Research Article

Cite This: ACS Catal. 2019, 9, 1373−1382 pubs.acs.org/acscatalysis

CO and H2 Activation over g‑ZnO Layers and w‑ZnO(0001)

Hao Chen,†,‡,∇ Le Lin,§,∇ Yifan Li,∥,∇ Rui Wang,⊥,# Zhongmiao Gong,⊥ Yi Cui,⊥ Yangsheng Li,†,‡
Yun Liu,† Xinfei Zhao,†,‡ Wugen Huang,†,‡ Qiang Fu,† Fan Yang,*,† and Xinhe Bao*,†
†
State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, iChEM, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, People’s Republic of China
‡
University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
§
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, People’s Republic of China
∥
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, People’s Republic of China
⊥
Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences,
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398 Ruoshui Road, Suzhou 215123, People’s Republic of China

#
Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, People’s Republic of
China
*
S Supporting Information

ABSTRACT: Graphene-like ZnO (g-ZnO) nanostructures (NSs) and thin

films were prepared on Au(111), and their reactivities toward CO and H2 were
compared with that of wurtzite ZnO (w-ZnO) (0001) single crystals. The
interaction and reaction between CO/H2 and the different types of ZnO
surfaces were studied using near-ambient-pressure scanning tunneling
microscopy (NAP-STM), X-ray photoelectron spectroscopy (XPS), and density
functional theory (DFT) calculations. The reactivity of the w-ZnO(0001)
surface toward CO and H2 was found to be more prominent than those on the
surfaces of g-ZnO/Au(111). CO oxidation took place primarily at the edge sites
of w-ZnO(0001) and the interface between g-ZnO NSs and Au(111), while g-
ZnO thin films on Au(111) appeared to be inert below 600 K. Similarly, the w-
ZnO(0001) surface could dissociate H2 at 300 K, accompanied by a substantial
surface reconstruction, while g-ZnO on Au(111) appeared inert for H2 activation at 300 K. DFT calculations showed that the
reactivities of ZnO surfaces toward CO could be related to the formation energy of oxygen vacancy (EOvf), which could be
related to the charge transfer to lattice oxygen atoms or surface polarity.
KEYWORDS: ZnO, CO oxidation, NAP-STM, XPS, oxygen vacancy, surface polarity

■ INTRODUCTION
Zinc oxide, ZnO, has received tremendous interest because of
its wide applications in the semiconductor,1 optical,2 and
chemical industries.3 ZnO-based catalysts have been used in a
number of industrial applications, such as the water-gas shift
reaction4−6 and methanol synthesis,7,8 and have been
increasingly recognized for novel catalytic processes, such as
the direct synthesis of light olefins from syngas.9,10 For
methanol synthesis, ZnO is considered as a major catalytic
component in the Cu/ZnO/Al2O3 catalyst for the hydro-
genation of carbon monoxide and carbon dioxide. However,
the role of ZnO has not been clear and has attracted
tremendous attention in current research.3,7,11 In syngas
conversion, Jiao et al.9 recently reported a direct and highly
selective process by using nanocomposite catalysts comprised
of metal oxides and zeolites. In this nanocomposite catalyst,
ZnO was employed as a main oxide component for the
activation of CO and H2. Yet, the mechanism of CO and H2
activation remains to be explored. To address the catalytic role
of ZnO, it is essential to study the interaction between ZnO
and reactants, such as CO, CO2, and H2, on well-defined
model catalysts.
Currently, model ZnO catalysts could be prepared via the
growth of ZnO layers on metal single crystals or through the
use of ZnO single crystals exposing different surface planes.
The syntheses of crystalline ZnO layers have been reported on
a number of planar metal surfaces, such as Pd(111),12
Pt(111),13,14 Au(111),15−17 Ag(111),18,19 Cu(111),18 and
brass(111).20 These crystalline ZnO thin films are stoichio-
metric, with a surface structure similar to the (0001) facet of
wurtzite ZnO, but become flattened and thus expose a
nonpolar graphene-like ZnO (g-ZnO) surface. The wurtzite
structure is the most stable phase of ZnO under ambient
conditions. Wurtzite ZnO (w-ZnO) (0001) is also a typical
polar oxide surface and exhibits reconstructed surface planes
with triangular islands and holes to compensate for the extra
Received: September 13, 2018
Revised: December 11, 2018
Published: December 31, 2018

