Applied Catalysis A, General 570 (2019) 120–129

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Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

Pd-Cu catalysts supported on anion exchange resin for the simultaneous T

catalytic reduction of nitrate ions and reductive dehalogenation of
organochlorinated pollutants from water
Corina Bradua,d, , Constantin Căpăţa, Florica Papab, Ligia Frunzac, Elena-Alina Olarua, Grégorio Crinid,
Nadia Morin-Crinid, Élise Euvrardd, Ioan Balintb, Irina Zgurac, Cornel Munteanub
a
University of Bucharest, PROTMED Research Centre, Splaiul Independenţei 91-95, sect. 5, 050107 Bucharest, Romania
b
Institute of Physical Chemistry of the Romanian Academy, 060021 Bucharest, Romania
c
National Institute of Materials Physics, 077125 Măgurele, Romania
d
Université de Bourgogne Franche-Comté, UMR 6249 Chrono-environnement usc INRA, UFR Sciences et Techniques, 25030 Besançon cedex, France

ARTICLE INFO ABSTRACT

Keywords: The present work proposes the simultaneous removal of these classes of pollutants by a catalytic hydrotreatment processes.
Pd-Cu catalyst For this purpose, bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu of 4:1) supported on macroporous strong base anion resin
Anion exchange resin were prepared by different methods. The catalysts were characterized (by XRD, SEM-EDX, XPS, AAS and H2
Nitrate reduction chemisorption) and tested in a continuous flow system. The selected catalyst preparation protocol consists in a two-step
Hydrodechlorination
method, which implies the deposition of palladium by ion exchange and the subsequent deposition of copper by controlled
Water treatment
reaction on the surface of the pre-reduced palladium. The ef-fectiveness of the catalyst in the simultaneous reduction of nitrate
and hydrodechlorination of 4-chlorophenol was demonstrated. By adjusting the initial pH and the flow rate of the aqueous
solution, nearly complete hy-drodechlorination of 4-chlorophenol can occur together with selective nitrate reduction at a
conversion of 95% and a selectivity to N2 of 92% (this value contains the contribution of all gaseous products, including the
eventually formed NOx). The bimetallic catalyst was found to remains relatively stable after 100 h of test time.

1. Introduction Organochlorine compounds are often characterized by high toxicity and

Nitrate ions and organochlorine compounds such as pesticides and their
degradation by-products are pollutants of concern found in nat-ural waters
originating mainly from agricultural areas [1].
The nitrogen cycle is altered by anthropogenic activities, particu-larly by
the intensive agricultural practices, which lead to a gradual increase of nitrate
ions concentration in natural water bodies. High concentration of nitrates in
surface water negatively affects aquatic ecosystems through its toxic effect on
aquatic fauna or by water eu-trophication. Excess nitrates in groundwater
(frequently used as a drinking water source) can lead to enhanced exposure of
human po-pulation being responsible for specific diseases such as
methemoglo-binemia and several types of cancer [2,3].
Contamination of natural waters by pesticide residues, especially
organochlorine compounds, also causes considerable concern. Despite their
usefulness in agriculture, pesticides may produce a wide range of toxic side
effects representing a potential hazard to the environment.
persistence, being designated as priority pollutants [4]. They are readily
bioaccumulated in aquatic and terrestrial organisms, being notorious for their
ability to biomagnify in the food chain.
Therefore, significant research efforts are devoted to the develop-ment of
practical methods which are able to effectively remove these pollutants from
natural waters, especially from those used as water supplies.
A series of physico-chemical and biological methods were devel-oped for
the elimination of nitrate ions from water. Among these, cat-alytic reduction
of nitrate is an attractive technique that would be suitable for water treatment
[5,6]. This method was reported for the first time by Vorlop and Take [7] and
presents several advantages. One of its major benefits is that no waste is
generated during the treatment process as in the case of ion exchange, reverse
osmosis or biological processes. Nevertheless, a crucial aspect remains the
catalyst selectivity issue because the presence of nitrite and ammonium ions
by-products is highly undesirable in drinking water.

Corresponding author at: University of Bucharest, PROTMED Research Centre, Splaiul Independenţei 91-95, sect. 5, 050107 Bucharest, Romania. E-mail address:
corina.bradu@g.unibuc.ro (C. Bradu).

