Journal of Catalysis 404 (2021) 96–108

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Facet-Dependent selectivity of CeO2 nanoparticles in 2-Propanol

conversion
Berlin Sudduth a, Dongmin Yun a, Junming Sun a, Yong Wang a,b,⇑
a
The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USA
b
Insititute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, USA

a r t i c l e i n f o a b s t r a c t

Article history: CeO2 nanoshapes, cubes with dominant (1 0 0) facets and octahedra with dominant (1 1 1) facets, were
Received 8 July 2021 synthesized to investigate the influence of surface structure on acid-base properties. An optimization
Revised 4 September 2021 of calcination temperatures, coupled with Raman and TEM, was employed to minimize the intrinsic
Accepted 11 September 2021
(Frenkel-type) defect sites and their potential complications on the facet studies involved in this work.
Available online 20 September 2021
The acid-base properties of these CeO2 nanoshapes were characterized with in situ pyridine and CO2
adsorption using infrared spectroscopy and quantified using pyridine, ammonia, and CO2 temperature-
Keywords:
programmed desorption (TPD). The (1 0 0) facet displayed weaker acid sites with lower site density than
Ceria
Facets
the (1 1 1) facet which had a similar density of base sites but those on the (1 0 0) facet were stronger. A
Acid-base properties strong correlation was observed between 2-propanol conversion and each facet’s acid-base properties.
2-Propanol CeO2 cubes exhibited greater base-site catalyzed dehydrogenation to acetone while the more acidic
Dehydrogenation CeO2 octahedra were more active in dehydration to propene.
Dehydration Ó 2021 Published by Elsevier Inc.

1. Introduction
The acid-base properties of solid metal oxides such as titania
(TiO2), zirconia (ZrO2), and ceria (CeO2) play key roles in catalytic
reactions [1–3]. Studies characterizing the acid-base properties of
such metal oxides commonly reported that coordinatively unsatu-
rated metal cations (Mn+) exposed on the surface act as Lewis acids,
while coordinatively unsaturated oxygen anions (O2–) act as Lewis
bases [4,5]. Surface functional groups can also influence acid-base
properties as demonstrated with hydroxyl groups (OH) which can
act as Brønsted acid or base sites depending on the metal oxide
[6,7]. The types and strengths of acid and base sites can vary signif-
icantly between different metal oxides [5,8,9], but surface science
and theoretical studies have shown that surface structure alone
may be a significant contributor. For example, in MgO [10] and
Al2O3 [11] studies, the coordination environment of the surfaces
leads to variations in acid-base properties. Acid-base properties
are often characterized by obtaining infrared (IR) spectra of the
metal oxide after adsorption of basic probe molecules (ammonia,
pyridine, and CD3CN) or acidic probe molecules (CO2, CHCl3 and
benzaldehyde) to identify acid or base sites, respectively
⇑ Corresponding author at: The Gene and Linda Voiland School of Chemical
Engineering and Bioengineering, Washington State University, Pullman, WA 99164,
USA.
E-mail address: yong.wang@pnnl.gov (Y. Wang).
[2,12,13]. The type and strength of these sites are determined by
IR features (peak frequency and intensity) of the adsorbed probe
molecules and changes to associated functional groups (e.g.,
hydroxyl groups) on the surface [6,14–17]. However, identifying
the structure–function relationships between metal oxide surfaces
and their acid-base catalytic behavior remains elusive owing to the
structural heterogeneity of active sites on traditional polycrys-
talline nanoparticles [5]. Additionally, it has been shown that the
concentration of oxygen defect sites varies depending on both
the exposed facet and the method of synthesis. The presence of
oxygen vacancies has been closely associated with the redox prop-
erties of CeO2 [18–20]; with more defective nanocrystals express-
ing increased reactivity in redox reactions regardless of the
dominant facet exposed [21,22]. The influence of oxygen vacancies
on acid-base properties is relatively less explored but may further
complicate the development of structure–function relationships;
some studies suggest defect sites increase the concentration of
Lewis acid sites [23–25].
Metal oxide nanoparticles with specific morphologies are
promising due to their more uniform surface terminations; analo-
gous to the crystallographically synthesized single crystals used in
surface science studies [26–28]. A recent study demonstrated that
both acid site density, presence of Brønsted acids, and the 2-
propanol adsorption species are influenced by the dominantly
exposed facet on TiO2 model nanoparticles [29]. These structural

