Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals
Abstract
Here, we report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (~200°C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, resulting in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron Xray adsorption techniques. Then, upon the conversion of metal lithium to LiOH in humid air, the Pd and Pt atoms undergo an alloying process, to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted “dissolutionalloying” method bypasses many complications intrinsic to conventional ion reductionbased nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and themore »
- Authors:
-
- Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Purdue Univ., West Lafayette, IN (United States)
- Northern Illinois Univ., DeKalb, IL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1341436
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 28; Journal Issue: 7; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Barkholtz, Heather M., Gallagher, James R., Li, Tao, Liu, Yuzi, Winans, Randall E., Miller, Jeffrey T., Liu, Di -Jia, and Xu, Tao. Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals. United States: N. p., 2016.
Web. doi:10.1021/acs.chemmater.6b00216.
Barkholtz, Heather M., Gallagher, James R., Li, Tao, Liu, Yuzi, Winans, Randall E., Miller, Jeffrey T., Liu, Di -Jia, & Xu, Tao. Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals. United States. https://doi.org/10.1021/acs.chemmater.6b00216
Barkholtz, Heather M., Gallagher, James R., Li, Tao, Liu, Yuzi, Winans, Randall E., Miller, Jeffrey T., Liu, Di -Jia, and Xu, Tao. Sun .
"Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals". United States. https://doi.org/10.1021/acs.chemmater.6b00216. https://www.osti.gov/servlets/purl/1341436.
@article{osti_1341436,
title = {Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals},
author = {Barkholtz, Heather M. and Gallagher, James R. and Li, Tao and Liu, Yuzi and Winans, Randall E. and Miller, Jeffrey T. and Liu, Di -Jia and Xu, Tao},
abstractNote = {Here, we report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (~200°C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, resulting in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron Xray adsorption techniques. Then, upon the conversion of metal lithium to LiOH in humid air, the Pd and Pt atoms undergo an alloying process, to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted “dissolutionalloying” method bypasses many complications intrinsic to conventional ion reductionbased nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.},
doi = {10.1021/acs.chemmater.6b00216},
journal = {Chemistry of Materials},
number = 7,
volume = 28,
place = {United States},
year = {Sun Mar 27 00:00:00 EDT 2016},
month = {Sun Mar 27 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Electrocatalyst approaches and challenges for automotive fuel cells
journal, June 2012
- Debe, Mark K.
- Nature, Vol. 486, Issue 7401
Nanoscale Metal–Organic Frameworks for the Co-Delivery of Cisplatin and Pooled siRNAs to Enhance Therapeutic Efficacy in Drug-Resistant Ovarian Cancer Cells
journal, February 2014
- He, Chunbai; Lu, Kuangda; Liu, Demin
- Journal of the American Chemical Society, Vol. 136, Issue 14
Applications of Colloidal Inorganic Nanoparticles: From Medicine to Energy
journal, September 2012
- Lohse, Samuel E.; Murphy, Catherine J.
- Journal of the American Chemical Society, Vol. 134, Issue 38
Coking- and Sintering-Resistant Palladium Catalysts Achieved Through Atomic Layer Deposition
journal, March 2012
- Lu, Junling; Fu, Baosong; Kung, Mayfair C.
- Science, Vol. 335, Issue 6073
Plasmonics: Merging Photonics and Electronics at Nanoscale Dimensions
journal, January 2006
- Ozbay, E.
- Science, Vol. 311, Issue 5758
Quantum plasmon resonances of individual metallic nanoparticles
journal, March 2012
- Scholl, Jonathan A.; Koh, Ai Leen; Dionne, Jennifer A.
- Nature, Vol. 483, Issue 7390
A DNAzyme-Gold Nanoparticle Probe for Uranyl Ion in Living Cells
journal, March 2013
- Wu, Peiwen; Hwang, Kevin; Lan, Tian
- Journal of the American Chemical Society, Vol. 135, Issue 14
Aerosol-Assisted Synthesis of Shape-Controlled CoFe 2 O 4 : Topotactic versus Direct Melt Crystallization
journal, February 2015
- Fu, Jie; DeSantis, Christopher J.; Weiner, Rebecca G.
