Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Overcoming immiscibility toward bimetallic catalyst library

Abstract

Bimetallics are emerging as important materials that often exhibit distinct chemical properties from monometallics. However, there is limited access to homogeneously alloyed bimetallics because of the thermodynamic immiscibility of the constituent elements. Overcoming the inherent immiscibility in bimetallic systems would create a bimetallic library with unique properties. Here, we present a nonequilibrium synthesis strategy to address the immiscibility challenge in bimetallics. As a proof of concept, we synthesize a broad range of homogeneously alloyed Cu-based bimetallic nanoparticles regardless of the thermodynamic immiscibility. The nonequilibrated bimetallic nanoparticles are further investigated as electrocatalysts for carbon monoxide reduction at commercially relevant current densities (>100 mA cm-2), in which Cu0.9Ni0.1shows the highest multicarbon product Faradaic efficiency of ~76% with a current density of ~93 mA cm-2. The ability to overcome thermodynamic immiscibility in multimetallic synthesis offers freedom to design and synthesize new functional nanomaterials with desired chemical compositions and catalytic properties.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Maryland, College Park, MD (United States)
  2. Univ. of Delaware, Newark, DE (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Univ. of Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1619249
Report Number(s):
BNL-215928-2020-JAAM
Journal ID: ISSN 2375-2548
Grant/Contract Number:  
SC0012704; CBET-1803200; ACI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 6; Journal Issue: 17; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Yang, Chunpeng, Ko, Byung Hee, Hwang, Sooyeon, Liu, Zhenyu, Yao, Yonggang, Luc, Wesley, Cui, Mingjin, Malkani, Arnav S., Li, Tangyuan, Wang, Xizheng, Dai, Jiaqi, Xu, Bingjun, Wang, Guofeng, Su, Dong, Jiao, Feng, and Hu, Liangbing. Overcoming immiscibility toward bimetallic catalyst library. United States: N. p., 2020. Web. doi:10.1126/sciadv.aaz6844.
Copy to clipboard
Yang, Chunpeng, Ko, Byung Hee, Hwang, Sooyeon, Liu, Zhenyu, Yao, Yonggang, Luc, Wesley, Cui, Mingjin, Malkani, Arnav S., Li, Tangyuan, Wang, Xizheng, Dai, Jiaqi, Xu, Bingjun, Wang, Guofeng, Su, Dong, Jiao, Feng, & Hu, Liangbing. Overcoming immiscibility toward bimetallic catalyst library. United States. https://doi.org/10.1126/sciadv.aaz6844
Copy to clipboard
Yang, Chunpeng, Ko, Byung Hee, Hwang, Sooyeon, Liu, Zhenyu, Yao, Yonggang, Luc, Wesley, Cui, Mingjin, Malkani, Arnav S., Li, Tangyuan, Wang, Xizheng, Dai, Jiaqi, Xu, Bingjun, Wang, Guofeng, Su, Dong, Jiao, Feng, and Hu, Liangbing. Sun . "Overcoming immiscibility toward bimetallic catalyst library". United States. https://doi.org/10.1126/sciadv.aaz6844. https://www.osti.gov/servlets/purl/1619249.
Copy to clipboard
@article{osti_1619249,
title = {Overcoming immiscibility toward bimetallic catalyst library},
author = {Yang, Chunpeng and Ko, Byung Hee and Hwang, Sooyeon and Liu, Zhenyu and Yao, Yonggang and Luc, Wesley and Cui, Mingjin and Malkani, Arnav S. and Li, Tangyuan and Wang, Xizheng and Dai, Jiaqi and Xu, Bingjun and Wang, Guofeng and Su, Dong and Jiao, Feng and Hu, Liangbing},
abstractNote = {Bimetallics are emerging as important materials that often exhibit distinct chemical properties from monometallics. However, there is limited access to homogeneously alloyed bimetallics because of the thermodynamic immiscibility of the constituent elements. Overcoming the inherent immiscibility in bimetallic systems would create a bimetallic library with unique properties. Here, we present a nonequilibrium synthesis strategy to address the immiscibility challenge in bimetallics. As a proof of concept, we synthesize a broad range of homogeneously alloyed Cu-based bimetallic nanoparticles regardless of the thermodynamic immiscibility. The nonequilibrated bimetallic nanoparticles are further investigated as electrocatalysts for carbon monoxide reduction at commercially relevant current densities (>100 mA cm-2), in which Cu0.9Ni0.1shows the highest multicarbon product Faradaic efficiency of ~76% with a current density of ~93 mA cm-2. The ability to overcome thermodynamic immiscibility in multimetallic synthesis offers freedom to design and synthesize new functional nanomaterials with desired chemical compositions and catalytic properties.},
doi = {10.1126/sciadv.aaz6844},
journal = {Science Advances},
number = 17,
volume = 6,
place = {United States},
year = {Sun Apr 26 00:00:00 EDT 2020},
month = {Sun Apr 26 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1126/sciadv.aaz6844
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Synthesis of bimetallic nanoparticles via conventional and non-equilibrium methods. Via conventional bimetallic synthesis methods, only readily miscible metals (shown in green) can mix with Cu while others (shown in red) form phase-segregated structures (such as core-shell). In contrast, via the non-equilibrium synthesis, Cu and other metals (X) canmore » be kinetically trapped in homogeneously mixed nanoparticles, regardless of their thermodynamic miscibility. The miscibility of Cu and X indicated in the left panel is drawn according to the binary phase diagrams with the composition of Cu0.9X0.1 (15).« less
All figures and tables (48 total)
Save / Share:
Export Metadata
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:

