SCHOOL OF CHEMICAL ENGINEERING

UNIVERSITI SAINS MALAYSIA

ENGINEERING CAMPUS

SEMESTER I

2018/2019

EKC 354 NANOMATERIALS IN CHEMICAL ENGINEERING

GROUP ASSIGNMENT

APPLICATIONS OF THE NANO ZERO VALENT IRON FOR

REMEDIATION OF HEAVY METALS

CHECKED BY

ASSOCIATE PROFESSOR DR. TAN SOON HUAT

PREPARED BY

GROUP 1

ALSHIDDIQ BIN ALLAZMI 133611

KHOO CHING YI 133626

YOU JIN JIE 133695

DATE OF SUBMISSION

10TH DECEMBER 2018

 TABLE OF CONTENT

1.0 ABSTRACT .................................................................................................... 3

2.0 INTRODUCTION ........................................................................................... 4
3.0 DISCUSSION .................................................................................................. 6
3.1 Kaolin-Supported Nanoscale Zero-Valent Iron for Removal of Pb2+ from
Aqueous Solution: Reactivity, Characterization and Mechanism
3.2 Mg(OH)2 Supported Nanoscale Zero Valent Iron Enhancing the Removal
of Pb(II) from Aqueous Solution
3.3 The Removal of Chromium (VI) and Lead (II) from Groundwater Using
Sepiolite-Supported Nanoscale Zero-Valent Iron (S-nZVI)
3.4 Heavy Metal Removal Using Nanoscale Zero-Valent Iron (nZVI): Theory
and Application
3.5 Simultaneous Removal of Cr(VI) and Phenol by Persulfate Activated with
Bentonite-Supported Nanoscale Zero-Valent Iron: Reactivity and
Mechanism
3.6 Fast and Highly Efficient Removal of Chromium (VI) Using Humus-
Supported Nanoscale Zero-Valent Iron: Influencing Factors, Kinetics and
Mechanism
3.7 Insights into the Simultaneous Removal of Cr6+ and Pb2+ by a Novel
Sewage Sludge-Derived Biochar Immobilized Nanoscale Zero Valent Iron:
Coexistence Effect and Mechanism
3.8 Enhanced Hexavalent Chromium Removal Performance and Stabilization
by Magnetic Iron Nanoparticles Assisted Biochar in Aqueous Solution:
Mechanisms and Application Potential
3.9 Performance of Pb(II) Removal by an Activated Carbon Supported
Nanoscale Zero-Valent Iron Composite at Ultralow Iron Content
4.0 CONCLUSION ............................................................................................... 26
5.0 REFERENCES ................................................................................................ 27

2
1.0 ABSTRACT

Nanoscale zero-valent iron (nZVI) has apparently became a good alternative for the
remediation of a wide variety of heavy metals especially Pb(II) and Cr(VI)
contaminated in wastewater from industry. It shows a high efficiency, low economic
and environmental costs. However, the tendency of nZVI particles to aggregate limits
its dispersivity and mechanical strength which significantly decrease its reactivity.
Therefore, a series of laboratory studies have been done by the expertized researchers
on the improvement of performance for the remediation of heavy metals by nZVI.
Supporting materials such as biochar, activated carbon, humus, kaolin, magnesium
hydroxide, bentonite and sepiolite have been introduced to nZVI through sodium
borohydride (NaBH4) reduction method. The removal of heavy metals by supported-
nZVI is normally carried out in batch system and the removal efficiency is analysed
from the residual concentration of heavy metals left in batch. One of the most concerned
element in the studies would be the reaction mechanism of the remediation process
proposed by the respective researchers. In this particular paper, nine published articles
regarding the removal of heavy metals by nZVI have been studied. Among the journals
chosen, reactions involved in the mechanisms are adsorption, reduction, oxidation,
precipitation, ion exchange and membrane filtration. It can be deduced the adsorption
method emerged as the most occurring reaction in almost every study. Besides, the
researchers have proven that the supported-nZVI is always performing better in the
removal of heavy metals as compared to that by bare nZVI.

3
2.0 INTRODUCTION

Water pollution by heavy metals is an issue of concern in the modern world that we live
in today. Water pollution has reached their peaks due to the development and
modernisation in our lives. The industrial effluents are considered to be the main
sources of water pollution. Wastewater from a wide range of industries like
electroplating, automotive and aeronautical industries, smelting of non-ferrous metal,
manufacturing of metal alloys and electronic products usually contain a complex and
varied mixture of heavy metal ions.

There are a lot of heavy metals including Magnesium (II), Copper (II), Calcium
(II) and others. Chromium (IV) and Lead (II) are two common heavy metals found in
the wastewater. Chromium (IV) is highly soluble in water and toxic to the aquatic
organisms even at low concentrations. Lead (II) is also a toxic metal that can cause
damage to the brain, red blood cells and kidneys. Thus, a maximum contaminant levels
in the wastewater is set by the Department of Environment in order to ensure the
wastewater released from the industries are environmentally benign and present
minimal environmental and health risk.

Wastewater treatment plants are installed in almost every industry. However, it

is challenging to treat wastewater because of the complex composition of wastewater.
Nanoscale zero valent iron (nZVI) is introduced as an ideal reagent to remove heavy
metal from industrial wastes. In the last few years, the reactions between nZVI and
heavy metals has caught increasing attention and a series of laboratory studies on the
nZVI reactions with heavy metal ions have been published.

Zero valent iron is an iron atom with zero valence electron. In other words, the
oxidation power of the iron atom is zero, neither positive nor negative. “Nanoscale” in
nZVI means that the size of the zero valent iron is in nano scale. nZVI consists of
[4]
metallic iron core and iron hydroxide shell. Nanoscale zero-valent iron (nZVI) is
promising in pollution abatement for its high reactivity and catalytic capability. For in-
situ remediation, nZVI presents better mobility and reactivity than micron-sized
materials, yielding much higher efficiency. [10]

However, nZVI easily tends to aggregate causing its reactivity will significantly
decrease. Therefore, several materials have been widely used as a carrier for nZVI
[7]
particles. The examples of carrier used are sepiolite, biochar, kaolin and bentonite.

4
 The nZVI particles bind on the surface of the carrier and higher efficiency can be
achieved in removing various types of pollutants like organic compounds and heavy
metals as compared to a bare nZVI particles. This is because the nZVI particles are
immobilised on the surface of the carriers. The carriers support the nZVI particles to
decrease the aggregation and improve the dispersivity. In short, supported nanoscale
zero valent iron shows a high efficiency and low economic and environmental cost in
the removal of heavy metal ions from the wastewater.

The remediation of heavy metal refers to the process of removing heavy metals.
The most common mechanisms performed to remediate heavy metals are the adsorption,
reduction, oxidation and precipitation. First, metal ions are adsorbed on the surface of
nZVI and followed by the reduction or oxidation of metal ions by the nZVI. In the end,
the reduced metal ions react with the nZVI to form precipitates. Once the precipitates
are removed, it is considered that the heavy metals are removed as well.

In the nutshell, it is very crucial to remove heavy metals before disposal. Nanoscale
zero valent iron (nZVI) plays a vital role in the remediation of heavy metals. The high
reactivity of nZVI made it more useful in the removal of heavy metal. Nevertheless,
there are still some technical challenges in nZVI applications that will affect the use of
this material in the remediation of heavy metals. Thus, more studies need to be carried
out to modify the characteristics of nZVI to make it as a new generation of wastewater
treatment technology.

𝑭𝒆𝟎 Iron Oxide Shell

Metallic Iron Core nZVI (Absorb and attract charged iron)
(High electron-donating power)

Figure 1: Core shell model of nanoscale zero-valent iron (nZVI)

5
3.0 DISCUSSION

Nine journals on the applications of nanoscale zero-valent iron (nZVI) for the
remediation of heavy metals have been studied and will be discussed further in the
following sections. The detailed discussion includes the synthesis of the supported
nZVI, batch experiment on the remediation of heavy metals by supported nZVI and the
reaction mechanism for the removal of heavy metals.

3.1 Kaolin-Supported Nanoscale Zero-Valent Iron for Removal of Pb2+ from

Aqueous Solution: Reactivity, Characterization and Mechanism [1]

The use of nanoscale zero-valent iron (nZVI) to remediate contaminated groundwater

is limited due to its lack of durability and mechanical strength. To address this issue,
the study loaded 20% (w/w) nZVI onto kaolinite as a supporting material to form K-
nZVI composite. It was found that more than 96% of Pb2+was remediated from aqueous
solution using K-nZVI.

3.1.1 Synthesis of Kaolin-Supported Nanoscale Zero-Valent Iron

The borohydride (NaBH4) reduction method was applied to prepare kaolin-

supported nanoscale zero-valent iron (K-nZVI) in solution by reducing ferric ion
(FeCl3·6H2O) to Fe0. The mixture of FeCl3·6H2O dissolved in ethanol solution
was first diverted into a three-open-necks flask containing kaolin loaded with
nZVI. Then, the solution was stirred vigorously and continuously for 1 hour under
a N2 atmosphere to disperse the kaolin clay. Then, drop by drop, the addition of
NaBH4 into the Fe3+-kaolin mixture was done while stirring continuously with an
electric rod under a N2 atmosphere. The mixture was stirred for another 20
minutes after the addition of sodium borohydride solution. Through vacuum
filtration, the prepared materials were separated from the liquid phase before its
resulting black solid was vacuum dried overnight at 70 ˚C.

3.1.2 Batch Experiment on Removal of Pb(II)

To prepare a Pb stock solution, Pb(NO3)2 was dissolved with distilled water in a

volumetric flask. Firstly, the stock solution with an initial pH of 5.10 was added
to K-nZVI with NaNO3 as a support electrolyte. The flask containing the mixture
was capped and placed on a rotary shaker at 30˚C. Then, the mixture was
centrifuged for 5 minutes at certain time intervals and the residual concentration

6
of Pb2+ in supernatant solution was determined using an atomic absorption
spectrometer with an acetylene flame.

3.1.3 Reaction Mechanism

Two strategies are involved in removing Pb2+ from aqueous solution by using K-
nZVI which are:

i. Adsorption of Pb2+ in aqueous solution on the surface of K-nZVI

ii. Reduction of adsorbed Pb2+ to Pb0 by K-nZVI before its deposition on K-

nZVI

Both strategies were well-explained through the occurred chemical reactions.

In basic solution:

1
Fe0 + 2H2 O + O2 → Fe2+ + 4OH −
2

In acid solution:

Fe0 + 2H2 O → Fe2+ + 𝐻2 + 2OH −

Adsorption of Pb2+ on the surface of K-nZVI:

Pb2+ + Kaolin → Pb2+ − Kaolin

Pb2+ + Fe3 O4 /γ − Fe2 O3 → Pb2+ − Fe3 O4 /γ − Fe2 O3

Reduction of adsorbed Pb2+ to Pb0:

Pb2+ − Kaolin + 2e → Pb0 − Kaolin

Pb2+ − Fe3 O4 /γ − Fe2 O3 + 2e → Pb0 − Fe3 O4 /γ − Fe2 O3

After the reduction of Pb2+ to Pb0 by K-nZVI, the removal of Pb2+ from aqueous
solution can be done since Pb0 has deposited on K-nZVI. Moreover, as a support
material, kaolin able to stabilize and disperse nZVI besides prevent nZVI from
aggregation. These properties have increased the reactivity of nZVI despite that
K-nZVI having a lower surface area than nZVI.

