Chemical Physics Letters 651 (2016) 161167

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Chemical Physics Letters

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Research paper

Oxidative dehydration reaction of glycerol into acrylic acid:

A rst-principles prediction of structural and thermodynamic
parameters of a bifunctional catalyst
Lvia Clara T. Lacerda a , Mara dos Santos Pires a , Silviana Corra a , Luiz Carlos A. Oliveira b ,
Teodorico C. Ramalho a,c,
a
Department of Chemistry, Federal University of Lavras, P.O. Box 3037, 37200-000 Lavras, MG, Brazil
b
Department of Chemical ,Federal University of Minas Gerais, Av. Antnio Carlos, 6627, Campus Pampulha Rua Passo da Ptria, 156 , Niteri, RJ,
Brazil,31270-901 Belo Horizonte, MG, Brazil
c
Center for Basic and Applied Research, University Hradec Kralove, Hradec Kralove, Czech Republic

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

Article history: The production of biodiesel generates crude glycerol as a byproduct. The search for glycerol conversion
Received 19 January 2016 routes has attracted the attention of researchers and thus, this work evaluated the properties of the
In nal form 15 March 2016 catalysts T-Nb2 O5 and T-Nb2 O5 /V treated with H2 O2 applied to the reaction of oxidative dehydration of
Available online 19 March 2016
glycerol. The peroxo groups from the treatment with H2 O2 had a greater oxidation capacity in relation
to those in the pure catalyst. Furthermore, the catalyst doped with vanadium presented lower energy
costs during the process. Those results might be helpful for designing new catalysts for the production
of strategic chemical products from glycerol.
2016 Elsevier B.V. All rights reserved.

1. Introduction especially projected for such reactions has a great strategic impor-
tance if the country is a large producer of biodiesel like Brazil, since
The environmental impacts caused by the use of fossil fuels have modications in the catalyst lead to changes in the conversion,
attracted the attention of the chemical industry. In this sense, the selectivity and yield of the reaction [8]. In order to rationalize how
diesel from petroleum has been replaced by biodiesel [1]. The pro- these materials work it is crucial to rst understand their proper-
duction of this fuel generates glycerol as byproduct, with a fraction ties. Computational chemistry has been an ally in this sense, since
of approximately 1 kg of glycerol for each 10 L of biodiesel, creating theoretical calculations allow to preview the energy involved in
an intense ow of waste with potentially signicant environmen- chemical processes, as well as precisely calculate the geometry,
tal impacts [2,3]. The generation of biodiesel has been increasing determining the transition states and intermediates, among other
each year mainly due to the benets that it brings when com- aspects [9].
pared to petroleum derived fuels. Consequently the generation of Oxides have stood out as catalysts to be applied in glycerol con-
the main byproduct, glycerol, is intensied, thus becoming less version reactions. This fact creates opportunities to use the niobium
onerous and more attractive for the synthesis of other chemical pentoxide (Nb2 O5 ). From the point of view of heterogeneous catal-
products [4,5]. ysis, the Nb2 O5 exhibits several functions and may act as an active
The excess glycerol may be converted into other useful chemi- phase promoter, a support, an acid solid and redox material, which
cal products. There are several possibilities for reactions in which are used in oxidation reactions [10].
it can be used, oxidation routes, reduction, halogenation, esteri- Many studies show that materials based on niobium are an
cation, among others [6]. The efciency and products of these interesting proposal for glycerol conversion reactions, both the
reactions will depend, among other factors, on the chosen cat- pure material and that modied. The catalysts based on niobium
alysts and their characteristics [7]. The synthesis of compounds associated to other metals, like vanadium and gold, are good exam-
ples [11].
The main products provided by the dehydration of glycerol
Corresponding author at: Chemistry Department, Federal University of Lavras, catalyzed by Nb2 O5 are acrolein and acetol. Currently a large part
37200-00 Lavras, Brazil. Tel.: +55 35 38291271.
of acrolein has been destined to the production of acrylic acid.
E-mail address: teo@dqi.ua.br (T.C. Ramalho). This product, besides representing the main raw material for the

http://dx.doi.org/10.1016/j.cplett.2016.03.038
0009-2614/ 2016 Elsevier B.V. All rights reserved.
162 L.C.T. Lacerda et al. / Chemical Physics Letters 651 (2016) 161167