© XXXX American Chemical Society 1373 DOI: 10.1021/acscatal.8b03687

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Figure 1. Structures of g-ZnO NSs and layers on Au(111). (a−c) STM images of g-ZnO NSs prepared by depositing Zn atoms in 1 × 10−7 mbar of
NO2 with the substrate temperature of Au(111) held at ∼450 K: (a) large-scale STM image showing both ML and BL g-ZnO NSs on the Au
terrace; STM images showing (b) a moiré structure (with supercell marked by the rhombus) and (c) the atomic lattice of ML ZnO NS (the inset
shows the structural model of ML g-ZnO NS (color representations: yellow, Au; red, Zn; gray, O)). (d−f) STM images of g-ZnO NSs prepared by
depositing Zn atoms in 1 × 10−7 mbar of NO2 with the substrate temperature of Au(111) held at 300 K: (d) large-scale STM image showing only
BL g-ZnO NSs on the Au terrace (the inset shows the structural model of BL g-ZnO NS (color representations: yellow, Au; red, Zn; gray, O)); (e)
high-resolution STM image of BL g-ZnO NS; (f) STM image of g-ZnO thin film with a layer thickness of ∼3.7 ML on Au(111). Scanning
parameters: (c) Vs = +0.30 V, It = 0.23 nA; (e) Vs= +1.4 V, It = 0.35 nA.

surface charge.21,22 The structural characters of the recon-
structed w-ZnO(0001) surface have not been clear at the
atomic level. Previous studies on ZnO layers supported on
Pt(111)14 and Pd(111)12 have suggested that the coplanar
structure of g-ZnO(0001) layers would turn into the wurtzite
structure of w-ZnO(0001) when the number of ZnO layers has
surpassed a critical thickness.23−25 It is thus interesting to
compare the reactivity of the g-ZnO(0001) layers with that of
the w-ZnO(0001) surface, owing to their structural similarity.
In this article, we studied the interaction and reaction
between CO/H2 and the surfaces of g-ZnO(0001) on Au(111)
and w-ZnO(0001), using near-ambient-pressure scanning
tunneling microscopy (NAP-STM), X-ray photoelectron
spectroscopy (XPS, including NAP-XPS), and density func-
tional theory (DFT) calculations. Our study analyzed the
structures of g-ZnO and w-ZnO, as well as their reactivity
differences toward CO and H2. We show that surface polarity
could be used as a descriptor for the reactivity of ZnO
structures.
The Au(111) single crystal was cleaned by cycles of Ar ion
sputtering (1 keV, 10 μA) and UHV annealing at ∼800 K. The
w-ZnO(0001) single crystal (MTI) was cleaned by cycles of Ar
ion sputtering (1 keV, 10 μA) and UHV annealing at ∼1000 K.
ZnO layers were prepared on Au(111) by evaporating Zn
atoms in the presence of ∼1 × 10−7 mbar of NO2 at various
substrate temperatures. NO2 molecules were dosed through
the stainless steel tube directed at the surface of Au(111). The
surface coverage of ZnO was estimated from the deposition
time. STM images were acquired using Pt/Ir tips with the bias
voltage (VS) applied to the sample. STM images were
processed with SPIP software from Image Metrology of
Denmark.
XPS spectra were analyzed by CasaXPS software with a
Shirley background subtraction and 70/30 Gaussian−Lor-
entzian fits. Zn 2p3/2 and O 1s XP spectra were used for the
calculation of the Zn:O ratio. From STM and XPS, the surface
of pristine BL g-ZnO is almost defect free and peaks of Zn
2p3/2 and O 1s are highly symmetric. Therefore, we considered