7
3.2 Mg(OH)2 Supported Nanoscale Zero Valent Iron Enhancing the Removal of
Pb(II) from Aqueous Solution [2]

In this article, the researchers aim to develop a novel composite by loading nZVI onto
Mg(OH)2 to form nZVI@Mg(OH)2. The performance of removing Pb(II) was
investigated by batch experiments. The results indicate that there is an existence of
synergy between nZVI and Mg(OH)2. Also, further mechanism attested that Mg(OH)2
played an important role by releasing OH- which can enhance the reduction of Pb(II).
3.2.1 Synthesis of Mg(OH)2-Supported Nanoscale Zero-Valent Iron

The preparation of Mg(OH)2 was done at room temperature and atmospheric

pressure through facile precipitation method. Briefly, NaOH solution was added
dropwise into the hybrid solution of MgSO4 and C3H8O3/H2O with the same
volumes. Vigorous stirring was applied through the titration process and the
resultant solution was stirred continuously for 6 hours after the titration. The
precipitation was centrifuged after aging for one day before being washed by
nanopure water and absolute ethanol. The product was then dried at 50˚C for use.

A modified liquid phase sodium borohydride reduction method was applied

to prepare Mg(OH)2 supported nZVI. Mg(OH)2 was first dispersed in absolute
ethanol through ultrasonic dispersion for 5 minutes. Then, FeSO4·7H2O was
dissolved in nanopure water before the resulting solution was mixed with the
suspension in a three-necked flask. Following that, the same volume of NaBH4
was titrated into the flask under a N2 environment. The flask was mechanically
stirred throughout the titration process and continuously stirred for 30 minutes
after the titration. Resulting black paste was collected and washed with nanopure
water and absolute ethanol. Before the product was stored for use, it was dried in
a vacuum oven at 45˚C overnight.

3.2.2 Batch Experiment on Removal of Pb(II)

Batch experiment for Pb(II) removal was conducted in a three-necked flask

equipped with a mechanical stirrer at room temperature under a N2 environment.
nZVI@Mg(OH)2 was first added into continuously stirred Pb(CH3COO)2 stock
solution. At certain time intervals, the suspension was extracted and centrifuged
to collect both liquid and solid samples. The liquid sample was used for Pb(II),
Fe(II/III) and Mg(II) concentration analysis whereas the solid example was dried

8
for Pb, Fe and Mg element content analysis. The pH value of the suspension was
monitored and recorded every one minute during the experiment.

3.2.3 Reaction Mechanism

Mechanism of Pb(II) removal by nZVI@Mg(OH)2 was proposed as a synergistic

sequestration process which includes adsorption, reduction, ion exchange
reaction and subsequent precipitation. The removal of Pb(II) experienced three
stages with reference to the variation of the solution pH value as shown below:

Figure 2: Stages of pH variation during Pb(II) removal by nZVI@Mg(OH) 2 [2]

At the beginning stage, Pb(II) was first attracted to the surface of nZVI particles
and Mg(OH)2 before the ion exchange reaction was initiated by the dissolution of
Mg(OH)2 as the following chemical equation:

Mg(OH)2 (s) → Mg 2+ + 2OH −

At the same time, nZVI particles partially reduced Pb(II) to Pb0.

Pb2+ + Fe0 → Fe2+ + Pb0 (s)

When it was accumulated to a certain concentration, the hydroxylation of Fe(II)

would be stimulated as follows:

Fe2+ + 2H2 O → Fe(OH)2 (s) + 2H +

Thus, pH value of the solution experienced slight increment as a result of the

competition among the proposed reactions above.

In the second stage, a rapid decline of the pH value of the solution caused by the
hydroxylation of Fe(II) has been witnessed. This is because the reduction of Pb(II)
has became dominant. Higher initial concentration of Pb(II) might lead to an

9
 earlier and larger extent of pH drop, indicating that the decline in pH value is
indeed a consequence of Pb(II) reduction.

The dissolution of Mg(OH)2 was continued in the third stage. An increment in

pH value of the solution was induced by the reaction between iron and water
which can be shown as:

Fe0 (s) + 2H2 O → Fe2+ + H2 (g) + 2OH −

Therefore, the precipitation of Pb(II) could happen in this stage and the chemical
equation of the precipitation is:

Pb2+ + 2OH − → Pb(OH)2 (s)

Analyses on the mechanism propose that the following properties of Mg(OH)2

play an important role in Pb(II) immobilization:

i. Dispersive and supportive

ii. nZVI particle aggregate-preventive function and

iii. intense inherent affinity to Pb(II)

Figure 3 summarized the proposed reaction mechanism of the Pb(II) removal by

nZVI@Mg(OH)2.

Figure 3: Summarization of Pb(II) removal by Mg(OH)2@nZVI [2]

10
3.3 The Removal of Chromium (VI) and Lead (II) from Groundwater Using
Sepiolite-Supported Nanoscale Zero-Valent Iron (S-nZVI) [3]

In this study, sepiolite-supported nanoscale zero valent iron (S-nZVI) was utilised to
observe the removal of chromium (VI) and lead (II) ions from groundwater. Sepiolite
was used to support the nZVI to overcome the aggregation of nZVI. Due to the low
surface acidity, narrow channel and poor thermal stability of natural sepiolite, sepiolite
is modified before the S-nZVI synthesis.

3.3.1 Synthesis of Sepiolite-Supported Nanoscale Zero-Valent Iron

A dispersion of sepiolite in HCl solution is utilised to prepare acid-activated

sepiolite (Asp). The suspension was stirred for 48 hours at room temperature.
Next, the solid was separated from the solution by centrifugation and followed by
washing with deionised water until the Cl- ions were completely removed. After
that, the acid-activated sample was dried at 110˚C for 2 hours and calcinated at
300˚C for 4 hours. Finally, the sample was sieved through a 160 mesh screen.

