Articles

https://doi.org/10.1038/s41929-019-0395-3

Imaging the dynamics of catalysed surface

reactions by in situ scanning electron microscopy
Cédric Barroo   1,2,3,5*, Zhu-Jun Wang   1,4,5*, Robert Schlögl1 and Marc-Georg Willinger   1,4,5*

Analytical methods that provide direct real-space information about the dynamics of catalysed reactions often require sim-
plified model systems and operate under high-vacuum conditions. There is thus a strong need for the development of meth-
ods that enable observation of active catalysts under relevant working conditions. Here, in situ scanning electron microscopy
is employed to study reaction dynamics and structure–activity correlations on surfaces. High sensitivity to changes in the
work function and surface composition enables the detection of monolayers of adsorbed molecular species on metal sur-
faces, which is used here to visualize catalytic NO2 hydrogenation on platinum. The initiation of reactive behaviours and
propagation of reaction fronts, as well as the spillover of activated species revealed in real-time and across a large pressure
range, demonstrate the power of in situ scanning electron microscopy as a surface science tool in the study of gas-phase- and
temperature-induced processes.

W
hether we want to study the synthesis, reactivity or age-
ing of catalytic materials, only experiments performed
during the ongoing process are able to capture the
information that is required to establish reliable structure–function
relationships. Catalysts are operating far from thermodynamic equi-
librium in an open system that exchanges heat and matter with the
surroundings. In their active state they are supposed to repeatably
facilitate sequences of reaction steps of a catalytic cycle. The combi-
nation of non-equilibrium conditions and inherent cyclic behaviour
(that is, the turnover frequency) of a catalytic reaction can result in
complex dynamics and the formation of dissipative structures that
are relevant to our understanding of catalytic function; catalysts
should thus be studied in their working state.
Conventional surface science methods have been applied as
powerful analytical tools for the investigation of fundamental
interactions and processes taking place on catalytically active sur-
faces; however, local observation of well-defined structures under
high-vacuum conditions can only provide an incomplete picture
about the behaviour of catalysts under industrially relevant con-
ditions. Extrapolation from quasi- to non-equilibrium conditions
is complicated by nonlinear and complex collective dynamics.
Consequently, there has been a growing interest to develop in situ
techniques that allow spatially resolved observations of catalysts in
their reactive state1–5. In this frame, in  situ transmission electron
microscopy has developed to a powerful technique for local inves-
tigations of temperature- and gas-phase-induced processes6–8; how-
ever, due to the highly localized and even atomic-scale information
provided by in  situ transmission electron microscopy, the ability
to study collective processes and dynamics is somehow limited.
Additional in situ methods are thus required to enable a multiscale,
context-embedded observation.
With a focus on studying the reaction dynamics rather than
the surface dynamics (that is, how the catalytic reaction proceeds
rather than how the catalyst’s surface changes during the reaction),
two main families of techniques have been successfully used to
image surface reactions: photoemission electron microscopy
(PEEM) and low-energy electron microscopy (LEEM) for the study
of flat, conductive samples (single crystals or foils)9–11 and field ion/
emission microscopy (FIM/FEM) for the analysis of tip-shaped
samples12,13. PEEM provides submicrometre resolution and a maxi-
mal field of view of a few hundred micrometres, whereas FIM/FEM
provides rather localized information at nanoscale resolution. Both
techniques can be operated at a maximum pressure of ~10−3 Pa. It
has only very recently been demonstrated that near-ambient-pres-
sure LEEM can be used to image surfaces under reaction pressures
of up to ~10 Pa (ref. 14). Scanning tunnelling microscopy15,16 and
ellipsomicroscopy for surface imaging17 enable measurements at
higher pressures, but they have rarely been used for the study of
reaction dynamics.
In the field of catalysis, analytical scanning electron microscopy
(SEM) plays an important role in the characterization of precursor
phases and ex  situ or post-mortem analysis of reaction-induced
changes of catalysts. With the development of variable pressure
SEM and environmental SEM (ESEM), the observation of mate-
rials in a reactive atmosphere and the study of reaction-induced
dynamics became possible18,19. It seems, however, that the potential
of in situ SEM is still not fully unfolded. In addition to its ease of
use, the ESEM combines some useful capabilities; for example, it
does not require ideally flat model surfaces and thus allows obser-
vation of samples with complex morphology; it provides a large
range of magnifications and higher spatial resolution than PEEM
or LEEM; and it can also be operated at pressures ranging from
10−5 Pa to near-ambient pressure20. Finally, it is not limited to the
study of conductive samples. Lately we have modified the set-up of
a conventional ESEM to use it as in situ tool for the investigation of
gas-phase-induced reactions that are relevant for catalysis21, corro-
sion22, material growth and decomposition23–25. Direct observation
of graphene growth by catalytic chemical vapour deposition on
different substrates at temperatures of up to 1,000 °C demonstrated
the high sensitivity of the secondary-electron signal to changes in

1
Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Berlin, Germany. 2Chemical Physics of Materials and Catalysis, Université
libre de Bruxelles, Brussels, Belgium. 3Interdisciplinary Center for Nonlinear Phenomena and Complex Systems (CENOLI), Université libre de Bruxelles,
Brussels, Belgium. 4Scientific Center for Optical and Electron Microscopy (ScopeM), ETH Zurich, Zurich, Switzerland. 5These authors contributed equally:
Cédric Barroo, Zhu-Jun Wang, Marc-Georg Willinger. *e-mail: cbarroo@ulb.ac.be; zhujun.wang@scopem.ethz.ch; marc.willinger@scopem.ethz.ch