■
EXPERIMENTAL SECTION
The experiments were carried out in three ultrahigh-vacuum
(UHV) systems. The first system was equipped with a NAP-
STM26,27 (SPECS, base pressure <3 × 10−10 mbar), mass
spectroscopy (Hiden), and cleaning facilities. The second
system was equipped with XPS (SPECS, Al Kα source, base
pressure <5 × 10−10 mbar), a high-temperature and high-
pressure reactor with cleaning facilities. The third system was
equipped with NAP-XPS (SPECS, base pressure <5 × 10−10
mbar) with a monochromatic Al Kα source. The exposure to
reaction gas was done by backfilling the chamber.
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that pristine g-ZnO is stoichiometric. In ex situ XPS studies,
the exposure of g-ZnO to high-pressure gas led to the
formation of a shoulder O 1s peak at ∼532.0 eV, which could
be attributed to water adsorption from the background during
high-pressure experiments.16 Thus, peak deconvolution was
used to separate the influence of the shoulder O 1s peak and
only the peak area of lattice O 1s was used to calculate the
Zn:O ratio after CO exposure. The analysis of XPS results is
displayed in Tables S1 and S2. For a comparison of the Zn:O
ratio, peak areas of Zn 2p3/2 and O 1s after CO exposure at
elevated temperatures were all normalized to their peak areas
after CO exposure at 300 K since there was no CO oxidation at
300 K for g-ZnO.
DOI: 10.1021/acscatal.8b03687
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DFT calculations were carried out on the basis of the Vienna
ab initio simulation packages (VASP 5.4).28−32 The exchange-
correlation potential effect was treated by the Perdew−Burke−
Ernzerhof (PBE) method33 at a level of the generalized
gradient approximation (GGA).34 The projector-augmented
wave (PAW)35 pseudopotentials were utilized to describe the
core electrons, and a plane-wave cutoff kinetic energy was set
to 400 eV. In addition, the van der Waals (vdW) dispersion
forces were corrected using the zero damping DFT-D3 method
of Grimme36 to account for the long-range interactions in this
system. An on-site Coulomb repulsion interaction, the effective
Ueff = U − J, was set at 4.7 eV for Zn 3d orbitals.37−41 Overall,
a spin-polarized effect was considered. For a BL g-ZnO film on
Au(111), the atomic structures included a (7 × 7) ZnO(0001)
overlayer on an (8 × 8) Au(111) slab with three atomic layers
(with the top layer relaxed).15 Here, ZnO layers were slightly
expanded with lattice mismatch 2.6%. A Γ point was specified
to sample the Brillouin zone. BL g-ZnO NS was constructed by
cutting the BL g-ZnO film to expose the step. For comparison,
the w-ZnO(0001) system21,42 was also constructed, where a (4
× 4)-ZnO(0001) supercell was employed with six layers; the
bottom two layers were frozen, and the top layer was partially
resected. A (2 × 2 × 1) Γ-centered grid was used for the k-
point sampling.
■ RESULTS AND DISCUSSION
Surface Structures of g-ZnO(0001) and w-ZnO(0001).
The growth and structures of ZnO NSs and thin films on
Au(111) are displayed in Figure 1. ZnO NSs were prepared by
evaporating Zn atoms onto Au(111) in the NO2 atmosphere.
Consistent with literature reports, ZnO layers on Au(111)
exhibit a flattened g-ZnO surface.15,43 When ZnO was
deposited at ∼450 K in NO2 and flashed at ∼450 K under
UHV, crystalline g-ZnO NSs of both monolayer (ML) and
bilayer (BL) thickness could be observed on the surface of
Au(111) (Figure 1a). Owing to the lattice mismatch between
g-ZnO and Au(111), a moiré pattern with a lattice spacing of
∼23 Å (Figure 1b) could be observed on g-ZnO. Since the
lattice spacing of Zn or O atoms is ∼3.3 Å (Figure 1c) in g-
ZnO NSs, a coincidence lattice was suggested to form between
the (7 × 7)-ZnO supercell and the (8 × 8)-Au(111) substrate
(Figure S1a), assuming the ZnO lattice is well aligned with the
major index of Au(111). The apparent height of ML ZnO NSs
is ∼1.8 Å, and the apparent height of BL ZnO NSs is ∼3.3 Å.
When ZnO was deposited at 300 K and annealed at 600 K in
NO2, one would observe dominantly BL g-ZnO NSs with
roundish shapes on the Au(111) surface (Figure 1d). The
atomic lattice of BL g-ZnO NSs was displayed in Figure 1e,
which showed the same lattice constant of g-ZnO as that of
ML g-ZnO NSs (Figure 1c). Note that the growth of g-ZnO at
elevated temperatures could cause embedded BL and ML g-
ZnO NSs (Figure S1b−e), which were formed by the
oxidation of AuZn surface alloy and could be differentiated
by their corresponding apparent heights (Figure S1f). STM
also showed the preferred growth of ZnO NSs on the fcc
domains of Au(111), which caused the reconstruction of
surface herringbones to surround ZnO NSs (Figure S1b). As
the coverage of ZnO increases on Au(111), ZnO thin films
covering the entire surface of Au(111) could be prepared.
Figure 1f shows the g-ZnO thin film of ∼3.7 ML thickness on
Au(111).
w-ZnO crystals along the (0001) direction typically expose
the polar surfaces of Zn-terminated ZnO(0001) or O-
