Catalysis Today 285 (2017) 226233

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Supported, bulk and bulk-supported vanadium oxide catalysts: A

short review with an historical perspective
M. Olga Guerrero-Prez
Universidad de Mlaga, Departamento de Ingeniera Qumica, E29071 Mlaga, Spain

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

Article history: The beginning is a very delicate time for understanding. Concepts are better understood when the stu-
Received 19 November 2016 dent knows the historic perspective. Their minds apprehend the evolution of knowledge and, to some
Received in revised form 19 January 2017 extent, share fundamental discoveries. Students will not understand, for example, the actual model of the
Accepted 21 January 2017
structure of an atom if they do not understand rst the models proposed by Thomson and Bohr. However,
Available online 27 January 2017
due to the high number of research papers that are nowadays published, sometimes researchers forget to
This paper is dedicated to Prof. Israel E. review some of the old papers in which the basis of knowledge were established, and those bases allow
Wachs on the occasion of his three decades to build new achievements, allow to understand where are we, and where are we going. In this context,
in academia. the main objective of the this article is to present the basis of knowledge regarding supported vanadium
oxide catalysts, with an historical point of view. It presents how the main achievements were described
Keywords: in this eld, and to do that, the literature century has been reviewed, and especially the progress in the
V2 O5 1980s and 1990s, since the inuence of synthesis method and oxide support, the structure of the active
Bulk-supported catalysts phases, and the concept of monolayer were established in those years. The nal part of this paper briey
Supported catalysts presents the evolution of knowledge that has taken place during the past decade in this eld, and some
Nanoscaled active phases
future trends are anticipated.
Mixed oxides
2017 Elsevier B.V. All rights reserved.

1. Bulk and supported vanadium oxide catalysts: once upon
a time a hundred years ago
Vanadium oxides are fascinating materials that are well-known
for their catalytic properties. Nowadays, these materials nd sev-
eral industrial applications such as gas sensors, electrochemical
and, optical switching devices, reversible cathode materials for Li
batteries, and as catalysts. For developing such applications, these
materials have been extensively studied during the past 100 years;
it is the aim of present paper to present a brief review about how the
knowledge that we have about vanadium oxide catalysts, specially
about supported vanadium oxide, and how it has been evolving
during the last century.
In 1922, Taylor published a nice review entitled Catalysis and
Catalytic Agents in Chemical Processes [1] in which V2 O5 and other
oxides, such as MoO3 and WO3 , appeared as catalytic agents for
oxidation of hydrocarbons reactions. Taylor pointed out the reason
of the catalytic activity of such oxides in that paper: The oxides
of well-dened stability are conspicuously absent (it refers to the
list of known catalysts). The oxides of the alkali metals, to a less
E-mail address: oguerrero@uma.es
extent those of the alkaline earths, denite irreducible oxides such
as magnesium oxide and aluminium oxide are not frequently to be
found among the oxide catalysts of oxidation. On the other hand,
the labile oxides such as those of iron, copper, manganese, silver,
vanadium, tungsten, molybdenum, uranium, chromium, cobalt and
cerium are frequently to be noted in a systematic study of such
oxide catalysts of oxidation. In view of what has been said with
regard to the catalyst as promoter of electronic instability in the
reacting molecules, it is interesting to observe that this large class
of catalytic agents is made up of compounds of elements which
all show a ready tendency to modify the conguration of electrons
surrounding their positive nuclei. In the older nomenclature they
are the oxides of polyvalent metals. It is undoubtedly due to this
variability of electronic conguration that their oxidation activity is
due. In this paper we nd a nice introduction to the catalysis of V2 O5
and other oxcides and to the advantages of the use of a catalytic
support: . . . the loss of catalytic activity can be largely suppressed
if the active material is spread upon an inert support. Thus, cat-
alytic supports, such as asbestos bers, magnesium sulphate, glass
wool or silica, have been used for more than one hundred years for
improving mechanical resistance of the solid catalysts, for achiev-
ing active sites isolation, and to reduce the amount of active phase
required for preparing an active catalyst. The question is, what is a
supported catalyst? When is a simple mixture of two oxides consid-

http://dx.doi.org/10.1016/j.cattod.2017.01.037
0920-5861/ 2017 Elsevier B.V. All rights reserved.
