Research Article

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX pubs.acs.org/journal/ascecg

Reusable Heterogeneous Tungstophosphoric Acid-Derived Catalyst

for Green Esterification of Carboxylic Acids
Jhonatan Luiz Fiorio,†,‡ Adriano Henrique Braga,† Carmen Luísa Barbosa Guedes,*,‡
and Liane Marcia Rossi*,†
†
Departamento de Química Fundamental, Instituto de Química,Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, 05508-000
São Paulo, SP, Brazil
‡
Departamento de Química, Centro de Ciências Exatas, Universidade Estadual de Londrina, 86057-970 Londrina, PR, Brazil
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ABSTRACT: Solid acid catalysts are environmentally friendly alternatives to the use of
mineral acids in a range of applications, including the esterification of carboxylic acids.
Here, a phosphorus- and nitrogen-doped, carbon-modified, fully heterogeneous solid acid
catalyst was prepared by pyrolysis of a mixture of melamine and tungstophosphoric acid at
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250, 500, and 750 °C under a nitrogen atmosphere provided. The structure of the different
catalysts was evaluated by surface area measurements, XRD, XPS, Raman spectroscopy, elemental analysis, and electron
microscopies. Pyrolysis at 500 °C created complex solid materials with larger surface area and significantly higher acidity, which
can be attributed to WO3 formation on a heteroatomic (N,P)-carbon structure. The 500 °C-treated heterogeneous catalysts
showed remarkably better activity for esterification of palmitic acid and were thus applied in the esterification of a broad range
of carboxylic acids with good overall yields. Furthermore, the solid acid catalyst can be easily recovered and recycled up to eight
times without significant loss of activity with no leaching of species to the reaction mixture.
KEYWORDS: carboxylic acid, esterification, tungstophosphoric acid, polymeric carbon nitride-like structure, biofuels

■ INTRODUCTION
Esters are a class of compounds used as important building
blocks for the fine and bulk chemical industry.1,2 Moreover,
they are found in numerous pharmaceuticals, agrochemicals,
fragrances, and polymers.3−5 Among a variety of synthetic
methods, esters are commonly prepared by the reaction of
carboxylic acids or activated acid derivatives, for example, acid
chlorides or anhydrides, with alcohols.6−8 The reaction is
usually catalyzed by heavy metals such as Cr or Mn, a
stoichiometric amount of acids such as sulfuric, sulfonic,
phosphoric, hydrochloric, and p-toluenesulfonic acids, or even
alkoxides such as sodium and potassium alkoxides.9 The use of
stoichiometric amounts (or excess) of toxic and expensive
reagents renders the process environmentally and economically
unsuitable. Furthermore, the common catalysts are quite
contaminative and corrosive, which always result in poor
selectivity, high energy consumption, and serious environ-
mental pollution.10,11 Despite all of these well-established
methodologies, the development of environmentally benign
and cost-effective procedures for the synthesis of esters
continues to attract significant interest.
Green synthetic approaches to prepare esters and overcome
the present drawbacks have received much attention. In this
respect, acidic solids have been investigated as heterogeneous
catalysts.12,13 A wide range of solid acids has already been
explored in esterification reaction including chalcogenides,14
acid clays,15,16 oxides,10,17,18 modified silica,19,20 polymers,21
and activated carbon.22−24 Heteropolyacids (HPAs) have been
effectively employed to catalyze the esterification of free fatty
acids (FFAs).25−27 These extremely acidic compounds are
anionic metal−oxygen clusters based on polyoxometalates
(POMs).28 The HPAs are environmentally friendly alternatives
to the use of mineral acids (H2SO4, HCl, or HF).29 However,
they show very high solubility in a range of polar solvents being
studied as a homogeneous catalyst;30,31 albeit usually, this type
of catalyst exhibited good catalytic activity and recovery, and
further reuse is costly.19,32,33 Therefore, to facilitate recovery
and easily reuse, a heterogeneous version has been prepared by
supporting or immobilizing the HPAs. Different studies have
been performed using immobilized HPAs on materials such as
silica34,35 and oxides36−38 for esterification reactions. To the
best of our knowledge, no reports preparing support HPAs on
a polymeric carbon nitride (PCN)-like structure have been
described for esterification reactions. The introduction of N
atoms influences the properties of the pristine carbon,
especially in terms of catalyst−reactant interactions, which
might affect the catalytic activity.39,40 Moreover, doping with
nitrogen atoms affects the acid−base character of the catalyst
surface.41 The structure of the immobilized HPA plays an
important role in general activity for esterification reactions, as
much as the density and strength of the acid sites when the
HPA is interacting with a solid.42 Different synthesis
approaches might lead to hybrid structures that can add
properties to the HPA, such as surface area enhancement and
tuning of acidity.
Herein, we report a straightforward method to prepare
sustainable heterogeneous catalysts based on HPAs and the
nitrogen-doped carbon structure by pyrolysis of melamine and
Received: March 19, 2019
Revised: July 13, 2019

