[en] Hollow bimetallic nanostructures are perfect systems to unravel the aging mechanisms of both Pt-based alloys and highly defective nanostructures used in proton-exchange membrane fuel cell (PEMFC) cathodes, since the mobility of their surface and bulk atoms leads to detectable chemical (i.e., Ni dissolution) and physical (i.e., decrease of the density of structural defects, collapse of the nanostructure, etc.) changes. In this study, we precisely and dynamically monitored these physicochemical changes on porous hollow PtNi/C nanoparticles during an aging procedure composed of 5000 potential cycles with linear ramps between 0.6 and 1.0 or 1.1 V vs RHE by using (i) synchrotron operando wide- and small-angle X-ray scattering (WAXS and SAXS), (ii) scanning transmission electron microscopy (STEM) in combination with X-ray energy dispersive spectroscopy (X-EDS), and (iii) electrochemical measurements. The synchrotron operando WAXS and SAXS results dynamically correlated the structural changes of the hollow NPs at both the atomic (Ni depletion, lattice parameter relaxation, variation in the density of structural defects, etc.) and nanometric (restructuring of the nanoparticles/collapse of the hollow nanostructure) level. They revealed that the collapse of the hollow nanostructure was always accompanied by a significant loss of the Ni content. The 0.6-1.1 V vs RHE aging protocol resulted in a more severe depreciation of the ORR associated with a larger restructuring of the nanoparticles in comparison to the 0.6-1.0 V vs RHE aging protocol, thus providing evidence that a critical potential exists for the stability of highly defective nanoalloys.
Disciplines :
Materials science & engineering Chemical engineering
Author, co-author :
Asset, Tristan
Gommes, Cédric ; Université de Liège - ULiège > Department of Chemical Engineering > Department of Chemical Engineering
Drnec, Jakub
Bordet, P
Chattot, R
Martens, I
Nelayah, J
Job, Nathalie ; Université de Liège - ULiège > Department of Chemical Engineering > Ingéniérie électrochimique
Maillard, F.
Dubau, Laetitia
Language :
English
Title :
Disentangling the Degradation Pathways of Highly Defective PtNi/C Nanostructures - An Operando Wide and Small Angle X-ray Scattering Study
Publication date :
2019
Journal title :
ACS Catalysis
eISSN :
2155-5435
Publisher :
American Chemical Society, Washington DC, United States - Washington
Cui, C.; Gan, L.; Li, H.-H.; Yu, S.-H.; Heggen, M.; Strasser, P. Octahedral PtNi Nanoparticle Catalysts: Exceptional Oxygen Reduction Activity by Tuning the Alloy Particle Surface Composition. Nano Lett. 2012, 12, 5885-5889, 10.1021/nl3032795
Beermann, V.; Gocyla, M.; Willinger, E.; Rudi, S.; Heggen, M.; Dunin-Borkowski, R. E.; Willinger, M.-G.; Strasser, P. Rh-Doped Pt-Ni Octahedral Nanoparticles: Understanding the Correlation between Elemental Distribution, Oxygen Reduction Reaction, and Shape Stability. Nano Lett. 2016, 16, 1719-1725, 10.1021/acs.nanolett.5b04636
Chen, C.; Kang, Y.; Huo, Z.; Zhu, Z.; Huang, W.; Xin, H. L.; Snyder, J. D.; Li, D.; Herron, J. A.; Mavrikakis, M.; Chi, M.; More, K. L.; Li, Y.; Markovic, N. M.; Somorjai, G. A.; Yang, P.; Stamenkovic, V. R. Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces. Science 2014, 343, 1339-1343, 10.1126/science.1249061