https://doi.org/10.1016/j.apcata.2018.11.002
Received 5 August 2018; Received in revised form 29 October 2018; Accepted 2 November 2018
Available online 03 November 2018
0926-860X/ © 2018 Elsevier B.V. All rights reserved.
C. Bradu et al.
Great efforts are made in order to obtain catalyst with high activity and
selectivity towards nitrogen formation. The catalysts developed for this
purpose are mainly supported bimetallic systems based on noble metals such
as Pd, Pt, Rh and Ru, promoted especially with Cu, Sn and In [8–11]. Pd-Cu
is, by far, the most studied metallic pair for this ap-plication and offers
promising prospects [12]. Generally, Pd-Cu cata-lysts were found to have
higher activity and/or selectivity to nitrogen than Pd-Sn or Pd-In catalysts
[13,14]. However, several studies claim that Pd-Sn catalysts perform better
than the Pd-Cu ones [15,16].
The nature of the support is also important, playing a crucial role in the
activity and selectivity of the catalytic system. Various carriers have been
proposed, γ-Al2O3, SiO2, TiO2, hydrotalcite and carbonaceous materials
being among the most common ones [17–21]. Ion exchange resins have also
been considered promising support candidates. There is a relatively small
number of studies dedicated to the investigation of this type of carrier.
The use of ion exchange resins as catalyst carriers for the selective
reduction of nitrate was proposed by Gašparovičova et al. [22–24]. Both
cation and anion exchange resins were studied. Although the presence of the
acid sites of the cation exchange resin contributes to increase the selectivity
towards N2 of the Pd-Cu supported catalysts (e.g. from 20%, for a resin free
of acid sites, to 60%, for a resin with acid sites), Pd-Cu catalysts deposited on
anion exchange resin showed higher specific activity (e.g. 94% selectivity to
nitrogen at 61% nitrate conversion) [22,23]. The superior performances of the
catalysts sup-ported on anion exchange resin were attributed to the higher
mobility of the anions compared to cation exchange resin support. It was also
highlighted that the selectivity to nitrogen is higher on anion exchange resin
carriers than on γ-Al2O3 [24]. Comparable results were obtained by Neyertz
et al. (2010) for the reduction of nitrate ions on Pd-Cu/anion exchange resin,
at a more elevated concentration, 150 ppm NO3−-N (expressed as nitrogen
from nitrate) instead of the usually employed concentration of 22.6 ppm
NO3−- N (100 ppm NO3−). More recently, N2 selectivity of 100% for
complete nitrate conversion was claimed for bimetallic Pd-Cu catalyst
supported on anion exchange resin [25]. This notable performance was
achieved in a batch reactor with NO3− pre-viously retained on catalyst surface
by ionic exchange and then main-tained for 6 to 24 h under 6 bar H2/CO2
pressure (hydrogen partial pressure of 3 bar) at moderate temperature (298 K
and 333 K). The selective conversion of NO3− to N2 is explained by the fast
retention of the HO−, resulted in NO3− hydrogenation process, on the ion
exchange sites of the resin vacated by NO3− consumption during reaction
pro-gress. A 100% selectivity to nitrogen has never been reported pre-viously.
The only drawbacks of this method could be the demanding time or
temperature and pressure requirements in the regeneration step.
To the best of our knowledge, the catalytic liquid-phase reduction of
nitrate on bimetallic catalysts supported on ion exchange resin was so far
investigated in semi-batch or batch reactors and no studies have been
published on fixed-bed reactors operating in continuous flow.
With respect to organochlorine compounds in water, several methods like
adsorption or advanced oxidation processes have been proposed for their
removal [26,27]. An alternative approach might be their catalytic
hydrodechlorination which leads to less toxic organic compounds, thereby
reducing the ecotoxicity of the treated water. Noble metals, preponderantly
Pd, on various supports have been stu-died for the liquid phase
hydrodechlorination of organochlorine com-pounds from water such as
organochlorine pesticides, chlorophenols and chloroacetic acids [11,28–30].
Complete dehalogenation of mono-and poly-chlorinated organic compounds
in aqueous solution (e.g. chloroacetic acids and chlorophenols at 0.02 - 0.2
mM) has been achieved in the presence of palladium-based catalysts using
hydrogen under ambient temperature and pressure [29,31,32].
The studies reported in the literature dedicated to treatment of poly-
contaminated waters are scarce. Preliminary catalytic reduction tests with tri-
and tetra-chloroethylene added to a nitrate solution were
121
Applied Catalysis A, General 570 (2019) 120–129
performed by Centi and Perathoner [33]. They reported a conversion of 90%
for chlorinated compounds (no other information provided) and suggested the
possibility of simultaneous removal of nitrate and halo-genated compounds.
Several studies investigated the influence of ni-trate and other inorganic
anions on the aqueous phase reduction of organochlorine compounds with
zero-valent iron or with hydrogen in the presence of Pd supported catalysts
[34–38]. Different results re-garding the influence of nitrate on the
hydrodehalogenation of organic compounds on Pd/Al2O3 catalysts were
reported. It was found that, the presence of nitrate at moderate to high
concentrations (0.37–1.29 mM) had no effect on the hydrodechlorination rate
of trichloroethylene (0.031 mM) [37]. Other authors concluded that the
hydrodehalogena-tion of 1,2-dibromo-3-chloropropane (0.018 mM) was
strongly affected by the presence of 0.45 mM nitrate, which lowered the
conversion of halogenated compounds with about 50% [38]. The absence of
any ef-fect of NO3− on trichloroethylene dehalogenation was explained by
the lack of activity of monometallic palladium catalyst on nitrate reduction
(no nitrate conversion). In contrast, in the study of hydrodehalogena-tion of
1,2-dibromo-3-chloropropane, 90% of NO3− was removed.
This work assesses the effectiveness of catalytic hydrotreatment process
for simultaneous removal of nitrate and 4-chlorophenol in aqueous solution.
For this purpose, bimetallic Pd-Cu catalysts supported on macroporous strong
base anion resin were prepared by different methods, characterized and tested
using a continuous flow system. The reasons for choosing anion exchange
resin as support are: (i) to ensure a high dispersion and controlled distribution
of the active components; (ii) to enable the NO3− internal diffusion.
2. Experimental
2.1. Bimetallic Pd-Cu catalyst synthesis
In this work, a series of bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu
of 4:1) supported on an anion exchange resin was prepared. The synthesis of
bimetal-resin catalysts was carried out via two main routes:
(i) introduction of both metals by ion exchange with the functional groups of
the resin; (ii) introduction of palladium by ion exchange and subsequent
deposition of copper by controlled surface reaction. The carrier was a
commercial anion exchange resin, A-520E Purolite, having poly-(styrene di-
vinyl benzene) matrix (S-DVB) with quaternary am-monium functional
groups (-CH2-N(CH3)3+) (ion exchange capacity of 2.8 molc kg−1; ionic
form: Cl−) and a macroporous texture (average pore size 50 nm), kindly
provided by Purolite Romania.
For the ion exchange route, the metal precursors were tetra-
chloropalladate(II) and tetrachlorocuprate(II) complexes (Reaction 1). The
precursor solutions were obtained by dissolution of PdCl2 (p.a. – Fluka) and
CuCl2·2H2O (p.a. – AppliChem) in a HCl solution (0.1–8.0 mM). The copper
deposition was carried out simultaneously or following palladium deposition.
The obtained catalysts are denoted as PdCu-1 and PdCu-2 respectively (Table
1). For the simultaneous de-position method, the dried A520E resin in the Cl−
ionic form (for 24 h, at 50 °C) was contacted with a solution containing both
metal pre-cursors and maintained under continuous mixing (GFL Test Tube
Rotator 3025, at 15 rpm) for 0.5–24 h. The reduction of metals previously re-
tained on the resin by ion exchange was achieved using a solution of sodium
formate (1.5 M) (contact time of 0.5 h, at 50 °C). Finally, the obtained
catalyst was washed with demineralized water until the complete elimination
of residual Cl− and HCOO− ions (verified through ion chromatography). In
the case of successive metal deposi-tion by ion exchange, an intermediate
reduction step with HCOONa was realised between the palladium and the
copper retention stages (Table 1).
2(S-DVB)-N(CH3)3+Cl− + [MCl4]2− → [(S-DVB)-N
(CH3)3+]2[MCl4]2− + 2Cl− (1)
C. Bradu et al. Applied Catalysis A, General 570 (2019) 120–129

Table 1
− − −1
Synthetized Pd-Cu/anionic resin catalysts and their performance in the reduction of NO 3 (Preliminary tests: NO3 initial concentration = 300 mg·L ; solution flowrate = 1.0
−1 −1
mL·min ; H2 flow rate = 25 mL·min , pHi = 6.0).
Catalyst, notation Metal deposition Metal amount, %** NO3− convertion,
%
First stage* Second stage* Pd Cu

Pd-0 Pd – ion exchange – 2.01 – 13.9

PdCu-1 Pd & Cu – ion exchange – 1.97 0.45 14.7
PdCu-2 Pd – ion exchange Cu – ion exchange 1.98 0.48 32.5
PdCu-3 Pd – ion exchange Cu – controlled surface reaction 2.01 0.49 48.8

* followed by reduction with HCOONa.

