Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts
Abstract
In this work, we present the synthesis of Ag–Ir alloys in the form of solid-solution nanoparticles (NPs). Ag and Ir are classically immiscible in the bulk and therefore the physical properties of Ag–Ir alloys are unknown. A convenient microwave-assisted, solution-phase method that employs readily available Ag(NO3) and IrCl3 precursors enables the preparation of small (2.5–5.5 nm) Ag–IrNPs with alloyed structures. Ag$$x$$Ir(100–$$x$$)NPs can be obtained by this method between $$x$$ = 6–31. The Ag–IrNPs resist dealloying upon heating up to 300 °C. Ir-rich Ag–IrNPs dispersed on amorphous silica are significantly more active gas-phase alkene hydrogenation catalysts than pure IrNPs. Density functional theory (DFT) and theoretical modeling studies reveal that the Ag–IrNPs—which are consistently larger than monometallic IrNPs prepared under the same conditions—have comparatively fewer strong H-binding edge sites. This promotes faster H atom transfer to coadsorbed alkenes. Ag–IrNPs supported on amorphous Co3O4 show a linear composition dependence in the selective hydrogenation of C$$=$$O versus C$$=$$C bonds: more Ag-rich Ag–IrNPs are more selective toward C$$=$$O hydrogenation of the α,β-unsaturated aldehyde crotonaldehyde, yielding the industrially desirable crotyl alcohol. Furthermore, deposition of Ag–IrNPs inside Co3O4 mesopores results in an additional ~56% selectivity enhancement.
- Authors:
-
[2];
[3];
[1];
[1]
- Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
- Univ. of Texas, Austin, TX (United States). Texas Materials Inst.
- Univ. of Texas, Austin, TX (United States). Dept. of Chemistry; Nanjing Univ., Nanjing, Jiangsu (China). School of Environment
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1543703
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 12; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; metallic nanoparticles; alloy nanoparticles; microwave synthesis; heterogeneous catalysis; crotonaldehyde hydrogenation; silver; iridium
Citation Formats
Guo, Hongyu, Li, Hao, Jarvis, Karalee, Wan, Haiqin, Kunal, Pranaw, Dunning, Samuel G., Liu, Yulu, Henkelman, Graeme, and Humphrey, Simon M. Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts. United States: N. p., 2018.
Web. doi:10.1021/acscatal.8b02103.
Guo, Hongyu, Li, Hao, Jarvis, Karalee, Wan, Haiqin, Kunal, Pranaw, Dunning, Samuel G., Liu, Yulu, Henkelman, Graeme, & Humphrey, Simon M. Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts. United States. https://doi.org/10.1021/acscatal.8b02103
Guo, Hongyu, Li, Hao, Jarvis, Karalee, Wan, Haiqin, Kunal, Pranaw, Dunning, Samuel G., Liu, Yulu, Henkelman, Graeme, and Humphrey, Simon M. Wed .
"Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts". United States. https://doi.org/10.1021/acscatal.8b02103. https://www.osti.gov/servlets/purl/1543703.