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terminated ZnO(000−1), where the accumulation of dipole
moments causes a divergence of surface energy. As a polarity
compensation mechanism, the surface of ZnO(0001) under-
goes a reconstruction to exhibit triangular surface terraces and
straight step edges (Figure 2a). The structural model used to
Figure 2. Surface structures of w-ZnO(0001) and ZnO thin films on
Au(111). (a) STM image of w-ZnO(0001) showing the reconstructed
surface with triangular islands and dark pits. (b) Structural model of
the w-ZnO(0001) surface (color representations: gray, Zn; red/pink,
O). (c) STM image of the ZnO film with a layer thickness of ∼4.5
ML on Au(111). (d) STM image of the ZnO film with a layer
thickness of ∼8 ML on Au(111).
simulate the w-ZnO(0001) surface is displayed in Figure 2b.
Large density of triangular pits have been suggested as Zn
vacancies, which maintained the charge neutrality of the
ZnO(0001) surface.21 In comparison, ZnO(0001) layers
grown on metal substrates eliminate the surface polarity by a
reconstruction to a planar graphene-like structure. While the
transition from g-ZnO to w-ZnO has been suggested for g-
ZnO layers on Pt(111) when the layer thickness of g-ZnO has
reached 5 ML,8 such a structural transition has not been
observed for g-ZnO films on Au(111). We tried to grow ZnO
thin films with a layer thickness of over 5 ML but found that
ZnO thin films exhibited the flat g-ZnO surface at ∼4.5 ML
thickness (Figure 2c) and would turn amorphous when the
layer thickness reached ∼8 ML (Figure 2d). Thus, we compare
the reactivity of g-ZnO thin films on Au(111) with that of bulk
w-ZnO(0001) surface directly in the following sections.
Interaction and Reaction between CO and g-ZnO. As
we studied the interaction and reaction between CO and g-
ZnO on Au(111), we examined mainly BL g-ZnO NSs and
thin films. ML g-ZnO NSs are not stable on Au(111) and
would reconstruct to BL g-ZnO NSs at elevated temperatures.
When BL g-ZnO NSs were exposed to 0.39 mbar of CO at 300
K, no adsorbates were observed on BL g-ZnO NSs on both
terrace and edge sites (Figure 3a,b). Similarly, g-ZnO thin films
of ∼3.7 ML thickness on Au(111) remained inert for CO
adsorption at 300 K when they were exposed to 0.36 mbar of
CO (Figure 3c,d) or higher (a few mbar of CO). Thus, both
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Figure 3. In situ STM images of BL g-ZnO NS and g-ZnO thin film
on Au(111) before and after exposure to high-pressure CO at 300 K.
BL g-ZnO NS before (a) and after (b) exposure of 0.39 mbar of CO.
g-ZnO thin film with layer thickness of ∼3.7 ML on Au(111) before
(c) and after (d) exposure of 0.36 mbar of CO. On both surfaces, no
changes were observed on the moiré structures after CO exposure.
BL g-ZnO NSs and thin films on Au(111) appeared inactive
for CO adsorption or reaction at 300 K.
We examined further the interaction and reaction between
CO and BL g-ZnO at elevated temperatures. Figure 4a shows
that the moiré pattern disappeared from the surface of BL g-
ZnO NSs after they were exposed to 0.27 mbar of CO at ∼420
K. In contrast to the smooth edges of BL g-ZnO NSs before
CO exposure, the edges of g-ZnO NSs appeared irregular after
CO exposure, indicating the occurrence of CO oxidation at
edge sites to form CO2 and leave step edges. After the
exposure to 0.27 mbar of CO at ∼480 K, the step edges of g-
ZnO NSs became highly corrugated (Figure 4b,c), which
suggested that Zn atoms at edge sites were destabilized in the
ZnO lattice, accompanying the consumption of edge O atoms
by CO, and would subsequently leave the ZnO lattice or
desorb from the surface. Consistently, Pan et al. reported that
the reactivity of CO oxidation on ZnO/Pt(111) was linear
with the density of interfacial sites between g-ZnO NSs and
Pt(111).41
Note that there are dark holes formed on the surface of BL
g-ZnO NSs after CO oxidation at ∼480 K. Figure 4d displays
an atomic resolution STM image of these dark features, which
could be assigned as O oxygen vacancy clusters on g-ZnO NSs
caused by the reaction between surface O atoms and CO. The
corresponding structure is illustrated in Figure 4e. The
observation of oxygen vacancy clusters corroborated that Zn
atoms could leave the original lattice position upon the loss of
oxygen atoms from neighboring sites. When BL g-ZnO NSs
were cooled to 300 K after the reaction with CO, their surfaces
could also appear with a (√3 × √3)R30° adsorbate structure
(Figure S2). Since NAP-XPS showed no carbonate peak in the
C 1s spectra (Figure 4f) and ex situ XPS showed a water peak
in the O 1s spectra (Figure S3), the adsorbate pattern in Figure
S2 could be attributed to background water adsorption.
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Consistently, DFT calculations (Figure S4) showed a rather
weak adsorption energy of CO2 (−0.30 eV) on the surface of
BL g-ZnO/Au(111).
The reaction between CO and g-ZnO NSs on Au(111) was
