Journal of Environmental Chemical Engineering 8 (2020) 104214

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Journal of Environmental Chemical Engineering

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Low-cost synthesis of Cu/α-Fe2O3 from natural HFeO2: Application in 4- T

nitrophenol reduction
Amal Elfiada,d,*, Federico Gallib,d, Laaldja Moddeur Boukhobzaa, Amar Djadounc,
Daria C. Boffitod
a
Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Algiers, Algeria
b
Dipartimento di Chimica, Universitá degli Studi di Milano, via Golgi 19, 20133, Milano, Italy
c
Laboratoire des Geéophysique, FSTGAT, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Algiers, Algeria
d
Department of Chemical Engineering, Polytechnique de Montréal, C.P. 6079, Succ. CV, Montréal, H3C 3A7, Québec, Canada

A R T I C LE I N FO A B S T R A C T

Editor: Teik Thye Lim Nitro-aromatic compounds pollute the aquatic environment and human being may ingest them through drinking
Keywords: water. Among these, 4-nitrophenol is the most common. In presence of an excess of NaBH4, 4-nitrophenol
Fe- Cu catalyst catalytically reduces to 4-aminophenol, which is not toxic. In this work, the Cu/α-Fe2O3 materials were suc-
Natural hematite cessfully prepared via a simple classical impregnation. The natural hematiteα-Fe2O3 support was obtained from
Goethite treatment natural goethite by a simple thermal treatment and supported on it a mass ratio of 5 % or20 % of Cu at room
4-Nitrophenol reduction temperature. The composition and the structural-morphological properties of natural α-Fe2O3 and Cu/α-Fe2O3
4-Aminophenol were identified by several characterization methods, including thermo gravimetric analysis (TGA), X-ray
Kinetic reaction
fluorescence (XRF), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron mi-
croscopy (SEM), energy dispersive X-ray spectroscopy (EDX), particle size distribution (PSD), and nitrogen
adsorption-desorption at 77 K. The Cu/α-Fe2O3 materials composite presented spherical and uniform particle,
high porosity, good copper dispersion and a mixture structural phase composition, all these characteristics and
the active site nature on her surface bring to approving the excellence catalytic performance of this solid
compared to the α-Fe2O3.The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) is completed in 250 s
over natural α-Fe2O3, and in 50 s over Cu/α-Fe2O3 (20 %Wt of Cu), the corresponding rate constant (k) for
reduction reaction was 0.09 s-1 per mg of Cu/α-Fe2O3 catalyst.

1. Introduction system [5]. Nitrophenols reductions to aminophenol in industrial

Pollutants such as dyes and pigments containing nitro compounds
which contaminate agricultural and industrial wastewaters : petro-
chemicals, pharmaceutical industries, textiles, printing, …etc. [1–3].
These substances are toxic and have a carcinogenic profile. After
treatment, industrial wastewaters are discharged as a fresh water and
the concentration of nitro-aromatic compounds are detected on the
order of the ppb. However, long-term exposure and assimilation of
nitro-aromatic compounds through drinking water may damage the
environment and possibly human being health [4]. Nitrophenols have
been listed as priority pollutants by the U.S Environmental Protection
Agency, because of their high solubility and stability in water [4]. 4-
nitrophenol (4-NP) is toxic and hardly degradable pollutant which da-
mages the central nervous system and the respiratory and digestive
wastewater are mostly concentrated, but an option to decrease their
concentration is possible. Aminophenol is a precursor in the manu-
facture of analgesics, antipyretics and other drugs. It is also a photo-
graphic developer, a corrosion inhibitor and a lubricant [6]. There are
several methods to remove this pollutant from wastewater like elec-
trochemical methods [7], hydrogenation reactions [8], Fenton-like re-
actions [9], photocatalysis [10,11] biological degradation [12] and
adsorption [13]. Most of the techniques mentioned above have lim-
itations, such as the production of secondary pollutants, disposal of the
catalyst sludge, formation of hazardous by-products, high energy re-
quirements and expensive post-processing [14]. Industry favors the
hetero-generous catalytic reduction using sodium borohydride NaBH4
as reducing agent [15]. In the presence of catalysts, NaBH4 yields a
stable chemical hydride [16]. 4-NP catalytic reduction to 4-

⁎
Corresponding author at: Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111,
Algiers, Algeria.
E-mail address: aelfiad@usthb.dz (A. Elfiad).

