DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy

Abstract

Graphene liquid cell electron microscopy has the needed temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. Yet, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl3, on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these conclusions with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl3 provides further insight into the liquidmore » cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, enabling new nanoscale materials science experiments to be conducted systematically in a reproducible manner.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1542379
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, and Alivisatos, A. Paul. Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy. United States: N. p., 2019. Web. doi:10.1021/jacs.9b00082.
Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, & Alivisatos, A. Paul. Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy. United States. https://doi.org/10.1021/jacs.9b00082
Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, and Alivisatos, A. Paul. Tue . "Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy". United States. https://doi.org/10.1021/jacs.9b00082. https://www.osti.gov/servlets/purl/1542379.
@article{osti_1542379,
title = {Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy},
author = {Hauwiller, Matthew R. and Ondry, Justin C. and Chan, Cindy M. and Khandekar, Prachi and Yu, Jessica and Alivisatos, A. Paul},
abstractNote = {Graphene liquid cell electron microscopy has the needed temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. Yet, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl3, on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these conclusions with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl3 provides further insight into the liquid cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, enabling new nanoscale materials science experiments to be conducted systematically in a reproducible manner.},
doi = {10.1021/jacs.9b00082},
journal = {Journal of the American Chemical Society},
number = 10,
volume = 141,
place = {United States},
year = {2019},
month = {2}
}

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

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Size effect on the melting temperature of gold particles
journal, June 1976


Dynamics and Removal Pathway of Edge Dislocations in Imperfectly Attached PbTe Nanocrystal Pairs: Toward Design Rules for Oriented Attachment
journal, February 2018

  • Ondry, Justin C.; Hauwiller, Matthew R.; Alivisatos, A. Paul
  • ACS Nano, Vol. 12, Issue 4
  • DOI: 10.1021/acsnano.8b00638

Perspectives on the Physical Chemistry of Semiconductor Nanocrystals
journal, January 1996

  • Alivisatos, A. P.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp9535506

Cancer Cell Imaging and Photothermal Therapy in the Near-Infrared Region by Using Gold Nanorods
journal, February 2006

  • Huang, Xiaohua; El-Sayed, Ivan H.; Qian, Wei
  • Journal of the American Chemical Society, Vol. 128, Issue 6, p. 2115-2120
  • DOI: 10.1021/ja057254a

Gold Nanorod Induced Warming of Embryos from the Cryogenic State Enhances Viability
journal, July 2017


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
  • DOI: 10.1039/C2CS35319A

Tunable Plasmonic Nanoparticles with Catalytically Active High-Index Facets
journal, May 2014

  • Jing, Hao; Zhang, Qingfeng; Large, Nicolas
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl5015734

Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications
journal, January 2010

  • Talapin, Dmitri V.; Lee, Jong-Soo; Kovalenko, Maksym V.
  • Chemical Reviews, Vol. 110, Issue 1
  • DOI: 10.1021/cr900137k

Chemical Synthesis of Novel Plasmonic Nanoparticles
journal, May 2009


Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface
journal, July 2003

  • Williamson, M. J.; Tromp, R. M.; Vereecken, P. M.
  • Nature Materials, Vol. 2, Issue 8
  • DOI: 10.1038/nmat944

In Situ Study of the Growth Kinetics of Individual Island Electrodeposition of Copper
journal, April 2006

  • Radisic, A.; Ross, F. M.; Searson, P. C.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 15
  • DOI: 10.1021/jp057549a

Electron microscopy of specimens in liquid
journal, October 2011

  • de Jonge, Niels; Ross, Frances M.
  • Nature Nanotechnology, Vol. 6, Issue 11, p. 695-704
  • DOI: 10.1038/nnano.2011.161

Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories
journal, June 2009


Opportunities and challenges in liquid cell electron microscopy
journal, December 2015


Exploring the Formation of Symmetric Gold Nanostars by Liquid-Cell Transmission Electron Microscopy
journal, June 2017


Dynamics of Nanoscale Dendrite Formation in Solution Growth Revealed Through in Situ Liquid Cell Electron Microscopy
journal, September 2018


Direct in Situ Determination of the Mechanisms Controlling Nanoparticle Nucleation and Growth
journal, September 2012

  • Woehl, Taylor J.; Evans, James E.; Arslan, Ilke
  • ACS Nano, Vol. 6, Issue 10
  • DOI: 10.1021/nn303371y

Facet development during platinum nanocube growth
journal, August 2014


In situ Study of Oxidative Etching of Palladium Nanocrystals by Liquid Cell Electron Microscopy
journal, June 2014

  • Jiang, Yingying; Zhu, Guomin; Lin, Fang
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl500670q

Single-particle mapping of nonequilibrium nanocrystal transformations
journal, November 2016


Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy
journal, August 2018


Interactions and Attachment Pathways between Functionalized Gold Nanorods
journal, January 2017


High-Resolution EM of Colloidal Nanocrystal Growth Using Graphene Liquid Cells
journal, April 2012


