J Mater Sci (2012) 47:20572071
DOI 10.1007/s10853-011-5918-5
REVIEW
Synthesis and applications of molybdenum (IV) oxide
Caleb A. Ellefson Oscar Marin-Flores
Su Ha M. Grant Norton
Received: 11 May 2011 / Accepted: 30 August 2011 / Published online: 16 September 2011
Springer Science+Business Media, LLC 2011
Abstract Molybdenum dioxide (MoO2) is a transition
metal oxide with unusual metal-like electrical conductivity
and high catalytic activity toward reforming hydrocarbons.
This review covers the synthesis techniques used to fabri-
cate MoO2 in a variety of morphologies and particle sizes.
Processing from molybdenum ore and reduction from
MoO3 are also covered, with emphasis on reduction
mechanisms and kinetic considerations. Discussions of
various solution-based and gas phase synthesis techniques
shed light on strategies to achieve various unique mor-
phologies, which leads into a brief discussion of nanoscale
MoO2. Nanoscale MoO2 is of interest for important tech-
nological applications including catalysts for partial oxi-
dation of hydrocarbons, solid oxide fuel cell anodes, and
high-capacity reversible lithium ion battery anodes.
Introduction
Molybdenum may be most well known as an alloying
element in various steels, such as 316 stainless steel and
most high strength steels, where it is used to improve
corrosion resistance. However, molybdenum compounds
have long been in use for a variety of applications.
Molybdenum disulfide, MoS2, is a solid lubricant because
C. A. Ellefson  M. G. Norton (&)
School of Mechanical and Materials Engineering, Washington
State University, P.O. Box 642920, Pullman, WA 99164-2920,
USA
e-mail: norton@mme.wsu.edu
O. Marin-Flores  S. Ha
Voiland School of Chemical Engineering and Bioengineering,
Washington State University, P.O. Box 642710, Pullman,
WA 99164-2710, USA
of its weakly bonded layered crystal structure, similar to
graphite. High temperature furnace elements are commonly
made of molybdenum disilicide (MoSi2).
Although molybdenum has oxidation states ranging from
?2 to ?6, oxides exist mainly in two forms: molybdenum
(IV) and molybdenum (VI) oxide. Hexavalent MoO3 is the
principal product of MoS2 roasting, and is also the main
molybdenum compound added in steel production. It is also
of interest as a semiconductor [1], a field-emitter [2], an
electrochomic material [3, 4], photochromic material [5],
and a gas sensor [68]. Tetravalent MoO2 exhibits metal-
like electronic conductivity [9] because of the existence of
delocalized electrons in its valence band [10]. Recently,
MoO2 has garnered much interest for rechargeable lithium
ion battery (LIB) anodes [e.g., 9]. Both MoO3 and MoO2
have been used extensively as a catalyst in hydrocarbon
reforming processes [e.g., 1113]. In particular, MoO2 has
been shown to be coke resistant [14] and sulfur tolerant [15]
during the partial oxidation of hydrocarbons. Because of its
electronic conductivity, MoO2 also has potential as an
anode material for fuel flexible solid oxide fuel cells [e.g.,
16, 17]. This review focuses on a comparison of synthesis
methods of MoO2 and an overview of current research
efforts in specific application areas.
Molybdenum (IV) oxide synthesis techniques
This section will present a review of MoO2 synthesis
techniques. First, the mineral processing of molybdenum
ores is briefly considered. Then, direct hydrogen reduction
of MoO3 will be discussed in detail. We will describe
hydrothermal and ambient temperature solution based
methods, non-solution methods, and because of special
interest, research into nanoscale MoO2 will be reviewed.
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Finally, morphologically unique MoO3, a precursor for
MoO2 synthesis, will be highlighted.
Mineral processing
Molybdenum is found in the earths crust primarily as the
mineral molybdenite (MoS2). After crushing, grinding, flo-
tation, and leaching of mined ore, molybdenite concentrate
is roasted in air at 500650 C yielding technical intermediate phases playing an unimportant role, and
molybdenum oxide, an impure product composed primarily
of MoO3 [18]. Many laboratory and industrial applications
require further purification of oxide products. Common
purification methods performed on an industrial scale are
given in Fig. 1. The first chemical treatment combines
MoO3 with sodium hydroxide to form a sodium molybdate
(Na2MoO4) precipitate. Sodium molybdate is commonly
used as a fertilizer, but has also been used in laboratory
settings to produce various pure molybdenum products.
The second chemical treatment synthesizes ammonium
molybdates in purified forms. Ammonium heptamolybdate
((NH4)6Mo7O24) is commonly used in solution chemistry
because it dissolves readily in water, forming MoO42-(aq)
species. The final purification method is sublimation and
condensation of MoO3. Further chemical processing of these
products produce other common laboratory molybdenum
precursors such as molybdenum chlorides (MoCl2, MoCl4,
MoCl5), molybdic acid (MoO3H2O), molybdenum acetate
(Mo2(O2CCH3)4), molybdenum ethoxide (C10H25O5Mo),
various other molybdenum compounds, and molybdenum
metal.
Direct reduction of MoO3
Traditionally, MoO2 has been produced by the reduction of
MoO3 in dry hydrogen at temperatures between 450 and
Fig. 1 Processing of technical molybdenum oxide
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J Mater Sci (2012) 47:20572071
550 C. Much research has been dedicated to the thermo-
dynamics and kinetics of this reaction. Hagg and Magneli
performed the first phase studies of molybdenum oxides in
1944 [19]. Later, Magneli and co workers [20, 21] detailed
the MoO2 crystal structure. Kihlborg [22, 23] identified
several intermediate oxides with valence states between 4?
and 6?. Early research simplified the direct reduction
reaction to a simple one step full reduction (Eq. 1) with
appearing under mild conditions (\450 C) with slow
reaction kinetics [24].
Full reduction:
MoO3 H2 MoO2 H2 O 1
Kennedy and Bevan [24] concluded that the reduction of
MoO3 followed the general mechanism proposed by
Anderson [25] for the reduction of metal oxides:
1. Chemisorption of hydrogen on the surface
2. Desorption of water, creating anion vacancies
3. Diffusion of the vacancies from the surface into the
bulk
4. Saturation of the crystal lattice with defects
5. Nucleation of the new phase
Kennedy proposed that the rate-limiting step in
reduction was the diffusion of anion vacancies (oxygen