@article{osti_1543703,
title = {Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts},
author = {Guo, Hongyu and Li, Hao and Jarvis, Karalee and Wan, Haiqin and Kunal, Pranaw and Dunning, Samuel G. and Liu, Yulu and Henkelman, Graeme and Humphrey, Simon M.},
abstractNote = {In this work, we present the synthesis of Ag–Ir alloys in the form of solid-solution nanoparticles (NPs). Ag and Ir are classically immiscible in the bulk and therefore the physical properties of Ag–Ir alloys are unknown. A convenient microwave-assisted, solution-phase method that employs readily available Ag(NO3) and IrCl3 precursors enables the preparation of small (2.5–5.5 nm) Ag–IrNPs with alloyed structures. Ag$x$Ir(100–$x$)NPs can be obtained by this method between $x$ = 6–31. The Ag–IrNPs resist dealloying upon heating up to 300 °C. Ir-rich Ag–IrNPs dispersed on amorphous silica are significantly more active gas-phase alkene hydrogenation catalysts than pure IrNPs. Density functional theory (DFT) and theoretical modeling studies reveal that the Ag–IrNPs—which are consistently larger than monometallic IrNPs prepared under the same conditions—have comparatively fewer strong H-binding edge sites. This promotes faster H atom transfer to coadsorbed alkenes. Ag–IrNPs supported on amorphous Co3O4 show a linear composition dependence in the selective hydrogenation of C$=$O versus C$=$C bonds: more Ag-rich Ag–IrNPs are more selective toward C$=$O hydrogenation of the α,β-unsaturated aldehyde crotonaldehyde, yielding the industrially desirable crotyl alcohol. Furthermore, deposition of Ag–IrNPs inside Co3O4 mesopores results in an additional ~56% selectivity enhancement.},
doi = {10.1021/acscatal.8b02103},
journal = {ACS Catalysis},
number = 12,
volume = 8,
place = {United States},
year = {Wed Oct 03 00:00:00 EDT 2018},
month = {Wed Oct 03 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 46 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Figure 1: (A) PXRD patterns for Ag, Ir and AgxIr(100‒x)NPs of different compositions; the corresponding theoretical reflection positions for Ag (JCPDS card # 01-087-0597) and IrNPs (JCPDS card # 01-087-0715) are also shown for reference. Inset: magnification of the (111) and (200) reflections. (B-G) TEM images for pure Ir NPsmore »
All figures and tables
(8 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Applied Catalysis: A Predictive Socioeconomic History
journal, May 2009
- Adams, Chris
- Topics in Catalysis, Vol. 52, Issue 8
Promotion of Iridium-Catalyzed Methanol Carbonylation: Mechanistic Studies of the Cativa Process
journal, March 2004
- Haynes, Anthony; Maitlis, Peter M.; Morris, George E.
- Journal of the American Chemical Society, Vol. 126, Issue 9
New acetyls techonologies from BP chemicals
book, January 1999
- Howard, Mark J.; Sunley, Glenn J.; Poole, Andrew D.
- Science and Technology in Catalysis 1998, Proceedings of the Third Tokyo Conference on Advanced Catalytic Science and Technology
High productivity methanol carbonylation catalysis using iridium
journal, May 2000
- Sunley, Glenn J.; Watson, Derrick J.
- Catalysis Today, Vol. 58, Issue 4
P-145: A Three-Spectrum White Organic Light Emitting Diode Base on a New Red Organometallic Iridium Complexes
journal, January 2005
- Shieh, Tien-shou; Yeh, Shu-Tang; Chu, Miao-Tsai
- SID Symposium Digest of Technical Papers, Vol. 36, Issue 1
Positive effect of coexisting SO2 on the activity of supported iridium catalysts for NO reduction in the presence of oxygen
journal, March 2003
- Yoshinari, Tomohiro; Sato, Kazuhito; Haneda, Masaaki
- Applied Catalysis B: Environmental, Vol. 41, Issue 1-2
CO Oxidation below Room Temperature over Ir/TiO2 Catalyst Prepared by Deposition Precipitation Method
journal, June 2002
- Okumura, Mitsutaka; Masuyama, Noriaki; Konishi, Eiko
- Journal of Catalysis, Vol. 208, Issue 2
“Ir-in-ceria”: A highly selective catalyst for preferential CO oxidation
journal, April 2008
- Huang, Y.; Wang, A.; Li, L.
- Journal of Catalysis, Vol. 255, Issue 2
Determination of Surface Coverage of Catalysts: Temperature Programmed Experiments on Platinum and Iridium Sponge Catalysts after Low Temperature Ammonia Oxidation
journal, July 1999
- van den Broek, A. C. M.; van Grondelle, J.; van Santen, R. A.
- Journal of Catalysis, Vol. 185, Issue 2
A High Yield Synthesis of Ligand-Free Iridium Oxide Nanoparticles with High Electrocatalytic Activity
journal, February 2011
- Zhao, Yixin; Hernandez-Pagan, Emil A.; Vargas-Barbosa, Nella M.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 5
Photovoltage Effects of Sintered IrO 2 Nanoparticle Catalysts in Water-Splitting Dye-Sensitized Photoelectrochemical Cells
journal, April 2014
- Swierk, John R.; McCool, Nicholas S.; Saunders, Timothy P.