 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
ered a supported catalyst? Where is the composition limit between
a supported catalyst (a small amount of a certain active phase such
as V2 O5 on the surface of another material that normally is another
oxide) and a simple mixture of oxides?
During the following decades, more efforts were done under-
stand the relationships between the structure of vanadium oxides
and their catalytic properties; for example, in 1957 [2], a paper by
Berets et al. discusses about the electronic properties and the struc-
ture defects, and their relationship with the catalytic activity. It is
also well known that in the fties, Mars and van Krevelen investi-
gated the reaction mechanism involved in the oxidation reactions
carried out by V2 O5 catalysts, and they postulated that a lattice oxy-
gen of the oxide catalysts was incorporated to the oxidation product
[3], then, such reduced site would be oxidized by the molecular
O2 reactant, recovering the original catalysts structure. The experi-
mental evidences of such mechanism have been found for different
oxidation reactions and several oxide catalysts [4]. In 1979, it was
described [5] that the catalytic properties of doped V2 O5 were
improved with respect to those of undoped bulk V2 O5 , this fact
was related with the possibility of having oxygen ion vacancies in
the doped sample. Several kinetic studies of reaction catalyzed by
V2 O5 catalysts were performed during 1960 s and 1970 s [610],
but the problem at that time was that the characterization tech-
niques were not able to give an idea about the real structure of
catalysts. So, it was not possible to perform studies about the rela-
tionships between structure and activity of catalysts. In addition,
most of these studies were performed by chemical engineers, and
were more focused on the reaction conditions and reactor proper-
ties than in the structure of catalysts, although it is also necessary
to understand which the structure of catalysts is in order to under-
stand the catalytic process. Some studies also focused on supported
V2 O5 catalysts [11], since up to that moment the major part of
the studies about supported catalysts focused on noble metals.
Although XRD was available, in those days it was difcult to charac-
terize V2 O5 catalysts. Some efforts were still necessary to develop
the adequate techniques for characterization of the surface of solids
under different conditions.
2. First steps on the discovery of the structure of supported
vanadium oxide catalysts
Around 1970, the catalysis researchers started to think that it
was important to characterize the structure of the catalysts in order
to identify the active phases and to establish relationships between
the structure and the activity of catalysts; this would allow the
design of more active and selective catalysts. One of the rst papers
that tried to describe the characterization of supported V2 O5 cata-
lysts was published in 1969 by Takahashi and coworkers [12]. In this
paper they prepared two supported V2 O5 catalysts using two differ-
ent supports, both around 5 wt% of V2 O5 , without considering the
surface area of aluminas and Neobead-Alundum. Both supported
catalysts were characterized by ESR, the spectrum of one of the
samples was found to be similar to that of bulk V2 O5 , whereas the
other was completely different. This nding was very important
since it demonstrated that the structure of the V2 O5 oxide changes
when it is supported. They did not take into consideration the sur-
face area of both supports, thus, it is likely that these two samples
had very different amounts of VOx units per nm2 , and this could
be the reason of such differences in the ESR spectra. One year later
[11], a paper was published in which the concept of effective sur-
face area was considered since it was found an optimum amount of
the active component (V2 O5 ) supported on the support (SiO2 in this
case). They assumed that the effective surface area is proportional
to the amount of the active component supported on the carrier,
227
and interpreted the dependence of the rate constant on the amount
of the supported active component.
During the 1970s, spectroscopy techniques such as FTIR (earlier)
and Raman (later) started to be applied for the characterization
of solids, and the spectra of the series of oxides were described
and catalogued. The catalysis researchers started to apply those
characterization techniques to supported catalysts and; in the
case of oxides, they discovered that Raman spectroscopy was a
very informative technique. Brown et al. published two papers in
1977 [13,14] that can be considered the rst rigorous study of
characterization of supported metal oxide catalysts with Raman
spectroscopy. They focused in supported MoOx catalysts, using
alumina and silica-alumina as supports. They pointed out that, in
contrast to the IR spectra, the Raman spectra are almost free for
a contribution of the oxide support, permitting the study of the
vibrations associated with the supported oxide active phases. They
determined that depending on the amount of MoOx incorporated,
bulk MoO3 was detected or not, thus, they propose that each sup-
port has a limit of MoOx units that can be incorporated resulting
in a saturation of the surface. They calculated a limit of approxi-
mately 20% MoO3 in this study, assuming a surface area of 200 m2 /g
for the support. Thus, this could be considered as the rst denition
of what a supported metal oxide catalyst is, establishing a limit of
active phase that can be incorporated to the support without the
presence of crystalline oxide structures. Below this limit, they could
not identify completely the nature of the supported MoOx phase,
described as tetrahedral MoO4 2 -, Al2 (MoO4 )2 , and other interac-
tion products. They also detected a Raman band near 950 cm1 ,
whose exact nature could not be described at that moment.
By 1985, Wachs published a seminal paper [15] that gave a step
ahead in this eld, introducing the modern concept of monolayer
coverage. Both XRD and LRS were used to characterize supported
VOx/TiO2 catalysts employed for o-xylene oxidation to phthalic
anhydride. In this paper two different types of VOx species on the
TiO2 support were described. Below monolayer coverage, surface
vanadia species coordinated to the TiO2 support are described and
characterized by a very broad Raman band, around 1000 cm1 , that
was described to belong to disordered surface phase of vanadium
oxide (Fig. 1). For coverages higher than monolayer, crystallites of
V2 O5 were found. It was demonstrated that the dispersed surface
vanadia species were the active phase for the oxidation reac-
tion, and subsequently, the catalysts with coverage close to the
monolayer were found to be the most active and selective. It was
described that the V2 O5 crystallites were detrimental for the cat-
alytic activity. In this paper, it was pointed out that the coordination
of the surface vanadia species could not be assigned by the Raman
data, and it was presented a XANES study by Kozlowski et al. [49]
that described the vanadia species supported on titania with two
terminal bonds (Fig. 2). Wachs suggestion that monolayer coverage
catalysts were more active was conrmed one year later, by the
group of Ross [16], which described as the most active and selec-
tive for the NOx reduction with ammonia the supported vanadium
catalysts with coverage close to monolayer. They found these sup-
ported catalysts with coverage close to monolayer as more active
and selective than commercial bulk catalysts, giving an important
step ahead in the design of catalysts with commercial applications.
In this line, several papers were published by 1986. Two papers
by Bond et al. [17,18], that described the characterization by XPS
and LRS of supported vanadium oxides on titania. They described
three types of VOx species and made an estimation of monolayer
capacities. The monolayer was dened in this study as 0.10 wt%
V2 O5 /nm2 , and they described the appearance of V2 O5 crystals
for coverages up to 4 monolayers, establishing three types of VOx
species. Below one monolayer they described VOx species as oxo-
hydroxy species bonded to two surface oxygens. Between one and
four as layers of amorphous V2 O5 and for contents up to 4 mono-
228 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
Fig. 1. Laser Raman spectra of low surface area V2 O5 /TiO2 (anatase) as a Function
of V2 O5 content (all spectra corrected for TiO2 (anatase) background).
Reproduced with permission from [15]
layers they described the formation of V2 O5 crystals. In this line,
and using TPR and a titration method for determining V surface
concentration, Glinski et al. also used this concept of monolayers
and double layers of vanadium pentoxide on supports [1921], and
describing the possibility of using all the hydroxyl groups present
of the surface of the calcined monolayer catalyst for the immobi-
lization of a second V2 O5 layer. In line with Wachs work [15], they
found better catalytic performance with the one-monolayer cata-
lysts. In contrast to the Bond [17] study, that described dispersed
surface vanadium oxide species bonded to two surface oxygens,
Glinski [19] described such species only bounded by one V-O-
support bond. In the line with this concept of multilayered catalysts,
Triro et al. [22,23] proposed a model, based on FTIR and XRD
studies, for the structure of VOx/TiO2 catalysts. In this model, the
monolayer was described as a V(IV) structure on the support that
was able to reduce to V(III) and V(V) structure was described on
the top of such V(IV) layer. This spectroscopic study revealed the
presence of V-OH species, but it must be considered that this spec-
troscopic study was performed on samples pretreated on vacuum at
673 K, being possible that such treatment had made the vanadium
species to lose some oxygen. By 1986 Haber [24] published a paper
focusing on the structure and redox properties of vanadium oxide
surface compounds using EXAFS and reduction-oxidation cycles.
Fig. 2. Reproduced with permission from [15].
They also conrm the best activity results around monolayer cov-
erage postulating monodispersed surface VO4 units as the active
phase. They also compared different oxide supports, nding that
vanadia supported on alumina to form dimeric and pyrovanadate
species, whereas only bulk V2 O5 was found on silica. They described
such monodispersed units as bounded by two bringing oxygens
and having two terminal oxygens. So at that stage, the concepts of
monolayer and structure of vanadium oxide dispersed on the sup-
port species were still not clear, although it was known that they
were the active species. Thus, during the next few years, several
groups [2531] focused on the characterization, by different tech-
niques, of the so-called monolayer structure. In all these works, the
effect of precursor and synthesis conditions on the structure for the
catalysts was also under debate. This was not an easy task since i)
such VOx species are in a low concentration, ii) the nature of such
species may change with the environment (temperature and atmo-
sphere) and iii) in order to characterize such species it is necessary
to analyze just the surface of the material, and most of the available
solid characterization techniques were giving information about
the bulk.
Wachs, again, gave a step ahead and by 1986 published a study
[31] in which the catalysts were characterized at different tem-
peratures. They studied supported VOx/TiO2 catalysts calcined in
the 110750 C temperature range and used several characteri-
zation techniques. They found that the structure of the catalysts
was strongly dependent on calcination temperature. For the cata-
lyst with high loading of vanadia, they detected the formation of
a mixed V-Ti-O phase that was detrimental for the catalytic activ-
ity, founding the optimum catalytic performance for the samples
calcined around 350575 C, where a complete monolayer of sur-
face vanadia exists on the titania support (Fig. 3). The importance
of this paper was that it underlined how the temperature and the
environment could affect to the structure of catalysts, being nec-
essary for the development of techniques able to characterize the
catalysts under reaction conditions or, at least, close to such con-
ditions. Such techniques will be developed later. In a second paper
[32], Wachs group identied the active phases during o-xylene oxi-
dation over VOx/TiO2 catalysts, founding two different sites, VOx
supported and V2 O5 crystallites, demonstrating how the nature of
the active phases can be modulated by the use of a support and con-
trolling the surface coverage. In this line, Haber group published a
paper [33] in which they studied the evolution of a supported TiO2
catalysts in the course of the reaction by analyzing the evolution of
mechanical mixtures of crystalline V2 O5 and TiO2 (anatase) during
the oxidation of o-xylene. During the time on stream experiments,
they observed an increase of conversion and selectivity that was
related with the spreading of V2 O5 over the surface of anatase under
reaction conditions. Such spreading of dispersed VOx species was
not possible when the bulk crystalline V2 O5 structure was used,
explaining by this manner the good catalytic properties that sup-
ported catalysts presented. Baiker et al. also published a study along
his line, showing that the amorphous V2 O5 was more active and
selective than crystalline V2 O5 during the methanol oxidation reac-
tion [34]. In line with these studies, Bergeret et al. [35], also proved
 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
Fig. 3. Model of the evolution of V2 O5 /TiO2 with calcination temperature.
Reproduced with permission from [31].
that the supported VOx species are homogeneously dispersed on
the surface of the support (in this case they used -alumina). They
characterized the catalysts by radial electron distribution (RED) and
found, in agreement with previous works, that the interatomic dis-
tances of vanadium pentoxide on alumina is different from that of
bulk V2 O5 .
In a very short period of time 19861988 [2040], many
papers were published focusing on different aspects of supported
VOx/TiO2 catalysts for several oxidation reactions, showing the
high interest that this catalytic system had at this point in time.
As it has been shown, at this moment it was known that the struc-
ture of the supported VOx species was different than that present
in bulk V2 O5 , showing the importance of the nature of support, and
the loading of supported vanadium species (coverage), since dis-
persed supported species can be found for coverages lower than one
monolayer, up to that amount, bulk V2 O5 species are not present. In
addition, the nature of these species changes with temperature and
atmosphere. Although all these studies indicated the dispersed cat-
alysts were more active and selective than the bulk ones, it was not
clear at that moment, what was the exact nature of these dispersed
surface metal oxide active phases.
3. Identifying the active sites of dispersed surface species
As has been shown, in the 1980s, there was a great interest
in commercially developing supported vanadium oxide catalysts
since they were very promising (active and selective in a wide range
of oxidation reaction, inexpensive, easy to prepare, mechanically
resistant, etc.). At the end of 80s, it was assumed that monolayer
supported vanadium oxide catalysts were more active than the
corresponding unsupported bulk catalysts, but a debate opened
regarding the nature of such supported VOx species. Subsequently,
many researcher groups were dealing with kinetic and charac-
terization studies in order to characterize how many different
vanadium oxide species can be found on the supports and which
are the active species. Bond and Flamerz published a study in which
they proposed a model for the isopropanol oxidation over sup-
ported VOx catalysts. They assumed that the dispersed VOx species
229
were different form the bulk, in line with previous works, and pro-
posed the terminal V O bond as the active site [38]. In this way,
and through spectroscopic studies (IR spectra of adsorbed aromatic
compounds), Davydov [39] concluded that aromatic molecules can
react with surface cations due to the formation of bonds with the
base OH-groups of surface oxides, pointing out the terminal V O
or V OH as the active functionalities.
During 19881990, there were several catalysis groups trying
to characterize the exact molecular nature of the surface vana-
dium oxide species presents in the so-called monolayer catalysts
[4044], how the synthesis method affects them [45], and which
species were involved in the reaction mechanisms [46,47]. The
exact denition of monolayer was not clear, since in some papers
[47] the catalyst was dened as monolayer and contained V2 O5
crystals and was described as having a heterogeneous structure.
Nowadays it can be assumed that a monolayer catalysts do not
contain V2 O5 crystallites, but, of course, this concept could be
ambiguous depending the characterization technique used to char-
acterize such species (for example, XRD cannot detect crystallites
smaller than 3 nm). In order to have a perspective about the impact
of monolayer concept on literature, and on the interest of the
researchers, Fig. 5 shows the number of articles published in this
eld since 1978 according to Scopus. Fig. 5A plots the articles with
supported vanadium oxide catalysts and 7 B with supported
metal catalysts. Fig. 5A shows two maxima, one around 19881993
according to this moment in which there was a high interest in
underlining the nature of the monolayer catalysts.
Some groups proposed, based on several characterization
techniques such as EXAFS and XANES, the existence of mono-
molecularly dioxo species for the supported vanadium oxide
surface species on titania [24,45,48,49], whereas other groups pro-
posed the existence of mono-oxo species, as well as the possibility
of polymeric surface vanadia species. A debate was also taking
place regarding the coordination of such surface vanadia species.
Many groups worked in these years to clarity these points. Wachs
[44,5056] investigations, based on solid state 51 V NMR and Raman
experiments, revealed that the molecular structure of the sup-
ported VOx species on titania is dependent on the coverage and
on degree of hydration. At low coverages and under hydrated con-
ditions, a broad Raman band near 940 cm1 was detected that
shifts to 990 cm1 when the loading was increased. The NMR study
revealed that the 990 cm1 band was due to octahedrally coordi-
nated surface vanadia species, which matched with the band found
in octahedral vanadia species present in decavanadate clusters.
This assignment was very important, since the structure of sodium
decavanadate had been found to contain one short vanadium-
oxygen bond, four intermediate vanadium-oxygen bonds, and one
long vanadium-oxygen bond [57]. On the other hand, the band
near 940 cm1 best matched with hydrated distorted tetrahedral
vanadia species. Upon dehydration, the hydrated surface vana-
dia species transformed the hydrated octahedral surface vanadia
species to tetrahedral coordination, change that was associated
with a shift in the Raman band to 10201040 cm1 , suggesting a
surface tetrahedral structure possessing one short terminal bond
and three long bridging bonds (Fig. 4). Busca et al. [58,59], through
several FTIR and Raman spectroscopies experiments, conrmed
this important point, and also concluded that vanadia structures
had only one short vanadium-oxygen bond. Further studies were
published also in this line [60], trying to uncover the effect of water
and other molecules as ammonia on the structure of these species,
for example, papers by Bell [61] and by Dumesic and Topse,
who studied the reducibility of vanadium and its effect on the
DeNOx reaction [62], this has later been elaborated by Topsoe
researchers, who showed the effect that the faceting of the sup-
port (TiO2 in their case) for the structure of dispersed species [63].
A hydrated vanadia gel was described to appear at room tempera-
230 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
Fig. 4. Structure of tetrahedral surface VO4 units proposed by Prof. Wachs.
Reproduced with permission from [66].
ture under hydrated conditions that decomposes upon dehydration
[63]. For temperatures below 230 C [64,65], it was observed that
the hydrogen-bonded surface vanadium oxide species were exten-
sively solvated by water, forming a hydrated surface vanadium
structure similar to decavanadate. This led to the theory that the
structure of supported metal oxides is determined by the net pH
at pzc and is a strong function of the specic oxide support and
surface vanadia loadings.
By 1990, as was described by Wachs [66], many advances had
been achieved regarding the knowledge of the nature of supported
vanadium oxide surface species, as is been shown above. But much
more work was still required, as it was mentioned in that [66]
paper: . . .. The molecular engineering of supported metal oxide
catalysts requires that we specify the synthesis method, oxide
Fig. 5. Number of articles published by year since 1978 (A) with supported vanadium oxide catalysts and (B) with supported metal oxide catalysts In title, abstract or
keywords, according to Scopus.
support, catalyst composition, calcination temperature, location
and structure of each of the above parameters upon the catalytic
properties of supported metal oxide catalysts needs to be exam-
ined. In this important paper [66], the concept of monolayer
was claried, which was described as the maximum amount of
vanadium oxide that can be formed in the two-dimensional vana-
dium oxide overlayer. This indicates that the monolayer coverage
depends on the oxide support surface area and concentration of
reactive surface hydroxyls. Above monolayer coverage, all the reac-
tive surface hydroxyls are essentially consumed [67]. Since Raman
spectroscopy is very sensitive to the presence of crystalline V2 O5
phases, it could be used for the determination of the monolayer
surface coverage [6671]. With this technique, it has been found
to be approximately 78 VOx per nm2 for many supports Al2 O3 ,
TiO2 , ZrO2 , Nb2 O5 , CeO2 , with the exception of silica, which exhib-
ited a maximum surface coverage of about 2.5 VOx per nm2 . In
the mentioned paper [66], the effect of synthesis method was also
examined, that had been also studied by other groups [45,72,73],
since there was a debate about the inuence of the precursor and
other parameters on the structure of the nal catalyst. By exami-
nation of several samples with different precursors and synthesis
methods, it was demonstrated [66] that the synthesis method is
not critical since it does not inuence the number of active surface
sites and the reactivity per site. Understanding that it is not critical
if during the synthesis method the precursors are removed and if
all the surface species are dispersed homogeneously on the surface
of the support, and obviously the temperature of calcination deter-
 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
mines also the nature of the oxide species. But the location and
molecular structures of the surface metal oxide species are also
not determined by the synthesis methods and are controlled by
the surface properties of the support. So, it was clear the strong
inuence of the oxide support on the number of active sites on the
surface of the catalysts. Several studies were performed in order
to evaluate the effect of the acid-base character and the reducibil-
ity of the support [74]. The number of active sites could be rst
calculated by quantication of adsorbed surface methoxy species
from the IR spectra, allowing the determination of TOF numbers
[75]. This study allowed correlation of the support effect with the
electronegativity of the support cation. Some years later, the num-
ber of active sites was calculated with methanol oxidation, a smart
molecule that yields different products depending if it is adsorbed
on a redox, acid or basic site [76]. With these techniques, Wachs
and coworkers were able to quantify the amount of surface VOx
monomer and polymer on different supports and they found that
their TOF values are identical for reactions involving only one oxy-
gen atom (for example, methanol to formaldehyde or propane to
propylene) [77]. In a complementary approach, it was also possible
to determine the fraction of polymeric vs. monomeric dispersed
vanadia on alumina by using UVvis spectroscopy [78].
By 1990, the structures of the supported vanadium oxide species
under both hydrated and dehydrated conditions were known, and
that they (and not the V2 O5 crystals) were the catalytic active
phases. In the next decade, in addition to the studies that underlined
the effect of support and the quantication of active sites, several
groups focused their interest in the identication of the active V-
O bond. Terminal V O bonds were proposed by many groups to
contain the critical oxygen involved in hydrocarbon oxidation reac-
tions [73,74], since being the most accessible bond it is logical to
think of it as the active site. However, the combination of Raman
and reactivity studies indicated that the reaction properties were
not related to the characteristics of the terminal V O bonds. The
lack of correlation between the characteristics of the terminal V O
bond and methanol and butane oxidation [68] and ethane oxidative
dehydrogenation [79], and oxygen-18 labeling experiments, show-
ing that the exchange time is approximately 20 times longer than
the characteristic reaction time [69,78], suggested that the terminal
V O bonds do not contain the critical oxygen that affects the reac-
tivity of supported vanadia catalysts during hydrocarbon oxidation
reactions.
4. Building the knowledge in the XXI century
By 2000, it was accepted knowledge about supported VOx cat-
alysts that the (1) dispersed surface vanadium oxide species were
more active than the bulk V2 O5 crystals, (2) dispersed species were
present as both isolated and polymeric for coverages below mono-
layer, and (3) crystals are obtained for coverages above monolayer.
It was also established that for coverages up to one monolayer, V2 O5
crystals could also form if a poor synthesis method is executed, thus,
it could be considered that for coverages up to this monolayer cov-
erage catalysts, it can be a mixture of oxides (V2 O5 and the support)
(scheme 1). The catalysts with coverage close to monolayer sub-
sequently has all the support surface covered by dispersed oxide
species and also some V2 O5 nanoparticles can be present, such cat-
alyst has been described as the most active [81,82]. It was also
known that the number of these supported dispersed vanadium
oxide species depends on the nature of support (accessible OH
groups and surface area) and not on the synthesis method. And it
was also described the effect of water molecules on the structure
of such species. More details about all these important achieve-
ments can be found elsewhere [8083]. All these insights allow the
molecular engineering of supported VOx catalytic systems, since
231
Fig. 6. Catalytic redox cycle of vanadium and migration cycle of antimony during
propane ammoxidation in V-Sb-O Catalysts.
Reproduced with permission from [101].
it is possible to control the number of catalytic active sites on the
support and their specic activity. Thus, it has been shown how
the fundamental knowledge about supported vanadium oxide cat-
alysts has mainly been developed over the past 20 years, from 1980
to 2000. These studies laid the foundations for developing other
important advances in the catalysis science, as for example the
development of other supported metal oxide catalytic systems, as
for example, the vanadium neighbors in the periodic chart as Cr,
Mo or Nb [8487].
Those studies also served for the development of several mixed-
oxide catalytic systems, supported and bulk, containing vanadium,
that have been also developed during the last years [88,89]. The
use of another compound modulates the activity of vanadium
oxide species, which are able to activate several hydrocarbons and
other starting materials. If the amount of the other compound is
quite low, it is considered a dopant, whereas if it is in the same
range of the vanadium, it is a mixed oxide. There are several well
know mixed oxide vanadium containing catalytic system that have
been developed during the last years, as for example VPO catalyst
[9092], that are commercially used for the transformation of n-
butane into maleic anhydride; VSbO [9396] that is used mainly
for ammoxidation reactions, or Mo-V multioxide system [96100]
used for propane transformation into acrylic acid. There are much
more mixed oxide catalytic systems that contain vanadium that
are used not only for partial oxidation process, as for example for
removal of pollutants, electrochemistry, and photochemistry appli-
cations, but a complete review of all of them exceeds the objective
of present review. In general, the use of the co-elements modu-
lates the vanadium oxide activity mainly by the stabilization of
reduced vanadium oxide species [101] (vanadium undergoes redox
cycles under reaction conditions and its oxidation state changes
continuously) (Fig. 6) and also by the modication of the capabil-
ity to adsorb/desorb reactants and intermediates of VOx species
[102,103] by the use of a co-element and/or a dopant. When more
than one element is present, the concept of monolayer may change
since in this case more than one monolayer is required in order
to have an active catalyst [104,105]. This is because in most cases
a mixed oxide active phase is required (for example in the case
of Sb-V-O system the formation of SbVO4 (rutile) and in the case
of Mo-based multioxide catalysts the active phases have been
described as M1 and M2) [93100]; such active phases are required
in order to stabilize vanadium species in its different oxidation
states and also for modulating the capability to adsorb/desorb
molecules of the catalysts, as has been mentioned. When the cover-
age is below monolayer, only dispersed surface VOx, SbOx or MoOx
species are detected and usually the activity is low since only VOx
are active in most of cases. When the coverage is near monolayer,
the two metals are able to interact, and the mixed oxide phase,
as SbVO4 may form [104106]. Since in these cases the surface of
232 M.O. Guerrero-Prez / Catalysis Today 285 (2017) 226233
Scheme 1. Structure proposed for Supported, Bulk and Bulk-Supported Vanadium oxide catalysts.