vacancies, in this case) from the surface to the bulk,
despite the reaction being linear with respect to time.
Diffusion limited processes are not normally linear in
nature [26]. It was suggested that anisotropy of the
orthorhombic MoO3 crystal structure explained this unu-
sual phenomenon; specifically, that oxygen vacancy dif-
fusion occurs primarily along {010} faces, and that the
surface area would not decrease greatly as the reaction
proceeds. Several studies seem to confirm the importance
of oxygen transport on {010} MoO3 planes during
reduction [27, 28]. Burch [29] reinforced the reaction
mechanism proposed by Kennedy, but proposed that the
rate-limiting step for reduction of MoO3 is the chemi-
sorption of hydrogen on active surface sites. It is sug-
gested that this mechanism provides a more reasonable
explanation for the linear rate behavior.
Later, the importance of multiple mixed-valence oxides
during reduction was stressed, most notably the ortho-
rhombic Mo4O11 phase. Previous failure to detect mixed-
valence phases in some studies is attributed to limitations
of the characterization technique employed. Standard in
situ X-ray diffraction (XRD) techniques may not have the
time resolution or sample penetration necessary to accu-
rately and comprehensively analyze a sample in reduction.
The detection of Mo4O11 prompted a consecutive two-step
reduction process [30].
J Mater Sci (2012) 47:20572071
Step 1:
4MoO3 H2 Mo4 O11 H2 O 2 hydrogen.
Step 2:
Mo4 O11 3H2 4MoO2 3H2 O 3
Lalik et al. [31] found both of the sequential reaction
processes unlikely based on in situ neutron powder
diffraction (NPD) studies. This study used a 30/70 H2/He
mixture flowing at 30 cm3/min for reduction at 550 C. The
results are summarized in Fig. 2, where the concentration of
the MoO2 and Mo4O11 phases increase at a similar rate
initially. The MoO2 concentration plateaus while the MoO3
is converted to the mixed valence phase. Finally, the mixed
valence phase is fully converted to MoO2.
Two reaction mechanisms were proposed to explain the
compositional progression in this experiment. The first,
a comproportionative reaction, explains the initial rise
and plateau in MoO2 concentration. Comproportionation
defines a reaction in which a species present in two dif-
ferent oxidation states, combines to form an intermediate
oxidation state, as seen in Eq. 5.
Full reduction:
MoO3 H2 MoO2 H2 O 4 addition to Mo4O11 and Mo18O52 by spectroscopic analysis.
Comproportionation:
MoO2 3MoO3 Mo4 O11 5 density functional study examined MoxOy (x = 13,
Partial reduction:
Mo4 O11 3H2 4MoO2 3H2 O 6 complex mixed valence phases [36]. A variety of hydrogen
The second mechanism, competitive nucleation, suggests
that MoO2 is never a reactant in the formation of Mo4O11, but
rather that kinetic considerations cause the plateau in MoO2
and the preferential formation of Mo4O11 in the intermediate
stages. In this case, Eq. 5 is replaced by a direct partial
Fig. 2 Fractional content of molybdenum oxide during hydrogen
reduction at 550 C. [data from Ref. 31]
2059
reduction conversion (Eq. 7) of MoO3 to Mo4O11 with
Partial reduction:
4MoO3 H2 Mo4 O11 H2 O 7
Lalick did not conclude whether comproportionation or
competitive nucleation is the actual reaction process
involved in MoO3 reduction.
Detection limitations are likely not the only reason that
mixed valence phases are not found in many in situ
reduction experiments. It has been proposed that the
appearance or lack of appearance of mixed valence phases
is a function of the reaction conditions and starting material
properties, especially oxygen vacancy concentration [29]
and initial MoO3 particle size [32]. In addition, Mo4O11 was
observed upon reduction with wet hydrogen, while Mo2O5
was observed upon reduction with dry hydrogen [29].
The importance of other mixed valence molybdenum
oxides has been emphasized more recently. Using in situ
XRD and X-ray absorbance spectroscopy (XAS), Ressler
et al. [33] reported the detection of Mo18O52 mixed valence
structure during the reduction of MoO3 with propene.
Cariati et al. [34] also identified Mo5O14 and Mo14O47 in
Nanowires containing MoO3 and conductive Mo5O14 have
recently been investigated in conductive composites [35]. A
y = 19) clusters, and determined that MoO3, Mo?, MoO?,
MoO2?, and MoO3? are the building blocks of larger, more
molybdenum bronzes (HxMoO3) have also been identified
[37, 38] and are of interest because of unique physical and
electrical properties, such as the topotactic insertion of
hydrogen into MoO3 and highly anisotropic transport
properties [39]. These phases are generally not seen in the
final products, but should not be discounted as unimportant
during molybdenum oxide reduction.
Schulmeyer [40] proposed chemical vapor transport
(CVT) for the reduction of MoO3. As illustrated in Fig. 3, a
gas transport phase (TP1) is formed from MoO3 (S1) and
subsequently nucleated as MoO2 (S2) over time (t ). This
transport process continues until only the S2 product
remains.
In order to account for the formation of Mo4O11, a
second transport phase (TP2) is assumed to have formed in
the process. Therefore, the overall reaction is given by
Chemical vapor transport:
MoO3 ! TP1 ! Mo4 O11 ! TP2 ! MoO2 8
Schulmeyer gives no mention of the nature or speciation of
either transport phase, but CVT is supported by the
observed lack of similarity in particle size and morphology
between reactant and product.
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Fig. 3 Schematic
representation of molybdenum
oxide reduction by CVT
t t
S1 Nucleus of S2
Molybdenum dioxide prepared by CVT shows the
presence of several oxide phases coexisting in a multilayer
structure resembling that of a coreshell arrangement. The
presence of multiple oxide phases, particularly in a core
shell arrangement, can be determined X-ray photoelectron
spectroscopy (XPS). Table 1 gives the molybdenum
3d binding energies for the metal in its four most common
oxidation states.
Solution based approaches to MoO2 synthesis
The reduction of MoO3 to MoO2 with hydrogen is relatively
simple and commercially viable. However, other methods
have been investigated with objectives including MoO2
particle size reduction, morphological alteration, and surface
area maximization. Many of the studies creating unique
morphologies seek a high surface area for applications, such
as LIB anodes. High surface area provides a greater active
site density for lithium ion intercalation, and thus a higher
charge density for the battery. High surface area is also
beneficial for catalysis as more active sites per volume allow
for greater reactant flow rates and more efficient reforming.
Many solution phase synthesis methods use hydrother-
mal processes to produce MoO2 directly. Because pro-
cesses at temperatures below 100 C have been largely
unsuccessful in precipitating MoO2 in solution, sealed
Mo2O72 +22H+ + 2N
NH2C6H4NH2 = 2M
MoO
O2 + 3H
H2O + 2
autoclaves are frequently employed for hydrothermal pro-
cesses. Chen et al. [41] charged a MoO3, ethylene glycol,
water suspension to a Teflon-lined stainless steel auto-
clave for 12 h at 180 C. Ethylene glycol is the reducing
Table 1 Binding energy of the most common oxidation states of
molybdenum
Oxidation state Binding energy (eV)
Mo3? 228.7
Mo4? 229.5
Mo5? 231.5
Mo6? 232.7
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J Mater Sci (2012) 47:20572071
TP1
t
Shrinking core Growing Nucleus S2
of S1 of S2
agent in this method, however, it is unclear whether the
reaction takes place at the solidliquid interface or fully in
solution. MoO3 is known to show moderate solubility in
water, forming hexavalent molybdate (MoO42-) or dimo-
lybdate (Mo2O72-) ions. A 3:1 volume mixture of deionized
water and glycol was found to produce the most pure
monoclinic MoO2 phase. This product was nanocrystalline:
about 7 nm particle diameter according to X-ray peak
broadening. Higher ethylene glycol content was found to
produce H0.93MoO3, a hydrogen molybdenum bronze, which
has attracted some interest as a hydrogen storage material.
Our group has used this method extensively to make catalytic
materials (shown for example in Fig. 4), which are active
toward the partial oxidation of hydrocarbons.
A study by Naouel et al. [42] clarifies the reaction
process of reducing molybdenum trioxide to molybdenum
dioxide by hydrothermal synthesis. A suspension of MoO3,
para-phenylenediamine (NH2C6H4NH2), and water was
charged to a sealed vessel for 24 h at temperatures ranging
from 160 to 220 C. The following reaction sequence is
proposed.
Hydrolysis:
2MoO3 H2 O Mo2 O7 2 2H 9
Reduction:
10
These reactions produce clusters of nanoparticles that
are bound together with a layer of organic material into
highly uniform microspheres, as shown in Fig. 5.
Wang et al. [43] investigated a template assisted
hydrothermal method with MoO3 nanofibers as templates.
Nanofibers were added to an autoclave with an acid
(pthalic, nitric, or sulfuric) and a reducing agent (ethanol or
hydrazine). The products seem to retain the overall nano-
fiber morphology, but after reduction are highly porous and
composed of agglomerated nanoparticles.
Yang et al. [44] also used MoO3 as a precursor for
nanostructured MoO2 in a hydrothermal process. MoO3,
assisting agent Fe2O3, reducing agent ethylene diamene,
J Mater Sci (2012) 47:20572071
Fig. 4 Scanning electron microscope (SEM) image of nanoparticle
MoO2 synthesized by hydrothermal method
and water were charged to an autoclave for 5 days at
200 C. The product of this reaction was a highly porous,
nano-sheet, tremella-like microstructure, shown in
Fig. 6a. The sheet thickness is \10 nm.
Several authors have investigated hydrothermal syn-
thesis of MoO2 using ammonium heptamolybdate (AHM)
as the molybdenum precursor. AHM is advantageous in
that it is safe, inexpensive, and highly soluble in water.
Liang et al. [45] dissolved AHM crystals in distilled water,
then added hydrazine hydrate (N2H4H2O) and charged the
solution to an autoclave for 12 h at 130 C. In this case, the
reduction clearly proceeds in solution with hydrazine act-
ing as the reducing agent. The product was amorphous, but
crystallized to pure monoclinic MoO2 upon heating in
argon to 400 C. Thermogravimetric (TG) and differential
thermal analysis (DTA) indicated the as-synthesized
material lost adsorbed water at about 170 C, and crystal-
lization occurred at 370 C. After heat treatment, SEM
reveals loosely agglomerated 400 nm spherical particles. In
similar experiments with ethylene glycol or ethylene dia-
mine added as surfactants, pure MoO2 was produced in
Fig. 5 Schematic representation and corresponding transmission electron microscope (TEM) image of MoO2 microsphere morphology. (Image
reprinted with permission [42])
2061
different morphologies [46]. The product with ethylene
glycol was sheet like, with an average diameter around
250 nm and average thickness less than 100 nm. The eth-
ylene diamine product was bar-like with length up to
15 lm, breadth of approximately 400 nm, and thickness
approximately 100 nm.
Guo et al. [47] used AHM as a precursor for the syn-
thesis of a hollow microsphere morphology MoO2. AHM
was added to water with cetyltrimethyl-ammonium bro-
mide (CTAB) and ethanol under constant stirring. After the
solution became turbid, it was transferred to an autoclave,
sealed, and heated to 180 C for 5 days. The end product,
seen in Fig. 6b, shows porous, micron-scale, hollow
spheres. Crystallite size was found to be approximately
35 nm according to X-ray peak broadening. Only a very
minor weight loss was observed by TG up to 335 C,
indicating that CTAB is probably not involved in the final
MoO2 product. For comparison, the authors compared
CTAB (a cationic surfactant), with dioctadecyldimethy-
lammonium bromide (DCAB, another cationic surfactant),
PEO20-PPO70-PEO20 (P123, a non-ionic surfactant), PEG-
400 (non-ionic), and sodium laurylsurfonate (SDS, anionic)
in the same process. Only the MoO2 product made with
DCAB was hollow spherical. The authors suggest that
cationic surfactants have electrostatic interactions with
negatively charged molybdate ions in solution and the
structure defining surfactant favors the microsphere
morphology.
A novel method by Liu et al. [48] produced amorphous
MoO2 nanoparticles in solution using c-ray radiation at
ambient temperature and pressure. AHM was dissolved in
water with a surfactant (either polyvinyl alcohol or sodium
dodecyl sulfate) and isopropanol (as a hydroxyl radical
scavenger). After irradiation in 70 kCi 60Co c-rays, MoO2
was precipitated. The product was held at 300 C for 12 h
in argon to form a crystalline material. X-ray diffraction
showed MoO2 with traces of MoO3. TEM found particles
narrowly distributed between 8 and 30 nm in size.
Increasing concentration of MoO3 seemed to correspond to
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Fig. 6 SEM images of MoO2

