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Ag0 and Au0 nanoparticles encapsulated in sol-gel matrices as catalysts in

reductive de-halogenation reactions

Article · September 2017

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 MICHAEL MEISTELMAN1, JAYDEEP ADHIKARY2, ARIELA BURG3, DROR SHAMIR4,
GREGORY GERSHINSKY5, DAN MEYERSTEIN2,6, YAEL ALBO*,1
*Corresponding author
1. Chemical Engineering, Biotechnology and Materials Department, Ariel University, Ariel, Israel
2. Chemical Sciences Department, Ariel University, Ariel, Israel
3. Chemical Engineering Department, Sami Shamoon College of Engineering, Beer-Sheva, Israel
4. Chemistry Department, Nuclear Research Centre Negev, Beer-Sheva, Israel
5. Chemistry Department, Bar-Ilan University, Ramat Gan, Israel
Yael Albo 6. Chemistry Department, Ben-Gurion University, Beer-Sheva, Israel

Ag0 and Au0 nanoparticles encapsulated

in sol-gel matrices as catalysts in
reductive de-halogenation reactions
KEYWORDS: Sol-gel matrices, Ag0 and Au0 nanoparticles, de-halogenation, water treatment, catalysis.

Abstract Halogenated pollutants have low solubility, are toxic, tend to accumulate in food chains and are the
contaminates most often found in the subsurface environment. Various approaches to achieve their
degradation have been applied, including bioremediation, chemical methods based on zero valent iron and bimetallic particles,
and electro-catalysis. In this review we discuss our recent results concerning Ag0 and Au0 nanoparticles incorporated within SiO2
matrices via the sol-gel synthesis route as heterogeneous catalysts for the reductive de-halogenation of halogenated organic
compounds by NaBH4. Matrices with different compositions were prepared in order to optimize the preparation procedure.
The reduction percentage and the product distribution are affected by the matrix composition and the reduction conditions; pH,
substrate concentration and NaBH4 rate of addition. The role of the encapsulated metal nanoparticles on the reductive
de-halogenation of halo-acetic acids is discussed.

INTRODUCTION nanoparticles entrapped in sol-gel matrices. Sol-gel entrapped

An enormous number of halogenated organic compounds
are routinely found in water, and are of great concern due to
their bioaccumulation, toxicity and persistence (1).
They make up a large part of the emerging persistent
organic pollutants and toxic compounds (2). These include
polychlorinated biphenyls, polybrominated diphenyl
ethers extensively used as brominated flame-retardants
and disinfection by-products usually generated during the
chlorine disinfection process (3). Various technologies have
been developed to degrade these kinds of halogenated
organic compounds to environmentally safe products, such
as biodegradation (4), electrochemical methods (5),
zero-valent metal (6), iron-based bimetallic catalysts and UV
irradiation (7). Even though, they are efficient catalysts for a
variety of important processes, noble metal nanoparticles
have not been used for the removal of halo-organic
compounds found in waste-water. In recent years, noble
metal nanoparticles have attracted tremendous attention
due to their potential applications in various fields such as
catalysis (8), sensors (9-13), optics (13) and fuel cells (14),
but they were not applied to resolve the important problems
associated with waste water treatment. We have successfully
reported on sol-gel entrapped gold catalysts for the de-
halogenation of bromo substituted acetic acid using
aqueous NaBH4 as the reducing agent (15).
To reduce the cost of our catalyst, and looking to make more
advancement in this field, we have purposely synthesized silver
nano particles are one of the most promising heterogeneous
catalysts (16) that have been applied in the catalysis of
various reactions including C-C bond formation, hydrosilylation
of alkene, solvent free alcohol oxidation etc. (17).
By performing reductive de-halogenation reactions, a new
environmentally important use of heterogeneous sol-gel
catalysts has emerged. Herein we discuss our recent results
concerning Ag0 and Au0 nanoparticles incorporated in
organically modified silica matrices (ORMOSIL) via the sol-gel
synthesis route as heterogeneous catalysts for the reductive
de-halogenation of halogenated organic compounds by
NaBH4 (Scheme 1). We have chosen bromoacetic acid (BAA)
as a model substrate to study the role of the encapsulated
metal nanoparticles in the reductive de-halogenation of
halo-acetic acid.
Scheme 1.
Schematic diagram
of reductive
dehalogenation
of bromoacetic
acid using sol-gel
entrapped silver
(Ag-cat) and gold
(Au-cat) catalyst.

Monographic special issue: Catalysis & Biocatalysis - Chimica Oggi - Chemistry Today - vol. 35(5) September/October 2017 23
Gold and silver nanoparticles were incorporated into
organically modified silica matrices by using the two
steps acid /base sol-gel syntheses route (15,18). HAuCl4
and AgNO3 were added to ethanol solutions containing
tetraethylorthosilicate (TEOS), trimethoxymethylsilane
(MTMOS) and (3-Aminopropyl)trimethoxysilane (APS) with
different compositions for the preparation of gold catalysts
(Au-cat) and silver catalysts (Ag-cat), respectively.
Au0 nanoparticles were obtained after the reduction
with sodium borohydride in the sol stage. However, the
reduction of silver was not done immediately after the
addition of silver nitrate, but after one week of ageing of
the gel matrix. The presence of a Ag0 or Au0 crystalline
phase in Ag-cat and Au-cat, respectively, was confirmed
by using PXRD. The PXRD pattern of the Ag-cat is Figure 1. PXRD pattern of Ag-cat having 0.050 mol% of Ag0. Inset
represented in Figure 1. The particle size was calculated zoomed out pattern.
using the Debye-Scherer equation and was found to be 6.3
± 0.2 and 24 ± 0.5 nm for the gold and silver nano particles,
respectively. We considered the (111) plane for such
calculation as this peak is stronger than the others.
A broad peak at 2θ = 22° implies the amorphous nature of
silica in Ag-cat (19). The IR spectra of the blank and doped
matrices confirm that the incorporation of the NPs does not
affect the chemical structure of the ORMOSILs obtained
(Figure 2). The UV/Vis spectrum of Ag-cat was taken under
sol conditions and is shown in Figure 3.
A sharp band at around 396 nm indicates that the size of
the Ag0-NPs is ca. 20 ± 3 nm, as reported earlier (20).

We have recently found that Au-cat can be used as a

catalyst in the reduction of both tribromo-acetic acid Figure 2. FTIR spectra of blank matrix and Ag-cat.
(TBAA) and BAA by NaBH4 (15). Acetic acid is the sole
product in the reduction of BAA, whereas a mixture
of acetic acid and succinic acid is obtained in the
reduction of TBAA. The relative yields and the degree of
de-halogenation depend on the relative concentrations
of the substrate to sodium borohydride as well as on the
rate of NaBH4 addition. The mechanism reported for the
reduction of TBAA suggests that both the (i) hydrogen
atoms obtained in the M°-NPs catalyzed hydrolysis of the
NaBH4 and (ii) the halogenated radicals formed during
the reaction are bound to the surface of the NPs. The rate
of addition of the borohydride affects the steady state
concentration of the hydrogens adsorbed to the NPs
surface and thus the redox potential of the NPs.
This explains the effect of the relative yields of the
succinic acid and acetic acid on the rate of addition of
borohydride. The formation of succinic acid proves that
.CH -
2-nBrnCO2 , n =1 or 2, are formed in the catalytic process.
A complete reduction of BAA and TBAA was obtained at
Figure 3. UV-vis spectrum Ag-cat in sol state. Inset: image of Ag-cat sol.
1:4 and 1:6 BAA to NaBH4 mole ratio, respectively.

The implementation of nanotechnologies in environmental

remediation processes will eventually depend on the
cost of the nanomaterials. Due to the much lower cost of
Figure 4. De-
silver as compared with other noble metals, Ag-cat has
halogenation of
been prepared and tested in the reduction of BAA. 93% BAA using Ag-cat
and 95% of the BAA was reduced to acetic acid at pH and Au-cat at pH
5.0 and pH 7.0.
5.0 and 7.0, respectively. However, only 45% and 40.7% ([BAA] = 1.4×10-
de-halogenation were obtained using Au-cat under the 3 (M), [NaBH ]
4
same reaction conditions (Figure 4). This result implies = 2.8×10-3 (M),
catalyst = 0.50 g).
higher catalytic efficiency of Ag-cat in the reductive de-
halogenation of BAA and therefore Ag-cat was chosen for
further studies.