- Chemistry of Materials, Vol. 27, Issue 5
High Activity Redox Catalysts Synthesized by Chemical Vapor Impregnation
journal, December 2013
- Forde, Michael M.; Kesavan, Lokesh; bin Saiman, Mohd Izham
- ACS Nano, Vol. 8, Issue 1
Platinum Availability for Future Automotive Technologies
journal, November 2012
- Alonso, Elisa; Field, Frank R.; Kirchain, Randolph E.
- Environmental Science & Technology, Vol. 46, Issue 23
Solvent extraction of platinum using amine based extractants in different solutions: A review
journal, February 2014
- Jha, Manis Kumar; Gupta, Divika; Lee, Jae-chun
- Hydrometallurgy, Vol. 142
Evaluation of a rapid technique for the determination of precious metals in geological samples based on a selective aqua regia leach
journal, January 1991
- Gowing, Charles J. B.; Potts, Philip J.
- The Analyst, Vol. 116, Issue 8
Preparation and Structural Analysis of Carbon-Supported Co Core/Pt Shell Electrocatalysts Using Electroless Deposition Methods
journal, August 2009
- Beard, K. D.; Borrelli, David; Cramer, Alison M.
- ACS Nano, Vol. 3, Issue 9
Platinum-Based Nanostructured Materials: Synthesis, Properties, and Applications
journal, June 2010
- Chen, Aicheng; Holt-Hindle, Peter
- Chemical Reviews, Vol. 110, Issue 6
Methanol-tolerant PdPt/C alloy catalyst for oxygen electro-reduction reaction
journal, July 2008
- Joo, Ji Bong; Kim, You Jung; Kim, Wooyoung
- Korean Journal of Chemical Engineering, Vol. 25, Issue 4
Highly Active Bimetallic PdPt and CoPt Nanocrystals for Methanol Electro-oxidation
journal, March 2012
- Kakade, Bhalchandra A.; Tamaki, Takanori; Ohashi, Hidenori
- The Journal of Physical Chemistry C, Vol. 116, Issue 13
Direct Colloidal Route for Pt-Covered AuPt Bimetallic Nanoparticles
journal, August 2010
- Xu, Zhichuan; Carlton, Christopher E.; Allard, Lawrence F.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 17, p. 2514-2518
Effect of Ligand−Metal Interactions on the Growth of Transition-Metal and Alloy Nanoparticles
journal, October 2006
- Samia, Anna C. S.; Schlueter, John A.; Jiang, J. Samuel
- Chemistry of Materials, Vol. 18, Issue 22
Palladium in fuel cell catalysis
journal, January 2009
- Antolini, Ermete
- Energy & Environmental Science, Vol. 2, Issue 9
Synthesis of bimetallic PtPd nanocubes on graphene with N,N-dimethylformamide and their direct use for methanol electrocatalytic oxidation
journal, January 2014
- Chen, Xiaomei; Cai, Zhixiong; Chen, Xi
- Carbon, Vol. 66
Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles
journal, March 2008
- Ferrando, Riccardo; Jellinek, Julius; Johnston, Roy L.
- Chemical Reviews, Vol. 108, Issue 3, p. 845-910
Supported Metal Clusters: Synthesis, Structure, and Catalysis
journal, May 1995
- Gates, B. C.
