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doi: 10.1093/jmicro/dfs096
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Review
Abstract
We have compiled our recent in-situ quantitative environmental transmission electron microscopy (ETEM) studies on typical gold nanoparticulate catalysts for the low-temperature oxidation of CO to describe the
issues surrounding the application of ETEM, with a special regard to
catalyst chemistry. Thanks to the recent development of high-resolution
environmental transmission electron microscopes that can work robustly
to accumulate observation data in controlled environments, we can deal
with the electron irradiation effects and heterogeneity of real catalysts.
We established a structural evolution diagram that summarizes the structure of catalysts under electron irradiation as a function of the electron
current density and the electron dose, D. By extrapolating to = 0,
D = 0, we could deduce the intrinsic catalysis structure (without electron
irradiation) in various environments, including reaction environments. By
numerically and statistically analyzing a substantial number of ETEM
images of gold nanoparticles, we established a morphology phase
diagram that summarizes how the majority of gold nanoparticles change
their morphology systematically as a function of the partial pressures of
CO and O2. Similar diagrams will be helpful in elucidating the phenomena
that directly correlate with the catalytic activity determined from ETEM
observations. Using these quantitative analyses, we could analyze Cs-corrected ETEM images of the catalysts. The surfaces of gold nanoparticles
were structurally reconstructed under reaction conditions, via interactions with CO molecules. CO molecules were observed on the surfaces of
catalysts under reaction conditions using high-resolution ETEM. Finally,
we discuss the potential of environmental transmission electron microscopy for quantitative in-situ microscopy at the atomic scale.
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Keywords
TEM,
catalyst,
electron
irradiation,
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Received
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Introduction
Since the invention of the transmission electron
microscope, several branches of transmission electron microscopy (TEM) have nucleated and grown.
Along with the essential branch that has pursued
higher spatial resolution, several pioneers have
created the invaluable branch of TEM that involves
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high-energy electrons transfer their energy and momentum and induce various elemental excitations
in the system, for example the excitation of plasmons and core electrons and the displacement of
atoms (knock-on damage). The cross sections of
electron scattering are different for each type of excitation. Although some excitations thermally relax
instantly, the system gradually undergoes irreversible processes with increases in the electron dose
and never returns to the initial state. In contrast, in
an ordinary catalytic reaction, the energy transfer
between a catalysis specimen and the gas molecules is far smaller than a few electron volt.
Therefore, electron irradiation effects cannot be
ignored in quantitative in-situ microscopy for catalyst chemistry.
The essential experimental quantities to describe
electron irradiation effects are the incident electron
energy, the electron current density and the electron dose D (D = ), where is the irradiation
time. Other important quantities are related to the
specimen and its environment; this includes the
temperature (as far as it is denable), the pressures
of the gases and the orientation of the crystalline
axes of a specimen in relation to an incident electron beam. The rst step toward quantifying the
electron irradiation effects is to systematically
measure a quantity of interest as a function of both
and D. By extrapolating the value at = 0 and
D = 0 using the systematic measurements, it is possible to deduce the intrinsic quantity (without electron irradiation). This extrapolation method can be
used to derive the structural changes produced by
the impact of even a single incident electron [58].
It is known that Au/TiO2 catalysts which are the
most commonly used gold nanoparticulate catalysts
are fragile under TEM observation. The structures
at the interface between the gold nanoparticles and
the TiO2 supports gradually become reorganized as
the observation time or electron dose is increased
[51]. Figure 2 summarizes the structures observed
in Au/TiO2 catalysts using ETEM, in different environments produced as a function of and D. In this
structural evolution diagram [51], gold nanoparticles
with decorations and pillars were observed in the
blue and red regions, respectively. Either gold nanoparticles with pillars or encapsulated gold nanoparticles were observed in the yellow regions. A blue,
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red or yellow triangle indicates the D at which decoration, pillars or encapsulation around a gold
nanoparticle were rst detected at a given current
density. HAADF-STEM, EELS and EDX analyses
conrmed that the decoration, pillar and encapsulation structures consisted of the TiO2 support material [51]. Under vacuum, the TiO2 supports were
heavily damaged and lost oxygen, as shown in the
black region in (a). The loss of oxygen from TiO2
under electron irradiation was measured quantitatively using EELS in combination with an analysis
using the rate theory of point defects [51,59]. In the
green regions of low and low D (Fig. 2), structural
reorganizations were not detected (on the length
scales observable using ETEM, which are limited
by the spatial resolution). By extrapolating the
structure at = 0 and D = 0 using the structure evolution diagram, the intrinsic structure in the
absence of electron irradiation can be deduced for
different environments, including reaction environments. Under reaction conditions, the major {111}
and {100} facets of gold nanoparticles were
exposed, and the particles displayed a polygonal
interface with the TiO2 support that was bounded
by sharp edges parallel to the <110> directions
(Fig. 3). Similar diagrams may be helpful in
deducing intrinsic structures and/or intrinsic phenomena in various chemical reactions that can be
produced in TEMs and ETEMs [51].
