Article

Cite This: Inorg. Chem. 2019, 58, 6016−6027 pubs.acs.org/IC

Surface, Subsurface, and Bulk Oxygen Vacancies Quantified by

Decoupling and Deconvolution of the Defect Structure of Redox-
Active Nanoceria
Rashid Mehmood,* Sajjad S. Mofarah, Wen-Fan Chen, Pramod Koshy, and Charles C. Sorrell
School of Materials Science and Engineering, Faculty of Science, UNSW Sydney, Sydney, NSW 2052, Australia
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Oxygen vacancy concentrations are critical to the redox/

Downloaded via UNIV POLITECNICA DE CATALUNYA on June 21, 2023 at 19:08:11 (UTC).

photocatalytic performance of nanoceria, but their direct analysis is

problematic under controlled atmospheres but essentially impossible under
aqueous conditions. The present work provides three novel approaches to
analyze these data from XPS data for the three main morphologies of
nanoceria synthesized under aqueous conditions and tested using in vacuo
analytical conditions. First, the total oxygen vacancy concentrations are
decoupled quantitatively into surface-filled, subsurface-unfilled, and bulk
values. Second, the relative surface areas are calculated for all exposed
crystallographic planes. Third, XPS and redox performance data are
deconvoluted according to the relative surface areas of these planes.
Correlations based on two independent empirical results from volumetric
surface XPS, combined with sequential deep XPS and independent EELS
data, confirm that these approaches provide quantitative determinations of the different oxygen vacancy concentrations.
Critically, the redox/photocatalytic performance depends not on the total oxygen vacancy concentration but on the
concentration of the active sites on each plane in the form of subsurface-unfilled oxygen vacancies. This is verified by the pH-
dependent performance, which can be increased significantly by exposing these vacancies to the surroundings. These
approaches have significance to the design and engineering of semiconducting materials exposed to the environment.

1. INTRODUCTION potential of the Ce3+ ↔ Ce4+ switching10 establishes a dynamic

Nanoceria (cerium oxide nanoparticles, CeO2‑x) recently has
attracted attention owing to its redox/photocatalytic, catalytic,
and acid−base properties for energy, environmental, and
biomedical applications. The potential performance of nano-
ceria is considered widely to be associated with the intrinsic
defects Ce3+ and charge-compensating oxygen vacancies (VÖ )
present at the surface or subsurface of the nanoparticles, where
continuous reversible Ce3+ ↔ Ce4+ switching and associated
changes in oxygen vacancy concentration ([VÖ ]) occur; changes
in the pH in aqueous media are known to be one of the means of
initiating this switching.1−9 The insuperable challenge to
researchers is that defect equilibria for semiconductors such as
CeO2‑x typically are described for anhydrous and high-
temperature conditions. Furthermore, there does not appear
to be any analytical instrumentation capable of directly assessing
defect equilibria under hydrated (water vapor) or aqueous
(liquid water) conditions. Consequently, the present work
presents an alternative method to assess these equilibria through
indirect approaches of characterization of nanoceria synthesized
under aqueous conditions, the defect structure of which is
retained during testing using in vacuo analytical conditions in air
and under vacuum.
Hypothetically, permanent annihilation (i.e., filling) of the VÖ
would require the formation of a covalent bond and the
associated electron sharing. However, the low reduction
equilibrium of transient charge compensation between the two
valences, where the VÖ provides the driving force for the
oxidation of adsorbed molecules, thereby establishing a weak
electrostatic bond; the low reduction potential for Ce3+ ↔ Ce4+
switching provides the driving force for the reverse reduction. In
effect, there is an equilibrium constant that effectively fixes the
Ce3+ concentration ([Ce3+]), even when the VÖ is occupied
transiently by adsorbed molecules.
The physicochemical, structural, and microstructural features
of nanoceria play an important role in determining the locations
and concentration of these VÖ . Consequently, the morpholo-
gies, exposed surface planes, surface areas, and grain sizes are
critical, and these depend principally on the synthesis
method.11−20 Synthesis of nanoparticles by methods involving
high temperatures not only reduces the concentrations of
surface vacancies but also produces hard agglomerates, which
cause discrepancies in the measurement of surface areas.21,22 On
the other hand, precipitation and hydrothermal methods tend to
produce monodisperse particles of higher [VÖ ]20 and soft
agglomerates, which potentially can be dispersed by agitation.23
These methods generally synthesize cubes, truncated octahedra,
and square rods, all of which expose one or more of the following
Received: February 4, 2019
Published: April 22, 2019

© 2019 American Chemical Society 6016 DOI: 10.1021/acs.inorgchem.9b00330

Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
facets: {100}, {110}, and {111},24 which play a key role in the
generation of reactive oxygen species (ROS) and the associated
Ce3+ ↔ Ce4+ redox chemistry through the presence of VÖ on
these planes.25−28 DFT calculations of the oxygen vacancy
formation energies of these low-index crystallographic planes10
highlight the role of the exposed facet, suggesting that each plane
has a specific Ce3+ ↔ Ce4+ equilibrium constant.
Since VÖ are critical to the redox/photocatalytic performance
of nanoceria, the concept of oxygen vacancies at the surface and
subsurface and in the bulk have been canvassed through
theoretical and experimental approaches,1−7,29−31 such as
density functional theory (DFT),2 X-ray photoelectron spec-
troscopy (XPS),3 synchrotron XPS,4 secondary ion mass
spectrometry (SIMS),5 and electron energy loss spectroscopy
(EELS).29−31 Although EELS is capable of analyzing the oxygen
concentration ([O]) and the inferred [VÖ ] at subnanometer
resolution, such an analysis cannot be done under aqueous
conditions.29,30 Furthermore, although EELS data can be used
to obtain lateral concentration profiles for single grains,31 data
for the depth concentration profiles remain unknown.
Consequently, the present work is designed to elucidate these
unknown issues by (1) decoupling the total [VÖ ] into its
component f illed (and thus deactivated for redox/photo-
catalysis) and residual unf illed (and thus available for redox/
photocatalysis) and (2) deconvoluting the total surface analytical
data (XPS and surface area) into their component contributions
from individual exposed crystallographic planes of nanoceria
synthesized under aqueous conditions.
2. EXPERIMENTAL SECTION
2.1. Materials. Cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O,
99.999 wt % trace metal basis), ammonium hydroxide solution
(NH4OH, 25 wt % in H2O), and methylene blue (dye content >82
wt %) were obtained from Sigma-Aldrich, Australia. Hydrogen peroxide
(H2O2, 30 vol % in H2O, Ajex Finechem) was obtained from Thermo
Fischer Scientific, Australia. Sodium hydroxide (NaOH, 98 wt %) was
obtained from Chem-Supply, Australia.
2.2. Synthesis of Nanoparticles. Nanoparticles were synthesized
by combination of wet-chemicals methods including precipitation and
hydrothermal reaction.15,16
2.2.1. Nanocubes (NC) and Nanorods (NR). Nanocubes were
synthesized by a precipitation−hydrothermal method, where a solution
of 30 mL of 0.9 M Ce(NO3)3·6H2O was magnetically stirred for 10 min
in a 250 mL Pyrex beaker, followed by the dropwise addition of 30 mL
of a 25 M NaOH solution using a 50 mL glass buret. The mixture was
magnetically stirred for 50 min at room temperature. The mixture was
centrifuged at 3000 rpm for 5 min, the supernatant decanted, and the
residual solid thick slurry was redispersed magnetically in a new rinsed
30 mL of 25 M NaOH solution. The mixture then was transferred to a
50 mL Teflon-lined autoclave reactor, placed in an oven, heated at 5
°C/min to 200 °C, soaked for 24 h, and cooled naturally. The resultant
suspension was transferred to a 50 mL plastic centrifuge tube, and any
residual solid was transferred following rinsing with deionized (DI)
water. This suspension was centrifuged at 2500 rpm for 10 min, the
supernatant decanted, the residual solid rinsed, and the suspension pH
measured. These four steps were undertaken a total of 10 times, which
was sufficient to stabilize the pH at ∼7. The final product was
transferred to a 250 mL Pyrex beaker, the residual solid was rinsed, and
the suspension was dried at 70 °C for 36 h. For nanorods, the procedure
was identical to the above except that the autoclaving was done at 130
°C.
2.2.2. Nanooctahedra (NO). In order to synthesize truncated
nanooctahedra (NO), solid Ce(NO3)3·6H2O was dissolved in DI water
in a 250 mL Pyrex beaker and magnetically stirred for 30 min to yield a
concentration of 0.9 M. H2O2 was added dropwise using a glass dropper
while monitoring the pH until it decreased to a value of ∼3.5. At this
6017
Article
point, NH4OH was added using the same method until the pH
increased to ∼10.0. The suspension was aged by magnetically stirring
for 36 h at 45 °C, after which it was transferred to a 50 mL plastic
centrifuge tube and subjected to procedures identical to those applied
to the nanocubes and nanorods.
For all three types of nanoparticles, which are photocatalytic, storage
between testing was done in the dark in an opaque closed container in
order to avoid light-induced reactions.13,14
2.3. Characterization of Nanoceria. 2.3.1. X-ray Diffraction
(XRD). The samples were prepared for mineralogical characterization by
hand grinding in an agate mortar and pestle and loading into aluminum
sample holders. The XRD powder diffraction was done using a Philips
X’Pert multipurpose X-ray diffractometer (MPD, Almelo, Nether-
lands), with Cu Kα radiation (0.15405 nm) at 20°−80° 2θ, with step
size 0.02° 2θ and scanning speed 5.5° 2θ/min. The peaks were analyzed
using X’Pert High Score Plus software.
The crystallite sizes and lattice strains were calculated from line
broadening using Scherrer’s formula and the Williamson−Hall formula,
respectively).33
2.3.2. Laser Raman Microspectroscopy. The nanoceria also were
characterized mineralogically by laser Raman microspectroscopy by
using a Renishaw inVia Raman microscope (Raman; Gloucestershire,
U.K., beam diameter 1.5 μm), which was equipped with a 35 mW
helium−neon green laser (514 nm), at 200−800 cm−1. The spectra
were fitted and calibrated using Renishaw WiRE 4.3 software. Relative
lattice strains were considered by peak shift.34
2.3.3. Surface Area and Particle Size. The specific surface areas of
the nanoparticles were determined by the Brunauer−Emmett−Teller
(BET) method using a Micromeritics Tristar-3000 (Norcross, GA).
Transmission electron microscopy (TEM) was used to image the
nanoparticles directly owing to agglomeration (Supporting Information
section 1, Figure S1). Fifty individual grains of each type of
nanoparticles were selected at random for determination of the average
particle size by image analysis using ImageJ (National Institutes of
Health, Bethesda, MD). The NC particles were of highly consistent
size. Approximately two-thirds of the NO particles were of consistent
size, with only small variation. The NR particles exhibited significantly
varying aspect ratios, so the length and width were determined as
averages, albeit with larger variations than those of the NC and NO
particles.
2.3.4. Transmission Electron Microscopy (TEM). Morphological
and structural characterization of the nanoceria particles was done by
TEM using a Philips CM200 (Eindhoven, Netherlands) operating at
200 kV. The samples were prepared by dispersion in ethanol and
dropping on a copper grid. TEM imaging was done using Gatan Digital
Micrograph 3.9 software. Selected area electron diffraction patterns
(SAED) of the nanoparticles were done at varying magnifications in
order to assess the lattice characteristics of the nanoceria particles. The
crystallographic planes were identified by fast Fourier transform
analysis using Gatan Microscopy Suite 3 (GMS3) software. The
corresponding interplanar spacings were confirmed using the reported
X-ray diffraction data for CeO2 (JCPDS 34−0394).
2.3.5. X-ray Photoelectron Spectroscopy (XPS). Surface chemical
analysis was done by XPS using a Thermo Fisher Scientific, ESCALAB
250Xi spectrometer (Loughborough, Leicestershire, U.K.; 20 °C, 10−7
Pa, 13.8 kV, 8.7 mA, monochromated Al Kα X-rays at 1487 eV, beam
diameter 500 μm, beam exposure time 30 min). Variations in [Ce3+]
and [Ce4+] were ±0.5 at. %. The data were analyzed using Thermo
Scientific Avantage software and the peak fitting was done by using the
standard Gaussian−Lorentzian shape function. Iterations were
performed using the Marquardt method. The standard deviations
between peak-fitting iterations always were <1.5%. All the peak
positions were matched with the standard National Institute of
Standards and Technology (NIST) XPS database. In order to analyze
the depth profiles of the nanoparticles, suspensions of nanoparticles
were prepared in ethanol and deposited on fused silica substrates for
analysis by deep XPS using the same instrument as for the surface XPS
analysis but with different operating parameters (13.4 kV, 10.8 mA,
monochromated AlKα X-rays at 1487 eV, beam diameter 500 μm). An
argon ion beam at 1 keV was used to etch an area of 2.5 mm × 2.5 mm at
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
Figure 1. TEM images of nanoceria: rows 1−3 TEM, high resolution TEM, and SAED patterns of (a−c) nanocubes (NC), (d−f) nanorods (NR), (g−
i) and nanooctahedra (NO).
a rate of 0.14 nm/s and sampling interval of 5 s. Tantalum pentoxide
(Ta2O5) was used as a calibration reference for the depth of etching.
The expected partial of the surface by argon ion beam is explained in
results and discussion.
2.4. Photocatalytic Activity. The photocatalytic performances of
all three morphologies of nanoceria were assessed in terms of
photobleaching of methylene blue (MB) under UV irradiation
separately at pH 6.0 and pH 9.0. Methylene blue dye solutions were
prepared by dissolving MB (10−5 M) in deionized water. Nanoceria
particles then were dispersed in the dye solution at a concentration of 2
mg/mL in a beaker, which then was placed in a light-obstructing
container. Irradiation was done using a UV lamp (UVP, 3UV-38, 8 W,
350 V, ∼50 Hz, 0.16 A, light intensity 0.39 mW/cm2 with the lamp
placed 9 cm above the solution) at illuminating intensity 1.6 × 10−17 J at
365 nm for 1 h and 7.9 × 10−17 J at 365 nm for 3 h. The pH values were
modified by addition of 1 M NaOH and 1 M HCl. Tests were done in
triplicate for both time points. The MB degradation from UV
irradiation was analyzed in terms of the change in the absorbance
peak height of MB (665 nm) using a PerkinElmer UV−visible
spectrometer.
3. RESULTS AND DISCUSSION
Cerium oxide nanocubes (NC), nanorods (NR), and nano-
ctahedra (NO) were produced by precipitation and hydro-
thermal synthesis in the absence of surfactant or capping agent.
All three morphologies occurred as essentially single phases and
not as mixtures. The X-ray diffraction (XRD) data for the three
morphologies (Supporting Information section 1, Figure S2a−
c) show that the degree of crystallinity is in the order NC > NR >
NO. A decrease in the degree of crystallinity is reflected in the
extent of residual lattice strain, which can be assessed by both X-
ray line broadening34 and laser Raman microspectroscopy peak
shift35 (Supporting Information section 1, Figure S2d). Both
sets of data (Supporting Information Section 2, Table S1) show
6018
Article
that the residual lattice strain (tensile) was in the converse order
NO > NR > NC, which confirms the degrees of crystallinity.
As the TEM data, discussed subsequently, reveal that the
nanoceria grains are single crystal, then the crystallite sizes
(Supporting Information Section 2, Table S1) and grain sizes
(Supporting Information Section 2, Table S2) should be
approximately the same. This is the case for the NR, where
the former (based on a spherical grain) is 11 nm and the latter
(based on the rod diameter) is 17 ± 9 nm. It also is the case for
the NO, where the former is 5 nm and the latter (based on the
cross section) is 7 ± 2 nm. However, there is a significant
difference between the two values for the NC, which are 20 nm
for the former and 58 ± 5 nm for the latter (based on the width).
If the size differences between the spherical and cubic
morphologies are calculated on the basis of the TEM data, the
crystallite sizes should be in the range 39−46 nm, which
represents a range of 26−27% disagreement, which is within the
ranges of variation for the other two morphologies.
However, there also is a crystallite size effect on the Raman
peak shift, where increasing crystallite size (or grain size for these
single-crystal nanoparticles) is inversely proportional to the red
shift.36 Since the observed red shift is in the order NO > NR >
NC and the grain size (using the smaller, more easily vibrated,
width of the NR) also shows the converse relationship, then the
red shift also may result from a particle size effect, which
generally is considered to be a result of phonon confinement7
and which results in the observed trend in asymmetric line
broadening. The longitudinal optical vibration at ∼600 cm−1 is
well established as being indicative of the presence of oxygen
vacancies (VÖ ), albeit invariably at low intensities.37,8
Supporting Information section 1, Figure S2d shows that the
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry Article

Figure 2. XPS spectra and relevant correlations of nanoceria: (a−c) morphology−valence correlation; (d−f) crystallographic deconvolution of the
relevant O 1s peaks.

Table 1. Correlation of [VÖ ] of Nanoceria with Redox/Photocatalytic Effectsa

concentrations (at. %)
O bon-
ded to Ce (XPS)
total total O filled total surface-adsorbed H2O residual unfilled adsorbed H2O on surface
[VÖ ]A Ce3+ Ce4+ sitesB VÖ C (XPS) VÖ D Ce3+ E
RedoxF
morphology [VÖ ]Tot [Ce3+]O [Ce4+]O [OSites] [VÖ ]Fill [H2O]Ads/Tot [VÖ ]Unfill [H2O]Ads/Ce3+ (MB)
NC 11.3 27.0 54.9 93.2 6.8 18.1 4.5 11.3 22 ± 7
NR 13.8 15.0 70.4 99.2 0.8 14.6 13.0 13.8 68 ± 4
NO 13.8 30.0 54.4 98.2 1.8 15.6 12.0 13.8 59 ± 2
a
Methods of determination of values (superscripts A−F) in table are given in the Supporting Information section 3, note 2

peak for NC is lost in the spectrum noise and the peak for NR is
obscured by the noise, but the peak for NO is unambiguous.
Transmission electron microscopy (TEM) and selected area
electron diffraction (SAED) data are presented in Figure 1. In
row 1, the particle morphologies, sizes, and the natures of
agglomeration can be seen. It may be noted that the commonly
observed corner-truncated and corner- and edge-truncated13
cubic morphologies were not observed. Although conversion of
the (100) facets of a perfect cube are known to reconstruct to the
(111) corner and (110) edge truncations under strongly
oxidizing conditions,12 other work16,17 shows that the
morphology is strongly dependent on the temperature and
NaOH concentration (i.e., pH). In row 2, the crystallographic
orientations of the morphologies are confirmed by correlations
between measured and reported interplanar spacings.38 In row
3, the diffraction spots of the SAED pattern of the NC confirm
the high degree of crystallinity. The XRD crystallinity data for
the NR and NO are confirmed by the nature of the rings, which
are sharper for the NR and more diffuse for the NO. The
crystallographic relations of the NR confirm (Supporting
Information section 1, Figure S3) that it exhibits {100} and
{110} pinacoids that form what are effectively the prism faces
and these are capped by {111} and {100} domes and a {110}
pinacoid. Since the only plane that is mutually perpendicular to
6019
the {100} and {110} planes is another {110} plane, this confirms
that the terminating pinacoid is a {110} plane, also as indicated
by others.27
The low-resolution TEM images demonstrate that all three
morphologies give the appearance of being agglomerated
(Supporting Information section 1, Figure S1). However, the
NC show corner-to-face contact; the TEM images demonstrate
the occasional presence of isolated NC, NR, or NO grains; and
there is no evidence of nanoparticle intergrowths; all of which
suggest that the nanoparticles did not form hard agglomerates.22
Hence, the face-to-face contact of the NR and NO indicates that
soft agglomerates22,23 formed as transient artifacts of the
synthesis processes as well as the dispersion process (viz.,
suspension in ethanol) used for TEM analysis. ImageJ39 was
used to process the TEM images in order to calculate the
dimensions of the nanoparticles, where 50 grains each of the NC
and NO revealed uniform sizes while the NR were of variable
aspect ratios, so average values for the dimensions of 50 NR were
determined (Supporting Information section 2, Table S2).
Finally, relative surface areas (RSA) for each surface-exposed
facet for all three morphologies are contrasted with the total
specific surface areas (SSA) (Supporting Information section 2,
Table S3). The RSA are calculated on the basis of perfect planar
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry Article

Figure 3. Structure−activity correlations and deep XPS of nanoceria: (a) redox/photocatalytic performance correlation with time at pH 6.0; (b)
redox/photocatalytic performance correlation with time at pH 9.0; (c) redox/photocatalytic performance correlations with [VÖ ]Tot and [VÖ ]Unfill; (d)
Microstructural and structural correlations with [VÖ ]Unfill; (e) depth profiles for [O] from deep XPS O 1s peak (depths from calibrated data based on
Ta2O5 depth profiles31) and EELS (positive locations [purple] inverted relative to negative locations [black] (Ce vacancies at greater depths not
shown); (f) depth profiles for [Ce3+] from deep XPS Ce 3d (depths from calibrated data based on Ta2O5 depth profiles31).

facets, but some degree of surface irregularity is inevitable in all
systems.
The surface XPS spectra for the Ce 3d region, which are
represented in Figure 2a−c, demonstrate the presence of both
valences of cerium.40 The identification of Ce3+ confirms the
presence of charge-compensating oxygen vacancies at the
surfaces and subsurfaces of the nanoparticles.32,40−42 Further-
more, the O 1s spectra are represented in Figure 2d−f, where the
binding energies of Ce 4+ −O, Ce 3+ −O, and Ce−H 2 O
(adsorbed) are given.11,41 The intensities and areas under the
peaks of the Ce3+-O and Ce−H2O regions have been
deconvoluted, which is discussed subsequently. The intensities
6020
of the Ce3+−O peaks in the O 1s spectra reflect the
concentrations of the oxygen vacancies.
Since, in principle, there is one oxygen vacancy per two Ce3+
ions, then the [Ce 3+ ] and the total oxygen vacancy
concentrations ([VÖ ]Tot) for all three morphologies can be
determined (Supporting Information section 3, note 1). These
calculations show that the order of [VÖ ]Tot (and hence
1
/2[Ce3+]) is NO = NR > NC, which suggests the expected
order of redox/photocatalytic performance.
The quantitative XPS data have been decoupled in order to
differentiate the total oxygen vacancy concentration ([VÖ ]Tot)
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
into filled ([VÖ ]Fill) and unfilled ([VÖ ]Unfill) oxygen vacancy
concentrations, which are given in Table 1.
Since it is required that the total number of O sites must
equate to [VÖ ]Tot + [Ce3+]O + [Ce4+]O = 100%, then the fact that
[OSites] are less than theoretical (100%) indicates that the
difference arises from the transient filling of the VÖ with OH− of
the H2O from the environment43 (the data have been
normalized to eliminate adventitious carbon and adventitious
oxygen associated with carbon; these data are given in
Supporting Information section 3, note 1). Consequently,
these inequalities allow the determination of the [VÖ ]Fill, which
have been transiently filled by the adsorbed OH−, and the
[VÖ ]Unfill, which are determined by the Ce3+ ↔ Ce4+ equilibrium
constants. This decoupling of the two different types of VÖ is
critical because the former are deactivated for redox/photo-
catalysis while the latter remain active, the concentrations of
which correlate with average decrease in methylene blue (MB)
dye degradation. The rationale for this decoupling is supported
by recent DFT calculations,2 which indicate that the formation
of the subsurface oxygen vacancies is energetically more favorable
than that at the surface.
The relevant experimental and redox/photocatalytic perform-
ance data are shown in Figure 3. Parts a−d of Figure 3 clearly
link the morphology to the [VÖ ]Unfill and corresponding redox/
photocatalytic performance. This is highlighted by the matched
data for the latter two figures (Figure 3a,b), which reveal NC ≪
NO < NR. Furthermore, the similarity in the data sets (1 h vs 5
h) shown in the former two figures indicates the rapidity of the
redox/photocatalytic reactions. Also, while the effect of pH also
is significant, the published data are for irregularly shaped
particles, which probably explains their contradictory
trends.42−46 The present work clarifies the relevant features.
At pH 6.0, the reducing conditions favor the presence of Ce3+,
which should enhance the performance. However, it is pH 9.0
and the oxidizing conditions favoring Ce4+ that are superior.
This surprising result is explained clearly by the speciation and
Pourbaix diagrams.47 That is, at pH 6.0, the surface of the CeO2‑x
experiences solubility of both Ce4+ (reductive) and Ce3+, so the
active sites are degraded continuously by partial removal of Ce3+
and associated surface and subsurface oxygen vacancies. In
contrast, at pH 9.0, a Ce(OH)4 passivating layer is established
on the surface of the CeO2‑x. When the UV radiation
decomposes it,48 this results in the conversion to the soluble
species Ce(OH)2+ (at all pH) and Ce(OH)3 (up to pH ∼ 9.7).47
This results in removal of the surface-filled oxygen vacancies
(incorporated in the gel layer) and exposure of the subsurface
oxygen vacancies directly to the solution. This explains the
significant increase in the redox/photocatalytic performance, as
shown in Figure 3c,d. As will be discussed subsequently, the
origin of the morphological correlation lies in the low-index
exposed crystallographic planes.
Furthermore, it is well-known that there are converse
correlations between the particle size and other structural
parameters,42 as shown in Figure 3d (also see Supporting
Information section 2, Table S4). In light of recent reports of the
role of the [VÖ ]Tot (and hence 1/2[Ce3+]),10,34 the redox/
photocatalytic performance should exhibit a converse correla-
tion with the particle size. In contrast, it is significant that parts c
and d of Figure 3 show that the present work does not support
the conventionally assumed direct relation between [Ce3+] and
the redox/photocatalytic performance. The data supporting this
apparent anomaly are given in Table 1, where it can be seen that
the [VÖ ]Unfill correlates with the redox/photocatalytic perform-
6021
Article
ance. More importantly, these data must be considered in light
of the effects of the morphology and the surrounding
environment.
A key striking observation for Table 1 (see Supporting
Information section 3, note 2, footnote D) is that the two
independently obtained sets of experimental data, which are the
[Ce3+] and the [H2O]Ads/Tot, yield equal values for [VÖ ]Tot and
[H2O]Ads/Ce3+ for all three morphologies with no variation
between the numerical values, viz., 100% precision. This triple
set of identities shows that the [H2O]Ads/Ce3+ is associated solely
with the Ce3+ ions and not Ce4+ ions. This association of the
adsorbed H2O and Ce3+ ions is expected since the Pourbaix
diagram47 shows that Ce4+ is not compatible with H2O, resulting
in reductive solubility. The equality between these two variables
actually is as expected because each oxygen vacancy in CeO2‑x is
integrated with an unpaired electron associated with each of the
two Ce3+ ions. These two electrons thus are available to interact
with the valence electrons of the OH− ions in a single adsorbed
H2O molecule. This is why there is a 1:1 ratio between the total
number of oxygen vacancies and the number of H2O molecules
adsorbed on the free surface (viz., Ce3+ ions) of the solid.
Furthermore, for redox/photocatalytic performance, it has
been established both theoretically and experimentally that
molecular oxygen dissolved in aqueous solutions can be
adsorbed at oxygen vacancy sites on nanoceria surfaces, thus
potentially generating a superoxide radical (••O2−) by accepting
one of the two unpaired electrons during continuous reversible
redox Ce3+ ↔ Ce4+ switching18 These superoxide radicals are
effectively ROS and so can enhance the redox/photocatalytic
performance of nanoceria.
The concept of f illed and unfilled oxygen vacancies suggests
that the former are accessed readily by environmental H2O
because they are located in the outermost surface monolayer
while the latter are blocked partially from access by H2O because
they are located at the adjacent subsurface monolayers. This
model has been explored in the present work by depth profiling
using deep XPS. However, this technique is contentious owing
to the established partial reduction of CeO2‑x by both the X-ray
beam49−51 and the Ar ion beam52,53 used in XPS. Examination of
the relevant literature for pure ceria (a summary of the key
studies is given in the Supporting Information, Table S5) reveals
that this reduction is a function of the beam power,50−53
exposure time,50,52 and particle size.4,8,31 While differentiation
between the surface altered by the Ar and X-ray beams and the
unaltered bulk has been demonstrated,50 the depth of the surface
alteration has been determined to be 1.5−2.052 or 2.0−3.0 nm,3
depending on X-ray beam power and time.
It appears that the only data reporting a cross sectional
compositional profile for pure ceria are those of Stroppa et al.,31
who used EELS to determine the [O] across single
coprecipitated octahedral (described as spherical) grains of
ceria (Figure 3e). These data reveal that the entire surface is
hyperstoichiometric in oxygen, which is surprising in light of
both the expectation of the presence of oxygen vacancies and the
partial reduction from the X-ray beam. More importantly, these
data indicate that there is a steep downward oxygen gradient
over the first monolayer (surface) and the adjacent one or two
monolayers (subsurface), below which the data trend toward a
constant oxygen concentration (bulk). The scatter in the bulk
data is likely to have resulted from variations in beam
penetration volume across each rounded grain, grain roughness,
the presence of Ce3+/Ce4+ clusters3, and/or the presence of
oxygen vacancy clusters.54 However, the spike to higher [O] at a
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
Table 2. Exposed Surface Planes, Relative Defect Concentrations, And Redox/Photocatalytic Performance As a Function of
Morphologya
relative deconvoluted surface data for exposed facets and their redox performances
morphology SSA (m2/g) [VÖ ]Tot exposed facets
NC 14 11.3 {100}
NR 105 13.8 {100}
{110}
{111}
NO 199 13.8 {100}
{111}
a
Methods of determination of values (superscripts A−F) in the table are given in Supporting Information section 3, note 3. bCalculated by rational
analysis using the RSA.
depth of 2.1 nm and the reverse trend in the subsurface can be
explained by the presence of metal vacancies, which is discussed
subsequently.
The nature of these EELS data31 was confirmed using deep
XPS depth profiling for powder films of all three morphologies,
as shown in Figure 3e. This correlation is significant partly
because the EELS data report point lateral analyses across single
equiaxed grains while the deep XPS data report planar depth
analyses into multiple grains of three different morphologies.
The largest change in oxygen concentration is over the first
monolayer (surface), followed by more gradual decreases over
the adjacent five monolayers (subsurface); the constancy of the
oxygen vacancy concentration at greater depths is clear (bulk).
In light of the expected partial reduction of the surface 1.5−
3.0 nm by an argon ion beam, the reliability of these data must be
considered. First, the bulk composition is not affected by the
beam,3,8,50,52 so the data at depths greater than ∼3.0 nm are
reliable. Second, since surface reduction takes place, this forces
the trend from the surface to the bulk to increasing [Ce3+],
which means that the overall trends of the curves are correct.
Third, the acquisition time of 5 s is substantially less than those
used in similar deep XPS studies (Supporting Information,
Table S4, 900 s at 1487 eV and 5400 s at 50 eV), so considerably
less reduction from the X-ray beam is expected in the present
work.
Since, as shown in Figure 3f, the bulk [Ce3+] from deep XPS of
∼7% is a maximum but the surface XPS data in Tables 1 and 2
are substantially higher, this apparent anomaly must be
explained. The reason for this lies in the two different
techniques. With deep XPS, each layer is etched and analyzed
sequentially over a period of 5 s at 1487 eV, so these data provide
local compositional information. In contrast, surface XPS, which
is analyzed over a period of 30 min at 1487 eV, provides
volumetric data over a larger region that corresponds
approximately to the depth of the surface + subsurface. Although
the surface XPS probe depth depends principally on the X-ray
beam power and time and the X-ray absorption coefficient of the
material, typical beam penetration depths are reported to be two
to three monolayers,55 1−3,56 2−5,57 and <10 nm.58 Thus, it is
expected that the surface XPS data would yield greater [Ce3+]
values than those from deep XPS, which is the case. In light of
the consistency of the data in Tables 1 and 2, it is concluded that
the surface XPS of the present work analyzed the monolayers
corresponding principally to the surface + subsurface.
These data confirm the perspective that ceria can be
differentiated into three regions:
• Across the first lattice spacing (surface and deep XPS) or
two lattice spacings (EELS), the [Ce3+] and [O] change
6022
Article
RSAA (%) [VÖ ]RelB [VÖ ]FillC [VÖ ]UnfillE RedoxRelFb
100 11.3 6.8 4.5 22
48 5.4 0.8 4.6 10.6
49 8.1 0D 8.1 55.5
3 0.3 0D 0.3 1.5
43 4.8 1.8 3 9.5
57 9 0D 9 49.5
significantly; this region contains VÖ transiently but
completely filled by OH−.
• Across the adjacent four (EELS) or five (deep XPS)
lattice spacings, the [Ce3+] and [O] change more
gradually; this region contains VÖ transiently but only
partially filled by OH−.
• At further depth in the grain, the [Ce3+] and [O] are
constant (deep XPS and EELS); this region contains
unfilled VÖ .
The data in Figure 3f are described in terms of the {100}
planar spacing (0.542 nm) since that is common to all three
morphologies; the planar spacings of the other two planes are
significantly different ({110} = 0.383 nm; {111} = 0.313 nm31).
The diameter of the beam for both surface and deep XPS is very
large (500 μm), so the profiles of a very large number of
randomly oriented grains were analyzed. In contrast, the EELS
data were for individual surface profiles across single grains (6.8
± 1.8 nm) at much greater resolution (interaction diameter 0.4
nm). The difference in the levels and trends of the EELS and
deep XPS data are likely to be a result of the interaction volume
as a function of beam location, where that for deep XPS remains
approximately constant but EELS is variable. A second point of
differentiation is that the grains analyzed by XPS are nominally
faceted, so the assumptions of the [Ce]/[O] and [Ce3+]/
[VÖ ]Tot stoichiometry ratios hold. In contrast, the EELS data are
for rounded grains, where such assumptions may not be entirely
accurate.
A key observation is confirmation that all [O] are oxygen
hyperstoichiometric, even in the bulk, which is in contradiction
with the Ce−O phase diagram.47 While charge compensation in
hypostoichiometric ceria (CeO2‑x) is achieved by Ce3+ ↔ Ce4+
redox, the achievement of oxygen hyperstoichiometry in CeO2+x
can be attained only through oxygen injection or cerium vacancy
formation. Since it is unlikely that interstitial oxygen would exist
simultaneously with oxygen vacancies, then this indicates that
the actual formula of ceria is better expressed as
where the bold type represents vacancies. The presence of
cerium vacancies is likely to enhance the redox/photocatalytic
effects owing to (1) a second such mechanism (in addition to
oxygen vacancies) for these processes, (2) the presence of the
associated unpaired electrons from Ce3+, and (3) the same effect
from increased surface roughness and hence surface area.59,60 It
is clear that the simultaneous presence of vacancies and
electrons suggests a mixed ionic-electronic conductor
(MIEC). While this has been established for doped ceria,61,62
it does not appear to have been suggested for the semi-
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
Figure 4. Mechanisms of action of nanoceria: (a) mechanism of H2O adsorption; (b) redox switching of Ce3+ ↔ Ce4+ (the mechanism for cerium
vacancies is effectively identical).
conductivity involving the intrinsic defects in ceria. It also is clear
that, if the charge deriving from the oxygen vacancies (VÖ ) does
not balance with the charge deriving from the cerium vacancies
(VÖ , VÖ ), then electronic charge compensation (e−, h*) must
occur.
While both cerium and oxygen vacancies have the potential to
contribute to the redox/photocatalytic performance of nano-
ceria by introduction of shallow midgap energy states,63−65 it is
the oxygen vacancies that are critical. Specifically, the outermost
surface monolayer, which is partially f illed by OH− ions, and the
gradient and scale of the adjacent monolayers are important
because they reflect the ease of access of both cerium and oxygen
vacancies to the adsorbed species that form free radicals and
reactive oxygen species (ROS). These concepts are elucidated
generally in the mechanisms of H2O adsorption and redox/
photocatalysis in Figure 4. The latter mechanism is validated by
the results for the methylene blue (MB) degradation by free
radicals and ROS shown in parts a−c of Figure 3, which
emphasize the dominant role of the subsurface-unfilled oxygen
vacancies. Hence, although the NO particles have the highest
measured and calculated surface areas (Supporting Information
Section 2, Table S3) and, more importantly, the highest [VÖ ]Tot,
it is the NR that exhibit the best redox/photocatalytic
performance, which is in agreement with other work.66,67 This
is explained by the data in Table 1, which show that the
6023
Article
morphology with the highest [VÖ ]Unfill is the NR. The
engineering of nanoceria surfaces to consist of surfaces with
high concentrations of subsurface-unf illed oxygen vacancies will
allow increased conversion of environmental H2O and O2
molecules into free •OH and ••O2− radicals, respectively, and
ROS,18,19,24 as illustrated in Figure 4. Further, since the oxygen
hyperstoichiometry decreases with depth into the grain, then it is
likely that both types of vacancies play the same role in redox/
photocatalysis.
For nanoceria, EELS generally has been applied to infer the
[VÖ ] at grain boundaries,29,30 although single grains have been
examined by Stroppa et al.31 However, the potential for VÖ or
VÖ formation has not been considered. The work of Stroppa et
al.31 is significant because the cross sectional analysis of
coprecipitated CeO2 was done on octahedral grains (albeit
modeled as spheres), for which the exposed facets were {200}
and {111}. While these planes were clear in high-resolution
TEM (HRTEM), this sensitivity was not possible with the high-
resolution high-angle annular dark field (HAADF) images that
were used for the cross sectional analyses. Hence, it was not
possible to determine which exposed facets were analyzed.
The present work elucidates these data using the RSA for each
plane. That is, the [VÖ ]Tot can be proportioned according to the
relative surface areas since it has been shown that both the [VÖ ]
and their formation energies for the individual planes are
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
constant, regardless of the morphology.67 As shown in Table 2,
the ([VÖ ]Tot is deconvoluted into [VÖ ]Rel, thereby representing
the associated relative oxygen vacancy concentration for each
plane. The redox performances also are deconvoluted into
RedoxRel according to the exposed facets of each nanoceria
morphology. Consequently, it is clear that there is a Ce3+ ↔ Ce4+
equilibrium constant for each plane. Furthermore, these
equilibrium constants are moderated by the nature of the
OH− electrostatic bond, the reduction potential, the oxygen
vacancy formation energy, and the planar surface area.
In Table 2, the [VÖ ]Fill from Table 1 are weighted entirely to
{100} for two reasons:
• The H2O adsorption energies are in the order:55
{100} = −158.37 kJ/mol > >{110} = −91.90
kJ/mol > {111} = −63.10 kJ/mol
• Table 2 stresses that H2O adsorption on {100} dominates
and effectively excludes those on {110} and {111}