** by AAS.

where M = Pd or Cu Quanta 3D FEG model, operating at 20 kV, equipped with an energy

The second preparation route consisted in a controlled surface re-action in
which copper ions were reduced by the hydrogen adsorbed on the pre-reduced
Pd surface. (Reaction 2) [39]. Thus, after the retention of palladium by ion
exchange and its reduction with sodium formate (stages described in the
precedent protocol), a Cu(NO3)2 solution ([Cu (NO3)2] = 3.0 g·L−1, pH < 3)
was contacted with the monometallic precursor for 0.5 h. at 50 °C. The
obtained catalyst, denoted as PdCu-3 (Table 1), was washed with
demineralized water until the complete elimination of residual NO3−, Cl− and
HCOO− ions (verified through
ion chromatography).
2Pd-H + Cu2+ → Pd2Cu + 2H+
The theoretical concentration of Pd and Cu in the bimetallic cata-lysts was
2% and 0.5%, respectively. Monometallic catalyst with 2% Pd (denominated
Pd-0) was also prepared for comparison.
dispersive X-ray (EDS) spectrometer, Apollo X. The analyses were per-
formed in high vacuum mode, with Everhart–Thornley secondary electron
(SE) detector. The preparation of the samples was minimal and consisted in
immobilizing the beads on a double-sided carbon tape, without coating.
2.3. Experimental setup and analytical methods
The catalytic reduction tests were carried out at room temperature
(21.0 ± 1.0 °C) in a continuous flow system with a fixed bed reactor (trickle
(2) bed reactor) containing 0.4 g catalyst (1cm3 bulk expanded volume). The
aqueous solution circulates at the flow rate of 0.25 to 1.0 mL·min−1,
concurrently with the gas flow (25 mL·min−1). The in-itial concentrations of
nitrate and 4-chlorophenol (4-CP) were 100 mg·L−1 and 50 mg· L−1

respectively. For the preliminary tests, a concentration of 300 mg L−1 NO3−

2.2. Catalyst characterization
The exposed Pd surface area on resin was estimated by H2 chemi-sorption
at 25 °C using a ChemBet-3000 Quantachrome Instrument equipped with a
thermal conductivity detector (TCD). Before the H2 chemisorption
measurements, the catalysts were reduced with H2 at 70 °C for 1 h then
cooled to room temperature under Ar flow to remove the adsorbed H2 on the
catalyst surface.
Atomic absorption spectrometry (AAS) was used to determine the metal
loading on catalysts. A Thermo Elemental, Solaar M5 atomic ab-sorption
spectrometer with flame atomizer was used in absorption mode (measuring
time = 4 s; air : acetylene flow = 1.2 L·min−1; bandwidth = 0.5 nm;
background - D2 Quadline lamp). For the ana-lysis, the samples were digested
in a microwave digester (Ethos Sel, Milestone) using a mixture of hydrogen
peroxide and HNO3 : HCl (3:1).
The crystalline structure of the active phase constituents was ana-lysed
with D8 Advance Bruker-AXS diffractometer using Cu Kα radiation (k = 1.54
Å). The diffraction patterns were recorded in the 2Ɵ = 30 −135° domain. The
average crystallite size was calculated from peak broadening by using a
Lorentzian function to fit the peak shapes.
was used. The pH correction (when necessary) was achieved using an
adequate NaNO3/HNO3 ratio (total NO3− concentration was maintained at
100 mg ·L−1). Prior steady-state establishment, the elimination of nitrate ions
from solution takes place both by ion exchange and catalytic reduction
pathways as suggested in Fig. 1.
The same experimental setup was employed to evaluate the reten-tion of
4-CP onto catalyst (by adsorption or by ion-exchange). The re-tention tests
were performed in Ar flow (25 mL·min−1) for different pH values.
The removal of nitrate, the formation of nitrite and ammonia, and the
release of the chloride anion by the anion exchange resin were quantified
through ion chromatography. The analyses were performed on a Dionex ICS-
900 apparatus equipped with a conductivity detector and anion or cation
suppressors. An AMMS 300 column was used for the anionic species. The
mobile phase was a solution of mixed sodium carbonate and sodium acid
carbonate flowing with 1 mL·min−1. For ammonia, a CMMS 300 column and
a solution of methanesulfonic acid as mobile phase were used. The
selectivities to nitrite, ammonium and molecular nitrogen were calculated by
the equations below:

X-ray photoelectron spectroscopy (XPS) measurements were carried out,

using a SPECS photoelectron spectrometer with a PHOIBOS 150 analyser, to
determine the chemical state of the active components in the synthesized
catalysts. The X-ray source, XR-50, operates on an Al anode (hν = 1486.7
eV) at 300 W, 24 mA and 12.5 kV. The acquisition was made with a pass
energy of 10 eV for individual spectra and 50 eV for the extended ones. The
samples were deposited on a silicon sub-strate, and a flood gun system was
used for neutralization of the sample charging. The C 1s line of the support
was used as standard for internal calibration. The data were fitted with Voigt
functions using SCF 2.3 software.

The distribution of the metals on the resin surface was evaluated by

Scanning Electron Microscopy coupled with Energy-dispersive X-ray Fig. 1. Schematic representation of nitrate removal over Pd-Cu/anionic resin catalysts.
spectroscopy (SEM-EDX), using a high-resolution microscope, FEI

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C. Bradu et al. Applied Catalysis A, General 570 (2019) 120–129

Fig. 2. Dependence of copper retention onto A520E resin on HCl concentration in precursor solution ([Cu] = 1.3 g·L −1).

S −=
n −
NO 2 t
NO2 x100 (at λ = 275 nm) and Zorbax SB-C18 column. The mobile phase was a
n − −n −
NO3 0 NO3 t (3) mixture of phosphate buffer solution (20 mM)/acetonitrile, with a ratio
n of 50/50, flowing with 1.2 mL/min.
+
NH4 t Chromatographic analyses were performed in duplicate. The con-
SNH+ = x100
4
n −
NO3 0
−n −
NO3 t (4) versions and selecvities were calculated using mean values of NO3−,
NO2− and NH4+ concentration in 5 aliquots collected in 2.5 h of time
S N = 100 − (SNO − + SNH+) (5) interval. An exception was made for the endurance test where the va-
2 2 4
lues were calculated for periods of 5 h (average calculated from 10
where nNO3−0 is the initial amount of nitrate (mmol) andnNO3−t , nNO 2−t and consecutive aliquots). Typical investigated steady-state period was 6 h
nNH4+t are the amounts of nitrate, nitrite and ammonium at the time t and 86 h for the endurance test. Also, three selected experiments were
(mmol). The selectivity to nitrogen was calculated by equation (5). The performed twice in order to verify the reproducibility. According with
SN2 value contains the contribution of all gaseous products, which our calculation, the relative uncertainty lies between 0.6% and 1.3% for
eventually are formed beside N2 (i.e. N2O or NO). This is considered −
NO3 and 4-CP conversions and between 0.9%–3.4% for the selectiv-
reasonable assumption since the NOx intermediates generated in the ities to nitrogen species.
reduction of nitrate (Reactions 3–9) on Pd-based catalysts (Pd, Pd-Cu, For the hydrodechlorination of 4-CP, the carbon mass balance of the
Pd-In) have been often reported to have negligible small concentration reaction was closed to > 95%. Total N mass balance cannot be calcu-
in the gas phase [25,40–45]. For bimetallic Cu-Pd catalysts with atomic lated since gaseous nitrogen species were not assessed.
ratio Pd/Cu = 0.25, the selectivity to N2O in the hydrogenation of ni- The Pd and Cu leaching, during the experiments was evaluated
trate or nitrite was significantly increased as reported by Nakamura through inductively coupled plasma mass spectrometry (ICP-MS)
et al. [46]. However, in the presence of bimetallic Pd-Cu catalyst with measurements, using a Thermo Fisher Scientific X Series 2 system II with
atomic ratio Pd/Cu ≥ 1, it is probable that N2O produced is rapidly an ESI-SC2 DX fast bundle autosampler. The analysis reliability was
reduced to nitrogen as suggested in [45] which could explain the low or assessed with certified reference materials (drinking water ERM-
undetectable concentration of N2O. Regarding the nitric oxide, its CA011b, European Reference Materials) and was within 10% of the
presence was evidenced exclusively in the adsorbed form [42,44]. certified values.
Nevertheless, the presence in our outlet gas of other nitrogen species
beside N2 cannot be ruled out completely. So, the calculated SN2 could
3. Results and discussion
be more precisely defined as selectivity to nitrogen gaseous species

