Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 1506−1515 pubs.acs.org/IECR

Citric Acid-Assisted Synthesis of Nanoparticle Copper Catalyst

Supported on an Oxide System for the Reduction of Furfural to
Furfuryl Alcohol in the Vapor Phase
N. J. Venkatesha*,† and S. Ramesh‡
†
Chemistry Research Center, Bangalore Institute of Technology, K.R Road V.V Pura, Bengaluru, Karnataka 560004, India
‡
Institute of condensed Matter and NanoscienceMolecules, Solids and Reactivity (IMCN/MOST) Universite catholique de
Louvain, Place Louis Pasteur, 1, Box L4.01.09, 1348 Louvain la-Neuve, Belgium
*
S Supporting Information

ABSTRACT: The simplest method of synthesizing metallic Cu

(111) nanoparticles on the zinc−aluminum mixed oxides was
found to be easily obtained by solid state grinding of all the three
metal nitrates and organic compounds in suitable proportions.
Organic compounds such as citric acid, formic acid, and
hydrazine were used, which act as reducing agents for Cu. The
catalysts were characterized by various physicochemical methods
such as X-ray diffraction, X-ray fluorescence, temperature
programmed reduction, high-resolution transmission electron
spectroscopy, X-ray photoelectron spectroscopy, field emission
scanning electron microscopy and N2-physisorption. The use of
citric acid resulted in Cu(111) nanoparticles with higher surface
area and better dispersion on the surface of mixed oxides. The
catalysts were used for the selective hydrogenation of furfural to
furfuryl alcohol under vapor phase conditions. Among the various catalysts studied, citric acid-assisted catalysis showed better
conversion with higher selectivity of desired product and deactivation free catalytic activity on stream more than 30 h.

1. INTRODUCTION
In the present situation, there is a growing awareness for the
use of renewable feed stock and the development of new
catalytic processes for the preparation of fuel and fine
chemicals. Furfural is one of the biomass derived starting
materials obtained from the rice husk and corn core, this was
used for the production of various industrially important
chemicals.1,2 Furfural [FAL] can used to produce furfuryl
alcohol [FOL] as an intermediate to the manufacture of lysine,
ascorbic acid, numerous lubricants,3,4 tetrahydrofurfuryl alco-
hol, 2-methylfuran, and tetrahydrofuran. The FOL was
produced through the hydrogenation reaction using both
vapor and liquid phase reactors. Among the various products,
FOL finds a variety of applications in the chemical industry; it
was mainly used for the production of various synthetic resins,
rubbers, fibers, and chemical resistant thermostatic resins which
are used for strengthening ceramics, molds for metal castings,
impregnating solutions, and carbon binders. It is also used as a
solvent for furan resins, pigments, varnishes, and as rocket fuel.
Also important, it is an intermediate for the manufacture of
lysine, vitamin C, lubricants, dispersing agents, and plasti-
cizers.5−9
In an industrial process copper chromite has been used
commercially for the selective hydrogenation of furfural to
furfuryl alcohol. The presence of Cr6+ causes severe environ-
mental pollution because of its high toxic nature and its higher
temperature with pressurized conditions; these are the main
disadvantage of this catalyst.5,6,10 Presently there are several
research groups working on this reaction using various
metallics, such as Pt, Pd, Ru, Cu, Ni, Cu, Zn, Ca, Al, Na,
bimetallic, Pd−Cu, Cu−Co, Pt−Sn, and ultrafine amorphous
alloys Ni−P, Ni−B, Ni−P−B, Co−B, Fe(NiFe)O4, and Ni−
Fe−B. Cu−Al layered double hydroxide (LDH) and Cu on
different supports Cr2O3, Al2O3, SiO2, SBA-15, and CaO11−18
used as catalysts for FAL hydrogenation has been reported,19
The reported catalytic systems involve the preparation of the
catalyst in metal oxide form, and before the reaction occurs, the
catalyst is to be reduced at harsh conditions with molecular
hydrogen for several hours. This process consumes much
hydrogen and energy; the former is found to be the future
alternative energy.20−22
In the present study a catalyst is prepared by the simplest
method and does not require further reduction before reaction,
making it economically viable for sustainable development. It
shows smaller metallic Cu particles, and their maximum (111)
Received: November 13, 2017
Revised: December 22, 2017
Accepted: January 15, 2018
Published: January 15, 2018