https://doi.org/10.1016/j.jece.2020.104214
Received 9 March 2020; Received in revised form 21 June 2020; Accepted 23 June 2020
Available online 24 June 2020
2213-3437/ © 2020 Published by Elsevier Ltd.
A. Elfiad, et al.
aminophenpl (4-AP) has became one of the most studied model reac-
tions to test the activity of catalysts [17]. Zhao et al. reviewed the main
synthesis procedures and tested the activity of diverse Au nanoparticles
for this reaction [18], while Shukla et al. studied the activity of Pt
nanoparticles supported on ceria [19]. In this way, Mourya et al. tested
the AgNPs in the 4-NP reduction, the reduction time was estimated
around 15 min for 100 % of conversion to 4-AP [20]. Scientific data is
available on several bimetallic noble metal catalysts for example:
AuNPs [21], Au/Pt [22], and Au/Pd [23]. All these catalysts converted
more than 99 % of 4-NP, but their precursors are expensive and the
synthesis is complex and lengthy. Transitions metals, such as Co [24],
Ni [25], Fe [26] and Cu [27] may be active as well as in the 4-NP
reduction. Among them, Cu is the most active. An approach to increase
the catalytic performance of Cu nanoparticles is to deposit them on
carriers to establish a synergistic metal-support action [27]. Lei Jin
et al. considered reduced graphene oxide (rGO) as a support, and Cu/
rGO completely reduced 4-NP in 6 min [28]. Darabi et al. [29,30] im-
proved the heteropoly compounds performance by adding Cu in the
bulk of the catalyst. Bordbar et al. [31] synthesized CuO/ZnO nano-
composite and converted 4-NP in 3 min. Elfiad et al. [32] tested Cu/
NaX for the 4-NP reduction and improved the total reduction to 4-AP in
60 s with a conversion > 99 %. Wang et al. [33] and Nasrollahzadeh
et al. [34] employed Cu/Fe3O4 and Nandanwar et al. used CuO/γ-Al2O3
catalysts [35]. Our work is original because we support Cu on natural
hematite (α-Fe2O3). We recently reported the fast and ecofriendly
synthesis of hematite [36]. In this paper we report for the first time an
inexpensive and environmentally friendly approach for the preparation
of Cu/α-Fe2O3; the Cu mass fraction was 5 % to 20 %; α-Fe2O3 derived
from natural HFeO2 ore iron via a one-step thermal treatment. We
deposited CuNPs on the surface of natural hematite with different
loadings. Both 5%Cu/α-Fe2O3 and 20 %Cu/α-Fe2O3 reduced 4-NP in
presence of NaBH4at ambient temperature.
2. Experimental section
2.1. Reagents
The catalyst precursor was copper nitrate trihydrate [Cu (NO3)23
H2O, 99 %], it was purchased from Sigma Aldrich. The substrate for the
degradation experiments was 4-nitrophenol (4-NP, 99 %); the reducing
agent was sodium borohydride (NaBH4, 97 %) by Fluka. We did not
purify the reagents further. Natural iron rock was the precursor of the
catalyst support. The Geology Laboratory (University of Science and
Technology Houari Boumedien) collected the natural ore iron rock in
the Melbou-Bejaia region (Algeria).
2.2. Catalyst preparation
We treated natural ore iron goethite via a thermal treatment process
to obtain hematite [36]. Detailed synthetic procedures of the natural α-
Fe2O3 were shown in the supporting information. The impregnated Cu/
α-Fe2O3 catalysts were prepared by impregnating α-Fe2O3 powder with
an appropriate amounts of copper nitrate (Cu (NO3)2 3 H2O) aqueous
solution, stirred (3500 rpm) at room temperature for 1 h. The obtained
solids were dried at 100 °C overnight. The samples were calcined at
different temperatures (Table 1) for 5 h with a heating rate of
5 °C.min-1.
2.3. Characterization
A TGA-Q50 (thermo gravimetric analysis Instruments) system
characterized the thermo gravimetric behavior of the precursors with a
temperature interval between 25 ◦C to 800 ◦C and a ramp of 10 ◦C
min−1 under an air flow of 10 l min−1. An X-ray fluorescence spec-
trometer PW1400 Philips Instrument evaluated the composition of
natural iron ore. An X-ray diffractometer (XRD, Philips PANanalytical
2
Journal of Environmental Chemical Engineering 8 (2020) 104214
Table 1
Catalysts and synthesis conditions.
Catalysts Cu loading Calcination temperature (°C) Abbreviations
(masse%)
Natural iron – – Fe-NAT
Fe-NAT – 750 α- Fe2O3
5%Cu/ α- Fe2O3 5 500 5CF500
20 %Cu/ α- Fe2O3 20 500 20CF500
20 %Cu/ α- Fe2O3 20 700 20CF700
USA X'pertdiffractometer) scanned the powder samples with Cu-
Kαradiation (λ = 1:5406 Å) and the scanning angle ranged from 10° to
80°. A scanning electron microscope (FE-SEM-JEOL JSM-7600 F) im-
aged the catalysts, and energy dispersive X-ray (EDX) analysis mea-
sured their superficial composition. A FEI Tecnaï 20 F transmission
electron microscopy (TEM) imaged the samples. Fe and Cu concentra-
tions were determined by Atomic Adsorption Spectroscopy (AAS)
(Shimadzu PERKIN-ELMER-2380). A Thermo Mattson Fourier
Transformation Infrared (FTIR) spectroscopy recorded all samples'
spectra from 400 cm-1 to 4000 cm−1 over a KBr pellet. A laser scat-
tering analyzer (LA-950 Horiba) quantified the particle size distribution
(PSD). To determine the textural properties of the prepared samples, N2
adsorption-desorption measurement was carried out at 77 K using a
Micrometrics Autosorb-1 (Quantachrome Instruments) after the sample
degassed at 200 °C in vacuum for 12 h.
2.4. Catalytic tests
The catalytic activity and stability of α-Fe2O3 and Cu/α-Fe2O3
materials tested in the reduction of 4-nitrophenol (4-NP) in the pre-
sence of excess NaBH4 at room temperature. In a typical process,
12.5 mL freshly prepared NaBH4 was added to a batch reactor that
contains 100 mL of aqueous solution of 4-Nitrophenol, then the mixed
solution was stirred at room temperature (25 ◦C) for 3 min. Here, the
final concentrations of 4-NP and NaBH4 were 5 × 10−5 mol.L-1 and
0.5 mol.L-1 respectively, and the pH of the solution was 11.5. After
wards, 3 ml of the mixed solution were transferred in a quartz cuvette,
and then 1 mg of as prepared catalyst was added to the cuvette solution.
The quartz glass was quickly subjected to UV–vis spectroscopy (JASCO
model V-530 spectrophotometer) and the absorbance of the solution
was in situ measured every several seconds in the scanning range of
200–500 nm. The maximum adsorption peak of 4-NP showed at
400 nm, the conversion of the reaction was calculated according to the
Eq. (1). To optimize the reaction conditions, a series of reactions were
performed using several catalyst amounts and several bases con-
centrations to obtain the best possible combination (Table S1). After the
reaction, a centrifuge separates the catalyst from the solution. Distilled
water and ethanol in sequence rinsed the catalyst removed the 4-AP
adsorbed on the catalyst surface. The catalysts dried in an overnight for
the next cycle. The catalysts were re-used in five successive tests with
fresh 4-NP and NaBH4 solution.
X4-NP = (A0-At/A0) *100 (1)
A0 is the absorbance at the beginning of the reaction (t = 0) and At is
the absorbance at sampling time t.
3. Results and discussion
3.1. Thermogravimetric analysis (TGA)
The TGA curve of natural α-Fe2O3 exhibits three distinct mass loss
regions (Fig. 1a). The first mass loss of 0.9 % occurs in the temperature
range of 25 °C–165 °C and belongs to the evaporation of water physi-
sorbed on the surface of natural goethite. The second mass loss of 9.1 %
occurs at 165 ◦C to 288 °C, and is due to the dehydroxylation of
A. Elfiad, et al.
Fig. 1. Thermal analysis (TGA) for (a) natural α-Fe2O3 (b) 5 %Cu/α-Fe2O3 (c) 20 %Cu/α-Fe2O3.
goethite α-FeO(OH) (identified by XRD) into hematite (α-Fe2O3)
[37,38]. The third mass loss accounts for a mass of 2.2 % and occurs
between 288 °C–347 °C. It corresponds to the decomposition of the re-
maining hydroxyl groups in goethite and partly to non-stoichiometric
hydroxyl units [39]. Above 350 °C there is no further mass loss, in-
dicating that α-Fe2O3 is stable. The TGA curve of 5%Cu/α-Fe2O3 and 20
%Cu/α-Fe2O3 are shown in the (Fig. 1b and c), respectively. The first
mass loss of 8.5 % and 9.8 % is between 25 °C–110 °C and 25 °C–174 °C
for the precursor containing a copper mass percentage of 5 % and 20 %,
respectively. These losses are attributed to the removal of physically