Bimetallic Nanocrystals: Syntheses, Properties, and Applications
journal, July 2016

Bimetallic Nanocrystals: Liquid-Phase Synthesis and Catalytic Applications
journal, January 2011

Biphasic Pd−Au Alloy Catalyst for Low-Temperature CO Oxidation
journal, August 2010

  • Xu, Jing; White, Tim; Li, Ping
  • Journal of the American Chemical Society, Vol. 132, Issue 30
  • DOI: 10.1021/ja102617r

Design of a Surface Alloy Catalyst for Steam Reforming
journal, March 1998

Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires
journal, June 2017

Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging
journal, November 2017

Synthesis of ultrasmall, homogeneously alloyed, bimetallic nanoparticles on silica supports
journal, November 2017

Selectivity Effects in Bimetallic Catalysis
journal, February 2016

Designing bimetallic catalysts for a green and sustainable future
journal, January 2012

  • Sankar, Meenakshisundaram; Dimitratos, Nikolaos; Miedziak, Peter J.
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35296f

Room Temperature Synthesis of Thermally Immiscible Ag−Ni Nanoalloys
journal, January 2009

  • Zhang, Zhenyuan; Nenoff, Tina M.; Huang, Jian Yu
  • The Journal of Physical Chemistry C, Vol. 113, Issue 4
  • DOI: 10.1021/jp8098413

Generation of mixed metallic nanoparticles from immiscible metals by spark discharge
journal, February 2009

  • Tabrizi, N. S.; Xu, Q.; van der Pers, N. M.
  • Journal of Nanoparticle Research, Vol. 12, Issue 1
  • DOI: 10.1007/s11051-009-9603-4

Laser synthesized nanoparticle alloys of metals with bulk miscibility gaps
journal, August 2018

  • Kane, Kenneth A.; Reber, Arthur C.; Khanna, Shiv N.
  • Progress in Natural Science: Materials International, Vol. 28, Issue 4
  • DOI: 10.1016/j.pnsc.2018.05.001

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
  • DOI: 10.1021/cr040090g

Electrochemical CO 2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity
journal, October 2017

  • Clark, Ezra L.; Hahn, Christopher; Jaramillo, Thomas F.
  • Journal of the American Chemical Society, Vol. 139, Issue 44
  • DOI: 10.1021/jacs.7b08607

Kinetic phases of Ag–Cu alloy films are accessible through photodeposition
journal, January 2019

  • Dettelbach, Kevan E.; He, Jingfu; Johnson, Noah J. J.
  • Journal of Materials Chemistry A, Vol. 7, Issue 2
  • DOI: 10.1039/C8TA10138H

Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model
journal, June 2018

  • Osowiecki, Wojciech T.; Ye, Xingchen; Satish, Pratima
  • Journal of the American Chemical Society, Vol. 140, Issue 27
  • DOI: 10.1021/jacs.8b04558

Global optimization of bimetallic cluster structures. I. Size-mismatched Ag–Cu, Ag–Ni, and Au–Cu systems
journal, May 2005

  • Rapallo, Arnaldo; Rossi, Giulia; Ferrando, Riccardo
  • The Journal of Chemical Physics, Vol. 122, Issue 19
  • DOI: 10.1063/1.1898223

A one-pot route to the synthesis of alloyed Cu/Ag bimetallic nanoparticles with different mass ratios for catalytic reduction of 4-nitrophenol
journal, January 2015

  • Wu, Wei; Lei, Mei; Yang, Shuanglei
  • Journal of Materials Chemistry A, Vol. 3, Issue 7
  • DOI: 10.1039/C4TA06567K

Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO
journal, October 2013

  • Zhu, Wenlei; Michalsky, Ronald; Metin, Önder
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409445p

A selective and efficient electrocatalyst for carbon dioxide reduction
journal, January 2014

  • Lu, Qi; Rosen, Jonathan; Zhou, Yang
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4242

High-rate electroreduction of carbon monoxide to multi-carbon products
journal, August 2018

Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate
journal, April 2019

Carbon Monoxide Gas Diffusion Electrolysis that Produces Concentrated C2 Products with High Single-Pass Conversion
journal, January 2019

Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide
journal, October 2018

Copper adparticle enabled selective electrosynthesis of n-propanol
journal, November 2018

Electrochemical Reduction of Carbon Monoxide to Hydrocarbons at Various Metal Electrodes in Aqueous Solution
journal, August 1987

  • Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
  • Chemistry Letters, Vol. 16, Issue 8
  • DOI: 10.1246/cl.1987.1665

How π back-donation quantitatively controls the CO stretching response in classical and non-classical metal carbonyl complexes
journal, January 2016

  • Bistoni, Giovanni; Rampino, Sergio; Scafuri, Nicola
  • Chemical Science, Vol. 7, Issue 2
  • DOI: 10.1039/C5SC02971F

Ligand effects in heterogeneous catalysis and electrochemistry
journal, May 2007

Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns
journal, December 2016

  • Ma, Sichao; Sadakiyo, Masaaki; Heima, Minako
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10740

Ultra-fast self-assembly and stabilization of reactive nanoparticles in reduced graphene oxide films
journal, August 2016

  • Chen, Yanan; Egan, Garth C.; Wan, Jiayu
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12332

The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold
journal, March 2017

  • Dunwell, Marco; Lu, Qi; Heyes, Jeffrey M.
  • Journal of the American Chemical Society, Vol. 139, Issue 10
  • DOI: 10.1021/jacs.6b13287

Monte Carlo simulations of segregation in Pt-Ni catalyst nanoparticles
journal, January 2005

  • Wang, Guofeng; Van Hove, M. A.; Ross, P. N.
  • The Journal of Chemical Physics, Vol. 122, Issue 2
  • DOI: 10.1063/1.1828033

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Second nearest-neighbor modified embedded-atom-method potential
journal, October 2000

Atomistic modeling of the Cu–Zr–Ag bulk metallic glass system
journal, October 2009

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    Fig. 1 (p. 5)figure
    Fig. 2 (p. 6)figure
    Fig. 3 (p. 8)figure
    Fig. 4 (p. 10)figure
    Fig. S1 (p. 21)figure
    Fig. S2 (p. 22)figure
    Fig. S3 (p. 23)figure
    Fig. S4 (p. 23)figure
    Fig. S5 (p. 24)figure
    Fig. S6 (p. 25)figure
    Fig. S7 (p. 26)figure
    Fig. S8 (p. 26)figure
    Fig. S10 (p. 27)figure
    Fig. S9 (p. 27)figure
    Fig. S11 (p. 28)figure
    Fig. S12 (p. 28)figure
    Fig. S13 (p. 28)figure
    Fig. S14 (p. 29)figure
    Fig. S15 (p. 30)figure
    Fig. S16 (p. 31)figure
    Fig. S17 (p. 32)figure
    Fig. S18 (p. 32)figure
    Fig. S19 (p. 33)figure
    Fig. 21 (p. 34)figure
    Fig. S20 (p. 34)figure
    Fig. S22 (p. 35)figure
    Fig. S23 (p. 36)figure
    Fig. S24 (p. 36)figure
    Fig. S25 (p. 37)figure
    Fig. S26 (p. 38)figure
    Fig. S28 (p. 39)figure
    Fig. S29 (p. 39)figure
    Fig. S30 (p. 40)figure
    Fig. S31 (p. 40)figure
    Fig. S32 (p. 41)figure
    Fig. S33 (p. 42)figure
    Fig. S34 (p. 42)figure
    Fig. S35 (p. 43)figure
    Fig. S36 (p. 44)figure
    Fig. S37 (p. 44)figure
    Fig. S38 (p. 45)figure
    Fig. S39 (p. 45)figure
    Fig. S40 (p. 45)figure
    Table S1 (p. 46)table
    Table S2 (p. 47)table
    Table S3 (p. 48)table
    Table S4 (p. 49)table
    Table S5 (p. 49)table
      [ × clear filter / sort ]
      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

      Similar Records in DOE PAGES and OSTI.GOV collections: