w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

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

The reactivity of well-dispersed zerovalent iron

nanoparticles toward pentachlorophenol in water
Chih-ping Tso, Yang-hsin Shih*
Department of Agricultural Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 106,
Taiwan, ROC

article info

abstract

Article history:

In order to prevent the aggregation of nanoparticles (NPs), surface modification or the

Received 5 August 2014

addition of a stabilizer are used for stabilization. However, the real reactivity of NPs is still

Received in revised form

unclear because of the surface coating. For different physical dispersion methods, the

26 November 2014

particle stabilization for nanoscale zerovalent iron (NZVI) particles and their reactivity are

Accepted 23 December 2014

studied. The particle properties of different preparations and their reactivity toward one

Available online 30 December 2014

polychlorinated aromatic compound, pentachlorophenol (PCP), with different electrolytes

are also evaluated. Ultrasonication (US) with magnetic stirring disperses NZVI and Pd/Fe

Keywords:

NPs well in water and does not affect the surface redox property a lot under the operating

Pentachlorophenol (PCP)

conditions in this study. The well-suspended NZVI cannot dechlorinate PCP but adsorption

Ultrasonication

removal is observed. Compared to shaking, which gives limited removal of PCP (about 43%),

Well-suspension

Pd/Fe NPs remove 81% and 93% of PCP from water in the US and the US/stirring systems,

Pd/Fe nanoparticles

respectively, which demonstrates that a greater surface area is exposed because of effec-

Anions

tive dispersion of Pd/Fe NPs. As the Pd doping increases, the dechlorination kinetics of PCP
is improved, which shows that a catalyst is needed. With US/stirring, chloride ions do not
significantly affect the removal kinetics of PCP, but the removal efficiency increases in the
presence of nitrate ions because PCP anions were adsorbed and coagulated by the greater
amount of iron (hydro)oxides that are generated from the reduction of nitrate on Pd/Fe.
However, bicarbonate ions significantly block the adsorption and reaction sites on the Pd/
Fe NP surface with US/stirring. The US/stirring method can be used to evaluate the actual
activity of NPs near the nanoscale. The use of Pd/Fe NPs with US/stirring removes PCP from
water effectively, even in the presence of common anions expect a high concentration of
bicarbonate.
2014 Elsevier Ltd. All rights reserved.

1.

Introduction

Pentachlorophenol (PCP) is widely used throughout the world

in disinfectants, biocides, wood preservatives and pesticides.
Therefore, PCP can be found in the air, surface water, soil, and

* Corresponding author. Tel./fax: 886 2 33669443.

E-mail address: yhs@ntu.edu.tw (Y.-h. Shih).
http://dx.doi.org/10.1016/j.watres.2014.12.038
0043-1354/ 2014 Elsevier Ltd. All rights reserved.

groundwater aquifers because of its environmental stability

(Goerlitz et al., 1985; Mannisto et al., 2001). An old shutdown
PCP factory in An-shun area of Taiwan is a seriously PCPcontaminated site with a high PCP concentration ranging
from 0.312 mg kg
1 to 110 mg kg
1 in the soil (Thuan and
Chang, 2012). PCP is a priority pollutant because of its