adsorbed water from the original precursors [39,40]. The second
thermal stage occurs in the range of 110 °C–385 °C and 175 °C–490 °C
with mass percentage losses of 5.2 % and 4.7 % for 5 %Cu/α-Fe2O3 and
20 %Cu/α-Fe2O3 respectively, which are due to the transition phase
and complete decomposition of copper nitrate into their corresponding
oxide CuO [39,41]. On the other hand, especially for 20 %Cu/α-Fe2O3,
the TGA curve shows a third mass loss (0,6 %) occurring in the range of
500 °C–562 °C, attributed to the solid-solid interaction between α-Fe2O3
and CuO forming CuFe2O4 spinel (Eq. (2)):
α-Fe2O3+CuO → CuFe2O4 (2)
The increase in mass loss of Cu supported hematite compared to
hematite may be associated to a higher loss of copper precursors and
the effect of the Cu impregnation on α-Fe2O3. The TGA data associated
with the formation and decomposition of the different phases agree
with the XRD analysis.
3.2. Chemical composition and crystal structure
The chemical compositions (wt %) of the natural goethite have been
examined by the X-ray fluorescence (XRF) analysis, the obtained results
reveal the presence of the iron as majority percentage (96.12 %) with
the minority other elements (SiO2 1.98 %, MnO2 1.60 % and MgO 0.30
%), the results indicated that our ore iron is not pure and contains some
impurities. In the other hand, the EDAX analysis spectrum of the nat-
ural ore iron (Fig. S1) show the presence of the same elements observed
by XRF, the appearance of copper pick indicated that the holder sample
used in this measure is made of copper.
3
Journal of Environmental Chemical Engineering 8 (2020) 104214
The diffraction peaks in the natural ore iron Fe-NAT (Fig. 2.A)
correspond mostly to goethite (α-FeOOH, JCPDS 08-097), and to hex-
agonal α-Fe2O3 hematite (JCPDS 33-664). XRD patterns changed after
calcination at 700 °C, where by all goethite's peaks disappear in favor of
hematite's, due to the Fe-O restructuring (Fig. 2a). The X-ray dif-
fractograms of the Cu/α -Fe2O3 materials with different copper
amounts and calcined at different temperature (500 and 700 °C) are
reported in Fig. 2B. Powder X-ray diffraction of 5CF500, 20CF500 and
20CF700 revealed the presence of the rhombo-hexagonal structure of α-
Fe2O3 (space group: R-3C), with lattice parameters of a = b =5.034 Å
and c =13.729 Å, which are in good agreement with standard reference
data (PDF-ICCD: 33-0664) [42,43].
The diffractograms of 20CF500 and 20CF700 solids exhibit a peak at
2θ = 38:7° corresponding to CuO phase (PDF-ICCD: 01-1117), with
lattice parameters a =4.653 Å, b =3.14 Å and c =5.108 Å, the 20CF700
material (Fig. 2d) contained another phase refracting at 2θ = 36.9°,
43.7°, 58.8°, and 62.2°. These diffraction lines belong to tetragonal type
CuFe2O4 spinel (ICCD: 34-0425), whose presence was confirmed by
TGA.
The 5CF500 solid does not contain CuO oxide and it preserved the
rhombohedral hematite structure, suggesting either a homogeneous
dispersion of CuO on the hematite matrix, or CuO particle size in the
nanometer scale [44], however, increasing the calcination temperature
(Fig. 2c-d) and the copper amount increases the crystallinity degree of
CuO. The diffraction patterns exhibits two peaks belonging to the (1 0
4) and (1 1 0) plans of α-Fe2O3, in Cu/α-Fe2O3these peaks slightly shift
from 32.9° and 35.6° to 33.2° and 35.8°, respectively (Fig. 2e). This
indicates the change of the α-Fe2O3 lattice parameters after the addition
of CuO [45].The mean crystallite size was determined from the line
broadening of the attributed XRD lines using the Williamson–Hall
method (Table 2).
3.3. Morphology and composition
We report representative SEM (scanning electron microscopy)
images for the sake of brevity. α-Fe2O3 (Fig. 3a) particles have shuttle-
like shape with relatively smooth surface. With the increase in the Cu
amount the shuttle-like shape disappears and the surface became
rougher (Fig. 3b–d). Comparing 20CF500 with 20CF700 (Fig. 3c-d), the
A. Elfiad, et al. Journal of Environmental Chemical Engineering 8 (2020) 104214