also measured sequentially by ex situ XPS. Before CO
exposure, XPS measurements showed that UHV annealing
up to 600 K did not cause obvious changes in the peak
intensity ratio of Zn 2p3/2 over O 1s (IZn/IO), which is
consistent with the intact moiré pattern of g-ZnO NSs in STM
at up to 600 K (Figure S5). Under 0.27 mbar of CO, IZn/IO
was found to increase with the reaction temperature (Figure
4g), because of the continuous reaction between lattice O and
CO to form CO2 which then leaves the surface. Figure 4h
shows that, upon CO reduction, the surface coverage of Zn
would also decrease with the increasing reaction temperature,
which is consistent with the etching of BL g-ZnO NSs in STM
at elevated temperatures. The reduction of ZnO and the
subsequent diffusion/desorption of Zn atoms became much
accelerated at ∼523 K and above, subsequently causing a sharp
increase in IZn/IO (Figure 4g). Meanwhile, Zn LMM Auger
spectra also showed that the intensity of Zn2+ decreased with
the increasing reaction temperature and the main peak shifted
to higher kinetic energies at above 523 K, indicating the
reduction of ZnO24 and consistent with ex situ XPS
measurements (Figure S3).
In contrast, g-ZnO thin films of ∼3.7 ML thickness on
Au(111) appeared inert to CO under reaction conditions
similar to those described above. NAP-STM shows that the
moiré lattice of the g-ZnO film could still be clearly resolved
(Figure 5a) and no obvious change in the surface morphology
was detected during in situ scanning under 0.27 mbar of CO at
∼460 K (Figure S6). After the evacuation of CO, no oxygen
vacancies or adsorbates were resolved on the film surface
(Figure 5b). Consistently, IZn/IO from ex situ XPS measure-
ments stayed nearly constant (Figure S7). Zn LMM spectra
also remained the same during CO exposure at elevated
temperatures, which confirmed the structural integrity of g-
ZnO thin films on Au(111). Similarly, a BL g-ZnO film on
Au(111) was also not reactive to CO under similar reaction
conditions (Figure S7). Thus, g-ZnO NSs on Au(111) are
much more active toward CO in comparison to the closed g-
ZnO thin films on Au(111).
Interaction and Reaction between CO and w-
ZnO(0001). To maintain charge neutrality at the surface,
Zn-terminated w-ZnO(0001) undergoes surface reconstruc-
tion to expose triangular islands with straight step edges at the
surface. These triangular islands could retain their structural
integrity at elevated temperatures (up to 530 K in our study)
as they were at room temperature (Figure S8). On exposure to
CO, the NAP-STM image (Figure 6a) showed no obvious
change at the step or pit sites at 300 K, although these step and
pit sites expose coordinatively unsaturated sites. Under 0.33
mbar of CO, no obvious changes were found in the surface
morphology of w-ZnO(0001) at ∼340 K (Figure 6b), where
triangular islands on w-ZnO remained with straight step edges.
However, the reaction between CO and w-ZnO(0001) could
be observed at higher temperatures. It was found that, when
the surface temperature was raised to ∼360 K, the surface of w-
ZnO(0001) changed drastically with the straight steps of the
ZnO terrace etched into a sawtooth shape and an increase in
the size of pits in the ZnO terrace (Figure 6c). In situ STM
images (Figure S9) showed further that the etching process
occurs from both the step edge and the inside rim of the pits.
DOI: 10.1021/acscatal.8b03687
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Figure 4. Reactivity of BL g-ZnO NSs on Au(111). (a) Large-scale STM image of BL g-ZnO NSs after exposure to 0.27 mbar of CO at ∼420 K.
The moiré pattern disappeared from the g-ZnO surface. (b) STM image of BL g-ZnO NS after exposure to 0.27 mbar of CO at ∼480 K. The
squared area is magnified in (c), and white arrows mark the corrugated edges formed by the reaction with CO. (d) Atomic resolution STM image
showing the missing neighboring oxygen atoms on BL g-ZnO NSs after the reaction with CO at ∼480 K. White grid lines are imposed to illustrate
the oxygen lattice. The corresponding structural model is displayed in (e). The dashed circles mark the missing atoms in (d). STM images in (a)−
(d) were taken at 300 K after the evacuation of CO. (f) NAP-XPS C 1s spectra for BL g-ZnO NSs on Au(111) under 0.4 mbar of CO at elevated
temperatures. The carbon peaks at ∼284 eV are attributed to contamination from the high-pressure background. Gaseous CO gives the peaks
above 291 eV. (g) XPS peak intensity ratio of Zn 2p3/2 over O 1s (IZn/IO) for BL g-ZnO NSs on Au(111) after exposing to 0.27 mbar CO at
various annealing temperatures (red line) and under UHV (blue line). (h) Zn LMM Auger peaks of BL g-ZnO NSs on Au(111) as a function of
annealing temperatures under 0.27 mbar of CO. Pristine BL g-ZnO NSs before reaction (black) and Zn metal films (purple) deposited on Au(111)
are also displayed for reference. Scanning parameters: (b) Vs = +1.8 V, It = 0.13 nA; (e) Vs = +0.028 V, It = 0.86 nA.