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

carcinogenicity and toxicity (Morales et al., 2014; Duan et al.,

2008; Zhu and Shan, 2009). However, the remediation
methods for PCP have been found to be inefficient mainly due
to its adsorption characteristics (Lindsey and Tarr, 2000).
Some of the intermediate products during the decomposition
of PCP, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in the environment, may be more
toxic than the original PCP (Harnly et al., 2000). In the past
decade, abiotic dechlorination using granular zerovalent iron
(ZVI) particles has garnered much interest (Su et al., 2012), but
the transformation of chlorinated organic compounds using
granular ZVI is slow and may not be complete (Morales et al.,
2002).
Nanoscale ZVI (NZVI) particles can remove several toxic
chemicals more promptly as compared to microscale ZVI
(MZVI) because they have a higher surface area than MZVI
(Tratnyek and Johnson, 2006; Shih and Tai, 2010). Compared
with NZVI, the bimetallic Fe nanoparticles (NPs) have exhibited higher potential for the dehalogenation of many halogenated aromatic compounds (Shih et al., 2009; Wang et al.,
2013; Zhao et al., 2014), especially Pd/Fe NPs can degrade PCP
(Shih et al., 2011). However, it is difficult to maintain the stability of Fe NPs in their original size during the reactions.
When Fe NPs aggregate and precipitate, their mobility and
reactivity in the environment are significantly reduced
(Glavee et al., 1995; He and Zhao, 2007). The aggregation of Fe
NPs depends upon their physical and chemical properties,
such as the size, the dosage and their surface characteristics,
as well as on the other chemical species in water (e.g., salinity,
solution composition, and the solution pH) (Mylon et al., 2004;
Yang et al., 2007; Hu et al., 2010). Therefore, various chemical
and physical dispersion methods have been proposed to prevent the aggregation of metallic nanoparticles (Wang et al.,
2013; Zhao et al., 2014; Dong and Lo, 2013; Kaifas et al., 2014;
Xie et al., 2014; Yang et al., 2014; Soukupova et al., 2015).
Chemical dispersion methods involve the use of solution
additives and surface modifiers such as adding carboxymethyl
cellulose, poly(methyl methacrylate), poly(ethylene glycol),
Tween 80, and chitosan (He and Zhao, 2007; Kaifas et al., 2014;
Soukupova et al., 2015; Parshetti and Doong, 2009; Wang and
Zhou, 2010; Kustov et al., 2011). These stabilizer molecules
provide inter-particle electrostatic forces and steric repulsion,
which are strong enough to overcome the interfacial forces
(He and Zhao, 2007; Harendra and Vipulanandan, 2008; He and
Zhao, 2005; Sakulchaicharoen et al., 2010). Although the
amendments can enhance the colloidal stability, they alter
the surface properties of NPs and affect their interaction with
contaminants (Kim et al., 2009; Phenrat et al., 2007; Tiraferri
et al., 2008). Modifiers can also affect the sorption and
desorption of contaminants so they limit the reaction rates of
the reactions that occur at the iron surface (Phenrat et al.,
2009).
However, different physical techniques, including highenergy ball milling, magnetic stirring, shaking and ultrasonication (US), are also used to disperse metal NPs (Xing,
2004; Imamura et al., 2005; Mondragon et al., 2012; Lowry
and Reinhard, 2001; Dickson et al., 2012; Lai et al., 2013). Of
these methods, US efficiently breaks down the particleeparticle interactions of nano-sized Fe NPs without the
need for synthetic modifiers (Dickson et al., 2012; Liang et al.,

373

2008; Rasheed et al., 2011). Moreover, using sonication irradiation, nanoparticles with hydrodynamic diameters smaller
than 150 nm remain in suspension for more than 7 days
(Dickson et al., 2012). However, the collapse of cavitation
bubbles may also allow the formation of oxidizing species,
superoxide radicals, and hydrogen peroxide during ultrasonic
irradiation (Chen et al., 2011; Hou et al., 2012). US could not
only disperse nanoparticles, but also could alter the surface
characteristics of Fe NPs, which might further affect the reaction efficiency. Therefore, the mechanisms of NZVI with
ultrasound could be complicated in the degradation of organic
compounds.
Electrolytes that are dissolved in the environment are an
important influencing factor on the reactivity of Fe aggregates
(Phenrat et al., 2007; Giasuddin et al., 2007; Shih et al., 2010;
Wang and Zhang, 1997) because they interact with ferrous
and ferric ions to form iron oxides or hydroxides on the iron
surface. The formation of passive layers on the surface of ZVI
causes a rapid decrease in the activity because it inhibits access for target compounds to the active sites (Agrawal et al.,
2002; Kober et al., 2002). There have been many studies of
the effect of anions on the removal reactions by Fe NPs, but
there has been little study of the performance of wellsuspended Fe NPs in the presence of anions. The aims of
this study are to investigate the feasibility of removing PCP
using well suspended Fe NPs under different physical
dispersion methods, to understand the reaction mechanisms
of Fe NPs assisted with ultrasonication, and to evaluate the
effect of common anions (chloride, nitrate and bicarbonate)
on the Fe NPs at close to nanoscale.

2.

Materials and methods

2.1.

Chemicals

Pentachlorophenol (PCP) was purchased from Sigma. Ferrous

sulfate heptahydrate, sodium chloride, sodium nitrate, sodium hydroxide, methanol, n-hexane and hydrochloric acid
were obtained from J. T. Baker. Sodium borohydride was
purchased from Shiyaku Kogyo Co. Ltd., Japan. Potassium
hexachloropalladate (IV) was provided by Acros. Sodium bi n. Chlorophenol
carbonate was purchased from Riedel-deHae
standard (DIN EN 12673 chlorophenols) including 19 chlorophenols was purchased from Supelco (USA). All organic solvents used for the study were of analytical grade. All solutions
were made in water that was purified using a Milli-Q system
(18.2 MU/cm).