Sepiolite supported nanoscale zero-valent iron (S-nZVI) with a sepiolite to

iron mass ratio 0f 9:1 was prepared. First, acid-activated sepiolite (Asp) was
added to Fe3+ solution. Then, the solution was stirred overnight using mechanical
stirrer at room temperature. NaBH4 was added drop-wise into the suspension
under vigorous agitation and a nitrogen atmosphere. The purpose to have a
nitrogen condition is to remove all the oxygen. The sepiolite particles turned into
black colour quickly and the mixture was consecutively stirred for 1/2 hour.
Separation of solid from the suspension was carried out by vacuum filtration.
Next, the solid obtained was washed several times with deionised water followed
by absolute ethyl alcohol. Lastly, S-nZVI was dried under vacuum condition at
60˚C overnight.

3.3.2 Batch Experiment on Removal of Cr(VI) and Pb(II)

The batch reaction was conducted in a centrifuge tube which consists of a given
amount of S-nZVI and a solution with a certain concentration of Cr(VI) and Pb(II).
The tubes containing S-NnVI and solution of Cr(VI) and Pb(II) were put in a
steam-bath vibrator at a speed of 200 rpm at 28˚C. Some vials were taken out
from the vibrator after a certain time interval. HCl or NaOH was used to adjust

11
the initial pH of the suspensions. Next, separation of the particles and an aqueous
phase was conducted by centrifugation at 8000 rpm for 3 minutes. A membrane
filter was applied to filter the supernatant samples. The removal efficiency of
Cr(VI) and Pb(II) by S-nZVI was carried out and compared to that by acid-
activated sepiolite and nZVI.

3.3.3 Reaction Mechanism

The removal mechanism of Cr(VI) and Pb(II) by S-nZVI is proposed as a two-

step interaction mechanism. First, Cr(VI) and Pb(II) in the solution were absorbed
on the S-nZVI surface. Due to the negative surface charged of S-nZVI, cations
such as Cr(VI) and Pb(II) were attracted to the surface.

Second, Cr(VI) and Pb(II) were reduced by Fe0 and precipitated on the
surface of S-nZVI. For instance, Cr(VI) was reduced to Cr(III) which was less
toxic by S-nZVI. Next, Cr(III) was immobilized by precipitation as Cr(OH)3 or
by incorporation into the iron oxide or iron hydroxide shell forming alloy-like
Cr3+-Fe3+ hydroxides. After S-nZVI reacted with Cr(VI) and Pb(II), flocculent
clusters with diffuse edges formed on the surface of reacted S-nZVI. These
flocculent clusters resulted from the redox reaction between Fe0, Fe2+ or H+ and
Cr(VI) or Pb(II) where the S-nZVI acted as a reductant in the aqueous solution.

Even though it was a two-step interaction mechanism, but both adsorption

and reduction occurred simultaneously on the surface of the S-nZVI. Cr(VI) and
Pb(II) were successfully remediated by S-nZVI where Cr(VI) was reduced to
Cr(III) while Pb(II) was converted to Pb0. At the same time, Fe(III) was formed
from the oxidation of Cr(VI), Pb(II) and by a simultaneous redox reaction
between water and O2.

Figure 4: Mechanism scheme for Cr(VI) and Pb(II) remediation by S-nZVI [3]

12
3.4 Heavy Metal Removal Using Nanoscale Zero-Valent Iron (nZVI): Theory and
Application [4]

In this study, pure nanoscale zero valent iron (nZVI) was used as a reagent for removing
different heavy metals and arsenic from wastewater. The nZVI process able to produce
stable effluent, is easy-to-operate and much more efficient than conventional
technologies. The extraordinary high removal capacities of nZVI proved that
nanomaterials able to provide truly green and cost-effective ways for wastewater
treatment.

3.4.1 Batch Experiment on Removal of Heavy Metals

The experiment was carried out under batch condition. Nanoscale zero valent iron
(nZVI) was mixed with wastewater or de-oinized water in four-necked flasks
equipped with mixers. N2 gas was purged continuously to the suspension during
the reaction in order to remove O2 gas. A pre-determined amount of Cu(II) stock
solution was spiked at time intervals. Settling experiment of nZVI was performed
together with the reagents including CuCl2, NaOH, FeCl3, Ca(OH)2, activated
alumina, nano-Fe2O3, polyferric sulphate (PFS) and polyacrylamide (PAM).

Wastewater samples at the outlet of each treatment unit were collected

regularly for analysis. 0.22-µm filter was used to filter the experiment sample.
Inductively coupled plasma optical emission spectroscopy (ICP-OES) and
inductively coupled plasma mass spectroscopy (ICP-MS) were used to measure
the concentration of heavy metal ions, Meanwhile, solid sample were dried and
acid-digested using a mixture of nitric and perchlorate acids.

3.4.2 Reaction Mechanism

nZVI can be divided into two parts which are metallic iron core and iron oxide
shell. Its metallic iron core possesses the well-characterized reducing or electron-
donating power while the iron oxide shell offers the coordinative and electrostatic
functions to absorb and attract charged ions. The metallic iron core is a relatively
strong reductant in water as it has a very negative standard potential. In addition,
it has a large surface area that allows fast release of electrons. Therefore, heavy
metal with more positive standard reduction potential such as Cu(II) can be easily
reduced.

13
 Fe + Cu2+ → Fe2+ + Cu

Fe + 2Cu2+ + H2 O → Fe2+ + Cu2 O + 2H +

Oxyanions like arsenate (AsO43-) and selenite (SeO42-) could also be reduced by
nZVI:

H2 AsO− +
4 + Fe + 3H → Fe
2+
+ H3 AsO3 + H2 O

Furthermore, As(V) could also react with Fe2+.