© 2018 American Chemical Society 1506 DOI: 10.1021/acs.iecr.7b04701

Ind. Eng. Chem. Res. 2018, 57, 1506−1515
Industrial & Engineering Chemistry Research
plane orientation on the surface showed deactivation free
catalytic activity of the CZA-based catalysts for the FAL
hydrogenation to FOL under reduction-free conditions.
Various organic compounds as hydrogen sources such as
hydrazine, citric acid, and formic acid were used for in situ
reduction of Cu, and the the prepared catalysts were
characterized by temperature programmed reduction (TPR),
high-resolution transmission electron spectroscopy (HRTEM),
scanning transmission electron microscopy (STEM), X-ray
photoelectron spectroscopy (XPS), X-ray fluorescence (XRF),
Brunauer−Emmett−Teller (BET) surface area analysis, and
powder X-ray diffraction (pXRD).
2. EXPERIMENTAL SECTION
2.1. Materials. Furfural and furfuryl alcohol was procured
from Sigma-Aldrich, India. Al(NO3)3·9H2O, Cu (NO3)2·3H2O,
and Zn(NO3)2·6H2O were purchased from SD fine chemicals.
Hydrazine hydrate, citric acid, and formic acid were obtained
from Merck, India, and used without further purification.
2.2. Catalyst Preparation. The catalysts were prepared by
taking 50 wt % of Cu(NO3)2, 20 wt % of Zn(NO3)2, and 30 wt
% of Al(NO3)2. To this mixture, 70 wt % organic compounds
was added and the mixture was ground well using mortar and
pestle. The sample was then dried at 120 °C for 3 h and
calcined under inert gas atmosphere for 4 h at 300 °C (with a
ramp rate of 5°/min). After that, the sample was cooled to
room temperature by maintaining the N2 flow at 20 mL per
min. The samples were stored in vacuum desiccator in airtight
bottles. The samples were designated as CZA, CZAC, CZAH,
and CZAF for samples without organic compound, and with
citric acid, hydrazine hydrate, and formic acid, respectively. The
CZA sample was reduced using H2 at 300 °C for 4 h and
designated as CZAD.
2.3. Catalyst Characterization. The prepared CZA
samples using organic compounds were characterized using
various techniques, such as XRD, BET, field emission scanning
electron microscopy (FE-SEM), TPR, XRF, Fourier transform
infrared (FT-IR), HRTEM, STEM and XPS.
Powder XRD measurements were performed for fresh and
spent catalysts, the 2θ values were between 10−80° obtained by
scanning at 2θ = 0.020° per step using a PAN alytical X’pert
PRO X-ray diffractometer with graphite monochromatized Cu
Kα radiation source (λ = 1.5406 Å). The Debye−Scherrer
equation was used to estimate the mean Cu crystallite size
based on the diffraction peaks of the Cu (111) plane.
Surface and pore characteristics of the catalysts were
measured using a Quanta Chrome Nova-1000 surface analyzer
under liquid nitrogen temperature. Prior to the measurements
sample were degassed at 300 °C for 4 h to remove preadsorbed
gas and moisture. The BET method was employed to measure
the quantity of nitrogen absorbed, and the cumulative volumes
of pores were obtained by the BJH method from the desorption
isotherms.
Morphology of the samples was recorded using a JEOL JSM-
6490 FESEM under high vacuum mode.
The reducibility of the sample was determined using a
BELCAT-II Microtrac (made in Japan) temperature-pro-
grammed reduction analyzer. The measurements were
performed by placing 50 mg of catalyst sample to the quartz
tube and ramping the temperature with a rate 10 °C/min,
under 20 mL/min of Ar up to 500 °C, and holding for 1 h.
Then the sample was cooled to room temperature and a stream
of 10% H2/Ar was flushed with a flow rate of 20 mL/min. After
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that, it was heated from 50 to 800 °C with a rate of 10 °C/min.
The amount of hydrogen consumed as a function of
temperature was monitored by a thermal conductivity detector
(TCD) detector.
The XPS analyses were performed on a SSX 100/206
photoelectron spectrometer from Surface Science Instruments
(USA) equipped with a monochromatized microfocused Al X-
ray source (powered at 20 mA and 10 kV). The samples
powder pressed in small stainless steel troughs of 4 mm
diameter were placed on an aluminum conductive carousel.
The pressure in the analysis chamber was around 10−6 Pa, and
the pass energy was set at 150 eV. The C-(C,H) component of
the C 1s peak of carbon was fixed to 284.8 eV to set the binding
energy scale. Data treatment was performed with the Casa XPS
program (Casa Software Ltd., UK), molar fractions were
calculated using peak areas normalized on the basis of
acquisition parameters and sensitivity factors provided by the
manufacturer.
TEM images of the fresh and used catalysts were obtained by
using FEI TITAN3 80−300 kV aberration corrected trans-
mission electron microscope having both HRTEM and STEM-
Z contrast imaging facility.
Dispersion of metallic Cu atoms were determined by pulsed
titration of N2O using BELCAT-2 TPX instrument Japan, the
catalysts of 200 mg were placed in the quartz tube (reduced
form). Helium gas was used as carrier gas at 10 mL min−1 and
the successive doses of 10% N2O/He gas were subsequently
titered into the He stream by means of a calibrated injection
valve (15 μL N2O pulse) at 60 °C temperature. The product
gases N2 and retained N2O were analyzed by TCD. The
amount of N2 and N2O was calibrated with the ZA sample,
N2O consumption and N2 liberated were calculated, both
giving good agreement values within 1% error.
Bulk Cu elemental analysis was carried out using a Horiba
XGT X-ray fluorescence instrument. A Shimadzu IRAffinity-1
FT-IR instrument was used to record the spectra of the samples
by the KBr pellet method with 4.0 cm−1 resolution in the
wavenumber range 4000−500 cm−1 to study the presence of
carbonaceous compounds in the catalysts after calcination
under N2 atmosphere. A complex formation was confirmed.
2.4. Catalytic Activity Test. The vapor phase hydro-
genation of furfural was carried out in a fixed-bed down flow
quartz reactor (400 mm long and 20 mm inner diameter)
under atmospheric pressure. The catalyst of 1.5 g was packed at
the center of the reactor between the plugs of glass wool and
the reactor was set to the desired reaction temperature (160−
280 °C). Furfural (LHSV 3.6 s−1) 1.8 mL/h was fed
continuously from the syringe pump (model NE-1000) to a
vaporizer, the vapors formed were mixed with H2 gas with a
ratio 15:1 of H2/furfural. This mixed gaseous stream was passed
through the reactor. The products were condensed in an ice-
cooled trap and analyzed by a chemito GC-1000 gas
chromatograph with TR-WAX capillary column (30 m length,
0.32 mm thickness, and 0.5 μm internal diameter) attached
with flame ionization detector. The calibration and quantifica-
tion of reactant (FAL) conversion and products (FOL, MF)
yield was made using standard samples purchased from Sigma
Aldrich, India.
3. RESULTS AND DDISCUSSION
3.1. Catalyst Characteristics. 3.1.1. Surface Character-
istics. Surface area and pore characteristics of CZA samples
were provided in Table1. The CZA sample prepared without
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Table 1. Surface Characteristics of the Prepared Catalysts 3.1.2. XRD Analysis. Powder X-ray diffraction patterns for all
the prepared catalysts are shown in Figure 2. The CZA catalyst
surface pore pore average TPR-H2
area volume diameter particle size consumption
catalyst (m2/g) (cm3/g) (Å) (nm) (mmol/g)
CZA 28.3 0.049 66 28 1.86
CZAC 48.3 0.083 54 14 0.13
CZAF 36.0 0.051 63 20 0.32
CZAH 38.0 0.061 62 20 0.45