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Articles
surface coverage26–28. The ability to distinguish individual layers of
atomically thin carbon sheets in few-layer graphene28 suggested
that the instrument should be capable of detecting modulations
of the work function and secondary-electron emission that are
caused by changes in surface coverage of a metal substrate with
atomic or molecular species. If that is true, it should then be pos-
sible to visualize reactions between adsorbed species on the surface
of a catalyst.
The hydrogenation of NO2 was chosen as a test reaction. This
reaction is relevant in the frame of automotive pollution control,
as it was highlighted by recent scandals in the automotive indus-
try. NO2 hydrogenation was previously studied on a single model
nanoparticle of platinum by field emission microscopy29–33. The
selected reaction presents several advantages: NO2 has a high stick-
ing coefficient34, adsorbed NO2 species are known to increase the
work function of platinum35 and nonlinear dynamics can emerge
during the reaction without oxidation of the catalyst at low pres-
sures. In FEM studies, the nonlinear behaviours are observed via
periodic variations of the brightness signal of the FEM pattern.
They are due to periodic variations of the local work functions
and induced by changes in the adsorbate-layer composition during
the reaction.
Here we show that nonlinear behaviours can also be detected
when the reaction is performed on platinum substrates inside the
chamber of an ESEM. Adsorbate induced modulations of the work
function can be detected as variations in the secondary-electron
signal and used to visualize reaction-induced changes in surface
coverage. Grain-orientation-dependent reactivity and propagation
of chemical waves, spillover coupling and formation of complex
spatio-temporal dynamics are observed and presented as a func-
tion of gas-phase composition, temperature and pressure. The high
flexibility of the SEM combined with the here demonstrated capa-
bility as surface science instrument for in situ studies will enable
a breakthrough in real-time observation of complex-shaped cata-
lysts across a large range of lateral scales and from high-vacuum to
near-ambient pressures.
Results
Proposed elementary steps. The reaction of NO2 with H2 is sup-
posed to produce water according to the mechanism discussed
in previous publications:31,33,36
Adsorption of the reactants on the platinum surface generates
NO*, O* and H* species:
NO2 þ n* $NO* þ O* þ ðn � 2Þ* ð1Þ
H2 þ 2* $2H* ð2Þ
The NO* can desorb or further dissociate, depending on the cov-
erage and temperature of the surface:
NO* $NOþ* ð3Þ
NO* þ m* $N* þ O* þ ðm � 1Þ* ð4Þ
N* þ N* ! N2 þ 2* ð5Þ
Finally, N2 and water are produced and leave the surface, creating
two and three vacant sites, respectively, allowing further reactants to
adsorb onto the surface and the process to continue. The reaction
can thus be considered as autocatalytic:33
2H* þ O* ! H2 O þ 3* ð6Þ
Nature Catalysis
Here, n* and m* represent the number of n or m free surface sites
and X* represents intermediate X adsorbed on a surface site.
Surface sensitivity to gas adsorption. The first set of experiments
was aimed at confirming the reactivity of a polycrystalline platinum
foil towards NO2 hydrogenation. Titration experiments were per-
formed at low pressure; that is, in the range between 10−4 to 10−2 Pa.
Adsorbed NO2 species and its dissociation products O(ads) increase
the work function of platinum surfaces35,37,38, whereas in the case of
NO(ads), the effect of the work function depends on the adsorption
mode39. As NO(ads) undergoes thermal desorption at the work-
ing temperatures40,41, its contributions to contrast modulation are
expected to be small. Overall, the adsorption of NO2 thus causes a
reduction of low-energy secondary-electron emission, which might
be detectable as a decrease in image brightness. As shown in the
sequence of SEM images that were recorded with the Everhart–
Thornley detector (Fig. 1a–c), the admission of NO2 into the cham-
ber of the ESEM induces an inhomogeneous, wavelike propagation
of darker contrast across the platinum foil. The observed appearance
and propagation of areas with reduced brightness and contrast is
indicative of an adsorption process. If brightness/contrast changes
were due to the increase of the pressure in the ESEM or due to the
properties of NO2 as an imaging gas (in the case of a gaseous second-
ary-electron detector42) then a homogeneous change in brightness
and contrast would be expected across the whole imaged region.
When hydrogen is subsequently introduced and the tempera-
ture increased, the initial brightness and contrast is reestablished,
indicating that the adsorbed layer can be reacted off. As shown in
Fig. 1d–f, the titration process is not homogeneous: it preferentially
initiates at specific surface features and grain boundary regions. The
behaviour presented in Fig. 1d–f strongly suggests the possibility of
detecting adsorption and desorption processes and thus reactivity
of the platinum surface towards NO2 hydrogenation.
Initiation of spatio-temporal dynamics. The hydrogen partial
pressure was varied at a fixed flow of NO2 once the reactivity of
the surface had been confirmed. The hydrogen concentration acts
as a control parameter in these experiments and is increased until
the moment when sustained activity is observed. Reaction-induced
changes in surface coverage should result in time-variant bright-
ness changes in the secondary-electron image under these condi-
tions. If these variations seem spatially coherent at scales that can be
resolved by the instrument, and at time scales that can be captured
within the achievable temporal resolution, it should be possible to
observe them. It is indeed known from PEEM and LEEM on well-
defined metal surfaces that reactions between adsorbed species can
be detected as contrast variations over time; they are caused by local
modulations of the work function due to reaction-induced changes
in surface coverage. The propagation of chemical waves is a typical
feature of 2D excitable systems, in which a local initiation centre
(that is, a pacemaker) induces a reaction that further propagates in
the form of chemical waves. Coupled reaction–diffusion dynamics
can give rise to complex spatio-temporal dynamics9. The observa-
tion of spatio-temporal surface dynamics by in  situ SEM would