Snyder, J.; McCue, I.; Livi, K.; Erlebacher, J. Structure/Processing/Properties Relationships in Nanoporous Nanoparticles as Applied to Catalysis of the Cathodic Oxygen Reduction Reaction. J. Am. Chem. Soc. 2012, 134, 8633-8645, 10.1021/ja3019498
Dubau, L.; Lopez-Haro, M.; Durst, J.; Guétaz, L.; Bayle-Guillemaud, P.; Chatenet, M.; Maillard, F. Beyond Conventional Electrocatalysts: Hollow Nanoparticles for Improved and Sustainable Oxygen Reduction Reaction Activity. J. Mater. Chem. A 2014, 2, 18497-18507, 10.1039/C4TA03975K
Dubau, L.; Asset, T.; Chattot, R.; Bonnaud, C.; Vanpeene, V.; Nelayah, J.; Maillard, F. Tuning the Performance and the Stability of Porous Hollow PtNi/C Nanostructures for the Oxygen Reduction Reaction. ACS Catal. 2015, 5, 5333-5341, 10.1021/acscatal.5b01248
Dubau, L.; Nelayah, J.; Moldovan, S.; Ersen, O.; Bordet, P.; Drnec, J.; Asset, T.; Chattot, R.; Maillard, F. Defects Do Catalysis: CO Monolayer Oxidation and Oxygen Reduction Reaction on Hollow PtNi/C Nanoparticles. ACS Catal. 2016, 6, 4673-4684, 10.1021/acscatal.6b01106
Asset, T.; Chattot, R.; Nelayah, J.; Job, N.; Dubau, L.; Maillard, F. Structure-Activity Relationships for the Oxygen Reduction Reaction in Porous Hollow PtNi/C Nanoparticles. ChemElectroChem 2016, 3, 1591-1600, 10.1002/celc.201600300
Le Bacq, O.; Pasturel, A.; Chattot, R.; Previdello, B.; Nelayah, J.; Asset, T.; Dubau, L.; Maillard, F. Effect of Atomic Vacancies on the Structure and the Electrocatalytic Activity of Pt-Rich/C Nanoparticles: A Combined Experimental and Density Functional Theory Study. ChemCatChem 2017, 9, 2324-2338, 10.1002/cctc.201601672
Asset, T.; Chattot, R.; Drnec, J.; Bordet, P.; Job, N.; Maillard, F.; Dubau, L. Elucidating the Mechanisms Driving the Aging of Porous Hollow PtNi/C Nanoparticles by Means of COads Stripping. ACS Appl. Mater. Interfaces 2017, 9, 25298-25307, 10.1021/acsami.7b05782
Chattot, R.; Asset, T.; Drnec, J.; Bordet, P.; Dubau, L.; Maillard, F. Atomic Scale Snapshots of the Growth Mechanism of Hollow PtNi/C Nanocatalysts for Oxygen Reduction Reaction. Nano Lett. 2017, 17, 2447-2453, 10.1021/acs.nanolett.7b00119
Asset, T.; Chattot, R.; Le Bacq, O.; Pasturel, A.; Drnec, J.; Bordet, P.; Nelayah, J.; Dubau, L.; Maillard, F. Porous Hollow PtNi/C Nanoparticles and Their Many Facets. ECS Trans. 2017, 80, 731-741, 10.1149/08008.0731ecst
Dubau, L.; Nelayah, J.; Asset, T.; Chattot, R.; Maillard, F. Implementing Structural Defects as a New Direction to Improve the Durability of PtNi/C Nanoparticles. ACS Catal. 2017, 7, 3072-3081, 10.1021/acscatal.7b00410
Cui, C.; Gan, L.; Li, H.; Yu, S.; Heggen, M.; Strasser, P. Octahedral PtNi Nanoparticle Catalysts: Exceptional Oxygen. Nano Lett. 2012, 12, 5885-5889, 10.1021/nl3032795
Cui, C.; 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, 10.1038/nmat3668
Dubau, L.; Maillard, F. Unveiling the Crucial Role of Temperature on the Stability of Oxygen Reduction Reaction Electrocatalysts. Electrochem. Commun. 2016, 63, 65-69, 10.1016/j.elecom.2015.12.011
