Reflections on the value of
rspa.royalsocietypublishing.org
Perspective
Cite this article: Thomas JM. 2017 Reflections
on the value of electron microscopy in the
study of heterogeneous catalysts. Proc. R.
Soc. A 473: 20160714.
http://dx.doi.org/10.1098/rspa.2016.0714
Received: 20 September 2016
Accepted: 17 November 2016
Subject Areas:
electron microscopy, materials science,
crystallography
Keywords:
electron crystallography, electron
tomography, structure, composition,
zeolites, selective oxidation catalysts,
nanomaterials
Author for correspondence:
John Meurig Thomas
e-mail: jmt2@cam.ac.uk
An invited Perspective to mark the award of
the Royal Society’s Royal Medal to the author
in 2016.
Shortly after I was invited to write this brief
Perspective article, my friend and collaborator,
and major innovator in the field of ultra-
fast electron microscopy, Professor Ahmed H.
Zewail, ForMemRS, passed away. I dedicate this
contribution to his memory.
electron microscopy in the
study of heterogeneous
catalysts
John Meurig Thomas
Department of Materials Science and Metallurgy, University of
Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, UK
JMT, 0000-0003-1147-8838
Electron microscopy (EM) is arguably the single most
powerful method of characterizing heterogeneous
catalysts. Irrespective of whether they are bulk and
multiphasic, or monophasic and monocrystalline,
or nanocluster and even single-atom and on a
support, their structures in atomic detail can be
visualized in two or three dimensions, thanks to high-
resolution instruments, with sub-Ångstrom spatial
resolutions. Their topography, tomography, phase-
purity, composition, as well as the bonding, and
valence-states of their constituent atoms and ions
and, in favourable circumstances, the short-range
and long-range atomic order and dynamics of
the catalytically active sites, can all be retrieved
by the panoply of variants of modern EM. The
latter embrace electron crystallography, rotation and
precession electron diffraction, X-ray emission and
high-resolution electron energy-loss spectra (EELS).
Aberration-corrected (AC) transmission (TEM) and
scanning transmission electron microscopy (STEM)
have led to a revolution in structure determination.
Environmental EM is already playing an increasing
role in catalyst characterization, and new advances,
involving special cells for the study of solid catalysts
in contact with liquid reactants, have recently
been deployed.
1. Introduction
During the past decade, major advances have occurred in
electron microscopy (EM) largely because of spectacular
instrumental, detector and computational developments.
First, there is the arrival of aberration-corrected (AC)
high-resolution electron microscopes of both the
2017 The Author(s) Published by the Royal Society. All rights reserved.
 (a) (b) 2

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0.5 nm

Si[112]
direct sub-angstrom
imaging of a crystal lattice

Figure 1. High-resolution electron microscopy (HREM) image of elemental silicon viewed along [112] direction. Filtered image
on right, with superimposed positions of each atom indicated in the lower diagram (after Nellist et al. [1]).

transmission (TEM) and scanning transmission (STEM) kind. This, in turn, has enabled almost
routine measurements to be made at sub-Ångstrom-unit resolution, as illustrated in figure 1 of
the individual atoms in elemental silicon [112] direction [1]. In addition, direct electron detectors
have now become available and they, in turn, have revolutionized electron crystallography (EC)
especially cyroelectron microscopy of macromolecular entities.
Moreover, as a result of improved electron spectrometers, it is now possible to record the
electron energy-loss spectrum (EELS) at high-resolution of individual atoms and ions in a
given structure and, thereby, determine their valence state and detailed atomic environment,
as well as measure high-resolution vibrational spectra of the structure to which the atom or
ion is bound [2,3]. Furthermore, electron tomography (ET), especially when using AC-STEM
microscopes of the type schematized in figure 2, has now become a quite popular and powerful
addition to the armoury of the electron microscopists [4–6].
In addition, when beam damage is inflicted by the primary electron beam, the procedure
of compressed sensing, as described in a recent paper [7] can be invoked. Given that energy-
dispersive detectors for X-ray analysis are now a regular feature of modern electron microscopes,
as well as electron spectrometers, it is readily possible to record several distinct signals, so that
it is legitimate to talk of multi-dimensional EM, as described more fully elsewhere [4,5]. In other
words, EDS (energy-dispersive X-ray signals) and EELS signals, as well as images and diffraction
patterns can all be simultaneously recorded.
All the above remarks apply to static imaging. But there have also been revolutionary
developments in ultra-fast four-dimensional (4D) EM—three dimensions (3D) of space and one of
time—most of these being brilliantly pioneered and exploited by Zewail and co-workers [8–13].
An illustration of the power of 4D EM is given in figure 3 taken from the paper read to this Society
by Zewail [14] in 2010.
Even prior to the arrival of the new developments in EM in the last decade,
considerable progress had been made using EM to characterize heterogeneous catalysts [15–18].
 3

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e-beam circular motion
of beam
x – y raster

X-ray X-rays specimen

spectrometer specimen

qA
diffracted
beam central
qH beam
BF ADF HAADF
precession
electron diffraction pattern
energy-loss
spectrometer

Figure 2. (Left) The STEM and associated detectors; high-angle-annular dark-field (HAADF) annular dark-field (ADF), and
bright-field (BF). If the BF detector is removed, transmitted electrons can pass through a spectrometer to form an energy-
loss spectrum. The tilting of the specimen performed in electron tomography (ET) experiments is illustrated schematically.
θ A ≈ 10 m rad; and θ H ≈ 50 m rad. (Right) Set-up for the precession electron diffraction.