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.9b01579

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tungstophosphoric acid. Different thermal treatments were
performed to produce a hybrid material that contains a
heteroatomic (N,P)-carbon structure. The material obtained
under optimal conditions (pyrolysis at 500 °C) constitutes an
excellent heterogeneous solid acid catalyst for the esterification
of a broad range of carboxylic acids. Notably, these catalysts
are easily recycled and can be reused in up to eight catalytic
cycles without significant loss of activity, with negligible metal
leaching.
■
EXPERIMENTAL SECTION
Materials and Methods. All the reagents used for the catalyst
preparation were of analytical grade, purchased from Sigma-Aldrich,
and used as received. Aliphatic and aromatic acids and standards for
GC analysis were purchased from Sigma-Aldrich, having the highest
grade available, and used as received. Methanol (99.5%) and ethanol
(99.5%) were purchased from Synth (Brazil) and used as received.
The Schlenk tube used for reactions was thoroughly cleaned with
aqua regia (HCl/HNO3 = 3:1, v/v), rinsed with copious pure water,
and then dried in an oven prior to use.
Catalyst Preparation. Typically, tungstophosphoric acid (0.5
mmol) and melamine (10 mmol) were stirred in 100 mL of ethanol
for 60 min at 60 °C. After, the solvent was dried at the rotavapor. The
as-obtained solid was ground to a fine powder and then pyrolyzed in
the desired temperature in an oven at a rate of 20 °C per minute and
held at fixed temperature for 2 h under a nitrogen atmosphere. The
final solids were identified as PCN + HPW with the temperature of
pyrolysis (250, 500, and 750 °C).
Catalyst Characterization. Isotherms of nitrogen physisorption
were acquired on a Micromeritics II 3020 equipment. The fresh
samples were degassed overnight at 200 °C, and afterwards, nitrogen
was dosed at N2 boiling temperature to obtain the surface area using
the BET equation; the pore volume and size were obtained from the
BJH equation.
X-ray diffraction (XRD) of the samples was recorded using a
Rigaku MiniFlex diffractometer with Cu Kα radiation (λ = 1.54 Å) at
a 2θ range from 20° to 90° with a 0.02° step size and a measuring
time of 5 s per step. Metal leaching into the supernatant solution was
measured by inductively coupled plasma optical emission spectrom-
etry measurements performed on a Spectro Arcos ICP OES. The
scanning electron microscopy (SEM) images were obtained using a
JEOL field emission gun microscope JSM 6330F operated at 5 kV.
The samples were prepared by drop-casting an aqueous suspension
containing the nanostructures over a silicon wafer, followed by drying
under ambient conditions. TEM analyses were performed with a
JEOL 2100F operating at 200 kV. Catalyst samples for TEM were
prepared by sonicating the catalyst powder in propan-2-ol. A drop of
the resulting dispersion was placed on a carbon-coated copper grid
(Ted Pella, Inc.). Elemental mapping was acquired by EDS on a
silicon-drift detector X-MaxN 100TLE from Oxford Instruments at
scanning-TEM mode with a spot size of 1.5 nm. Thermogravimetry
analysis (TG/DTG) was recorded in a Linseis STA I 1500
equipment, and the analyses were performed in a dynamic nitrogen
atmosphere (50 mL min−1) with a heating rate of 10 C° min−1 from
room temperature up to 850 °C.
Raman spectroscopy was used to evaluate the formation and
structure of tungsten oxides after pyrolysis at 250, 500, and 750 °C.
The spectra were recorded on the as-prepared sample in a Renishaw
inVia Raman microscope, with a He−Ne laser (633 nm) and 8 mW
power. Different regions of the sample were measured to account for
the possible inhomogeneity of the sample.
XPS spectroscopy was performed on the catalyst pyrolyzed at 500
°C to study the surface composition. Spectra were recorded at SXS
beamline of Brazilian Synchrotron Light Laboratory (LNLS) with an
InSb double-crystal monochromator at 1840 eV of excitation energy.
The photoemission spectra were acquired in a vacuum level of 10−9
mbar, with fixed energy pass mode (40 eV) using a SPECSLAB II
Phoibos analyzer. The spectra were fitted with CASA XPS software,