NO3− + H2 → NO2− + H2O (6) 3.1. Catalyst preparation

2 NO2− + H2 → 2 NO + 2 HO− (7) It was found that immobilization of metals by ion exchange onto the
2 NO + H2 → N2O + H2O (8) resin depends on acidity of precursor solutions. The effect of the HCl
concentration on the metal retention from precursor solution was sig-
2 NO + 5 H2 → 2 NH4+ + 2 HO− (9) nificant in the case of copper. As an example, for Cu2+ solutions of
N2O + H2 → N2 + H2O (10) 1.3 g·L−1, the HCl concentration was varied from 0.5 to 8.0 M. The
maximum copper retention was obtained for HCl 6.0 M (see Fig. 2).
2 NO2− + 3 H2 → N2 + 2 H2O + 2 HO− (11) This outcome might be explained by the interplay of two phenomena:
− + − (i) dependence of [CuCl4]2− complex formation on the concentration of
NO2 + 3 H2 → NH4 + 2 HO (12) chloride ions; (ii) competition between [CuCl4]2− and Cl− for the ex-
The concentrations of 4-chlorophenol and phenol (identified as the change sites of resin. Thus, low concentrations of HCl may be in-
only hydrodechlorination reaction product) were measured using a sufficient for the formation and stabilization of the [CuCl4]2− complex
Varian ProStar liquid chromatograph equipped with an UV-VIS detector [47], while an excessive Cl− concentration would limit the retention of

123
C. Bradu et al.
Fig. 3. Micro-photos of Pd deposition on A520E spherical beads: (a) [HCl] = 0.3 M, contact time of 0.5 h; (b) [HCl] = 0.5 M, contact time of 1 h; (c) [HCl] = 2.0 M, contact time of 24
h. (complete retention of palladium on the ion exchange resin).
[CuCl4]2− on the ion exchange sites due to the competition between the two
anions.
The amount of Pd deposited onto resin was only slightly affected by the
HCl concentration (data not shown). However, the variation the HCl
concentration from 0.1 to 6.0 M and/or the contact time between pre-cursor
solution and anionic resin (0.5–24 h), induced changes in Pd radial
distribution. Thus, peripheral to uniform distribution of palla-dium could be
obtained, as illustrated in Fig. 3. We have chosen a broad shell distribution of
metal (see Fig. 3b) because it is a convenient compromise between an optimal
use of the support and minimization of mass-transport phenomena, which is
an important factor in NH4+ for-mation mechanism [19].
It is worth mentioning that copper retention from the Cu(NO3)2 solution
on the palladium monometallic catalyst was complete by controlled surface
reaction. It can be safely assumed that the Cu de-position occurred on pre-
reduced Pd surface (see catalyst character-isation).
3.2. Preliminary tests
The catalysts prepared as afore mentioned, were subjected to pre-liminary
tests for nitrate reduction. In the beginning, the removal of nitrate ions takes
place both by ion exchange and catalytic reduction pathways (Fig. 1). After a
period of 390–520 minutes, depending on the catalyst, the steady-state was
attained, and the elimination of nitrate ions can be assumed to take place only
by catalytic reduction process. The nitrate removal degree calculated at
steady-state for PdCu-1, PdCu-2 and PdCu-3 bimetallic catalysts as well as
for Pd-0 monometallic reference, is present in Table 1.
It is generally accepted that copper acts as a promoter in the first reaction
step consisting in nitrate conversion to nitrite [21,48,49]. As expected, all
bimetallic Pd-Cu catalysts lead to higher nitrate conver-sion than the
monometallic Pd catalyst (Table 1). Comparing the bi-metallic catalysts, it
can be observed that the second metal deposition procedure strongly affect
catalyst performance. Higher nitrate removal was obtained for the catalyst
prepared by deposition of copper by controlled surface reaction on the pre-
reduced palladium, PdCu-3. This might be the result of a better contact
between the two metals achieved in the case of PdCu-3, as compared to
catalyst in which cooper was introduced by ion exchange, especially to PdCu-
1 prepared by si-multaneous deposition of cooper and palladium.
Assuming that cooper is oxidized during redox conversion of nitrate to
nitrite and then subsequently reduced by palladium activated hy-drogen
(Reactions 10 and 11), a close contact Pd-Cu is required to enable the
hydrogen spill-over from noble metal to promoter [49,50]. These results are in
agreement with those obtained by Neyertz et al. (2010), who found a higher
nitrate conversion for resin supported Pd-Cu catalyst prepared by controlled
surface deposition of copper, as compared to Pd-Cu catalyst obtained by ion
exchange. A two-step method was also considered more favourable for the
preparation of Pd-Cu/Al2O3 catalysts versus a single step procedure as higher
selectivity
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Applied Catalysis A, General 570 (2019) 120–129
to nitrogen was obtained [12]. However, Gašparovičová et al. [22] obtained a
more active catalyst by simultaneous deposition of Pd and Cu onto cation
exchange resin, as compared to a successive deposition method.
NO3− + 2Cu ⇆ Cu2O + NO2− (13)
Cu2O + 2Pd-H ⇆ 2 CuPd + H2O (14)
Based on the results obtained in terms of nitrate removal degree, PdCu-3
was selected for further investigations.
3.3. Catalyst characterization
It is expected that selected deposition protocol ensures a good dis-persion
of the metal onto support. To verify this assumption, catalysts with higher
metal contents were prepared (palladium up to 7%, keeping similar Pd-Cu
ratio). The palladium crystallite dimension cal-culated from the XRD
diffractograms was around 7 nm for the bime-tallic PdCu-3 catalyst (2% Pd).
Increasing palladium content to 4% and 7%, the crystallite average size
remains practically unchanged (Table 2). This reveals a suitable dispersion of
palladium deposited through the ion exchange method.
It should be noted that the XRD diffraction pattern of Pd-Cu cata-lysts
showed only the main characteristic peaks of palladium metal with face-
centered-cubic structure. The characteristic diffraction lines of copper could
not be observed (Fig. 4). The low crystallinity of the cooper phase is a
pertinent explanation for the absence of XRD dif-fraction lines [51].
The PdCu-3 diffractogram does not provide any information re-garding a
possible Pd-Cu interaction, but the calculated lattice para-meter (Table 2)
allowed us to assume that the formation of a Pd-Cu alloy is possible. Thus, an
average composition of the nanocrystals calculated from XRD data according
to Vegard's law:
aalloy = x·aPd +(1 − x)aCu
where a represents the lattice constant (aPd = 3.8907 Å, aCu = 3.6149 Å) and
x is the fraction of the element was found to be
Pd Cu .
98.8 1.2
The chemisorption of H2 was used to asses Pd qualitatively and
quantitatively on monometallic and bimetallic catalysts (H2 is adsorbed
selectively only by the exposed Pd sites). The stoichiometry of the
Table 2
Lattice parameter and crystallite size of palladium in the bimetallic Pd-Cu catalyst with
different metal load.
Palladium content, % Lattice parameter a, Å Crystallite size,
( ± 0.0005) nm
( ± 0.5)
2 3.8875 7.4
4 3.8894 7.1
7 3.8908 7.3
C. Bradu et al. Applied Catalysis A, General 570 (2019) 120–129

Fig. 4. XRD pattern of bimetallic Pd-Cu catalyst with different metal load.

Fig. 5. SEM-EDX analysis of PdCu-3 catalyst.

adsorption H:Pd atoms was assumed to be 1:1 [52]. The H2 chemi-sorption
also reveals a good dispersion of palladium. The surface area of exposed
palladium for the monometallic catalyst (Pd-0) is around 2.37 m2·g−1 but
decreases to 1.15 m2·g−1 for the bimetallic PdCu-3 catalyst. The explanation
in exposed metal surface area is that Pd sur-face became partially covered
with copper phase. This result is sup-ported by SEM-EDX investigations. The
bimetallic catalyst of choice (PdCu-3) was analysed by Scanning Electron
Microscopy and the metals were mapped on the cross section of the catalyst
beads by Energy-dis-persive X-ray spectroscopy (Fig. 5). The palladium
mapping shows that the metal is generally well distributed in a broad shell,
with a higher density of particles on the outer part and no visible
agglomeration as a
result of the selected preparation protocol. The copper deposited in the second
stage by catalytic reduction follows the same pattern as the first metal,
confirming thus the deposition of copper on the palladium sur-face.
The composition and chemical state of the catalytic active phase of PdCu-
3 was also evaluated by XPS. In the region of Pd3d, well sepa-rated spin-orbit
components ( = 5.26 eV) are present, that were also found in the spectra of
our samples. The XPS spectra are shown in Fig. 6, together with the results of
their decomposition into components using Voigt functions. The curve fitting
shows that Pd3d spectra of the samples consist of two main doublets
characteristic for palladium atoms in different oxidation states. The Pd in
metallic state, with binding

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Fig. 6. Position of the binding energy for deconvoluted XPS peaks of (a) Pd3d5/2 and Pd3d3/2 core level and (b) Cu2p3/2 core level for PdCu-3 catalyst: fresh (up) and after the
endurance test (down).

energy (BE) at 335.0–335.3 eV, was the predominant component (≈ 86%)

[53,54]. The position of the 337.0–337.4 eV band in the Pd3d5/2 region is
indicative of Pd2+. This BE value is intermediate between those of PdO and
of PdCl2 reported in the literature [54–56].
It is probable that palladium reduction is not complete, and a small part of
the metal subsists in the chloride form. The spectrum of, [PdCl4]2− precursor
retained by ion exchange on resin shows in Pd3d5/ 2 region a characteristic
BE band at 337.2 eV (SI, Fig. S1). The surface oxidation of the palladium in
contact with air during drying and storage of the catalyst cannot be fully
excluded. The presence of Pd2+-Pd° mixture might have a beneficial
contribution in the hydrodechlorina-tion process. It was reported that both
electro-deficient and zero-valent species are required for the
hydrodechlorination of the organic chlori-nated compounds [32].

Cu2p3/2 binding energies are located near 932.5 eV (Fig. 7b). Al-though
the multivalent state of Cu complicates the discrimination be-tween distinct
Cu species, the deconvoluted peak located at 932.1 eV is close to metallic Cu°
state but can be also attributed to Cu+ in Cu2O (932 eV). The satellites
characteristic for the 2+ oxidation state cannot be well distinguished (XPS
Fig. 7. The evolution of the nitrate, nitrite, ammonium and chloride ions concentrations
spectra of Cu for binding energy in the range of 920–980 eV are presented in
SI, Fig. S2). Therefore, it can be said that copper is preponderantly found in during the hydrotreatment process (NO3− initial concentration = 100 mg·L−1; solution
flow rate of 1.0 mL·min−1; H2 pressure of 1 atm; pHi 6.1).
metallic state and/or as Cu+ [20]. Unfortunately, the Auger CuLMM spectrum
could not be used to discriminate between different oxidation states of copper
due to its very poor resolution.
processes. After this period, NO3− concentration gradually increased reaching
a plateau at 30 mg L−1 when the ion-exchange sites have been exhausted (as
can be deduced from the drop of Cl− concentration of effluent). The dynamic
3.4. Catalytic tests of the nitrite concentration followed a similar trend which is consistent with
the partial retention of NO2− on the resin sites. Since the NH4+ was not
3.4.1. Nitrate reduction retained on the resin, its equilibrium concentration in the effluent was more
The selected catalyst (PdCu-3) was firstly tested for nitrate reduc-tion rapidly established compared to NO3− and NO2−. The steady-state was
reaction. A first experiment was carried out at nitrate solution flow rate of 1.0 attained, after the complete displacement of Cl− from the ion-exchange
mL·min−1 (without pH correction) and H2 pressure of 1 atm. As can be centres of the resin by NO3−, when the removal of nitrate underwent only by
observed from Fig. 7, the nitrate was completely removed within the first 6 h catalytic re-duction. After the steady-state was reached, the conversion of
of experiment. The complete elimination of NO3− was achieved through nitrate
combined ion-exchange and catalytic reduction

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C. Bradu et al. Applied Catalysis A, General 570 (2019) 120–129

pressure was not anymore considered as an effective strategy in our case.

The negative influence of high pH values on the selectivity toward N2 is

well known [6]. The pH control is classically achieved by addition of strong
acids, such as HCl, by bubbling CO2, or by using formic acid both as
reductant and in situ source of CO2 [16,49,58,59]. Catalysts containing acid
sites, like carboxylic group, are also proposed to pre-vent the excessive
increase of pH during the reaction [22,60]. Ac-cording to the literature data, it
is recommended to maintain the pH in the range of 5.0–6.0, which is true for
batch systems [16,18,57,58]. In a continuous flow system, a gradient of pH is
generated along the cata-lytic bed. Thus, the experiments were started with
more acidic solutions (initial pH of 2.7–3.1). In order to limit the number of
anionic species competing for the sites of ion exchanging resin carrier, the pH
correc-tion was realized by conveniently adjusting the NaNO3/HNO3 ratio
(the total NO3− concentration was kept at 100 mg ·L−1). The conversion
values measured in this case are similar with those obtained for a so-lution
with initial pH of 6.1. Moreover, the selectivity to the molecular nitrogen was
higher, increasing up to 93% (Table 3).
Fig. 8. Flow rate influence on the conversion and selectivity of the nitrate re-duction on
− −1
PdCu-3 (NO3 initial concentration = 100 mg·L ; H2 pressure of 1 atm; pHi 6.1).

3.4.2. Hydrodechlorination of 4-chlorophenol

was established at around 70%. As expected, the increase of contact time by
lowering the flow rate of the aqueous solution lead to aug-mentation in nitrate
conversion (Fig. 8). The conversion of NO3− was higher than 93% for a flow
rate of 0.50 mL·min−1 and 100% at 0.25 mL·min−1. There was also an
enhancement of selectivity towards molecular nitrogen from 49% to 65%, due
to the further reduction of nitrite intermediate. In contrast, the undesired
increase of selectivity to ammonium from 19% to 32% was observed.
Literature data reveal that the selectivity of catalytic nitrate re-duction
strongly depends on pH and on hydrogen pressure, which correlates with its
solubility in the aqueous solution [39,50]. Lowering the hydrogen pressure is
typically achieved by diluting H2 either with N2 or CO2 [10,40]. The use of
carbon dioxide contributes also to pH adjustment by acting as a buffer,
avoiding thus the pH increase due to hydroxide ions formation (Reactions
4,6,8 and 9). Generally, it was observed that ammonia generation is hindered
at low hydrogen pres-sure [57].
Thus, to limit the formation of ammonium, the hydrogen partial pressure
was lowered to 0.50 and 0.25 atm by dilution with Ar (we avoided using N 2
which is a reaction product). The nitrate solution flow rate for these catalytic
tests was 0.5 mL·min−1. In these experimental conditions, a reduction in
ammonium selectivity could be observed, but the gain in nitrogen selectivity
is not significant, since the selectivity to nitrite increases as well (Table 3).
Moreover, the conversion drops with 14–23%, when the hydrogen pressure
was reduced to 0.50 and 0.25 atm, respectively. Consequently, the reduction
of hydrogen partial
Table 3
Influence of H2 partial pressure and pH on catalyst performances. (For the H2 partial
pressure tests, the initial pH was 6.1; For pH tests, the H2 pressure was of 1 atm; Nitrate
solution flowrate was 0.5 mL·min−1 for all tests).
The 4-chlorophenol (4-CP) was chosen as a model pollutant for
hydrodechlorination reaction due to its simple molecular structure and the
large number of studies reported on the phenolic compounds. In addition, 4-
CP is frequently present in the anthropic impacted sites being a degradation
product of a series of pesticides such as 2,4-di-chlorophenoxiacetic acid and
pentachlorophenol [61–63].
The S-DVB polymer is a good sorbent for phenols in water and it finds
some applications in this field [64]. Moreover, phenols retention by ion
exchange on the functional groups of the resin could be ex-pected. Indeed,
retention tests performed for 4-CP (50 mg ·L−1), at different pH values show
that the chlorinated phenol could be retained on the A520E resin both by
sorption on the S-DVB matrix and by ion exchange mechanism, depending on
the solution pH. As can be seen in Fig. 9, a more important retention of 4-CP
accompanied by chloride release from the resin ion exchange centres is
obtained at pH of 9.8, as compared to the pH of 5.9. It can be assumed that
sorption on the S-DVB matrix is the predominant route of 4-CP retention at
pH below the pKa of the organic molecule (pKa 4-CP = 9.41), while at pH
above the pKa, retention of 4-CP occurs in an increased proportion through
ion exchange. Anyway, considering that the present experiments are per-
formed in acidic medium (selected condition: 3.1 < pH < 7.7), the retention of
4-CP and/or phenol resulted in the hydrodechlorination process (pKa phenol =
9.95) takes place preponderantly by sorption.
The 4-CP hydrodechlorination tests performed with PdCu-3 catalyst
revealed its high efficiency for this reaction. Complete conversion of 4-CP to
phenol (the only reaction product) was obtained for the para-meters selected
for the nitrate reduction process (aqueous solution flow rate of 0.5 mL·min−1,
initial pH of 3.1 and H2 pression of 1 atm). The conversion of the 4-CP was
evaluated for a time longer than 800 min, after the end of the sorption
process. The reaction advancement fol-lowed the calculation of carbon mass
balance.

Parameters Conversion, % Selectivity, %

3.4.3. Simultaneous removal of nitrate and of 4-chlorophenol
Further the PdCu-3 catalyst was tested for simultaneous reduction of
NO2− NH4+ N2 NO3− and dehalogenation of 4-CP under the previously selected con-
ditions. After the steady-state has been reached, the conversion of 4-CP
pH2, atm and that of NO3− are of 97% and 93% respectively, while the selectivity
1.00 93.5 15.8 20.3 63.9
0.50 79.2 18.1 16.9 65.0 to nitrogen of 90% is slightly smaller than for the simple nitrate re-
0.25 69.7 18.3 12.0 69.7 duction process. This small decrease could be assigned to the compe-
pHi/pHf * tition between nitrite ions and 4-CP for the active sites of monometallic
6.1/10.9 93.5 15.8 20.4 63.8 palladium.
3.1/8.7 94.4 1.1 6.1 92.8
2.7/4.1 87.5 1.1 8.8 90.1
Fine tuning of the experimental parameters, aqueous solution flow
rate and pH, led to the improvement of hydrotreatment process per-
* - pHi – initial pH (of the nitrate solution); pHf – final pH (of the treated formances Thus, for an initial pH of 2.9 and a flow rate of
solution). 0.4 mL·min−1, the nitrate conversion reached 95% with a selectivity to

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C. Bradu et al. Applied Catalysis A, General 570 (2019) 120–129

−1 −1
Fig. 9. Time dependence of 4-CP retention on PdCu-3: at pHi 5.9 (a); and 9.8 (b) ([4-CP] = 50 mg·L ; solution flow rate of 0.5 mL·min ; Ar pressure of 1 atm).

total). Insignificant leaching of palladium was found, the global loss is

estimated at less than 0.02% of the amount contained by the fresh
catalyst. As expected, the copper leaching was higher, especially in the
first ten hours. The maximal concentration of copper in treated water
was of 5.8 μg·L−1. However, the amount of leached copper did not
exceed 0.3% of the initial amount.
Furthermore, the XPS analysis revealed that there are no significant
differences between palladium spectra of fresh and spent catalyst. An
additional contribution situated at 935.7 eV was detected for the used
catalyst as compared to the fresh sample (Fig. 6). This value is a bit far
from the BE for CuO: The corresponding species might be copper hy-
droxide. The presence of Cu2+ in the used catalyst is in agreement with
the role expected for metallic copper in the nitrate reduction [50].

4. Conclusion

Fig. 10. Catalytic performance of PdCu-3 for simultaneous removal of nitrate It was found that the performances of the bimetallic Pd-Cu catalyst
and 4-CP ([NO3−] = 100 mg·L−1 [4-CP] = 50 mg·L−1; pHi of 2.9; solution flow supported on S-DVB anion exchange resin in the selective reduction of
rate of 0.4 mL·min−1; H2 pressure of 1 atm). nitrate strongly depend on the second metal deposition procedure. The
selected preparation protocol consisted in a two-step method, implying
Table 4 the deposition of palladium by ion exchange and the subsequent de-
Endurances tests ([NO3−] = 100 mg·L−1 [4-CP] = 50 mg·L−1; pHi of 2.9; so- position of copper by controlled reaction on the surface of the pre-re-
−1
lution flow rate of 0.4 mL·min ; H2 pressure of 1 atm). duced palladium. This protocol allowed a controlled deposition of
Time, h 15-20 95-100 metals on the support assuring: (i) a good dispersion of Pd (confirmed
by XRD and H2 chemisorption); (ii) controlled radial distribution of
− −1
NO3 –N, mg·L 1.11 2.20 metals in the resin bead (confirmed by SEM-EDX) and (iii) suitable
NO2− –N, mg·L−1 0.47 0.64 proximity between Pd and Cu (confirmed by SEM-EDX and H2 chemi-
NH4+ –N, mg·L−1 1.15 1.42
NO3− conversion, % 95.1 90.2 sorption). The catalyst obtained through this method, PdCu-3 shows
N2 selectivity, % 92.5 89.9 high nitrate removal degree and high selectivity in the reduction of
4-CP, mg·L−1 0.69 0.85 NO3− to gaseous nitrogen.
4-CP conversion, % 98.6 98.3 The effectiveness of the PdCu-3 catalyst in the simultaneous re-
duction of nitrate and hydrodechlorination of 4-CP was demonstrated
as well. Nearly complete hydrodechlorination of 4-CP can be achieved
nitrogen of 93% and the conversion of 4-CP was 99% (Fig. 10 and
simultaneously with selective nitrate reduction at a conversion of 95%
Table 4).
and a selectivity to N2 of 92% (calculated disregarding NOx contribu-
tion), by adjusting the initial pH and the flow rate of the aqueous so-
3.4.4. Catalyst stability lution.
Endurance test was performed to assess the catalyst stability. It can The PdCu-3 catalyst was found to be relatively stable for 100 h of
be observed that after 100 h of running, the catalyst performances, in running. The conversion of nitrate decreasing slightly from 95% to
terms of nitrate conversion and selectivity toward nitrogen, are little 90%, while the conversion of 4-CP seems to be unaffected. Moreover, it
affected (Table 4). The conversion diminished only with 5%, and the is noteworthy that the metals leaching was insignificant for Pd and
selectivity to N2 with less than 3%. Regarding the hydrodechlorination, moderate for Cu.
the conversion of 4-CP remains unaffected. Considering the promising results obtained in this work the next
`The amount of metals leached from the catalyst during the re- planned research step will consist of testing our proof concept for real
ductive treatment process was also evaluated. The Pd and Cu con- waters at laboratory scale as well as at pilot scale.
centrations were measured at different time intervals (10 samples in