- Chemical Reviews, Vol. 95, Issue 3
Composition-Controlled Synthesis of Bimetallic PdPt Nanoparticles and Their Electro-oxidation of Methanol
journal, September 2011
- Liu, Yi; Chi, Miaofang; Mazumder, Vismadeb
- Chemistry of Materials, Vol. 23, Issue 18
Platinum and Palladium Nano-Structured Catalysts for Polymer Electrolyte Fuel Cells and Direct Methanol Fuel Cells
journal, July 2013
- Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang
- Journal of Nanoscience and Nanotechnology, Vol. 13, Issue 7
Recent progress in the development of anode and cathode catalysts for direct methanol fuel cells
journal, September 2013
- Tiwari, Jitendra N.; Tiwari, Rajanish N.; Singh, Gyan
- Nano Energy, Vol. 2, Issue 5
Synthesis of colloidal metal and metal alloy nanoparticles for electrochemical energy applications
journal, January 2013
- You, Hongjun; Yang, Shengchun; Ding, Bingjun
- Chem. Soc. Rev., Vol. 42, Issue 7
Recent advances in catalysts for direct methanol fuel cells
journal, January 2011
- Zhao, Xiao; Yin, Min; Ma, Liang
- Energy & Environmental Science, Vol. 4, Issue 8
Strategic Synthesis of Trimetallic Au@Pd@Pt Core−Shell Nanoparticles from Poly(vinylpyrrolidone)-Based Aqueous Solution toward Highly Active Electrocatalysts
journal, May 2011
- Wang, Liang; Yamauchi, Yusuke
- Chemistry of Materials, Vol. 23, Issue 9
Engineering Preformed Cobalt-Doped Platinum Nanocatalysts For Ultraselective Hydrogenation
journal, November 2008
- Tsang, Shik Chi; Cailuo, Nick; Oduro, William
- ACS Nano, Vol. 2, Issue 12
Strategic Design of Three-Dimensional (3D) Urchin-Like Pt–Ni Nanoalloys: How This Unique Nanostructure Boosts the Bulk Heterojunction Polymer Solar Cells Efficiency to 8.48%
journal, December 2014
- Chou, Shang-Wei; Chen, Hsieh-Chih; Zhang, Zhiyun
- Chemistry of Materials, Vol. 26, Issue 24
Advanced Platinum Alloy Electrocatalysts for the Oxygen Reduction Reaction
journal, April 2012
- Wang, Chao; Markovic, Nenad M.; Stamenkovic, Vojislav R.
- ACS Catalysis, Vol. 2, Issue 5
Stable Oxygen Reduction Electrocatalysts from Presynthesized PdPt Nanoparticles on Carbon
journal, October 2010
- Slanac, Daniel A.; Li, Lin; Stevenson, Keith J.
- ECS Transactions, Vol. 33, Issue 1
Monodisperse FePt Nanoparticles and Ferromagnetic FePt Nanocrystal Superlattices
journal, March 2000
- Sun, S.
- Science, Vol. 287, Issue 5460
Naked metal nanoparticles from metal carbonyls in ionic liquids: Easy synthesis and stabilization
journal, September 2011
- Vollmer, Christian; Janiak, Christoph
- Coordination Chemistry Reviews, Vol. 255, Issue 17-18
Sonochemical Synthesis of Iron Colloids
journal, January 1996
- Suslick, Kenneth S.; Fang, Mingming; Hyeon, Taeghwan
- Journal of the American Chemical Society, Vol. 118, Issue 47
Synthesis of Highly Crystalline and Monodisperse Maghemite Nanocrystallites without a Size-Selection Process
journal, December 2001
- Hyeon, Taeghwan; Lee, Su Seong; Park, Jongnam
- Journal of the American Chemical Society, Vol. 123, Issue 51, p. 12798-12801
Synthesis and Characterization of Magnetic Nanoalloys from Bimetallic Carbonyl Clusters
journal, July 2009
- Robinson, Ian; Zacchini, Stefano; Tung, Le D.
- Chemistry of Materials, Vol. 21, Issue 13
Ionic Liquids for the Synthesis and Stabilization of Metal Nanoparticles
journal, October 2013
- Janiak, Christoph
- Zeitschrift für Naturforschung B, Vol. 68, Issue 10
Synthesis, characterization and antibacterial investigation of silver–copper nanoalloys
journal, January 2011
- Taner, Merve; Sayar, Nilufer; Yulug, Isik G.
- Journal of Materials Chemistry, Vol. 21, Issue 35
Fabricating a Homogeneously Alloyed AuAg Shell on Au Nanorods to Achieve Strong, Stable, and Tunable Surface Plasmon Resonances
journal, August 2015
- Huang, Jianfeng; Zhu, Yihan; Liu, Changxu
- Small, Vol. 11, Issue 39
NiFe Nanoparticles: A Soft Magnetic Material?
journal, March 2007
- Margeat, Olivier; Ciuculescu, Diana; Lecante, Pierre
- Small, Vol. 3, Issue 3
Characterization of Copper nanoparticles obtained by laser ablation in liquids
journal, August 2012
- Muniz-Miranda, M.; Gellini, C.; Simonelli, A.
