skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity

Abstract

For the practical application of nanocatalysts, it is desirable to understand the spatiotemporal fluctuations of nanocatalytic activity at the single-nanoparticle level. Here we use time-lapsed superresolution mapping of single-molecule catalysis events on individual nanoparticles to observe time-varying changes in the spatial distribution of catalysis events on Sb-doped TiO 2 nanorods and Au triangle nanoplates. Compared with the active sites on well-defined surface facets, the defects of the nanoparticle catalysts possess higher intrinsic reactivity but lower stability. Corners and ends are more reactive but also less stable than flat surfaces. Averaged over time, the most stable sites dominate the total apparent activity of single nanocatalysts. However, the active sites with higher intrinsic activity but lower stability show activity at earlier time points before deactivating. Unexpectedly, some active sites are found to recover their activity (“self-healing”) after deactivation, which is probably due to desorption of the adsorbate. Finally, our superresolution measurement of different types of active catalytic sites, over both space and time, leads to a more comprehensive understanding of reactivity patterns and may enable the design of new and more productive heterogeneous catalysts.

Authors:
 [1];  [2];  [1];  [3];  [1];  [1];  [4]
  1. Chinese Academy of Sciences (CAS), Changchun (China). Changchun Inst. of Applied Chemistry, State Key Lab. of Electroanalytical Chemistry; Chinese Academy of Sciences (CAS), Changchun (China). Changchun Inst. of Applied Chemistry, Jilin Province Key Lab. of Low Carbon Chemical Power
  2. Univ. of California, Berkeley, CA (United States). Dept. of Mechanical Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Kavli Energy Nano Science Inst.
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington D.C. (United States). Light-Material Interactions in Energy Conversion (LMI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1370554
Grant/Contract Number:  
SC0001293; AC05-06OR23100
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 29; Related Information: LMI partners with California Institute of Technology (lead); Harvard University; University of Illinois, Urbana-Champaign; Lawrence Berkeley National Laboratory; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
solar (photovoltaic); solid state lighting; phonons; thermal conductivity; electrodes - solar; materials and chemistry by design; optics; synthesis (novel materials); synthesis (self-assembly); single-molecule nanocatalysis; optical superresolution imaging; photocatalysis; surface; restructuring

Citation Formats

Zhang, Yuwei, Lucas, J. Matthew, Song, Ping, Beberwyck, Brandon, Fu, Qiang, Xu, Weilin, and Alivisatos, A. Paul. Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity. United States: N. p., 2015. Web. doi:10.1073/pnas.1502005112.
Zhang, Yuwei, Lucas, J. Matthew, Song, Ping, Beberwyck, Brandon, Fu, Qiang, Xu, Weilin, & Alivisatos, A. Paul. Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity. United States. doi:10.1073/pnas.1502005112.
Zhang, Yuwei, Lucas, J. Matthew, Song, Ping, Beberwyck, Brandon, Fu, Qiang, Xu, Weilin, and Alivisatos, A. Paul. Mon . "Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity". United States. doi:10.1073/pnas.1502005112. https://www.osti.gov/servlets/purl/1370554.
@article{osti_1370554,
title = {Superresolution fluorescence mapping of single-nanoparticle catalysts reveals spatiotemporal variations in surface reactivity},
author = {Zhang, Yuwei and Lucas, J. Matthew and Song, Ping and Beberwyck, Brandon and Fu, Qiang and Xu, Weilin and Alivisatos, A. Paul},
abstractNote = {For the practical application of nanocatalysts, it is desirable to understand the spatiotemporal fluctuations of nanocatalytic activity at the single-nanoparticle level. Here we use time-lapsed superresolution mapping of single-molecule catalysis events on individual nanoparticles to observe time-varying changes in the spatial distribution of catalysis events on Sb-doped TiO2 nanorods and Au triangle nanoplates. Compared with the active sites on well-defined surface facets, the defects of the nanoparticle catalysts possess higher intrinsic reactivity but lower stability. Corners and ends are more reactive but also less stable than flat surfaces. Averaged over time, the most stable sites dominate the total apparent activity of single nanocatalysts. However, the active sites with higher intrinsic activity but lower stability show activity at earlier time points before deactivating. Unexpectedly, some active sites are found to recover their activity (“self-healing”) after deactivation, which is probably due to desorption of the adsorbate. Finally, our superresolution measurement of different types of active catalytic sites, over both space and time, leads to a more comprehensive understanding of reactivity patterns and may enable the design of new and more productive heterogeneous catalysts.},
doi = {10.1073/pnas.1502005112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 29,
volume = 112,
place = {United States},
year = {2015},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Real-Time Single-Molecule Imaging of the Spatial and Temporal Distribution of Reactive Oxygen Species with Fluorescent Probes:  Applications to TiO 2 Photocatalysts
journal, January 2008