microstructures a Tremella-like
[44], b hollow microsphere
[47], c nanocast mesoporous
[9], d nanowire [56], e pinaster
[57], f nanostar [58] (Images
reprinted with permission)

a minor increase in particle size. Higher concentrations of Hydrolysis:

both surfactants corresponded to a decrease in particle size. BH 
4 2H2 O BO2 4H2 11
Although the mechanism of reduction is not discussed in
detail, it is suggested that c-ray radiation produces hydrate This study employed a sodium molybdate precursor and
electrons (e- aq), which are strong reducing agents. These in produced mixtures of MoO2 and Na0.88Mo6O17 bronze. The
turn reduce molybdates in solution to MoO2 nanoparticles. product is initially amorphous and is crystallized fully upon
Shi et al. [9] used nanocasting on KIT-6 silica templates heating to 350 C. The generalized competing reactions to
to produce ordered mesoporous MoO2 nanostructures. produce the reduced oxide and the bronze are given as
Phosphomolybdic acid (PMA) filled the silica mesopores, MoO2 precipitation:
and then was heated to 500 C in 10% H2/Ar. During this Na2 MoO4 NaBH4 2H2 O NaBO2 MoO2
heat treatment PMA is decomposed, reduced from Mo6? to 2NaOH 3H2 12
Mo4?, and crystallized as MoO2. The SiO2 template is then
removed using 4% HF. SEM and TEM confirm a highly Bronze precipitation:
ordered MoO2 structure. The Brunauer, Emmett, Teller Na2 MoO4 NaBH4 3  g  dH2 O
(BET) method estimates a surface area of 66 m2/g. A high NaBO2 Nag MoO3d 2  dNaOH 13
resolution SEM image of this structure is given in Fig. 6c.
4  0:5g  dH2
Tsang et al. [49] used alkali-metal borohydrides (e.g.,
NaBH4) to reduce transition metal oxides in solution at Greater borohydride concentration was found to
ambient temperature and pressure. The borohydride increase MoO2 yield. Higher borohydride concentrations
quickly hydrolizes in solution by were thought to strengthen the reducing power of the

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J Mater Sci (2012) 47:20572071
solution, thereby promoting the lower-valent MoO2. Pure
MoO2 is formed at pH 10 and 1, while mixtures of MoO2,
Mo4O11, and Na0.88Mo6O17 were produced at pH 4 and 7.
This phenomenon is explained by two opposing effects.
First, the reducing power of tetrahydroborate increases
with decreasing pH. Second, at lower pH molybdate ions
condense, making reduction more difficult. So, at high pH
monomeric molybdates, MoO42-, are easily reduced; and
at low pH the hydroborate has high reducing power. The
detrimental (to MoO2 formation) combined effect at more
neutral pH results in the formation of other species.
In a similar study, the reduction of aqueous K2MoO4
with aqueous KBH4 was investigated systematically [50].
The results were similar to the study with sodium boro-
hydride. An amorphous phase is formed, which crystallizes
at 350400 C. However, unlike the previous study, the
competing effects of reducing power and condensation of
molybdates in solution does not produce counterintuitive
trends. In this study, reducing power of the borohydride
increases with increasing concentration of borohydride at
any given pH. Similarly, decreasing pH always results in a
higher concentration of MoO2 in the product. This study
also produced Mo4O11 as a secondary phase, along with
KxMoyOz bronzes.
Koziej et al. [51] used a non-aqueous solution method to
synthesize MoO2 nanoparticles. Molybdenum dioxide
chloride (MoO2Cl2) was charged with benzyl alcohol and
acetophenone to an autoclave for 48 h at 200 C. This
reaction produces 2 nm spheres, which aggregate into
larger (up to 200 nm in length), highly crystalline, elon-
gated nanoparticles. Interestingly, the authors reported a
phase transition (from hexagonal to monoclinic) as the
nanospheres aggregated to form larger elongated particles.
Similar phenomena have been observed in numerous
materials, including alumina [52] and zirconia [53].
Zach et al. [54] used electrochemical step edge deco-
ration to deposit MoO2 nanowires on higly ordered pyro-
lytic graphite (HOPG). Sodium molybdate was dissolved in
Fig. 7 Schematic
representation and SEM image
of edge-step electrodeposited
MoO2 nanowires (Image
reprinted with permision [54])
2063
water and adjusted to pH 8.5, producing MoO42- ions in
solution. Then, with the HOPG plate employed as the
working electrode in a three-electrode cell, MoO2 was
deposited by
Electrodeposition:
MoO4 2 2H2 O 2e MoO2 4OH 14
The nucleation energy barrier is lower on step edges than
on terraces of a clean surface of HOPG, therefore, nano-
wires can be grown preferentially at step edges, as seen in
Fig. 7. MoO2 nanowires can be grown specifically at step
edges between -0.6 and -1.10 V. Short deposition times
produced nanowires with diameters of 1015 nm, while
longer depositions produce diameters up to 700 nm.
Patil et al. [55] studied thin films electrodeposited from
AHM solution onto fluorine-doped tin oxide (FTO) coated
glass. The resulting films are amorphous, and crystallize upon
argon annealing to 450 C. Film thickness increased with
deposition time up to a plateau at about 20 s. It is proposed that
MoO42- ions are reduced to MoO2 with bonded hydroxide,
and that annealing eliminates the bonded hydroxide. Band gap
measurements are reported to vary between 2.6 and 2.8 eV,
depending weakly on film thickness.
Non-solution approaches to MoO2 synthesis
Several experiments have attempted to make unique mor-
phology MoO2 by non-solution approaches. These pro-
cesses are essentially thermal evaporation of molybdenum
metal under vacuum. Zhou et al. [56] grew MoO2 nano-
wires on a silicon substrate by heating a molybdenum boat
to 1100 C in flowing argon. The resulting nanowires,
shown to be pure monoclinic MoO2, grew perpendicular to
the substrate. The wires grow straight with diameter of
50120 nm, and are up to 4 lm long, as shown in Fig. 6d.
The proposed mechanism is given in Fig. 8. Unstable
MoOx condenses on the surface, and reacts with residual
oxygen in the chamber to form stable MoO2. After the seed
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Fig. 8 Mechanism of thermal evaporation for deposition of
nanowires
is planted on the substrate, MoO2 grows preferentially in
the wire direction. The authors also successfully formed
MoO3 nanowires by heating the as-grown MoO2 nanowires
to 400 C in an argonoxygen mixture. Alternatively,
molybdenum metal nanowires were formed by heating as-
grown MoO2 nanowires to 800 C in flowing hydrogen.
Zhang et al. [57] used thermal evaporation to deposit a
unique pinaster-like structured MoO2 film on a silicon sub-
strate. The substrate was placed over a boat filled with
molybdenum metal powder, and was heated to 1300 C
under vacuum. X-ray diffraction showed a pure monoclinic
MoO2 phase. The unique pinaster morphology has a trunk
with a diameter of 0.83 lm and a length about 12 lm.
Approximately 8 nm nanowires protrude from the trunk
along its length. Also, a relatively long (12 lm) nanowire
grew at the end of each trunk, which the authors identified as
a potential field emission point. Figure 6e shows an SEM
image of this unique morphology. Similar to Zhou et al., the
authors propose a vaporsolid (VS) mechanism for growth
with residual chamber oxygen reacting with unstable gas-
eous molybdenum to form MoO2.
In a similar study, Khademi et al. [58] grew nanostar
MoO2. A boat of molybdenum metal powder was heated to
1300 C and molybdenum oxide condensed on a silicon
substrate. Star-shaped nanorods grew perpendicular to the
surface with a layer of spherical nanoparticles separating
the substrate and the star-shaped nanorods. XRD showed
crystalline Mo4O11 and crystalline MoO2, and TEM indi-
cated that the nanorods were primarily MoO2, while the
spherical layer was Mo4O11. XPS showed a mixture of
Mo6?, Mo5?, Mo4?, and Mod? (0 \ d \ 4). The wall
thickness of the MoO2 nanostars (shown in Fig. 6f) is
approximately 50 nm.
Dillon et al. [59] use hot-wire chemical vapor deposition
(HWCVD) to synthesize molybdenum nanoparticles for
application in rechargeable LIB anodes. In this procedure, a
molybdenum filament is resistively heated to *1400 C in
an environment of flowing argon and oxygen. The product
collects on the quartz tube as the filament slowly oxidized.
Optimized synthesis occurred at 300 C with an atmosphere
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J Mater Sci (2012) 47:20572071
of 4% oxygen. Molybdenum metal, MoO2, and MoO3 were
identified, and the particles ranged from 10 to 25 nm. This
material performed remarkably well in as a negative elec-
trode in a novel lithium ion battery (See Table 3).
MoO3 synthesis methods
Because MoO3 is so easily reduced by either hydrogen or
another reducing gas, it is pertinent to briefly cover the
MoO3 products synthesized in research applications. Sev-
eral studies have produced unique MoO3 morphologies by
hydrothermal reactions, mimicking MoO2 synthesis meth-
ods, with the use of an autoclave at temperatures between
120 and 200 C. The products include nanoparticles
[60, 61], nanorods [62, 63], nanobelts [6467], and nanof-
ibers [68]. Ambient pressure solution products include
aerogel structures [69], whiskers [70], nanoparticles [71],
nanorods [72], nanoplatelets [73], nanoflowers [2], and
lamellar mesostructured mixed molybdenum (V/VI) oxide
[74]. Films of MoO3 have been formed by electrodeposition
[75], RF sputtering [7, 76, 77], and vacuum evaporation [5].
Figure 9 gives some examples of the range of MoO3 mor-
phologies recently synthesized.
Any of these hexavalent oxide products can easily be
converted to MoO2 by a simple hydrogen reduction above
450 C. However, retaining MoO3 morphology, particle
size, or surface area is challenging. If the reduction of
MoO2 to MoO3 is fully in solid state, it involves a signif-
icant density change as well as a change in crystal struc-
ture. If the reduction involves vapor transport, there is little
reason to expect the condensed MoO2 product to resemble
its MoO3 precursor. Studies have suggested overall particle
growth upon reduction from molybdenum oxide [78, 79].
Alternatively, Hu et al. synthesized MoO2 nanorods by
cleaving MoO3 nanobelts during reduction in hydrogen at
550 C. The proposed growth mechanism includes break-
ing bonds selectively along the [001] direction with crack
initiation at defects, such as oxygen vacancies [80]. This
mechanism might serve to explain the result of Yang et al.
[81], where MoO3 reduced with ethanol vapor retained the
MoO3 bulk microstructure while cleaving into nanocrys-
tals. Burch [29] also finds MoO2 to be a solid-state process
where MoO2 is likely to retain the general morphological
habit of the MoO3 from which it was reduced.
Nanoparticle molybdenum oxide
Nanomaterials have been of great interest for decades
[8284], and are especially applicable to catalysis [85, 86],
fuel cells [87], and lithium ion batteries [88, 89]. Table 2
summarizes molybdenum oxide synthesis methods,
including the average smallest dimension as stated in the
reference.
J Mater Sci (2012) 47:20572071 2065

