Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging
Abstract
Compared with their monometallic counterparts, bimetallic nanoparticles often show enhanced catalytic activity associated with the bimetallic interface. Direct quantitation of catalytic activity at the bimetallic interface is important for understanding the enhancement mechanism, but challenging experimentally. Here using single-molecule super-resolution catalysis imaging in correlation with electron microscopy, we report the first quantitative visualization of enhanced bimetallic activity within single bimetallic nanoparticles. We focus on heteronuclear bimetallic PdAu nanoparticles that present a well-defined Pd–Au bimetallic interface in catalyzing a photodriven fluorogenic disproportionation reaction. Our approach also enables a direct comparison between the bimetallic and monometallic regions within the same nanoparticle. Theoretical calculations further provide insights into the electronic nature of N–O bond activation of the reactant (resazurin) adsorbed on bimetallic sites. Subparticle activity correlation between bimetallic enhancement and monometallic activity suggests that the favorable locations to construct bimetallic sites are those monometallic sites with higher activity, leading to a strategy for making effective bimetallic nanocatalysts. The results highlight the power of super-resolution catalysis imaging in gaining insights that could help improve nanocatalysts.
- Authors:
-
- Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
- Publication Date:
- Research Org.:
- Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1406929
- Alternate Identifier(s):
- OSTI ID: 1417631; OSTI ID: 1507709
- Grant/Contract Number:
- SC0001057; SC0004911
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 3 Journal Issue: 11; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chen, Guanqun, Zou, Ningmu, Chen, Bo, Sambur, Justin B., Choudhary, Eric, and Chen, Peng. Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging. United States: N. p., 2017.
Web. doi:10.1021/acscentsci.7b00377.
Chen, Guanqun, Zou, Ningmu, Chen, Bo, Sambur, Justin B., Choudhary, Eric, & Chen, Peng. Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging. United States. https://doi.org/10.1021/acscentsci.7b00377
Chen, Guanqun, Zou, Ningmu, Chen, Bo, Sambur, Justin B., Choudhary, Eric, and Chen, Peng. Wed .
"Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging". United States. https://doi.org/10.1021/acscentsci.7b00377.
@article{osti_1406929,
title = {Bimetallic Effect of Single Nanocatalysts Visualized by Super-Resolution Catalysis Imaging},
author = {Chen, Guanqun and Zou, Ningmu and Chen, Bo and Sambur, Justin B. and Choudhary, Eric and Chen, Peng},
abstractNote = {Compared with their monometallic counterparts, bimetallic nanoparticles often show enhanced catalytic activity associated with the bimetallic interface. Direct quantitation of catalytic activity at the bimetallic interface is important for understanding the enhancement mechanism, but challenging experimentally. Here using single-molecule super-resolution catalysis imaging in correlation with electron microscopy, we report the first quantitative visualization of enhanced bimetallic activity within single bimetallic nanoparticles. We focus on heteronuclear bimetallic PdAu nanoparticles that present a well-defined Pd–Au bimetallic interface in catalyzing a photodriven fluorogenic disproportionation reaction. Our approach also enables a direct comparison between the bimetallic and monometallic regions within the same nanoparticle. Theoretical calculations further provide insights into the electronic nature of N–O bond activation of the reactant (resazurin) adsorbed on bimetallic sites. Subparticle activity correlation between bimetallic enhancement and monometallic activity suggests that the favorable locations to construct bimetallic sites are those monometallic sites with higher activity, leading to a strategy for making effective bimetallic nanocatalysts. The results highlight the power of super-resolution catalysis imaging in gaining insights that could help improve nanocatalysts.},
doi = {10.1021/acscentsci.7b00377},
journal = {ACS Central Science},
number = 11,
volume = 3,
place = {United States},
year = {Wed Nov 01 00:00:00 EDT 2017},
month = {Wed Nov 01 00:00:00 EDT 2017}
}
https://doi.org/10.1021/acscentsci.7b00377
Web of Science
Works referenced in this record:
Ligand effects in heterogeneous catalysis and electrochemistry
journal, May 2007
- Bligaard, T.; Nørskov, J. K.