It has been suggested that gold nanoparticles
change their morphology in gases [29,31,60], although the results from these studies do not agree.
When and D were maintained in the range indicated in green in a structural evolution diagram
[51], we observed a reversible, environmentdependent change in the morphology of gold nanoparticles, even under electron irradiation. In an Au/
CeO2 catalyst, which is more robust than Au/TiO2
[50], the morphology of gold nanoparticles changed
from faceted to a roundish morphology after the
introduction of O2 gas in vacuum. After removing
the O2 gas, the morphology of the gold nanoparticles reverted to a faceted morphology.
Subsequently, 1 vol% CO/air was introduced under
vacuum. The major {111} and {100} facets appeared
clearly in 1 vol% CO/air. After removing the 1 vol%
CO/air, the morphology of the gold nanoparticles
appeared to be faceted, as in the proceeding observations in vacuum. The same morphology change
was observed in Au/TiO2 using aberration-corrected
ETEM, as shown in Fig. 3. As was described in
[50], and as will be described in the Section
Heterogeneity of real catalysts, a reversible morphology change in the majority of gold nanoparticles
indicates that the oxygen gas activation sites are
located at the interface between the gold nanoparticles and the metal oxide support.
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Fig. 6. No pressure gap [57]. The Au{100}-hex reconstructed surface remained stable under CO gas with lower (100 Pa) to higher (2000 Pa)
pressures of 1 vol% CO/air (Au/CeO2). The images of the rectangular regions are enlarged and shown at the bottom. The images were
recorded using a Cs-corrected ETEM. (Reproduced with permission from The American Association for the Advancement of Science).
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Concluding remarks
We have demonstrated the potential of recently
developed ETEMs for quantitative in-situ microscopy at the atomic scale, especially for the chemistry of catalysts in gases. The issues associated with
the application of ETEM to catalyst chemistry were
addressed using systematic, numerical and statistical ETEM analyses. Taking into account the electron
irradiation effects, the heterogeneity of real catalysts, the pressure gap and the temperature gap, we
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Fig. 7. Glimpse of gas molecules on the surface of catalysts under reaction conditions [57]. (a) Observed and (b) simulated image of the Au
{100}-hex reconstructed structure with CO molecules. (c) Simulated image of Au{100}-hex reconstructed structure without CO molecules.
Lateral intensity scans of (a), (b) and (c) are shown in (d), (e) and (f ), respectively. Line scans normal to the surface of (a), (b) and (c) are
shown in (g), (h) and (i), respectively. The oscillation intensity in observation (d) can be accounted for by considering the adsorbed CO
molecules, as shown in (e). The Au{100}-hex reconstructed surface without CO molecules could not reproduce the oscillating intensity, as
shown in (f ). The images were recorded using a Cs-corrected ETEM. (Reproduced with permission from The American Association for the
Advancement of Science).
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11 Flower H M (1972) High voltage electron microscopy of environmental reactions. J. Microsc. 97: 171190.
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12 Hashimoto H, Naiki T, Eto T, and Fujiwara K (1968) High temperature gas reaction specimen chamber for an electron microscope.
Jpn. J. Appl. Phys. 7: 946952.
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Funding
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Acknowledgements
The authors are indebted to their collaborators in the projects, especially Yoshikazu Homma, Masatake Haruta and Masanori Kohyama. They
are thankful to Yasufumi Kuwauchi and Tetsuya Uchiyama for their
invaluable contributions to the ETEM studies. They also thank Tomoki
Akita, Keju Sun, Satoshi Ichikawa, Shingo Tanaka, Koji Tanaka, Hideo
Kohno, Yutaka Ohno, FEI Company, especially Joerg R. Jinschek,
Stephan Kujawa and Stan Konings and FEI Japan, especially Ryohei
Matsumoto for their invaluable contributions.
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