https://doi.org/10.1016/j.jcat.2021.09.009
0021-9517/Ó 2021 Published by Elsevier Inc.
B. Sudduth, D. Yun, J. Sun et al.
differences resulted in increased acid site catalyzed dehydration of
2-propanol observed on TiO2(1 0 1) due to a lower activation bar-
rier associated with the molecularly adsorbed reaction mechanism
compared to that of TiO2 (0 0 1) which was supported by DFT calcu-
lations. CeO2 with different nanoshapes have been hydrothermally
synthesized which possess well-defined surface structures [30–
32]. CeO2 nanoshapes in the form of octahedra dominantly expos-
ing the (1 1 1), cubes exposing the (1 0 0), and rods with a mixture
of (1 1 0) and (1 0 0) facets provide an opportunity to probe these
specific surface structures while providing meaningful reactivity
measurements on high surface area nanocrystals. The surface-
dependent acid-base properties of well-defined ceria nanocrystals
were investigated by Wu et al., by means of in situ IR spectroscopy
and temperature programmed desorption (TPD) [33]. It was sug-
gested that the strengths of Lewis acid sites (Ce cations) are rela-
tively similar regardless of the shape of the ceria nanocrystals
while the amount and strength of base sites (O anions and hydro-
xyl groups) are shape and defect dependent. However, the relative
quantity of acid sites on these CeO2 nanoshapes, the contribution
of defect density and the impact of these acid-base properties on
a catalytic reaction has yet to be investigated.
In this study, we characterized the acid-base properties of CeO2
nanocrystals with well-defined (1 1 1) facets in the form of octahe-
dra and (1 0 0) facets in the form of cubes using in situ IR spec-
troscopy and temperature programmed desorption. CeO2(1 1 1),
Fig. 1a, is the most stable surface with the exposed O and Ce each
having a single coordination vacancy [34]. Scanning tunneling
microscopy (STM) [35], atomic force microscopy (AFM) [36] and
ion scattering [36] studies have shown that CeO2(1 1 1) is termi-
nated by a layer of O. A simple truncation along CeO2(1 0 0) results
in an unstable surface due to the dipole caused by the presence of
twice as many O as Ce in adjacent layers. This dipole is eliminated
when half of the surface O are moved from the top face to the bot-
tom face [37]. This rearrangement has been supported by STM [38]
and high-resolution transmission election microscopy (HRTEM)
[39,40] experiments which suggest the surface is not terminated
by O or Ce exclusively, but a mixture of both ions. The O and Ce
on the CeO2(1 0 0) structure in Fig. 1b is the reconstructed configu-
ration [41] in which both ions have two coordination vacancies.
In addition to studying the two different surface facets, the
effect of defects on acid-base properties was studied by varying
Fig. 1. Top and side views of (a) CeO2(1 1 1) and (b) reconstructed CeO2(1 0 0)
surfaces. Ce is shown in blue and O in red. The coordinated vacancies (CV) of the
first layer O and second layer Ce are indicated. (SINGLE COLUMN). (For interpre-
tation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
97
Journal of Catalysis 404 (2021) 96–108
the calcination temperatures of the synthesized nanoshapes. Com-
mercial CeO2 was also studied due to its unique defect density and
polycrystalline structure. The catalytic behavior of these different
CeO2 nanocrystals was examined using 2-propanol dehydrogena-
tion and dehydration as a probe reaction. 2-propanol has been
widely used to study acid-base catalysis of metal oxides
[9,29,42–45] because, while ethanol and 1-propanol follow similar
pathways, 2-propanol tends to be more sensitive to differences in
acid-base properties [27,46]. The strength and amount of acid
and base sites of ceria nanocrystals are reflected in 2-propanol con-
version and selectivity toward acetone and propene.
2. Experimental methods
2.1. Catalyst preparation
CeO2 nanoshapes (cubes and octahedra) were synthesized using
hydrothermal methods with a Ce(NO3)3
6H2O (Sigma-Aldrich
99.99%) cerium source and a NaOH precipitator, as reported else-
where [30,32]. Briefly, the morphology of the ceria was determined
by varying the concentrations of the precursors and the hydrother-
mal treatment conditions. CeO2 cubes (denoted as CeO2-C) were
synthesized using an aqueous solution of 36 g Ce(NO3)3
6H2O in
350 mL of DI water and an aqueous solution of 2.17 g NaOH in
50 mL DI water while ceria octahedra (denoted as CeO2-O) used
15 g and 0.025 g of each respective precursor. The two precursor
solutions were mixed at room temperature before being placed
in a four 125 mL Teflon lined steel autoclave and heated to
180 °C for 24 h (cubes) or 12 h (octahedra). The resulting CeO2 pre-
cipitate was separated via centrifuge and washed with deionized
water and ethanol three times each in an ultrasonic bath. Impuri-
ties, such as the sodium used during synthesis, has been shown to
influence the acid-base properties of CeO2 but additional dilute
acid and base washes have shown to minimize the effect of impu-
rities [33]. Removal of additional sodium impurities was accom-
plished by further washing the products with a solution of 0.1 M
NH4OH before three additional water rinses followed by washing
with a 0.1 M HNO3 and three final water rinses with each rinse
being done in an ultrasonic bath [47]. The washed precipitate
was dried at 50 °C for 12 h and calcined for 4 h in air. Calcination
temperatures were varied from 450 to 750 °C as a means of con-
trolling ceria defect density [23]. Commercial ceria (denoted as
CeO2-Com) was obtained from Sigma-Aldrich (99.995%) and used
without any further modification.
2.2. Catalyst characterization
Samples were prepared for TEM characterization by dispersing
approximately 1 mg of the powder CeO2 in 5 mL of ethanol. These
solutions were sonicated for 20 min, added dropwise over a nickel
200 mesh TEM grid with Formvar/carbon coating, and dried over-
night under a heat lamp in air. TEM was performed using an FEI
Technai G2 20 Twin operated at 200 kV and equipped with a 4 k
Eagle CCD camera. Brunauer-Emmett-Teller (BET) analysis was
used to determine the specific surface areas (SSA) of the CeO2 sam-
ples. Approximately 0.5 g of samples were placed in quartz tubes
and degassed under vacuum at 300 °C for 3 h. N2 adsorption and
desorption isotherms were obtained at 77 K using surface area
analyzer (Tristar II, Micromeritics). In situ Raman spectroscopy
was used to measure the defect density of the ceria catalysts.
About 50 mg of samples were loaded into an in situ reactor cell
(Linkam CCR1000) and heated to 400 °C for 1 h under 10% O2/He
(20 mL/min). The pretreated samples were cooled to 100 °C before
measurements from 0 to 1400 cm1 using a Raman spectroscope
(Horiba LabRAM HR 800) equipped with a 532 nm (Ventus LP
B. Sudduth, D. Yun, J. Sun et al.
532) laser source and Synapse CCD (Charge Coupled Device) detec-
tor. XRD patterns were obtained using a Rigaku MiniFlex X-ray
diffractometer using Cu-Ka (k = 1.54178 A).€ Normal operating
power was 40 kV, 30 mA and measurements were obtained from
2h of 3° to 90° at scanning speeds of 0.5°/min. Diffuse reflectance
infrared Fourier transform spectroscopy (DRIFTS) was conducted
using a Bruker Tensor 27 FTIR spectrometer equipped with a Har-
rick Praying Mantis attachment by averaging 256 scans with a
spectral resolution of 4 cm1. For analysis of the surface hydroxyl
groups, samples were pretreated at 400 °C for 1 h under 10% O2/
He flow (20 mL/min) and cooled to 150 °C before spectral acquisi-
tion under He flow (20 mL/min). The hydroxyl group vibrations are
difference spectra using potassium bromide (KBr) at 150 °C as the
reference background.
2.3. Acid and base site characterization
Pyridine (Py = C5H5N) adsorption in the previous mentioned
DRIFTS equipment was used to probe the surface acid sites of each
ceria catalyst. Samples were pretreated with 10% O2/He at 400 °C
for 1 h and cooled to ambient temperature under He (20 mL/
min). He (10 mL/min) was used as a carrier gas and flowed through
a bubbler with pyridine at room temperature to continuously fill a
0.5 mL loop attached to a six-way valve. Pulses of pyridine were
injected from the loop to the catalysts using He (20 mL/min) until
saturation, as monitored by the pyridine signal (m/z = 79) from an
online quadrupole mass spectrometer (QMS, Quadra 220, Pfeiffer)
attached to the effluent stream. Samples were purged under He
flow (20 mL/min) for 30 min before acquiring spectra. Spectra col-
lected at the various desorption temperatures used the pretreated
ceria at the same temperature, before pyridine adsorption, as the
background. A similar procedure was followed for DRIFTS analysis
of CO2 adsorption and desorption. After pretreatment, 10% CO2/He
(20 mL/min) is introduced at room temperature until saturation.
Samples are then purged under He flow (20 mL/min) for 30 min
before acquiring room temperature spectra and increasing the
temperature to 400 °C at a ramp rate of 10 °C/min. The pretreated
CeO2 at the various temperatures, before CO2 adsorption, were
used as the background.
Temperature-programmed desorption of various probe mole-
cules was performed using a chemisorption unit (AutoChem II
2920 Chemisorption Analyzer, Micromeritics) coupled with an
online QMS (Quadra 220, Pfeiffer). Samples were measured to
matching surface areas and loaded into a quartz tube supported
by quartz wool. Each sample was first pretreated at 400 °C under
10% O2/He flow (50 mL/min) for 1 h before cooling to ambient tem-
perature and exposing the sample to the probe molecule.
Ammonia-TPD (NH3-TPD) was conducted by then exposing the
sample to 10% NH3/He (50 mL/min) until saturation. The sample
was purged under 5% Ar/He flow (50 mL/min) for 2 h to remove
physically adsorbed ammonia. The temperature was then
increased to 600 °C at a ramping rate of 10 °C/min under 5% Ar/
He flow (50 mL/min). The QMS was used to measure the argon tra-
cer (m/z = 40) and desorbed NH3 (m/z = 16) during TPD. The QMS
response was calibrated by flowing various concentrations of
NH3 with the Ar/He carrier. Carbon dioxide-TPD (CO2-TPD) was
conducted by exposing the sample to 10% CO2/He (50 mL/min)
until saturation. The sample was purged under 5 %Ar/He flow
(50 mL/min) for 2 h to remove physically adsorbed carbon dioxide.
The temperature was then increased to 600 °C at a ramping rate of
10 °C/min under 5 %Ar/He flow (50 mL/min). The QMS was used to
measure the argon tracer (m/z = 40) and desorbed CO2 (m/z = 44)
during TPD. The QMS response was calibrated by flowing various
concentrations of CO2 with the Ar/He carrier. Pyridine-TPD (Py-
TPD) was conducted by exposing the sample to pulses of Py vapor
98
Journal of Catalysis 404 (2021) 96–108
generated in a flask of Py held at room temperature with 10 mL/
min He flow until saturation. The sample was purged under 5%
Ar/He flow (50 mL/min) for 2 h to remove physically adsorbed
pyridine. The temperature was then increased to 600 °C at various
ramping rates (2, 5, 15 °C/min) under 5% Ar/He flow (50 mL/min).
The QMS was used to measure the argon tracer (m/z = 40) and des-
orbed pyridine (m/z = 79) during TPD.
2.4. Catalyst activity tests
The dehydrogenation and dehydration of 2-propanol was used
as a probe reaction to test the catalytic activity of the CeO2
nanoshapes. Isothermal rate measurements were carried out in a
fixed-bed flow reactor with catalyst packed into a quartz tube.
Approximately 50 mg of the CeO2 samples were diluted with inert
SiC at a 1:10 CeO2:SiC mass ratio to prevent temperature gradients.
A syringe pump was used to inject the 2-propanol upstream of the
catalyst and heated to 180 °C to ensure complete evaporation and
mixing with a He carrier gas before reaching the reactor. The outlet
of the reactor was heated to 150 °C to avoid product condensation.
An online Micro-GC (Agilent 490) equipped with four columns
(Molsieve, CP-PoraPLOT U, aluminum oxide column and CP-Sil 5
CB) and TCD detectors was used to analyze the reaction products.
Catalysts were pretreated with dry air (50 mL/min) at 400 °C
before lowering the reactor to the desired reaction temperature.
Selectivity and activity were monitored with an inlet 2-propanol
partial pressure of 6 kPa (weight hourly space velocity of
7.5 g2-propanolh1g-1
CeO2) at 10 °C increments between the tempera-
tures of 250 and 290 °C. Fresh, pretreated catalysts were used for
measurements at each temperature. Reaction rates were measured
under the differential kinetic regime (conversions below 5%) and
normalized to turnover frequencies (TOF) based on the surface area
of the CeO2 catalysts as obtained by BET.
3. Results and discussion
3.1. Physical and structural properties
For a meaningful comparison of acid and base properties of
CeO2, the concentration of intrinsic (Frenkel-type) defects may be
minimized to reduce the potential impact of these defects on the
acid-base moieties [25,33,48]. It should be highlighted that the
intrinsic defects are different from oxygen vacancies. The oxygen
vacancies are dynamically formed upon reduction while the intrin-
sic defects are present in the fully oxidized CeO2 structure, com-
monly caused by the relocation of oxygen anion (O2–) from
tetrahedral to octahedral coordination [21,49]. For this purpose,
Raman spectroscopy and TEM imaging were carried out to find
the optimum calcination temperature which produces the desired
ceria nanoshape with the minimum intrinsic defect concentration.
Fig. 2 shows the Raman spectra of CeO2-C and CeO2-O calcined at
different temperatures. Regardless of the calcination temperature
and shape of ceria nanocrystals, Raman spectra of ceria show an
intense peak at 465 cm1, assigned to the Ce-O vibration mode
(F2g) whose intensity was used to normalize the entire spectra
for comparisons [21]. Two weak Raman bands at 241 and
598 cm1 were also observed which represent the second-order
transverse acoustic (2TA) and defect-induced (D) vibrational
modes of CeO2, respectively [50,51]. The relative intensity (ID/
IF2g) between the defect-induced vibrational mode at 598 cm1
(ID) and F2g bands at 465 cm1 (IF2g) at different temperatures, as
shown in Fig. 2c, was used to determine the change of defect den-
sity of CeO2 [21]. For both nanoshapes, defect density decreases as
calcination temperatures increase, a result of the collapse of tetra-
hedral sites where the intrinsic defects sites were present [23].
B. Sudduth, D. Yun, J. Sun et al. Journal of Catalysis 404 (2021) 96–108