thus demonstrate that the method provides sufficient sensitivity to
detect reactions between adsorbed species on metallic surfaces.
Figure 2 shows SEM images that were recorded while H2 was
slowly added to the NO2 flow using an ultra-high-vacuum (UHV)
leak valve. During the experiments, the magnification was gen-
erally chosen such that several grains could be monitored at the
same time. The initially low brightness of the surface indicates full
coverage by NO2 and/or O(ads) (Fig. 2a)35,37,38. A gradual increase
of the H2 flow combined with simultaneous imaging allows a con-
trolled transition of the system into its active regime. The onset of
reactivity is first observed as a change in brightness on some grains
and along grain boundaries, indicating that the adsorbed layer is
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Nature Catalysis
pNO2
a b
d e
315 °C
Fig. 1 | Surface sensitivity of the ESEM instrument. a–c, A sequence of SEM images showing that the dissociative adsorption of NO2 on a platinum
foil induces a decrease in brightness due to work function changes. Conditions of acquisition: T = 306 °C; initial chamber pressure = 10−5 Pa. NO2 was
introduced until the pressure reached ~10−2 Pa ðpchamber ¼ pNO2 Þ. d–f, Subsequent introduction of H2 and heating from 315 °C to 347 °C induces a reaction.
I
It is detected as increase of brightness and recovery of the initially clean surface. Conditions of acquisition: pNO2  pH2  102 Pa. Scale bar: 100 µm.
starting to react off (Fig. 2b). The H2 flow was kept constant from
this point onwards. Once NO2 and H2 are delivered at a constant rate
and a well-balanced ratio, the sequence of readsorption, reaction
and desorption can happen repetitively and, thus, eventually result
in the emergence of spatio-temporal behaviours. As can be seen in
Fig. 2 and Supplementary Video 1, only some of the grains show ini-
tial activity (manifested by a change in brightness and appearance of
wavelike contrast variations, inactive grains remain in a low-bright-
ness state). It is well known that a single crystal surface with a well-
defined crystallographic orientation will be active for the reaction
only in a restricted parametric region ðT; pNO2 ; pH2 Þ. This paramet-
ric region depends on the orientation Iof the grains, as the surface
structure influences the sticking coefficients of NO2 and the activa-
tion energies for dissociation, reaction, diffusion and/or desorption
of the involved species. In the case of a polycrystalline sample, it
is thus expected that not all of the grains are simultaneously reac-
tive under specific experimental conditions; however, because of the
structure of the sample as a whole (that is, the presence of intercon-
nected grains with different crystallographic orientations), a reac-
tive grain can stimulate reactivity on an initially unreactive grain.
Spatial coupling is most likely enabled through the diffusional flow
of mainly hydrogen species, which can easily diffuse at the working
temperatures9,43,44. Such a process can be observed in Fig. 2, where
grain A seems to be non-reactive (Fig. 2b) but becomes reactive near
the grain boundary by spillover coupling with grain B (see arrows
in Fig. 2c). After activity is initiated, grain A develops its own spe-
cific dynamics with an associated periodicity and initiation centre
(labelled × in Fig. 2d). Similarly, reactivity of the active grain C (and
later of grain D) is transferred to grain A through surface diffusion
coupling (Fig. 2d–f). The active areas expand with time and propa-
gate into so-far-inactive areas, which seem dark due to dominating
NO2(ads)/O(ads)35,37,38 coverage. During the gradual activation of
the surface, one can see how different dynamics can emerge for a
single grain, also depending on the neighbouring grains that can
act as pacemaker (by triggering the light-off as chemical clocks). In
cases where areas of different dynamics merge or when two chemi-
cal waves collide on a single grain, the dominant dynamics expand
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Articles
10–2 Pa
c
f
347 °C
I
whereas the other wave pattern disappears. This can be seen in
Fig. 2d,e, where the active region transferred from B ‘collides’ with
the active region transferred from C, and similarly in Fig. 2f–h
where the active region transferred from grain D collides with
the dominant dynamics on grain A. As indicated by the arrows in
Fig. 2c and as can be observed in Supplementary Video 1, reaction
fronts can propagate along specific surface features and along grain
boundaries in the form of chemical waves. Spillover can therefore be
transferred across grains through excitability; reaction fronts initi-
ated by spillover from one grain can travel along chemical wave-
guides or chemical channels through an excitable surface layer on
another grain and induce spillover onto further grains; thus acting
over extended distances. These observations prove the importance
of spillover effects and intergrain coupling in the emergence of com-
plex dynamics and, most importantly, in the global reactivity of a
catalyst. Due to spillover, the catalytic activity of a platinum foil is
not the same as the sum of the catalytic activities of all the facets
taken separately.
Grain-dependent spatio-temporal dynamics. Simultaneous
imaging of surface dynamics on different grains (as exemplified in
Fig. 2), coupled with grain orientation analysis by electron back-
scatter diffraction (EBSD), allows us to draw some initial conclu-
sions about the reactivity of differently oriented grains. According
to EBSD, variations in brightness due to the onset of reactivity were
first observed on {110}-type surfaces (such as grain B), the (100)
grain on the bottom left and the (111) grain near the top-right cor-
ner (see Fig. 2i and Supplementary Fig. 1). Although the (100) grain
shows an irregular, flickering contrast with a dominance of the
bright surface state, the more open {110}-type facets show a com-
plex pattern of propagating reaction–diffusion fronts with a spiral
pattern. In the case of the (111) grain, the surface is mostly seen
in the bright state, indicating either a low average NO2 coverage or
a non-reactive state under these conditions. The observed reactive
oscillating behaviour and the pronounced activity of {011}- and
{001}-type grains agree well with earlier FEM observations, accord-
ing to which the most active facets are of {012}, {011} and {001}
Articles Nature Catalysis

