Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin]

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit; Park, Hyun-Uk; Kwon, Young-Uk; Skumryev, Vassil

doi:10.1039/c7nr05768g

Title: Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin]

Journal Article · Tue Sep 12 00:00:00 EDT 2017 · Nanoscale

DOI:https://doi.org/10.1039/c7nr05768g· OSTI ID:1421971

^[1]; Prasai, Binay ^[1]; Shastri, Sarvjit ^[2]; Park, Hyun-Uk ^[3];

^[3]; Skumryev, Vassil ^[4]

Central Michigan University, Mt. Pleasant, MI (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Sungkyunkwan University, Suwon (Korea). Department of Chemistry
Institucio Catalana de Recerca i Estudis Avançats (ICREA), Barcelona (Spain); Universitat Autònoma de Barcelona (Spain). Department of Physics

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction, respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.

Cite

Export

Save

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

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

DOE Contract Number:: AC02-06CH11357; SC0006877

OSTI ID:: 1421971

Journal Information:: Nanoscale, Vol. 9, Issue 40; ISSN 2040-3364

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

References (44)

Large enhancements of magnetic anisotropy in oxide-free iron nanoparticles Monson, Todd C.; Venturini, Eugene L.; Petkov, Valeri Journal of Magnetism and Magnetic Materials, Vol. 331 https://doi.org/10.1016/j.jmmm.2012.11.026	journal	April 2013
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Magnetism from the Atom to the Bulk in Iron, Cobalt, and Nickel Clusters Billas, I. M. L.; Chatelain, A.; de Heer, W. A. Science, Vol. 265, Issue 5179 https://doi.org/10.1126/science.265.5179.1682	journal	September 1994
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
Coherent X-ray diffraction imaging of strain at the nanoscale Robinson, Ian; Harder, Ross Nature Materials, Vol. 8, Issue 4 https://doi.org/10.1038/nmat2400	journal	April 2009
Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure Stamenkovic, Vojislav; Mun, Bongjin Simon; Mayrhofer, Karl J. J. Angewandte Chemie International Edition, Vol. 45, Issue 18 https://doi.org/10.1002/anie.200504386	journal	April 2006
Magnetic moments of iron clusters: a simple theoretical model Aguilera-Granja, F.; Montejano-Carrizales, J. M.; Morán-López, J. L. Physics Letters A, Vol. 242, Issue 4-5 https://doi.org/10.1016/S0375-9601(98)00184-4	journal	June 1998
The Application of the Logistic Function to Experimental Data. Reed, L. J.; Berkson, Joseph The Journal of Physical Chemistry, Vol. 33, Issue 5 https://doi.org/10.1021/j150299a014	journal	May 1929
Orbital angular momentum microlaser Miao, Pei; Zhang, Zhifeng; Sun, Jingbo Science, Vol. 353, Issue 6298 https://doi.org/10.1126/science.aaf8533	journal	July 2016
Air-stable superparamagnetic metal nanoparticles entrapped in graphene oxide matrix Tuček, Jiří; Sofer, Zdeněk; Bouša, Daniel Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12879	journal	September 2016
Clarifying stability, probability and population in nanoparticle ensembles Barnard, Amanda S. Nanoscale, Vol. 6, Issue 17 https://doi.org/10.1039/C4NR01504E	journal	January 2014
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
Effect of particle size and surface structure on adsorption of O and OH on platinum nanoparticles: A first-principles study Han, B. C.; Miranda, C. R.; Ceder, G. Physical Review B, Vol. 77, Issue 7 https://doi.org/10.1103/PhysRevB.77.075410	journal	February 2008
Phonon density of states of self-assembled isolated Fe-rich Fe-Pt alloy nanoclusters Roldan Cuenya, B.; Croy, Jason R.; Ono, L. K. Physical Review B, Vol. 80, Issue 12 https://doi.org/10.1103/PhysRevB.80.125412	journal	September 2009
Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors Calle-Vallejo, F.; Tymoczko, J.; Colic, V. Science, Vol. 350, Issue 6257 https://doi.org/10.1126/science.aab3501	journal	October 2015
Distribution of magnetization of a cold ferromagnetic cluster beam Xu, Xiaoshan; Yin, Shuangye; Moro, Ramiro Physical Review B, Vol. 78, Issue 5 https://doi.org/10.1103/PhysRevB.78.054430	journal	August 2008
Electronic and Atomic Structure, and Magnetism of Transition-Metal Clusters Alonso, J. A. Chemical Reviews, Vol. 100, Issue 2 https://doi.org/10.1021/cr980391o	journal	February 2000
Oxygen Reduction on Well-Defined Core−Shell Nanocatalysts: Particle Size, Facet, and Pt Shell Thickness Effects Wang, Jia X.; Inada, Hiromi; Wu, Lijun Journal of the American Chemical Society, Vol. 131, Issue 47 https://doi.org/10.1021/ja9067645	journal	December 2009
Metallic Iron Nanoparticles for MRI Contrast Enhancement and Local Hyperthermia Hadjipanayis, Costas G.; Bonder, Michael J.; Balakrishnan, Srinivasan Small, Vol. 4, Issue 11 https://doi.org/10.1002/smll.200800261	journal	November 2008
A simple d-band model for the magnetic property of ferromagnetic transition-metal clusters Zhao, Jijun; Chen, Xiaoshuang; Sun, Qiang Physics Letters A, Vol. 205, Issue 4 https://doi.org/10.1016/0375-9601(95)00532-8	journal	September 1995
X-ray spectroscopy studies on the surface structural characteristics and electronic properties of platinum nanoparticles Bayindir, Z.; Duchesne, P. N.; Cook, S. C. The Journal of Chemical Physics, Vol. 131, Issue 24 https://doi.org/10.1063/1.3276917	journal	December 2009
Deciphering chemical order/disorder and material properties at the single-atom level Yang, Yongsoo; Chen, Chien-Chun; Scott, M. C. Nature, Vol. 542, Issue 7639 https://doi.org/10.1038/nature21042	journal	February 2017
Crystallography Open Database – an open-access collection of crystal structures Gražulis, Saulius; Chateigner, Daniel; Downs, Robert T. Journal of Applied Crystallography, Vol. 42, Issue 4 https://doi.org/10.1107/S0021889809016690	journal	May 2009
Theoretical study of the structures and stabilities of iron clusters Besley, Nicholas A.; Johnston, Roy L.; Stace, Anthony J. Journal of Molecular Structure: THEOCHEM, Vol. 341, Issue 1-3 https://doi.org/10.1016/0166-1280(95)04207-M	journal	October 1995
Applications of magnetic nanoparticles in biomedicine Pankhurst, Q. A.; Connolly, J.; Jones, S. K. Journal of Physics D: Applied Physics, Vol. 36, Issue 13 https://doi.org/10.1088/0022-3727/36/13/201	journal	June 2003
Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts Ma, Xianfeng; Xin, Hongliang Physical Review Letters, Vol. 118, Issue 3 https://doi.org/10.1103/PhysRevLett.118.036101	journal	January 2017
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
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Magnetic Properties of Nanostructured Materials Leslie-Pelecky, Diandra L.; Rieke, Reuben D. Chemistry of Materials, Vol. 8, Issue 8 https://doi.org/10.1021/cm960077f	journal	January 1996
Magnetic moments of iron clusters with 25 to 700 atoms and their dependence on temperature Billas, Isabelle M. L.; Becker, J. A.; Châtelain, A. Physical Review Letters, Vol. 71, Issue 24 https://doi.org/10.1103/PhysRevLett.71.4067	journal	December 1993
Size and Shape of Protein Molecules at the Nanometer Level Determined by Sedimentation, Gel Filtration, and Electron Microscopy Erickson, Harold P. Biological Procedures Online, Vol. 11, Issue 1 https://doi.org/10.1007/s12575-009-9008-x	journal	May 2009
Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles Ferrando, Riccardo; Jellinek, Julius; Johnston, Roy L. Chemical Reviews, Vol. 108, Issue 3, p. 845-910 https://doi.org/10.1021/cr040090g	journal	March 2008
Magnetic structure of free iron clusters compared to iron crystal surfaces Šipr, O.; Košuth, M.; Ebert, H. Physical Review B, Vol. 70, Issue 17 https://doi.org/10.1103/PhysRevB.70.174423	journal	November 2004
Size effects in the magnetic anisotropy of embedded cobalt nanoparticles: from shape to surface Oyarzún, Simón; Tamion, Alexandre; Tournus, Florent Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14749	journal	October 2015
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Thickness-dependent electronic structure and interfacial behaviors of iron on faceted MgO(111) films Xue, Mingshan; Guo, Qinlin Chemical Physics Letters, Vol. 551 https://doi.org/10.1016/j.cplett.2012.09.034	journal	November 2012
Simple theory for the electronic and atomic structure of small clusters Tománek, D.; Mukherjee, S.; Bennemann, K. H. Physical Review B, Vol. 28, Issue 2 https://doi.org/10.1103/PhysRevB.28.665	journal	July 1983
Structure and phonon density of states of supported size-selected F57eAu nanoclusters: A nuclear resonant inelastic x-ray scattering study Roldan Cuenya, B.; Ono, L. K.; Croy, J. R. Applied Physics Letters, Vol. 95, Issue 14 https://doi.org/10.1063/1.3236539	journal	October 2009
Periodicity and Atomic Ordering in Nanosized Particles of Crystals Petkov, Valeri; Bedford, Nick; Knecht, Marc R. The Journal of Physical Chemistry C, Vol. 112, Issue 24 https://doi.org/10.1021/jp801195c	journal	May 2008
Three-dimensional atomic-scale structure of size-selected gold nanoclusters Li, Z. Y.; Young, N. P.; Di Vece, M. Nature, Vol. 451, Issue 7174 https://doi.org/10.1038/nature06470	journal	December 2007
Rational syntheses of core-shell Fex@Pt nanoparticles for the study of electrocatalytic oxygen reduction reaction Jang, Ji-Hoon; Lee, Eunjik; Park, Jinwoo Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02872	journal	October 2013
Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co Toda, Takako; Igarashi, Hiroshi; Uchida, Hiroyuki Journal of The Electrochemical Society, Vol. 146, Issue 10, p. 3750-3756 https://doi.org/10.1149/1.1392544	journal	January 1999
Isostructural polymorphs: qualitative insights from energy frameworks Jha, Kunal Kumar; Dutta, Sanjay; Kumar, Vijay CrystEngComm, Vol. 18, Issue 43 https://doi.org/10.1039/C6CE01501H	journal	January 2016
Accuracy of pair distribution function analysis applied to crystalline and non-crystalline materials Toby, B. H.; Egami, T. Acta Crystallographica Section A Foundations of Crystallography, Vol. 48, Issue 3 https://doi.org/10.1107/S0108767391011327	journal	May 1992

Similar Records

Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights

Journal Article · Wed Jun 17 00:00:00 EDT 2020 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1421971

Yang, An-Chih; Choksi, Tej; Streibel, Verena; +11 more

Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt₁ atoms

Journal Article · Fri Aug 23 00:00:00 EDT 2019 · Nature Communications · OSTI ID:1421971

Wang, Hui; Liu, Jin -Xun; Allard, Lawrence F.; +11 more

Correlating 3D Surface Atomic Structure and Catalytic Activities of Pt Nanocrystals

Journal Article · Fri Jan 08 00:00:00 EST 2021 · Nano Letters · OSTI ID:1421971

Kim, Sungin; Kwag, Jimin; Machello, Chiara; +12 more

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY

Title: Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin]

Citation Formats

References (44)

Similar Records

Related Subjects