- The Journal of Physical Chemistry C, Vol. 118, Issue 30
Facile Synthesis of Iridium Nanocrystals with Well-Controlled Facets Using Seed-Mediated Growth
journal, July 2014
- Xia, Xiaohu; Figueroa-Cosme, Legna; Tao, Jing
- Journal of the American Chemical Society, Vol. 136, Issue 31
Partially oxidized iridium clusters within dendrimers: size-controlled synthesis and selective hydrogenation of 2-nitrobenzaldehyde
journal, January 2016
- Higaki, Tatsuya; Kitazawa, Hirokazu; Yamazoe, Seiji
- Nanoscale, Vol. 8, Issue 22
Selective hydrogenation of levulinic acid to 1,4-pentanediol in water using a hydroxyapatite-supported Pt–Mo bimetallic catalyst
journal, January 2015
- Mizugaki, T.; Nagatsu, Y.; Togo, K.
- Green Chemistry, Vol. 17, Issue 12
High-pressure high-temperature stability of hcp-Ir Os1− (x = 0.50 and 0.55) alloys
journal, April 2017
- Yusenko, Kirill V.; Bykova, Elena; Bykov, Maxim
- Journal of Alloys and Compounds, Vol. 700
Iridium nanoparticles stabilized by metal organic frameworks (IrNPs@ZIF-8): synthesis, structural properties and catalytic performance
journal, January 2012
- Zahmakiran, Mehmet
- Dalton Transactions, Vol. 41, Issue 41
Development Plus Kinetic and Mechanistic Studies of a Prototype Supported-Nanoparticle Heterogeneous Catalyst Formation System in Contact with Solution: Ir(1,5-COD)Cl/γ-Al 2 O 3 and Its Reduction by H 2 to Ir(0) n /γ-Al 2 O 3
journal, July 2010
- Mondloch, Joseph E.; Wang, Qi; Frenkel, Anatoly I.
- Journal of the American Chemical Society, Vol. 132, Issue 28
Initial Experimental Design Methodology Incorporating Expert Conjecture, Prior Data, and Engineering Models for Deposition of Iridium Nanoparticles in Supercritical Carbon Dioxide
journal, July 2013
- Casciato, Michael J.; Vastola, Justin T.; Lu, J. C.
- Industrial & Engineering Chemistry Research, Vol. 52, Issue 28
An Efficient and Recyclable Catalytic System Comprising Nano-Iridium(0) and a Pyridinium Salt of nido -Carboranyldiphosphine for the Synthesis of One-Dimensional Boronate Esters via Hydroboration Reaction
journal, August 2011
- Zhu, Yinghuai; Jang, Shi Hui Agnes; Tham, Yue Hao
- Organometallics, Vol. 31, Issue 7
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts
journal, April 2010
- Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli
- Nature Chemistry, Vol. 2, Issue 6
The Promotional Effect of Gold in Catalysis by Palladium-Gold
journal, October 2005
- Chen, M.
- Science, Vol. 310, Issue 5746
Atomic Ensemble and Electronic Effects in Ag-Rich AgPd Nanoalloy Catalysts for Oxygen Reduction in Alkaline Media
journal, May 2012
- Slanac, Daniel A.; Hardin, William G.; Johnston, Keith P.
- Journal of the American Chemical Society, Vol. 134, Issue 23
Nanoscale-Phase-Separated Pd–Rh Boxes Synthesized via Metal Migration: An Archetype for Studying Lattice Strain and Composition Effects in Electrocatalysis
journal, September 2013
- Sneed, Brian T.; Brodsky, Casey N.; Kuo, Chun-Hong
- Journal of the American Chemical Society, Vol. 135, Issue 39
Noble metal alloy complex nanostructures: controllable synthesis and their electrochemical property
journal, January 2015
- Liu, Hui-ling; Nosheen, Farhat; Wang, Xun
- Chemical Society Reviews, Vol. 44, Issue 10
Composition-Dependent Electrocatalytic Activity of Palladium–Iridium Binary Alloy Nanoparticles Supported on the Multiwalled Carbon Nanotubes for the Electro-Oxidation of Formic Acid
journal, July 2015
- Bao, Jianming; Dou, Meiling; Liu, Haijing
- ACS Applied Materials & Interfaces, Vol. 7, Issue 28
Bimetallic nickel-iridium nanocatalysts for hydrogen generation by decomposition of hydrous hydrazine
journal, January 2010
- Singh, Sanjay Kumar; Xu, Qiang
- Chemical Communications, Vol. 46, Issue 35
A solvent evaporation plus hydrogen reduction method to synthesize IrNi/C catalysts for hydrogen oxidation
journal, January 2014
- Zhang, Weiwei; Li, Li; Ding, Wei
- J. Mater. Chem. A, Vol. 2, Issue 26
Microwave Synthesis of Classically Immiscible Rhodium–Silver and Rhodium–Gold Alloy Nanoparticles: Highly Active Hydrogenation Catalysts
journal, November 2014
- García, Stephany; Zhang, Liang; Piburn, Graham W.