a b c
B

t=0s t = 2 min 52 s t = 5 min 36 s

d e f

t = 7 min 32 s t = 8 min 54 s t = 15 min 26 s

g h i

111

t = 16 min 01 s t = 16 min 04 s
001 101

Fig. 2 | Grain-dependent surface dynamics and spillover. a, Platinum foil under a pure NO2 atmosphere; low brightness indicates coverage of the surface
with NO2/O(ads). b, Grain-dependent change in brightness and onset of reactivity is observed once the H2 flow reaches a critical value. c, Spillover across
grain boundaries induces transfer of activity from active to initially inactive grains (marked with arrows). d, The initially non-reactive grain A becomes
partially reactive. The dynamics of the surface reaction are characterized by a specific periodicity and initiation centre (marked ×). A new initiation centre
(marked by *) results in spillover from grain C to A. e, In a collision of two chemical waves, the dominant dynamics prevail (here the ones originating from ×).
f,g, Spillover from grain D to A with its own initiation centre (marked by +). h, Another collision between two different chemical waves in which the
dominant dynamic overrides the other. i, An EBSD grain orientation map recorded after the in situ experiments, showing colour-coded information about
the orientation of platinum grains. In situ imaging conditions: T = 175 °C; pNO2 : pH2  ≈ 1:10; ptot ≈ 10−2 Pa. Scale bar: 100 µm.
I I

crystallographic orientations, with {113} and {111} being less active
or inactive30–33. Regarding the activation of initially inactive grains
by spillover, we observe two types of behaviours that are related to
surface reactivity and therefore grain orientation. As can be seen in
Supplementary Video 1, there are grains where spillover can induce
a reaction front that propagates across the whole grain. According
to the EBSD data, these are grains with surfaces close to a [101] ori-
entation, but with a slight inclination towards [111]. In other cases,
spillover first activates the region close to the grain boundary and
reactivity only gradually propagates further into still-unreactive
areas from there. It seems that the rather stable initial coverage is
gradually replaced by a less stable, more reactive configuration in
such a process. The initial coverage was obtained in a pure NO2
atmosphere whereas subsequent adsorption processes occur in the
presence of hydrogen. The higher reactivity could thus be explained
by hydrogen coadsorption and diffusion, as well as the presence of
intermediate species (vide infra).
It is important to address the potential role of the electron beam
in these experiments before attempting a deeper analysis of the
observations. The first and most crucial point for the investigation
of chemical dynamics by in situ SEM is to avoid surface contami-
nation during imaging. This requires working under very clean
conditions and eventually involves long-time annealing of samples
(see Methods). Furthermore, observation at elevated temperatures
(T ≈ 150–200 °C) is beneficial, as it reduces or even eliminates
contamination build-up during imaging. Depending on the type
of reaction, surface processes can even induce a self-cleaning.
Contamination-related limitations therefore need to be evaluated
individually for each type of system studied. In the here-presented
NO2 hydrogenation, contamination was not an issue once the
samples were clean. The second point that has to be considered in
the study of reaction dynamics is related to electron beam-induced
artefacts. We have carefully evaluated possible effects of the elec-
tron beam by changing the local dose rate through changes in the
scanning resolution, pixel dwell time and beam current. We have
mimicked beam on–off experiments by moving the sample posi-
tion and quickly changing the magnifications and observing con-
sistencies across imaged areas. We can conclude from these that
the primary beam hitting the surface does not locally affect the
observed dynamics. Whether the secondary electrons (which have