3Fe2+ + 2HAsO2−
4 → Fe3 (AsO4 )2 (s) + 2H
+

Due to the low solubility of Fe3(AsO4)2, precipitations are formed and

typically play a crucial role in removing concentrated As(V). In short, Fe(II)
precipitation is the key of the massive As-removal capacity. Therefore, Fe(II)
need to be in excess and can be gained from the reduction of Cu(II), corrosion of
nZVI by water and the reaction between nZVI and the protons which are released
by the deprotonation process of H3AsO4 or H2AsO4- .

For metal cations whose standard potential are negative or close to that of
iron like Zn(II) and Ni(II), reduction is invalid on them hence another mechanism
is carried out. Those mechanisms are electrostatic attraction and chemical
adsorption, precipitation with hydroxide ions and co-precipitation with iron
corrosion product. nZVI corrosion by water produces Fe(II) and hydroxide ions
OH-, which are vital element for co-precipitation. Iron oxide shell of nZVI and its
corrosion products also provides the coordinative and electrostatic function to
attract charged ions.

Figure 5: Schematic diagram of heavy metal removal using nZVI [4]

14
3.5 Simultaneous Removal of Cr(VI) and Phenol by Persulfate Activated with
Bentonite-Supported Nanoscale Zero-Valent Iron: Reactivity and Mechanism [5]

The bentonite-supported nanoscale zero valent iron (B-nZVI) is used for removal of
Cr(VI). Bentonite is used as a support and the B-nZVI acts as a catalyst to activate
persulfate for simultaneous removal of Cr(VI) and organic compounds. In this study, it
only focuses on the removal of the heavy metal which is Cr(VI).

3.5.1 Synthesis of Bentonite-Supported Nanoscale Zero-Valent Iron

The preparation of bentonite-supported nZVI (B-nZVI) was done using liquid-

phase reduction reaction. Shortly, a solution of ethanol and distilled water with
4:1 volume ratio was used to dissolve ferric chloride hexahydrate before the
addition of bentonite into the mixture. Under N2 atmosphere, the suspension was
well-mixed with electric stir bar for 10 minutes. Drop by drop, NaBH4 was added
into the stirring suspension until the formation of a black solid. Following that,
the suspension was stirred for another 20 minutes continuously. The black solid
product was obtained by vacuum filtration before being rinsed by ethanol and
dried at 75 ˚C under vacuum overnight.

3.5.2 Batch Experiment on Removal of Cr(VI)

After the bentonite-supported nZVI was prepared, stock solutions of Cr(VI),

phenol and per-sulfate were prepared in double distilled water prior to each batch
experiment. Then, batch experiments were conducted in a conical flask
containing mixed solution of Cr(VI) and phenol at 25◦C. It was carried out by
putting the flask in a thermostatic shaker bath with a rotation speed of 150 rpm at
atmospheric pressure. The initial pH was kept at 3 within the reaction time of 30
min. Aliquots of reaction solution were taken from the tubes periodically at
certain time intervals. After centrifugation, ethanol was added to quench any
radical reactions for subsequent analysis.

3.5.3 Reaction Mechanism

Cr(VI) species can be existed as CrO42-, HCrO4-, H2CrO4-, HCr2O72- or Cr2O72-

depending on the solution pH values. At low pH values, HCrO4- is the prevalent
form of Cr(VI) species. Cr(VI) reduction by nZVI can be described in the
following reaction equations :

15
 Fe0 + HCrO4− + 7H + → Cr 3+ + Fe3+ 4H2 O

2Fe0 + Cr2 O2− +

7 + 14H → 2Cr
3+
+ 2Fe2+ + 7H2 O

In addition, the aqueous Fe3+ is more easily released into solution from the B-
nZVI at acidic conditions. Subsequently, the as-formed aqueous Fe2+ react with
dissolved oxygen for the generation of reactive oxygen species (such as O2·- and
H2O2) via the equations as followed:

2𝐹𝑒 0 + 𝑂2 + 4𝐻 + → 2𝐹𝑒 2+ + 2𝐻2 𝑂

−
𝐹𝑒 2+ + 𝑂2 → 𝐹𝑒 3+ + 𝑂2∙
−
𝐹𝑒 2+ + 𝑂2∙ + 2𝐻 + → 𝐹𝑒 3+ + 𝐻2 𝑂2
−
2𝑂2∙ + 2𝐻 + → 𝑂2 + 𝐻2 𝑂2

Lastly, the as-formed and H2O2 react with Cr(VI) to form lower valence states of
chromium.
−
3𝑂2∙ + 𝐶𝑟 6+ → 𝐶𝑟 3+ + 3𝑂2

2𝐻𝐶𝑟𝑂4− + 3𝐻2 𝑂2 + 8𝐻 + → 2𝐶𝑟 3+ + 3𝑂2 + 8𝐻2 𝑂

The above proposed reaction mechanism for the simultaneous removal of Cr(VI)
by B-nZVI/PS combined system can be summarized into a schematic diagram as
presented in Figure 6.

Figure 6: Proposed reaction mechanism for the removal of Cr(VI) by B-nZVI/PS [5]

16
3.6 Fast and Highly Efficient Removal of Chromium (VI) Using Humus-Supported
Nanoscale Zero-Valent Iron: Influencing Factors, Kinetics and Mechanism [6]

In this study, H-nZVI is used for removal of chromium, Cr(VI) in groundwater. Humus
is used as a support material to overlap the aggregation of nZVI. It is used because of
its high durability, good mechanical strength and dispersion.