Fig. 7. Bulk catalyst nanoparticles are illustrated in the middle. Leftwards arrow illustrates sintering phenomena occurring during reaction. Rightwards arrow illustrates
support-stabilized bulk nanoparticles.
Reproduced with permission from [107].
the support is covered by small crystallites of active phase, the term
bulk-supported or nanoscaled active phase catalyst, have been pro-
posed [106108] (Fig. 7). When comparing bulk with bulk-support
catalysts, the advantages of these catalysts are that the amount of
active phase (more expensive than the support) is reduced and the
mechanical properties are improved, being the catalytic properties
of both surfaces quite similar [109].
An important issue that must be solved in the next years is
the characterization of surfaces of these bulk-support catalytic
systems. Although it has been shown in preset paper the effort
that have been done along this line, and in spite to the important
advances performed during the last 2030 years, it is still neces-
sary the development of characterization techniques able to give
information about the active phase (a small amount supported on
a support that constitutes the major portion of the mass of the
material) that is on the surface (most of the characterization tech-
niques of solids give information about the bulk), and, in addition,
under real operating conditions. In this sense, most efforts have
been concentrated in developing operando reactors that are able to
provide information of the catalytic activity and about the structure
with any characterization technique in a single experiment. These
operando techniques permit the identication of active phases, and
of the changes that happen under reaction conditions, in order to
explain reaction mechanisms and also catalyst deactivation paths.
In addition, they can be used for continuous on-site monitoring of
industrial processes [69,110116].
It has been shown how the knowledge about supported vana-
dium oxide-based catalysts has been developed during the latest
100 years. Understanding the catalytic properties of the supported
VOx phases, identifying the active ones, and then including more
elements in order to modulate the catalytic properties. It has been
also demonstrated how it is necessary to characterize the structure
of the surface of the catalyst and to identify the active phase in order
to establish the relationships between the molecular structure and
the activity of catalysts, in order to rationally design catalysts with
desired characteristics. The pioneering contributions by Wachs and
his research group in this eld have also been shown, with an
historical perspective, since it is not possible to write a review
on supported vanadium oxide catalysts without acknowledging
their important fundamental contributions to this eld during the
last few decades. Indeed, Fig. 5A and B shows an explosion of
papers starting around 1995, right after important papers, about
vanadium [67,68] and other metal oxide catalysts (Nb2 O5 , CrO3 ,
MoO3 , WO3 , Re2 O7 etc.) published by Wachs upon his incorpora-
tion to Academia. Recent Wachs work focuses on understanding
the surface metal oxide phases present in other mixed oxide cat-
alysts, such as bulk pure metal oxides, zeolite-supported metal
oxides, bulk mixed oxides, polyoxometalates and clays. That work
has shown [117] that surface VOx species are always also present
for bulk oxides and bulk solid solutions and they were found to
be the catalytic active sites for all types of the V-containing mixed
oxides. These ndings reveal the generality of surface vanadium
oxide phases in V-containing mixed oxide catalytic materials.
Acknowledgements
To all the researchers that have been working to advance catal-
ysis science. Due to all their efforts, a great step in the rational
design of catalysts has been possible during the past few years.
Given that catalysts are useful for organic and inorganic synthesis,
and for energy and environmental applications, they have seriously
contributed to make a better world. I would like to especially ded-
icate this review to Prof. Wachs on his three decades in academia
since his research work was inspiration for my initial research in
heterogeneous catalysis.
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