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Nature Catalysis
a far larger cross-section for the generation of radical species at
the surface or in the gas phase) have an effect is difficult to say
because it is not possible to image the surface without them. They
are locally generated, but propagate along different trajectories
through the gas phase towards the detector. Effects related to gas-
phase interactions would thus be less localized spatially compared
with the primary beam. Although we cannot completely exclude
that the electron beam has an impact on the sticking coefficients,
adsorption and desorption rates and surface dynamics, the effect
would certainly be very small compared with the effect of the sur-
face structure, gas composition and temperature: these were the
parameters that we varied that, independent of imaging condi-
tions, consistently gave rise to the complex behaviours observed.
A comparison with PEEM, which is also based on secondary-elec-
tron imaging, would certainly be interesting, also to compare pos-
sible roles of different excitation mechanism (ultraviolet light or
X-rays versus the primary electron beam in SEM).
A further source of artefacts is related to the use of a scanning
technique. Surface dynamics can only be captured without alias-
ing artefacts if the scanning speed is at least twice as fast as the fre-
quency of the spatio-temporal dynamics. Most of the videos were
recorded at the rate of ~1 to ~0.3 frames per second (fps). Some of
the chemical waves and rotating spirals seem to stand still or even
move backwards as a consequence of aliasing (see Supplementary
Video 1). Furthermore, although the scan of individual lines is fast
and thus reproduces the actual intensity profile along the horizon-
tal, fast-scan direction, the scan speed in the perpendicular direc-
tion (that is, from line to line) is slower. This leads to a compression
of waves that are running against the slow-scan direction, and an
expansion of those running against it. Slow scanning of fast dynam-
ics thus results in shape distortions of travelling waves and spirals.
However, by scanning reduced areas with less pixels at a high scan
rate, it is possible to capture more than 100 frames per second. This
is sufficiently fast to capture rotating spirals without aliasing arte-
facts (see Supplementary Video 2). Considering that each transition
from dark to bright contrast corresponds to a light-off and, thus, a
reaction of the adsorbed layer, direct imaging of the surface reactiv-
ity can be used to abstract grain orientation dependent rates (that is,
kinetics by imaging)11.
Spatio-temporal dynamics under steady-state conditions. After
briefly touching the onset of reactivity and the activation of initially
inactive grains by spillover, we performed experiments at differ-
ent NO2/H2 ratios and temperatures in the attempt to reveal initial
trends in the relationship between reaction conditions and grain-
dependent spatio-temporal dynamics. Each of the images shown in
Fig. 3 were recorded under steady-state conditions; that is, when
no further areal spread or change in activity could be observed.
By subtracting reference images of the initially NO2-covered sur-
face from each recorded image frame, the background originating
from grain-dependent channelling and work-function contrast, was
removed. The remaining contrast variations are then only due to
changes in the secondary-electron emission caused by the reaction
between adsorbed species on the surface: noise-level darkness thus
corresponds to NO2(ads) or O(ads)35,37,38 coverage, while the bright
state is due to transient H2O(ads)45 or an empty surface.
Under steady-state conditions, the reactivity of most grains is
revealed in the form of propagating chemical waves and intrigu-
ing, often disordered, spiral patterns. As already observed during
the initiation phase (Supplementary Video 1), the highly active
{100} grains show a low average NO2 coverage and only flicker-
ing contrast variations without any detectable coherent structure.
Aside from the active areas, there are grains and domains where
the surface remains dark and non-reactive, such as in Fig. 3a,b. The
presence of non-reactive areas in active grains even under station-
ary conditions is an interesting point, they are most likely to be
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Articles
manifestations of local structural inhomogeneities for which EBSD
and secondary-electron imaging is not sensitive. For example,
local variations in terrace size, step- and kink-density could result
in slightly increased stability of the initially adsorbed NO2 layer.
Alternatively, such unreactive areas could also be caused by poi-
soning of the surface due to non-reactive intermediates that do not
undergo thermal desorption, but that can be desorbed by increas-
ing the temperature. As shown in Fig. 3a–c, the reaction conditions
have a large effect on reaction dynamics and the observable spatio-
temporal pattern. Slight changes of the NO2/H2 ratio, temperature
or pressure can lead to activation or deactivation of complete grains
or portions of their surface. In Fig. 3a, for example, grains with a
surface orientation close to [113] (that is, the pink-coloured grains
in the EBSD map, Fig. 3d) are at least partially active at 172 °C. At a
slightly lower temperature (164 °C), these grains remain in a dark,
non-reactive state, reflecting the lower activity of {113}-like surfaces
(Fig. 3b). It is important to note that hysteresis effects and, thus, the
history of experimental conditions, play an important role in the
analysis of surface reactivity. Such effects are the reason why some
grains with a slight inclination from the [110] orientation towards
the [111] or [100] orientations (the green-yellow and green-blueish
colours, respectively, in the inverse pole figure map) are active at
a lower temperature (Fig. 3b), but seem inactive and with a dark
surface at a slightly higher temperature (Fig. 3a). Experiments that
were performed at an even higher temperature (196 °C) showed that
a reduction of the NO2 sticking coefficient can be compensated by a
slightly higher NO2/H2 ratio and that it is possible to find conditions
under which reactivity is observed on all but the [111]-like surfaces
(Fig. 3c). A comparison of the spatio-temporal patterns shows that
the lateral spacing between the individual chemical waves on all of
the grains seems larger at 172 °C (Fig. 3a) than at 164 °C (Fig. 3b).
This is indicative of increased reaction and diffusion rates at higher
temperatures, as also confirmed by comparative experiments that
were performed at 210 °C and 250 °C under otherwise similar con-
ditions (see Supplementary Fig. 1). An increase of the NO2/H2 ratio,
on the other hand, results in a shortening of the refractory phase
(compare Fig. 3c with Fig. 3a,b). Real-time imaging under different
pressure and NO2/H2 conditions proves that the surface dynamics
are very sensitive to the reaction conditions and provide a first hint
on the relationships between temperature, pressure and the type of
dynamics. The experiments summarized in Fig. 3 also confirm that
individual grains are active only in a restricted parametric region
(T, pNO2 , pH2 ) and that the surface reactivity strongly depends on
grainI orientation
I and therefore the structure of the platinum sur-
face. We could not find any stationary conditions under which the
{001} and {111} surfaces were simultaneously active. However, a
systematic mapping of the phase diagram by in situ SEM is possible
and will enable detailed studies on the effect of temperature and gas
composition at different pressures. Yet, due to the above-mentioned
hysteresis effects, it is advisable to reset the surface by high-tem-
perature annealing between experiments that are performed under
different conditions.
We want to further point out the high sensitivity of the second-
ary-electron signal to changes in the surface coverage. Figure 4
shows an analysis of the variation in the brightness level across
chemical waves and reveals the brightness difference between active
and inactive domains on a grain. The regions that were chosen here
correspond to the above-mentioned cases in which activity gradu-
ally extends into so-far-unreactive areas of grains. As can be seen,
chemical waves are reproduced in the secondary-electron images
with a saw-tooth-like change in brightness between reaction fronts:
a sharp transition from the dark to bright state due to the light-off is
followed by a gradual and apparently linear decrease in brightness
during the refractory phase. The ability to detect different coverage-
induced contrast levels demonstrates the high surface sensitivity
of the method. As discussed previously, the darker regions are
Articles Nature Catalysis