High-resolution electron microscopy (HREM) had uncovered many important matters of direct
relevance to heterogeneous catalysis, and it is instructive to refer to just three of them here:

(i) The enigma of strong metal support interaction (SMSI)

At one time, it seemed puzzling to observe that catalytically active nanoparticles of
precious metals, such as Rh, lost their activity after use at high temperatures. It seemed
implausible when it was suggested that the support could be so mobile as to encage
the active metal catalyst. But HREM studies showed convincingly that this was indeed
possible in situations where the interaction between the metal and its support, typically
Rh on TiO2 , was strong (figure 4).
(ii) Existence of surface structures different from the underlying (bulk) structure
Figure 5 clearly illustrates the reality of situations where the bulk catalyst is
fundamentally different from that which exists at the surface. In the oxidation catalyst
of composition La2 CuO4 , which smoothly converts CO to CO2 in O2 , the catalytically
active phase does not exhibit this stoichiometry or structure, but a different, simpler
one, the C-phase of La2 O3 . It would be instructive to re-examine this catalytic system
using annular dark-field EM, just as was done recently by Pennycook et al. [20]. In
the hands of these investigators, AC-STEM has enabled atomic resolution imaging at
significantly reduced beam energies and electron doses. It has also made possible the
quantitative determination of the composition and occupancy of atom columns using the
atomic number (Z)-contrast annular dark-field (ADF) [21] imaging available in STEM.
 4D electron microscopy: imaging, diffraction and spectroscopy
t4
4
real space: t4 Fourier space: t3
t3 t2
images t2 diffraction t1
t1

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electron-generating

...................................................
–

pulse
electron
– +

source
–
+ +

nm Dt

specimen
energy space:

excitation
FEELS

pulse
intensity

e
tim

CCD
energy

Figure 3. 4D electron imaging in real, Fourier and energy spaces. The conceptual design of Caltech’s UEM-2 is presented on the
right; a single-electron trajectory is depicted within the UEM. The atomic-scale (femtosecond) temporal resolution characteristic
of the apparatus allows for the visualization of dynamical processes in real time. Shown on the left are typical UEM frames of real-
space images and diffraction patterns, together with three-dimensional maps of femtosecond-resolved electron-energy-loss
spectra (FEELS). Image reproduced from [14].

3 nm 3 nm decorating
layer
Rh –
Rh Rh Rh Rh Rh
Rh(111)

3.52 Å

011 -
101
-
011
TiO2-A [111] TiO2-A [111]

Figure 4. Typical example (after [19]) of strong metal-support interaction, designated SMSI. When the Rh/TiO2 catalyst is raised
to an elevated temperature in H2 (approx. 500°C) the support is seen to climb over the Rh, thus diminishing its catalytic activity.

Pennycook et al. [20] employed rapid scanning to both drive and directly observe the
atomic-scale dynamics, using combined high-resolution imaging and high-resolution
EELS, in the transformation of Mn3 O4 into MnO. This EM study clarified the complex
atomic mechanism involved in the changes at the oxide catalyst.
Such is the power of modern STEM instruments that my colleagues (Midgley, Collins et
al.) have been able to observe a thin veneer on the surface of crystallites of CeO2 , where
the CeIII , rather than the normal CeIV ions predominate.
(iii) Atomic structure of ultrafine metal nanoparticles and the catalytic significance of crystallographic
twinning

An early study [22] by my colleagues and me of the structure of nanoparticles of Pt catalysts

revealed a strong propensity for twinning (figure 6). Very recent work by Behrens et al. [23]
 surface profile imaging of La2CuO4
5
2 nm
La

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Cu

C-La2O3

La2CuO4

Figure 5. When surface profiling of an oxide catalyst (nominally La2 CuO4 ) is investigated by HREM, the surface phase is found
to be different (La2 O3 ) from that of the bulk [18].

have convincingly shown—see figure 7—that the catalytic activity of nanoparticles of Cu in the
methanol synthesis reaction are crucially governed by the number of twin boundaries that exist in
the Cu particles [23]. (In this case, it is also thought that minute traces of Znδ+ ions, preferentially
accumulated at the termini of the twin planes, play an important role in the catalytic turnover.)
I now turn to the two main themes of this article:

(a) single-atom heterogeneous catalysts and

(b) nanoporous oxidic catalysts of the single-site variety.

2. Single-atom heterogeneous catalysts

In the study of nanoparticle and nanocluster mono-metallic [24,25] and bimetallic [26]
heterogeneous catalysts over the years, it has long been suspected that individual atoms, detached
from the nanoparticles (containing 104 to 107 atoms) or nanoclusters (containing 4 to 20 atoms),
were the true loci of catalytic action (figure 8).
Recently, several studies [27–37] have provided incontrovertible proof that individual
atoms are indeed capable of effecting a number of catalytic reactions, especially selective
hydrogenations, as well as the water-gas shift reaction:

CO + H2 O  CO2 + H2 .