production of paints and coatings, is also used for the fabrication of vanadium isomorphically replaced on the representative cell of
of superabsorbent polymers, acrylics and hygienic products [12]. the pure catalyst Nb2 O5 .
Besides production via acrolein oxidation, acrylic acid may also The oxidative dehydration reaction of glycerol was thermo-
be obtained directly from glycerol through the oxidative dehydra- dynamically studied by identifying and optimizing the geometry
tion of this molecule. In general, a mixture of acid catalysts and of the intermediates in the presence of the catalysts Nb2 O5
catalysts of oxidation is used to obtain these products. However the and Nb2 O5 /V treated with H2 O2 [18]. The mechanism was pro-
selectivity of the acrylic acid to these catalysts is low [13]. Thus, posed based on previous experimental and theoretical studies
a current challenge is to directly produce acrylic acid via a more searching for routes to obtain acrylic acid [1923]. The energy
simplied manner. released/absorbed in each reaction step is dened by Eqs. (1) or
An alternative is the previous treatment of niobium pentoxide (2), as follows:
with H2 O2 , that allows the obtainment of a bifunctional catalyst
due to the appearance of oxidative groups on the surface of the Estep(n) = EDFT/interm(n) EDFT/interm(n1) (1)
material: the peroxo groups which, combined with the acid sites,
Estep(n) = EDFT/interm(n) [EDFT/interm(n1) + EDFT/H2 O ] (2)
may simultaneously promote the dehydration and oxidation, thus
increasing the catalyst activity [14]. in which Estep is the total energy of the intermediate, n is the
Thus, the Nb2 O5 structure modied by previous treatment with identication number of the intermediate and EDFT/H2 O is the total
H2 O2 and doping with vanadium was built and studies were energy of the free water.
conducted by means of theoretical calculation with the aim of
developing bifunctional catalysts applied to the conversion of glyc-
3. Results and discussion
erol into acrylic acid.
3.1. Structural analysis of the catalysts Nb2 O5 and Nb2 O5 /V

2. Computational methods In order to investigate the catalyst properties, models of the

Nb2 O5 bulk were built and projected on the (001), (100) and (101)
To study the properties of catalysts, ab initio calculations were planes. The structures were optimized and the most stable geom-
performed using the adf-band package, a program that enables cal- etry corresponded to the (001) plane, shown in Figure 1. The
culations of periodic conditions. The total energy was calculated increasing order of the energy values found, E001 < E100 < E101 , is in
via density functional theory (DFT) [15] and basis set TZP. The accordance with experimental studies of X-ray diffraction for this
functional Generalized Gradient Approximation GGA-PBE [16] was material [24].
selected to calculate the geometries. These parameters are espe- The isomorphic substitution of vanadium (V) in the crystal
cially directed toward solids and have already been successfully Nb2 O5 may modify the properties of the catalyst, which makes
used in similar systems [17]. the evaluation of structural and electronic changes caused by the
The structure of niobium pentoxide was constructed based presence of this doping agent highly important. The rst step
on the T-Nb2 O5 crystal described by Valencia-Balvn [17]. The was the analysis of the preferential position of vanadium in the
Space Group Pbam and crystallographic parameters a = 6.1761, crystal. To this end, an atom of vanadium was replaced by an
b = 29.4250 and c = 3.9237 A were used. The bulk model was gen- atom of niobium in Positions 1, 2, 3 and 4 of the (001)Nb2 O5
erated in a 2 2 2 supercell and the (001) surface was built. The model (Figure 2). The relative energies for the structures Nb2 O5 /V1,
Nb2 O5 /V catalyst was theoretically produced with about 7% (w/w) Nb2 O5 /V2, Nb2 O5 /V3 and Nb2 O5 /V4 were 0.76, 1.15, 0.00 and

Figure 1. Model of the Nb2 O5 system. (a) Side view and (b) Top view. Nb atoms are represented in pink (major spheres) and O atoms in red (small spheres). (For interpretation
of the references to color in this gure legend, the reader is referred to the web version of this article.)
 L.C.T. Lacerda et al. / Chemical Physics Letters 651 (2016) 161167 163

Figure 2. Structure of the oxide after replacing Nb by an atom of V. (a) Nb2 O5 /V1, (b) Nb2 O5 /V2, (c) Nb2 O5 /V3 and (d) Nb2 O5 /V4.

0.15 kcal/mol, respectively. The energies obtained when vana- (photoelectron spectroscopy X-ray) characterizing the niobium
dium was in Positions 3 and 4 were lower when compared to pentoxide doped with vanadium predicted this behavior [19].
Positions 1 and 2. This result suggests that the incorporation of However even this small amount of vanadium present on the sur-
this element in the niobium oxide bulk structure is more favor- face has the capacity to cause relevant changes in the catalyst
able than on the surface. In fact, an experimental study by XPS properties.

Figure 3. Oxidative dehydration mechanism of glycerol into acrylic acid catalyzed by Nb2 O5 (a) rst part and (b) second part.
164 L.C.T. Lacerda et al. / Chemical Physics Letters 651 (2016) 161167

3.2. Mechanism of glycerol oxidative dehydration

The mechanism seeks to clarify the glycerol dehydration route

into the products acetol, 2,3-dihydroxypropene, 1,3-propenediol,
3-hydroxypropanal and acrolein, followed by the oxidation of
acrolein into acrylic acid (Figure 3a and b). The interaction of glyc-
erol with the Nb2 O5 surface may occur in two sites of the catalyst:
the rst with acid properties in which the dehydration of glycerol
into acrolein and other products occurs, and the second with oxi-
dizing properties where the oxidation of acrolein into acrylic acid
Figure 4. Illustration of the intramolecular interaction among hydroxyls of the
occurs. Intermediate 4A to form a molecule of water.
Since the calcination temperature of T-Nb2 O5 increases,
Brnsted acid sites are hardly found because of the absence of
3.3. Thermodynamic analysis
hydroxyl groups on the catalyst surface, giving rise to Lewis acid
sites (Figure 3) [25]. It should be kept in mind, however, that the
The reagents, products and intermediates of the glycerol oxida-
number of those Lewis acid sites should decrease after the hydro-
tive dehydration mechanisms were optimized. The computations
gen peroxide treatment. Therefore the proposal is that the glycerol
were performed using two different models, all with the peroxo
is adsorbed by the Lewis acid sites, in which the Nb atom of the
group in their surface where we call oxidation site. The catalysts
surface (in high oxidation state) is able to make -type interac-
used were pure niobium oxide (Nb2 O5 /H2 O2 ) and then the replace-
tions with the hydroxyl oxygen. It is also worth noting that Foo and
ment of vanadium in the oxidizing site (Nb2 O5 /V1/H2 O2 ). Table 1
collaborators showed that, under high vacuum conditions, glyc-
provides the results of the thermodynamic analysis of the glyc-
erol forms stable multidentate alkoxy species through its primary
erol into acrylic acid conversion mechanism, in the presence of
hydroxyl groups with the vicinal Lewis sites of Nb2 O5 [26]. How-
catalysts.
ever, the presence of peroxo groups, from the hydrogen peroxide
From the thermodynamic analysis, we veried the feasibility of
treatment, can generate a bifunctional catalyst (Nb2 O5 /H2 O2 ), in
the glycerol conversion into other products. Our ndings suggest
which the occurrence of vicinal acid sites decreases signicantly
that the process occurs with negative and positive energies. In this
and are much scarcer than in the pure catalyst. In fact, previous
case, it is possible to predict conditions that must be imposed to
experimental studies have reported a progressive decrease in acid-
the system in order to maintain the conversion at desirable levels.
ity of these materials with pretreatment with hydrogen peroxide
According to the theoretical results, the three main reaction
[27].
products, acrolein, acetol and acrylic acid, can be formed in large