using organic compounds as reducing agent showed the least

surface area (28 m2/g), pore volume (0.049 cm3/g), and more
average pore diameter. As usual, copper oxide particles are not
uniformly distributed on mixed oxides and resulted in low
surface area. This confirms that the particle size is bigger than
others. The citric acid CZAC sample showed the highest
surface area and a pore volume with the least average pore
diameter and particle size, due to the smaller particle size. As
expected, the Cu species is much smaller compared to its oxide
form. The higher surface area of the sample is caused by the
complexation of citric acid with metal ions and upon calcination
under N2 atmosphere decomplexation leading to the generation
of metallic species, whereas the formic acid and hydrazine
samples showed lower surface area and pore volume with
higher average pore diameter and agglomeration of particles
leading to larger size.
The complex formation between the Cu2+ ions and citric was
confirmed by the FT-IR spectrum. Figure 1 showed that spectra
Figure 1. FT-IR spectra of complex, citric acid, and CZAC samples.
of citric acid, which has three main bands, one main intense
band between 1799 to 1649 cm−1 for the CO stretching, a
broader band at 3649−3084 cm−1 for the acid O−H (both acid
and alcohol) stretching with hydrogen bonding, the band
between 1479 and 1385 cm−1 for the C−O stretching. The
spectra of the Cu−citric acid complex showed a shift of the
CO and C−O stretching band at 1608 and 1423 cm−1
respectively, with a decrease in intensity at 3387 cm−1 being
due to a decrease in the bond strength of O−H (acid)
stretching by complex formation with the Cu metal ion. The
spectra also show one small sharp band at 3547 cm−1 from the
OH (alcohol) of citric acid with the absence of hydrogen
bonding. The spectra of CZAC after the calcination at 300 °C
under N2 showed the absence of carbonaceous moieties in the
sample, which is in good agreement with the CHNS analysis.
1508
Figure 2. XRD patterns of (a) CZA, (b) CZAC, (c) CZAF, and (d)
CZAH.
showed that diffraction peaks at 2θ value 32.48 (110), 35.38
(002), 35.53 (1̅11), 38.64 (111), 38.97 (200), and 46.85 (2̅02)
are attributed to the CuO form with monoclinic symmetry
(JCPDS 80-0076) with ZnO, Al2O3 and no peaks observed for
metallic Cu. The organic compound samples showed major
diffraction peaks at 43.32 (111), 50.45 (200), and 74.13 (220)
that corresponded to metallic copper and possess face-centered
lattice with cubic symmetry (JCPDS 04-0836). Also very
minute peaks at 36.50 (111), 42.42 (200) and 61.55 (220) were
present for Cu2O having a primitive lattice with cubic symmetry
(JCPDS 77-0199).20,23 This information evidently proves that
in the nitrogen atmosphere the Cu2+ species converts to the Cu
species in the presence of hydrogen produced by the
decomposition of organic compounds (citric acid, formic
acid, and hydrazine) during calcination.
3.1.3. HRTEM Analysis. Figure 3 shows transmission electron
micrographs of the prepared catalysts. Alumina was hardly
detected in all the catalytic samples and mainly found in the
amorphous phase. Various morphologies were detected for the
CZA catalysts, such as round and irregular shaped Cu particles.
The catalyst prepared without reducing agent (Figure 3A)
resulted in bigger particle size and irregular shape of copper and
zinc-alumina oxides clusters, whereas the CZAC catalyst
exhibited a marked interface between Cu and zinc−alumina
oxide particles. The Cu particles were in spherical shape, and
surfaces of the metal particles typically covered the smaller
ZnO. Additionally, homogeneous, smaller Cu particles of 9 nm
were observed. The latter samples (CZAF and CZAH)
exhibited inhomogeneous particle shapes which tended to
agglomerate and form indistinct structures, which may be
related to the structure of the organic compound used.
3.1.4. TPR Analysis. The reduction profiles of all prepared
catalysts are shown in Figure 4 and consumption hydrogen is
provided in Table 2. The TPR profile of CZA consists of one
broad and intense peak between the temperature range of 160
to 300 °C; the deconvolution can bifurcate into two peaks, one
centered at 230 °C and another at 265 °C. As per the literature
survey,24−28 the CuO particles reduction temperature will vary
and depend on the size, dispersion, and crystallinity. The CZA
sample has bigger crystalline particles of CuO as evident by the
TEM and SEM images, and it consumed 3.25 mmol g−1 of H2.
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Figure 3. HRTEM images of CZA samples: (A) CZA, (B) CZAC, (C) CZAF, and (D) CZAH.

particle size being not well dispersed, when compared to the

amount needed when the catalyst is prepared without any
reducing agent. This clearly demonstrates the role of reducing
agent during the catalyst preparation.
3.1.5. STEM and SAED Analysis. The particle size
distribution and microstructures of Cu nanoparticles of CZAs
samples were further confirmed by STEM images (Figure 5).
All the samples at higher resolution showed fringe images, and
from that we calculated d(hkl)-spacing values for Cu species
which are in the fcc lattice form. These d-values were calculated
Figure 4. TPR profiles of (a) CZA, (b) CZAC, (c) CZAF, and (d)
by using digital Micrograph 3 software. The calculated values
CZAH.
were between two lines from three different organic
compounds. The CZAs sample showed similar patterns with
Table 2. Metal Dispersion by Pulsed Titration of N2Oa
the values of d(111) = 0.205 nm and d(200) = 0.179 nm. The CZA
amount of surface Cu in sample prepared without organic compound has the majority of
N2 O Cu atoms area of Cu samples CuO species, and it showed the values of d(111) = 0.245 nm
consumed on surface atoms (XRF) % Cu
catalysts (μmol/g) (mmol/g) (m2/g) (mmol/g) dispersion majorly with d(200) = 0.232 nm. Very small amounts of Cu2O
CZA 30.54 0.284 11.71 1.58 18 species are also observed with d(111) = 0.245 nm and d(200) =
CZAC 94.22 0.876 36.14 1.51 58 0.213 nm being in good agreement with the diffraction peaks of
CZAF 64.05 0.597 24.57 1.53 39 all the samples.29 SAED patterns of CZAC, CZAH, and CZAF
CZAH 69.92 0.651 26.82 1.48 44 samples showed the presence of Cu metallic phases and the
a formation of different planes (002), (11̅ 1), (200), and (111).
Pulsed chemisorption of N2O by TPX instrument, bulk Cu analysis
by XRF. Figure 5 and the CZA sample showed the CuO phase with
different planes (002), (111), (200), (220), and (311) in the
SAED patterns; these are also in good agreement with the XRD
The catalysts prepared using organic compounds as reducing and STEM analyses.
agents showed no significant TPR reduction peaks, which 3.1.6. SEM and EDXA. The morphology of the CZA samples
clearly indicated that copper species are reduced to metallic and distribution of Cu species on the surface was studied by
form during the catalyst preparation step. All the reducing elemental mapping. The scanning electron micrograph of the
agents used to convert Cu2+ to Cu are effective for the samples show that the metal oxides are mixed well throughout
reduction. Citric acid, formic acid, and hydrazine first resulted the entire catalyst without forming any separated clusters. The
in metal complex formation and during calcinations at 300 °C EDXA profile shows that the catalyst surface is composed of
under inert atmosphere the metal complex decomposes. Cu, Zn, and Al species. The SEM images of CZA (Figure 6)
Decomposition results in hydrogen generation, which converts showed an agglomeration of Cu−Zn clusters over Al2O3. The
Cu2+ species into metallic Cu species by in situ reduction. TPR distribution of metal clusters is consistent throughout the
profiles of these samples showed that the peak at 175 °C surface of Al2O3. The CZAC catalyst almost resulted in a
indicates these samples require a lower temperature and a uniform plate-like structure. CZAH and CZAF showed smaller
negligible amount of hydrogen for the reduction of Cu2O Cu−Zn clusters and better dispersion of Cu−Zn clusters over
particles. The particles are present in negligible amounts and Al2O3.
also are smaller and are highly dispersed, while in the case of 3.1.7. XPS Analysis. The XPS technique gives insights into
the formic acid sample, a peak is seen at a slightly higher the oxidation state of copper species on the surface of the
intensity, confirming that formic acid has less of a tendency to catalysts prepared with and without reducing agents. The Cu 2p
reduce the CuO species. Some of the Cu2O species remain in photoelectron spectra of prepared catalysts are shown in Figure
the sample, and these species are less dispersed and are bigger 7. The figure gives the information about the oxidation state of
with irregular shape, needing a greater amount of hydrogen surface Cu species in CZA, CZAC, CZAF, and CZAH samples.
(0.34 mmol g−1) for a complete reduction to get the Cu The catalyst prepared without organic compound (CZA)
species. The hydrazine, being a strong reducing agent results in showed a broad peak centered at 933.99 eV for the Cu(2+)O
metallic copper even at room temperature, but the particle size and peaks in the region between 940.5 and 944.5 and 962 eV
of the ground mixture was more comparable to that of the correspond to satellite shakeup peaks that show the presence of
CZAC. In all the cases, the amount of hydrogen consumed for CuO species in the samples. Whereas the catalysts prepared
the reduction is greater (0.47 mmol g−1), due to the higher with organic reducing agents shows a sharp peak at 932.4
1509 DOI: 10.1021/acs.iecr.7b04701
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Figure 5. STEM images of CZA and CZAC and SAED patterns of CZAC.
Figure 6. SEM images of (A) CZA, (B) CZAC, (C) CZAF, (D) CZAH, and (E) EDXA pattern of CZAC.
representing together with the absence of typical satellite peaks
at 940−945 eV for the Cu2+ species related to the unoccupied
3d states, the reduced copper species in the form of Cu and/or
Cu+. CZAC samples give only a single sharp peak at 932.34 eV
and the absence of a satellite peak confirms the presence of
only Cu metallic species. However, CZAF samples showed an