- Applied Physics A, Vol. 110, Issue 4
Low-temperature aqueous-phase reforming of ethanol on bimetallic PdZn catalysts
journal, January 2015
- Xiong, Haifeng; DeLaRiva, Andrew; Wang, Yong
- Catalysis Science & Technology, Vol. 5, Issue 1
Structural evolution of an intermetallic Pd–Zn catalyst selective for propane dehydrogenation
journal, January 2015
- Gallagher, James R.; Childers, David J.; Zhao, Haiyan
- Physical Chemistry Chemical Physics, Vol. 17, Issue 42
Dynamic Structure of a Working Methanol Steam Reforming Catalyst: In Situ Quick-EXAFS on Pd/ZnO Nanoparticles
journal, February 2011
- Föttinger, Karin; van Bokhoven, Jeroen A.; Nachtegaal, Maarten
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 5
Stability of bimetallic Pd–Zn catalysts for the steam reforming of methanol
journal, July 2008
- Conant, T.; Karim, A.; Lebarbier, V.
- Journal of Catalysis, Vol. 257, Issue 1
Direct Synthesis of Bimetallic Pd 3 Ag Nanoalloys from Bulk Pd 3 Ag Alloy
journal, November 2012
- Lin, Chi-Kai; Lin, Yan-Gu; Wu, Tianpin
- Inorganic Chemistry, Vol. 51, Issue 24
Hydrogen Spillover Enhanced Hydriding Kinetics of Palladium-Doped Lithium Nitride to Lithium Imide
journal, April 2009
- Lin, Chikai; Xu, Tao; Yu, Jiamei
- The Journal of Physical Chemistry C, Vol. 113, Issue 19
Synthesis of Supported Platinum Nanoparticles from Li−Pt Solid Solution
journal, February 2010
- Xu, Tao; Lin, Chikai; Wang, Chao
- Journal of the American Chemical Society, Vol. 132, Issue 7
Toward new technologies for the production of lithium
journal, May 1998
- Sadoway, Donald R.
- JOM, Vol. 50, Issue 5
Systematic Exploration of Synthesis Pathways to Nanoparticulate ZnPd
journal, July 2012
- Luo, Yuan; Sun, Yuhan; Schwarz, Ulrich
- Chemistry of Materials, Vol. 24, Issue 15
WinXAS a Program for X-ray Absorption Spectroscopy Data Analysis under MS-Windows
journal, March 1998
- Ressler, T.
- Journal of Synchrotron Radiation, Vol. 5, Issue 2, p. 118-122
Theoretical x-ray absorption fine structure standards
journal, July 1991
- Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I.
- Journal of the American Chemical Society, Vol. 113, Issue 14
The Scherrer Formula for X-Ray Particle Size Determination
journal, November 1939
- Patterson, A. L.
- Physical Review, Vol. 56, Issue 10
Bond length contraction in gold nanoparticles
journal, September 2010
- Szczerba, Wojciech; Riesemeier, Heinrich; Thünemann, Andreas F.
- Analytical and Bioanalytical Chemistry, Vol. 398, Issue 5
Controlling ZnO morphology for improved methanol steam reforming reactivity
journal, January 2008
- Karim, Ayman M.; Conant, Travis; Datye, Abhaya K.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 36
Works referencing / citing this record:
Effects of Pt metal loading on the atomic restructure and oxygen reduction reaction performance of Pt-cluster decorated Cu@Pd electrocatalysts
journal, January 2019
- Bhalothia, Dinesh; Lin, Cheng-Yang; Yan, Che
- Sustainable Energy & Fuels, Vol. 3, Issue 7
Platinum-trimer decorated cobalt-palladium core-shell nanocatalyst with promising performance for oxygen reduction reaction
journal, January 2019
- Dai, Sheng; Chou, Jyh-Pin; Wang, Kuan-Wen
- Nature Communications, Vol. 10, Issue 1
Sub-nanometer Pt cluster decoration enhances the oxygen reduction reaction performances of NiO x supported Pd nano-islands
journal, January 2020
- Bhalothia, Dinesh; Dai, Sheng; Wang, Sheng-Po
- Sustainable Energy & Fuels, Vol. 4, Issue 2