Examples are shown in figures 9 and 10. Details of these studies are given in the work
of Flyzani-Stephanopoulos et al. [31,32,36,37] of Zhang et al. [27–30] and Perez-Ramirez and
co-workers [34], see also Christopher et al. [38] and Thomas & Leary [39] From these studies, it is
quite clear that individual atoms of the platinum group metals are the active centres for catalytic
turnover. (We note, in passing, that in many of the reactions for which nanoparticles of Au on
various supports are the catalysts, Fu et al. [40,41] showed that the nanoparticles were spectator
species, and that it was Au–O moieties that served as catalytically active centres.)
 6

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20 Å

twin boundaries
(111) fringes
2.35 Å

2.04 Å
(002) fringes

2.35 Å

twin boundaries
c twin boundaries

twin boundaries
12°

Figure 6. HREM images of ultrafine nanoparticles of Pt are seen to be rich in twin boundaries.

At the Dalian Institute of Chemical Physics much work has been carried out, using individual
atoms of the platinum group metals (Ir, Pt especially) supported on non-stoichiometric FeOx . Wei
et al. [29] have demonstrated that single-atom catalysts (SACs) of Pt on FeOx are excellent catalysts
for the chemoselective hydrogenation of a variety of nitroarenes to their amino products (without
hydrogenating benzene rings or carbonyl groups attached to them) under mild conditions,
typically at 40°C, with contact times ranging from 10 to 120 min, conversions of 90–100% and
selectivities from 90 to 99.7% [29].
Later, Lucci et al. [32] showed how effective their so-called ‘single-atom alloys’—see also [40]—
where isolated, individual atoms of Pt on a Cu support can selectively hydrogenate 1,3-butadene
to 1-butene, an industrially important reaction used to eliminate impurities of the diene in
propylene gas that is extensively utilized for polymerization (figure 9).
SACs are, in effect, the reductio ad absurdum of the single-site heterogeneous catalysts that are
well known in other contexts [42–44]. The key question, so far as their longevity is concerned, is
how stable and secure is the solitary catalytically active atom on its support? Clearly, the nature
of the bonding between the SAC and its support is crucial. An ingenious way of boosting the
stability and minimizing the tendency for surface diffusion was devised by Perez-Ramirez and
co-workers [34] and further discussed by Thomas [35] My group at Cambridge with Midgley,
 (a) 2 nm (b) 111 100 110 disordered
7
overlayer

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twin boundary

...................................................
twin boundaries
111 100 211 522 2 nm

(c) 2 nm 100 111 211 110 (d)

A

C
tw
in
twin boundary B bo
disordered un
da
ry
overlayer
A

Figure 7. Recent work by Behrens et al. [23] using HREM, reveals that twin boundaries in Cu catalysts (used for the synthesis
of methanol from CO + H2 mixtures) are rich in twin boundaries. There is a correlation between catalytic activity and the
concentration of twin boundaries (see the text).

Leary, Furnvial et al. [45,46] have recently been collaborating with Perez-Ramirez et al. to
investigate such systems as Ir on C3 N4 —the support described by Vilé et al. [34]—which, in its
graphitic form, has monatomic depressions into which SACs like Pd fit snugly (figure 10).
This catalyst is active in the three-phase selective partial hydrogenation of alkynes in flow
mode, and both in activity and selectivity surpasses those of nanoparticle Pd. In our joint work
with the Perez-Ramirez group, we have been able—thanks to the assistance of Dr Ramasse at
Super STEM in Daresbury—to image several SACs composed of one or other of Ir, Pt, Ru and
Pd on C3 N4 supports. One micrograph (figure 11) reveals individual atoms of Ir on C3 N4 , with a
slight tendency for the Ir atoms to form loosely attached pairs.
In collaboration with Vajda et al. in the US, and Ramasse, UK, my colleagues and I have
recently studied [48] the energetics of single atoms of Cu on a graphene oxide. This sample was
prepared by Vaja & Toy [49] using a novel ‘cluster’ deposition method of laying down atoms
and their clusters, in soft-landing mode, on to the chosen support. The micrograph (figure 12)
shows well-separated individual atoms of Cu that are rather loosely bound to the graphene
oxide. We have studied the diffusion of these single Cu atoms across the surface at ambient
temperature. The observed behaviour exhibits anomalous symptoms, which are still the subject
of investigation.
Processes such as surface diffusion are not only important in heterogeneous catalysis, but also
in epitaxial growth and in the phenomenon of Ostwald ripening [50,51].

(a) Catalytic and optical properties of discrete Pt nanoparticles bound to nanoparticles

of colloidal Au
This subsection is not directly concerned with heterogeneous catalysis per se [7]. The dendritic
Pt nanoparticles visible in figure 13 are active, proven plasmonic catalysts, but the prime reason
 2 nm 8

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Au/TiO2 Au/TiO2
10 nm

Au/C

1 nm

Figure 8. Illustrative examples of minute clusters of Au on a titania support (top) and on an activated carbon support (bottom).
Sub-nanometre clusters (white circles) of size approx. 5 Å diameter and containing 10 Au atoms are observed, together with
individual Au atoms (black circles). (Micrographs kindly provided by P. L. Gai).

for discussing them here is to illustrate the importance of both electron tomography (ET) [52] and
compressed sensing [53] as vitally important techniques in the electron microscopic investigations
of nanoporous and plasmonic catalysts. Full details are given in [52]. For a pedagogically
interesting example of direct observation of catalytic conversions promoted by surface plasmons,
see the work of Novo et al. [46] on Au nanocrystals.