Figure 5. Reactivity of g-ZnO thin films with a layer thickness of ∼3.7 ML on Au(111). (a) NAP-STM image of g-ZnO thin film under 0.27 mbar
of CO at ∼460 K. (b) STM image of a g-ZnO thin film after the evacuation of CO and cooling to 300 K. The moiré structure of g-ZnO thin films
was preserved throughout CO treatments. (c) Zn LMM Auger peaks of a g-ZnO thin film on Au(111) after exposing to 0.27 mbar CO at various
annealing temperatures. A pristine g-ZnO thin film before the reaction (black) and Zn metal film (purple) deposited on Au(111) are also displayed
for reference.

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Figure 6. Reactivity of the w-ZnO(0001) surface toward CO. NAP-STM images of the w-ZnO(0001) surface under 0.33 mbar of CO at elevated
temperatures: (a) at 300 K and (b) at ∼340 K (no obvious changes in the surface morphology were observed); (c) at ∼360 K (the steps appeared
etched and pits appeared enlarged due to the reaction between lattice O and CO); (d, e) under 0.33 mbar of CO at ∼530 K (small triangular
islands disappeared and the curvature of steps increased; white arrows indicate the etched steps). (f) NAP-XPS C 1s spectra for w-ZnO(0001)
under 0.4 mbar of CO at elevated temperatures. The carbonate peak at ∼289 eV, marked by a dashed rectangle, appeared between 300 and 500 K.
Gaseous CO gave the peaks at above 291 eV. The carbon peaks at ∼284 eV were attributed to contamination from high-pressure background. (g)
STM image after the evacuation of 0.33 mbar of CO and cooling to 300 K. The terrace appeared highly disordered with adsorbates.