Direction-Specific Interactions Control Crystal Growth by Oriented Attachment
journal, May 2012


Direct Observation of Nanoparticle Superlattice Formation by Using Liquid Cell Transmission Electron Microscopy
journal, February 2012

  • Park, Jungwon; Zheng, Haimei; Lee, Won Chul
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn203837m

Direct Observation of Interactions between Nanoparticles and Nanoparticle Self-Assembly in Solution
journal, May 2017


In situ microscopy of the self-assembly of branched nanocrystals in solution
journal, April 2016

  • Sutter, Eli; Sutter, Peter; Tkachenko, Alexei V.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11213

Nanometer Resolution Elemental Mapping in Graphene-Based TEM Liquid Cells
journal, January 2018


Strategies for Preparing Graphene Liquid Cells for Transmission Electron Microscopy
journal, May 2018


Nanocuvette: A Functional Ultrathin Liquid Container for Transmission Electron Microscopy
journal, February 2017


In Situ Kinetic and Thermodynamic Growth Control of Au–Pd Core–Shell Nanoparticles
journal, August 2018

  • Tan, Shu Fen; Bisht, Geeta; Anand, Utkarsh
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b05217

Developing New Measurement Capabilities with Nanochannel Liquid Phase TEM
journal, August 2018

  • Yesibolati, Murat Nulati; Sun, Hongyu; Canepa, Silvia
  • Microscopy and Microanalysis, Vol. 24, Issue S1
  • DOI: 10.1017/S1431927618001770

New Strategies for Probing Energy Systems with In Situ Liquid-Phase Transmission Electron Microscopy
journal, May 2018


Experimental procedures to mitigate electron beam induced artifacts during in situ fluid imaging of nanomaterials
journal, April 2013


The Use of Graphene and Its Derivatives for Liquid-Phase Transmission Electron Microscopy of Radiation-Sensitive Specimens
journal, December 2016


Radiation-induced synthesis of mono- and multi-metallic clusters and nanocolloids
journal, January 1998

  • Belloni, Jacqueline; Mostafavi, Mehran; Remita, Hynd
  • New Journal of Chemistry, Vol. 22, Issue 11
  • DOI: 10.1039/a801445k

Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation
journal, February 2011


Electron beam induced chemistry of gold nanoparticles in saline solution
journal, January 2015

  • Hermannsdörfer, J.; de Jonge, N.; Verch, A.
  • Chemical Communications, Vol. 51, Issue 91
  • DOI: 10.1039/C5CC06812F

Formation of Au Nanoparticles in Liquid Cell Transmission Electron Microscopy: From a Systematic Study to Engineered Nanostructures
journal, November 2017


Radiolysis of silver ion solutions in ethylene glycol: solvated electron and radical scavenging yields
journal, February 2005


Radiation-induced synthesis of metal nanoparticles in ethers THF and PGMEA
journal, October 2013


Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy
journal, September 2014

  • Schneider, Nicholas M.; Norton, Michael M.; Mendel, Brian J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp507400n

Control of Electron Beam-Induced Au Nanocrystal Growth Kinetics through Solution Chemistry
journal, July 2015


Quantifying the Nucleation and Growth Kinetics of Electron Beam Nanochemistry with Liquid Cell Scanning Transmission Electron Microscopy
journal, October 2018


The Science and Art of Carving Metal Nanocrystals
journal, January 2017


Oxidative etching for controlled synthesis of metal nanocrystals: atomic addition and subtraction
journal, January 2014

  • Long, Ran; Zhou, Shan; Wiley, Benjamin J.
  • Chemical Society Reviews, Vol. 43, Issue 17
  • DOI: 10.1039/C4CS00136B

Shape-Controlled Synthesis of Palladium Single-Crystalline Nanoparticles: The Effect of HCl Oxidative Etching and Facet-Dependent Catalytic Properties
journal, December 2013

  • Zhang, Jinfeng; Feng, Chao; Deng, Yida
  • Chemistry of Materials, Vol. 26, Issue 2
  • DOI: 10.1021/cm403591g

Selectivity on Etching: Creation of High-Energy Facets on Copper Nanocrystals for CO 2 Electrochemical Reduction
journal, March 2016


Using Graphene Liquid Cell Transmission Electron Microscopy to Study in Situ Nanocrystal Etching
journal, January 2018

  • Hauwiller, Matthew R.; Ondry, Justin C.; Alivisatos, A. Paul
  • Journal of Visualized Experiments, Issue 135
  • DOI: 10.3791/57665

Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method
journal, May 2003

  • Nikoobakht, Babak; El-Sayed, Mostafa A.
  • Chemistry of Materials, Vol. 15, Issue 10
  • DOI: 10.1021/cm020732l

Universal Noble Metal Nanoparticle Seeds Realized Through Iterative Reductive Growth and Oxidative Dissolution Reactions
journal, May 2014