additional peak along with Cu species. There is a small peak
which is due to (deconvoluted peak at 933.34 eV) the presence
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of small amount of unreduced species (Cu2O). The formic acid
used may not be sufficient enough to reduce all the copper
present in the catalyst species (it will produce the least amount
of hydrogen during calcination among the reducing agents
used). Hydrazine being a strong reducing agent, still resulted in
three kinds of copper being present after the calcination under
inert atmosphere. The sample CZAH showed a broad peak
which is in the range that falls to all three kinds of Cu species,
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Figure 7. XPS spectra of catalyst samples.
but by the consideration of area under the curve upon
deconvolution, it is confirmed that there three peaks which
have the ratio of area of the peaks at binding energies. The
peaks are observed at 932.34, 933.34, and 933.99 eV with the
ratio of 72:19:9 corresponding to the Cu, Cu2O, and CuO,
respectively.30−32 XPS results confirm that all the reducing
agents used resulted in metallic copper either in the preparation
step or during calcination; however the degree of reducing
capacity depends on the strength and number of hydrogen
produced during calcination. Citric acid resulted exclusively in
metallic copper, whereas other reducing agents result in a
mixture of species with the majority being Cu, merging well
with the reduction profiles obtained by TPR and XRD. From
these observations Cu species only existed for CZAC samples,
and CZAF and CZAH samples exhibited all three kinds of Cu
species, but the ratio of Cu2O and CuO species was very less
compared to the Cu, which indicated that these results are in
good agreement with STEM and XRD results.
3.1.8. Cu Dispersion by N2O Chemisorption. Oxygen
chemisorption via N2O decomposition on CZAs catalyst
samples were considered to determine the surface Cu atoms
on the catalysts. Initially, N2O decomposition on CZAs were
confirmed. Table 2 shows the results of N2O consumption and
dispersion and surface area of metallic Cu. These measurement
for CZAs samples were carried at 60 °C by sequential injection
of N2O and calculated by following the previous report, by
considering the Cu density 14.9 × 1019 atoms per unit surface
area.33,34 The pulsed titration results of CZAs samples showed
N2O consumption in the following order CZA < CZAH <
CZAF < CZAC. These results directly evident that the
presence of metallic Cu on the zinc−alumina mixed oxide
cluster. Among the CZAs samples CZAC showed more amount
of N2O consumption, it showed that, there is more number of
Cu (58%) atoms on the surface, whereas CZA has only 11%,
CZAF 39%, and CZAH 44% of Cu atoms on the surface. This
is evident that citric showed more dispersion than formic acid
and hydrazine.
3.2. Catalytic Activity. FAL hydrogenation was performed
under vapor phase conditions for all the prepared catalysts, and
it was found that CZAC showed a maximum conversion of 76%
with a FOL selectivity of 96% and 4% MF. The reaction
pathway of furfural hydrogenation follows the addition of
activated molecular hydrogen to the carbonyl (aldehyde) group
of the FAL. Initially the addition of hydrogen to the carbonyl
carbon leads to the formation of an alkoxide intermediate
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followed by the addition of a second hydrogen on the oxygen of
alkoxide to form an alcohol.35 Furfuryl alcohol upon
dehydration leads to the formation of a cation, in which a
further reduction results in methyl furan. Furfural hydro-
genation is more active in the presence of Cu metallic species
especially on the (111) plane.36,37 The exposed species in the
catalyst has weak interaction with elongation of the CO bond
rather than the furanic ring of FAL. Furfural tends to adsorb on
the catalyst surface through carbonyl oxygen in a η1 (O)-
aldehyde configuration as previously reported in the
literature.38−41 DFT calculations, reported by earlier workers,
predict a strong repulsion of the Cu (111) surface to the furan
ring. This is presumably due to the 3d orbital of the surface Cu
atoms and the antibonding orbital of the aromatic furan
ring.12,36,42−45
Catalytic activity was studied by varying the reaction
parameters such as effect of the reaction temperature, time
on stream, and furfural flow for vapor phase hydrogenation of
furfural to furfuryl alcohol over CZAC catalyst. These have
been discussed in the preceding sections.
3.2.1. On Stream Stability Behavior. Time on stream
behavior was studied for 30 h. Initially (first 6 h) 78% FAL
conversion with 92% and 8% selectivity toward FOL and MF
respectively, was observed. After 6 h, the conversion of FAL
slightly decreased to 74% with a slight increase in selectivity for
FOL (97%) with decreased MF selectivity (3%). This confirms
deactivation free stable catalytic activity up to 30 h. A further
increase in stream time for more than 30 h showed a slight
decreased of FAL (8%) conversion, and the selectivity of FOL
reached almost to 100%. A typical time on stream activity of
CZAC catalyst was shown in Figure 8. It exhibited a steady and
stable activity and selectivity (MF was negligible and not
considered for studies).
Figure 8. Time on stream behavior on CZAC for FAL conversion.
Reaction conditions: temperature, 200 °C; LHSV = 3.6 h−1; H2/FAL
= 3; atmospheric pressure.
3.2.2. Effect of Reaction Temperature. The temperature has
significant effect on vapor phase hydrogenation of FAL over the