because [VÖ ]Fill is in the order:
NC{100} = 6.9% > > NO{100} + {111} = 1.8%
> NR{100} + {111} + {110} = 0.8%
Consequently, the concentration of unfilled oxygen vacancies
([VÖ ]Unfill) for each plane can be calculated by difference from
[VÖ ]Rel.
The deconvoluted data for the redox/photocatalytic perform-
ance in Table 2 show that the ranking of the effectiveness of the
planes in the NR and the corresponding RSA are in the
respective orders:
{110} > {100} > {111}
49% > 48% > >3%
This relation is identical to evaluations by density functional
theory (DFT) calculations of oxygen vacancy formation
energies for these exposed crystallographic planes.26,68 Since
the {110} planes have the highest [VÖ ]Unfill, they have the
highest RSA, and they are unique to NR, then these confirm the
superior performance of this morphology. Hence, it is the
contribution of the {110} planes that dominates the redox/
photocatalysis results. In contrast, the ranking of the
effectiveness of the planes in NO and the corresponding RSA
are not in the same respective relative orders for the two other
planes:
{111} > {100}
57% > 43%
Again, the reason for this is shown in Table 2, where the values
for [VÖ ]Unfill and the RSA correspond with this order.
These DFT data as well as those differentiating between
surface and subsurface oxygen vacancies2,68 emphasize the
importance of the deconvolution because both morphologies
exhibit the same [VÖ ]Tot but this is not the parameter that
determines the redox/photocatalytic performance; it is the
[VÖ ]Unfill. Thus, the present work not only supports the view that
subsurface oxygen vacancies exist on the three principal low
index crystallographic planes, but it also identifies these defects
as the active sites for redox/photocatalysis.
More specifically, the XPS data and their analyses highlight
the following points:
6024
Article
(1) All of the data in the present work are for ceria in an
aqueous environment, for which there are no analytical
methods for the determination of structural defects.
(2) The deep XPS data illustrate the compositional trends
between surface + subsurface (low [Ce3+]) and bulk (high
[Ce3+]), the latter of which is considered to be an accurate
value and the former of which must be at a lower [Ce3+].
(3) The deep XPS and surface XPS data do not agree because
the former provides local and sequential compositional
data as a function of depth while the latter provides
volumetric data for a larger volume of the solid.
(4) The EELS and deep XPS data demonstrate the same
trends and support the conclusion that ceria is oxygen-
rich, the ionic charge compensation and associated
stoichiometry of which require the presence of cerium
vacancies.
(5) The surface XPS data for the total [Ce3+] can be used to
determine the total oxygen vacancy concentration. These
data also can be used to decouple total oxygen vacancy
concentration into f illed and unfilled oxygen vacancy
concentrations.
(6) The surface XPS data for the concentration of total
surface-adsorbed H2O can be used to determine the
concentration of transiently surface-f illed oxygen vacan-
cies, which then can be used to determine the
concentration of subsurface-unf illed oxygen vacancies.
(7) The preceding data are verified by the differences between
the surface XPS data for the concentration of total surface-
adsorbed H2O and the total oxygen vacancy concen-
trations (i.e., 1/2[Ce3+]), which give identical values for
the total oxygen vacancy concentrations.
(8) The [Ce3+] determined by surface XPS and decoupled
into f illed and unf illed oxygen vacancies depends on the
Ce3+ ↔ Ce4+ equilibrium constant.
(9) While EELS appear to be one of the few methods with the
precision and sensitivity for chemical analyses at the
subnanometer range, it can be used only to infer oxygen
vacancy concentrations; the present method demon-
strates that surface XPS data can be used not only to
calculate the total oxygen vacancy concentrations but also
to decouple these into f illed and unf illed oxygen vacancy
concentrations.
(10) EELS using point lateral depth probing of single grains and
deep XPS using planar depth probing of multiple grains
represent complementary chemical analytical techniques
at subnanometer and nanometer resolutions, respectively.
(11) The general assumption that there is one oxygen vacancy
for every two Ce3+ ions is confirmed, although this
actually consists of the sum of the f illed and unf illed
oxygen vacancy concentrations.
(12) The surface-adsorbed water is associated solely with Ce3+
ions and not with Ce4+ ions on the free surface. The
number of Ce3+ ions on the free surface is the sum of the
two equal numbers of the oxygen vacancies and the
surface-adsorbed water.
(13) The OH− ions of environmental H2O transiently and
partially fill the oxygen vacancies. More specifically, these
OH− ions and H2O transiently and partially fill the
outermost surface monolayer oxygen vacancies, which are
deactivated for redox/photocatalysis. The access to the
oxygen vacancies at the subsurface adjacent monolayers by
the OH− ions of H2O is attenuated with increasing depth
into the grain and so these vacancies are partially filled and
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
unfilled. The unfilled subsurface oxygen vacancies remain
active sites for redox/photocatalysis.
(14) The consistency of the surface XPS, deep XPS, and EELS
data indicate that the defect structures established during
the aqueous synthesis conditions were retained during the
vacuum testing conditions.
(15) The effect of pH is critical in that the expected benefit of
acidic (reduction to form Ce3+) conditions is contradicted
by the superior redox/photocatalytic performance of
basic conditions.
(16) The preceding phenomenon results from the dissolution
of Ce3+ and loss of associated oxygen vacancies from the
surface of CeO2‑x under acidic conditions while basic
conditions result in the formation of a protective
passivating layer of Ce(OH)4, which, upon decomposi-
tion from exposure to UV radiation, exposes the unfilled
subsurface oxygen vacancies.
(17) Ceria contains not only oxygen vacancies but cerium
vacancies, the latter of which are imposed by the
confirmation of oxygen hyperstoichiometry on the surface
and in the bulk. These cerium vacancies also may
contribute to the redox/photocatalytic effects owing to
the associated unpaired electrons.
(18) The bulk of the grain contains a constant level of unfilled
oxygen vacancies, of which the contribution, if any, to the
redox/photocatalytic activity remains unknown.
(19) Since the oxygen vacancy concentration never has been
deconvoluted according to the exposed facets, it remains
unrecognized that the effect of morphology on the redox/
photocatalytic performance of ceria is a function of the
equivalent exposed crystallographic planes. Each of these
exposed facets exhibits a Ce3+ ↔ Ce4+ equilibrium
constant, which is moderated by the nature of the OH−
electrostatic bond, the reduction potential, the oxygen
vacancy formation energy, and the planar surface area.
(20) The match (NR) and nonmatch (NO) between the DFT
calculations for the oxygen vacancy formation energies for
the three low-index crystallographic planes and the redox/
photocatalytic performance are a reflection of the roles of
the oxygen vacancy formation energy and the planar
surface area in the Ce3+ ↔ Ce4+ equilibrium constants for
the different exposed crystallographic planes.
4. CONCLUSIONS
The present work reports data for the structural parameters and
redox/photocatalytic performance of three morphologies of
nanoceria. A critical observation is that the defect structures
established during synthesis in aqueous environments are
retained during testing under vacuum conditions, which is
confirmed by the consistency of three different sets of
experimental data. The overall data analysis introduces three
novel procedures that enable volumetric surface XPS data to be
used to determine quantitative data for surface, subsurface, and
bulk oxygen vacancy concentrations. First, the total oxygen
vacancy concentration is decoupled in order to differentiate
between (a) deactivated transiently f illed oxygen vacancies in
the outermost surface monolayer and (b) active sites in the form
of unf illed oxygen vacancies at the adjacent subsurface
monolayers. Second, the relative surface areas for each low-
index exposed crystallographic plane for all three morphologies,
each of which has a Ce3+ ↔ Ce4+ equilibrium constant, are
calculated. Third, the combined data allow the deconvolution of
6025
Article
the XPS and redox/photocatalytic performance data accord-
ingly. The key outcome of these procedures is the quantitative
determination that the redox/photocatalytic performance
depends not on the total oxygen vacancy concentration for
each plane assumed from the [Ce3+] from surface XPS but on
the concentration of the residual unfilled oxygen vacancies as
determined by the present analysis. Furthermore, the perform-
ance can be increased significantly through the imposition of
basic pH conditions. These result in the formation of a Ce(OH)4
passivating layer, which is decomposed by UV radiation, thereby
exposing the unfilled oxygen vacancies directly to the
surrounding environment. The data analysis also introduces
the importance of the acquisition of sequential deep XPS data,
which provide the bulk stoichiometry, identify the relative
stoichiometry at the surface, and indicate the trend between
these two across the subsurface. Furthermore, deep XPS and
corresponding EELS data demonstrate that oxygen hyper-
stoichiometry requires the formation of cerium vacancies, which