Fig. 2. Normalized Raman spectra of CeO2-C (a) and CeO2-O (b) calcined at 450, 550, 650, and 750 °C. All spectra were normalized to the height of the dominant band at
465 cm1. (c) The defect density (Raman band peak area at 593 cm1 /peak area at 463 cm1) as a function of calcination temperature (°C). (d) Normalized Raman spectra of
CeO2-C, CeO2-O, and CeO2-Com calcined under the conditions used for the remainder of the study. (2-COLUMN).

The morphological stability of ceria nanocrystals was deter-
mined using TEM. Fig. 3 shows TEM images obtained for CeO2
nanoshapes (CeO2-C and CeO2-O) calcined at different tempera-
tures (450, 550, 650, and 750 °C). The morphology of CeO2-C
remained stable up to 450 °C and began to show changes above
550 °C, first with the rounding of the edges and corners and even-
tually with complete loss of their initial cubic shape at 700 °C. In
contrast, the ceria octahedra are thermally stable up to 700 °C,
indicating that CeO2 octahedra are robust and largely stable at
higher temperatures. These observations are consistent with DFT
calculations which predict that CeO2(1 1 1) has the lowest surface
energy of ceria’s low index surfaces [34]. Based on these results,
calcination temperatures of 450 and 700 °C were used for CeO2-C
and CeO2-O, respectively. These conditions assure the minimum
concentration of intrinsic defect without morphological change. A
comparison of the Raman spectra for the synthesized CeO2
nanoshapes and the as-obtained commercial CeO2 is shown in
Fig. 2d indicating that the defect density of the samples are
CeO2-C > CeO2-O > CeO2-Com.
TEM images of the synthesized CeO2-C calcined at 450 °C, CeO2-
O calcined at 700 °C and CeO2-Com are shown in Fig. 4. Analysis of
the TEM images indicates that the average particle sizes of CeO2-C
(Fig. 4a), CeO2-O (Fig. 4b) and CeO2-Com (Fig. 4c) are approxi-
mately be 47, 28, and 43 nm, respectively. The CeO2-C contain
mostly the (1 0 0) plane and a small portion of the (1 1 0) plane,
while the surface of CeO2-O dominantly expose the (1 1 1) plane,
as indicated in our previous contribution [52]. By contrast, the
morphology of the CeO2-Com, however, is not well defined. The
main shape of commercial CeO2 is truncated octahedra containing
a majority of (1 1 1) with truncated ends exposing the (1 0 0) planes.
The XRD patterns of the CeO2-Com, CeO2-C, and CeO2-O are
shown in Fig. 5. Each CeO2 nanocrystals exhibits peaks at 28.5°,
33.1°, 47.5°, 56.4°, 59.1°, 69.4°, 76.7°, 79.1°, and 88.5°, which are
associated with the (1 1 1), (2 0 0), (2 2 0), (3 1 1), (2 2 2), (4 0 0),
(3 3 1), (4 2 0), (4 2 2)} facets of pure cubic fluorite structure (space
group Fm3m 225), as identified in JCPDS 34–0394. None of the
nanocrystals exhibit any peaks from Ce(OH)3 or Ce(OH)CO3 impu-
rities which indicates sufficiently high calcination temperatures