Fig. 2. (A) XRD patterns of the natural Fe-NAT and α-Fe2O3. (B) XRD patterns of the (a) α-Fe2O3, (b) 5CF500, (c) 20CF500 and (d) 20CF700.

crystallinity increases with the calcined temperature from 500 ◦C to
700 °C, exhibiting a more ordinate morphology. In conclusion, the mass
percentage of Cu and the calcination temperature influence the mor-
phology of Cu/α-Fe2O3 composite oxide.
The transmission electron microscopy (TEM) determined the size
and morphology of the nanoparticles (Fig. 4). The original morphology
of α-Fe2O3 nanoparticles is non-uniform, spherical with an average
diameter of 50 nm, these agglomerates formed by a superposition of
nonmetric size particles. The TEM image of 5CF500 displays spherical
grains (37 nm) more uniform than α-Fe2O3 particles (Fig. 4b). However,
TEM images of the 5CF500 catalyst show that the solid is constituted of
the small particles (3 nm) dispersed on the surface, these particles can
be attributed to the CuO phase. Increasing the Cu content to 20 %
slightly increases the CuO particle size to 40 nm and decrease theα-
Fe2O3 particle size to 11 nm (Fig. 4c). The TEM image of the 20CF700
shows uniform and homogenous spherical particles with average dia-
meter around 15–53 nm (Fig. 4d). The increase in the particle size with
the calcination temperature is due to the formation of CuFe2O4 phase
together with sintering. The TEM data agree with the XRD, SEM and
surface area analysis (Table 2).
The EDXA analysis is determined the composition of nanoparticles
(Table 2, Fig. 3). The EDS spectrum of the Cu-Fe oxide confirmed the
presence of Fe and Cu (which is in agreement with the XRD a result
discussed earlier (Fig. 2)) and O peaks in the samples; with the Si and
Mg impurity, the origin of these impurities was proved previously by
XRF analysis. The atomic absorption analysis (AAS) agrees with the

Table 2
Catalysts textural properties and particle size distribution.
Samples Calculated Composition by AAS Composition by S BET pore Average pore PSD Particle size Crystallite size byXRD (nm)
composition % EDX (m2/g) volume diameter (nm) by TEM (nm)
Wt% Wt% (cm3/g)
O Fe Cu Mean size α-Fe2O3 CuO CuFe2O3
Cu Fe Cu Fe (μm)

α-Fe2O3 / 70 / 69.51 /// 38 0.23 19.50 28 50 29.65 – –

5CF500 5 66.5 4.86 67 30 61 6 42 0.24 17.72 25 3−37 27.12 – –
20CF500 20 52 20.12 53.09 31 54 12 29 0.21 20.1 41 11−40 22.25 11.5 –
20CF700 20 52 20.15 52.63 30 55 13 10 0.20 25.9 85 15−53 20.52 50.50 18.33

4
A. Elfiad, et al. Journal of Environmental Chemical Engineering 8 (2020) 104214

Fig. 3. SEM/EDS images of the (a) α-Fe2O3, (b) 5CF500, and (c) 20CF500, (d) 20CF700.

Fig. 4. TEM images of (a) α-Fe2O3, (b) 5CF500, (c) 20CF500, and (d) 20CF700.

5
A. Elfiad, et al.
Fig. 5. FT-IR spectra of (a) α-Fe2O3, (b) 5CF500, (c) 20CF500, and (d)
20CF700.
expected stoichiometry (Table 2).
3.4. Fourier Transformation Infrared (FT-IR) spectroscopy
Two main absorption bands in the range 467 cm−1 to 565 cm−1
characterize hematite (Fig. 5a). They both correspond to metal oxygen
(Fe O) stretching [46]. The Cu/α-Fe2O3 samples exhibit the same peaks
as hematite, but the bands associated with the Fe-O vibration shift to
higher wave numbers (Fig. 5b–c). This difference ascribes to the in-
teraction between Cu and O [47]. The FT-IR results correlate with the
TGA and XRD analyses, and confirm the formation of CuO and CuFe2O4
for 20CF500 and 20CF700, respectively.
3.5. Nitrogen adsorption/desorption isotherms
All samples exhibit similar shape of isotherms of type-IV according
to the IUPAC classification, typical of mesoporous materials
(2 nm–50 nm), accompanied by an H2 hysteresis loop (Fig. 6). Ag-
glomerates of spherical particles generally constitute solids character-
ized by this type of hysteresis [48]. From the BET surface area, average
pore diameter and corresponding pore volumes (Table 2), we deduce
that the pore size distribution is in the range of 19 nm–26 nm for all
samples, which indicates that α-Fe2O3 and Cu-Fe are mesoporous cat-
alysts. The incorporation of 5 % and 20 % of Cu increases the pore
Fig. 6. N2 adsorption isotherm of (a) α-Fe2O3, (b) 5CF500, (c) 20CF500, and
(d) 20CF700.
6
Journal of Environmental Chemical Engineering 8 (2020) 104214
Fig. 7. Particles size distributions of (a) α-Fe2O3, (b) 5CF500, (c) 20CF500, and
(d) 20CF700.
volume, due to the placement of copper species in the hematite pores
leading to their enlargement. We attribute the higher BET surface area
of 5CF500 compared to the pure hematite to the creation of new pores,
and to the increase in the total pore volume.
The BET surface area decreases from 38 m2 g−1 to 29 m2 g−1 for α-
Fe2O3and 20CF500. This indicates that CuO blocks some of the active
sites accessible for nitrogen adsorption when the loading of Cu in-
creases. A higher calcination temperature (500 ◦C vs. 700 °C) decreased
the surface area of about 30 % (20CF700 vs. compared to 20CF500). This
decrease correlates with the crystallization of new phases (confirmed by
the appearance of the spinel phase in XRD and TGA).
3.6. Particle size distribution (PSD)
Hematite α-Fe2O3 particle diameter is the smallest (mean size:
28 μm), whereas 20CF700 has the largest diameter (85 μm) (Table 2).
After the addition of 5 % of Cu, the particle size distribution does not
change and mean size ∼ 25 (Fig. 7b). When the copper loading in-
creases to 20 %, the PSD curve becomes bimodal, with a peak at around
600 μm (Fig. 7c). This secondary peak is attributed to the agglomera-
tion of 20CF500 particles in the aqueous solution during the PSD
measurement.
The average size of 20CF500 was 41 μm. In the sample calcined at
700 °C (20CF500), the two peaks from the bimodal distribution seem to
merge in one larger peak. The main PSD peak shifts at higher diameter
because of particle sintering at higher calcination temperature (700 ◦C
vs. 500 °C). However, the particles do not agglomerate in water during
the analysis because, being bigger, they are more stable than those of
20CF500. The PSD analysis is consistent with the TEM images.
3.7. UV-visible (UV-vis) spectroscopy
4-NP adsorption peak is centered at 317 nm. After adding the so-
dium borohydride (NaBH4) at room temperature, the solution changes
its color from yellow to bright yellow (Fig. 8a–f), and the absorption
peak immediately shifts to 400 nm [49] indicating. the formation of 4-
nitrophenolate ions under alkaline condition [50].The absorption peak
at 400 nm did not shift over 2.5 h, which confirms that the 4-NP cata-
lytic reduction does not occur without a catalyst, i.e. sodium borohy-
dride cannot reduce 4-NP itself [32,51]. Nevertheless, after adding the
nanocatalyst to 4-nitrophenolate ion, the color changes quickly, and the
intensity of absorption peak at 400 nm gradually decreases with time: a
new peak at 305 nm appears, corresponding to 4-aminophenol (4-AP)
A. Elfiad, et al. Journal of Environmental Chemical Engineering 8 (2020) 104214

Fig. 8. (a) UV–vis absorption spectra of a solution of 4-nitrophenol (4-NP) with and without NaBH4. (b) Time-dependent UV–vis absorption spectra for the reduction
of 4-NP with NaBH4 without catalyst. (c-f) Time-dependent UV–vis absorption spectra for the reduction of 4-NP in the presence of: α-Fe2O3 (c), 5CFT500 (d),
20CFT500 (e), 20CFT700 (f).

