A Journal of

Accepted Article
Title: The Reductive De-halogenations of Mono and Tribromo Acetic
Acids by NaBH4 Catalysed by Gold Nanoparticles Entrapped in
Sol-Gel Matrices Follow Different Pathways

Authors: Jaydeep Adhikary, Michael Meistelman, Ariela Burg, Dror

Shamir, Dan Meyerstein, and Yael Albo

This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700069

Link to VoR: http://dx.doi.org/10.1002/ejic.201700069

European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
The Reductive De-halogenations of Mono and Tribromo Acetic
Acids by NaBH4 Catalysed by Gold Nanoparticles Entrapped in
Sol-Gel Matrices Follow Different Pathways
Jaydeep Adhikary,[a] Michael Meistelman,[b] Ariela Burg,[c] Dror Shamir,[d] Dan Meyerstein,[a,e] and Yael
Albo*[b]
Abstract: An efficient, green and reusable gold nano-particles
entrapped in an organically modified sol-gel silica matrix catalyses
the reduction of monobromo and tribromoacetic acids by NaBH4.
Interestingly, the reduction of tribromoacetic acid yields succinic acid
along with acetic acid while monobromoacetic acid is reduced to
merely acetic acid. The relative yields of succinic acid and acetic
acid depend on the rate of addition of the BH4-. In slow addition,
succinic acid is obtained as the major product. The variable product
distribution is achieved due to the different pathways of the de-
halogenation.
Introduction
Chlorine disinfection is being used in the provision of safe
[1]
drinking water and is widely used in disinfection of
wastewater.[2] However, these disinfection processes result in
the production of several toxic by-products due to the reaction
between chlorine and organic matter in water.[3] It was reported
[2]
that some brominated disinfection by-products (BDBP) are
also produced during chlorine disinfection processes due to
bromide traces.[4] The presence of trace concentrations of
bromide ion in drinking water has major implications regarding
health effects associated with disinfection by products. It has
been shown that often BDBP represent higher developmental
toxicity and growth inhibition than their chlorinated analogues. [5,6]
Tribromoacetic acid (TBAA) and monobromoacetic acid (MBAA)
are typical BDBP, with high toxicity, genotoxicity,
carcinogenicity.[7] An effective treatment of BDBP which will
provide some guidance for the provision of safe drinking water is
thus urgently needed. In most of the examples in the literature,
chlorinated disinfection by products were taken as the
substrates for studies on the removal of halo-organic
[a]
Dr. Jaydeep Adhikary, Prof. Dan Meyerstein
Chemical Sciences Dep., Ariel University, Ariel, Israel.
[b]
Michael Meistelman, Dr. Yael Albo
Chemical Engineering Dep., Ariel University, Ariel, Israel. E-mail:
yaelyt@ariel.ac.il
[c]
Dr. Ariela Burg
Chemical Engineering Dep., Sami Shamoon College of Engineering, Beer-
Sheva, Israel.
[d]
Dr. Dror. Shamir
Chemistry Dep., Nuclear Research Centre Negev, Beer-Sheva, Israel.
[e]
Prof. Dan Meyerstein
Chemistry Dep., Ben-Gurion University, Beer-Sheva.
compounds from drinking water.[8] Only few examples have been
found where de-halogenation of BDBP have been studied and in
those cases they used zero valent iron, silver catalyst, iron
based bimetallic catalysts and UV irradiation. [9]
De-halogenations of other halo-organic compounds
were studied previously by many groups. [10] Most of them used
TiO2 and Pd based catalysts for the de-halogenation. However
the exceptionally effective catalytic species, [11] Au° nanoparticles
(Au°-NPs), were used only rarely for the de-halogenation
process.[10e] The catalysis, by Au°-NPs, of the de-halogenation
of haloacetic acids has not been reported up to date. Therefore,
TBAA and MBAA have been chosen as substrates in the
present study for the reductive de-halogenation using BH4-
catalysed by sol-gel entrapped Au°-NPs.
Herein, are reported the synthesis and structural
investigation of Au°-NPs sol-gel entrapped in the mesopores of
organically modified sol-gel silica (ORMOSIL) matrices. To the
best of our knowledge, only two applications of Au°-NPs
entrapped in organically modified silica (ORMOSIL) were
reported. [12,13]
Ramaraj et. al. encapsulated Au°/Ag° bimetallic
NPs in methyl-modified silica for electrocatalytic reduction and
sensing of H2O2 and Pagliaro et. al. reported ORMOSIL-
entrapped gold nanoparticles applied for 1-phenylethanol
oxidation. In the present study, the matrices have been
employed in the de-halogenation of MBAA and TBAA using
and NaBH4 as the reducing agent. It was previously reported that
TBAA is consecutively de-brominated to dibromoacetic acid
(DBAA) then to MBAA and finally into acetic acid (AA) (Scheme
1).[14] Surprisingly, the results reported herein point out that Au°-
NPs catalyse the de-bromination of TBAA via a different
pathway yielding succinic acid (SA) as the major product.
However, the reduction of MBAA proceeds via the literature
reported mechanism (Scheme 2). Furthermore, even the rate of
the addition of the reducing agent, NaBH 4, affects the relative
yields of the products during TBAA reduction.
Succinic acid and its derivatives are widely used in
industry as specialty chemicals with applications in polymers,
foods, pharmaceuticals and cosmetics. In addition, succinic
acid has also some biological importance. There are three