a b

c d 7,2,9
5,4,9 3,1,10
5,0,1
7,1,11 11,3,13
18,2,4 13,2,14
2,1,12
4,3,9 11,1,12
5,1,12
9,4,12 1,0,12 1,0,2 14,2,17
3,1,4
5,4,9

4,0,5 15,1,15
12,2,14 10,1,11 3,2,9
7,1,12
12,1,17 12,1,17
11,1,12
8,2,13
111 2,1,12
9,1,10 4,3,6
112
4,0,7 4,3,10
113 5,3,12
6,1,8
001 012 101 11,1,11

Fig. 3 | Condition-dependent nonlinear dynamics. a, Platinum foil imaged under the following conditions: T = 172 °C; pNO2 : pH2  ≈ 1:10; ptot = 3.6 × 10−2 Pa.
I temperature
b, As in a, but recorded at slightly lower temperature: T = 164 °C; pNO2 : pH2  ≈ 1:10; ptot = 3.6 × 10−2 Pa. c, Further change in I and reaction
I grain
atmosphere: T = 196 °C; pNO2 : pH2  ≈ 1:8; ptot = 8.7 × 10−3 Pa. d, An EBSD I orientation map of the platinum foil, colour-coded for the crystallographic
direction perpendicular toI the surface.
I The inset of c is a colour legend of the EBSD map. Scale bar: 200 µm.

supposed to be a result of the presence of NO2(ads) or O(ads)35,37,38,
whereas the brighter regions are due to transient H2O(ads)45 or an
empty surface. We are not currently able to say anything about the
contribution of intermediate species, and further work is neces-
sary to undoubtedly correlate the brightness variations to the sur-
face species. However, the linear decrease in brightness during the
refractory phase is indicative for a gradual building up of surface
coverage. Observations—according to which an increase in NO2
partial pressure results in a shortening of the refractory phase—
further corroborate this conclusion. The behaviour in the studied
regime is thus typical for a relaxation-type oscillation. Under fixed
reaction conditions, the minimal distance between two successive
waves is defined by the propagation speed of the reaction front
through the excitable surface layer and the duration of the refrac-
tory phase. Depending on the reactivity of the surface, further
time can pass until the next light-off is triggered, either through
a leading centre that acts as pacemaker, or through spillover from
a neighbouring grain. Here the observed lateral distance between
chemical waves lies in the micrometre range, but is strongly
grain dependent and changes drastically with reaction conditions
(see discussion of Fig. 3).
As can be seen in Fig. 4, the brightness oscillations due to the
reaction are offset with respect to the brightness level of the ini-
tially adsorbed NO2 layer. The low brightness of the unreactive area
confirms the earlier conclusion, according to which a higher cover-
age and more stable configuration can be established in a pure NO2
atmosphere compared with the coverage that builds up during the
refractory phase, in presence of hydrogen and possible intermediate
species. This interpretation fits to the observation that activity on
such grains is only obtained once the rather stable initial layer is
removed. Whether, and to which degree a structural response and
reconstruction of the platimum surface is involved in the gradual
activation of initially inactive grains needs further investigations.
Due to the higher spatial resolution of SEM compared with
LEEM or PEEM, it should be possible to obtain new insights about
the role of surface defects and possible causes of destabilization that
result in spontaneous wavebreaking on spiral arms and the for-
mation of multiple spiral cores. As can be observed in Fig. 5 and
in Supplementary Video 3, spiral cores can either be pinned to a
surface defect or meander across the surface of a grain during the
reaction. This could be due to the presence of several defects that
are in competition with eachother, or the presence of less coherent
dynamics that are sensitive to fluctuations46. Supplementary Figs. 1
and 2 also highlight the role of surface defects during the catalytic
reaction (in Supplementary Fig. 2, a propagating wavefront scatters,
splits and later recombines on a specific surface defect at 210 °C;
however, in Supplementary Fig. 1 the very same defect acts as lead-
ing centre and triggers the reaction at the core of a spiral when the
temperature is increased to 250 °C). Such observations demonstrate
that in situ SEM will enable studies on the parameter dependence
of the transition from rigidly rotating spiral waves to meander-
ing spiral waves and more generally, investigations on the relation
between surface features and their role as active sites under specific
reaction conditions.
After demonstrating the high sensitivity and ability of visu-
alizing travelling chemical waves by in  situ SEM, the next step
involves observing the same reaction at higher pressures. We have
thus conducted experiments at pressures of up to 120 Pa using the