2.2.

The synthesis of Fe bimetallic nanoparticles

NZVI particles and Pd/Fe bimetallic (Pd/Fe) nanoparticles were

chemically synthesized in an anaerobic chamber (Coy Lab)
and used immediately. An aqueous solution of ferrous sulfate
was reduced, using sodium borohydride at a molar ratio for
2
of 2.0, with vigorous stirring (14,000 rpm) at ambient
BH

4 /Fe
temperature. The obtained black nanoparticle suspension
was filtered through a 0.45 mm membrane and then washed
with pH 4 sulfuric acid and deionized water several times to
remove the residual reagents and salts. Pd/Fe NPs were

374

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

synthesized by injecting potassium hexachloropalladate (IV)

solution into fresh NZVI suspension under the anaerobic
condition. After synthesis, the concentration of Pd ions in
solution decreased from 16.4 mg/L to 0.06 mg/L, that is, over
99% of Pd ions were deposited and reduced on NZVI surface.
The Pd/Fe NPs were then rinsed several times with deionized
and deoxygenated ultrapure water to remove chloride ions.
The concentrations of Fe and Pd were quantified using an
inductively coupled plasma spectrophotometer (ICP). The
hydrodynamic particle size of the suspended nanoparticles
was measured by dynamic light scattering (DLS) (Nano-ZS,
Malvern). The atomic and molecular structures of the crystals
of the Pd/Fe NPs were determined using X-ray diffraction
(XRD, National Synchrotron Radiation Research Center,
Taiwan). During XRD analysis, these nanoparticle samples
were stored in plastic bags with their original solutions.

2.3.

Dispersion techniques

The PCP stock solution was prepared by dissolving PCP in

methanol/water (1:200, v/v) as the stock solution and this was
stored at 4  C. In order to compare the different dispersion
techniques, a shaker (LM-530R, YIH DER), a magnetic stirrer
(PC-420D, Corning), an US probe (Ultrasonic 250, HOYU), as
well as a combination of a magnetic stirrer and an US probe
(US/stir) were used to disperse Fe nanoparticles.
For shaking, the batch reactions were conducted in 5 mL
amber vials, sealed with Teflon-lined septa. Each vial contained 2 mL of PCP stock solution, 2.5 mL of Fe NPs suspension,
and around 0.5 mL deoxygenated ultrapure water to eliminate
headspace, which was prepared in the anaerobic chamber. An
orbital shaker operating at 150 rpm was used. For the US
(23 kHz and a rated output power of 250 W) and US/stirring
systems, all of the time-dependent experiments were performed in the anaerobic chamber. The removal rates of PCP
increased with an increase in output intensity of US from 0 to
75 W, accompanied with a decrease in hydrodynamic particle
size of Pd/Fe NPs (Figure S1). However, the increase of US

output intensity from 75 W to 250 W did not significantly

enhance the removal but increased the particle size. The
output intensity of the US probe about 30% of 250 W (i.e. 75 W)
was chosen in this study. The 10 mL of PCP stock solution and
12.5 mL Fe NPs suspension were placed in a 100 mL beaker,
which was covered with aluminum foil in a water bath and
maintained at a constant temperature of 25  C during sonication. The initial concentration of the PCP in all reactors was
5.0 mg/L. The Fe dosage for all the experiments quantified
using ICP was 4.5 g L
1. The setting for the US/stirring system
is shown in Scheme 1. The magnetic stirring rate was 120 rpm.
The solution pH and the reduction potential were monitored
during these reactions.
The effect of nanoparticle dosage, Pd loading and anions on
the removal of PCP by well-suspended Fe NPs was determined.
Individual solutes of three common anions were used in sodium form (i.e. chloride, nitrate and bicarbonate) without a
buffer.

2.4.