Fig. 9 SEM images of MoO3 microstructures. a Nanobar [62], b nanobelt [65], c nanopalatelet [73], and d nanoflower [2] (Images reprinted
with permission)

Table 2 Summary of nanoscale

Synthesis method Product Size (nm) Morphology Reference
molybdenum oxide synthesis
techniques Hydrogen reduction of nanobars MoO2 100200 Nanorod 80
Ethanol vapor reduction MoO2 100 Aggregated sphere 81
Hydrothermal MoO2 50200 Sphere, bar, flake 45, 46
Hydrothermal MoO2 2050 Sphere 41
Hydrothermal MoO2 80200 Nanofiber, particle 43
Hydrothermal MoO2 10 Tremella 44
Hydrothermal MoO3 6090 Nanorod 62
Hydrothermal MoO3 50900 Nanobelt 64
Hydrothermal MoO3 50 Nanorod 63
Hydrothermal MoO3 50400 Nanobelt 66
Hydrothermal MoO3 50100 Nanobelt 61
Hydrothermal MoO3 20100 Nanofiber 65
Hydrothermal MoO3 50150 Nanorod 72
Hydrothermal MoO3 200300 Nanobelt 67
Microwave hydrothermal MoO3 50500 Nanoflower 2
Solvothermal MoO2 520 Nanorod 51
Solvothermal MoO3 100 Sphere 60
Solvothermal MoO3 100 Fiber 68
Solgel MoO3 10100 Sphere 71
Solgel MoO3 10100 Nanoplatelet 73
Gamma-ray radiation MoO2 830 Sphere 48
Nanocast on silica tempalte MoO2 8 Mesoporous 9
Hot-wire CVD MoO2 530 Sphere 59
Thermal evaporation MoO2 50100 Nanowire 56
Thermal evaporation MoO2 50 Nanostars 58
Thermal evaporation MoO2 8 Pinaster-like 57
Electrochemical deposition MoO2 1015 Nanowire 54
RF sputtering MoO3 10100 Thin film 76

123
2066
Applications
Partial oxidation of hydrocarbons
Molybdenum oxides have been used in various hydrocar-
bon reforming applications for decades. Griffith [9092]
was the first to evaluate MoO2 as a catalyst for the
decomposition of hydrocarbons. MoO3 has been utilized
for the oxidation of propene [93, 94]. Partially reduced
MoO3 and MoO2 have been investigated for the isomeri-
zation of alkanes [13, 95, 96], hexanes [97], and heptanes
as well as the dehydration of propanol [10].
A bifunctional mechanism has been proposed to explain
the catalytic activity of MoO2 for the isomerization of
hydrocarbons [98]. First, metallic sites (Mo4? in MoO2)
dissociate hydrogen to produce active hydrogen atoms.
These active hydrogen atoms bond with surface oxygen to
form Brnsted acid functional groups [12]. There is
ongoing work focusing on MoO2 as a catalyst for the
partial oxidation of hydrocarbons, seeking the efficient
production of hydrogen [14, 99, 100]. Using isooctane as a
model fuel, partial oxidation can be given by
Partial oxidation:
C8 H18 4O2 , 8CO 9H2 15
The proposed mechanism for this catalytic reaction is similar
to that described by Mars and Van Krevelen [101], whereby
the catalyst undergoes cycles of oxidation and reduction.
First, the hydrocarbon is decomposed on the oxide surface
and Mo4? ions gain electrons from hydrocarbon molecules.
Next, lattice oxygen diffuses to the surface of the catalyst and
combines with smaller hydrocarbon molecules, forming
carbon oxides, hydrogen, and water. Finally, gaseous oxygen
replenishes the lattice oxygen lost in the reaction. This
mechanism is summarized in Fig. 10.
Fig. 10 Illustration of the
MarsVan Krevelen mechanism
123
J Mater Sci (2012) 47:20572071
Catalytic testing has shown success in reforming iso-
octane, premium gasoline, Jet-A, and biodiesel with high
hydrogen yield. A significant issue in reforming commer-
cial fuels is the high concentrations of sulfur and coking
precursors. Sulfur poisoning and coking quickly deacti-
vates traditional catalysts, such as nickel. Molybdenum
dioxide has demonstrated excellent sulfur tolerance and
coking resistance, as shown in Fig. 11a, b, respectively.
The reforming environment is critical for the effective
performance of the MoO2 catalyst. Exhaustive thermody-
namic calculation and experimental study [14] has shown a
relatively narrow stability window for MoO2 in oxygen-
containing reforming environments at 550900 C.
Figure 12 shows calculated stability of the species in the
MoOC system at 850 C. At this temperature, oxygen to
carbon (O2/C) ratios above 1.0 promote oxidation to MoO3,
while O2/C ratios below 0.5 may promote coke formation
or reduction to molybdenum carbide (Mo2C).
MoO2 catalysts are severely limited by this environ-
mental instability. A proposed solution involves doping
MoO2 with redox stable species such as Ti, Si, and Sn.
Altering bond energies in the crystal lattice should change
the redox properties of the catalyst, while retaining the
catalytic activity. Studies on silicon [102] and rare earth
oxide [103] doping have already shown potential to
increase stability. Based on past success [e.g., 104, 105],
research into titanium doping is ongoing, and seeks to
evaluate the phase stability and catalytic activity of a single
phase MoxTi(1-x)O2 catalyst.
Direct solid oxide fuel cell (SOFC) anode material
Solid oxide fuel cells (SOFC) are an attractive option in
alternative energy production. Traditional SOFC anodes
are a nickelzirconia cermet where hydrogen reacts with
J Mater Sci (2012) 47:20572071 2067

(a) (b)
100%
Hydrogen yield, Carbon conversion 90%
80%
70%
60%
50%
40%
30% Carbon conversion: 0 ppmw BT
Carbon conversion: 1000 ppmw BT
20%
Hydrogen yield: 0 ppmw BT
10%
Hydrogen yield: 1000 ppmw BT
0%
0 50 100 150 200 250 300 350 400 450
Time on-stream (minutes)

Fig. 11 a Catalytic performance of MoO2 at different benzothiophene (BT) concentrations and b comparison between the performance of MoO2
and a nickel catalyst for the partial oxidation of premium gasoline

Fig. 12 Ternary phase diagram O

MoOC at 850 C and 1 atm 1: MoO3(L) + gas Standard
2: MoO2+MoO3(L)+gas Gibbs Free Energy (J/mol)

3: Mo+MO2C+MoO2 -2 x 104
4: Mo2C+MoO2+gas 0.1 0.9
5: MoC+Mo2C+gas
6: MoC+gas 1 -12x 104
0.2 0.8
7: MoC+C+gas

0.3 2 0.7 (O2/C=1.17)

Pure MoO2

0.4 0.6 (O2/C=0.75)

0.5 4 6 0.5 (O2/C=0.50)

0.6 0.4

0.7 0.3

0.8
3 5 7 0.2

0.9 0.1

Mo C
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

charge-carrying oxygen ions to form water. Nickel pro- increase the applicability of SOFC power generation
vides the electrical conductivity necessary for charge immensely. Not only does eliminating a reformer save
transfer. Zirconia ensures a good interface with the elec- space, weight, and complexity, but also using commercial
trolyte and continues oxygen ion conductivity into the fuel allows power generation anywhere there is gasoline,
porous anode. Traditional SOFC anodes require pure H2 as Jet-A, or any other available hydrocarbon fuel.
fuel, and are subject to deactivation because of coke for- The addition of small amounts (about 1%) molybdenum
mation [106] or sulfur poisoning [107] if fueled by com- to a traditional Ni/yttria-stabilized zirconia (YSZ) anode
mercial fuels. Because of its fuel flexibility and electrical was found to vastly improve coking tolerance in fuel cells
conductivity, MoO2 has been identified as a promising running on methane [108]. Ioroi et al. [109] tested carbon-
direct-fueled SOFC anode material [16, 17]. Eliminating a supported Pt/MoOx composite anodes in proton exchange
pre-reformer and enabling use of commercial fuels would membrane (PEM) fuel cells, and found them to be highly

123
2068
CO tolerant at 100 ppm in H2. Other studies have found
improved CO tolerance when molybdenum was added to
PtRu catalysts for PEM fuel cells running on methanol
[110] and hydrogen [111]. Recently, a highly conductive
strontium molybdate (SrMoO4)/YSZ anode was tested
[112]. The molybdate was deposited on porous YSZ by wet
impregnation, and produced power when fueled by
hydrogen and methane.
Research in our group is ongoing into fabricating and
testing pure MoO2 and MoO2 ? Ni/YSZ SOFC anodes.
Figure 13 shows a composite anode on a YSZ electrolyte.
Molybdenum oxide-based SOFC anodes have the same
stability range as partial oxidation catalysts; therefore,
similar doping procedures are under investigation to pro-
vide greater flexibility for the anode fuel environment.
Lithium-ion battery anodes
As energy storage needs continue to increase, battery
technology must advance to allow greater efficiency.
Lithium ion batteries have been studied extensively since
the 1980s [113115] and have been very successfully
commercialized. However, research continuously seeks
improvements in electrode materials, especially in terms of
enhancing storage capacity [e.g., 88, 116, 117]. Activated
carbon has been the standard anode material for commer-
cial LIBs and has a theoretical storage capacity of
372 mAh/g [118]. Intercalation, the insertion of Li? ions
into the carbon anode, occurs by
Lithium intercalation in carbon:
xLi xe 6C Lix C6 16
The theoretical storage capacity is reached if x = 1 upon
full intercalation. Using non-graphitic carbon (e.g.,
Fig. 13 SEM fracture surface image of a Ni/YSZ ? MoO2 anode on
a YSZ electrolyte
123
J Mater Sci (2012) 47:20572071
nanotubes, modified graphite) x has been shown to exceed
1, and storage capacity has exceeded the theoretical value
[119]. Non-carbon materials, including MoO2, have also
been extensively studied as LIB anodes. In MoO2 based
anodes, intercalation occurs by
Lithium intercalation in MoO2:
MoO2 xLi xe Lix MoO2 17
Murphy explored the possibility of lithium intercalation
into MoO2 in 1978 [120]. Auborn and Barberio [121] first
established the potential of a MoO2 anode in 1987, but also
found several practical issues that needed addressing. First,
there is a phase transition upon intercalation when the
concentration reaches Li0.5MoO2. Cycling was found to be
reversible above this composition (x [ 0.5), but was irre-
versible when discharged past x = 0.5. Once a cell is
discharged through the phase transition, the capacity
decreases rapidly with cycling. Second, particle size has a
significant influence on charge capacity of the MoO2
anode. Unmilled powder was found to reach as little as
10% of the theoretical charge capacity, whereas milled
material reached 95% of the theoretical value. This
observation suggests that ion diffusion through MoO2 is
limiting, and a radial concentration gradient is formed in
large particles. With this in mind, much of the later
research into MoO2 LIB anodes has examined high surface
area materials.
Manthiram and Tsang [122] studied amorphous MoO2?d
(d * 0.3) as a LIB anode. The results show a highly
reversible capacity of *220 mAh/g between 3 and 1 V,
corresponding to a lithium insertion of *1.1. However,
cell cyclability decreased dramatically upon discharge
below 1 V.
In a series of studies, Liang et al. investigated two dif-
ferent MoO2 morphologies as LIB anodes. First,
Fig. 14 LIB anode performance of MoO2 synthesized by a reduction
in ethanol vapor (times), and by a hydrothermal method (square,
circle, triangle). Cycling in the range 0.013.00 V versus Li metal
J Mater Sci (2012) 47:20572071 2069