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Nature Catalysis Articles
a b c

111

001 101

d e f

Fig. 4 | 3D Visualization of coverage-dependent brightness variations. Analysis of the secondary-electron signal intensity shows that oscillating
reactions happen in a brightness regime that is above the dark level of the initially adsorbed NO2(ads)/O(ads) layer. The activity on the grains shown
is only gradually initiated by the removal of the initial, more stable coverage. a, An area abstracted from Supplementary Video 1. b, A colourized 3D
representation of the contrast levels that were generated for the region indicated by a red square in a. c, The corresponding EBSD map from which the
(9,4,12) orientation of the selected grain was deduced. d–f, Another cut-out from the same video (d) with contrast variations (e) and the EBSD map of
that area (f). The central grain shows a (5,3,12) orientation. Scale bars: 100 µm (d), 20 µm (e).

low-vacuum mode of the ESEM and a gaseous secondary-electron t t+2s

detector (large field detector). As in previous experiments, NO2 was
first introduced into the chamber and H2 was subsequently slowly
added. The reactive behaviour that is observed once the bifurcation
point was reached is presented in Fig. 6 and Supplementary Video 4
for an experiment performed at 13 Pa. Starting from an initially
dark, fully NO2/O(ads)-covered state (Fig. 6a), the initiation of the
reaction occurs simultaneously at sparsely distributed active sites on
the surface of the sample. From there, the reaction fronts propagate
concentrically at a speed of ~1.5 µm s−1 (Fig. 6b–d). This speed is in t+4s t+6s
good agreement with the velocity of reaction–diffusion fronts that
are observed on different systems47–49. Although the reaction front
of the first light-off still propagates, readsorption of NO2 starts at
the centre of the bright circular areas as evidenced by the growing
dark areas (Fig. 6c,d). Readsorption seems to be faster than com-
pared with the reaction of the initial NO2/O(ads) layer as the lateral
spacings between the reaction fronts and the regrown dark areas
decrease with time. In agreement with the low-pressure experi-
ments, the subsequent coverages do not reach the stability of the
initial layer. This is reflected by an increased number of initiation Fig. 5 | Stationary and moving spiral cores. A series of SEM images
centres during the second light-off and fast removal of the read- showing that spiral cores can be pinned (for example, at a structural
sorbed layer, as shown in Fig. 6d,e. The surface then passes through defect) or move across the surface of an active grain. T = 161 °C;
another state of near-full coverage (Fig. 6f) and ignition from a few pNO2 : pH2  ≈ 1:10. Scale bar: 10 µm.
sparsely distributed active centres (Fig. 6e). After that, the system I I
finally switches to a dynamic state that is characterized by prop-
agating chemical waves at much smaller scales (see Fig. 6h,i and final 2D dissipative structure is reached could be a sign for a pos-
more magnified images in Fig. 6j–l). This switching and emergence sible structural modification of the surface or the accumulation and
of a new dynamical behaviour happens ~150 s after the first initia- presence of intermediate species that modulate the surface reactiv-
tion of the reaction. The propagation speed of ~0.12 µm s−1 is about ity. Overall, the observations fit to a propagating oscillating reaction
one-order-of-magnitude lower than the large-scale propagations. that occurs at the surface, phenomenologically similar to the behav-
The passage of the system through an initiation period before the iour observed at low pressure. An interesting difference concerns