  • Naito, Kazuya; Tachikawa, Takashi; Fujitsuka, Mamoru
  • The Journal of Physical Chemistry C, Vol. 112, Issue 4
  • DOI: 10.1021/jp076335l

Monitoring Gold Nanorod Synthesis by Localized Surface Plasmon Resonance
journal, November 2006

  • Gulati, Amneet; Liao, Hongwei; Hafner, Jason H.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 45
  • DOI: 10.1021/jp061269t

Large triangular single crystals formed by mild annealing of self-organized silver nanocrystals
journal, September 2007

  • Courty, A.; Henry, A. -I.; Goubet, N.
  • Nature Materials, Vol. 6, Issue 11
  • DOI: 10.1038/nmat2004

CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions
journal, April 2014


Probing Photocatalytic Active Sites on a Single Titanosilicate Zeolite with a Redox-Responsive Fluorescent Dye
journal, November 2009

  • Tachikawa, Takashi; Yamashita, Soichiro; Majima, Tetsuro
  • Angewandte Chemie International Edition, Vol. 49, Issue 2
  • DOI: 10.1002/anie.200904876

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
  • DOI: 10.1038/nnano.2012.18

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
  • DOI: 10.1021/ja201415j

Platonic Gold Nanocrystals
journal, July 2004

  • Kim, Franklin; Connor, Stephen; Song, Hyunjoon
  • Angewandte Chemie International Edition, Vol. 43, Issue 28
  • DOI: 10.1002/anie.200454216

Oscillatory Kinetics in Heterogeneous Catalysis
journal, May 1995


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
  • DOI: 10.1021/ja409011y

Chemical Imaging of Spatial Heterogeneities in Catalytic Solids at Different Length and Time Scales
journal, June 2009

  • Weckhuysen, Bert M.
  • Angewandte Chemie International Edition, Vol. 48, Issue 27
  • DOI: 10.1002/anie.200900339

Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012

  • Buurmans, Inge L. C.; Weckhuysen, Bert M.
  • Nature Chemistry, Vol. 4, Issue 11
  • DOI: 10.1038/nchem.1478

Single-molecule, single-particle observation of size-dependent photocatalytic activity in Au/TiO2 nanocomposites
journal, January 2011

  • Wang, Nan; Tachikawa, Takashi; Majima, Tetsuro
  • Chemical Science, Vol. 2, Issue 5
  • DOI: 10.1039/c0sc00648c

Structure and Chemical State of the Pt(557) Surface during Hydrogen Oxidation Reaction Studied by in Situ Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy
journal, August 2013

  • Zhu, Zhongwei; Melaet, Gérôme; Axnanda, Stephanus
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja406497s

Effect of growth rate on quartz defects
journal, June 1983


Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles
journal, November 2008


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
  • DOI: 10.1021/ja309948y

Super-Resolution Mapping of Reactive Sites on Titania-Based Nanoparticles with Water-Soluble Fluorogenic Probes
journal, December 2012