The glycerol may undergo dehydration by two different hydro-
amounts, depending on the conditions imposed on the system. The
xyls. If the oxygen adsorbed belongs to the terminal hydroxyl group,
production of acetol is an exotermal process with ENb2 O5 /H2 O2 =
the dehydration starts with the hydroxyl group bonded to the cen-
14.75 and ENb2 O5 /V/H2 O2 = 18.99 kcal/mol, while its less sta-
tral carbon (Route A), but if it belongs to the central hydroxyl group,
ble isomer, the 2,3-dihydroxipropanone, requires an energy near
the terminal hydroxyl suffers the dehydration (Route B) (Figure 3a).
20 kcal/mol to be formed.
This happens because the Nb O bond formed in the intermediates
The dehydration of glycerol into acrolein is an endother-
1A and 1B weakens the O H bonding, thus making the hydrogen
mic process with ENb2 O5 /H2 O2 = 9.71 and ENb2 O5 /V/H2 O2 =
susceptible to the attachment of the other oxygen of the molecule,
4.94 kcal/mol favored by high reaction temperatures, while
forming water (Intermediates 2A and 2B). Since the water is a good
the oxidation of acrolein into acrylic acid is an exother-
leaving group, it leaves the glycerol molecule generating a positive
mic process with ENb2 O5 /H2 O2 = 24.22 and ENb2 O5 /V/H2 O2 =
charge in the carbon atom (Intermediates 3A and 3B). The forma-
33.76 kcal/mol, favored by low reaction temperatures. This
tion of a more stable carbocation is possible in this step, thus the
energetic impasse requires adequate operational conditions that
intermediate 3 B may induce the formation of the (C O) bond
provide both the consumption of glycerol and acrolein with the pro-
together with the desorption of Product 1, acetol. Product 2 can
duction of acrylic acid. The other products involved in the reaction,
occur in keto-enol equilibrium with acetol, even in lower propor-
tions. On the other hand, from the Intermediate 3A the formation of
(C C) bond may originate the Intermediate 4A and then Product Table 1
Energies, in kcal/mol, released/absorbed in the oxidative dehydration steps of
3 and its tautomer, Product 4.
glycerol.
The mechanism now will start from the Intermediate 4
(Figure 3b), which will lead to the products of interest. In this case Step E (Nb2 O5 /H2 O2 ) E (Nb2 O5 /V/H2 O2 )
the formation of the (C C) bond in 4A may promote the appear- 1A 59.07 51.07
ance of a water molecule (Intermediate 5A). This is possible when 1B 51.59 45.99
the system acquires a conformation that allows the occurrence 2A 44.13 16.14
2B 5.45 21.03
of an intramolecular dehydration process through the interaction 3A 7.28 12.03
between two hydroxyls of this intermediate (Figure 4). 3B 48.96 29.21
The water removal in this case originates the carbocation 6 A 3 B 73.10 55.44
(Figure 3b). The formation of acrolein occurs when the positive 4A 3.75 4.12
Desorption 1 12.21 11.49
charge is transferred to the neighbor carbon, thus forming the sec-
Desorption 2 31.88 37.30
ondary carbocation (Intermediate 6A) and inducing the formation Desorption 3 15.24 5.67
of the (C O) bond and desorption of the product. Step 7A marks Desorption 4 5.38 11.47
the beginning of acrolein oxidation into acrylic acid with the attack 5A 23.53 15.89
of oxygen from the peroxo group on the positively charged carbon 6A 50.56 55.07
6 A 43.37 53.45
(Intermediate 7A). The transference of hydrogen to the oxygen that 7A 35.56 37.58
interacts in the catalyst acid site and the formation of the acrylate 8A 24.32 22.15
group (Intermediate 8A) then occurs. The nal step involves the Desorption 5 25.33 17.10
acrylic acid desorption. Desorption 6 12.98 18.33
 L.C.T. Lacerda et al. / Chemical Physics Letters 651 (2016) 161167 165