The loss of edge O atoms by reacting with CO caused an
imbalance of surface charges. To maintain the charge
neutrality, Zn atoms also diffused away from the step edges,
such that the surface of ZnO(0001) appeared etched.
When the surface temperature was further raised to ∼530 K,
the steps of w-ZnO(0001) were etched severely and no
triangle steps were obvious from the surface due to the
enhanced CO2 desorption at higher temperature (Figure 6d,e).
Apparently, the etching speed is faster at the step edge in
comparison to that from inside the pits. When CO reacts with
lattice O on w-ZnO(0001), O atoms at the step edges or the
inside rim of pits are both undercoordinated and favored sites
for CO oxidation. However, the structural model (Figure S10)
shows that the triangular islands expose 2-coordinated O
atoms at corner sites of step edges, which are expected to be
more reactive than 3-coordinated O atoms at step sites.
Meanwhile, the inside rim of pits does not expose 2-
coordinated O atoms. Since the removal of corner O atoms
could trigger sequential removal of Zn atoms and the
generation of new corner O atoms, step edges of w-
ZnO(0001) could exhibit higher activity in CO oxidation in
comparison to the inner rim of pits on w-ZnO(0001).
NAP-XPS on w-ZnO(0001) showed the presence of a small
carbonate peak in the C 1s spectra (Figure 6f) between 300
and 500 K, indicating a strong adsorption of CO2 on
w-ZnO(0001). Our DFT calculations (Figure S4) also
suggested a strong adsorption energy of CO2 at −1.79 eV on
the terrace sites of w-ZnO(0001). The formation of carbonate
could block active sites on w-ZnO(0001) for CO oxidation.
However, our STM study has shown that the continuous
etching of step edges could be observed at above 360 K on w-
ZnO(0001). Thus, the formation of carbonates was likely
caused by CO2 adsorption on surface terraces. At high
1378
temperatures, the presence of surface carbonates is an
equilibrium between the adsorption and desorption of CO2.
The lifetime of surface carbonates might be too short to be
caught in NAP-STM measurements. Although NAP-STM did
not resolve surface carbonates at high temperatures, the
appearance of surface carbonates on w-ZnO(0001) could be
observed at 300 K after the evacuation of CO (Figure 6g). In
comparison, w-ZnO(0001) is more active than g-ZnO NSs or
thin film on Au(111) in the reaction with CO.
Reaction between H2 and ZnO at 300 K. The
interaction and reaction between H2 and g-ZnO/w-ZnO
were also compared under NAP conditions and demonstrated
a reactivity trend similar to that described above. Figure 7a
displays STM images of BL g-ZnO NSs under 1.69 mbar of H2
at 300 K, which showed that the surface of g-ZnO NSs remains
intact, with the surface moiré pattern well preserved. In
contrast, the exposure of w-ZnO(0001) to 1.33 mbar of H2 at
300 K leads to significant changes on the surface of w-
ZnO(0001), where a high density of triangular clusters
emerged and caused the roughening of the w-ZnO(0001)
surface (Figure 7b). The hydrogenation of the w-ZnO(0001)
surface at 300 K could be confirmed from ex situ XPS
measurements (Figure 7c), which detected the appearance of a
shoulder OH peak at 531.4 eV in the O 1s spectra. The 0.2 eV
shift of the lattice O peak toward higher binding energy could
be attributed to band bending induced by H2 adsorption.44
Upon the dissociation of H2 on w-ZnO(0001), the extra
charge from hydrogen adsorption caused an imbalance in
surface dipole moments and O atoms are likely to be lifted to
form OH species, so that the charge neutrality could be
preserved at the surface. These OH groups are responsible for
surface reconstruction and the formation of triangular clusters
on w-ZnO(0001). The planar Zn-terminated w-ZnO(0001)
DOI: 10.1021/acscatal.8b03687
ACS Catal. 2019, 9, 1373−1382
ACS Catalysis
Figure 7. H2 activation over BL g-ZnO NSs on Au(111) and w-
ZnO(0001). (a) STM image of BL g-ZnO NSs on Au(111) after
exposure to 1.69 mbar of H2 (image taken after the evacuation of H2).
No obvious changes were observed in the moiré structures of g-ZnO
or the herringbone structures of Au(111). (b) STM image of w-
ZnO(0001) after exposure to 1.33 mbar of H2 at 300 K (image taken
after the evacuation of H2). Significant morphology changes took
place on w-ZnO(0001) with the appearance of high-density triangular
clusters (marked by white circles). The side length of triangular
clusters is ∼3 nm. (c) XPS O 1s spectra of w-ZnO(0001) before (red)
and after (orange) exposure to 100 mbar of H2. (d) STM image of the
recovery of the w-ZnO(0001) surface after cycles of Ar ion sputtering
and UHV annealing at ∼1000 K.
surface was only recovered after cycles of Ar ion sputtering and
UHV annealing at ∼1000 K (Figure 7d). Our study thus shows
w-ZnO(0001) is more reactive toward the dissociative
adsorption of H2 than g-ZnO.
Comparison of the Reactivities between CO and g-
ZnO/w-ZnO. From the text above, we have compared the
reactivities of g-ZnO on Au(111) and w-ZnO(0001). The
surface of w-ZnO(0001) was found to exhibit a reactivity
higher than that of g-ZnO NSs or thin films on Au(111).
Among the different forms of g-ZnO, BL g-ZnO NSs are more
reactive toward CO than BL g-ZnO thin films. The reactivity
comparison was made on the basis of the reaction between CO
and lattice oxygen atoms on the various ZnO structures. Yet,
such a comparison could still provide an indication for the
reactivity of ZnO structures in general, since CO oxidation on
oxide surfaces has usually been suggested to occur via the
Mars−van Krevelen mechanism:45 i.e., CO molecules would
react directly with lattice oxygen atoms.
DFT calculations were performed to understand the reaction
between CO and BL g-ZnO NS/film on Au(111) or w-
ZnO(0001). Figure 8 displays the potential energy diagram of
CO oxidation on BL g-ZnO NS and w-ZnO(0001). Consistent
with experimental studies, CO molecules were found to adsorb
weakly on these surfaces. The exothermic process of CO
oxidation could take place via a CO reaction with lattice O,
and the formation of CO2* is more exothermic on w-
ZnO(0001) than on BL g-ZnO NS. Here, we assume that the
formation energy of O vacancy (EOvf) could be used to
1379
Research Article
Figure 8. DFT-calculated potential energy diagrams for CO oxidation
over supported BL g-ZnO NS and w-ZnO(0001). The optimized
structures of BL g-ZnO NS and w-ZnO(0001) are shown in panels
(color representations: yellow, Au; gray, Zn; red, O; pink, O; black,
C). The dashed circles mark the formation of O vacancies. Asterisks
(*) represent surface adsorption sites, and Ov indicates surfaces with
oxygen vacancy.
describe the reactivity difference of these oxide surfaces. Our
calculations (Table 1) show that EOvf is −2.29 eV for w-
ZnO(0001), −1.48 eV for BL g-ZnO NS, and −0.83 eV for BL
g-ZnO film (Figure S11). The sequence of EOvf on these
surfaces agrees well with the reactivity trend for CO oxidation
as measured in experimental studies: w-ZnO(0001) > BL g-
ZnO NS > BL g-ZnO film.
Through the analysis of projected density of states (pDOS)
and charge density differences, the trend in EOvf could be
understood and the reactivities of lattice oxygen atoms in
different ZnO structures could be derived, consistent with
experimental studies. Figure 9a shows that O atoms on w-
ZnO(0001) have richer 2p states around the Fermi level in
comparison to O atoms in BL g-ZnO NS. This means that O
in BL g-ZnO NS has stronger bonding in comparison to O on
w-ZnO, as also reflected in the analysis of charge density
differences (Figure 9b,c). Bader charge analysis also suggested
a charge transfer from ZnO to Au(111) at 0.02 |e| per ZnO,
implying the reactivity of g-ZnO NS is affected by the
interaction between Au(111) and ZnO. In fact, the enhanced
catalytic activity exhibited at the metal/oxide interface has
often been attributed to (1) the presence of dual catalytic sites
and (2) the electronic properties of supported oxide NSs tuned
by interfacial interaction. Taking the ZnO/Cu(111) system as
an example, Mahapatra et al.46 have suggested that the ZnO/
Cu interface is highly active for catalyzing CO oxidation and
the water-gas shift reaction. Palomino et al.47 showed that the
ZnO/Cu interface is key to the enhanced binding and
conversion of CO2 in methanol synthesis. The reactivity at
the g-ZnO/Au interface is expected to be much lower than that
of the g-ZnO/Cu interface, owing to the inertness of Au and
the weaker interaction between ZnO and Au. DFT
calculations39 have shown that the interfacial electron transfer
is more significant from Cu(111) to ZnO in comparison to the
electron transfer from ZnO to Au(111).
Further, the surface polarity of w-ZnO and BL g-ZnO NS
could be used as an indicator to explain the discrepancy in
reactivity. The strength of polarity48 can be estimated with
1
Dz = N ∑ qizi , where qi is the Bader charge value, zi is the z
coordinate of the atom, and N is the number of Zn−O pairs.
The average surface rumpling of BL g-ZnO NS is 0.07 Å,
which is much smaller than that of w-ZnO(0001) (0.31 Å). In
combination with the charge of atoms from the surface layer,
w-ZnO(0001) was found to exhibit surface polarity higher
DOI: 10.1021/acscatal.8b03687
ACS Catal. 2019, 9, 1373−1382
ACS Catalysis Research Article