Dubau, L.; Maillard, F.; Chatenet, M.; Guetaz, L.; Andre, J.; Rossinot, E. Durability of Pt[Sub 3]Co/C Cathodes in a 16 Cell PEMFC Stack: Macro/Microstructural Changes and Degradation Mechanisms. J. Electrochem. Soc. 2010, 157, B1887-B1895, 10.1149/1.3485104
Dubau, L.; Durst, J.; Maillard, F.; Guétaz, L.; Chatenet, M.; André, J.; Rossinot, E. Further Insights into the Durability of Pt3Co/C Electrocatalysts: Formation of "Hollow" Pt Nanoparticles Induced by the Kirkendall Effect. Electrochim. Acta 2011, 56, 10658-10667, 10.1016/j.electacta.2011.03.073
Dubau, L.; Maillard, F.; Chatenet, M.; André, J.; Rossinot, E. Nanoscale Compositional Changes and Modification of the Surface Reactivity of Pt3Co/C Nanoparticles during Proton-Exchange Membrane Fuel Cell Operation. Electrochim. Acta 2010, 56, 776-783, 10.1016/j.electacta.2010.09.038
Lopez-Haro, M.; Dubau, L.; Guétaz, L.; Bayle-Guillemaud, P.; Chatenet, M.; André, J.; Caqué, N.; Rossinot, E.; Maillard, F. Atomic-Scale Structure and Composition of Pt3Co/C Nanocrystallites during Real PEMFC Operation: A STEM-EELS Study. Appl. Catal., B 2014, 152-153, 300-308, 10.1016/j.apcatb.2014.01.034
Dubau, L.; Lopez-Haro, M.; Castanheira, L.; Durst, J.; Chatenet, M.; Bayle-Guillemaud, P.; Guétaz, L.; Caqué, N.; Rossinot, E.; Maillard, F. Probing the Structure, the Composition and the ORR Activity of Pt3Co/C Nanocrystallites during a 3422h PEMFC Ageing Test. Appl. Catal., B 2013, 142-143, 801-808, 10.1016/j.apcatb.2013.06.011
Maillard, F.; Dubau, L.; Durst, J.; Chatenet, M.; André, J.; Rossinot, E. Durability of Pt3Co/C Nanoparticles in a Proton-Exchange Membrane Fuel Cell: Direct Evidence of Bulk Co Segregation to the Surface. Electrochem. Commun. 2010, 12, 1161-1164, 10.1016/j.elecom.2010.06.007
Borup, R.; Meyers, J.; Pivovar, B.; Kim, Y. S.; Mukundan, R.; Garland, N.; Myers, D.; Wilson, M.; Garzon, F.; Wood, D.; Zelenay, P.; More, K.; Stroh, K.; Zawodzinski, T.; Boncella, J.; Mcgrath, J. E.; Inaba, M.; Miyatake, K.; Hori, M.; Ota, K.; Ogumi, Z.; Miyata, S.; Nishikata, A.; Siroma, Z.; Uchimoto, Y.; Yasuda, K.; Kimijima, K.; Iwashita, N. Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation. Chem. Rev. 2007, 107, 3904-3951, 10.1021/cr050182l
Shao-Horn, Y.; Sheng, W. C.; Chen, S.; Ferreira, P. J.; Holby, E. F.; Morgan, D. Instability of Supported Platinum Nanoparticles in Low-Temperature Fuel Cells. Top. Catal. 2007, 46, 285-305, 10.1007/s11244-007-9000-0
Ferreira, P. J.; la O', G. J.; Shao-Horn, Y.; Morgan, D.; Makharia, R.; Kocha, S.; Gasteiger, H. a. Instability of Pt/C Electrocatalysts in Proton Exchange Membrane Fuel Cells. J. Electrochem. Soc. 2005, 152, A2256-A2271, 10.1149/1.2050347
Meier, J. C.; Galeano, C.; Katsounaros, I.; Topalov, A. A.; Kostka, A.; Schu, F.; Mayrhofer, K. J. J. Degradation Mechanisms of Pt/C Fuel Cell Catalysts under Simulated Start-Stop Conditions. ACS Catal. 2012, 2, 832-843, 10.1021/cs300024h
Zhang, J.; Lima, F. H. B.; Shao, M. H.; Sasaki, K.; Wang, J. X.; Hanson, J.; Adzic, R. R. Platinum Monolayer on Nonnoble Metal-Noble Metal Core-Shell Nanoparticle Electrocatalysts for O2 Reduction. J. Phys. Chem. B 2005, 109, 22701-22704, 10.1021/jp055634c
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, 10.1039/c2ee03590a