99
B. Sudduth, D. Yun, J. Sun et al.
Fig. 3. (Top) TEM images of CeO2-C calcined at (a) 450 °C, (b) 550 °C, (c) 650 °C and (d) 750 °C. (Bottom) TEM images of CeO2-O calcined at (e) 450 °C, (f) 550 °C, (g) 650 °C and
(h) 750 °C. (2-COLUMN).
were used [30]. The average crystallite size of CeO2-Com, CeO2-C,
and CeO2-O estimated using Scherrer equation are 40, 44, and
29 nm, respectively, comparable with estimates from TEM imag-
ing. The BET surface areas of CeO2-C, CeO2-O and CeO2-Com are
10.4, 25.3 and 17.6 m2/g, respectively. The physical properties of
each CeO2 sample are summarized in Table 1.
3.2. Acid sites characterization
In situ IR spectroscopy has been extensively used to analyze the
acid properties (e.g., type and strength) of metal oxides [12]. Pyri-
dine is commonly used as a probe molecule because its vibrational
modes are sensitive to adsorption at Lewis and Brønsted acid sites.
DRIFTS spectra of pyridine adsorbed on CeO2-Com, CeO2-C, and
CeO2-O are shown in Fig. 6a. The spectra were acquired after
adsorption at room temperature, purging under He flow for
30 min, and desorption at 150 °C for 30 min to remove
hydrogen-bonded pyridine [1]. The bands around 1600 and
1443 cm1 are associated with the v8a and v19b modes of
adsorbed pyridine on Lewis acid sites, respectively [5,53]. All three
CeO2 nanoparticles exhibit pyridine adsorbed on Lewis acid sites.
The Lewis acid strength of a metal oxide’s cations sites has been
Fig. 4. TEM images of (a) CeO2-C calcined at 450 °C, (b) as-obtained CeO2-Com, (c) CeO2-O calcined at 700 °C. (2-COLUMN).
100
Journal of Catalysis 404 (2021) 96–108
shown to influence the vibrational frequency of pyridine’s v8a
mode, with stronger acid sites causing a blue shift of this mode
[54,55]. The v8a mode of each CeO2 nanoparticle appears at the
same 1600 cm1 frequency suggesting that pyridine is unable to
distinguish any differences in the strengths of each surface’s Ce
cations. This is consistent with previous studies comparing pyri-
dine adsorption on CeO2 nanoshapes or different metal oxides
[12,33]. Pyridine is too strong a basic molecule to produce measur-
able shifts in the v8a mode if the acid site strengths are relatively
similar and the vibrational modes of a weaker base, like deuterated
acetonitrile, are more sensitive to small changes in acid site
strength. The surface OH groups of the CeO2 nanoparticles exhibit
no Brønsted acidity as the v19b mode of protonated pyridine (i.e.,
ring vibration) is not observed at 1540 cm1. DRIFTS spectra of the
hydroxyl region after Py adsorption (Figure S1) shows that, while
no Brønsted acid associated pyridine vibrations could be seen at
150 °C, pyridine is hydrogen bonded to all three sample as evi-
denced by the negative peaks most prominent in the bridged Ce-
OH region (3686 – 3633 cm1).
While Py-IR was able to identify the types of acid sites on the
CeO2 nanoparticles, it was unable to determine the quantity of
these sites
NH3-TPD is often employed to investigate these charac-
B. Sudduth, D. Yun, J. Sun et al.
Fig. 5. XRD patterns of CeO2-Com, CeO2-C, and CeO2-O. (SINGLE COLUMN).
teristics of metal oxides as it binds to both Lewis and Brønsted acid
[56–58]. A comparison of the NH3-TPD profiles of the CeO2 cata-
lysts is shown in Fig. 6b. All three nanoshapes exhibit slight NH3
desorption when the temperature is elevated above ambient tem-
perature with an increase in desorption above 70 °C. The NH3 des-
orption behavior of CeO2-Com and CeO2-O are similar and have the
same desorption maximum at 119 °C with the remaining NH3 des-
orbed as temperature reaches 250 °C. On the other hand, CeO2-C
rapidly reach peak desorption at 100 °C suggesting CeO2-C have
slightly weaker acid sites than the (1 1 1) dominant CeO2-Com
and CeO2-O. Integration of the NH3 desorption peak areas allows
for the quantification of the total amount of acid sites and, after
normalizing to the surface area, the density of the acid sites on
the CeO2. CeO2-Com possess the highest density of acid sites
(1.13 NH3/nm2), closely followed by CeO2-O (0.94 NH3/nm2), with
CeO2-C having the lowest (0.60 NH3/nm2).
Pyridine-TPD was used to further distinguish differences in
Lewis acid site strength between the three nanoshapes. Three sep-
arate TPD experiments were performed using different tempera-
ture ramp rates (b = 2, 5, 15 °C) and the desorption peak
temperature (TM) from each desorption profile was used to deter-
mine the energy of desorption for each CeO2 nanoparticle using the
Arrhenius equation and assuming first order desorption kinetics,
kd ¼ Ad expðEd =RTÞ
2lnðTM Þ  lnðbÞ ¼ Ed =RTm þ lnðEd =RAd Þ
where Ed is the energy of desorption and Ad is the exponential
prefactor. A summary of the Py-TPD results is shown in Fig. 7
where 2lnðTM Þ  lnðbÞ is plotted versus 1/TM. The individual des-
orption profiles can be found in Figure S2. Pyridine desorbed with-
out significant oxidation or decomposition as no products of these
reactions were be observed via QMS. Particle size and bed height
were similar for each sample to minimize the influence of read-
Table 1
Summary of the physical properties of the CeO2 nanoshapes.
Sample Dominant Facet BET SSA (m2/g)
CeO2-Com (1 1 1) 17.6
CeO2-C (1 0 0) 10.4
CeO2-O (1 1 1) 25.3
101
Journal of Catalysis 404 (2021) 96–108
sorption on the observed trends. The linear equation obtained by
altering b and tracking its influence on TM provides a slope Ed/R
[59]. The energy of desorption was determined highest on CeO2-
Com (141 kJ/mol), slightly lower on CeO2-O (132 kJ/mol), and low-
est on CeO2-C (93 kJ/mol). These values are consistent with the
NH3-TPD results which suggested greater acid site strengths on
CeO2-Com and CeO2-O with noticeably weaker acid sites on
CeO2-C.
There are clear differences in the acid site properties among
three ceria samples: (1 1 1) dominant CeO2-Com, (1 1 1) dominant
CeO2-O, and (1 0 0) dominant CeO2-C. While calcination tempera-
tures were used to minimize the defect density of these samples,
some have suggested that defects increase the density of acid sites
on CeO2 [23,25,47]. Thus, it was important to explore the effect of
defect density on the CeO2 nanoshapes’ acid site densities. Fig. 8a
details the changes in acid site density with increasing calcination
temperature for both CeO2-O and CeO2-C. There is no clear trend
between calcination temperature and acid site density. There is a
small decrease from 1.14 to 0.85 mmol NH3 / nm2 when octahedra
are calcined at 450 °C and 750 °C, respectively, while cubes expe-
rience a slight increase from 0.6 to 0.72 mmol NH3 / nm2 with the
same calcination temperature increase. In a previous study mea-
suring the acid site density of polycrystalline CeO2 with increasing
temperature [23], the density was normalized to the mass of the
CeO2, which does not account for the decrease in specific surface
area after increased calcination temperatures, and may explain this
discrepancy. When the acid site density is directly compared to the
defect densities, as shown in Fig. 8b, there is a clear difference
between the two CeO2 nanoshapes regardless of their defect den-
sity. After cubes are calcined at 750 °C, under which conditions it
experiences significant morphological changes to the more stable
(1 1 1) facet, the acid site density begins converging with those
measured for octahedra. This observation provides further evi-
dence that the acid properties of CeO2 are dependent on their
exposed facet and that defect density, while it may still play a role,
does not fully explain these differences.
3.3. Base site characterization
CO2 is a simple acidic probe molecule commonly used to probe
the two types of basic sites on metal oxides, hydroxyl groups and
surface oxygen anions [12,60,61]. CO2 forms bicarbonate species
from interactions with basic OH groups and a range of carbonate
species from oxygen anions which can be identified by their char-
acteristic IR vibrational modes whose assignments are summarized
in Table 2 and based on previous CO2 adsorption studies [13,62,63].
Fig. 9 shows in situ DRIFTS spectra collected after ambient temper-
ature adsorption of CO2 on CeO2-C and CeO2-O, respectively, and
purging at increased temperatures. IR spectra after adsorption of
CO2 on CeO2-Com are similar to those from CeO2-O and can be
found in Figure S3.
Bicarbonate vibrations [HCO3–: mas(CO3–) = 1635 cm1, ms(CO3–
) = 1405 cm1, and d(OH) = 1208 cm1] can be seen on CeO2-C indi-
cating that the surface OH on the (1 0 0) surface are basic in nature
and persist up to 250 °C. Analysis of the hydroxyl group region dur-
ing CO2 desorption, shown in Figure S4, shows the CO2 interacts
with the OH species on CeO2-C as indicated by the negative peak
Particle Size (nm) Defect Density (ID/IF2g)
43 0.009
47 0.016
28 0.012
B. Sudduth, D. Yun, J. Sun et al.
Fig. 6. Acid site characterization of the CeO2-Com, CeO2-C and CeO2-O. (a) DRIFTS spectra of pyridine adsorbed on the ceria nanoshapes after desorption at 150 °C. The
characteristic locations of modes associated with Lewis and Brønsted acid sites are indicated with dashed lines. (b) QMS profiles of desorbed NH3 during NH3-TPD normalized
by the surface area of the loaded CeO2 sample. Quantity of desorbed NH3 calculated using the area under the desorption profile. (2-COLUMN).
at 3711 cm1 which is the characteristic vibration of terminal Ce-
OH and the stretching mode vibration of the bicarbonate at
3629 cm1. CeO2-O exhibit a smaller shoulder centered around
1627 cm1 which may be attributed to bicarbonate, but the hydro-
xyl group region is largely unchanged during CO2 adsorption sug-
gesting that CeO2-O’s hydroxyls are less basic than those on
CeO2-C.
There are numerous peaks assigned to bidentate, monodentate
and bridged carbonates between 1000 and 1700 cm1 in the spec-
tra of each nanoshape. This confirms the presence of surface oxy-
gen with Lewis base behavior on all three nanoshapes though
there are clear surface dependent differences in the relative distri-
bution of these carbonates between the (1 0 0) dominant CeO2-C
and (1 1 1) dominant CeO2-O and CeO2-Com. Bridged (1695, 1465,
Fig. 7. Pyridine desorption peak temperatures (Tm) during Py-TPD under varying
temperature ramp rates (b). (SINGLE COLUMN).
102
Journal of Catalysis 404 (2021) 96–108
1246, 1053 cm1) and monodentate (1584, 1405, 1053 cm1) car-
bonates contribute to most of the remaining features found in
CeO2-C’s spectra. Bridged carbonates appear to desorb at a similar
temperature as the bicarbonate species with their features largely
disappearing above 200 °C while monodentate species remain up
to 300 °C. Bidentate carbonate (1584 and 1293 cm1) formation
occurs upon CO2 reacting with a Lewis acid-base pair such as a
coordinatively unsaturated surface Ce cation and O anion. These
features are relatively weak on the cubes but stable up to 300 °C.
In contrast with CeO2-C, CeO2-O and CeO2-Com spectra are
dominated by bidentate carbonate peaks (1575, 1295,
1023 cm1) with no clear features associated with neither bridged
nor monodentate carbonates. Although the bidentate carbonate
features are much stronger at low temperatures on the (1 1 1) dom-
inant nanoshapes, they are completely desorbed by 200 °C which
suggests that the Lewis acid-base pairs on this facet are weaker
than those on CeO2-C’s (1 0 0) facet. This is consistent with the sur-
face Ce cations and O anions being more coordinatively unsatu-
rated on the (1 0 0) facet.
Oxygen anions act as Lewis base sites while the cerium cations
are Lewis acid sites, but the surfaces of metal oxides nanoparticles
are hydroxylated under normal conditions, creating a population of
amphoteric hydroxyl groups on the surface. The acidity or basicity
of these hydroxyl groups depends on the metal oxide and the coor-
dination of the OH groups [7,42,64]. Highly coordinated OH groups
are more strongly polarized by the cations which loosens the bond
to hydrogen, making it easier to deprotonate, thus having acidic
characteristics. Single coordinated OH groups have a stronger ten-
dency to dissociate as OH– ions, making them easier to exchange
for other anions, thus having basic characteristics. Fig. 10a displays
the IR spectra of the OH stretching region for the CeO2 nanoshapes.
Bands around 3709 cm1 are assigned to terminal OH and bridged
OH appear around 3637 cm1. CeO2-Com and CeO2-O are domi-
nated by bridged OH which is consistent with theoretical studies
suggesting bridged OH are most stable on the CeO2(1 1 1) surface
[65]. There is a minor band associated with terminal OH groups
on CeO2-Com which may be a result of the more heterogenous nat-
ure of these nanoparticles. CeO2-O have the weakest band associ-
ated with terminal OH whose limited presence may be due to
B. Sudduth, D. Yun, J. Sun et al. Journal of Catalysis 404 (2021) 96–108

Fig. 8. Acid site density as measured using NH3-TPD of CeO2-O and CeO2-C calcined at different temperatures as a function of (a) calcination temperature and (b) defect
density as measured in Raman. (2-COLUMN).