B DOI: 10.1021/acssuschemeng.9b01579
Research Article
with Shirley background subtraction, and using a convoluted
Gaussian/Lorentzian function. Binding energies were referred to the
C 1s level (284.8 eV).
Determination of Acid Sites from Isopropanol Dehydration.
Isopropanol dehydration was performed at atmospheric pressure in a
fixed-bed quartz reactor (Hiden Analytical CatLab PCS). Isopropanol
was fed to the reactor by flowing Ar (10 mL min−1) through a
saturator maintained at 15 °C (to give a partial pressure of 0.22 kPa).
The final gas composition was 2.8 mL min−1 IPA/25 mL min−1 Ar.
The catalysts were first heated under an inert atmosphere, 50 mL
min−1 of Ar, to remove adsorbed molecules. Afterward, the catalysts
were heated under flow of IPA from room temperature up to 250 °C
in intervals of 25 °C. This final temperature was chosen to avoid
decomposition or reaction of the PCN structure in the sample treated
at 250 °C. The reactor outlet composition was measured by an online
mass spectrometer (Hiden Analytical) carefully calibrated; the mass
fragments m/z of 45 was chosen for IPA identification, 41 for
propene, and 43 for acetone. The formation rate of propene at 125 °C
(temperature with conversion of ∼20% for the most active catalyst)
was taken to estimate the number of acid sites, following the
procedure described by Ai.43
Catalyst Evaluation: Esterification Reaction. The catalytic
activity of the as-obtained solid acid catalyst was evaluated in the
esterification of palmitic acid with methanol as a model reaction. In a
typical procedure, palmitic acid (0.1 mmol), 20 mg of catalyst, and
methanol (2.0 mL) were added to a Schlenk tube. The flask was
sealed, the resulting mixture was vigorously stirred using a Teflon-
coated magnetic stirrer, and the temperature was maintained at the
desired temperature with an oil bath on a hot stirring plate connected
to a digital controller (ETS-D5 IKA). After the desired time, the
catalyst was removed by centrifugation, and the products were
analyzed by GC with an internal standard to determine the yield of
the products.
For the recycle experiments, after each catalytic experiment under
the above typical reaction conditions, the catalyst was recovered from
the reaction system by centrifugation, washed twice with ethanol, and
dried in vacuum. The spent catalyst was tested again under identical
reaction conditions just by adding to the reactor a new amount of
substrate and solvent.
GC analyses were carried out with a Shimadzu GC-2010 equipped
with an RTx-5 column (30 m × 0.25 mm × 0.25 mm) and an FID
detector. Method: Ti = 40 °C, Tf = 200 °C, 17 min, T FID, and
T SPLIT = 200 °C. Internal standard: biphenyl.
■
RESULTS AND DISCUSSION
A series of solid acid catalysts were prepared by mixing
tungstophosphoric acid (HPW, H3PW12O40·xH2O) with
melamine in ethanol, followed by removal of the solvent and
subsequent pyrolysis of the recovered solid at different
temperatures (250 to 750 °C for 2 h under a N2 atmosphere)
to deliver a solid acid catalyst. The catalysts were evaluated in
the esterification of palmitic acid at 80 °C, showing a strong
dependence of the activity with the pyrolysis temperature. The
material pyrolyzed at 250 °C leads to a low yield of methyl
palmitate 2a (2% of 2a, Table 1, entry 1). The best activity was
obtained by performing the pyrolysis at 500 °C (Table 1, entry
2), with a yield of 2a of 86%. A significant decrease in the
catalytic activity was noticed with an increase in the pyrolysis
temperature to 750 °C, resulting in only 5% yield of 2a (Table
1, entry 3). To improve the yield further, the reaction
temperature was raised to 100 °C, furnishing the quantitative
yield of 2a as determined by GC analysis (Table 1, entry 4). A
pyrolyzed material prepared without HPW gave only 1% yield
of 2a (Table 1, entry 5). Furthermore, the reaction carried out
using WO3 as a sole catalyst gave 23% yield of 2a after 8 h
(Table 1, entry 6). This implies that the structure formed with
HPW is crucial to achieve activity for this transformation.
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Table 1. Catalyst Evaluation in the Esterification of Palmitic

Acid 1aa

entry catalyst temperature yield of 2a (%)b

1 PCN + HPW − 250 °C 80 2
2 PCN + HPW − 500 °C 80 86
3 PCN + HPW − 750 °C 80 5
4 PCN + HPW − 500 °C 100 >99
5 PCN 100 1
6 WO3 commercial 100 23
a
Reaction conditions: 0.1 mmol of 1a, 20 mg of catalyst, 2 mL of
methanol, temperature, 8 h. bDetermined by GC using an internal
standard technique. Figure 2. Hot filtration test to determine homogeneous catalysis
contribution in esterification of 1a. Reaction conditions: 0.1 mmol of
Moreover, although HPW itself could be used to perform the 1a, 20 mg of catalyst, 2 mL of methanol, 100 °C.
transformation, it could not be easily recovered at the end of
the reaction, implying the production of waste and to the liquid phase. In addition, ICP AES analysis of the liquid
consumption of energy to purify the reaction. The soluble mixture obtained from the recycling experiments showed
HPW was not tested here since it does not constitute a negligible amounts of W metal (detection limit: 0.10 ppm).
heterogeneous catalyst. SEM images of the material after pyrolysis at 250, 500, and
Stability, ease of separation, and recyclability are important 750 °C (Figure 3) consist of irregular microsized agglomerated
parameters for practical applications of the heterogeneous particles. The catalyst pyrolyzed at 250 °C (Figure 3a,b) shows
catalysts. With the results of Table 1, the solid PCN + HPW − a rice husk-like morphology with some irregular particles, while
500 °C was chosen for further investigations. The PCN + the other catalyst is composed exclusively of irregular particles.
HPW − 500 °C catalyst was tested in successive reaction and The transmission electron microscopy (TEM) images of the
was able to perform the esterification of 1a for up to eight catalyst pyrolyzed at 500 °C (Figure 4b,e) show a layered
times using the same catalyst portion without any further structure, which indicates that pure PCNs consist of stacked
treatment. As depicted in Figure 1, a slight decrease was graphitic planes constructed from the melamine building
units.33,44−46 The characteristic layered structure of PCN was
well retained in the nanocomposite even with the introduction
of HPW. Furthermore, STEM-EDS elemental mapping
(Figure 5) discloses a uniform distribution of W, O, N, and
P in the catalyst prepared at 500 °C. Nitrogen was taken from
a careful deconvolution of the EDS spectrum due to the low
amount of this element. The elemental mapping of Figure 5
shows the formation of a well-dispersed composite material of
N- and P-doped WO3, which is in agreement with XRD and
Raman spectroscopy results.
The thermal behavior of the material was studied by TG-
DTG analyses in a N2 atmosphere (Figure 6a). The TG curve
of the sample shows two weight loss steps at 300 and 505 °C.
The first weight loss of ∼46% between 250 and 400 °C could
be attributed to the release of H2O and the organic ligand. On
further heating, a weight loss of ∼11% between 400 and 500
Figure 1. Recycling experiments using the PCN + HPW − 500 °C °C may be ascribed to the loss of acidic protons and the
catalyst. Reaction conditions: 0.1 mmol of 1a, 20 mg of catalyst, 2 mL decomposition of the Keggin structure.33 The structure of the
of methanol, 100 °C, 8 h.
catalyst was further studied with X-ray diffraction (XRD). The
XRD patterns of the catalyst obtained after pyrolysis at 500
noticed after the second run, but the desired product 2a was and 750 °C present an additional set of peaks, which are
obtained in up to 80% yield even after eight runs, and the different from those characteristics of tungstophosphoric acid
