of Power Sources, Vol. 195, Issue 7 https://doi.org/10.1016/j.jpowsour.2009.10.009	journal	April 2010
Ammonia oxidation kinetics on bimetallic clusters of platinum and iridium: A theoretical approach Estejab, Ali; Botte, Gerardine G. Molecular Catalysis, Vol. 445 https://doi.org/10.1016/j.mcat.2017.11.025	journal	February 2018
New Insights into Electrochemical Ammonia Oxidation on Pt(100) from First Principles Pillai, Hemanth Somarajan; Xin, Hongliang Industrial & Engineering Chemistry Research, Vol. 58, Issue 25 https://doi.org/10.1021/acs.iecr.9b01471	journal	June 2019
In Situ Electrocatalytic Infrared Spectroscopy for Dynamic Reactions Liu, Hengjie; Qi, Zeming; Song, Li The Journal of Physical Chemistry C, Vol. 125, Issue 44, 24289-24300 https://doi.org/10.1021/acs.jpcc.1c07689	journal	October 2021
Electrochemical Oxidation of Ammonia over Rare Earth Oxide Modified Platinum Catalysts Katayama, Yu; Okanishi, Takeou; Muroyama, Hiroki The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/acs.jpcc.5b01710	journal	April 2015
In Situ Attenuated Total Reflection Infrared Spectroscopy on Electrochemical Ammonia Oxidation over Pt Electrode in Alkaline Aqueous Solutions Matsui, Toshiaki; Suzuki, Shohei; Katayama, Yu Langmuir, Vol. 31, Issue 42 https://doi.org/10.1021/acs.langmuir.5b02330	journal	July 2015
Surface Structure Engineering of PtPd Nanoparticles for Boosting Ammonia Oxidation Electrocatalysis Liu, Zhenzhong; Li, Yi; Zhang, Xiangsong ACS Applied Materials & Interfaces, Vol. 14, Issue 25 https://doi.org/10.1021/acsami.2c04711	journal	June 2022
Regulating Competitive Adsorption on Pt Nanoparticles by Introducing Pb to Expedite Hydrogen Production via Ammonia Oxidation Jiang, Zexing; Yu, Tianqi; Chen, Jinli ACS Applied Nano Materials, Vol. 6, Issue 3, 1889-1897 https://doi.org/10.1021/acsanm.2c04862	journal	January 2023
Tuning Pt–Ir Interactions for NH ₃ Electrocatalysis Sacré, Nicolas; Duca, Matteo; Garbarino, Sébastien ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b02942	journal	January 2018
Ternary PtIrNi Catalysts for Efficient Electrochemical Ammonia Oxidation Li, Yi; Li, Xing; Pillai, Hemanth Somarajan ACS Catalysis, Vol. 10, Issue 7 https://doi.org/10.1021/acscatal.9b04670	journal	March 2020
Applications of the photoelastic modulator to polarization spectroscopy Hipps, K. W.; Crosby, G. A. The Journal of Physical Chemistry, Vol. 83, Issue 5 https://doi.org/10.1021/j100468a001	journal	March 1979
Application of polarization-modulated Fourier transform infrared reflection-absorption spectroscopy to the study of carbon monoxide adsorption and oxidation of a smooth platinum electrode Golden, William G.; Kunimatsu, Keiji; Seki, Hajime The Journal of Physical Chemistry, Vol. 88, Issue 7 https://doi.org/10.1021/j150651a004	journal	March 1984
Surface-Enhanced Infrared Absorption Spectroscopic Studies of Adsorbed Nitrate, Nitric Oxide, and Related Compounds. 3. Formation and Reduction of Adsorbed Nitrite at a Platinum Electrode Rima, Farhana Rahman; Nakata, Kou; Shimazu, Katsuaki The Journal of Physical Chemistry C, Vol. 114, Issue 13 https://doi.org/10.1021/jp911027q	journal	March 2010
Surface-Enhanced Infrared Absorption Spectroscopic Studies of Adsorbed Nitrate, Nitric Oxide, and Related Compounds 2: Nitrate Ion Adsorption at a Platinum Electrode Nakata, Kou; Kayama, Yota; Shimazu, Katsuaki Langmuir, Vol. 24, Issue 8 https://doi.org/10.1021/la703476m	journal	April 2008
Ammonia–Oxygen Fuel Cell Cairns, E. J.; Simons, E. L.; Tevebaugh, A. D. Nature, Vol. 217, Issue 5130 https://doi.org/10.1038/217780a0	journal	February 1968