Table 2
General assignment of IR bands from CO2 adsorption and TPD on CeO2-C, CeO2-O, and CeO2-Com.

Species v(CO3) d(OH) v(OH)

CeO2-C bicarbonate 1635, 1405 1208 3629
bridged carbonate 1695, 1465, 1246, 1053
monodentate carbonate 1584, 1405, 1053
bidentate carbonate 1584, 1293, 1023
CeO2-O CeO2-Com bicarbonate 1627
bidentate carbonate 1575, 1295, 1023

slight variations in the surface structure at the edges and corners of mation upon CO2 reacting with basic OH primarily occurring on
the nanoparticles. CeO2-C are predominately populated with the CeO2-C. The broad band at 3473 cm1 on CeO2-C and CeO2-O is
more basic terminal OH with only a minor presence of bridged likely due to cerium oxyhydroxide impurities [66] which appear
OH groups. These results are consistent with the bicarbonate for- to be largely inactive or inaccessible to both acidic (e.g., CO2) and

Fig. 9. DRIFTS spectra on (a) CeO2-C and (b) CeO2-O after CO2 adsorption at room temperature and purged under He flow at increased desorption temperatures. (2-COLUMN).

103
B. Sudduth, D. Yun, J. Sun et al.
Fig. 10. (a) IR spectra of hydroxyl groups on CeO2-Com, CeO2-C, and CeO2-O. (b) QMS profiles of desorbed CO2 (m/z = 44) from CeO2-Com, CeO2-C, and CeO2-O normalized by
surface area of the loaded CeO2 sample. (2-COLUMN).
basic (e.g., pyridine) probe molecules as suggested by the minimal
changes to the spectra in this region after adsorption (Figure S1
and Figure S4).
Having identified the basic site types using CO2 DRIFTS, CO2-
TPD, shown in Fig. 10b, was used to characterize the overall
strength and quantity of the basic sites. CO2 was adsorbed at ambi-
ent temperature and purged under He flow for 2 h to remove phy-
sisorbed CO2. Each CeO2 nanoshape immediately begins to desorb
CO2 upon increasing the temperature above ambient temperature.
The (1 1 1) dominant CeO2-Com and CeO2-O have a single, low tem-
perature desorption peak at 98 °C. CeO2-C demonstrate a broader
desorption profile from 50 °C to 250 °C with a low temperature
desorption peak around 100 °C and a high temperature desorption
peak at approximately 170 °C. The higher CO2 desorption temper-
atures seen from CeO2-C may be attributed to monodentate and
bidentate carbonates species whose features are visible in the IR
spectra up to 300 °C. The increased decomposition temperatures
of monodentate and bidentate carbonates over bicarbonate and
bridged carbonate species are consistent with previous investiga-
tions of CO2 desorption from CeO2 materials [33,67]. Integration
of the CO2 desorption peak areas allows for the quantification of
the total number of base sites which is summarized in Table 3.
CeO2-C possess the highest density of base sites (0.57 CO2/nm2),
followed by CeO2-Com (0.54 CO2/nm2), with CeO2-O having the
lowest (0.45 CO2/nm2).
To summarize the acid-base properties measured: (1 1 1) domi-
nant CeO2-O and CeO2-Com have a higher density of stronger acid
sites while the (1 0 0) dominant CeO2-C have considerably stronger
base sites with a comparable site density. These properties will be
Table 3
Summary of the acid-base properties of CeO2-Com, CeO2-O, and CeO2-C.
Sample Acid Site Density Py Desorption Base Site Density
(NH3/nm2) Energy (KJ/mol) (CO2/nm2)
CeO2-Com 1.13 141 0.54
CeO2-C 0.60 93 0.57
CeO2-O 0.94 132 0.45
104
Journal of Catalysis 404 (2021) 96–108
a referenced for their impact on the acid-base sensitive 2-propanol
probe reaction detailed in the following section.
3.4. 2-Propanol conversion
The 2-propanol transformations were carried out under He flow
and constant 2-propanol partial pressure. Pure He was chosen
because, although 2-propanol conversion is more active and stable
under oxidizing conditions, only acetone is produced at low tem-
peratures and complete oxidation to CO2 occurs at elevated tem-
peratures [9]. Example time-on-stream plots for 2-propanol
conversion under He over each sample can be seen in the support-
ing information (Fig. S5-7). Each CeO2 sample displayed 100%
combined selectivity to the dehydrogenation product, acetone, or
the dehydration product, propene. Only trace amount of decompo-
sition products (e.g., CO, CO2, CH4) were observed. Overall conver-
sion of 2-propanol under these conditions is kept below 5% to
ensure the reaction remains within the kinetic region.
During the first 30 min of 2-propanol conversion over each
sample there is a decrease in acetone rates and a slight increase
in propene rates. 2-propanol has been shown to act as a reductant
under UHP conditions, this is particularly evident in 2-propanol
TPD on CeO2(1 0 0) films on which the acetone production depletes
available surface O [68]. On both CeO2(1 1 1) and CeO2(1 0 0), sur-
face reduction decreases the amount of acetone formed in favor
of propene production during 2-propanol TPD [69]. In the current
studies, the initial decrease in acetone formation and the corre-
sponding increase in propene may be explained by a partial reduc-
tion of surface CeO2 catalysts by 2-propanol. The effects of
reduction are most clearly seen on the CeO2-C samples which typ-
ically displays greater than 60% decrease in acetone formation
rates during the first 30 min. In contrast, acetone formation rates
on CeO2-O and CeO2-Com only decrease by approximately 30%.
This is consistent with UHP studies demonstrating that 2-
propanol acts as a reductant during 2-propanol TPD on
CeO2(1 0 0) but is a poor reductant of CeO2(1 1 1) [69]. The presence
of surface defects on CeO2-O increases its reducibility in compar-
ison to pristine CeO2(1 1 1) single crystal films [22]. To minimize
potential complications from deactivation and differences in the
extents of reduction dependent on the nanoshape and reaction
B. Sudduth, D. Yun, J. Sun et al. Journal of Catalysis 404 (2021) 96–108

Fig. 11. (a) Acetone and propene production rate normalized by sample surface area during 2-propanol conversion over CeO2-Com, CeO2-O, and CeO2-C (a) normalized by
sample surface area and (b) normalized by number of base sites and acid sites as determined by CO2 and NH3 TPD, respectively. 6 kPa 2-propanol feed at 270 °C,
WHSV = 7.5 g2-propanol / hr / gCeO2. (2-COLUMN).

temperature, this study evaluates the initial reaction rates by
extrapolating the experimental results within the first 20 min of
time-on-stream. Conducting the reaction under He flow causes
the samples to reduce and deactivate over time but highlights
surface-dependent dehydration and dehydrogenation rates. Note
that TEM analysis of the CeO2 samples after 2-propanol conversion
up to 450 °C shows no observable morphological changes
(Figure S8).
The initial production rates for acetone and propene during
6 kPa 2-propanol feed at 270 °C are shown in Fig. 11a. CeO2-O
and CeO2-Com have dehydrogenation rates of 0.0093 and
0.0095 lmol-acetone/m2/s, respectively, while CeO2-C exhibit a
greater rate of acetone production at 0.0141 lmol-acetone/m2/s.
So, despite the observation that the number of basic sites is similar
between the three CeO2 nanocrystals, CeO2-C are able to produce
the basic product at higher rates which suggests that the observed
differences in the strengths of these sites play a key role. The rates
for dehydration of 2-propanol suggest the opposite trend, in that
CeO2-O and CeO2-Com have rates of 0.0062 and 0.0049 lmol-
propene/m2/s, respectively, while CeO2-C produce much less pro-
pene at 0.0003 lmol-propene/m2/s. The observed difference in
propene production between the (1 1 1) dominant CeO2-O and
CeO2-Com and the (1 0 0) dominant CeO2-C is consistent with the
higher density and strength of acid sites, as measured by NH3-
TPD, for the (1 1 1) dominant nanocrystals.
To clarify whether the strength of the acid and base sites plays a
role in 2-propanol dehydrogenation and dehydration rates, or just
the differences in site density, the initial acetone and propene pro-
duction rates normalized by the number of base and acid sites,
respectively, are plotted in Fig. 11b. Dehydrogenation to acetone

Fig. 12. Arrhenius plots of 2-propanol dehydrogenation and dehydration on CeO2-C ( ), CeO2-Com ( ), and CeO2-O (▲) CeO2 normalized by surface area. 6 kPa 2-propanol,
250 – 290 °C, WHSV = 7.5 g2-propanolh1g-1
CeO2 (2-COLUMN).