  • Tachikawa, Takashi; Yonezawa, Tomoyuki; Majima, Tetsuro
  • ACS Nano, Vol. 7, Issue 1
  • DOI: 10.1021/nn303964v

Probing Redox Photocatalysis of Trapped Electrons and Holes on Single Sb-doped Titania Nanorod Surfaces
journal, February 2012

  • Xu, Weilin; Jain, Prashant K.; Beberwyck, Brandon J.
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja210010k

Observation of a Quadrupole Plasmon Mode for a Colloidal Solution of Gold Nanoprisms
journal, April 2005

  • Millstone, Jill E.; Park, Sungho; Shuford, Kevin L.
  • Journal of the American Chemical Society, Vol. 127, Issue 15
  • DOI: 10.1021/ja043245a

Molecular dynamics studies of brittle fracture in vitreous silica: Review and recent progress
journal, June 2005


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
  • DOI: 10.1038/nature04502

Exploring the Spatial Distribution and Transport Behavior of Charge Carriers in a Single Titania Nanowire
journal, June 2009

  • Tachikawa, Takashi; Majima, Tetsuro
  • Journal of the American Chemical Society, Vol. 131, Issue 24
  • DOI: 10.1021/ja900194m

Oscillatory CO oxidation on Pt(110): Modeling of temporal self‐organization
journal, June 1992

  • Krischer, K.; Eiswirth, M.; Ertl, G.
  • The Journal of Chemical Physics, Vol. 96, Issue 12
  • DOI: 10.1063/1.462226

Sub-diffraction-limit imaging by stochastic optical reconstruction microscopy (STORM)
journal, August 2006

  • Rust, Michael J.; Bates, Mark; Zhuang, Xiaowei
  • Nature Methods, Vol. 3, Issue 10
  • DOI: 10.1038/nmeth929

Halide Anions as Shape-Directing Agents for Obtaining High-Quality Anisotropic Gold Nanostructures
journal, August 2012

  • DuChene, Joseph S.; Niu, Wenxin; Abendroth, John M.
  • Chemistry of Materials, Vol. 25, Issue 8
  • DOI: 10.1021/cm3020397

Super-Resolution Reactivity Mapping of Nanostructured Catalyst Particles
journal, November 2009

  • Roeffaers, Maarten B.  J.; De Cremer, Gert; Libeert, Julien
  • Angewandte Chemie International Edition, Vol. 48, Issue 49
  • DOI: 10.1002/anie.200904944

Coarse Grained Molecular Dynamics Simulation of Nanoconfined Water
journal, February 2013

  • Eslami, Hossein; Jaafari, Bahram; Mehdipour, Nargess
  • ChemPhysChem, Vol. 14, Issue 5
  • DOI: 10.1002/cphc.201200873

Molecular dynamics simulation of the diffusion of nanoconfined fluids
journal, May 2013

  • Mehdipour, Nargess; Mousavian, Neda; Eslami, Hossein
  • Journal of the Iranian Chemical Society, Vol. 11, Issue 1
  • DOI: 10.1007/s13738-013-0274-9

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
  • DOI: 10.1038/nmat2319

Large-Scale Synthesis of TiO 2 Nanorods via Nonhydrolytic Sol−Gel Ester Elimination Reaction and Their Application to Photocatalytic Inactivation of E. c oli
journal, August 2005

  • Joo, Jin; Kwon, Soon Gu; Yu, Taekyung
  • The Journal of Physical Chemistry B, Vol. 109, Issue 32
  • DOI: 10.1021/jp052458z

Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007

  • Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
  • Science, Vol. 317, Issue 5834, p. 100-102
  • DOI: 10.1126/science.1141483

Microfluidic-based measurements of cytochrome P450 enzyme activity of primary mammalian hepatocytes
journal, January 2010

  • Anderson, Keith; Cooper, Jonathan M.; Haswell, Stephen J.
  • The Analyst, Vol. 135, Issue 6
  • DOI: 10.1039/c0an00031k