  • O’Brien, Matthew N.; Jones, Matthew R.; Brown, Keith A.
  • Journal of the American Chemical Society, Vol. 136, Issue 21
  • DOI: 10.1021/ja503509k

Hydrogen Bonds of gamma-FeOOH.
journal, January 1978


Bubble and Pattern Formation in Liquid Induced by an Electron Beam
journal, December 2013

  • Grogan, Joseph M.; Schneider, Nicholas M.; Ross, Frances M.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl404169a

Standard potentials of half-reactions involving + 1 and + 3 gold in chloride medium
journal, December 1962


Standard electrode potential of Fe3+ + e- = Fe2+ from 5-35.deg.
journal, July 1972

  • Whittemore, Donald O.; Langmuir, Donald
  • Journal of Chemical & Engineering Data, Vol. 17, Issue 3
  • DOI: 10.1021/je60054a002

Photochemical processes for water treatment
journal, March 1993

  • Legrini, O.; Oliveros, E.; Braun, A. M.
  • Chemical Reviews, Vol. 93, Issue 2
  • DOI: 10.1021/cr00018a003

Growth of Au on Pt Icosahedral Nanoparticles Revealed by Low-Dose In Situ TEM
journal, March 2015


A comparison of surface forces and interfacial properties of mica in purified surfactant solutions
journal, February 1981


Molecular layering of water at surfaces and origin of repulsive hydration forces
journal, November 1983

  • Israelachvili, Jacob N.; Pashley, Richard M.
  • Nature, Vol. 306, Issue 5940
  • DOI: 10.1038/306249a0

Imaging Nanobubbles in Water with Scanning Transmission Electron Microscopy
journal, April 2011

  • White, Edward R.; Mecklenburg, Matthew; Singer, Scott B.
  • Applied Physics Express, Vol. 4, Issue 5
  • DOI: 10.1143/APEX.4.055201

Growth dynamics and gas transport mechanism of nanobubbles in graphene liquid cells
journal, February 2015

  • Shin, Dongha; Park, Jong Bo; Kim, Yong-Jin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7068

Distortion in Two-Dimensional Shapes of Merging Nanobubbles: Evidence for Anisotropic Gas Flow Mechanism
journal, September 2016


Observation and Quantification of Nanoscale Processes in Lithium Batteries by Operando Electrochemical (S)TEM
journal, February 2015


The influence of iron on water radiolysis in cement-based materials
journal, August 2010


LXXIII.—Oxidation of tartaric acid in presence of iron
journal, January 1894


Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry
journal, January 2006

  • Pignatello, Joseph J.; Oliveros, Esther; MacKay, Allison
  • Critical Reviews in Environmental Science and Technology, Vol. 36, Issue 1
  • DOI: 10.1080/10643380500326564

Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O in Aqueous Solution
journal, April 1988

  • Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips
  • Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2
  • DOI: 10.1063/1.555805

The photo-Fenton reaction — an effective photochemical wastewater treatment process
journal, June 1993

  • Ruppert, G.; Bauer, R.; Heisler, G.
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 73, Issue 1
  • DOI: 10.1016/1010-6030(93)80035-8

Tailoring Longitudinal Surface Plasmon Wavelengths, Scattering and Absorption Cross Sections of Gold Nanorods
journal, March 2008

  • Ni, Weihai; Kou, Xiaoshan; Yang, Zhi
  • ACS Nano, Vol. 2, Issue 4
  • DOI: 10.1021/nn7003603

Selective etching of gold nanorods by ferric chloride at room temperature
journal, January 2009

  • Zou, Renxian; Guo, Xia; Yang, Jian
  • CrystEngComm, Vol. 11, Issue 12
  • DOI: 10.1039/b911902g

Works referencing / citing this record:

Liquid cell transmission electron microscopy and its applications
journal, January 2020

  • Pu, Shengda; Gong, Chen; Robertson, Alex W.
  • Royal Society Open Science, Vol. 7, Issue 1
  • DOI: 10.1098/rsos.191204

A novel ultrasensitive surface plasmon resonance-based nanosensor for nitrite detection
journal, January 2019

  • Miao, Pandeng; Liu, Zhongdong; Guo, Jun
  • RSC Advances, Vol. 9, Issue 31
  • DOI: 10.1039/c9ra02460c

The radiation chemistry of focused electron-beam induced etching of copper in liquids
journal, January 2019

  • Lami, Sarah K.; Smith, Gabriel; Cao, Eric
  • Nanoscale, Vol. 11, Issue 24
  • DOI: 10.1039/c9nr01857c

In Situ Liquid Cell TEM Studies on Etching and Growth Mechanisms of Gold Nanoparticles at a Solid–Liquid–Gas Interface
journal, August 2019

  • Hutzler, Andreas; Fritsch, Birk; Jank, Michael P. M.
  • Advanced Materials Interfaces, Vol. 6, Issue 20
  • DOI: 10.1002/admi.201901027