also can be expected to contribute to redox/photocatalysis. The
approaches of the present work provide guidance to the
engineering of different morphologies, sizes, and aspect ratios
of the nanoceria grain morphologies that can be synthesized by
precipitation and hydrothermal processes. They also have
significant practical ramifications to semiconductors as these
materials inevitably are exposed to water vapor in the
environment.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00330.
Transmission electron microscopy, X-ray diffraction, X-
ray photoelectron spectroscopy, laser Raman micro-
spectroscopy, surface areas, and photocatalytic redox
performance data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*(R.M.) E-mail: r.mehmood@unsw.edu.au.
ORCID
Rashid Mehmood: 0000-0003-4073-7835
Wen-Fan Chen: 0000-0002-2917-3875
Author Contributions
R.M. designed the project; undertook the syntheses, character-
ization, TEM imaging, and data analysis; wrote the first draft of
the manuscript; and worked on all subsequent drafts. S.S.M.
assisted in TEM imaging and data analysis. W.-F.C. assisted in
Raman analysis. P.K. assisted with the data analysis. C.C.S.
provided the concepts for the data analysis, worked on all
subsequent drafts of the manuscript, and supervised the overall
project.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to acknowledge grant support from the
Australian Research Council (DP170104130), scholarship
support (R.M.) through an Australian Government Research
Training Program (RTP) Scholarship, and the characterization
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry
facilities of the Mark Wainwright Analytical Centre at UNSW
Sydney.
■
REFERENCES
(1) Esch, F.; Fabris, S.; Zhou, L.; Montini, T.; Africh, C.; Fornasiero,
P.; Comelli, G.; Rosei, R. Electron localization determines defect
formation on ceria substrates. Science 2005, 309, 752−755.
(2) Murgida, G. E.; Ganduglia-Pirovano, M. V. Evidence for
subsurface ordering of oxygen vacancies on the reduced CeO2(111)
surface using density-functional and statistical calculations. Phys. Rev.
Lett. 2013, 110, 246101.
(3) Holgado, J. P.; Alvarez, R.; Munuera, G. Study of CeO2 XPS
spectra by factor analysis: reduction of CeO2. Appl. Surf. Sci. 2000, 161,
301−315.
(4) Kato, S.; Ammann, M.; Huthwelker, T.; Paun, C.; Lampimaki, M.;
Lee, M.-T.; Rothensteiner, M.; Van-Bokhoven, J. A. Quantitative depth
profiling of Ce3+ in Pt/CeO2 by in situ high-energy XPS in a hydrogen
atmosphere. Phys. Chem. Chem. Phys. 2015, 17, 5078−5083.
(5) Lane, J. A.; Kilner, J. A. Oxygen surface exchange on gadolinia
doped ceria. Solid State Ionics 2000, 136-137, 927−932.
(6) Paidi, V. K.; Savereide, L. S.; Childers, D. J.; Notestein, J. M.;
Roberts, C. A.; van Lierop, J. Predicting NOx catalysis by quantifying
Ce3+ from surface and lattice oxygen. ACS Appl. Mater. Interfaces 2017,
9, 30670−30678.
(7) Yao, S. Y.; Xu, W. Q.; Johnston-Peck, A. C.; Zhao, F. Z.; Liu, Z. Y.;
Luo, S.; Senanayake, S. D.; Martinez-Arias, A.; Liu, W. J.; Rodriguez, J.
A. Morphological effects of the nanostructured ceria support on the
activity and stability of CuO/CeO2 catalysts for the water-gas shift
reaction. Phys. Chem. Chem. Phys. 2014, 16, 17183−17195.
(8) Wu, Z.; Li, M.; Howe, J.; Meyer III, H. M.; Overbury, S. H.
Probing defect sites on CeO2 nanocrystals with well-defined surface
planes by Raman spectroscopy and O2 adsorption. Langmuir 2010, 26,
16595−16606.
(9) Paun, C.; Safonova, O. V.; Szlachetko, J.; Abdala, P. M.;
Nachtegaal, M.; Sa, J.; Kleymenov, E.; Cervellino, A.; Krumeich, F.;
Van-Bokhoven, J. A. Polyhedral CeO2 nanoparticles: Size-dependent
geometrical and electronic structure. J. Phys. Chem. C 2012, 116, 7312−
7317.
(10) Yu, P.; Hayes, S. A.; O’Keefe, T. J.; O’Keefe, M. J.; Stoffer, J. O.
The phase stability of cerium species in aqueous systems II. The
Ce(III/IV)-H2O-H2O2/O2 system. Equilibrium considerations and
Pourbaix diagram calculations. J. Electrochem. Soc. 2006, 153, C74−
C79.
(11) Hsieh, C.-C.; Roy, A.; Rai, A.; Chang, Y.-F.; Banerjee, S. K.
Characteristics and mechanism study of cerium oxide based random
access memories. Appl. Phys. Lett. 2015, 106, 173108.
(12) Tinoco, M.; Fernandez-Garcia, S.; Lopez-Haro, M.; Hungria, A.
B.; Chen, X.; Blanco, G.; Perez-Omil, J. A.; Collins, S. E.; Okuno, H.;
Calvino, J. J. Critical influence of nanofaceting on the preparation and
performance of supported gold catalysts. ACS Catal. 2015, 5, 3504−
3513.
(13) Kuchibhatla, S. V.; Karakoti, A. S.; Baer, D. R.; Samudrala, S.;
Engelhard, M. H.; Amonette, J. E.; Thevuthasan, S.; Seal, S. Influence of
aging and environment on nanoparticle chemistry - implication to
confinement effects in nanoceria. J. Phys. Chem. C 2012, 116, 14108−
14114.
(14) (a) Trovarelli, A. Catalytic properties of ceria and CeO2-
containing materials. Catal. Rev.: Sci. Eng. 1996, 38, 439−520.
(b) Kumar, A.; Das, S.; Munusamy, P.; Self, W.; Baer, D. R.; Sayle,
D. C.; Seal, S. Behavior of nanoceria in biologically-relevant
environments. Environ. Sci.: Nano 2014, 1, 516−532.
(15) Mehmood, R.; Ariotti, N.; Koshy, P.; Yang, J.-L.; Sorrell, C. C.
pH-Responsive Morphology-controlled redox behaviour and cellular
uptake of nanoceria in fibrosarcoma. ACS Biomater. Sci. Eng. 2018, 4,
1064−1072.
(16) Mehmood, R.; Wang, X.; Koshy, P.; Yang, J.-L.; Sorrell, C. C.
Engineering oxygen vacancies through construction of morphology
maps for bio-responsive nanoceria for osteosarcoma therapy.
CrystEngComm 2018, 20, 1536−1545.
6026
Article
(17) Sakthivel, T.; Das, S.; Kumar, A.; Reid, D. L.; Gupta, A.; Sayle, D.
C.; Seal, S. Morphological phase diagram of biocatalytically active ceria
nanostructures as a function of processing variables and their
properties. ChemPlusChem 2013, 78, 1446−1455.
(18) Gaynor, J. D.; Karakoti, A. S.; Inerbaev, T.; Sanghavi, S.;
Nachimuthu, P.; Shutthanandan, V.; Seal, S.; Thevuthasan, S. Enzyme-
free detection of hydrogen peroxide from cerium oxide nanoparticles
immobilized on poly(4-vinylpyridine) self-assembled monolayers. J.
Mater. Chem. B 2013, 1, 3443−3450.
(19) Yao, S. Y.; Xu, W. Q.; Johnston-Peck, A. C.; Zhao, F. Z.; Liu, Z.
Y.; Luo, S.; Senanayake, S. D.; Martinez-Arias, A.; Liu, W. J.; Rodriguez,
J. A. Morphological effects of the nanostructured ceria support on the
activity and stability of CuO/CeO2 catalysts for the water-gas shift
reaction. Phys. Chem. Chem. Phys. 2014, 16, 17183−17195.
(20) Garvie, L. A. J.; Buseck, P. R. Determination of Ce4+/Ce3+ in
electron-beam-damaged CeO2 by electron energy-loss spectroscopy. J.
Phys. Chem. Solids 1999, 60, 1943−1947.
(21) Koirala, R.; Pratsinis, S. E.; Baiker, A. Synthesis of catalytic
materials in flames:opportunities and challenges. Chem. Soc. Rev. 2016,
45, 3053−3068.
(22) Tsantilis, S.; Pratsinis, S. E. Soft- and hard-agglomerate aerosols
made at hightemperatures. Langmuir 2004, 20, 5933−5939.
(23) Djuricic, B.; Pickering, S. Nanostructured cerium oxide:
preparation and, properties of weakly-agglomerated powders. J. Eur.
Ceram. Soc. 1999, 19, 1925−1934.
(24) Ren, H.; Koshy, P.; Chen, W. F.; Qi, S.; Sorrell, C. C.
Photocatalytic materials and technologies for air purification. J. Hazard.
Mater. 2017, 325, 340−366.
(25) Yuan, Q.; Duan, H. H.; Li, L. L.; Sun, L. D.; Zhang, Y. W.; Yan, C.
H. Controlled synthesis and assembly of ceria-based nanomaterials. J.
Colloid Interface Sci. 2009, 335, 151−167.
(26) Jiang, Y.; Adams, J. B.; Van-Schilfgaarde, M. V. Density-
functional calculation of CeO2 surfaces and prediction of effects of
oxygenpartial pressure and temperature on stabilities. J. Chem. Phys.
2005, 123, 064701.
(27) Yang, Y.; Mao, Z.; Huang, W.; Liu, L.; Li, J.; Li, J.; Wu, Q. Redox
enzyme-mimicking activities of CeO2 nanostructures: Intrinsic
influence of exposed facets. Sci. Rep. 2016, 6, 35344.
(28) Rodriguez, J. A.; Ma, S.; Liu, P.; Hrbek, J.; Evans, J.; Perez, M.
Activity of CeOx and TiOx nanoparticles grown on Au (111) in the
water-gas shift reaction. Science 2007, 318, 1757−1760.
(29) Feng, B.; Sugiyama, S.; Hojo, H.; Ohta, H.; Shibata, N.; Ikuhara,
Y. Atomic structures and oxygen dynamics of CeO2 grain boundaries.
Sci. Rep. 2016, 6, 20288.
(30) Hojo, H.; Mizoguchi, T.; Ohta, H.; Findlay, S. D.; Shibata, N.;
Yamamoto, T.; Ikuhara, Y. Atomic structure of a CeO2 grain boundary:
the role of oxygen vacancies. Nano Lett. 2010, 10, 4668−4672.
(31) Stroppa, D. G.; Dalmaschio, C. J.; Houben, L.; Barthel, J.;
Montoro, L. A.; Leite, E. R.; Ramirez, A. J. Analysis of dopant atom
distribution and quantification of oxygen vacancies on individual Gd-
doped CeO2 nanocrystals. Chem. - Eur. J. 2014, 20, 6288−6293.
(32) Paier, J.; Penschke, C.; Sauer, J. Oxygen defects and surface
chemistry of ceria: quantum chemical studies compared to experiment.
Chem. Rev. 2013, 113, 3949−3985.
(33) Jamshidijam, M.; Mangalaraja, R. V.; Akbari-Fakhrabadi, A.;
Ananthakumar, S.; Chan, S. H. Effect of rare earth dopants on structural
characteristics of nanoceria d by combustion method. Powder Technol.
2014, 253, 304−310.
(34) Muhammed Shafi, P.; Chandra Bose, A. Impact of crystalline
defects and size on X-ray line broadening: a phenomenological
approach for tetragonal SnO2 nanocrystals. AIP Adv. 2015, 5, 057137.
(35) Filtschew, A.; Hofmann, K.; Hess, C. Ceria and its defect
structure: new insights from a combined spectroscopic approach. J.
Phys. Chem. C 2016, 120, 6694−6703.
(36) Spanier, J. E.; Robinson, R. D.; Zhang, F.; Chan, S.-W.; Herman,
I. P. Size-dependent properties of CeO2‑y nanoparticles as studied by
Raman scattering. Phys. Rev. B: Condens. Matter Mater. Phys. 2001, 64,
245407.
DOI: 10.1021/acs.inorgchem.9b00330
Inorg. Chem. 2019, 58, 6016−6027
Inorganic Chemistry Article