Figure 5. Density of states (DOS) of the structures: (a) Nb2 O5 , (b) Nb2 O5 /H2 O2 , (c) Nb2 O5 /V and (d) Nb2 O5 /V/H2 O2 . Valence bands of the Nb atoms; 0 conduction bands of
the O atoms of the peroxo group and Valence bands of the O atoms.

i.e. the tautomers 1,3-propanediol and 3-hydroxypropanal, do mainly in steps that involve oxidation. Considering the higher
not have an energetically favorable production according to the energy of the oxygen bands after the treatment, the electrons are
obtained data. Thus, we can infer that in the presence of the stud- more distributed on the surface, and therefore more susceptible
ied catalysts, the mechanism from Step 4A preferentially follows to interactions with glycerol during the oxidation reaction.
the reaction path to form acrolein and acrylic acid instead of the The dehydration reaction is related to the Lewis acidity of atoms
desorption Steps 3 and 4 (Figure 3a and b). from metals on the surface. This acidity is commonly associated to
From our ndings, for the T-Nb2 O5 /V/H2 O2 system, the V atom the non-protic systems resulting from the interaction with metals
does not introduce any changes in the mechanism, but only in through their incomplete d orbitals, which are able to receive
the reaction energetics, that can facilitate the occurrence of some electrons. Table 2 presents the VDD charges (Voronoi deforma-
steps. The results of the thermodynamic analysis indicate that the tion density) [28] of the Nb and V atoms in the active sites of
catalysts Nb2 O5 /H2 O2 and Nb2 O5 /V/H2 O2 have certain selectivity the rst layer of the pure Nb2 O5 and Nb2 O5 /V structures, as well
for the production of acrylic acid in relation to the other stud- as in the presence of peroxo groups. The attendance of oxidizing
ied products. Furthermore, the catalyst Nb2 O5 /V/H2 O2 presented groups makes the Nb2 and V2 atoms in the site where the dehy-
lower energy costs during the mechanism (Table 1), mainly in the dration occurs less positive, and this is related to the generation
steps involving the acrolein oxidation by peroxo groups, thus show- of a lower tendency to receive electrons. Therefore we may infer
ing a higher potential of glycerol conversion into acrylic acid when that the presence of the peroxo group may not favor dehydration
compared to Nb2 O5 /H2 O2 catalyst. These results are in accordance steps.
with experimental studies that showed a higher glycerol conver- The variation of the electrophilic character of niobium atoms on
sion when the reaction was catalyzed with niobium pentoxide the surface is very small when compared to the Nb2 O5 and Nb2 O5 /V
doped with vanadium [19].
Table 2
Charge of the Nb and V atoms of the rst layer in the structure of Nb2 O2 and Nb2 O5 /V.
3.4. Inuence of the treatment with H2 O2 and doping with V
System VDD charge
The electronic properties of the catalysts Nb2 O5 and Nb2 O5 /V Nb1 Nb2 V1 V2
were studied with peroxo groups in their surface, which came from
Nb2 O5 0.778 0.779
the H2 O2 treatment. Such groups decreased the band gap values Nb2 O5 /H2 O2 0.729 0.685
of the N2 bO5 catalyst from 2.6 to 1.5 eV and from 2.7 to 1.1 eV in Nb2 O5 /V1 0.782 0.448
the Nb2 O5 /V catalyst. Furthermore the presence of peroxo groups Nb2 O5 /V1/H2 O2 0.702 0.346
displaced the oxygen band to higher energy values (Figure 5). This Nb2 O5 /V2 0.774 0.447
Nb2 O5 /V2/H2 O2 0.759 0.327
data may indicate catalyst higher activity after the H2 O2 treatment,
166 L.C.T. Lacerda et al. / Chemical Physics Letters 651 (2016) 161167

Figure 6. (a) Length of Nb O and V O bond in Intermediate 6A and (b) formation of the peroxo group on the surface due to the interaction of the Nb2 O5 and Nb2 O5 /V
catalysts with H2 O2 .(M = Nb or V).

catalysts (Table 2). Therefore, the advantage of the vanadium pres- the simultaneous presence of vanadium and peroxo groups can
ence can be related to a synergetic effect between V and Nb atoms, leverage the process to obtain acrylic acid directly from glycerol.
leading to a higher catalytic performance for the doping structure. Surprisingly, this conversion can occur using only a bifunctional
In fact, structural and electronic parameters are affected by the structure as a catalyst in the reaction medium. Thus, we strongly
presence of vanadium atoms in the material structure. For instance, feel that those results might be helpful for designing new catalysts
the O O bond length of the peroxo group in Nb2 O5 /V/H2 O2 is for the production of strategic chemical products, such as acrylic
longer and weaker than in Nb2 O5 /H2 O2 . This scenario also elec- acid, from glycerol.
tronically favors the orbital superposition between carbocation
(Intermediate 6A) and the peroxo group on the material surface
Acknowledgements
(Figure 6a), resulting in an easier formation of the (carbocation)
C O (peroxo group) chemical bond and Intermediate 7A.
We are honestly thankful to the Brazilian agencies FAPEMIG,
Furthermore, the advantage of the replacement (Nb V) can
CAPES and CNPq for all the nancial support, fellowships and schol-
also be related to the higher amount of peroxo groups formed on the
arships. This work was also supported by Excellence project FIM.
Nb2 O5 /V/H2 O2 surface. In fact other authors have already observed
that vanadium compounds react faster with H2 O2 to form reactive
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