Analytic methods

The concentration of PCP was quantified using high performance liquid chromatography (HPLC, Agilent 1200) with a UV/
Vis detector and gas chromatography (GC, Agilent 6890) with a
micro-electron capture detector or mass spectrometer (Agilent 5975B). The mobile phase was a mixture of methanol and
1% H3PO4 (80:20 v/v) at a flow rate of 1.0 mL min
1 and the
wavelength was set at 254 nm for PCP analysis. The GC was
equipped with an HP-5 column (30 m  0.25 mm, 0.25 mm film).
The carrier gas was ultra-high-purity N2 of 99.999% and the
flow rate was 60 cm/s. The injector temperature was 250  C,
the oven temperature was maintained at 80  C for 2 min and
then increased at 7  C/min to 280  C, at which temperature
was maintained for 5 min. The detector temperature was
320  C. For byproduct analysis, chlorophenols were separated
using a GC program with an initial temperature of 60  C for
2 min, ramping at 20  C/min to 140  C with 0.5 min holding,
1  C/min to 150  C with 0.5 min holding, and 15  C/min to
300  C with 3 min final holding time. The flow rate was 30 cm/
s. The anion concentrations (chloride and nitrate) in the solutions were monitored using ion chromatography (IC, Metrohm, Switzerland) after filtering through a 0.22 mm filter
(Minisart, non-pyrogenic).

2.5.

Kinetic experiments

At selected time intervals, aliquots were withdrawn using a

magnet to separate the Fe nanoparticles. The ratio of the final
aqueous PCP concentration to its initial concentration is
defined as the residual fraction. The removal rate constant is
described by a pseudo-first order reaction.
Ct C0 e
kt

(1)

1

Scheme 1 e Schematic of the main experimental setup

employed in the present study.

where C0 and Ct are the initial concentration (mg L ) and the

concentration at reaction time t (min), in the aqueous phase of
the reacted vial, and k is the measured rate constant (min
1).
The Pd/Fe particles were dried and extracted with hexane
and concentrated HCl, until there was no PCP residue in the
extract. This was then used to determine whether PCP and its

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

derivatives had been adsorbed on the Fe surface. The ratio of

the measured adsorbed PCP concentration to its initial concentration is defined as the adsorption fraction. The degradation
efficiency is calculated by subtracting the initial PCP from the
residual and the adsorption PCP fractions.
Removal efficiency% C0
Cfinal


C0  100

Degradation efficiency% C0
adsorption fraction
Cfinal


C0  100

(2)

(3)
where Cfinal is the final PCP concentration (mg L
1) in the
aqueous phase.
Dechlorination efficiency can be expressed as the ratio of
the measured chloride concentration (M

Cl, mM) to the theoretical chloride concentration (M

Cl0, mM) from the complete
dechlorination of PCP.
Dechlorination efficiency% M

Cl

3.

5  M

Cl 0  100

(4)

Results and discussion

3.1.
The removal of PCP using different iron NPs for
different dispersion systems
The range of the particle sizes for the synthesized NZVI and
Pd/Fe NPs was 50e100 nm shown in the TEM images
(Figure S2); however, the hydrodynamic particle sizes of these
two nanoparticles in aqueous solutions were more than 10 mm
(about 34 mme58 mm) measured by DLS. Because of the magnetic attractive force and the van der Waals forces between
these iron NPs, they tend to from aggregates in solution
(Giasuddin et al., 2007; Shih et al., 2010; Wang and Zhang,
1997). Four different dispersion methods were used to suspend particles in solution, but the size remained on the
microscale except for the ultrasonic method. The average
particle size of the Pd/Fe NPs decreased from the microscale
(34 mm) to the nanoscale (123 nm) after US for 60 min (Fig. 1).

375

The same trend was observed for NZVI. Since Pd/Fe NPs were
generated from NZVI, more aggregates of Pd/Fe NPs could
form during their synthesis, which might result in the larger
particle size of Pd/Fe NPs than NZVI after ultrasonication. An
ultrasonic probe has also been used to disperse other metal
nanoparticle aggregates to a small particle size (Tso et al.,
2010).
In order to determine the effect of well-suspended Fe NPs
on the removal of PCP, comparative experiments were performed for the four different dispersion methods: the
shaking, the stirring, the US and the US/stirring system. No
obvious PCP removal was noted for NZVI in a shaking system.
PCP was removed using NZVI in the US system, but no
chloride ions were measured, which showed that no
dechlorination occurred, as shown in Figure S3 (discussed
later). Obviously, PCP is not removed in the US system, which
shows that the US power used in this study does not eliminate PCP. Fig. 2a shows the results for the removal experiments that were conducted under the same operating
conditions of a temperature of 25  C, an initial pH value of
about 6.7, an iron dosage of 4.5 g L
1 and a Pd loading of 0.1%
(w/w). Using US dispersion in both the US and the US/stirring
systems, Pd/Fe NPs were well dispersed in aqueous solutions
(Figure S4) and the reactant molecules were not removed.
The average particle size is 295 176 nm during the irradiation time.
In the presence of Pd/Fe NPs, the PCP removal efficiency
was only around 43% and 74% for the shaking system and the
stirring system after 1 h but 81% and 93% for the US and the
US/stirring systems, respectively (Fig. 2a). The removal rates
for PCP for the shaking, the stirring, the US and the US/stirring
systems were 0.01, 0.05, 0.06 and 0.13 min
1, respectively. The
adsorption fractions of PCP for the US, the stirring, and the US/
stirring systems were about 70%, 64%, and 73%, which were
much higher than that for the shaking system (12%) (Fig. 2b).
When large NP aggregates become smaller, there is more
surface area for the reaction. Using the US probe, Pd/Fe NPs
revert to a nanoscale size so there are more active sites than
nano-aggregates. The increased removal of PCP in US systems

Fig. 1 e DLS results of NZVI and Pd/Fe nanoparticles under US probe irradiation.

376

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

is due to an increase in PCP adsorption on the Pd/Fe NP

surface.
Several dechlorination products (2,3,4,5-tetrachlorophenol
(TeCP), 2,3,4,6-TeCP, 2,3,4-trichlorophenol (TCP), and 3,4,5TCP) were identified in the US/stirring system. Three
byproducts (2,3,4,5-TeCP, 2,4,5-TCP, and 3,4,5-TCP) were
detected in the stirring system; however, only 2,3,4,5-TeCP
were found in the shaking system, which indicated further
dechlorination occurred in other systems but not in the
shaking system although it had more degradation of parent
compound, PCP.

3.2.
The removal mechanism for PCP using Pd/Fe NPs in
US dispersion systems
The XRD spectra for the Pd/Fe NPs, before and after irradiation
with US, are shown in Fig. 3. A weak peak at 44 , representing
the crystal structure of zerovalent iron, and some peaks for
iron (hydro)oxides were observed for our synthesized Pd/Fe
nanoparticles. It might be because the zerovalent iron was
amorphous, oxidized by the reduction process of Pd ions by
NZVI surface, or oxidized during the specimen preparation for

XRD. No significant increase in oxidized metals was observed

in a comparison of the XRD spectra for Pd/Fe before and after
US irradiation. This demonstrates that the reactive oxygen
species (ROS) that are generated by cavitation under US do not
affect the character of the Pd/Fe surface. In general, an increase in the power and duration of US results in the generation of more ROS, due to cavitation (Hou et al., 2012).
However, under the operating conditions in this study, cavitation does not destroy PCP (Fig. 2a) and seems not to modify
the Pd/Fe nanoparticle surface.
Using US, the removal rates for PCP are accelerated by
adsorption because there is good dispersion of Pd/Fe for both
the US and the US/stirring systems shown in Scheme S1. Fe
particles in natural water are almost charged because there
are Fe (hydro)oxides on the iron surface that can be ionized.
This surface charge is opposite in sign to that of the existing
ionized PCP (pka 4.75), in common neutral pH, so there is an
electrostatic attraction between the PCP anions in solution
and the generally positive Fe hydroxides on the Pd/Fe nanoparticle surface (Scheme S2). The same interactive force attracts PCP anions and chlorides that are released from PCP
near a positively charged Fe surface in water. The adsorption
of PCP on the Pd/Fe NPs surface also increases when the
particle size decreases, for systems using US. Kim and
Carraway (2000) also noted that PCP losses occur because of
strong sorption on ZVI and bimetallic ZVI, rather than by
dechlorination.

3.3.
The effect of Pd doping on the removal of PCP using
well-dispersed Fe NPs
The addition of Pd onto iron nanoparticles increased the
removal rate and the degradation of PCP as compared to NZVI
(Fig. 4a). For the US/stirring system, when the Pd loading
increased from 0 % to 0.2 %, the removal rate constants for PCP
generally increased from 0.038 to 0.14 min
1. For the US/stirring system, more than 90% PCP was removed after 40 min
with different amounts of Pd doping. Most of the PCP was
adsorbed on the Pd/Fe surface and only 12% of PCP was
degraded in the presence of 0.05% Pd (Fig. 4b). When the Pd
doping increased to 0.2%, the degradation faction of PCP

Fig. 2 e (a) Removal reactions of PCP with Pd/Fe NPs under

various suspended system and (b) the degradation,
adsorption, and residual fractions of PCP reacted with Pd/
Fe. PCP initial concentration was 5 mg/L, Pd/Fe dosage was
4.5 g L1 and Pd content was 0.1% (w/w).

Fig. 3 e XRD spectra of Pd/Fe nanoparticles and those after

reactions under various conditions.

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

377

3.4.
The effect of anions on the removal of PCP using Pd/
Fe NPs

increased to around 30% but the adsorption fraction

decreased to 75%. Obviously, the increase of Pd doping can
enhance the degradation.
From the measurement of chloride ions, the dechlorination
rate constants and dechlorination efficiencies for PCP for Pd/
Fe NPs with different Pd contents are shown in Fig. 5. When
the Pd loading increased from 0.05 % to 0.2 %, the dechlorination rate constants for PCP increased from 0.0024 to
0.0064 min
1 (Fig. 5a), which were calculated from the generation of chloride and the pseudo-first order kinetics. Since no
significant dechlorination of PCP is observed for zerovalent
iron NPs, even with US irradiation (Fig. 5b), the well-dispersed
Fe NPs remove PCP by adsorption onto the iron surface. There
is also a strong linear relationship between Pd doping and the
dechlorination efficiency (R2 is 0.968) of well dispersed Pd/Fe
NPs. The dechlorination of PCP increased from 12 to 30 %
when Pd loading increased from 0.05 % to 0.2 %. When the Pd
loading increases, more hydrogen, which is generated during
the corrosion of iron, is adsorbed onto the Pd and increases
the reactivity (Cheng et al., 1997). The process of iron oxidation
is also accelerated by the galvanic contact between Pd and
iron (Cheng et al., 1997; Yan et al., 2010; Cwiertny et al., 2006).
Both of these effects result in the increased dechlorination of
PCP.

The effect of anions on the removal of PCP, using welldispersed Pd/Fe NPs, is determined using three common
electrolytes e NaCl, NaNO3 and NaHCO3 e in a US/stirring
dispersion system (Fig. 6a). In the presence of chloride, the
removal rate for PCP increased slightly from 0.12 min
1 to
0.16 min
1 when the chloride concentration increased from
5 mM to 10 mM, which compared to 0.099 min
1 for pure water
(Fig. 6), but the dechlorination efficiency did not increase,
compared to that for pure water (Fig. 7). In general, chloride
promotes corrosion and increases the reactivity of granular
iron toward chlorinated compounds (Devlin and Allin, 2005;
Gotpagar et al., 1999; Johnson et al., 1998). However, in this
dispersion system, chloride does not significantly affect the
reaction rate or the degradation efficiency.
For nitrate, the removal rate constants increased from 0.26
to 0.54 min
1, when the concentration of nitrate was raised
from 5 mM to 10 mM, and most of the PCP was removed in the
presence of nitrate (Fig. 6). Compared to pure water and other
anion systems, the presence of nitrate accelerated the kinetics. However, nitrate generally inhibits the reduction
power of zerovalent iron nanoparticles, because it competes

Fig. 4 e (a) Removal reactions of PCP with Pd/Fe NPs with

various Pd dosage in the US/stirring system and (b) the
degradation, adsorption, and residual fractions of PCP
reacted with Pd/Fe. PCP initial concentration was 5 mg L1
and Fe dosage was 4.5 g L1.

Fig. 5 e Effect of Pd dosage on (a) the dechlorination

reaction rates and (b) dechlorination efficiencies of PCP by
Pd/Fe nanoparticles under US/stirring system. PCP initial
concentration was 5 mg L1 and Fe dosage was 4.5 g L1.

378

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

Fig. 6 e (a) Effect of anions on the removal of PCP by Pd/Fe

under US/stirring. (b) The relation between the reaction
rate constants and anions. PCP initial concentration was
5.0 mg/L, iron dosage was 4.5 g/L, and Pd content was 0.1%.

with chemicals that have a high oxidation state, such as

halogenated compounds. Since nitrate obtains electrons from
the iron surface and reduces them to nitrite and ammonia,
using iron powder (Alowitz and Scherer, 2002) and NZVI (Shih
et al., 2009), the concentrations of nitrate, nitrite and ammonium were measured. Over 99% of the nitrate was transformed by Pd/Fe NPs and about 72% and 63% of these
transformed nitrate ions were further reduced to ammonium
the presence of 5 mM and 10 mM nitrate, respectively. This

Fig. 7 e The degradation, adsorption, and residual fractions

of PCP reacted with Pd/Fe in the presence of anions under
US/stirring system after 40 min.

result demonstrates that nitrate is reduced by Pd/Fe NPs,

during the degradation of PCP. The reduction of nitrate by iron
is also a corrosive process, which causes more iron (hydro)
oxides to form a film on the iron surface. In the XRD analysis
(Fig. 3), the specific peaks for zerovalent metals almost disappeared and more peaks for iron oxides were found than for
other treatments. In particular, magnetite (Fe2Fe23O4) was
observed on the Pd/Fe nanoparticle surface in the presence of
nitrate. Fig. 7 shows that the adsorption fraction for PCP in the
presence of nitrate (about 89%) is the highest among these
anions. This result is consistent with the nitrate transformation and the XRD observation and only around 10% is
degraded by Pd/Fe NPs. Since the electrochemical reduction of
PCP is mediated in the range,
1.6 to
2.3 V (Ross et al., 1997;
Lin and Tseng, 1999), which is higher than the reduction potential of nitrate (0.88 V), the Pd/Fe surface reacts with the
nitrate first and generates iron (hydro)oxides. The fast
removal kinetics is mainly due to the adsorption or coagulation of PCP on these iron oxides.
In the presence of bicarbonate, the removal rate for PCP
was significantly reduced in the same dispersion system as
that used for the anions (Fig. 6). When the bicarbonate concentration increased from 0 to 10 mM, the reaction rate constant decreased from 0.099 to 0.023 min
1 and the removal
efficiency after 40 min decreased from 96 to 46 % (Fig. 6a). The
degradation and adsorption fractions were less than those for
other anions and that for pure water (Fig. 7), which demonstrated that bicarbonate blocks the reactive and attachment
sites for PCP on the Pd/Fe surface. However, no significant
peaks for metal oxides on Pd/Fe surface were observed (Fig. 3).
These inneresphere complexes form passivation layers that
inhibit the adsorption and degradation of PCP by Pd/Fe
nanoparticles (Phenrat et al., 2007; Agrawal et al., 2002; Kober
et al., 2002). The solution pH also increased from 5.4 to 8.9 in
the presence of 10 mM bicarbonate. Because the chemical
reduction of polychlorinated aromatic compounds by NZVI
favors acidic conditions (Shih et al., 2009), this high solution
pH, buffered by hydrogen carbonate, significantly decreases
the rate of degradation PCP by Pd/Fe NPs.

4.

Conclusions

The effect of physically mixing zero-valent iron nanoparticles,

with or without Pd, on the removal of PCP by Pd/Fe NPs is
studied. The US/stirring system, suspends NZVI and Pd/Fe NPs
most effectively of any of the dispersion methods, at about the
nanoscale. Since NP aggregates become smaller, most of the
PCP is removed by adsorption onto the iron surface because
there is a larger surface area. Under the operating conditions,
US does not degrade PCP, even with NZVI, and does not affect
the surface characteristics of Pd/Fe. When the Pd doping on
the Pd/Fe NPs increases, the dechlorination kinetics for PCP
increases in the US/stirring system. The actual activity of wellsuspended Pd/Fe NPs is evaluated for different electrolytes
that are commonly found in treatment systems. In the presence of common anions, nitrate ions are reduced by wellsuspended Pd/Fe NPs and more (hydro)oxides are generated,
which increases the adsorption or coagulation of PCP from
water, while chloride ions only cause a slight increase in the

w a t e r r e s e a r c h 7 2 ( 2 0 1 5 ) 3 7 2 e3 8 0

removal kinetics. However, bicarbonate significantly inhibits

the removal of PCP because bicarbonate could form complexes with metal cations from Pd/Fe and then precipitate on
the iron surface, which blocks the adsorption and reaction
sites. These better understandings of the real activity and
removal mechanisms of well-dispersed Pd/Fe as well as the
common ion effect can facilitate the application of NPs in
water treatments and the environmental remediation.

Acknowledgments
The authors gratefully acknowledge the financial support of
the Ministry of Science and Technology of Taiwan, R. O. C.
(Contract 101-2313-B-002-035-MY3).

Appendix A. Supplementary data

Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.watres.2014.12.038.

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