- ACS Nano, Vol. 8, Issue 11
Microwave-Assisted Synthesis of Pd x Au 100– x Alloy Nanoparticles: A Combined Experimental and Theoretical Assessment of Synthetic and Compositional Effects upon Catalytic Reactivity
journal, June 2016
- Kunal, Pranaw; Li, Hao; Dewing, Beth L.
- ACS Catalysis, Vol. 6, Issue 8
Oxygen Reduction Reaction on Classically Immiscible Bimetallics: A Case Study of RhAu
journal, January 2018
- Li, Hao; Luo, Long; Kunal, Pranaw
- The Journal of Physical Chemistry C, Vol. 122, Issue 5
Microwaves in organic synthesis. Thermal and non-thermal microwave effects
journal, January 2005
- de la Hoz, Antonio; Díaz-Ortiz, Ángel; Moreno, Andrés
- Chem. Soc. Rev., Vol. 34, Issue 2
Synthesis of Inorganic Solids Using Microwaves
journal, April 1999
- Rao, K. J.; Vaidhyanathan, B.; Ganguli, M.
- Chemistry of Materials, Vol. 11, Issue 4, p. 882-895
Microwave-Assisted Synthesis of Colloidal Inorganic Nanocrystals
journal, November 2011
- Baghbanzadeh, Mostafa; Carbone, Luigi; Cozzoli, P. Davide
- Angewandte Chemie International Edition, Vol. 50, Issue 48
In Situ Observation of Nonequilibrium Local Heating as an Origin of Special Effect of Microwave on Chemistry
journal, April 2010
- Tsukahara, Yasunori; Higashi, Ayano; Yamauchi, Tomohisa
- The Journal of Physical Chemistry C, Vol. 114, Issue 19
Beneficial Effects of Microwave-Assisted Heating versus Conventional Heating in Noble Metal Nanoparticle Synthesis
journal, October 2012
- Dahal, Naween; García, Stephany; Zhou, Jiping
- ACS Nano, Vol. 6, Issue 11
Epitaxial Growth of Heterogeneous Metal Nanocrystals: From Gold Nano-octahedra to Palladium and Silver Nanocubes
journal, June 2008
- Fan, Feng-Ru; Liu, De-Yu; Wu, Yuan-Fei
- Journal of the American Chemical Society, Vol. 130, Issue 22
Silver Chloride as a Heterogeneous Nucleant for the Growth of Silver Nanowires
journal, April 2013
- Schuette, Waynie M.; Buhro, William E.
- ACS Nano, Vol. 7, Issue 5
25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well-Controlled Properties
journal, September 2013
- Xia, Xiaohu; Wang, Yi; Ruditskiy, Aleksey
- Advanced Materials, Vol. 25, Issue 44
Transition Metal Nanocluster Formation Kinetic and Mechanistic Studies. A New Mechanism When Hydrogen Is the Reductant: Slow, Continuous Nucleation and Fast Autocatalytic Surface Growth
journal, October 1997
- Watzky, Murielle A.; Finke, Richard G.
- Journal of the American Chemical Society, Vol. 119, Issue 43
Nanocluster Size-Control and “Magic Number” Investigations. Experimental Tests of the “Living-Metal Polymer” Concept and of Mechanism-Based Size-Control Predictions Leading to the Syntheses of Iridium(0) Nanoclusters Centering about Four Sequential Magic Numbers †
journal, December 1997
- Watzky, Murielle A.; Finke, Richard G.