CZAC sample. Figure 9 shows the conversion of FAL and FOL
selectivity as a function of temperature range between 160−280
°C. Increased conversion with the increase in temperature was
observed. Maximum conversion (84%) and selectivity of FAL
(98%) was observed at 200 °C. The selectivity toward the FOL
reduces with increase in reaction temperature on account of
formation of the double hydrogenated product methyl furan
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Figure 9. Effect of temperature on hydrogenation of FAL over CZAC.
Reaction conditions: atmospheric pressure; H2/FAL ratio = 3; LHSV
= 3.6 h−1; time = 4 h.
(MF) as a side-product. The formation of MF is due to
hydrogenalysis of the alcoholic group at higher reaction
temperature. Thus, 240 °C seems to be an optimum
temperature for FAL conversion in yielding higher amounts
of FOL with a negligible amount of MF.
3.2.3. Effect of Furfural Flow. FAL conversion and FOL
selectivity were measured as a function of FAL flow rate
(LHSV) from 2.36 to 9.86 h−1 under the optimized conditions
of 200 °C with a H2/FAL ratio of 3. The results are shown in
Figure 10. The reaction was performed using CZAC catalyst
Figure 10. Conversion of FAL and selectivity of FOL at various FAL
flow rates over CZAC for FAL hydrogenation. Reaction conditions:
temperature, 200 °C; H2/FAL ratio = 3; atmospheric pressure, time =
4 h.
sample. A very low LHSV (2.4 h−1) favors the formation of MF
and causes a decrease in the selectivity toward FOL. At an
appropriate LHSV, 3.6 h−1 and more than that, the conversion
of FAL decreased with an increase in selectivity toward FOL
with decreased selectivity of MF. This is attributed to reduced
contact time between the catalyst and reactant. Hence LHSV
1512
Article
3.6 h−1 was considered as the optimal flow of FAL to get
maximum conversion, and more important industrial needed
product FOL, and minimize the side product MF.
3.3. Comparison of CZA’s Catalyst Samples for
Hydrogenation Reaction. Under optimized reaction con-
ditions, at 200 °C, H2/FAL ratio = 3 and LHSV is 3.6 h−1. The
comparison between the different catalysts was studied. The
copper species in the CZA catalyst were reduced using
molecular hydrogen (CZAD), and the activity results were
given in Table 2. Among the catalysts studied, the CZA sample
showed the least activity of 34% FAL conversion with 23 and
11% yields of FOL and MF, respectively. The CZAD sample
showed 80% conversion with yields of 65% FOL, 10% MF, and
5% furan, whereas, CZAC showed maximum conversion (88%)
with a high yield of FOL (81%) and a very less amount of MF
7%, other catalysts CZAF and CZAH were shown to increase
conversion and yield but still less than the CZAC (Table 3). At
a reaction temperature of 240 °C, all the catalysts showed
slightly increased conversion with varied product yield
distribution. At higher temperature, the yield of MF was
increased and also a minor amount of furan was also observed.
This provides information about the cause of increased
temperature for the C−C bond breaking in the MF leading
to a more stabilized furan formation. The conversion and yield
of the more important product FOL was selectively formed
more in CZAC, because it showed a maximum of Cu species
with active (111) plane exposed on the surface with lower
particle size, whereas CZAD, CZAF, and CZAH showed
increased particle size, and in addition to Cu (111) species,
there is some amounts of Cu+ species that can also observed,
leading to decreased conversion and yield of desired product.
The CZA catalysts showed the least conversion and product
because it contains only Cu2O in the presence of molecular
hydrogen during the reaction, showing very less activity. Also
particles are agglomerated leading to higher particle size.
3.4. Correlation between the Surface Cu Species and
FOL Yield. The Cu species has a main role in conversion,
because metallic Cu species are responsible for the reduction
reaction. The more dispersed Cu species becomes available for
the reactant molecule adsorption leading to reduction of the
carbonyl group to the alcohol group. The catalysts synthesis
using organic compounds showed improved hydrogenation,
because of the complex formation with the organic compound,
and are dispersed well on the surface because this Cu species
surface area will be higher. CZA prepared without using the
organic compound has very less dispersion as evident by the
N2O titration consequently surface area of the Cu species is
lesser and also availability of the Cu species on the surface is
too less so that. The new factor called efficiency of surface H2
occupancy was found to be useful for the prediction of product
yield and conversion of reactant. So to check the effect of the
Cu particle size, surface area, and dispersion responsibility on
the yield, correlations were made on the FOL yield with
individual factors. Table 4 shows the good correlation for all the
factors: particle size (0.96), Cu surface area (0.94), and
dispersion (0.96). An increase or decrease in any one the
factors will directly effect the product and conversion. The
factor called efficiency surface hydrogen occupancy (ESHO),
the product of surface Cu area, particle size, and dispersion, was
correlated with FOL yield to determine the combined influence
of all the three factors. It showed a better correlation coefficient
(0.99) with lower particle size and better dispersion of Cu
DOI: 10.1021/acs.iecr.7b04701
Ind. Eng. Chem. Res. 2018, 57, 1506−1515
Industrial & Engineering Chemistry Research Article