catalyst could be easily recovered by filtration or centrifugation (H3PW12O40). The increase in calcination temperature
processes. generates an intensification of signals shown in diffractograms
A hot filtration test was performed to demonstrate that the of the materials pyrolyzed at 500 and 750 °C (Figure 6b). As
catalytic activity was not related to the presence of expected, the material pyrolyzed at 250 °C shows incipient
homogeneous species (Figure 2). First, a catalytic test was signals characteristic of HPW with a Keggin structure.33,35,47
run to ∼50% conversion and then stopped. The heterogeneous Moreover, the XRD patterns of the catalysts prepared at 500
catalyst (PCN + HPW − 500 °C) was removed by filtration, and 750 °C exhibit the monoclinic WO3 phase (JCPDS
and the recovered liquid phase was again exposed to reaction number 43-1035).48−50 In the Raman spectra of the catalyst
conditions. No further conversion was obtained, which (Figure 6c) pyrolyzed at 250 °C, no peaks assigned to tungsten
suggests the absence of a catalytically active metal leaching oxide were presented, agreeing well with the heterogeneous
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Figure 3. SEM images of the catalyst pyrolyzed at (a, b) 250 °C, (c, d) 500 °C, and (e, f) 750 °C.
Figure 4. TEM images of material pyrolyzed at (a, d) 250 °C, (b, e)
500 °C, and (c, f) 750 °C.
structure observed on SEM images for this material (Figure
3a,b). In contrast, the overall bands of the catalyst pyrolyzed at
500 and 750 °C fall very close to the wavenumbers of the
strongest modes of monoclinic WO3.51 The bands at 269 and
267 cm−1 were attributed to bending vibration of the bridging
oxygen [δ(W−O−W)], whereas those at 685 and 691 cm−1
and 805 and 797 cm−1 were ascribed to the stretching
vibration of O−W−O [ν(O−W−O)].52,53 The peaks observed
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at a low frequency at 137 and 135 cm−1 were attributed to the
lattice modes, which are characteristic features of the
monoclinic phase.54 The shift observed might be related with
carbon that gets into the interstitial position and has some
interaction with WO3 that may induce the distortion of WO6
octahedron, causing a pair of W−O bond (on the plane of
octahedron) to become shorter and another pair to become
longer.55 Nitrogen adsorption−desorption isotherms were
collected to investigate the specific surface area, pore size,
and pore volume of the catalysts (Figure 6d and Table 2). The
adsorption isotherm for the catalyst pyrolyzed at 500 °C has
features between types II and IV, with hysteresis loop
resembling type H4 and an obvious capillary condensation
step, characteristics of mesoporous materials according to the
IUPAC classification.56 The PCN + HPW − 500 °C catalyst
has the largest surface area of 31 m2 g−1, and the catalyst
obtained at 250 °C showed the lowest surface area (Table 2).
The pore size distribution (PSD) was calculated by the BJH
equation; the PCN + HPW − 500 °C catalyst showed both
micro- and mesopores, mainly in the range of 58 Å in large
volume and the highest pore volume of 0.053 cm3 g−1.
The detailed composition and bonding configurations of N,
W, and P for the catalyst pyrolyzed at 500 °C were examined
by X-ray photoelectron spectroscopy (XPS). The W 4f XPS
spectrum (Figure 7a) presented two peaks at the binding
energy of 35.6 and 37.7 eV, which correspond to the
characteristic W 4f5/2 and W 4f7/2 peaks of W6+, respectively,
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Figure 5. STEM image of PCN + HPW − 500 °C and EDS elemental mapping images.