Table 3 Summary of MoO2

Morphology Charge capacity (mAh/g) Cycles Reference
LIB anode performance
Amorphous particles 220 15 122
Particles (*300 nm) 400 40 45
Porous spheres 480 40 46
Aggregated nanoparticle 381 20 81
Nanoparticle 620 50 59
Tremella-like 538 20 44
Mesoporous 750 30 9
MoO2/C nanorods 760 20 123
MoO2/C nanowires 350 20 124
Elongated nanoparticles 300 200 51

aggregated 400 nm spherical particles were formed by a
hydrothermal method from AHM. Second, elongated 700 by
100 nm particles were synthesized from an oxalate precursor
by a low temperature method. The initial charge capacities
were found to be 769 and 484 mAh/g, respectively [45].
There was a rapid decrease in cyclability below 2 V. Upon
cycling, the capacity of the elongated grains increased
slightly until cycle 13, then decreased slowly until cycle 40,
where the anode retained about 83% of the initial value [46].
The authors claim the increase in capacity up to cycle 13 can
be attributed to electrochemical grinding, whereby the
particle size in the anode decreases, exposing more surface
area and thus improving capacity.
Yang et al. [81] tested a MoO2 LIB anode made from
ethanol-reduced MoO3. TEM showed that the material was
composed of agglomerated nanoparticles with an average
diameter of approximately 100 nm. The initial charge
capacity was 318 mAh/g at 5.0 mA/cm2, and no decrease
in capacity was observed over 20 cycles between 0.01 and
3.0 V, as seen in Fig. 14. About 85% of the reversible
capacity was between 1.0 and 2.0 V. Another study by
Yang et al. [44] tested tremella-like nanostructured MoO2
(seen in Fig. 5a) as a LIB anode. The initial charge
capacity was 538 mAh/g at 0.5 mA/cm2, but only 314 and
259 mAh/g at 2.5 and 5 mA/cm2, respectively. In all three
cases, the capacity rose slightly up to about 8 cycles, and
had approximately the initial value after 20 cycles. This
trend is seen in Fig. 14. In this study, a very high lithium
insertion value of up to 3.2 was achieved.
Shi et al. used nanocast mesoporous MoO2 (Fig. 5c) as
an LIB anode material [9]. The anode held a charge of
750 mAh/g with no decrease in capacity after 30 cycles.
This high capacity was attributed to the mesoporous
materials high surface area (66 m2/g) and low electrical
resistivity (*0.01 Xcm).
The elongated nanoparticle structures investigated by
Koziej et al. [51] showed an initial charge capacity of
375 mAh/g between 3.0 and 0.0 V. The LIB anode
shows very good cyclability, retaining 300 mAh/g after
200 cycles.
Ji et al. and Gao et al. [123, 124] investigated carbon/
MoO2 hybrid nanostructures as materials for LIB anodes.
Ji produced a 36.6 wt% anode that had a stable capacity
of 760 mAh/g between 3.0 and 0.0 V. Gaos MoO2/C
hybrid nanowires achieved a capacity of over 350 mAh/g
at a rate of 1000 mA/g for 20 cycles. An initial capacity of
600 mAh/g was attained at a rate of 200 mA/g, but the
capacity decreased significantly over 20 cycles. Table 3
summarizes the performance of MoO2-based anodes for
lithium ion batteries.
Additional research is required in order to make MoO2 a
viable LIB anode material, especially with regard to
charging rates and long term cycling stability.
Conclusions
Molybdenum dioxide exhibits growing potential for a
number of applications. It can be synthesized in several
highly specific morphologies by a variety of techniques.
MoO2 is easily obtained by reduction of MoO3 by hydro-
gen or other reducing gases above 450 C. Studies also
found success making a wide variety of MoO2 and MoO3
products by solution-phase and gas-phase approaches.
Several of these studies seek high surface area products for
application in lithium ion battery anodes. Other groups
have recently used MoO2 as a catalyst for partial oxidation
logistics of fuels such as biodiesel, gasoline, and Jet-A. In
an extension of this research, MoO2 is being tested as an
anode material for direct-fueled solid oxide fuel cell anode
that is resistant to coking and sulfur poisoning.
Acknowledgements This work was supported financially by the
National Science Foundation GOALI Program (Grant No. CBET-
1034308) and by Boeing Commercial Airplanes.
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