3. Nanoporous oxidic catalysts of the single-site variety

This is very much the age of nanoporous solids. Not only has the number of distinct kinds
of mesoporous silicas increased enormously in the past few decades, but there has also been
an almost exponential growth in the number of nanoporous metal oxides, both simple and
mixed: TiO2 , ZrO2 , GeO2 , MgO, Cr2 O3 , Al2 O3 , etc. (table 1). Furthermore, there are nanoporous
covalent solids, nanoporous carbons, not to mention the 200 or so structurally distinct kinds of
zeotypes (embracing alumino-silicates and alumino-phosphates). In addition, over 30 000 distinct
types of metal-organic-frameworks (MOFs) have now been identified, some of which exhibit
quite high thermal stability. So far as the solid-state chemist devoted to the design of ever-
more powerful single-site catalysts is concerned, very many of the numerous nanoporous solids
currently available possess high crystallographic order.
In addition to the availability of microporous oxidic solids (with pore diameters up to approx.
14 Å diameter), there is a multitude of mesoporous solids possessing pore diameters from 15 Å
upwards to several hundred Å units. Some of these (mesoporous) solids exhibit chirality, and can
 (a)
9
(i) (ii) H (iii)
H2

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Ha

Pd/Cu H on Pd/Cu

Cu

Pt

H2
(b)

d = 0.21 nm, Cu (111)

Cu H
Pt
2 nm Cu
Pt

Figure 9. (a) STM images showing atomically dispersed Pd atoms at a Cu(111) surface and hydrogen atoms that have dissociated
and spilled over onto the Cu surface. (i) Pd is alloyed into the Cu(111) surface preferentially above the step edges as evidenced
by the rumpled appearance of the upper terrace (scale bar 50 Å). (Insert) Atomic resolution of the Pd/Cu alloy on the upper
terrace showing individual, isolated Pd atoms in the surface layer appearing as protrusions (scale bar, 20 Å). (ii) Schematic
showing dissociation and spillover at individual, isolated Pd atom sites in the Cu surface layer. (iii) Islands of H atoms imaged
after hydrogen uptake appear as depressed regions on the clean Cu(111) lower terrace (scale bar, 50 Å). (Insert) High-resolution
image of individual hydrogen atoms on Cu(111) (scale bar, 20 Å). Images recorded at 5 K. (b) Mechanistic aspects of the selective
hydrogenation of 1,3-butadiene to 1-butene using a platinum-copper nanoparticle catalyst at the single-atom limit (by kind
permission of M. Flytzani-Stephanopoulos).

be prepared as homochiral polymorphs, but to a much lesser degree than the porous MOFs now
widely available.
It is chemically rather straightforward to introduce well-defined single catalytically active
sites into these nanoporous hosts, and the various ways of doing so (either during formation
or by post synthesis modification) have been described elsewhere [42–44,66,69]. One of the key
features of nanoporous, well-ordered solids is that they possess very large surface areas. It
means, therefore, that the number of catalytically active sites—spatially well separated from one
 palladium atom 10

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Figure 10. Schematic of a single-atom Pd catalyst comprising isolated Pd atoms on a solid support of C3 N4 (carbon, grey,
nitrogen, purple), which acts as a catalyst [34] for hydrogenation reactions. Strong bonds to the nitrogen atoms firmly anchor
the Pd atoms in roughly triangular pores in the stacked, two-dimensional layers of the support, see also [35].

single atom catalysts

1 nm

[Ir]mpg-C3N4

–0.19 nm –0.29 nm

Figure 11. HREM image of individual Ir atoms bound to a C3 N4 support (after [47]).
 (a) (b) (c) 11

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(d)

(e)

Figure 12. HREM image of single Cu atoms supported on graphene oxide—see text (after Furnival et al. [48]).

another so as to secure uniformity of performance—is very large per unit mass (or volume) of the
designed catalyst.
From the very early days of the study and use of pentasil zeolites, like ZSM-5 and ZSM-11
(termed MFI and MEL in the International Zeolite notation), EM has played a progressively more
powerful part.
Even before the 3D, X-ray-derived crystal structure of ZSM-5 was determined, HREM had
unequivocally established [70] the nature of the distribution of the pores and general internal
porosity of this important catalyst. In the ensuing 20 years, my group had evolved [15] a well-
defined set of procedures for the structural elucidation of microporous and mesoporous catalysts
and molecular sieves by HREM.

