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CO and H2 Activation Over G ZnO Layers and W ZnO
CO and H2 Activation Over G ZnO Layers and W ZnO
■ INTRODUCTION
Zinc oxide, ZnO, has received tremendous interest because of
and reactants, such as CO, CO2, and H2, on well-defined
model catalysts.
its wide applications in the semiconductor,1 optical,2 and Currently, model ZnO catalysts could be prepared via the
chemical industries.3 ZnO-based catalysts have been used in a growth of ZnO layers on metal single crystals or through the
number of industrial applications, such as the water-gas shift use of ZnO single crystals exposing different surface planes.
reaction4−6 and methanol synthesis,7,8 and have been The syntheses of crystalline ZnO layers have been reported on
increasingly recognized for novel catalytic processes, such as a number of planar metal surfaces, such as Pd(111),12
the direct synthesis of light olefins from syngas.9,10 For Pt(111),13,14 Au(111),15−17 Ag(111),18,19 Cu(111),18 and
methanol synthesis, ZnO is considered as a major catalytic brass(111).20 These crystalline ZnO thin films are stoichio-
component in the Cu/ZnO/Al2O3 catalyst for the hydro- metric, with a surface structure similar to the (0001) facet of
genation of carbon monoxide and carbon dioxide. However, wurtzite ZnO, but become flattened and thus expose a
the role of ZnO has not been clear and has attracted nonpolar graphene-like ZnO (g-ZnO) surface. The wurtzite
tremendous attention in current research.3,7,11 In syngas structure is the most stable phase of ZnO under ambient
conversion, Jiao et al.9 recently reported a direct and highly conditions. Wurtzite ZnO (w-ZnO) (0001) is also a typical
selective process by using nanocomposite catalysts comprised polar oxide surface and exhibits reconstructed surface planes
of metal oxides and zeolites. In this nanocomposite catalyst, with triangular islands and holes to compensate for the extra
ZnO was employed as a main oxide component for the
activation of CO and H2. Yet, the mechanism of CO and H2 Received: September 13, 2018
activation remains to be explored. To address the catalytic role Revised: December 11, 2018
of ZnO, it is essential to study the interaction between ZnO Published: December 31, 2018
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- The Au(111) single crystal was cleaned by cycles of Ar ion
structed w-ZnO(0001) surface have not been clear at the sputtering (1 keV, 10 μA) and UHV annealing at ∼800 K. The
atomic level. Previous studies on ZnO layers supported on w-ZnO(0001) single crystal (MTI) was cleaned by cycles of Ar
Pt(111)14 and Pd(111)12 have suggested that the coplanar ion sputtering (1 keV, 10 μA) and UHV annealing at ∼1000 K.
structure of g-ZnO(0001) layers would turn into the wurtzite ZnO layers were prepared on Au(111) by evaporating Zn
structure of w-ZnO(0001) when the number of ZnO layers has atoms in the presence of ∼1 × 10−7 mbar of NO2 at various
surpassed a critical thickness.23−25 It is thus interesting to substrate temperatures. NO2 molecules were dosed through
compare the reactivity of the g-ZnO(0001) layers with that of the stainless steel tube directed at the surface of Au(111). The
the w-ZnO(0001) surface, owing to their structural similarity. surface coverage of ZnO was estimated from the deposition
In this article, we studied the interaction and reaction time. STM images were acquired using Pt/Ir tips with the bias
between CO/H2 and the surfaces of g-ZnO(0001) on Au(111) voltage (VS) applied to the sample. STM images were
and w-ZnO(0001), using near-ambient-pressure scanning processed with SPIP software from Image Metrology of
tunneling microscopy (NAP-STM), X-ray photoelectron Denmark.
spectroscopy (XPS, including NAP-XPS), and density func- XPS spectra were analyzed by CasaXPS software with a
tional theory (DFT) calculations. Our study analyzed the Shirley background subtraction and 70/30 Gaussian−Lor-
structures of g-ZnO and w-ZnO, as well as their reactivity entzian fits. Zn 2p3/2 and O 1s XP spectra were used for the
differences toward CO and H2. We show that surface polarity calculation of the Zn:O ratio. From STM and XPS, the surface
could be used as a descriptor for the reactivity of ZnO of pristine BL g-ZnO is almost defect free and peaks of Zn
structures. 2p3/2 and O 1s are highly symmetric. Therefore, we considered
■
that pristine g-ZnO is stoichiometric. In ex situ XPS studies,
the exposure of g-ZnO to high-pressure gas led to the
EXPERIMENTAL SECTION
formation of a shoulder O 1s peak at ∼532.0 eV, which could
The experiments were carried out in three ultrahigh-vacuum be attributed to water adsorption from the background during
(UHV) systems. The first system was equipped with a NAP- high-pressure experiments.16 Thus, peak deconvolution was
STM26,27 (SPECS, base pressure <3 × 10−10 mbar), mass used to separate the influence of the shoulder O 1s peak and
spectroscopy (Hiden), and cleaning facilities. The second only the peak area of lattice O 1s was used to calculate the
system was equipped with XPS (SPECS, Al Kα source, base Zn:O ratio after CO exposure. The analysis of XPS results is
pressure <5 × 10−10 mbar), a high-temperature and high- displayed in Tables S1 and S2. For a comparison of the Zn:O
pressure reactor with cleaning facilities. The third system was ratio, peak areas of Zn 2p3/2 and O 1s after CO exposure at
equipped with NAP-XPS (SPECS, base pressure <5 × 10−10 elevated temperatures were all normalized to their peak areas
mbar) with a monochromatic Al Kα source. The exposure to after CO exposure at 300 K since there was no CO oxidation at
reaction gas was done by backfilling the chamber. 300 K for g-ZnO.