105
B. Sudduth, D. Yun, J. Sun et al.
Table 4
Summary of initial 2-propanol dehydrogenation and dehydration production rates. Apparent activation energies (Ea) and preexponential factors (A) for 2-propanol
dehydrogenation and dehydration.
Sample Dehydrogenation Rate Dehydration Rate
(lmol-acetone/m2/s) (lmol-propene/m2/s)
Commercial 0.0095 0.0049
Octahedra 0.0093 0.0062
Cubes 0.0141 0.0003
over the CeO2-C remains the highest at 0.0025 acetone/base-site/s
while CeO2-O and CeO2-Com produce 0.0021 and 0.0020 acetone/
base-site/s, respectively. This suggests that the stronger basic sites
of (1 0 0) dominant CeO2-C compared to those of the (1 1 1) domi-
nant CeO2-O and CeO2-Com are responsible for increased rate of
dehydrogenation. Similarly, dehydration to propene remains great-
est over the (1 1 1) dominant CeO2-O and CeO2-Com, producing
0.00066 and 0.00047 propene/acid-site/s, respectively, while
CeO2-C only produce 0.00019 propene/acid-site/s. This is due to
increased strength of the acid sites on CeO2-O and CeO2-Com as
observed in their higher temperature desorption profiles during
NH3-TPD and the larger calculated pyridine desorption energy.
Arrhenius plots for each sample’s initial dehydrogenation and
dehydration rates are shown in Fig. 12. The apparent activation
energies for dehydrogenation to acetone were calculated to be
47, 74, and 69 kJ/mol for CeO2-C, CeO2-O, and CeO2-Com, respec-
tively. The apparent activation energies for dehydration to propene
were calculated to be 76, 170, and 164 kJ/mol for CeO2-C, CeO2-O,
and CeO2-Com, respectively. The apparent activation energy for
dehydrogenation to acetone is lower for all three CeO2 nanocrys-
tals than that for dehydration to propene. These activation energy
differences and the overall increased production rate for acetone
over propene are in agreement with the consensus from 2-
propanol studies on metal oxides with varying acid-base proper-
ties which demonstrate that CeO2 is a more basic metal oxide
[9,46]. Interestingly, while CeO2-C produce much less propene than
CeO2-O or CeO2-Com, the activation energy for dehydration over
CeO2-C is significantly less than its (1 1 1) dominant counterparts.
This suggests that the decreased density of acid sites on CeO2-C
plays the largest factor in its rate of dehydration, which is demon-
strated by a calculated pre-exponential factor ten orders of magni-
tude lower, as summarized in Table 4.
4. Conclusions
CeO2-C with well-defined (1 0 0) crystal facets and CeO2-O
exposing the (1 1 1) facet were synthesized and their acid and base
sites were characterized using in situ DRIFTS spectroscopy and TPD
of basic and acidic probe molecules. CeO2-C exhibit stronger base
sites while CeO2-O and CeO2-Com have a higher density of stronger
acid sites. These acid-base characteristics are reflected in 2-
propanol dehydrogenation and dehydration. CeO2 samples with
dominant (1 1 1) facet such as CeO2-O demonstrate greater dehy-
dration activity to propene facilitated by the higher strength and
number of acid sites. The higher coordination vacancy of O anions
on the CeO2(1 0 0) surface increases the rate of dehydrogenation to
acetone while the lower density of weaker acid sites and more
basic surface hydroxyls limit its dehydration activity.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Journal of Catalysis 404 (2021) 96–108
Dehydrog. Ea Dehydrat. Ea Dehydrog. A (s1) Dehydrat. A (s1)
(kJ/mol) (kJ/mol)
69 164 4.3x104 5.7x1012
74 170 1.1x105 1.3x1014
47 76 4.7x102 2.2x104
Acknowledgements
This work was supported by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, Division of Chem-
ical Sciences, Geosciences, and Biosciences’ Catalysis Program
(FWP-47319).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcat.2021.09.009.
References
[1] K.-I. Tanaka, A. Ozaki, Acid-Base Properties and Catalytic Activity of Solid
Surfaces, J. Catal. 8 (1967) 1–7, https://doi.org/10.1016/0021-9517(67)90274-
6.
[2] K. Tanabe, M. Misono, H. Hattori, New Solid Acids and Bases, Their Catalytic
Properties (1990). https://www.sciencedirect.com/bookseries/studies-in-
surface-science-and-catalysis/vol/51.
[3] K. Tanabe, H. Hattori, in: G. Ertl, H. Knoezinger, J. Weitkamp (Eds.) Handbook of
Heterogeneous Catalysis, Wiley-VCH, Weinheim, 1997, pp. 404-412.
https://doi.org/10.1002/9783527619474.
[4] J.-M. Basset, B.C. Gates, J.-P. Candy, A. Choplin, M. Leconte, F. Quignard, C.
Santini (Eds.), Surface Organometallic Chemistry: Molecular Approaches to
Surface Catalysis, Springer Netherlands, Dordrecht, 1988.
[5] M.I Zaki, M.A Hasan, F.A Al-Sagheer, L. Pasupulety, In situ FTIR spectra of
pyridine adsorbed on SiO2–Al2O3, TiO2, ZrO2 and CeO2: general
considerations for the identification of acid sites on surfaces of finely divided
metal oxides, Colloids Surf. Physicochem. Eng. Aspects 190 (3) (2001) 261–
274, https://doi.org/10.1016/S0927-7757(01)00690-2.
[6] H.P. Boehm, H. Knözinger, in: J.A. Anderson, M. Boudart (Eds.) Catal. Sci.
Technol., Springer, Berlin, 1983, pp. 40-189. https://doi.org/10.1007/978-3-
642-93229-8.
[7] H.P. Boehm, Acidic and basic properties of hydroxylated metal oxide surfaces,
Discuss. Faraday Soc. 52 (1971) 264–275, https://doi.org/10.1039/
DF9715200264.
[8] M.I. Zaki, M.A. Hasan, L. Pasupulety, Surface Reactions of Acetone on Al2O3,
TiO2, ZrO2, and CeO2: IR Spectroscopic Assessment of Impacts of the Surface
AcidBase Properties, Langmuir 17 (2001) 768–774, https://doi.org/10.1021/
la000976p.
[9] D. Haffad, A. Chambellan, J.C. Lavalley, Propan-2-ol transformation on simple
metal oxides TiO2, ZrO2 and CeO2, J. Mol. Catal. A: Chem. 168 (1-2) (2001)
153–164, https://doi.org/10.1016/S1381-1169(00)00516-1.
[10] C. Chizallet, M.L. Bailly, G. Costentin, H. Lauron-Pernot, J.M. Krafft, P. Bazin, J.
Saussey, M. Che, Thermodynamic bronsted basicity of clean MgO surfaces
determined by their deprotonation ability: Role of Mg(2+)-O(2-) pairs, Catal.
Today 116 (2006) 196–205, https://doi.org/10.1016/j.cattod.2006.01.030.
[11] D.T. Lundie, A.R. McInroy, R. Marshall, J.M. Winfield, P. Jones, C.C. Dudman, S.F.
Parker, C. Mitchell, D. Lennon, Improved description of the surface acidity of
eta-alumina, J. Phys. Chem. B 109 (2005) 11592–11601, https://doi.org/
10.1021/jp0405963.
[12] M. Tamura, K.-i. Shimizu, A. Satsuma, Comprehensive IR study on acid/base
properties of metal oxides, Appl. Catal., A, 433–434 (2012) 135-145.
https://doi.org/10.1016/j.apcata.2012.05.008.
[13] C. Binet, M. Daturi, J.-C. Lavalley, IR study of polycrystalline ceria properties in