3.6.1 Synthesis of Humus-Supported Nanoscale Zero-Valent Iron

The preparation of humus-supported nZVI was initiated by the stirring of the

mixed solution consisting of humus (300 mesh) and ferric solution (ethanol:water
= 7:3) for 6 hours at room temperature after 20 minutes of ultrasonic dispersion.
Following that, the excess Fe3+ was filtered and washed with deionised water.
NaBH4 was then added drop-wise into the mixture under constant stirring for 30
minutes and N2 environment. The resulted producted was rinsed thrice with
deionized water and ethanol to remove excess impurities. Lastly, the H-nZVI
particles were vacuum dried for 12 hours at 65 ˚C.

3.6.2 Batch Experiment on Removal of Cr(VI)

After the preparation of stock solution of Cr(VI), appropriate amount of Cr(VI)

solution was added into centrifuge tubes together with H-nZVI. During the
reaction time, the solution initial pH was kept at 6.5 to ensure the consistency of
the results obtained. The experiment processes were carried out at 25 ˚C at 200
rpm for roughly one and a half hours. The sample of resultant solution was then
filtered through a 0.22 μm filter membrane.

3.6.3 Reaction Mechanism

Figure 7: Mechanism of the interaction of Cr(VI) with H-nZVI [6]

17
Figure 7 demonstrates the interaction between Cr(VI) and H-nZVI. Cr(VI) in
aqueous solution was first absorbed on the H-nZVI surface. Then, Cr(VI) was
reduced by Fe0 and co-precipitated or precipitated on the surface of H-nZVI
material. Futhermore, Cr(VI) was reduced to the Cr(III) by H-NZVI and
immobilized by precipitation as Cr(OH)3 or by incorporation into the iron
hydroxide/iron oxide on the surface forming Cr3+-Fe3+ hydroxides, but the
formation of these hydroxides may inhibit electron transfer from the Fe0 to the
surface, thus having negative impact on the redox process and causing a decrease
of Cr(VI) removal, especially at high Cr(VI) concentrations. The high specific
surface area of humus surface give numerous reactive sites to capture Cr(VI).

18
3.7 Insights into the Simultaneous Removal of Cr6+ and Pb2+ by a Novel Sewage
Sludge-Derived Biochar Immobilized Nanoscale Zero Valent Iron: Coexistence
Effect and Mechanism [7]

In this study, simultaneous removal of Cr6+ and Pb2+ by a novel sewage sludge-derived
biochar immobilized nanoscale zero valent iron (SSB-nZVI) was investigated. Most of
the biochar derived from sewage sludge had low surface area due to the lack of porous
structure. Thus, a promosing pore-forming agent such as starch was used as an addictive
to form a porous structure on the biochar. As a result, the removal efficiency was
improved significantly.

3.7.1 Synthesis of Biochar-Supported Nanoscale Zero-Valent Iron

The biochar/nZVI composite was synthesized using the sewage sludge and the
starch by a facile two-steps method. The sludge collected was having some pre-
treatment. The sludge was washed using double distilled water and dried at 100-
110˚C for one night. Next, the sample was ground and sieved through a 100 mesh
sieve and lastly stored in a closed bottle.

Starch was added into the solution containing ethanol and double distilled
water in a conical flask with stirring. After that, pre-treated sewage sludge was
added into the solution. The mixture was stirred for 480 minutes in order to make
sure completely uniform immersion. The mixture was dried and put into a
crucible, then heated to 600˚C for 180 minutes under N2 atmosphere.

3.7.2 Batch Experiment on Removal of Cr6+ and Pb2+

The experiment was carried out in a flask containing a solution of Cr6+ and Pb2+
with mechanical stirring under aerobic condition. After a certain time intervals,
some samples were collected. Next, the samples were centrifuged and a filter was
used to separate the powders. The solution pH was adjusted to 4 with H2SO4 and
NaOH solutions.

For reusable experiments, centrifugation and filtration were performed in

order to recycle the SSB-nZVI remained in the reaction solution. The residual
solid was washed with double distilled water and dried under vacuum overnight.
After that, the dried solid can be used for the new run.

19
3.7.3 Reaction Mechanism

A possible mechanism on the removal of Cr6+ and Pb2+ using SSB-nZVI involved
two main steps which are the adsorption and reduction processes. First step is
adsorption of both Cr6+ and Pb2+ over the porous structure of the SSB-nZVI and
followed by reduction and precipitation of both Cr6+ and Pb2+ over nZVI particles.

Most of Cr6+ species was adsorbed to the SSB-nZVI surface due to its
porous structure with surface iron hydroxyl groups. Reduction was then occurred
on Cr6+ and Cr3+ formed. Cr3+ species then reacted with O2 and OH- to produce
Cr2O3 and Cr(OH)3 which formed precipitate on the SSB-nZVI surface.

2Fe0 + O2 + 4H + → 2Fe2+ + 2H2 O

Fe0 + HCrO4− + 7H + → Cr 3+ + Fe3+ + 4H2 O

2Fe0 + Cr2 O2− +

7 + 14H → 2Cr
3+
+ 2Fe2+ + 7H2 O

3Fe2+ + HCrO4− + 7H + → Cr 3+ + 3Fe3+ + 4H2 O

Meanwhile, for Pb2+ species, most of Pb2+ species were attracted and
immobilized on the SSB-nZVI surface. Same mechanism was happened on Pb2+.
Reduction occurred and Pb(OH)2 or PbO was formed via the precipitation process.
Small fraction of Pb0 was formed due to the reduction of SSB-nZVI.