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C. Bradu et al.
Acknowledgement
The authors thank the Executive Agency for Higher Education, Research,
Development and Innovation Funding of Romania (UEFISCDI) for the
financial support under the PNII Project No. 100/ 2012.
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.apcata.2018.11.002.
References
[1] C. Ravier, L. Prost, M.H. Jeuffroy, A. Wezel, L. Paravano, R. Reau, Land use policy 42
(2015) 131–140.
[2] N.S. Bryan, H. van Grinsven, The Role of Nitrate in Human Health, in: D.L. Sparks (Ed.),
Advances in Agronomy, Vol. 119 Academic Press Elsevier, 2013, pp.
154–176.
[3] D.M. Klurfield, N.S. Bryan, J. Loscalzo (Eds.), Nitrite and Nitrate in Human Health and
Disease. Nutrition and Health, Humana Press, Cham, 2017, pp. 311–336.
[4] List of Priority Substances in the Field of Water Policy- Annex II of the Directive
2008/105/EC, (2008) (Accessed 14 November 2017), http://eur-lex.europa.eu/ legal-
content/EN/TXT/HTML/?uri=CELEX:32008L0105&from=EN.
[5] T.J. Strathmann, C.J. Werth, J.R. Shapley, A. Street, R. Sustich, J. Duncan,
N. Savage (Eds.), Nanotechnology Applications for Clean Water, second ed.,
William Andrew Publishing, Oxford, 2014, pp. 339–349.
[6] J. Martínez, A. Ortiz, I. Ortiz, Appl. Catal. B 207 (2017) 42–59.
[7] K.D. Vorlop, T. Tacke, Chem. Ing. Tech. 61 (1989) 836–837.
[8] J. Hirayama, R. Abe, Y. Kamiya, Appl. Catal. B 144 (2014) 721–729.
[9] Y. Wang, J. Qu, H. Liu, C. Hu, Catal. Today 126 (2007) 476–482.
[10] I. Witonska, S. Karski, J. Rogowski, N. Krawczyk, J. Mol. Catal. A Chem. 287 (2008)
87–94.
[11] B.P. Chaplin, M. Reinhard, W.F. Schneider, C. Schüth, J.R. Shapley,
T.J. Strathmann, C.J. Werth, Environ. Sci. Technol. 46 (2012) 3655–3670.
[12] A. Pintar, J. Batista, J. Levec, T. Kajiuchi, Appl. Catal. B 11 (1996) 81–98.
[13] A. Pintar, J. Batista, I. Muševič, Appl. Catal. B 52 (2004) 49–60.
[14] L. Lemaignen, C. Tong, V. Begon, R. Burch, D. Chadwick, Catal. Today 75 (2002) 43–
48.
[15] U. Prüsse, M. Kröger, K.D. Vorlop, Chem. Ing. Tech. 69 (1997) 87–90.
[16] U. Prusse, M. Hahnlein, J. Daum, K.D. Vorlop, Catal. Today 55 (2000) 79–90.
[17] O.S.G.P. Soares, J.J.M. Órfão, M.F.R. Pereira, Catal. Lett. 139 (2010) 97–104.
[18] O.S.G.P. Soares, J.J.M. Órfão, M.F.R. Pereira, Desalination 279 (2011) 367–374.
[19] A.E. Palomares, C. Franch, A.A. Corma, Catal. Today 172 (2011) 90–94.
[20] F. Papa, I. Balint, C. Negrila, E.A. Olaru, I. Zgura, C. Bradu, Ind. Eng. Chem. Res. 53
(2014) 19094–19103.
[21] N. Barrabés, J. Sá, Appl. Catal. B 104 (2011) 1–5.
[22] D. Gašparovičová, M. Králik, M. Hronec, Collect. Czech. Chem. Commun. 64 (1999)
502–514.
[23] D. Gašparovičová, M. Králik, M. Hronec, A. Biffis, M. Zecca, B. Corain, J. Mol. Catal.
A Chem. 244 (2006) 258–266.
[24] D. Gašparovičová, M. Králik, M. Hronec, Z. Vallusova, H. Vinek, B. Corain, J. Mol.
Catal. A Chem. 264 (2007) 93–102.
[25] Y. Kim, M.Y. Kim, M. Choi, Chem. Eng. J. 289 (2016) 423–432.
[26] A.R. Ribeiro, O.C. Nunes, M.F.R. Pereira, A.M.T. Silva, Environ. Int. 75 (2015)
129
Applied Catalysis A, General 570 (2019) 120–129
33–51.
[27] M.B. Ninković, R.D. Petrović, M.D. Laušević, J. Serb. Chem. Soc. 75 (2010)
565–573.
[28] G.S. Pozan, I. Boz, J. Hazard. Mater. 136 (2006) 917–921.
[29] J. Zhou, Y. Han, W. Wang, Z. Xu, H. Wan, D. Yin, Appl. Catal. B 134–135 (2013) 222–
230.
[30] N. Jadbabaei, T. Ye, D. Shuai, H. Zhang, Appl. Catal. B 205 (2017) 576–586.
[31] S. Zheng, D. Zhu, U.D. Patel, S. Suresh, J. Colloid Interface Sci. 319 (2008)
462–469.
[32] J.A. Baeza, L. Calvo, M.A. Gilarranz, A.F. Mohedano, J.A. Casas, J.J. Rodriguez, J.
Catal. 293 (2012) 85–93.
[33] G. Centi, S. Perathoner, Appl. Catal. B 41 (2003) 15–29.
[34] Y. Liu, T. Phenrat, G.V. Lowry, Environ. Sci. Technol. 41 (2007) 7881–7887.
[35] K. Ritter, M.S. Odziemkowski, R. Simpgraga, R.W. Gillham, D.E. Irish, J. Contam.
Hydrol. 65 (2003) 121–136.
[36] O. Schlicker, M. Ebert, M. Fruth, M. Weidner, W. Wüst, A. Dahmke, Ground Water 38
(2000) 403–409.
[37] G.V. Lowry, M. Reinhard, Environ. Sci. Technol. 35 (2001) 696–702.
[38] D.P. Siantar, C.G. Schreier, C.S. Chou, M. Reinhard, Water Res. 30 (1996)
2315–2322.
[39] F. Epron, F. Gauthard, J. Barbier, Appl. Catal., A 237 (2002) 253–261.
[40] J. Wärnå, I. Turunen, T. Salmi, T. Maunulasa, Chem. Eng. Sci. 49 (1994)
5763–5773.
[41] Y. Yoshinaga, T. Akita, I. Mikami, T. Okuhara, J. Catal. 207 (2002) 37–45.
[42] S.D. Ebbesen, B.L. Mojet, L. Lefferts, J. Catal. 256 (2008) 15–23.
[43] Y. Liou, C. Lin, S. Weng, H.H. O U, S.L. Lo, Environ. Sci. Technol. 43 (2009)
2482–2488.
[44] R. Zhang, D. Shuai, K.A. Guy, J.R. Shapley, T.J. Strathmann, C.J. Werth,
ChemCatChem 5 (2013) 313–321.
[45] S. Jung, S. Bae, W. Lee, Environ. Sci. Technol. 48 (2014) 9651–9658.
[46] K. Nakamura, Y. Yoshida, I. Mikami, T. Okuhara, Appl. Catal. B 65 (2006) 31–36.
[47] H. Yi, F.F. Xia, Q. Zhou, D. Zeng, J. Phys. Chem. A 115 (2011) 4416–4426.
[48] F. Epron, F. Gauthard, C. Pineda, J. Barbier, J. Catal. 198 (2001) 309–318.
[49] M.A. Bahri, L. Calvo, M.A. Gilarranz, J.J. Rodriguez, F. Epron, Appl. Catal. B 141
(2013) 138–139.
[50] W. Gao, N. Guan, J. Chen, X. Guan, R. Jin, H. Zeng, Z. Liu, F. Zhang, Appl. Catal. B 46
(2003) 341–351.
[51] M. Yamauchi, R. Abe, T. Tsukuda, K. Kato, M. Takata, J. Am. Chem. Soc. 133 (2011)
1150–1152.
[52] N. Mahata, Surf. Interfaces 4 (2016) 51–54.
[53] R. State, F. Papa, T. Tabakova, I. Atkinson, C. Negrila, I. Balint, J. Catal. 346 (2017)
101–108.
[54] M. Brun, A. Berthet, J.C. Bertolini, J. Electron Spectrosc. Relat. Phenom. 104 (1999) 55–
60.
[55] M.C. Militello, S.J. Simko, Surf. Sci. Spectra 3 (1994) 402–409.
[56] S. Sharma, B.D. Mukri, M.S. Hegde, J. Chem. Soc., Dalton Trans. 40 (2011)
11480–11489.
[57] Y.X. Chen, Y. Zhang, G.H. Chen, Water Res. 37 (2003) 2489–2495.
[58] U. Prüsse, K.D. Vorlop, J. Mol. Catal. A Chem. 173 (2001) 313–328.
[59] A. Garron, F. Epron, Water Res. 39 (2005) 3073–3081.
[60] A. Roveda, A. Benedetti, F. Pinna, G. Strukul, Inorg. Chim. Acta 349 (2003)
203–208.
[61] M.D. Mikesell, S.A. Boyd, J. Environ. Qual. 14 (1985) 337–340.
[62] C. Guillard, J. Disdier, C. Monnet, J. Dussaud, S. Malato, J. Blanco, M.I. Maldonado,
J.M. Herrmann, Appl. Catal. B 46 (2003) 319–332.
[63] P. Benoit, E. Barriuso, S. Houot, R. Calvet, Eur. J. Soil Sci. 47 (1996) 567–578.
[64] C. Pãcurariu, G. Mihoc, A. Popa, S.G. Munteanu, R. Ianoº, Chem. Eng. J. 222 (2013)
218–227.