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Articles
a b
t=0s t = 14 s
e f
t = 68 s t = 95 s
i j
t = 196 s t = 252 s
Fig. 6 | Nonlinear dynamics observed at higher pressure. a–l, The sequence shows the emergence of a structured pattern with a typical length scale of
a few micrometres from larger scale propagating waves. Conditions of acquisition: T = 180 °C; Ptot = 13 Pa. The red square in panel i corresponds to the
magnified regions presented in panels j–l. Scale bars: 100 µm (a–i); 20 µm (j–l).
the brightness change during the refractory phase: instead of a grad-
ual darkening, the change from the bright to dark state is relatively
abrupt, indicating much faster readsorption at higher pressures.
This is reasonable and a possible cause for the different dynamics50.
The results prove the robustness of the NO2 + H2 system, and the
ability to detect reaction dynamics also with the gaseous second-
ary-electron detector. Such experiments are needed to correlate
the behaviour of the reaction over several orders of magnitude in
pressure, and thus, for a narrowing of the pressure gap.
We have not observed any signs of subsurface oxygen or struc-
tural/morphological modifications of the catalyst surface during
the reaction thus far, we are therefore not able to draw any conclu-
sions about adsorbate- or reaction-induced surface reconstructions.
With the ESEM it is possible to perform experiments at pressures
of up to 2,000 Pa and, with some modifications, even up to 1 bar
(ref. 20). We tested the observability of surface reactivity up to 120 Pa
(see Supplementary Fig. 3). If reactivity can still be visualized at
higher pressures, we might be able to study reaction-induced sur-
face modifications that get more substantial at higher chemical
potential of the gas phase16,51,52.
Future work will therefore be focused on mapping the kinetic
phase diagram and the detection of the structural response of the
platinum surface, as well as on finding possible effects related to a
coupling of the dynamics through the gas phase.
Discussion
In this work, we have demonstrated the capability of in situ SEM
as a surface science tool that is sufficiently sensitive to image
Nature Catalysis
c d
t = 27 s t = 38 s
g h
t = 122 s t = 174 s
k l
t = 288 s t = 323 s
adsorption and desorption processes through the associated
modulation of the secondary-electron signal intensity. Due to its
versatility and ability to work across a large range of pressures,
in situ SEM extends the capability of LEEM and PEEM and thus
enables a further narrowing of the materials and pressure gap.
A large range of magnifications as well as seamless zoom from
overview imaging of millimetre-sized areas to high-resolution
imaging at nanometre resolution allows context-embedded
observation across scales and the study of short- and long- range
coupling effects in a very effective way.
The observations made here for the case of NO2 hydrogenation
show how real-time imaging in combination with EBSD mapping
enables a direct assessment of the structure–reactivity correlation
on a working catalyst. Surface reactivity is detected in the form
of chemical waves that propagate across the surface of individual
grains of the polycrystalline platinum catalyst. Propagating reac-
tion fronts—in combination with the oscillatory behaviour of the
reaction—give rise to complex spatio-temporal dynamics with
intriguing spiral patterns. Individual reaction fronts are sepa-
rated by a refractory phase; during this phase, the surface cover-
age gradually builds up until the next light-off can be triggered.
The sensitivity of the secondary-electron signal is sufficient to
detect variations in coverage and differentiate between contrast
levels that are associated with more or less stable configurations of
the adsorbate layer. Direct imaging of propagating reaction fronts
reveals how spillover across grain boundaries can induce activity
on so-far-non-reactive grains. It furthermore shows that scatter-
ing of chemical waves at grain boundaries and their propagation
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Nature Catalysis
along chemical waveguides can transmit the effect of spillover
across extended distances, thus highlighting the important role
of spillover for the activity of the whole system. Experiments per-
formed at different temperature, pressure and NO2/H2 ratios illus-
trate the high sensitivity and strong dependence of the reaction
dynamics on the surface structure and reaction conditions. Similar
phenomena related to propagating chemical waves and oscillatory
behaviour were observed over five orders of magnitude in pressure,
demonstrating the robustness of the system and the importance of
collective behaviours in the description of the catalytic reactivity of
surfaces. Nonlinear dynamics are therefore not confined to model
surface science studies that are performed under UHV conditions,
but are rather an integral part of catalytic processes and should be
accounted for in their description.
As in situ SEM is rather unconstrained regarding the shape com-
plexity of a sample and furthermore suitable also for the study of
non-conductive samples, this work can be extended to the study
of surface reactivity, spillover and the effect of interfaces on sup-
ported metal catalysts. Finally, this work demonstrates how much
more information one can get from SEM when working under clean
conditions. Regardless of the impressive development of the instru-
ments, most commercially available scanning electron microscopes
still provide relatively poor vacuum levels, preventing observation
of clean and defined surfaces (the same is true for most transmis-
sion electron microscopes). In view of the development of the
method, the realization of a UHV-capable environmental SEM—
such as already proposed by Banbury in 197253—should receive
some priority.
Methods
In situ experiments were performed in a commercial ESEM (FEI Quanta 200F)
that is equipped with an oil-free vacuum system, a home-built heating stage and a
gas feeding unit. Platinum foils and single crystal samples were cleaned ex situ and
then mounted in the ESEM, where they were first exposed to alternating annealing
in hydrogen at 1,000 °C and oxygen at around 800 °C to remove surface impurities
and finally, a long-term annealing in ~10 Pa of H2 at 1,000 °C for several hours.
After annealing, the temperature was decreased and the clean samples exposed to
the reactive gas mixtures. The methodology used was to set a working temperature,
introduce a given amount of NO2 gas into the ESEM chamber and subsequently
introduce H2 until the emergence of nonlinear behaviours could be observed. The
base pressure of the system lies in the ~10−5 Pa range and observations of surface
dynamics were observed at pressures ranging from 10−4 to 120 Pa. Secondary-
electron images were recorded using the Everhart–Thornley detector at pressures
up to ~2 × 10−2 Pa and with a large field gaseous secondary-electron detector
at pressures above 1 Pa. Once surface reactions were observed, all the control
parameters (T, pNO2 , pH2 ) and imaging conditions were kept constant to ensure
that the variations
I of brightness
I only reflect variations of the surface composition.
Surface grain orientation maps were recorded using a FEI Quanta 200F ESEM
that is equipped with a Hikari EBSD camera.
Data availability
All recorded images and data that support the findings of this study are available
from the corresponding author on reasonable request.
Received: 16 March 2019; Accepted: 1 November 2019;
Published: xx xx xxxx
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Acknowledgements
The authors want to acknowledge Dr Karsten Kunze for recording the EBSD map and
ScopeM for the use of the equipment. C.B. thanks the Fonds de la Recherche Scientifique
(F.R.S.-FNRS) and Wallonie–Bruxelles International (Excellence grant WBI.WORLD)
for financial support.
Author contributions
C.B., Z.-J.W. and M.-G.W. designed and performed the experiments and analysed the
data. Z.-J.W. and M.-G.W. modified the ESEM set-up for in situ observations of gas–solid
interactions. All authors contributed to the writing of the manuscript, and all authors
have given approval to the final version.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41929-019-0395-3.
Correspondence and requests for materials should be addressed to C.B., Z.-J.W.
or M.-G.W.
Reprints and permissions information is available at www.nature.com/reprints.
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