Table 3 order is correct. We calculated the rate constants (k) dividing the ap-
Activity tests: reduction of 4-nitrophenol to 4-aminophenol at room tempera- parent rate constant (kapp) by the initial mass of the catalyst (Eq. (4)):
ture.
k=k app/ initial catalysts’ mass (4)
Catalysts Reaction times Conversion (%) kapp(s−1) K (s−1. kg−1)
(s) The rate constant of 20CF700 is the highest (Table 3), this indicates
that increasing of the Cu amount and the calcination temperature in-
α-Fe2O3 250 99.51 0.011 ± 0.0025 11 ± 0.0025
5CF500 115 99.86 0.039 ± 0.0021 39 ± 0.0021 creases the reaction rate. Indeed, increasing the reaction temperature
20CF500 80 99.85 0.056 ± 0.0012 56 ± 0.0012 increases the crystallinity of the sample, i.e. the concentration of the
20CF700 50 99.93 0.090 ± 0.0033 90 ± 0.0033 active phase. The reaction rate constants reported in the present work
for the 4-NP reduction are higher than the other catalysts reported in
literature, whereby expensive metal composites are usually the pre-
(Fig. 8c–f) [52]. UV–vis spectra exhibit an isosbestic point (Fig. 8d) for cursors (Table 4).
the two absorption bands indicating that the 4-NP gradually converts to The Langmuir–Hinshelwood (LH) model was proposed as me-
4-AP with no byproduct [53]. The Cu/ α-Fe2O3 catalysts are more ac- chanism for our reaction. The reduction of 4-NP consists of three me-
tive than α-Fe2O3 (Table 3). The time to complete the reaction de- chanistic steps (Fig. 10): the diffusion and adsorption of 4-NP on to the
creases with increasing of Cu amount. 4-NP completely reduces to 4-AP metal catalysts surface, and the electron transfer from borohydride ion
in 250 s, 115 s, 80 s, and 50 s for α-Fe2O3, 5CF500, 20CF500, and BH4− (donor) to 4-NP (acceptor) by metal catalysts [56]. Here, Fe and
20CF700, respectively. Cu metal particles of catalysts facilitate the electron transfer to the 4-
NP, which eliminates the reaction kinetic barrier [50]. BH4− adsorbs on
3.8. Reaction kinetics the catalyst's surface and liberates an hydrogen as hydride. The hydride
anion transfers to the Fe/NPs or Cu/NPs, yielding a metal-hydride
The concentration of NaBH4 was much higher than that of 4-NP and complex. Simultaneously, the nitro group of 4-nitrophenolate ion re-
thus considered as constant during the course of the reaction. duces by capturing the hydride from the metal-hydride complex
Therefore, the reduction reactions were assumed to be pseudo first [57,58]. Eventually, 4-AP forms from 4-hydroxylaminophenol (stable
order with respect to the concentration of 4-NP [54] (Eq. (3)). More- intermediate) after three hydro-deoxygenation reactions. The last step
over, a NaBH4 excess protects 4-AP from oxidation [55][56]. is the desorption of 4-AP from the surface of catalyst [59].
According to the Table 3, the Cu/α-Fe2O3 catalysts show relatively
ln Ct/C0=-ln At/A0=kapp*t (3)
higher catalytic activity than α-Fe2O3 alone. It is suggested that the α-
kapp is the apparent reaction constant. The slope of the plot of ln Ct/C0 Fe2O3NPs as support play an active part in the catalysis, yielding a
versus t determined the kinetic parameters (Fig. 9a-b). The linearity synergistic effect with copper nanoparticles. In addition, the α-Fe2O3
obtained in Fig. 9a confirms that the assumption of the pseudo first support offered a large number of active sites which were prevented the

7
A. Elfiad, et al. Journal of Environmental Chemical Engineering 8 (2020) 104214

Fig. 9. (a) ln (At/A0) versus time for the reduction of 4-NP (b) At/A0 versus time for the reduction of 4-NP.