(a) Full structure determination by electron crystallography

Thanks largely to the subsequent work of my former colleague, Osamu Terasaki, [71,72]
numerous structural determinations have been made by EC of very many mesoporous silicas,
and of the corresponding mesoporous carbons prepared, such as CMK-1 and CMK-4 (derived
by moulding with organic material such as sucrose, as described by Ryoo [73,74]). The 3D
structure model of MCM-48 (which has interesting mesopores that facilitate intra-crystal diffusion
of reactants), shown in figure 14 was determined by EC. The prime advantage of using the EC
technique for mesoporous silica—and for several other ordered nanoporous solids—compared
with traditional X-ray single crystal diffraction, is that HREM images can be taken and the phases
of crystal structure factors (CSFs) are immediately available from the Fourier transform of the
image. Additionally, the stronger interactions (by several orders of magnitude, approx. 104 ) of
electrons with matter compared with X-rays, enables very small crystals, down to several tens of
unit cells in size, to be investigated.
 (a) x 12
yz

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70 nm

15 nm
y
z

(b) x
y z

m
75 n

15 nm
y
z

(c)
20 nm
x
y
z

top face
{111}

z
bottom face
x orthoslice {111}
(d) x y
z
30 nm

z
65 nm x

Figure 13. Volume rendering visualizations of the four Pt-decorated Au nanoprisms studied by electron tomography. (a,b)
Planar approximately 7 nm thick Au nanoprisms with lower and higher amounts of Pt NP growth, respectively (total thickness
approximately 15 nm). (c) Smaller (edge length approx. 110 nm) but thicker (approx. 14 nm) Au nanoprism with extensive Pt NP
growth (combined thickness approx. 25 nm). The inset orthoslice reveals well-defined convex {111} facets of the Au nanoprism.
(d) Pt−Au nanoprism with twisted morphology [7].

Such conditions allow datasets to be obtained for 3D CSFs from HREM images taken down
different zone axes. The structure of MCM-48 determined in this way (figure 14) exactly follows
the so-called G-surface with a thickness of approximately 13 Å. The wall separates the structure
Table 1. A selection of new families of nanoporous solids.a
13
description principal authors references

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homochiral metal-organic porous materials Kim [54]
..........................................................................................................................................................................................................

high surface-area oxides obtained by an active carbon route Schüth [55]

..........................................................................................................................................................................................................

nanoporous metal-containing nickel phosphates Ferey [56]

..........................................................................................................................................................................................................

ordered mesoporous materials in catalysis Schüth [57]

..........................................................................................................................................................................................................

family of nanoporous materials based on amino acid backbone Rosseinsky [58]

..........................................................................................................................................................................................................

metal-organic-frameworks prospective industrial applications Mueller [59]

..........................................................................................................................................................................................................

heterogeneous asymmetric catalysis with homochiral Lin [60]

metal-organic-frameworks
..........................................................................................................................................................................................................

kinetic gate-opening process in a flexible porous coordination polymer Kitagawa [61]

..........................................................................................................................................................................................................

nanoporous oxides: confluence of homogeneous and heterogeneous catalysis Thomas [62]

..........................................................................................................................................................................................................

functional materials: from hard to soft porous frameworks Thomas [63]

..........................................................................................................................................................................................................

designing heterogeneous catalysts by incorporating Lillerud and Olsbye [64]

enzyme-like functionalities to MOFs
..........................................................................................................................................................................................................

modular and predictable assembly of porous organic molecular crystals Jones [65]
..........................................................................................................................................................................................................

chemistry and applications of MOFs O’Keeffe and Yaghi [66]

..........................................................................................................................................................................................................

topological analysis of MOFs O’Keeffe and Yaghi [67]

..........................................................................................................................................................................................................
a Taken from table 5.3 of [68].

into two enantiomeric channel systems, which are not in any way connected with each other [75].
A typical set of HREM images of MCM-48, taken with incident electrons parallel to [100](a),
[110](b), and [111](c), is shown in figure 14, with the corresponding Fourier diffractograms (FD)
inserted in each image. These FDs are complex in general and their moduli is a function of
wavevectors. From the extinction rules, the space group was found to be Ia3d. (Fuller details
of how contrast transfer functions are incorporated into the final determination are given in the
many papers of Terasaki—see, in particular [71]). An ordered nanoporous carbon formed from
MCM-48, such as CMK-1 or CMK-4, has had its structures determined also by EC as outlined
above. CMK-1 and CMK-4 are prepared by impregnating calcined MCM-48 with sucrose solution
in the presence of sulfuric acid. After drying the resulting mixture, the impregnation step is
repeated, before the whole is carbonized under vacuum at approximately 1170 K. Finally, the
silica template is dissolved at 373 K in aqueous NaOH, leaving the final CMK product [73].

(b) Other methods of elucidating nanoporous structures by high-resolution electron

microscopy
It is not necessary to go through detailed structural determination of the type described for
MCM-48 above in order to gain fresh insights that are crucial for an understanding of catalytic
action [15]. Thus, a few HREM images taken down one or two zone axes can reveal the essential
nature of the structure of the zeolitic catalyst. We cite two examples:
First, the selective oxidation catalyst developed by the Exxon Central Research (ECR-1)
Laboratory; Second, the Brønsted-acid catalyst known as ZSM-23, developed by the
Mobil Company.
As seen in figure 16, ECR-1 turns out, from HREM imaging, to be an intimate twin of the
well-known natural zeolites mordenite and mazzite, shown in projection in figure 16a. And the
zeolitic catalyst ZSM-23 is a recurrently twinned version of the synthetic zeolite Theta-1 (TON)
(figure 16b).
 (a) (b) 14

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004
022
–
022 –
220
50 nm 50 nm

(c)

–
022
–
220

50 nm

Figure 14. HREM images of MCM-48. Incident electrons are parallel with [100] (a), [110] (b), and [111] (c). Corresponding Fourier
diffractograms (FDs) are inserted in each image (by kind permission of O. Terasaki).