Table 1. Summary of DFT Calculation Results of BL g-ZnO on Au(111) and w-ZnO(0001)

sitea EOvf/eVb q/|e|c R/Åd CNe polarity/Df
BL g-ZnO film −0.83 −1.13 0.06 4 0.02
NS −1.48 −1.13 0.07 3 0.77
w-ZnO(0001) corner −2.29 −0.83 −0.31 2 1.47
step −1.99 −1.10 3
a
Sites for the formation of O vacancy. bThe formation energy of O vacancy (EOvf) is defined as EOvf = Eafter + ECO2− (Ebefore + ECO), where Ebefore is
the total energy of the pristine structure without O vacancy, Eafter is the total energy of the reacted structure with one O vacancy, and ECO and ECO2
are the energies of CO and CO2 molecules at their optimized gas-phase geometries, respectively. cBader charge analysis.49 dAverage rumpling of
surface ZnO layer. eCoordination number of active O site. fCalculated surface or boundary polarity (also called dipole48).

of w-ZnO. In contrast, g-ZnO on Au(111) appeared inert

under 1.69 mbar of H2 at 300 K. The differences in reactivity
among BL g-ZnO NSs or thin films on Au(111) and w-
ZnO(0001) could be rationalized from the differences in EOvf
and further attributed to the charge transfer on oxygen atoms
and surface polarity.

■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b03687.
Additional images and data as described in the text
(PDF)

■ AUTHOR INFORMATION
Corresponding Authors
*E-mail for F.Y.: fyang@dicp.ac.cn.
*E-mail for X.B.: xhbao@dicp.ac.cn.
ORCID
Figure 9. (a) DFT-calculated projected density of states correspond- Qiang Fu: 0000-0001-5316-6758
ing to O 2p orbitals of supported BL g-ZnO NS (red) and w-
ZnO(0001) (blue). Charge density differences of edge O sites at (b) Fan Yang: 0000-0002-1406-9717
BL g-ZnO NS on Au(111) and (c) w-ZnO(0001). Blue circles Xinhe Bao: 0000-0001-9404-6429
indicate a decrease in local electron densities, and yellow circles Author Contributions
indicate an increase. ∇
H.C., L.L., and Y.L. contributed equally to this work.
Notes
(1.47 D) than that of BL g-ZnO NS (0.77 D). The surface of
The authors declare no competing financial interest.

■
BL g-ZnO NS could become more stable through depolariza-
tion with respect to w-ZnO. Inversely, the higher polarity of w-
ZnO could induce more flexibility of lattice O and thereby
ACKNOWLEDGMENTS
higher activity toward CO molecules (Table 1). This work was financially supported by the Ministry of Science

■ SUMMARY
The reactivities of g-ZnO(0001) NSs and thin films on
Au(111) and the w-ZnO(0001) surface toward CO and H2
were investigated using NAP-STM, XPS, and DFT calcu-
lations. On Au(111), crystalline g-ZnO NSs and thin films of
and Technology of China (2017YFB0602205,
2016YFA0202803), the Strategic Priority Research Program
of the Chinese Academy of Sciences (XDB17020200), and the
Natural Science Foundation of China (21473191, 91545204).
We thank Junfa Zhu, Haibin Pan, Xusheng Zheng and Lihui
Wu at BL10B beamline in National Synchrotron Radiation
Laboratory for experimental assistance.

different layer thicknesses could be prepared with their surface
structures resolved at atomic resolution. At elevated temper-
atures, CO oxidation took place primarily at the edge sites of
w-ZnO and the interface between g-ZnO NSs and Au(111).
The desorption of CO2 left oxygen and zinc vacancies at the
surfaces. In contrast, g-ZnO thin films with a layer thickness
between 2 and 4 ML on Au(111) are inert for CO oxidation
under similar reaction conditions. From the onset reaction
temperature, the reactivity trend could be found as w-
ZnO(0001) > BL g-ZnO NSs > BL g-ZnO thin films.
Similarly, the w-ZnO(0001) surface exhibited a much higher
reactivity toward the dissociative adsorption of H2 at 300 K,
where OH groups induced the reconstruction and roughening
■
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