(37) McBride, J. R.; Hass, K. C.; Poindexter, B. D.; Weber, W. H. (56) Chen, W.-F.; Koshy, P.; Sorrell, C. C. Effects of film topology and
Raman and x-ray studies of Ce1‑x RExO2‑y, where RE = La, Pr, Nd, Eu, contamination as a function of thickness on the photo-induced
Gd, and Tb. J. Appl. Phys. 1994, 76, 2435−2441. hydrophilicity of transparent TiO2 thin films deposited on glass
(38) Lu, M.; Zhang, Y.; Wang, Y.; Jiang, M.; Yao, X. Insight into substrates by spin coating. J. Mater. Sci. 2016, 51, 2465−2480.
several factors that affect the conversion between antioxidant and (57) Gorzalski, A. S.; Donley, C.; Coronell, O. Elemental composition
oxidant activities of nanoceria. ACS Appl. Mater. Interfaces 2016, 8, of membrane foulant layers using EDS, XPS, and RBS. J. Membr. Sci.
23580−23590. 2017, 522, 31−44.
(39) Schindelin, J.; Arganda-Carreras, I.; Frise, E.; Kaynig, V.; Longair, (58) Lenser, C.; Gunkel, F.; Sohn, Y. J.; Menzler, N. H. Impact of
M.; Pietzsch, T.; Preibisch, S.; Rueden, C.; Saalfeld, S.; Schmid, B.; defect chemistry on cathode performance: A case study of Pr doped
Tinevez, J. Y.; White, D. J.; Hartenstein, V.; Eliceiri, K.; Tomancak, P.; Ceria. Solid State Ionics 2018, 314, 204−211.
Cardona, A. Fiji: an open-source platform for biological-image analysis. (59) Jaiswar, S.; Mandal, K. D. Evidence of enhanced oxygen vacancy
Nat. Methods 2012, 9, 676−682. defects inducing ferromagnetism in multiferroic CaMn7O12 Manganite
(40) Dutta, P.; Pal, S.; Seehra, M. S.; et al. Concentration of Ce3+ and with sintering time. J. Phys. Chem. C 2017, 121, 19586−19601.
oxygen vacancies in cerium oxide nanoparticles. Chem. Mater. 2006, 18, (60) Wang, D.; Jin, J.; Xia, D.; Ye, Q.; Long, J. The effect of oxygen
5144−5146. vacancies concentration to the gas-sensing properties of tin dioxide-
(41) Sudarsanam, P.; Mallesham, B.; Durgasri, D. N.; Reddy, B. M. doped Sm. Sens. Actuators, B 2000, 66, 260−262.
Physicochemical characterization and catalytic CO oxidation perform- (61) Cheng, S.; Chatzichristodoulou, C.; Søgaard, M.; Kaiser, A.;
ance of nanocrystalline Ce-Fe mixed oxides. RSC Adv. 2014, 4, 11322− Hendriksen, P. V. Ionic/electronic conductivity, thermal/chemical
expansion and oxygen permeation in Pr and Gd co-doped ceria
11330.
PrxGd0.1Ce0.9‑xO1.95‑δ. J. Electrochem. Soc. 2017, 164, F1354−F1367.
(42) Deshpande, S.; Patil, S.; Kuchibhatla, S. V. N.T.; Seal, S. Size
(62) Maheshwari, A.; Wiemhofer, H.-D. Optimized mixed ionic-
dependency variation in lattice parameter and valency states in
electronic conductivity in two-phase ceria-zirconia composite with
nanocrystalline cerium oxide. Appl. Phys. Lett. 2005, 87, 133113.
cobalt oxide and Na2CO3 as suitable additives. J. Mater. Chem. A 2016,
(43) Mansingh, S.; Padhi, D. K.; Parida, K. M. Enhanced visible light
4, 4402−4412.
harnessing and oxygen vacancy promoted N, S co-doped CeO2 (63) Cui, H.; Liu, H.; Shi, J.; Wang, C. Function of TiO2 lattice defects
nanoparticle: a challenging photocatalyst for Cr(VI) reduction. Catal. toward photocatalytic processes: View of electronic driven force. Int. J.
Sci. Technol. 2017, 7, 2772−2781. Photoenergy 2013, 2013, 364802.
(44) Mandal, B.; Mondal, A. Solar light sensitive samarium-doped (64) Ni, M.; Leung, M. K. H.; Leung, D. Y. C.; Sumathy, K. A review
ceria photocatalysts: microwave synthesis, characterization and photo- and recent developments in photocatalytic water-splitting using TiO2
degradation of acid orange 7 at atmospheric conditions and in the for hydrogen production. Renewable Sustainable Energy Rev. 2007, 11,
absence of any oxidizing agents. RSC Adv. 2015, 5, 43081−43091. 401−425.
(45) Song, S.; Xu, L.; He, Z.; Chen, J.; et al. Mechanism of the (65) Queisser, H. J.; Haller, E. E. Defects in semiconductors some
photocatalytic degradation of C.I. reactive black 5 at pH 12.0 using fatal, some vital. Science 1998, 281, 945−950.
SrTiO3/CeO2 as the catalyst. Environ. Sci. Technol. 2007, 41, 5846− (66) Liu, Z.; Li, X.; Koshy, P.; Hart, J. N.; Sorrell, C. C.; et al. Planar-
5853. dependent oxygen vacancy concentrations in photocatalysis by CeO2
(46) Ravishankar, T. N.; Ramakrishnappa, T.; Nagaraju, G.; nanoparticles. CrystEngComm 2018, 20, 204−212.
Rajanaika, H. Synthesis and characterization of CeO2 nanoparticles (67) Nolan, M.; Parker, S. C.; Watson, G. W. The electronic structure
via solution combustion method for photocatalytic and antibacterial of oxygen vacancy defects at the low index surfaces of ceria. Surf. Sci.
activity studies. ChemistryOpen 2015, 4, 146−154. 2005, 595, 223−232.
(47) Channei, D.; Phanichphant, S.; Nakaruk, A.; Mofarah, S. S.; (68) Ganduglia-Pirovano, M. V.; Da Silva, J. L. F.; Sauer, J. Density-
Koshy, P.; Sorrell, C. C. Aqueous and surface chemistries of functional calculations of the structure of near-surface oxygen vacancies
photocatalytic Fe-doped CeO2 nanoparticles. Catalysts 2017, 7, 45. and electron localization on CeO2 (111). Phys. Rev. Lett. 2009, 102,
(48) Fang, Z.; Thanthiriwatte, K. S.; Dixon, D. A.; Andrews, L.; Wang, 026101.
X. Properties of cerium hydroxides from matrix Infrared spectra and
electronic structure calculations. Inorg. Chem. 2016, 55, 1702−1714.
(49) El-Fallah, J.; Hilaire, L.; Roméo, M.; Le Normand, F. Effect of
surface treatments, photon and electron impacts on the ceria 3d core
level. J. Electron Spectrosc. Relat. Phenom. 1995, 73, 89−103.
(50) Roméo, M.; Bak, K.; El-Fallah, J.; Le Normand, F.; Hilaire, L.
XPS study of the reduction of cerium dioxide. Surf. Interface Anal. 1993,
20, 508−512.
(51) Paparazzo, E.; Ingo, G. M.; Zacchetti, N. X-ray induced reduction
effects at CeO2 surfaces: An x-ray photoelectronspectroscopy study. J.
Vac. Sci. Technol., A 1991, 9, 1416.
(52) Zhang, J.; Wong, H.; Yu, D.; Kakushima, K.; Iwai, H. X-ray
photoelectron spectroscopy study of high-k CeO2/La2O3 stacked
dielectrics. AIP Adv. 2014, 4, 117117.
(53) Liu, X.; Zhou, K.; Wang, L.; Wang, B.; Li, Y. Oxygen Vacancy
clusters promoting reducibility and activity of ceria nanorods. J. Am.
Chem. Soc. 2009, 131, 3140−3141.
(54) Grzybek, G.; Stelmachowski, P.; Gudyka, S.; Indyka, P.; Sojka, Z.;
Guillén-Hurtado, N.; Rico-Pérez, V.; Bueno-López, A.; Kotarba, A.
Strong dispersion effect of cobalt spinel active phase spread over ceria
for catalytic N2O decomposition: the role of the interface periphery.
Appl. Catal., B 2016, 180, 622−629.
(55) El-Atwani, O.; Allain, J. P.; Ortoleva, S. In-situ probing of near
and below sputter-threshold ion-induced nanopatterning on
GaSb(100). Nucl. Instrum. Methods Phys. Res., Sect. B 2012, 272,
210−213.

6027 DOI: 10.1021/acs.inorgchem.9b00330

Inorg. Chem. 2019, 58, 6016−6027