Figure 6. (a) TG (solid) and DTG (dashed) curves for the melamine and HPW mixture. (b) XRD pattern of the catalyst at different pyrolysis
temperatures. (c) Raman spectra of the pyrolyzed catalyst at 250 to 750 °C and (d) N2 adsorption−desorption isotherms.

Table 2. Textural Characterization of Samples Pyrolyzed at be deconvoluted into four types of phosphorus species (Figure
Different Temperatures 7c), namely, phosphorus doped in the graphene structure
(130.6 and 133.6 eV) and P−O−C and P−O bonds of
SBET pore volume pore size
catalyst (m2 g−1) (cm3 g−1) (Å) phosphate (135.7 and 140.1 eV),62,63 supporting the presence
PCN + HPW − 250 °C 0.2 0.002 128 of phosphorus as a heteroatom doping the catalyst structure.
PCN + HPW − 500 °C 31.0 0.053 58 Moreover, quantitative XPS elemental composition of the
PCN + HPW − 750 °C 4.0 0.012 76 catalyst (Table 3) indicates a surface composed of 67.2% W,
27.1% P, and 5.8% N. The bulk concentration measured from
and the peak at 41.1 eV, which is attributed to W 5p3/2.53 In elemental analysis (ICP-OES and CHN) for the PCN + HPW
the N 1s XPS spectrum region (Figure 7b), the two main − 500 °C catalysis is given in Table 3 to better compare the
contributions observed can be attributed to pyridinic N species distribution of the components in the catalyst material. After
(binding energy of ∼399.9 eV) and a combination of pyrrolic pyrolysis treatment, the recovered material contains similar
and graphitic N species (∼401.8 eV).57−60 Moreover, DFT bulk and surface concentration of W, but the surface is
calculation studying proton affinity, pKa, and the local softness enriched with the PCN structure. With these results, we can
indicates that pyridinic N displays a strong basicity in terms of address that the catalyst is consisted of WO3 very finely
both Brønsted and Lewis bases,61 supporting the fact that the dispersed with debrides of (N,P)-doped carbon structures.
presence of this type of N-configuration could give better From TEM results (Figures 4b,e and 6), graphene/graphitic
catalytic performances. The P 2p XPS spectrum region could structures could not be observed, meaning that the PCN
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8). The detected products from IPA decomposition were

mostly propene and very low amounts of di-isopropyl ether (as

Figure 8. Product distribution as a function of the reaction

temperature in the dehydration of IPA over the catalyst pyrolyzed
at 500 and 750 °C: (a) propene and (b) di-isopropyl ether. The
catalyst pyrolyzed at 250 °C showed no activity for the IPA
dehydration reaction.

low as 1% for PCN + HPW − 500 °C, Figure 8a), and similar
behavior was previously reported in supported HPW
catalysts.64,65 The catalyst prepared at 250 °C showed no
activity in the reaction. As expected, the catalyst prepared at
500 °C showed the highest activity in the reaction, the
conversion of IPA increases with increasing reaction temper-
ature of up to 200 °C, and the temperature of total IPA
conversion was observed. Moreover, a further increase in the
pyrolysis temperature to 750 °C causes a decrease in the
catalytic activity, leading to low conversion of IPA, which may
be attributed to complete decomposition of the Keggin
structure to WO3.64 The measured acid sites (Table 4)

Table 4. Determination of Acid Sites from Isopropanol

Dehydration at 125 °C
IPA conversion apparent number of acid sites
catalyst (%) (μmol/s gcat)
250 °C 0 0
500 °C 20.2 0.20
750 °C 2.0 7.3 × 10−4

