Revealing the Phase Separation Behavior of Thermodynamically Immiscible Elements in a Nanoparticle

Chen, Peng-Cheng; Gao, Mengyu; Yu, Sunmoon; Jin, Jianbo; Song, Chengyu; Salmeron, Miquel; Scott, Mary C.; Yang, Peidong

doi:10.1021/acs.nanolett.1c02225

Revealing the Phase Separation Behavior of Thermodynamically Immiscible Elements in a Nanoparticle

Journal Article · Tue Jul 20 00:00:00 EDT 2021 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.1c02225· OSTI ID:1821155

^[1]; ^[2]; ^[2]; ^[1]; Song, Chengyu ^[3]; ^[2]; Scott, Mary C. ^[2]; ^[2]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Phase-separation is commonly observed in multimetallic nanomaterials, yet it is not well understood how immiscible elements distribute in a thermodynamically stable nanoparticle. Herein, we studied the phase-separation of Au and Rh in nanoparticles using electron microscopy and tomography techniques. The nanoparticles were thermally annealed to form thermodynamically stable structures. HAADF-STEM and EDS characterizations reveal that Au and Rh segregate into two domains while their miscibility is increased. Using aberration-corrected HAADF-STEM and atomic electron tomography, we show that the increased solubility of Au in Rh is achieved by forming Au clusters and single atoms inside the Rh domains and on the Rh surface. Furthermore, based on the three-dimensional reconstruction of a AuRh nanoparticle, we can visualize the uneven interface that is embedded in the nanoparticle. Finally, the results advance our understanding on the nanoscale thermodynamic behavior of metal mixtures, which is crucial for the optimization of multimetallic nanostructures for many applications.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1821155