oxidised and reduced states, Catal. Today 50 (2) (1999) 207–225, https://doi.
org/10.1016/S0920-5861(98)00504-5.
[14] N. Sheppard, in: R.F. Willis (Ed.) Vibrational Spectroscopy of Adsorbates,
Springer, Berlin, 1980, pp. 165-176. https://doi.org/10.1007/978-3-642-
88644-7.
[15] J.B. Peri, in: J.R. Anderson, M. Boudart (Eds.) Catal. Sci. Technol., Springer,
Berlin, 1984. https://doi.org/10.1007/978-3-642-93247-2
[16] A.A. Davydov, in: C.H. Rochester (Ed.) Infrared Spectroscopy of Adsorbed
Species on the Surface of Transition Metal Oxides, Wiley, Chichester, 1990.
https://doi.org/10.1002/sia.740170510.
106
B. Sudduth, D. Yun, J. Sun et al.
[17] A.T. Bell, Methods of Surface Characterization, in: J. Yates, T.E. Madey (Eds.),
Vibrational Spectroscopy of Molecultes on Surfaces, Plenum Press, New York,
1987, pp. 105–133, https://doi.org/10.1007/978-1-4684-8759-6.
[18] E. Mamontov, T. Egami, R. Brezny, M. Koranne, S. Tyagi, Lattice Defects and
Oxygen Storage Capacity of Nanocrystalline Ceria and Ceria-Zirconia, J. Phys.
Chem. B 104 (47) (2000) 11110–11116, https://doi.org/10.1021/jp0023011.
[19] P. Dutta, S. Pal, M.S. Seehra, Y. Shi, E.M. Eyring, R.D. Ernst, Concentration of Ce3
+ and Oxygen Vacancies in Cerium Oxide Nanoparticles, Chem. Mater. 18 (21)
(2006) 5144–5146, https://doi.org/10.1021/cm061580n.
[20] Y. Madier, C. Descorme, A.M. Le Govic, D. Duprez, Oxygen Mobility in CeO2 and
CexZr(1–x)O2 Compounds: Study by CO Transient Oxidation and 18O/16O
Isotopic Exchange, J. Phys. Chem. B 103 (1999) 10999–11006, https://doi.org/
10.1021/jp991270a.
[21] Z. Wu, M. Li, J. Howe, H.M. Meyer, S.H. Overbury, Probing Defect Sites on CeO2
Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O-
2 Adsorption, Langmuir 26 (21) (2010) 16595–16606, https://doi.org/10.1021/
la101723w.
[22] Y. Li, Z. Wei, F. Gao, L. Kovarik, R.A.L. Baylon, C.H.F. Peden, Y. Wang, Effect of
Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for
Oxidative Dehydrogenation of Methanol, ACS Catalysis 5 (5) (2015) 3006–
3012, https://doi.org/10.1021/cs502084g.
[23] Y. Wang, F. Wang, Q. Song, Q. Xin, S. Xu, J. Xu, Heterogeneous Ceria Catalyst
with Water-Tolerant Lewis Acidic Sites for One-Pot Synthesis of 1,3-Diols via
Prins Condensation and Hydrolysis Reactions, J. Am. Chem. Soc. 135 (4) (2013)
1506–1515, https://doi.org/10.1021/ja310498c.
[24] H. Metiu, S. Chrétien, Z. Hu, B. Li, X. Sun, Chemistry of Lewis Acid-Base Pairs on
Oxide Surfaces, J. Phys. Chem. C 116 (19) (2012) 10439–10450, https://doi.org/
10.1021/jp301341t.
[25] S. Zhang, Z.Q. Huang, Y.Y. Ma, W. Gao, J. Li, F.X. Cao, L. Li, C.R. Chang, Y.Q. Qu,
Solid frustrated-Lewis-pair catalysts constructed by regulations on surface
defects of porous nanorods of CeO2, Nat. Commun. 8 (2017) 11, https://doi.
org/10.1038/ncomms15266.
[26] D.R. Mullins, P.M. Albrecht, T.-L. Chen, F.C. Calaza, M.D. Biegalski, H.M.
Christen, S.H. Overbury, Water Dissociation on CeO2(100) and CeO2(111) Thin
Films, J. Phys. Chem. C 116 (36) (2012) 19419–19428, https://doi.org/10.1021/
jp306444h.
[27] D.R. Mullins, S.D. Senanayake, T.-L. Chen, Adsorption and Reaction of C1-C-3
Alcohols over CeOx(111) Thin Films, J. Phys. Chem. C 114 (40) (2010) 17112–
17119, https://doi.org/10.1021/jp103905e.
[28] D.R. Mullins, M.D. Robbins, J. Zhou, Adsorption and reaction of methanol on
thin-film cerium oxide, Surf. Sci. 600 (7) (2006) 1547–1558, https://doi.org/
10.1016/j.susc.2006.02.011.
[29] F. Lin, Y. Chen, L. Zhang, D. Mei, L. Kovarik, B. Sudduth, H. Wang, F. Gao, Y.
Wang, Single-Facet Dominant Anatase TiO2 (101) and (001) Model Catalysts to
Elucidate the Active Sites for Alkanol Dehydration, ACS Catalysis 10 (7) (2020)
4268–4279, https://doi.org/10.1021/acscatal.9b0465410.1021/
acscatal.9b04654.s001.
[30] H.-X. Mai, L.-D. Sun, Y.-W. Zhang, Rui Si, W. Feng, H.-P. Zhang, H.-C. Liu, C.-H.
Yan, Shape-selective synthesis and oxygen storage behavior
of ceria nanopolyhedra, nanorods, and nanocubes, J. Phys. Chem. B 109 (51)
(2005) 24380–24385, https://doi.org/10.1021/jp055584b10.1021/jp055584b.
s001.
[31] K ZHOU, X WANG, X SUN, Q PENG, Y LI, Enhanced catalytic activity of ceria
nanorods from well-defined reactive crystal planes, J. Catal. 229 (1) (2005)
206–212, https://doi.org/10.1016/j.jcat.2004.11.004.
[32] H. Tan, J. Wang, S. Yu, K. Zhou, Support Morphology-Dependent Catalytic
Activity of Pd/CeO2 for Formaldehyde Oxidation, Environ. Sci. Technol. 49 (14)
(2015) 8675–8682, https://doi.org/10.1021/acs.est.5b01264.
[33] Z. Wu, A.K.P. Mann, M. Li, S.H. Overbury, Spectroscopic Investigation of
Surface-Dependent Acid Base Property of Ceria Nanoshapes, J. Phys. Chem. C
119 (13) (2015) 7340–7350, https://doi.org/10.1021/acs.jpcc.5b00859.
[34] M. Nolan, S. Grigoleit, D.C. Sayle, S.C. Parker, G.W. Watson, Density functional
theory studies of the structure and electronic structure of pure and defective
low index surfaces of ceria, Surf. Sci. 576 (1-3) (2005) 217–229, https://doi.
org/10.1016/j.susc.2004.12.016.
[35] H. Nörenberg, G.A.D. Briggs, Surface structure of CeO2(111) studied by low
current STM and electron diffraction, Surf. Sci. 402–404 (1998) 734–737,
https://doi.org/10.1016/S0039-6028(97)00999-0.
[36] D.R. Mullins, P.V. Radulovic, S.H. Overbury, Ordered cerium oxide thin films
grown on Ru(0001) and Ni(111), Surf. Sci. 429 (1-3) (1999) 186–198, https://
doi.org/10.1016/S0039-6028(99)00369-6.
[37] J.C. Conesa, Computer Modeling of Surfaces and Defects on Cerium Dioxide,
Surf. Sci. 339 (3) (1995) 337–352, https://doi.org/10.1016/0039-6028(95)
00595-1.
[38] H. Nörenberg, J.H. Harding, The surface structure of CeO2(001) single crystals
studied by elevated temperature STM, Surf. Sci. 477 (1) (2001) 17–24, https://
doi.org/10.1016/S0039-6028(01)00700-2.
[39] Y. Lin, Z. Wu, J. Wen, K.R. Poeppelmeier, L.D. Marks, Imaging the Atomic
Surface Structures of CeO2 Nanoparticles, Nano Lett. 14 (1) (2014) 191–196,
https://doi.org/10.1021/nl403713b.
[40] M. Bugnet, S.H. Overbury, Z.L. Wu, T. Epicier, Direct Visualization and Control
of Atomic Mobility at 100 Surfaces of Ceria in the Environmental Transmission
Electron Microscope, Nano Lett. 17 (12) (2017) 7652–7658, https://doi.org/
10.1021/acs.nanolett.7b0368010.1021/acs.nanolett.7b03680.s00110.1021/
acs.nanolett.7b03680.s00210.1021/acs.nanolett.7b03680.s00310.1021/acs.
nanolett.7b03680.s004.
107
Journal of Catalysis 404 (2021) 96–108
[41] M. Nolan, Hybrid density functional theory description of oxygen vacancies in
the CeO2 (110) and (100) surfaces, Chem. Phys. Lett. 499 (1-3) (2010) 126–