Supporting information for this article is given via a link at the end of possible metabolic pathways leading towards succinate: the
the document.

1
This article is protected by copyright. All rights reserved.
European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
oxidative part of the citric acid cycle, the reductive part of the gold demonstrates four diffraction peaks attributable to Au°-
[15]
citric acid cycle, and the glyoxylate bypass. Nowadays, NPs, with face-centered cubic phase at 2 = 38.27, 44.40, 64.68
succinic acid is manufactured biochemically from glucose using and 77.55° that can be perfectly related to the (111), (200), (220)
several bacteria like an engineered Anaerobiospirillum and (311) crystal planes, respectively. Only two peaks at 2 =
succiniciproducens, an engineered Eschericia coli, and most 38.17 and 44.30 were observed in the case of 0.054 mol% of
recently via an engineered Mannheimia succiniciproducens.[16] In gold, Au-cat. The other two peaks at higher two theta were not
that consequence, our green and reusable gold catalyst could observed probably due to the low concentration of Au°-NPs in
play an imperative role in producing SA. Au-cat. The broad band for the (111) and (200) reflections for
the Au°-NPs, indicates that the size of the particles is in the
O 2e- + H+ Br - O
-
2e + H + Br - -
O 2e + H
+
Br -
O
nanometer range after immobilization without any aggregation.
[17,18]
The particle size of Au°-NPs in Au-cat was calculated using
Br3C OH Br2HC OH BrH2C OH H3C OH the Debye-Scherer equation and was found to be 6.3 ± 0.2 nm.
TBAA DBAA MBAA AA
The results for the (111) plane were used for this calculation as
Scheme 1. The proposed pathway for the degradation of TBAA according to a this peak is stronger than the others. Such a crystalline phase
[14]
literature report. could not be detected in the PXRD spectrum of the blank matrix
i.e. characteristic to amorphous silica (not presented here). With
Au-cat,

(i) BrCH2COOH
NaBH4(slow addition)
CH3COOH (65%)
the increase in Au° loading, the colour of the matrices changes
H2O, 5h, stir (AA)
from light pink to ruby (Figure S1).
Au-cat,
NaBH4(slow addition)
(ii) Br3CCOOH CH3COOH (15%) COOHCH2CH2COOH (80%)
H2O, 5h, stir (AA) (SA)

+ BrCH2COOH(5%) Blank matrix

4 Au-cat
(MBAA)

Scheme 2. Au°-NPs entrapped in ORMOSIL catalysed de-halogenation of

%T

MBAA and TBAA. 2

-1
0 2910 cm

Results and Discussion 3472 cm

-1 2973 cm
-1
1628 cm
1418 cm
-1

-1
1280 cm
-1

1100 cm
-1 934 cm
-1
785 cm
-1

4000 3500 3000 2500 2000 1500 1000 500

As Au°-NPs entrapped within the pores of a gel cannot be cm-1
accessed by HRTEM, the prepared matrices were characterized Figure 1. FTIR spectra of blank matrix and Au-cat.
by FTIR, PXRD and UV-vis spectroscopy. The identification of
the possible functional groups present in the blank and Au-cat
matrices was achieved by FTIR spectroscopy (Figure 1). The (111) Au matrix (0.27 mol% of Au NPs)
800 Au-cat(0.054 mol% of Au NPs)
-1
broad band with a peak at 3472 cm is assigned to the
stretching vibrations of –OH groups present in the silica matrix.
600 (200)
Intensity