Cu nanoparticles from forming agglomerates, leading to the uniform
dispersion of the CuNPs which are responsible for the high catalytic
activity exhibited by Cu/α-Fe2O3 materials. Since, the lowest crystal-
lites size (calculate by XRD) and the smallest particle size (Table 2) of
the Cu-Fe catalysts facilitate the electron transfer and accelerate the
kinetic reaction.
It can be observed that the apparent rate constant (kapp) increases in
the order Kapp 5CF500 < Kapp 20CF500 < Kapp 20CF700, this classification
reveal that (i) No correlation between the specific surface area and the
catalytic activity. (ii) The highest catalytic activity was related to the
highest copper amount (copper %Wt) on hematite surface, which has
more available actives sites with appropriate surface areas. (iii) The
excellence catalytic performance directly correlated the pores radius
values (Table 3). As can be seen from Fig. S2, the rate constants increase
with the pores diameter of catalysts, these results indicated that the
highest pores values have the ability to accept the 4-nitrophenol mo-
lecules leading the high adsorption on catalyst surface. This is im-
portant since it is acknowledged that good adsorption is an important
step to accelerate the reaction kinetic and facilitate the 4-NP reduction.
As a result, it is wise comprehending that the pores diameter affects the
reduction reaction and the probability of acquiring the reaction not
only on the surface but also inside the mesopore structure.
The superior activity of 20CF700 compared to 20CF500 ascribes to
the copper ferrite CuFe2O4 (Fig. 2), which is more active in the re-
duction of 4-NP compared to single metal phase [68] due to the metal
ions distribution among tetrahedral and octahedral sites. The
octahedral sites expose metal cations on the surface and act as a
medium to transfer electrons from BH4− to 4-NP. In CuFe2O4 both
Cu2+ and Fe3+ are present, and the transfer of electron between Cu+-
Cu2+ and Fe2+-Fe3+ ion pairs, enhances its catalytic activity [69].Our
catalytic system has higher activity compared to noble metal catalysts
(Table 4). Moreover its synthesis is unexpensive and ecofriendly.
3.9. Catalysts recycle
All samples completely convert 4-NP to 4-AP and they are stable
within the first two runs (Fig. 11). After five cycles, the stability de-
creases and the conversions drop to 86.5 %, 88.7 %, 87.3 %, and 88.1 %
for α-Fe2O3, 5CF500, 20CF500, and 20CF700, respectively. We ascribe the
decrease to the loss of catalyst during washing and separation and/or
the aggregation and destruction of the sample's surface structure by
external forces, such as centrifugation, washing, and drying of the
catalyst during the successive recycling steps.
4. Conclusion
We synthesized α-Fe2O3 via a simple thermal treatment of natural
goethite. We supported Cu over hematite with impregnation at ambient
temperature. Cu amount influences the textural and structural propri-
eties of the catalyst, but all the samples were mesoporous. Cu/α-Fe2O3
is active in the 4-nitrophenol reduction (initial concentration of 5 mmol
L−1) to 4-aminophenol in the presence of NaBH4. The reaction

Table 4
Literature data on the reduction of 4-nitrophenol by NaBH4 over different catalysts.
Catalyst 4-NPconcentration Catalysts Times (min) Kapp reference

Ag 4 mM 0.5 g/l 30 0,47.10−3 s-1 [60]

Ag–Au 4 mM 0.5 g/l 4 3,8.10−3 s-1 [60]
RGS@AuNs 0.2 mmol 0.8 mg 5 15,01.10−3 s-1 [61]
Ag/iron oxide 7,95.10−5M 4.10−4g 35 0.305 min−1 [62]
Au/Fe3O4 1,10−3 M 0.49 mg 7 10.10−2 min-1 [63]
Pt/Fe2O3 5 mg 12 0.24mn−1 [64]
Cu 5mol.l−1 1mg 3,5 3,8.10−3mn-1 [65]
CuO 2.5 mM 5 mg 22 / [31]
Cu-Fe 10_4 mol L_1 4 mg L_1 5 0.69 min_1 [66]
Cu/graphene 1 mM 1 mg 6 / [28]
CuO/ɤ-Al2O3 4,3.10−5 mol/L 0.05 g 12 17,37.10−2 min1 [35]
CuO/ZnO 2.5 mM 5 mg 3 / [31]
Cu@Fe3O4 1.5 mM 0.5 mg.mL_1 0.66 0.047s−1 [67]
Cu1.3/Fe3O4 5 mM L_1 1 mg mL_1 3.5 0.71 min−1 [65]
5CF500 1mg 5 ×10−3 1.5 0.039 s−1 This work
20CF500 1mg 5 ×10−3 1.3 0.056 s−1 This work
20CF700 1mg 5 ×10−3 0.8 0.090 s−1 This work

8
A. Elfiad, et al. Journal of Environmental Chemical Engineering 8 (2020) 104214

Fig. 10. Scheme of the 4-NP reduction to 4AP by NaBH4.

Acknowledgements

The authors gratefully acknowledge the support of the Natural

Sciences and Engineering Research Council of Canada (NSERC). This
research was undertaken, in part, thanks to funding from the Canada
Research Chairs program.

Appendix A. Supplementary data

Supplementary material related to this article can be found, in the

online version, at doi:https://doi.org/10.1016/j.jece.2020.104214.

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