- Electrochimica Acta, Vol. 52, Issue 18
Site-Specific Growth of Au–Pd Alloy Horns on Au Nanorods: A Platform for Highly Sensitive Monitoring of Catalytic Reactions by Surface Enhancement Raman Spectroscopy
journal, May 2013
- Huang, Jianfeng; Zhu, Yihan; Lin, Ming
- Journal of the American Chemical Society, Vol. 135, Issue 23
Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution
journal, November 2016
- Zhong, Jin-Hui; Jin, Xi; Meng, Lingyan
- Nature Nanotechnology, Vol. 12, Issue 2
Geometry-Assisted Three-Dimensional Superlocalization Imaging of Single-Molecule Catalysis on Modular Multilayer Nanocatalysts
journal, September 2014
- Han, Rui; Ha, Ji Won; Xiao, Chaoxian
- Angewandte Chemie International Edition, Vol. 53, Issue 47
Implementation of laser induced fluorescence in a pulse radiolysis experiment – a new way to analyze resazurin-like reduction mechanisms
journal, January 2014
- Balcerzyk, A.; Baldacchino, G.
- The Analyst, Vol. 139, Issue 7
Bimetallic Nanocrystals: Syntheses, Properties, and Applications
journal, July 2016
- Gilroy, Kyle D.; Ruditskiy, Aleksey; Peng, Hsin-Chieh
- Chemical Reviews, Vol. 116, Issue 18
Optical Super-Resolution Imaging of Surface Reactions
journal, March 2017
- Chen, Tao; Dong, Bin; Chen, Kuangcai
- Chemical Reviews, Vol. 117, Issue 11
Quantitative super-resolution imaging uncovers reactivity patterns on single nanocatalysts
journal, February 2012
- Zhou, Xiaochun; Andoy, Nesha May; Liu, Guokun
- Nature Nanotechnology, Vol. 7, Issue 4
Evidence for Crystal-Face-Dependent TiO 2 Photocatalysis from Single-Molecule Imaging and Kinetic Analysis
journal, May 2011
- Tachikawa, Takashi; Yamashita, Soichiro; Majima, Tetsuro
- Journal of the American Chemical Society, Vol. 133, Issue 18
Platonic Gold Nanocrystals
journal, July 2004
- Kim, Franklin; Connor, Stephen; Song, Hyunjoon
- Angewandte Chemie International Edition, Vol. 43, Issue 28
Catalysis on singly dispersed bimetallic sites
journal, August 2015
- Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia
- Nature Communications, Vol. 6, Issue 1
Super-Resolution Mapping of Photogenerated Electron and Hole Separation in Single Metal–Semiconductor Nanocatalysts
journal, January 2014
- Ha, Ji Won; Ruberu, T. Purnima A.; Han, Rui
- Journal of the American Chemical Society, Vol. 136, Issue 4
Sub-particle reaction and photocurrent mapping to optimize catalyst-modified photoanodes
journal, February 2016
- Sambur, Justin B.; Chen, Tai-Yen; Choudhary, Eric
- Nature, Vol. 530, Issue 7588
Copper nanoparticle heterogeneous catalytic ‘click’ cycloaddition confirmed by single-molecule spectroscopy
journal, August 2014
- Decan, Matthew R.; Impellizzeri, Stefania; Marin, M. Luisa
- Nature Communications, Vol. 5, Issue 1
Bifunctional Ag@Pd-Ag Nanocubes for Highly Sensitive Monitoring of Catalytic Reactions by Surface-Enhanced Raman Spectroscopy
journal, May 2015
- Li, Jumei; Liu, Jingyue; Yang, Yin
- Journal of the American Chemical Society, Vol. 137, Issue 22
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
Defining Rules for the Shape Evolution of Gold Nanoparticles
journal, August 2012
- Langille, Mark R.; Personick, Michelle L.; Zhang, Jian
- Journal of the American Chemical Society, Vol. 134, Issue 35
Catalytically highly active top gold atom on palladium nanocluster
journal, October 2011
- Zhang, Haijun; Watanabe, Tatsuya; Okumura, Mitsutaka
- Nature Materials, Vol. 11, Issue 1
Single-Molecule Catalysis Mapping Quantifies Site-Specific Activity and Uncovers Radial Activity Gradient on Single 2D Nanocrystals
journal, January 2013
- Andoy, Nesha May; Zhou, Xiaochun; Choudhary, Eric
- Journal of the American Chemical Society, Vol. 135, Issue 5
The Promotional Effect of Gold in Catalysis by Palladium-Gold
journal, October 2005
- Chen, M.