The framework-substituted microporous alumino-phosphates selective oxidation catalysts [44]

are rather beam-sensitive and not amenable to the EC method described above for MCM-48.
A combined approach entailing computation and HREM imaging was used [76] to solve this
structure of Co-ALPO-36, which has very many catalytic uses [44].

(c) Summarizing verdicts on the value of high-resolution electron microscopy in elucidating

structures of zeolitic catalysts
Up until the early 1980s, there was much confusion in the open and especially the Patent literature
concerning identification of a large number of new zeolitic catalysts. One classic example involved
the debate between the US companies Union Carbide and their new zeolite, termed silicalite,
and the Mobil Company and their new zeolite, ZSM-5. Were their structures distinct? The
definitive answer came partly from a combination of powder X-ray diffraction, and, especially,
from magic angle-spinning 29 Si NMR. It was unequivocally established, [77,78] that, structurally,
silicalite and ZSM-5 were identical so far as the tetrahedral sites were concerned. ZSM-5 simply
had some Al3+ isomorphously replacing Si4+ sites, whereas silicalite was ‘pure’ SiO2 . Silicalite
I was structurally identical, but compositionally distinct from ZSM-5, and silicalite II was
 15

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168 Å (2u.c.)

2u.c.)
Å(
168

Figure 15. Two views of the structure of the zeolite MCM-48 determined by electron crystallography (EC). (Reprinted with
permission from Thomas et al. [15]. Copyright © American Chemical Society.)

likewise related to ZSM-11. The former microporous catalyst has what the International Zeolite
Association describes as a MFI framework, the latter an MEL framework. Earlier investigations
had speculated that an almost infinite series of pentasil zeolite catalysts could exist between
various sequences of the end-members ZSM-5 and ZSM-11. EM duly confirmed that this was a
reality. My colleague, Millward and I showed [79,80] that various sequences of ZSM-5, intimately
connected at sub-unit cell level, with ZSM-11 were readily visible in HREM images (figure 17).
We note in passing that the exceptionally powerful [81] selective oxidation catalyst, TS-1, has
isomorphous substitution of Ti4+ in place of Si4+ (figure 18).
New, and highly interesting kinds of zeolites continue to be synthesized, the catalytic
properties of which remain to be fully explored. Thus, from Corma’s group in Spain, multi-
pore zeolites have been synthesized (and some of their catalytic applications examined) [82].
Also, there is the report of a multi-dimensional extra-large [83] pore zeolite with 20 × 14 × 12
ring channels, [82] which, as yet, has been produced in coexistence with GeO2 and the structure
of which has been solved (by Zou et al. [71]) using ET and rotation electron diffraction. In the
characterization of these two new types of nanoporous catalysts, EM plays a major part.
As well as the straightforward aluminosilicate nanoporous (predominantly microporous)
solids, there are also increasingly prominent organo-silica hybrid mesoporous solids, such as
the one described by Inagaki et al. [84] shown in figure 19, and the fascinating range of
organic–inorganic zeolites produced by the ENI company in Italy (see [85] and references
 (a)
16

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b

c b

Z D Z Z D Z
A
Z (mazzite) + D (mordenite) Z (mazzite) + D (mordenite)

(b)

theta-1 s s theta-1

ZSM-23

Figure 16. (a) HREM reveals that zeolite ECR-1 is a sub-emit-cell level intergrowth (recurrent) of mordenite and magzite layers.
(b) Schematic of ZSM-23 structure, revealed by HREM to be a recurrently twinned version of the zeolite theta-1 (TON). (Reprinted
with permission from Thomas et al. [15]. Copyright © American Chemical Society.)

therein) where they incorporate simple organic groups (mainly -CH2 -) into known zeolite
frameworks. To date, to quote Millini & Bellussi [85] ‘the attention has been primarily focussed on
the preparation and structure characterization of the materials and little information has been published on
the possible applications of these hybrid crystalline phases’. It is fully realized, however, that because
of the presence of an abundance of well-defined C–H bonds—in both the Japanese and Italian
 140 Å 17

i i i i s i i i i

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[001] s i i i i i i s

[100]
70 Å

C
[001]
A
[100] B 90 Å

Figure 17. (Top) Schematic drawing of an example of seven recurrent ZSM-5 structures interspersed by one ZSM-11. (Bottom)
HREM images with accompanying diffraction patterns of various parts of a ‘nominally pure’ ZSM-5 specimen.