(220)
(311)
(HOH) band at 1628 cm-1 is due to adsorbed water since both 400

(111)
the matrices are hydrophilic in nature. The bands at 2973 and 200 (200)

-1
2910 cm are assigned to the stretching modes (anti symmetric 0
40 50 60 70 80
and symmetric, respectively) of the Si-CH3 bond. The 2degree

corresponding deformation modes appear at 1418 and 1280 Figure 2. PXRD pattern of the matrices having 0.054 mol%(Au-cat) and 0.27

cm , respectively. The asSi-O-Si band is broad with unresolved

-1 mol% of Au°-NPs.

components and a maximum absorption around 1100 cm -1. The UV-vis spectrum of the Au-cat was taken in sol condition
and is represented in the supplementary file (Figure S2). A
sSi-O-Si band overlaps with the (Si)-CH3 mode detected at
sharp peak at 515 nm. indicates that the size of Au°-NPs is ~ 10
785 cm-1. The band at 934 cm-1 is assigned as Si-OH. All the
nm. as reported earlier.[19]
important bands of the blank silica matrix are also found in the
MBAA and TBAA were chosen as substrates to study the
matrix after entrapping the Au°-NPs, indicating that incorporation
reductive de-halogenation. Details of the catalytic procedure are
of the Au°-NPs does not alter the internal structure of the matrix.
reported in the experimental section. The gold matrices
Figure 2 shows the PXRD patterns of gold matrices
prepared from 100% Tetraethyl orthosilicate (TEOS) had poor
containing 0.27 and 0.054 mol% gold (mol of gold vs. mol of
catalytic activity, probably due to the small porosivity of such
silicone) The PXRD pattern of the sample with 0.27 mol% of

2
This article is protected by copyright. All rights reserved.
European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
matrices.[20] Therefore matrices consisting of different ratios of
Figure 3b. Effect of the molar ratio of TBAA and NaBH4 on the products
Trimethoxymethylsilane (MTMOS) and TEOS were prepared. It distribution. Aqueous NaBH4 solution was added dropwise over a period of 3.5
h.
was found that gold catalyst (Au-cat) with 30% MTMOS and
70% TEOS worked superiorly to the other matrices. Au°-NPs are known to catalyse the reaction of BH4-
[21]
Consequently, all the reported results are for matrices with this with water to form H2 and borate and the reduction of p-
[22]
composition. The effect of the load of Au°-NPs, 0.027 to 0.27 nitrophenol to form p-aminophenol. The first step in these

mol%, (mol of gold vs. mol of silicone) into the matrix was processes clearly is:

studied. It was observed that the matrix consisting 0.054 mol%

worked commandingly. Further
concentration did not affect the yield of the products.
First, Au-cat catalysed reductive de-halogenation of
MBAA by NaBH4 was studied. It was found that at 1:4 ratio of
MBAA to NaBH4 (optimized), 100% MBAA was converted into
acetic acid. However, slow addition of the same amount of
NaBH4 resulted in 65% conversion of MBAA to AA.
Surprisingly, acetic and succinic acid are formed in the
Au-cat catalysed de-halogenation of TBAA (Figure 3). However,
in the analogous reduction of trichloroacetic acid (TCAA) the
only product is acetic acid. Four other experimental observations
shed light on the plausible mechanisms of Au°-NPs catalysed
de-halogenation by BH4-:
1. The relative yields of succinic acid and acetic acid
depend on the rate of addition of BH4 to the
suspension (Figure 3).
2. The total degree of de-halogenation depends on
the amount and the rate of addition of BH4 (Figure
3).
3. No (-CBr2COOH)2 or (-CHBrCOOH)2 are observed
as intermediates.
4. Also in the reduction of CHBr2COOH succinic acid
is a major product.
Substrate : NaBH4=1:10
Substrate : NaBH4=1:6
Substrate : NaBH4=1:4
H2O
increase in the gold (1) (Au°-NP) + nBH4-  {(Au°-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) {(Au°-NP)-H4n}-4n + mH3O+ {(Au°-NP)-H4n+m}m-4n + mH2O
The equilibrium constant of reaction (2) depends on
the the pH of the solution. If the redox potential is below the
over-potential for H2 release from the Au°-NPs then reaction (2)
will be followed by either:
(3) {(Au°-NP)-H4n+m}m-4n  {(Au°-NP)-H4n+m-2}m-4n + H2
or by:
(4) {(Au°-NP)-H4n+m}m-4n + H3O+/H2O
{(Au°-NP)-H4n+m-1}m+1-4n + H2 + H2O/OH-
In the presence of CH3-kBrkCO2H the {(Au°-NP)-
-
H4n+m} m-4n
might react via one of the following mechanisms:
(5) {(Au°-NP)-H4n+m}m-4n + CH3-kBrkCO2H 
{(Au°-NP)-H4n+m-1}m-4n+1 + CH4-kBrk-1CO2H + Br-
-
(6) {(Au°-NP)-H4n+m}m-4n + CH3-kBrkCO2H 
{(Au°-NP)-H4n+m}m-4n+1 + .CH3-kBrk-1CO2H + Br-
(7) {(Au°-NP)-H4n+m}m-4n + CH3-kBrkCO2H 
{(Au°-NP)-H4n+m-1}m-4n + .CH3-kBrk-1CO2H + H+ +Br-
Reaction (5) is a hydride transfer reaction, such reactions
were proposed in the Au°-NPs catalysed reduction of p-
TBAA
DBAA nitrophenol by BH4-.[23] This type of reaction cannot lead to the
MBAA
SA
AA formation of dimers, i.e. succinic acid. Reaction (6) is an electron
transfer process whereas reaction (7) is a bromide abstraction

Substrate : NaBH4=1:2
by a hydrogen atom bound to the surface of the Au°-NPs. Both

No NaBH4
these reactions were not observed up to date, but in the case of
0 10 20 30 40 50 60 70 80 90 100 110 CBr3CO2H one of them, at least, should occur as only the
% Yield
radicals formed in these reactions might yield succinic acid as a
Figure 3a. Effect of the molar ratio of TBAA and NaBH4 on the products
distribution. Aqueous NaBH4 solution was added in one time. final product.
The radicals formed in reaction (6) & (7) are formed
TBAA
DBAA
near the surface of the nano-particles and are therefore
Substrate : NaBH4=1:10
MBAA
SA expected to react with them via:
Substrate : NaBH4=1:6 AA

(8) {(Au°-NP)-H4n+m}m-4n+1/{(Au°-NP)-H4n+m-1}m-4n + .
CH3-kBrk-
Substrate : NaBH4=1:4

1CO2H  {(Au°-NP)-H4n+m-CH3-kBrk-1CO2H} m-4n+1

/{(Au°-NP)-
Substrate : NaBH4=1:2
m-4n
H4n+m-1-CH3-kBrk-1CO2H}
No NaBH4
in analogous reactions to those of other alkyl radicals with Au°-
0 10 20 30 40 50 60 70 80 90 100 110

% Yield NPs.[24] Alternatively they might react via:

3
This article is protected by copyright. All rights reserved.
European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
(9) {(Au°-NP)-H4n+m}m-4n+1/{(Au°-NP)-H4n+m-1}m-4n + .
CH3-kBrk- pollutants using a green approach is proposed. Of special
1CO2H  {(Au°-NP)-H4n+m-1} m-4n+1
/{(Au°-NP)-H4n+m-2} m-4n
+ CH4- interest are the observations that:
kBrk-1CO2H 1. Radicals are intermediates in the catalytic de-
i.e. via hydrogen atom abstraction, the rate constants of such halogenation process.
reactions are not known but recent results for M°-NPs, including 2. The detailed mechanism of the process differs for
Au°-NPs, suggest that they are fast. [25] different substrates.
Succinic acid will be formed via dimerization of two radicals on 3. The rate of addition of the reducing agent, BH4-,
the surface of the nanoparticles in analogous to the formation of has a major effect on the detailed mechanism of
ethane in recation of methyl radicals on the surface of Au°-NPs: the de-halogenation of TBAA. The slower the
[24a] addition the higher the yields of the desired
(10){(Au°-NP)-H4n+m-(CH3-kBrk-1CO2H)l} m-4n+1
/{(Au°-NP)-H4n+m-1- products. This is probably correct for other
(CH3-kBrk-1CO2H)l} m-4n
 reductions by BH4-.
{(Au°-NP)-H4n+m-(CH3-kBrk-1CO2H)l-2}m-4n+1/{(Au°-NP)-H4n+m-1- 4. The total degree of de-halogenation depends on
(CH3-kBrk-1CO2H)l-2} m-4n
+ (-CH3-kBrk-1CO2H)2 NaBH4 dosage. A similar result was reported for
followed by de-bromination of these dimers. Clearly the {(Au°- the bromate reduction by BH4- catalysed by a
NP)-H4n+m-(CH3-kBrk-1CO2H)l}m-4n+1/{(Au°-NP)-H4n+m-1-(CH3-kBrk- metal – organic framework. [27]
m-4n
1CO2H)l} intermediates can also decompose via:
(11){(Au°-NP)-H4n+m-(CH3-kBrk-1CO2H)l}m-4n+1/{(Au°-NP)-H4n+m-1-
Experimental Section
(CH3-kBrk-1CO2H)l}m-4n
{(Au°-NP)-H4n+m-1-(CH3-kBrk-1CO2H)l-1}m-4n+1/{(Au°-NP)-H4n+m-2- Physical Methods and Materials: Infrared spectra (4000–