130, https://doi.org/10.1016/j.cplett.2010.09.016.
[42] M.I. Zaki, N. Sheppard, An Infrared Spectroscopic Study of the Adsorption and
Mechanism of Surface-Reactions of 2-propanol on Ceria, J. Catal. 80 (1983)
114–122, https://doi.org/10.1016/0021-9517(83)90235-X.
[43] G.A.M. Hussein, N. Sheppard, M.I. Zaki, R.B. Fahim, Infrared spectroscopic
studies of the reactions of alcohols over group IVB metal oxide catalysts. Part
1.-Propan-2-ol over TiO2, ZrO2 and HfO2, J. Chem. Soc., Faraday Trans. 1, 85
(1989) 1723-1741. http://dx.doi.org/10.1039/F19898501723.
[44] W. Turek, A. Krowiak, Evaluation of oxide catalysts’ properties based on
isopropyl alcohol conversion, Appl. Catal., A, 417–418 (2012) 102-110.
https://doi.org/10.1016/j.apcata.2011.12.030.
[45] S.A. Fuente, C.A. Ferretti, N.F. Domancich, V.K. Díez, C.R. Apesteguía, J.I. Di
Cosimo, R.M. Ferullo, N.J. Castellani, Adsorption of 2-propanol on MgO surface:
A combined experimental and theoretical study, Appl. Surf. Sci. 327 (2015)
268–276, https://doi.org/10.1016/j.apsusc.2014.11.159.
[46] D. Kulkarni, I.E. Wachs, Isopropanol oxidation by pure metal oxide catalysts:
number of active surface sites and turnover frequencies, Appl. Catal., A 237 (1-
2) (2002) 121–137, https://doi.org/10.1016/S0926-860X(02)00325-3.
[47] A.K.P. Mann, Z. Wu, F.C. Calaza, S.H. Overbury, Adsorption and Reaction of
Acetaldehyde on Shape-Controlled CeO2 Nanocrystals: Elucidation of
Structure-Function Relationships, ACS Catalysis 4 (8) (2014) 2437–2448,
https://doi.org/10.1021/cs500611g.
[48] S. Agarwal, L. Lefferts, B.L. Mojet, Ceria Nanocatalysts: Shape Dependent
Reactivity and Formation of OH, Chemcatchem 5 (2) (2013) 479–489, https://
doi.org/10.1002/cctc.201200491.
[49] S. Agarwal, X. Zhu, E.J.M. Hensen, B.L. Mojet, L. Lefferts, Surface-Dependence of
Defect Chemistry of Nanostructured Ceria, J. Phys. Chem. C 119 (22) (2015)
12423–12433, https://doi.org/10.1021/acs.jpcc.5b02389.
[50] T. Taniguchi, T. Watanabe, N. Sugiyama, A.K. Subramani, H. Wagata, N.
Matsushita, M. Yoshimura, Identifying Defects in Ceria-Based Nanocrystals by
UV Resonance Raman Spectroscopy, J. Phys. Chem. C 113 (46) (2009) 19789–
19793, https://doi.org/10.1021/jp9049457.
[51] J.E. Spanier, R.D. Robinson, F. Zheng, S.W. Chan, I.P. Herman, Size-dependent
properties of CeO2-y nanoparticles as studied by Raman scattering, Phys. Rev.
B 64 (2001) 8, https://doi.org/10.1103/PhysRevB.64.245407.
[52] Y. Li, Z.H. Wei, F. Gao, L. Kovarik, C.H.F. Peden, Y. Wang, Effects of CeO2 support
facets on VOx/CeO2 catalysts in oxidative dehydrogenation of methanol, J.
Catal. 315 (2014) 15–24, https://doi.org/10.1016/j.jcat.2014.04.013.
[53] F. Bonino, A. Damin, S. Bordiga, C. Lamberti, A. Zecchina, Interaction of CD3CN
and Pyridine with the Ti(IV) Centers of TS-1 Catalysts: a Spectroscopic and
Computational Study, Langmuir 19 (2003) 2155–2161, https://doi.org/
10.1021/la0262194.
[54] D. Haffad, A. Chambellan, J.C. Lavalley, Characterisation of acid-treated
bentonite. Reactivity, FTIR study and Al-27 MAS NMR, Catal. Lett. 54 (1998)
227–233, https://doi.org/10.1023/A:1019064930150.
[55] A. Travert, A. Vimont, J.C. Lavalley, V. Montouillout, M.R. Delgado, J.J.C. Pascual,
C.O. Arean, Evidence for discrepancy between the surface Lewis
acid site strength and infrared spectra of adsorbed molecules: The case of
boria-silica, J. Phys. Chem. B 108 (2004) 16499–16507, https://doi.org/
10.1021/jp0479365.
[56] S. Wang, L. Zhao, W. Wang, Y. Zhao, G. Zhang, X. Ma, J. Gong, Morphology
control of ceria nanocrystals for catalytic conversion of CO2 with methanol,
Nanoscale 5 (2013) 5582–5588, https://doi.org/10.1039/C3NR00831B.
[57] C. Lahousse, F. Maugé, J. Bachelier, J.-C. Lavalley, Acidic and basic properties of
titania-alumina mixed oxides; active sites for propan-2-ol dehydration, J.
Chem. Soc., Faraday Trans. 91 (17) (1995) 2907–2912, https://doi.org/10.1039/
FT9959102907.
[58] C.D. Baertsch, K.T. Komala, Y.-H. Chua, E. Iglesia, Genesis of Brønsted Acid Sites
during Dehydration of 2-Butanol on Tungsten Oxide Catalysts, J. Catal. 205 (1)
(2002) 44–57, https://doi.org/10.1006/jcat.2001.3426.
[59] R. Vanselow, R. Howe, Chemistry and Physics of Solid Surfaces V (1984),
https://doi.org/10.1007/978-3-642-82253-7.
[60] S. Chen, T. Cao, Y. Gao, D. Li, F. Xiong, W. Huang, Probing Surface Structures of
CeO2, TiO2, and Cu2O Nanocrystals with CO and CO2 Chemisorption, J. Phys.
Chem. C 120 (38) (2016) 21472–21485, https://doi.org/10.1021/acs.
jpcc.6b0615810.1021/acs.jpcc.6b06158.s001.
[61] Z. Cui, J. Gan, J. Fan, Y. Xue, R. Zhang, Size-Dependent Surface Basicity
of Nano-CeO2 and Desorption Kinetics of CO2 on Its Surface, Ind. Eng.
Chem. Res. 57 (32) (2018) 10977–10984, https://doi.org/10.1021/acs.
iecr.8b01247.
[62] K.R. Hahn, M. Iannuzzi, A.P. Seitsonen, J. Hutter, Coverage Effect of the CO2
Adsorption Mechanisms on CeO2(111) by First Principles Analysis, J. Phys.
Chem. C 117 (4) (2013) 1701–1711, https://doi.org/10.1021/jp309565u.
[63] S. Agarwal, X. Zhu, E.J.M. Hensen, L. Lefferts, B.L. Mojet, Defect Chemistry of
Ceria Nanorods, J. Phys. Chem. C 118 (8) (2014) 4131–4142, https://doi.org/
10.1021/jp409989y.
[64] M.I. Zaki, H. Knözinger, Carbon monoxide — A low temperature infrared probe
for the characterization of hydroxyl group properties on metal oxide surfaces,
Mater. Chem. Phys. 17 (1-2) (1987) 201–215, https://doi.org/10.1016/0254-
0584(87)90056-3.
[65] G. Vicario, G. Balducci, S. Fabris, S. de Gironcoli, S. Baroni, Interaction of
Hydrogen with Cerium Oxide Surfaces: a Quantum Mechanical Computational
Study, J. Phys. Chem. B 110 (2006) 19380–19385, https://doi.org/10.1021/
jp061375v.
B. Sudduth, D. Yun, J. Sun et al.
[66] A. Badri, C. Binet, J.-C. Lavalley, An FTIR study of surface ceria hydroxy groups
during a redox process with H2, J. Chem. Soc., Faraday Trans. 92 (1996) 4669–
4673, https://doi.org/10.1039/FT9969204669.
[67] G. Finos, S. Collins, G. Blanco, E. del Rio, J.M. Cíes, S. Bernal, A. Bonivardi,
Infrared spectroscopic study of carbon dioxide adsorption on the surface of
cerium–gallium mixed oxides, Catal. Today 180 (1) (2012) 9–18, https://doi.
org/10.1016/j.cattod.2011.04.054.
108
Journal of Catalysis 404 (2021) 96–108
[68] D.R. Mullins, The surface chemistry of cerium oxide, Surf. Sci. Rep. 70 (1)
(2015) 42–85, https://doi.org/10.1016/j.surfrep.2014.12.001.
[69] D.R. Mullins, P.M. Albrecht, F. Calaza, Variations in Reactivity on Different
Crystallographic Orientations of Cerium Oxide, Top. Catal. 56 (15-17) (2013)
1345–1362, https://doi.org/10.1007/s11244-013-0146-7.