Ti Si

Figure 18. Isomorphous substitution of Si by Ti in TS-1 (after Bellusi et al. [81]).

 organic-silica hybrid mesoporous crystal
18

(a) (b)

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...................................................
38 Å

b
10 nm
a
(c)
7.6 Å
image b

7.6 Å
b c
10 nm
image a a

An ordered mesoporous organic-silica hybrid material

with a crystal-like wall structure. c
a

Figure 19. (a–c)A typical organo-silica hybrid microporous crystal, of the type yet to be exploited in heterogeneous catalysis—
see text (after Inagaki et al. [84] see also [85]).

preparations—it is possible to insert functional groups that are able to coordinate metal complexes
for specific redox reactions or chiral junctural groups for enantioselective conversions that are
not feasible in conventional zeolites. This is potentially a rich area of future investigation, and
can extend the work of Thomas et al. in grafting enantioselective catalysts on to mesoporous
silicas [44,86].

(i) An illustrative example of electron tomography yields topography of heterogeneous catalysts

My colleagues and I have previously drawn attention [87] to how, using the set-up
depicted in figure 2, high-angle-annular dark-field (HAADF)-STEM tomography of a supported
heterogeneous catalyst reveals a great deal both about the topography of the support and the
distribution of the nanoclusters and nanoparticles catalysts upon it. We first draw attention to the
bimetallic (Pt-Ru) nanocluster catalysts supported on mesoporous silica where such nanocatalysts
may be almost invisible using conventional bright-field TEM, yet can be readily distinguished
from the lighter support using HAADF-STEM imaging, [21] owing to the strong Z-dependence
of the HAADF signal. From the ET reconstruction, as outlined elsewhere, [87] the pore volume,
surface-area, mean diameter, overall porosity and catalyst loading can be determined. The surface
dimension of the pore network was found to be fractal in nature. Moreover, by classifying the
surface curvature of the support, the nanocatalysts were found to be anchored at ‘saddle points’
on the support surface (figure 20a). In another example (figure 20b), a combination of AC-STEM
and HAADF-STEM tomography identified the propensity for Au nanoparticle catalysts on a
titania support to reside in crevices between the individual titania grains.
Very recently, my colleagues (Midgley and Leary) have examined by electron tomography
the novel catalysts of Lee, and colleagues, at the University of Aston. These are composed of
a macroporous host which also contains mesopores. Electron tomography confirms that minute
Pt nanoparticles reside largely within the mesopores and the larger Pd nanoparticles within the
macropores.
 (a) 19
concave saddle
convex

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(Pt, Ru)

20 nm
(Pt, Ru)-SiO2

Au (111)
(b)
3D reconstruction d = 0.24 nm
Au (c)
TiO2
anatase (004)

boundary

anatase (004)

anatase (200)

20 nm

Figure 20. (a) Electron tomographic (ET) reconstruction of (Pt, Ru) nanocluster catalyst supported on a disordered mesoporous
silica. The visualization of the silica has been colour-coded according to the local Gaussian curvature [87]. The nanocluster
catalysts (red) appear to prefer to anchor themselves at the (blue) saddle points. (b) Surface-rendered visualization of an ET
supported on titania (blue). The nanocluster catalysts are located in the crevices between titania crystallites confirmed by the
AC-STEM image in panel (c) (Thomas et al. [87]).

(ii) A striking example of the determination of the structure of a complex solid oxide catalyst
by aberration-corrected scanning transmission electron microscopy
It has been known for some time that there are complex oxides, containing several distinct
elements (e.g. Mo, V, Nb, etc.), that can selectively oxidize propane directly to acrylic acid in
air or O2 , and ammoxidize the same reactant to acrylonitrite, each of these products being
extensively used

CH3 CH2 CH3 → CH2 = CH-COOH

 (c) HAADF STEM 20
(a)

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2 nm

b
(d) BF STEM

a
2 nm

2 nm

(b)
(e)

Mo
V2
Te12
Mo3 20%
V3 occ.
Mo4
Mo5 Te13
Mo6
Mo11 Nb9 Mo7
V7
Mo8
Mo1 Mo10
V1
2 nm

Figure 21. (a) High-resolution HAADF-STEM images showing the [001] projection of the M1 phase of the selective oxidation
catalyst. (b) Rendering of the model M1 structure from simultaneously refined powder X-ray and neutron data. (c) High-
resolution HAADF-STEM image showing areas with occupied heptagonal channels within the white oval. (d) High-resolution BF
STEM image of the same area. (e) Magnified portion of the [001] projection. These images have not been processed. After Pyrz
et al. [88].

CH3 CH2 CH3 → CH2 CH-CN.

In a definitive paper by my former colleagues, Buttrey and co-workers [88], reviewed later by
me [89], the essential nature of this complicated catalyst could be discerned from an analysis of
the HAADF-STEM images taken down the [001] axis (figure 21).
It was even possible to read off the atomic coordinates and site occupancies from their
EM study.