2Fe0 + 3Pb2+ + 4H2 O → 3Pb0 + 2FeOOH + 2H +

Fe2+ + H2 O → FeOH + + H +

FeOH + + Pb2+ → PbOH + + Fe2+

PbOH + + H2 O → Pb(OH)2 + H +

Figure 8: Reaction mechanism for simultaneous removal of Cr6+and Pb2+ by SSB-nZVI [7]

20
3.8 Enhanced Hexavalent Chromium Removal Performance and Stabilization by
Magnetic Iron Nanoparticles Assisted Biochar in Aqueous Solution:
Mechanisms and Application Potential [8]

Biochar (BC) is introduced as a support for the nZVI in this study for the removal of
the Cr6+. It is used as an improvement of colloidal stabilization and positive surface
change for the enhancement of the Cr6+ removal.

3.8.1 Synthesis of Biochar-Supported Nanoscale Zero-Valent Iron

The biochar was derived from the collected the wetland reed obtained in Harbin,
China. The raw biochar was prepared by torrefaction of the biomass powder at
600 ˚C for one and a half hours under N2 atmosphere after passing through a 2
mm sieve. The biochar was ready for usage after cooling to room temperature.
The synthesis procedures of biochar-supported nZVI was similar as mentioned in
previous sections by using sodium borohydride reduction method where NaBH4
was added drop by drop to the mixture of biochar and solution contained nZVI
particles. The resulting product was rinsed by ethanol and distilled water before
being vacuum filtered and dried for overnight.

3.8.2 Batch Experiment on Removal of Cr(VI)

Potassium dichromate (K2Cr2O7) was dissolved to prepare the stock solution of

Cr6+. Solid sample was of biochar-supported nZVI was added into a batch reactor
consisting of Cr6+ solution. Aliquot samples were collected at certain time
intervals and filtered through a 0.22 μm filter membrane when the reactor being
stirred at 250 rpm at room temperature. After that, 1,5-diphenylcarbazide (DPC)
colorimetric method with a UV-vis spectrophotometer was applied to determine
the residual Cr6+ concentration and the respective removal efficiency.

3.8.3 Reaction Mechanism

As the reaction proceeded, Cr6+ content decreased as the Cr3+ content increased,
illustrating that most of Cr6+ were converted to Cr3+ on the surface of nZVI-BC.
The existence of Cr6+ might be derived from electrostatic adsorption by positive
charge or complexation with organic groups. Then, the C-C content decreased
with an increase in C-O and O-C=O content, indicating that more oxygen
containing groups emerged the surface C-H bond provided the reduction

21
reactivity, resulted in the oxidization of surface organic groups. Thus, it is shown
that Cr6+ was reduced to low valent Cr3+, then was captured and immobilized via
complexation or precipitation.

Figure 9: Schematic diagram of Cr6+ removal mechanism [8]

22
3.9 Performance of Pb(II) Removal by an Activated Carbon Supported Nanoscale
Zero-Valent Iron Composite at Ultralow Iron Content [9]

The study has synthesized activated carbon supported nanoscale zero-valent iron
composite (nZVI/Ac) at ultralow iron content and used it to remove Pb(II) from
aqueous solution. The nZVI/Ac with ultralow iron content showed a highly efficient
Pb(II) removal performance with 95% of Pb(II) eliminated within 5 minutes.

3.9.1 Synthesis of Activated Carbon-Supported Nanoscale Zero-Valent

Iron

Figure 10: Scheme of the preparation procedure for nZVI/AC

Figure 10 illustrates the scheme of the synthesis procedure used for the
preparation of nZVI/AC composites. Firstly, FeSO4·7H2O was dissolved in a
mixed solvent containing ultrapure water and ethanol together wth PEG-200 as
the surfactant. The mixture was then stirred under N2 atmosphere for 2 hours.
The procedure was followed by the impregnation of activated carbon (AC) in
the solution for another 120 minutes. After that, the same volume of NaBH4
solution was added drop by drop by a peristaltic pump. After the addition of
NaBH4, the mixed solution was stirred vigorously for 30 minutes before being
vacuum filtered to obtain nZVI/AC composites. The product was rinsed
alternately with ultrapure water and anhydrous ethanol and the resultant samples
were dried at 70˚C in a vacuum oven overnight followed by storage in a vacuum
desiccator. The overall synthesis reaction by liquid phase reduction can be
written as:

𝐹𝑒 2+ (𝑎𝑞) + 2𝐵𝐻4− (𝑎𝑞) + 6𝐻2 𝑂 → 𝐹𝑒 0 (𝑠) ↓ +2𝐵(𝑂𝐻)3 + 7𝐻2 ↑

23
3.9.2 Batch Experiment on Removal of Pb(II)

The preparation for stock solution of Pb(II) was done by dissolving Pb(NO3)2
with ultrapure water in a volumetric flask. Batch experiment was conducted in
conical flask consisting nZVI/AC composites agitated by a rotary shaker and a
digital constant temperature otary shaker equipped with a thermostatic water bath.
Supported nZVI was added into Pb(II) solution and aliquot of the sample was
obtained at certain time intervals before being filtred through a membrane filter.
Then, the residual Pb(II) concentration was measured using ICP-OES
(Inductively Coupled Plasma Optical Emission Spectrometry) and the removal
efficiency of Pb(II) was calculated as:

𝐶0 − 𝐶𝑡
𝑅(%) = × 100%
𝐶0

where R is the removal efficiency of Pb(II); C0 is the initial concentration of Pb(II)

in the solution; Ct is the concentration of Pb(II) at the adsorption time t.

3.9.3 Reaction Mechanism

The first stage of the mechanism is initiated by the direct precipitation between
Pb(II) in solution and OH- generated by the reduction of H2O by the supported
nZVI to generate Pb(OH)2.

Following that, Pb(OH)2 formed interacts with carbon dioxide dissolved in

the solution to give rise to the formation of white lead with given chemical
formula of [2PbCO3·Pb(OH)2]. At the same time, other Pb (II) from the solution
adsorbs quickly on the surface of nZVI/AC and some of the adsorbed Pb (II)
either directly or indirectly reduced to to Pb0 by the supported nZVI or the in situ
generated Fe(II).