Recent advances in electrocatalysts for electro-oxidation of ammonia Zhong, C.; Hu, W. B.; Cheng, Y. F. J. Mater. Chem. A, Vol. 1, Issue 10 https://doi.org/10.1039/C2TA00607C	journal	January 2013
The utility of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) in surface and in situ studies: new data processing and presentation approach Monyoncho, Evans A.; Zamlynny, Vlad; Woo, Tom K. Analyst, Vol. 143, Issue 11, 2563-2573 https://doi.org/10.1039/C8AN00572A	journal	April 2018
Recent progress in ammonia fuel cells and their potential applications Jeerh, Georgina; Zhang, Mengfei; Tao, Shanwen Journal of Materials Chemistry A, Vol. 9, Issue 2 https://doi.org/10.1039/D0TA08810B	journal	January 2021
PtRu nanocubes as bifunctional electrocatalysts for ammonia electrolysis Xue, Qi; Zhao, Yue; Zhu, Jingyi Journal of Materials Chemistry A, Vol. 9, Issue 13, 8444-8451 https://doi.org/10.1039/D1TA00426C	journal	March 2021
Unveiling the particle size effect and surface reactivity of Pt/C nanoparticles for ammonia electrooxidation using in situ infrared spectroscopy Aligholizadeh K., Niloofar; Reddy N., Ashwini; Monyoncho, Evans A. Industrial Chemistry & Materials, Vol. 1, Issue 4, 542-552 https://doi.org/10.1039/D3IM00063J	journal	September 2023
Shape-enhanced ammonia electro-oxidation property of a cubic platinum nanocrystal catalyst prepared by surfactant-free synthesis Zhang, Changlin; Hwang, Sang Youp; Peng, Zhenmeng Journal of Materials Chemistry A, Vol. 1, Issue 45 https://doi.org/10.1039/c3ta13641h	journal	January 2013
Temperature-Dependent Kinetics and Reaction Mechanism of Ammonia Oxidation on Pt, Ir, and PtIr Alloy Catalysts Song, Liang; Liang, Zhixiu; Ma, Zhong Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0181815jes	journal	January 2018
Review—Ammonia Oxidation Electrocatalysis for Hydrogen Generation and Fuel Cells Adli, Nadia Mohd; Zhang, Hao; Mukherjee, Shreya Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0191815jes	journal	January 2018
Impregnated Electroreduced Pt on Ru/C as an Anode Catalyst for Direct Methanol Fuel Cells Muthukumar, Volga; Chetty, Raghuram Journal of The Electrochemical Society, Vol. 166, Issue 15 https://doi.org/10.1149/2.0221915jes	journal	January 2019
Polarization Modulation FT-IR Spectroscopy of Surfaces and Ultra-Thin Films: Experimental Procedure and Quantitative Analysis Buffeteau, T.; Desbat, B.; Turlet, J. M. Applied Spectroscopy, Vol. 45, Issue 3 https://doi.org/10.1366/0003702914337308	journal	March 1991
A Facile and Surfactant-Free Electrochemical Synthesis of PtIr Nanocubes towards Ammonia Electro-Oxidation Tang, Yusu; Geng, Dinglei; Cheng, Zhihao Metals, Vol. 13, Issue 5, 901 https://doi.org/10.3390/met13050901	journal	May 2023
Gum Kondagogu/Reduced Graphene Oxide Framed Platinum Nanoparticles and Their Catalytic Role Venkateshaiah, Abhilash; Silvestri, Daniele; Ramakrishnan, Rohith K. Molecules, Vol. 24, Issue 20, p. 3643 https://doi.org/10.3390/molecules24203643	journal	October 2019

Similar Records

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study

Journal Article · Thu Feb 19 19:00:00 EST 2015 · Journal of Physical Chemistry. C · OSTI ID:1405312

CO electrooxidation on well-characterized Pt-Ru alloys

Journal Article · Wed Jan 12 23:00:00 EST 1994 · Journal of Physical Chemistry; (United States) · OSTI ID:5182735

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia electrooxidation
bimetallic nanoparticles (Pt-Ir
Pt-Ru)
engineered catalyst supports (ECSs)
polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS)

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

Citation Formats

References (58)

Similar Records

Related Subjects