Table 3. Conversion and Yield of Products under Different Catalysts for Hydrogenation of FALa
200 °C 240 °C
CZA CZAD CZAC CZAF CZAH CZA CZAD CZAC CZAF CZAH
FAL conversion (%) 34 80 88 78 75 38 86 91 84 83
yield (%) FOL 23 65 83 70 69 20 62 77 70 68
MF 11 10 05 08 06 08 16 11 12 10
furan 05 08 03 03 05
a
Reaction conditions: H2/FAL ratio = 3; atmospheric pressure, LHSV, 3.6 h−1.

Table 4. Correlation between the Different Factors with FAL Conversion and FOL Yield
catalysts surface area of Cu atoms (m2/g) average particle size (nm) % Cu dispersion ESHOa (103) FAL conversion FOL yield TOF (h−1)
CZA 11.71 28 18 5.90 34 23 14.6
CZAC 36.14 14 58 29.34 88 83 32.4
CZAF 24.57 20 39 21.50 78 70 26.3
CZAH 26.82 20 44 24.78 78 69 25.8
correlation r 0.98 0.94 0.96 0.999
a
ESHO: Efficiency surface H2 occupancy

particle influence on a higher surface area, and showed better
catalytic activity for the FAL hydrogenation to yield FOL.
3.5. Characteristics of Used Catalysts. The used catalyst
sample was characterized to know the deactivation and stability
using XRD, N2-physisorption, and HRTEM. The results
showed stable and deactivation free catalytic activity. The
XRD pattern (Figure 11) showed major peaks at 43.317 (111),
Figure 11. XRD pattern of (CZACR) used catalysts.
50.449 (200), and 74.126 (220) responsible for the Cu metallic
species and minor peaks for the CuO and Cu2O, which
16.6 nm, which confirms deactivation free activity for more
than 30 h of reactants stream.
4. CONCLUSION
The solid state dry synthesis of metallic copper on mixed oxides
using organic compound as reducing agents was reported. The
metal complexes decomposed during the calcination, produces
hydrogen which results in situ reduction of copper on the oxide
cluster surface. The structure and composition of organic the
compound used play an important role in morphology and
reduction behavior of the final catalyst. Citric acid-assisted
synthesis (CZAC) resulted in better dispersion of metallic
copper nanoparticles on mixed oxides with higher surface area.
The CZAC catalyst showed the best performance more than 30
h on-stream for the catalytic hydrogenation of furfural to
furfuryl alcohol with higher selectivity. The term efficiency
surface hydrogen occupancy (ESHO) was coined to correlate
the effect of metallic dispersion, particle size, and their surface
area for the hydrogenation reaction; it showed a better
correlation coefficient. This can be extended to industrial
catalysis. This method of synthesis showed to be less energetic
and more economic for industrial catalyst synthesis.

■
indicates that the catalyst retained almost all its characteristics
after use. The surface and pore characteristics measured by the ASSOCIATED CONTENT
BET method showed a slightly decreased surface area of 43 m2/
g with a pore volume of 0.076 cm3/g and average pore diameter * Supporting Information
S

of 53.12 Å. The HRTEM images of CZAC (Figure 12) showed The Supporting Information is available free of charge on the
some agglomeration of particles with increased particle size of ACS Publications website at DOI: 10.1021/acs.iecr.7b04701.

Figure 12. HRTEM images of (A) CZAC and (B) CZACR catalysts.

1513 DOI: 10.1021/acs.iecr.7b04701

Ind. Eng. Chem. Res. 2018, 57, 1506−1515
Industrial & Engineering Chemistry Research
Comparison of different catalysts with our catalyst, UV−
visible spectra of CZAs catalysts for the confirmation of
complex formation and reaction mechanism (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: venkatesha.312@gmail.com. Tel.: 9901003120.
ORCID
N. J. Venkatesha: 0000-0002-9091-9744
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to thank the Rajya Vokkaligara Sangha
and Principal of Bangalore Institute of Technology for the
facilities provided. The authors also extended their thanks to
Prof. S. M. Shivaprasad, ICMS JNCASR, Mr. G. Vijaykumar
and Mr. Eranjaneya, Central College BUB, for XRD, Mr.
Srikanth, NCL Pune, for TPR measurements and Mr. M.
Shivakumar, BMSCE, for SEM.
■
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