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 15 Vol. 21; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Plasmonic/Magnetic Bifunctional Nanoparticles Peng, Sheng; Lei, Changhui; Ren, Yang Angewandte Chemie International Edition, Vol. 50, Issue 14 https://doi.org/10.1002/anie.201007794	journal	March 2011
Ultrafast Self-Assembly Using Ultrasound: A Facile Route to the Rapid Fabrication of Well-Ordered Dense Arrays of Inorganic Nanostructures Ethirajan, Anitha; Punniyakoti, Sathya; D'Olieslaeger, Marc Angewandte Chemie International Edition, Vol. 52, Issue 37 https://doi.org/10.1002/anie.201301980	journal	July 2013
Surface Segregation in Bimetallic Nanoparticles: A Critical Issue in Electrocatalyst Engineering Liao, Hanbin; Fisher, Adrian; Xu, Zhichuan J. Small, Vol. 11, Issue 27 https://doi.org/10.1002/smll.201403380	journal	March 2015
Size dependent microstructure for Ag–Ni nanoparticles Srivastava, C.; Chithra, S.; Malviya, K. D. Acta Materialia, Vol. 59, Issue 16 https://doi.org/10.1016/j.actamat.2011.07.022	journal	September 2011
Size dependent spinodal decomposition in Cu-Ag nanoparticles Radnóczi, G.; Bokányi, E.; Erdélyi, Z. Acta Materialia, Vol. 123 https://doi.org/10.1016/j.actamat.2016.10.036	journal	January 2017
Study of the stability of small AuRh clusters found by a Genetic Algorithm methodology Buendía, Fernando; Vargas, Jorge A.; Johnston, Roy L. Computational and Theoretical Chemistry, Vol. 1119 https://doi.org/10.1016/j.comptc.2017.09.008	journal	November 2017
Miedema Calculator: A thermodynamic platform for predicting formation enthalpies of alloys within framework of Miedema’s Theory Zhang, R. F.; Zhang, S. H.; He, Z. J. Computer Physics Communications, Vol. 209 https://doi.org/10.1016/j.cpc.2016.08.013	journal	December 2016
The effect of Au domain size on the CO oxidation catalytic activity of colloidal Au–FeOx dumbbell-like heterodimers Najafishirtari, Sharif; Guardia, Pablo; Scarpellini, Alice Journal of Catalysis, Vol. 338 https://doi.org/10.1016/j.jcat.2016.03.002	journal	June 2016
Accumulation-Driven Unified Spatiotemporal Synthesis and Structuring of Immiscible Metallic Nanoalloys Rajeeva, Bharath Bangalore; Kunal, Pranaw; Kollipara, Pavana Siddhartha Matter, Vol. 1, Issue 6 https://doi.org/10.1016/j.matt.2019.10.017	journal	December 2019
Unconventional Alloys Confined in Nanoparticles: Building Blocks for New Matter Feng, Jicheng; Chen, Dong; Pikhitsa, Peter V. Matter, Vol. 3, Issue 5 https://doi.org/10.1016/j.matt.2020.07.027	journal	November 2020
Hybrid Au–SiO ₂ Core–Satellite Colloids as Switchable SERS Tags Rodríguez-Fernández, Denis; Langer, Judith; Henriksen-Lacey, Malou Chemistry of Materials, Vol. 27, Issue 7 https://doi.org/10.1021/acs.chemmater.5b00128	journal	March 2015
Multicomponent Plasmonic Nanoparticles: From Heterostructured Nanoparticles to Colloidal Composite Nanostructures Ha, Minji; Kim, Jae-Ho; You, Myunghwa Chemical Reviews, Vol. 119, Issue 24 https://doi.org/10.1021/acs.chemrev.9b00234	journal	December 2019
Tandem Catalysis for CO ₂ Hydrogenation to C ₂ –C ₄ Hydrocarbons Xie, Chenlu; Chen, Chen; Yu, Yi Nano Letters, Vol. 17, Issue 6 https://doi.org/10.1021/acs.nanolett.7b01139	journal	May 2017
Unlocking the Potential of Nanoparticles Composed of Immiscible Elements for Direct H ₂ O ₂ Synthesis Kim, Donghun; Nam, Hyobin; Cho, Young-Hoon ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b00451	journal	August 2019
Nanoscale Alloying, Phase-Segregation, and Core−Shell Evolution of Gold−Platinum Nanoparticles and Their Electrocatalytic Effect on Oxygen Reduction Reaction Wanjala, Bridgid N.; Luo, Jin; Loukrakpam, Rameshwori Chemistry of Materials, Vol. 22, Issue 14 https://doi.org/10.1021/cm101109e	journal	July 2010
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
One-Pot Synthesis and Characterization of Size-Controlled Bimagnetic FePt−Iron Oxide Heterodimer Nanocrystals Figuerola, Albert; Fiore, Angela; Di Corato, Riccardo Journal of the American Chemical Society, Vol. 130, Issue 4 https://doi.org/10.1021/ja078034v	journal	January 2008
Surface Composition Tuning of Au–Pt Bimetallic Nanoparticles for Enhanced Carbon Monoxide and Methanol Electro-oxidation Suntivich, Jin; Xu, Zhichuan; Carlton, Christopher E. Journal of the American Chemical Society, Vol. 135, Issue 21 https://doi.org/10.1021/ja402072r	journal	May 2013
Tip-Directed Synthesis of Multimetallic Nanoparticles Chen, Peng-Cheng; Liu, Guoliang; Zhou, Yu Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b05139	journal	July 2015
Microscopic Investigation of Chemoselectivity in Ag–Pt–Fe ₃ O ₄ Heterotrimer Formation: Mechanistic Insights and Implications for Controlling High-Order Hybrid Nanoparticle Morphology Hodges, James M.; Morse, James R.; Williams, Mary Elizabeth Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b10254	journal	December 2015
Structural Evolution of Three-Component Nanoparticles in Polymer Nanoreactors Chen, Peng-Cheng; Du, Jingshan S.; Meckes, Brian Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b03163	journal	July 2017