4. Epilogue
There are several other important applications of EM to the study of heterogeneous catalysts.
For example, there are the advances in environmental TEM that have occurred beyond the
work described by Zewail and me in Chapter 4 of our book [11] by investigators, such as Gai
et al. [90], Helveg and co-workers [91], Grunwaldt et al. [92] and Browning [93], and the ingenious
recent study of Park et al. [94]. The last named group constructed a special cell (composed of
windows made of graphene) to enable them to follow freely rotating Pt nanoparticles in a liquid
 (a)
21
E-beam in
TEM

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GLC of
freely rotating
particles

(b) (d)

particle 1 particle 2

(c) (e)

Figure 22. Schematic illustration of in situ TEM imaging of Pt nanocrystals freely rotating in a so-called ‘graphene liquid cell’
(GLC), and 3D EM density maps calculated from individual Pt nanoparticles in solution (after Park et al. [94]).

environment. This constitutes a breakthrough in the potential that EM has for the future study
of heterogeneous catalysts that function in a liquid (or gas-liquid) environment (figure 22). And
this approach, coupled with in situ synchrotron X-ray diffraction [95] has already been profitably
exploited in charting the development of intracrystalline mesoporosity in commercially important
zeolitic catalysts.
 biomechanics: dynamics single- 22
of solvation by single nanoparticle
of DNA (2013) phase transition
environmental SUEM particle imaging by
of amyloid (2013) (2013)

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(2013) 4D scanning transmission

...................................................
electron microscopy
(2011)
surface dynamics subparticle ultrafast
by 4D scanning electron irreversible spectrum imaging
microscopy (SUEM) chemical reactions (2012, 2013)
(2011) (2011)
applications of 4D ultrafast electron microscopy (UEM)

chirped
macromolecular 4D Lorentz imaging pulses
structural dynamics electron microscopy (2012)
control of (2011) (2010)
nanocantilevers slicing
nanofriction electron pulses
(2011) 4D electron (2010)
tomography (2012)
motion (2010) biological
of complex imaging
nanostructures dynamics of
carbon nanotubes (2010)
Kikuchi ultrafast
(2005– )

(2010)
(2009, 2010, 2012) PINEM nanodiffraction
(2009, 2010, 2012, (2011, 2012)
nanomechanical 2012, 2013)
dynamics of motion of cantilevers
chemical bonding (2009) convergent
beam UEM single-pulse
(2009) phase transformation
femtosecond- (2009)
resolved EELS (2009)
(2008) nanoscale
mechanical drumming
picosecond (2008)
morphology change and
nanoscale resonance single-pulse
(2008, 2009) crystallization
(2008)
ultrafast electron
imaging theory VO2
(2006, 2007, 2008) phase transition
(2006, 2007)
of techniques

4D ultrafast electron microscopy (UEM)

development

(2005– ) [1M-47M]

ultrafast electron ultrafast electron

diffraction (UED) crystallography (UEC)
(1991– ) [1D-34D] (2004– ) [1C-22C]

Figure 23. Illustration of the wealth of ‘sub-techniques’ emanating from Zewail’s introduction in 1991 of ultra-fast electron
diffraction, ultra-fast EC and 4D ultra-fast EM [95].

Several other categories of heterogeneous catalysts, like the core-shell bimetallic ones of minute
dimension, the designed bimetallic [Au-Pd] nanoparticles for efficient photocatalytic production
of hydrogen [96], and the wide range of oxidic and other nanocatalysts investigated at the Max
Planck Institutes in Berlin and Muelheim [97], are all now addressable using the highest ever
attained spatial and chemical resolution. The EM approach has already reached its climax so
far as aberration-correction is concerned. Now the territory of catalytic significance that needs
to be charted is that involving progressively faster time resolution. In this connection, it is
instructive to recall the very last joint work that Zewail and I did on elucidating the nature of
the catalytically active site in a multiply-bonded Ti[iv]oxo unit in a low-coordinate titanosilicate
photocatalyst [98,99].
Zewail and I and our colleagues, using his classic 4DEM approach [98], activated this
catalytically active centre by laser-induced electron transfer to form a stretched [single bonded]
Ti[iii]oxo unit. The femtosecond dynamics revealed exceptional Ti-O bond disruption, making
the oxo very basic for interaction with a proton on water or on the carbon of carbon dioxide.
23
Commenting recently on this work the eminent photochemist, H. G. Gray, said [100]: ‘This
groundbreaking work has given us [for the first time] snapshots of early events in water splitting

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[as well as carbon dioxide reduction] catalytic cycles!’
Many more adventures in 4D-EM can also be expected simply by pondering the wealth of
variants of ultra-fast EM depicted in the characteristically evocative and spectacular illustration
contained in one of the last publications [101] of Ahmed Zewail (figure 23).
Competing interests. I declare I have no competing interests.
Funding. Funding for administrative support was received from the Kohn Foundation.
Acknowledgements. I am grateful for support from the Kohn Foundation, and for permission to reproduce results
of others, especially those of my former colleagues Osamu Terasaki, Paul Wright, Doug Buttrey, Rik Brydson,
Wuzong Zhou, David Jefferson, Robert Schlögl, Pratibha Gai, Kenneth Harris and my current colleagues Paul
Midgley, Rowan Leary and Alex Eggeman. I am also grateful to Professor Miretta Flytzani-Stephanopoulos
for providing figure 9 of this article. Especial thanks go to Professor Avelino Corma for the cover illustration.

Author profile
Apart from his work in the development and exploitation of
electron microscopy in solid-state chemistry, John Meurig Thomas has
designed and characterized in situ numerous heterogeneous catalysts.
He was awarded the Royal Medal of the Royal Society for Physical
Sciences in 2016, for his pioneering work in single-site heterogeneous
catalysts and their use in green chemistry and clean technology.

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