- Chemistry of Materials, Vol. 9, Issue 12
Transition-Metal Nanocluster Size vs Formation Time and the Catalytically Effective Nucleus Number: A Mechanism-Based Treatment
journal, September 2008
- Watzky, Murielle A.; Finney, Eric E.; Finke, Richard G.
- Journal of the American Chemical Society, Vol. 130, Issue 36
Shape Control of Colloidal Metal Nanocrystals
journal, March 2008
- Tao, Andrea R.; Habas, Susan; Yang, Peidong
- Small, Vol. 4, Issue 3
Thermal decomposition behaviors of PVP coated on platinum nanoparticles
journal, January 2005
- Du, Y. K.; Yang, P.; Mou, Z. G.
- Journal of Applied Polymer Science, Vol. 99, Issue 1
Dehydrogenation Selectivity of Ethanol on Close-Packed Transition Metal Surfaces: A Computational Study of Monometallic, Pd/Au, and Rh/Au Catalysts
journal, December 2017
- Li, Hao; Henkelman, Graeme
- The Journal of Physical Chemistry C, Vol. 121, Issue 49
Tunability of the Adsorbate Binding on Bimetallic Alloy Nanoparticles for the Optimization of Catalytic Hydrogenation
journal, April 2017
- Luo, Long; Duan, Zhiyao; Li, Hao
- Journal of the American Chemical Society, Vol. 139, Issue 15
Crotonaldehyde hydrogenation by gold supported on TiO2: structure sensitivity and mechanism
journal, April 2004
- Zanella, R.
- Journal of Catalysis, Vol. 223, Issue 2
Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity
journal, February 2016
- Freakley, S. J.; He, Q.; Harrhy, J. H.
- Science, Vol. 351, Issue 6276
Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts
journal, September 2016
- Matsubu, John C.; Zhang, Shuyi; DeRita, Leo
- Nature Chemistry, Vol. 9, Issue 2
Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction
journal, August 2017
- Li, Siwei; Xu, Yao; Chen, Yifu
- Angewandte Chemie International Edition, Vol. 56, Issue 36
In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co 3 O 4 Interface
journal, September 2016
- Kennedy, Griffin; Melaet, Gérôme; Han, Hui-Ling
- ACS Catalysis, Vol. 6, Issue 10
Hard Templating Pathways for the Synthesis of Nanostructured Porous Co 3 O 4
journal, February 2007
- Rumplecker, Anja; Kleitz, Freddy; Salabas, Elena-Lorena
- Chemistry of Materials, Vol. 19, Issue 3
Adsorption of Gases in Multimolecular Layers
journal, February 1938
- Brunauer, Stephen; Emmett, P. H.; Teller, Edward
- Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms
journal, January 1951
- Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.
- Journal of the American Chemical Society, Vol. 73, Issue 1
Crotonaldehyde hydrogenation on Ir supported catalysts
journal, December 2000
- Reyes, P.; Aguirre, M. C.; Pecchi, G.
- Journal of Molecular Catalysis A: Chemical, Vol. 164, Issue 1-2
High surface area mesoporous Co3O4 from a direct soft template route
journal, January 2012
- Dahal, Naween; Ibarra, Ilich A.; Humphrey, Simon M.
- Journal of Materials Chemistry, Vol. 22, Issue 25
Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998
- Zhao, Dongyuan; Feng, Jianglin; Huo, Qisheng
- Science, Vol. 279, Issue 5350, p. 548-552
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Works referencing / citing this record:
Synthesis, Characterization and Antifungal Activity of Fe(III) Metal–Organic Framework and its Nano-composite
journal, November 2019
- Tella, Adedibu C.; Okoro, Hussein K.; Sokoya, Samuel O.
- Chemistry Africa, Vol. 3, Issue 1
Single-atom Fe and N co-doped graphene for lithium-sulfur batteries: a density functional theory study
journal, July 2019
- Zeng, Qing-Wen; Hu, Ri-Ming; Chen, Zhi-Bin
- Materials Research Express, Vol. 6, Issue 9
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.