1374 DOI: 10.1021/acscatal.8b03687
ACS Catal. 2019, 9, 1373−1382
ACS Catalysis Research Article
DFT calculations were carried out on the basis of the Vienna terminated ZnO(000−1), where the accumulation of dipole
ab initio simulation packages (VASP 5.4).28−32 The exchange- moments causes a divergence of surface energy. As a polarity
correlation potential effect was treated by the Perdew−Burke− compensation mechanism, the surface of ZnO(0001) under-
Ernzerhof (PBE) method33 at a level of the generalized goes a reconstruction to exhibit triangular surface terraces and
gradient approximation (GGA).34 The projector-augmented straight step edges (Figure 2a). The structural model used to
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.
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.
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 temperatures, the presence of surface carbonates is an
imbalance of surface charges. To maintain the charge equilibrium between the adsorption and desorption of CO2.
neutrality, Zn atoms also diffused away from the step edges, The lifetime of surface carbonates might be too short to be
such that the surface of ZnO(0001) appeared etched. caught in NAP-STM measurements. Although NAP-STM did
When the surface temperature was further raised to ∼530 K, not resolve surface carbonates at high temperatures, the
the steps of w-ZnO(0001) were etched severely and no appearance of surface carbonates on w-ZnO(0001) could be
triangle steps were obvious from the surface due to the observed at 300 K after the evacuation of CO (Figure 6g). In
enhanced CO2 desorption at higher temperature (Figure 6d,e). comparison, w-ZnO(0001) is more active than g-ZnO NSs or
Apparently, the etching speed is faster at the step edge in thin film on Au(111) in the reaction with CO.
comparison to that from inside the pits. When CO reacts with Reaction between H2 and ZnO at 300 K. The
lattice O on w-ZnO(0001), O atoms at the step edges or the interaction and reaction between H2 and g-ZnO/w-ZnO
inside rim of pits are both undercoordinated and favored sites were also compared under NAP conditions and demonstrated
for CO oxidation. However, the structural model (Figure S10) a reactivity trend similar to that described above. Figure 7a
shows that the triangular islands expose 2-coordinated O displays STM images of BL g-ZnO NSs under 1.69 mbar of H2
atoms at corner sites of step edges, which are expected to be at 300 K, which showed that the surface of g-ZnO NSs remains
more reactive than 3-coordinated O atoms at step sites. intact, with the surface moiré pattern well preserved. In
Meanwhile, the inside rim of pits does not expose 2- contrast, the exposure of w-ZnO(0001) to 1.33 mbar of H2 at
coordinated O atoms. Since the removal of corner O atoms 300 K leads to significant changes on the surface of w-
could trigger sequential removal of Zn atoms and the ZnO(0001), where a high density of triangular clusters
generation of new corner O atoms, step edges of w- emerged and caused the roughening of the w-ZnO(0001)
ZnO(0001) could exhibit higher activity in CO oxidation in surface (Figure 7b). The hydrogenation of the w-ZnO(0001)
comparison to the inner rim of pits on w-ZnO(0001). surface at 300 K could be confirmed from ex situ XPS
NAP-XPS on w-ZnO(0001) showed the presence of a small measurements (Figure 7c), which detected the appearance of a
carbonate peak in the C 1s spectra (Figure 6f) between 300 shoulder OH peak at 531.4 eV in the O 1s spectra. The 0.2 eV
and 500 K, indicating a strong adsorption of CO2 on shift of the lattice O peak toward higher binding energy could
w-ZnO(0001). Our DFT calculations (Figure S4) also be attributed to band bending induced by H2 adsorption.44
suggested a strong adsorption energy of CO2 at −1.79 eV on Upon the dissociation of H2 on w-ZnO(0001), the extra
the terrace sites of w-ZnO(0001). The formation of carbonate charge from hydrogen adsorption caused an imbalance in
could block active sites on w-ZnO(0001) for CO oxidation. surface dipole moments and O atoms are likely to be lifted to
However, our STM study has shown that the continuous form OH species, so that the charge neutrality could be
etching of step edges could be observed at above 360 K on w- preserved at the surface. These OH groups are responsible for
ZnO(0001). Thus, the formation of carbonates was likely surface reconstruction and the formation of triangular clusters
caused by CO2 adsorption on surface terraces. At high on w-ZnO(0001). The planar Zn-terminated w-ZnO(0001)
1378 DOI: 10.1021/acscatal.8b03687
ACS Catal. 2019, 9, 1373−1382
ACS Catalysis Research Article
■
*
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
and Technology of China (2017YFB0602205,
2016YFA0202803), the Strategic Priority Research Program
of the Chinese Academy of Sciences (XDB17020200), and the
Au(111) and the w-ZnO(0001) surface toward CO and H2 Natural Science Foundation of China (21473191, 91545204).
were investigated using NAP-STM, XPS, and DFT calcu- We thank Junfa Zhu, Haibin Pan, Xusheng Zheng and Lihui
lations. On Au(111), crystalline g-ZnO NSs and thin films of 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-
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