Whereas the other Pb(II) are precipitated and trapped by OH- from the
reduction of H2O in the voids of the oxides film. In addition, these reactions are
accompanied by the formation of new adsorptive sites on the surface of aging
oxides of the supported nZVI.

24
Figure 11: Schematic of Pb(II) removal by as-synthesized nZVI/AC [9]

25
4.0 CONCLUSION

Among the nine journals studied, eight of them have loaded supporting materials such
as biochar, activated carbon, humus, kaolin, magnesium hydroxide, bentonite and
sepiolite onto nZVI. The studies have proven that the removal efficiency of supported-
nZVI is much better than the bare nZVI. The proposed reason is that nZVI particles
immobilized on the surface of supporting materials and it helps to decrease the tendency
of nZVI particles to aggregate and enhance the dispersivity.

Based on the studies referred, it can be found that most of the procedures used to
synthesis supported-nZVI is sodium borohydride reduction method where solid
materials are obtained. This is because sodium borohydride solution is a good reducing
reagent since it is very effective for the reduction of aldehydes and ketones to respective
alcohol. Also, it is much milder reducing agent and comparatively safe. Furthermore,
batch reactor is the most favourable reactor used to conduct the experiments regarding
the remediation of heavy metals by nanoscale zero-valent iron.

The methods in remediation of heavy metals by nanoscale zero valent ion are
basically including adsorption, reduction, oxidation, precipitation, ion exchange and
membrane filtration. The adsorption method seems to be the most occurring reaction in
the journals studied. This is due to its highly effective outcomes, simplicity,
convenience and renewability. Also, both Pb(II) and Cr(VI) are the heavy metals that
most studies focus on with the reason of their high occurrence in treated water.

To conclude, more studies need to be conducted to functionalize the

nanomaterials with better performance in wastewater treatment, specifically
remediation of heavy metals, in the near future. More Malaysian researchers are
encouraged to step into the studies on nanomaterial and nanotechnology as it’s
becoming a worldwide hot topic in science and technology field of study in the recent
decades.

26
5.0 REFERENCES

[1] Xin Zhang, Shen Lin, Zuliang Chen, Mallavarapu Megharaj, Ravendra Naidu
(2011). Kaolin-Supported Nanoscale Zero-Valent Iron for Removal of Pb2+ from
Aqueous Solution: Reactivity, Characterization and Mechanism. Water Research,
45, 3481-3488.

[2] Minghui Liu, Yonghao Wang, Luntai Chen, Yan Zhang, Zhang Lin (2015).
Mg(OH)2 Supported Nanoscale Zero Valent Iron Enhancing the Removal of Pb(II)
from Aqueous Solution. Applied Materials & Interfaces, 7, 7961-7969.

[3] Rongbing Fu, Yingpin Yang, Zhen Xu, Xian Zhang, Xiaopin Guo, Dongsu Bi
(2015). The Removal of Chromium (VI) and Lead (II) from Groundwater Using
Sepiolite-Supported Nanoscale Zero-Valent Iron (S-nZVI). Chemosphere, 138,
726-734.

[4] Shaolin Li, Wei Wang, Feipeng Liang, Wei-xian Zhang (2016). Heavy Metal
Removal Using Nanoscale Zero-Valent Iron (nZVI): Theory and Application.
Journal of Hazardous Materials, 322, 163-171.

[5] Zeng-Hui Diao, Xiang-Rong Xu, Hui Chen, Dan Jiang, Yu-Xi Yang, Ling-Jun
Kong, Yu-Xin Sun, Yong-Xia Hu, Qin-Wei Hao, Ling Liu (2016). Simultaneous
Removal of Cr(VI) and Phenol by Persulfate Activated with Bentonite-Supported
Nanoscale Zero-Valent Iron: Reactivity and Mechanism. Journal of Hazardous
Materials, 316, 186-193.

[6] Rongbing Fu, Xian Zhang, Zhen Xu, Xianpin Guo, Dongsu Bi, Wei Zhang (2016).
Fast and Highly Efficient Removal of Chromium (VI) Using Humus-Supported
Nanoscale Zero-Valent Iron: Influencing Factors, Kinetics and Mechanism.
Separation and Purification Technology, 174, 362-371.

[7] Zeng-Hui Diao, Jian-Jun Du, Dan Jiang, Ling-Jun Kong, Wen-Yi Huo, Cui-Mei
Liu, Qi-Hang Wu, Xiang-Rong Xu (2018). Insights into the Simultaneous
Removal of Cr6+ and Pb2+ by a Novel Sewage Sludge-Derived Biochar
Immobilized Nanoscale Zero Valent Iron: Coexistence Effect and Mechanism.
Science of the Total Environment, 642, 505-515.

27
[8] Shishu Zhu, Xiaochen Huang, Dawei Wang, Li Wang, Fang Ma (2018).
Enhanced Hexavalent Chromium Removal Performance and Stabilization by
Magnetic Iron Nanoparticles Assisted Biochar in Aqueous Solution: Mechanisms
and Application Potential. Chemosphere, 207, 50-59.

[9] Xuejiao Liu, Dengguo Lai, Yin Wang (2018). Performance of Pb(II) Removal by
an Activated Carbon Supported Nanoscale Zero-Valent Iron Composite at
Ultralow Iron Content. Journal of Hazardous Materials, 361, 37-48.

[10] Zhanqiang Fang, Xiuqi Qiu, Ruixiong Huang, Xinhong Qiu, Mingyu Li (2011).
Removal of Chromium in Electroplating Wastewater by Nanoscale Zero-Valent
Metal with Synergistic Effect of Reduction and Immobilization. Desalination,
280, 224-231.

28