Figure 7. XPS spectra of (a) W 4f, (b) N 1s, and (c) P 2p of the
catalyst pyrolyzed at 500 °C.
structure is consisted of small ensembles with the amorphous
structure.
To get insights into the acidic properties of the developed
catalyst, we studied the dehydration reaction of isopropanol
(IPA). The IPA dehydration reaction starts at 125 °C (Figure
indicate that PCN + HPW − 500 °C possess the highest
acidity. According to the experimental results and previous
work, we believe that the phosphorus- and nitrogen-doping
structures from PCN + HPW − 500 °C can act as Brønsted
acid sites during IPA dehydration since propene formation
requires Brønsted acid sites.66,67 The formation of DIE in both
PCN + HPW − 500 °C and PCN + HPW − 750 °C, although
in very low extension, reflects the existence of basic sites, which

Table 3. Bulk Elemental Analysis and Surface Chemical Composition Obtained by XPS Quantitative Analysis to the Catalyst
PCN + HPW − 500 °C
parameter W 4f7/2 W 4f5/2 P 2p3/2 P 2p1/2 atomic P N 1s N 1s
binding energy (eV) 37.7 35.6 133.6 135.7 130.6 399.9 401.9
surface concentration (atom %) 67.2 27.1 1.9 3.9
Wa Pa Nb Cb
bulk concentration (%) 71.2 1.0 0.12 0.07

a
Measured by ICP-OES. bMeasured by CHN.