- Science, Vol. 310, Issue 5746
Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting
journal, February 2006
- Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-i, Hiroshi
- Nature, Vol. 439, Issue 7076
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993
- Dronskowski, Richard; Bloechl, Peter E.
- The Journal of Physical Chemistry, Vol. 97, Issue 33
In Situ Single-Nanoparticle Spectroscopy Study of Bimetallic Nanostructure Formation
journal, July 2016
- Smith, Jeremy G.; Chakraborty, Indranath; Jain, Prashant K.
- Angewandte Chemie International Edition, Vol. 55, Issue 34
A chemical and theoretical way to look at bonding on surfaces
journal, July 1988
- Hoffmann, Roald
- Reviews of Modern Physics, Vol. 60, Issue 3
Single-Molecule Electrocatalysis by Single-Walled Carbon Nanotubes
journal, December 2009
- Xu, Weilin; Shen, Hao; Kim, Yoon Ji
- Nano Letters, Vol. 9, Issue 12
The Excited-State Interaction of Resazurin and Resorufin with Aminesin Aqueous Solutions. Photophysics and Photochemical Reaction¶
journal, October 2002
- Bueno, C.; Villegas, M. L.; Bertolotti, S. G.
- Photochemistry and Photobiology, Vol. 76, Issue 4
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles
journal, September 2014
- Kim, Dohyung; Resasco, Joaquin; Yu, Yi
- Nature Communications, Vol. 5, Issue 1
Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics
journal, November 2008
- Xu, Weilin; Kong, Jason S.; Yeh, Yun-Ting E.
- Nature Materials, Vol. 7, Issue 12
Density functional theory in surface chemistry and catalysis
journal, January 2011
- Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
Interfacial Effects in Iron-Nickel Hydroxide-Platinum Nanoparticles Enhance Catalytic Oxidation
journal, May 2014
- Chen, G.; Zhao, Y.; Fu, G.
- Science, Vol. 344, Issue 6183
Podlike N-Doped Carbon Nanotubes Encapsulating FeNi Alloy Nanoparticles: High-Performance Counter Electrode Materials for Dye-Sensitized Solar Cells
journal, May 2014
- Zheng, Xiaojia; Deng, Jiao; Wang, Nan
- Angewandte Chemie International Edition, Vol. 53, Issue 27
Single-Particle Study of Pt-Modified Au Nanorods for Plasmon-Enhanced Hydrogen Generation in Visible to Near-Infrared Region
journal, May 2014
- Zheng, Zhaoke; Tachikawa, Takashi; Majima, Tetsuro
- Journal of the American Chemical Society, Vol. 136, Issue 19
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014
- Guo, X.; Fang, G.; Li, G.
- Science, Vol. 344, Issue 6184
Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012
- Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
- Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
The Role of Atomic Ensembles in the Reactivity of Bimetallic Electrocatalysts
journal, September 2001
- Maroun, F.
- Science, Vol. 293, Issue 5536
High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles
journal, December 2014
- Ristanović, Zoran; Kerssens, Marleen M.; Kubarev, Alexey V.
- Angewandte Chemie International Edition, Vol. 54, Issue 6
Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity
journal, July 2015
- Zhang, Yuwei; Lucas, J. Matthew; Song, Ping
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 29
Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions
journal, November 2013
- Cordes, Thorben; Blum, Suzanne A.
- Nature Chemistry, Vol. 5, Issue 12
One-Pot, High-Yield Synthesis of 5-Fold Twinned Pd Nanowires and Nanorods
journal, April 2009
- Huang, Xiaoqing; Zheng, Nanfeng
- Journal of the American Chemical Society, Vol. 131, Issue 13, p. 4602-4603