24 Monographic special issue: Catalysis & Biocatalysis - Chimica Oggi - Chemistry Today - vol. 35(5) September/October 2017
Matrices with different molar ratios of TEOS and MTMOS
were prepared to examine the effect of different matrix
compositions on the yield of acetic acid. No significant
alteration of the yield of acetic acid was obtained while the
mole percentage of the MTMOS was increased from 10%
to 30%. However, Ag-cat made by 100% TEOS produced a
smaller yield of acetic acid (Figure 5). The effect of MTMOS
on the catalytic process may be attributed to the more
hydrophobic surrounding of the NPs in the presence of
MTMOS that inhibits charge distribution and increases the
reduction potential of the NPs.
Figure 5. De-halogenation of BAA catalysed by Ag-cat prepared
by using different ratios of TEOS and MTMOS at pH 5.0 and pH 7.0.
([BAA] = 1.4×10-3 (M), [NaBH4] = 2.8×10-3 (M), catalyst = 0.50 g).
Increasing the concentrations of both BAA and NaBH4 by
ten times affords a slight decrease in the relative degree of
dehalogenation (Figure 6). This is probably due to the saturation
of the active sites at high concentrations of the reactants. This
result may be improved by increasing the relative concentration
of the sodium borohydride as was demonstrated previously for
the Au-cat in the reduction of both BAA and TBA (15).
Figure 6. De-halogenation of BAA catalysed by Ag-cat (10 times
more) using NaBH4 (10 times more) at pH 5.0. ([BAA]= 1.4×10-2 (M),
[NaBH4] = 2.8×10-2 (M), catalyst = 0.50 g).
The ability of different noble metal nanoparticles including
Au0 and Ag0 to catalyze the reaction of BH4- with water to
form H2 and borate (21) and the reduction of p-nitrophenol to
form p-aminophenol have been extensively studied (22).
The first steps in these processes involve the binding of
hydrogens atoms to the surface of the NPs:
H O
2
(1) (M°-NP) + nBH4- → {(M°-NP)-H4n}-4n + nB(OH)3
Clearly this is a complex process and some partially oxidized
BH4- are formed as intermediates. In aqueous solutions, this
reaction is probably followed by:
(2) {(M°-NP)-H4n}-4n + mH3O+ ⇐⇒ {(M°-NP)-H4n+m}m-4n + mH2O
Monographic special issue: Catalysis & Biocatalysis - Chimica Oggi - Chemistry Today - vol. 35(5) September/October 2017
The hydrogen atoms in {(M°-NP)-H4n+m}m-4n clearly have a
partial negative charge.
Acetic acid will be formed either by a hydride transfer
reaction in a similar manner to that previously proposed for
the reduction of p-nitrophenol by BH4- catalysed by different
noble metal NPs (23):
(3) {(M°-NP)-H4n+m}m-4n + CH2BrCO2H →{(M°-NP)-H4n+m-1}m-4n+1
+ CH3CO2H + Br-
However, a radical involved mechanism should also be
considered as a possible pathway, as already reported in
the case of TBA reduction. These radicals are formed either
by an electron transfer process or via bromide abstraction
by a hydrogen atom bound to the surface of the NPs. In this
reaction pathway, acetic acid will be obtained by hydrogen
abstraction.
(4) {(M°-NP)-H4n+m}m-4n+1/{(Au°-NP)-H4n+m-1}m-4n + .CH2CO2H →
{(M°-NP)-H4n+m-1}m-4n+1/{(M°-NP)-H4n+m-2}m-4n + CH3CO2H
Or by:
(5) {(M°-NP)-H4n+m}m-4n+1/{(Au°-NP)-H4n+m-1}m-4n + .CH2CO2H →
{(M°-NP)-(H4n+m)-CH2CO2H}m-4n+1/{(Au°-NP)-(H4n+m-1)-CH2CO2H}m-4n
followed by:
(6) {(M°-NP)-(H4n+m)-CH2CO2H}m-4n+1/{(Au°-NP)-(H4n+m-1)-
CH2CO2H}m-4n + H3O+ →
{(M°-NP)-H4n+m}m-4n+2/{(Au°-NP)-H4n+m-1}m-4n+1 + CH3CO2H + H2O
Incorporation of Au0 into the inner mesopores of ORMOSIL results
in a stable catalyst that can be reused in many reaction cycles
(15, 17). Such stability was also demonstrated by the Ag-cat.
The catalyst was washed extensively with water, dried well and
reused in subsequent reaction runs under the same conditions.
The yields in each cycle do not vary significantly over three
cycles, indicating the high stability of the catalyst (Figure 7).
Figure 7. Recyclability and reusability test of Ag-cat.
Under similar reaction conditions, but in the absence of the
catalyst no de-halogenation was noticed. Also in absence of
NaBH4 but in the presence of catalytic amount of Ag-cat no
reduction is observed.
25
CONCLUSIONS
The results presented herein indicate that Ag0
nanoparticles entrapped in sol-gel matrices are more
efficient than that of the gold catalyst towards reductive
de-halogenation of bromoacetic acid. Here, silver
nanoparticles have been introduced for the first time for
use in the removal of halogenated organic pollutants
present in polluted water using a green approach. The
efficiency of silver catalyst over gold nanoparticles might
be due to one or more of the following reasons:
1. The size of gold nanoparticles obtained from PXRD is
smaller than that of the silver nanoparticles. This might
change the redox potential of the particles in the
presence of BH4- and change the competition
between the reaction of {(M°-NP)-H4n+m} m-4n with
BrCH2COO - and the release of H2 in the M°-NPs
catalyzed hydrolysis of BH 4-.
2. Due to their very small size, the Au°-NPs may be
entrapped deep inside the pores of the sol-gel
matrices, and therefore not all the nanoparticles are
accessible to the BH4- and/or the bromoacetic acid.
However, the size of Ag°-NPs decreases the probability
of this phenomenon.
3. The number of active hydrogen atoms on the surface
of the NPs is affected by the over potential for H2
release from the M°-NPs according to the reaction
below:
{(Au°-NP)-H 4n+m} m-4n → {(Au°-NP)-H4n+m-2} m-4n + H2
The over potential of Ag0 and Au0 NPs are not known, but
it surely affects the reduction process and the catalytic
efficiency.
The applicability of a new technology is highly dependent
on the cost effectiveness of the suggested process.
This is even more relevant regarding environmental
technologies due to relatively low market values
characteristic to this field. The ability to obtain
reproducible catalysts by using sol-gel technology,
the catalytic amount of silver and gold used in the
preparation of the matrices and stability of the catalyst
obtained are important advancements towards
the implementation of highly active noble metal
nanoparticles in water remediation processes.
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