Transformative Heterointerface Evolution and Plasmonic Tuning of Anisotropic Trimetallic Nanoparticles Lin, Mouhong; Kim, Gyeong-Hwan; Kim, Jae-Ho Journal of the American Chemical Society, Vol. 139, Issue 30 https://doi.org/10.1021/jacs.7b04202	journal	July 2017
Dumbbell-like Bifunctional Au−Fe ₃ O ₄ Nanoparticles Yu, Heng; Chen, Min; Rice, Philip M. Nano Letters, Vol. 5, Issue 2 https://doi.org/10.1021/nl047955q	journal	February 2005
Size effect on the cohesive energy of nanoparticle Qi, W. H.; Wang, M. P. Journal of Materials Science Letters, Vol. 21, Issue 22, p. 1743-1745 https://doi.org/10.1023/A:1020904317133	journal	November 2002
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
An informatics guided classification of miscible and immiscible binary alloy systems Zhang, R. F.; Kong, X. F.; Wang, H. T. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-09704-1	journal	August 2017
GENFIRE: A generalized Fourier iterative reconstruction algorithm for high-resolution 3D imaging Pryor, Alan; Yang, Yongsoo; Rana, Arjun Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-09847-1	journal	September 2017
Reversible loss of core–shell structure for Ni–Au bimetallic nanoparticles during CO2 hydrogenation Zhang, Xiaoben; Han, Shaobo; Zhu, Beien Nature Catalysis, Vol. 3, Issue 4 https://doi.org/10.1038/s41929-020-0440-2	journal	March 2020
Understanding and controlling the structure and segregation behaviour of AuRh nanocatalysts Piccolo, Laurent; Li, Z. Y.; Demiroglu, Ilker Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep35226	journal	October 2016
Thermodynamics of nanoalloys Calvo, Florent Physical Chemistry Chemical Physics, Vol. 17, Issue 42 https://doi.org/10.1039/C5CP00274E	journal	January 2015
Building up strain in colloidal metal nanoparticle catalysts Sneed, Brian T.; Young, Allison P.; Tsung, Chia-Kuang Nanoscale, Vol. 7, Issue 29 https://doi.org/10.1039/C5NR02529J	journal	January 2015
Strain-induced restructuring of the surface in core@shell nanoalloys Panizon, Emanuele; Ferrando, Riccardo Nanoscale, Vol. 8, Issue 35 https://doi.org/10.1039/C6NR03560D	journal	January 2016
Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts Roling, Luke T.; Mavrikakis, Manos Nanoscale, Vol. 9, Issue 39 https://doi.org/10.1039/C7NR04779G	journal	January 2017
Monitoring in situ the colloidal synthesis of AuRh/TiO ₂ selective-hydrogenation nanocatalysts Konuspayeva, Zere; Berhault, Gilles; Afanasiev, Pavel Journal of Materials Chemistry A, Vol. 5, Issue 33 https://doi.org/10.1039/C7TA03965D	journal	January 2017
Alloys in catalysis: phase separation and surface segregation phenomena in response to the reactive environment Zafeiratos, Spiros; Piccinin, Simone; Teschner, Detre Catalysis Science & Technology, Vol. 2, Issue 9 https://doi.org/10.1039/c2cy00487a	journal	January 2012
Transition from core–shell to Janus chemical configuration for bimetallic nanoparticles Langlois, Cyril; Li, Z. L.; Yuan, Jun Nanoscale, Vol. 4, Issue 11 https://doi.org/10.1039/c2nr11954d	journal	January 2012
Successful synthesis and thermal stability of immiscible metal Au–Rh, Au–Ir andAu–Ir–Rh nanoalloys Shubin, Yury; Plyusnin, Pavel; Sharafutdinov, Marat Nanotechnology, Vol. 28, Issue 20 https://doi.org/10.1088/1361-6528/aa6bc9	journal	April 2017
Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies Fèvre, Mathieu; Le Bouar, Yann; Finel, Alphonse Physical Review B, Vol. 97, Issue 19 https://doi.org/10.1103/PhysRevB.97.195404	journal	May 2018
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles Tao, F.; Grass, M. E.; Zhang, Y. Science, Vol. 322, Issue 5903 https://doi.org/10.1126/science.1164170	journal	November 2008
Polyelemental nanoparticle libraries Chen, P. -C.; Liu, X.; Hedrick, J. L. Science, Vol. 352, Issue 6293 https://doi.org/10.1126/science.aaf8402	journal	June 2016
Interface and heterostructure design in polyelemental nanoparticles Chen, Peng-Cheng; Liu, Mohan; Du, Jingshan S. Science, Vol. 363, Issue 6430 https://doi.org/10.1126/science.aav4302	journal	February 2019
Size effect on alloying ability and phase stability of immiscible bimetallic nanoparticles Xiao, S.; Hu, W.; Luo, W. The European Physical Journal B, Vol. 54, Issue 4 https://doi.org/10.1140/epjb/e2007-00018-6	journal	December 2006
The Surface Free Energies of Solid Chemical Elements: Calculation from Internal Free Enthalpies of Atomization Mezey, L. Z.; Giber, J. Japanese Journal of Applied Physics, Vol. 21, Issue Part 1, No. 11 https://doi.org/10.1143/JJAP.21.1569	journal	November 1982
A practical guide to evaluating colocalization in biological microscopy Dunn, Kenneth W.; Kamocka, Malgorzata M.; McDonald, John H. American Journal of Physiology-Cell Physiology, Vol. 300, Issue 4 https://doi.org/10.1152/ajpcell.00462.2010	journal	April 2011
Size-dependent phase diagrams of metallic alloys: A Monte Carlo simulation study on order–disorder transitions in Pt–Rh nanoparticles Pohl, Johan; Stahl, Christian; Albe, Karsten Beilstein Journal of Nanotechnology, Vol. 3 https://doi.org/10.3762/bjnano.3.1	journal	January 2012

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Revealing the Phase Separation Behavior of Thermodynamically Immiscible Elements in a Nanoparticle

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