F DOI: 10.1021/acssuschemeng.9b01579
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decomposes IPA through an E2 mechanism, as proposed by
Gervasini et al.68 on a Li+-modified SiO2 surface.
The efficiency and limitations of the developed catalyst were
explored in the scope of the reaction as a general and practical
procedure for esterification of other aliphatic carboxylic acids
with methanol, ethanol, prop-2-en-1-ol, and n-propanol as
esterifying reagents under optimized reaction conditions
(Table 5) to investigate the possibility of the scope of the
Table 5. Esterification of Aliphatic Carboxylic Esters with
the PCN + HPW − 500 °C Catalysta
a
Reaction conditions: 0.1 mmol of carboxylic acid, 20 mg of catalyst,
2 mL of alcohol, 100 °C. GC yields are shown. b60 °C.
reaction to biodiesel-like molecules and related esters derived
from biomass. As shown in Table 5, most carboxylic acids
underwent esterification to afford the corresponding esters in
moderate to excellent yields (59 to 99%). In addition, the
procedure was found to be highly effective in the synthesis of
commercially used flavoring agents such allyl heptanoate 2h,
which was obtained in up to 70% yield. Methyl butyrate 2i, an
important ester used in perfumes and as a food flavoring, could
be obtained by the esterification of butyric acid with methanol
in a moderate yield of 59%. The catalyst follows the expected
tendency of a decrease in the conversion with an increase in
the alcohol chain length (2a, 2b, and 2c). This effect might be
due to enhanced electron-donating properties, which can
destabilize the protonated transition state. Moreover, C3
alcohols (of higher pKa) adsorb strongly to the catalyst
surface, which favors alkoxide formation, and it might lead to
blocking of catalytic active sites.18 From methanol (2a) to
butanol (2c), the conversion decreased from >99% in 8 h
reaction to 65% in 12 h reaction. Thus, a decrease in activity is
expected for longer-chain alcohols. Increasing the acid chain
length had less pronounced impact in reactivity, and long-chain
acids were also efficiently converted to esters. Short-chain
carboxylic acids react faster under even lower temperature than
long-chain ones. This behavior is in agreement with a previous
study, which demonstrated that the esterification of long-chain
carboxylic acids is rate-limited not only by restricted access to
active sites but also by the inductive effect.18
To further extend the scope of esterification reactions, a
broad range of aromatics containing electron-donating or
electron-withdrawing carboxylic acids was evaluated under the
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Research Article
best conditions. Most carboxylic acids underwent esterification
to afford the corresponding esters in moderate to excellent
yields (25 to 98%). Even though moderate to good yields of
benzylic ester (Table 6, 4a−4i) were observed, in all cases, the
Table 6. PCN + HPW − 500 °C Catalyzed the Esterification
of Benzylic Carboxylic Acidsa
a
Reaction conditions: 0.1 mmol of carboxylic acid, 20 mg of catalyst,
2 mL of alcohol, 100 °C. GC yields are shown.
sensitive groups such as halide, cyanide, and hydroxyl were well
tolerated. Interestingly, α,β-unsaturated carboxylic acids were
also tolerated by the developed catalytic system, being
converted to the corresponding esters without any observable
reaction at the double bond (Table 6, 4j and 4k). The
esterification of furan-2-carboxylic acid to its corresponding
methyl ester 4p, an important food flavoring compound, could
be realized by the catalytic system. The developed catalyst
proved to be also suitable to selectively convert acid substrates
in moderate yields such as phenylpropiolic acid (4m), 1-
naphthoic acid (4n), 3-cyclohexene-1-carboxylic acid (4o),
and thiophene-2-carboxylic acid (4q).
On the basis of the experimental results and previous
findings, we believe that the high catalytic activity shown by
the PCN + HPW − 500 °C should be associated with the
Lewis and Brønsted−Lowry acid sites created during the
thermal treatment of the HPW and melanin mixture,69 as
much as the significantly higher surface area of this catalyst,
even at the expense of some loss of the Keggin structure to
produce WO3. In contrast, soluble HPW-catalyzed esterifica-
tion of palmitic acid in conditions with lower HPW/palmitic
acid ratio than the one used here gave conversions as good as
∼80%,47 showing that our system is a very promising
heterogeneous catalyst. In this regard, considering the
complexity of the developed material, we believe that N
atoms introduced in the catalytic material might play a pivotal
role in boosting the catalytic activity, helping increase the
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
stability and being more resistant to the leaching process,47 in
complete contrast with previous results, which usually shows
reduction of activity of acid catalysts upon heterogenization. A
similar behavior was previously observed when 12-tungsto-
phosphoric acid was supported in zirconia; the zirconia-
supported HPW retains its catalytic activity in the esterification
of palmitic acid with methanol upon immobilization over
zirconia, and conversions even higher than those observed
under homogeneous conditions were obtained due to the
active contribution of the support.47 Moreover, we demon-
strate that PCN + HPW − 500 °C could be a promising
catalyst for the one-pot transformation of grease (free fatty
acids, FFAs) to biodiesel via simultaneous esterification of
FFAs and transesterification of triglycerides with methanol.
■
CONCLUSIONS
We have successfully prepared a novel solid acid catalyst via
pyrolysis of a mixture of melamine and HPW at 500 °C, which
exhibited excellent activity and stability upon recycles for the
esterification of a range of carboxylic acids. The solid acid
catalyst exhibited a remarkable stability under these conditions
and could be easily removed from the reaction mixture by
simple filtration and reused eight times without any significant
loss of activity. Regarding the catalytic performance and
recyclability in this type of transformation, the developed solid
acid catalyst might be a potential catalyst for the green and
economic production of biodiesel from waste grease via one-
pot transformation.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: carmen@uel.br (C.L.B.G.).
*E-mail: lrossi@iq.usp.br (L.M.R.).
ORCID
Jhonatan Luiz Fiorio: 0000-0001-7435-7430
Adriano Henrique Braga: 0000-0003-4227-6550
Liane Marcia Rossi: 0000-0001-7679-0852
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful to the Brazilian government agencies
FAPESP (grant 2016/16738-7), CNPq, and CAPES for the
financial support. Our thanks are also extended to the Brazilian
Synchrotron Light Laboratory (LNLS) for use of its SXS
experimental facilities (proposal SXS-20170205) and for the
Brazilian National Nanotechnology Laboratory for the TEM
facility (proposal TEM-21182). We also thank Douglas
Galante for the assistance and use of micro-Raman facility at
the TGM beamline of LNLS/CNPEM.
■
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