Chattot, R.; Asset, T.; Bordet, P.; Drnec, J.; Dubau, L.; Maillard, F. Beyond Alloying Effects: Microstrain-Induced Enhancement of the Oxygen Reduction Reaction Kinetics on Various PtNi/C Nanostructures. ACS Catal. 2017, 7, 398-408, 10.1021/acscatal.6b02356
Calle-Vallejo, F.; Tymoczko, J.; Colic, V.; Vu, Q. H.; Pohl, M. D.; Morgenstern, K.; Loffreda, D.; Sautet, P.; Schuhmann, W.; Bandarenka, A. S. Finding Optimal Surface Sites on Heterogeneous Catalysts by Counting Nearest Neighbors. Science 2015, 350, 185-189, 10.1126/science.aab3501
Bandarenka, A. S.; Varela, A. S.; Karamad, M.; Calle-Vallejo, F.; Bech, L.; Perez-Alonso, F. J.; Rossmeisl, J.; Stephens, I. E. L.; 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, 10.1002/anie.201205314
Qin, W.; Szpunar, J. A. Origin of Lattice Strain in Nanocrystalline Materials. Philos. Mag. Lett. 2005, 85, 649-656, 10.1080/09500830500474339
Qin, W.; Nagase, T.; Umakoshi, Y.; Szpunar, J. A. Relationship between Microstrain and Lattice Parameter Change in Nanocrystalline Materials. Philos. Mag. Lett. 2008, 88, 169-179, 10.1080/09500830701840155
Li, M.; Zhao, Z.; Cheng, T.; Fortunelli, A.; Chen, C.-Y.; Yu, R.; Zhang, Q.; Gu, L.; Merinov, B. V.; Lin, Z.; Zhu, E.; Yu, T.; Jia, Q.; Guo, J.; Zhang, L.; Goddard, W. A.; Huang, Y.; Duan, X. Ultrafine Jagged Platinum Nanowires Enable Ultrahigh Mass Activity for the Oxygen Reduction Reaction. Science 2016, 354 (6318), 1414-1419, 10.1126/science.aaf9050
Li, Y.; Hart, J. L.; Taheri, M. L.; Snyder, J. D. Morphological Instability in Topologically Complex, Three-Dimensional Electrocatalytic Nanostructures. ACS Catal. 2017, 7, 7995-8005, 10.1021/acscatal.7b02398
Gusak, A. M.; Zaporozhets, T. V.; Tu, K. N.; Gösele, U. Kinetic Analysis of the Instability of Hollow Nanoparticles. Philos. Mag. 2005, 85, 4445-4464, 10.1080/14786430500311741
Castanheira, L.; Dubau, L.; Maillard, F. Accelerated Stress Tests of Pt/HSAC Electrocatalysts: An Identical-Location Transmission Electron Microscopy Study on the Influence of Intermediate Characterizations. Electrocatalysis 2014, 5, 125-135, 10.1007/s12678-013-0173-y
Drnec, J.; Ruge, M.; Reikowski, F.; Rahn, B.; Carla, F.; Felici, R.; Stettner, J.; Magnussen, O. M.; Harrington, D. A. Initial Stages of Pt(111) Electrooxidation: Dynamic and Structural Studies by Surface X-Ray Diffraction. Electrochim. Acta 2017, 224, 220-227, 10.1016/j.electacta.2016.12.028
Ruge, M.; Drnec, J.; Rahn, B.; Reikowski, F.; Harrington, D. A.; Carla, F.; Felici, R.; Stettner, J.; Magnussen, O. M. Structural Reorganization of Pt(111) Electrodes by Electrochemical Oxidation and Reduction. J. Am. Chem. Soc. 2017, 139, 4532-4539, 10.1021/jacs.7b01039
Conway, B. E. Electrochemical At Noble Metals Oxide Film Formation As a Surface-Chemical Process. Prog. Surf. Sci. 1995, 49, 331-452, 10.1016/0079-6816(95)00040-6
Jerkiewicz, G.; Vatankhah, G.; Lessard, J.; Soriaga, M. P.; Park, Y. S. Surface-Oxide Growth at Platinum Electrodes in Aqueous H2SO4 Reexamination of Its Mechanism through Combined Cyclic-Voltammetry, Electrochemical Quartz-Crystal Nanobalance, and Auger Electron Spectroscopy Measurements. Electrochim. Acta 2004, 49, 1451-1459, 10.1016/j.electacta.2003.11.008