(CH3-kBrk-1CO2H)l-1} m-4n
+CH4-kBrk-1CO2H
i.e. via a combination between the bound alkyl radical and a
bound hydrogen atom.
At present the relative rate constants of reactions (5)-
(7), (8)-(9) and (10)-(11) are unknown and therefore there is no
answer to the question why succinic acid is not formed in the de-
bromination of MBAA. It seems reasonable to assume that the
difference stems from the difference between the properties of
the radicals: .CH2CO2H and .CBr2CO2H. This could be due to the
400 cm-1) were recorded at room temperature using a Perkin Elmer
Spectrum One spectrometer in transmittance mode with KBr pellets
containing 1% in weight powder samples. Powder X-ray diffraction
(PXRD) was measured using a X’Pert Pro diffractometer using the CuK
radiation ( = 0.154 nm). The scanning for PXRD was made for a 2
angle from 20 to 1000, with a step time of 2s. UV-vis spectrum was
measured using an Agilent 8453 diode-array spectrophotometer. The de-
halogenation of the halo-acetic acids was monitored by applying an
HPLC system (Jasco) with a UV/Vis detector (= 210 nm) along with a
HPLC column of Agilent (Eclipse XDB-C18, 5 µm) with a dimension of

electron withdrawing properties of Br vs. H. The latter 4.6×150 mm. The eluent: H2O : CH3CN = 98:2 with 0.2 % H3PO4, pH 2.0,
flow 1.0 mL/min.
suggestion is clearly not the source of the observed effect as the
Tribromoacetic acid, dibromoacetic acid, monobromoacetic
de-chlorination of CCl3CO2H does not yield succinic acid.
acid, trichloroacetic acid, Trimethoxymethylsilane and (3-
However probably when the BH4- is added slowly the
Aminopropyl)trimethoxysilane were obtained from Alfa Aesar.
number of hydrogen atoms/hydrides, (4n + m)/(4n + m -1) bound Tetraethylorthosilicate and gold(iii) chloride trihydrate were purchased
at steady state to the Au°-NPs is smaller. Therefore the from Aldrich. NaBH4 was bought from Strem Chemicals.
competition between reactions (3) and/or (4) with reactions (5)- Syntheses: Synthesis of Au-cat with the composition of 30 mol %
(7) will favour the latter, as observed. This will also favour MTMOS and 70 mol % TEOS has been achieved by adopting a slightly

reaction (8) over reaction (9) and reaction (10) over reaction (11) modified procedure of that reported previously. [13] Briefly, 90 µL of HCl
was added to 6.0 mL of ice cold water and the mixture was poured into a
and thus explain why the yield of succinic-acid is larger when the
solution containing 2.5 mL of Trimethoxymethylsilane (MTMOS) 8.8 mL
BH4- is added slowly to the solution.
of Tetraethylorthosilicate (TEOS) and 13.3 mL of ethanol. The mixture
was stirred in an ice bath for 10 minutes. 125 µL (3-
Aminopropyl)trimethoxysilane (APS) was then added to the mixture. 5.0
Conclusions
mL of ice cold aqueous solution of 3×10-3 M HAuCl4.3H2O was then
The results reported herein point out that Au°_NPs entrapped in
added drop wise. The reduction of Au(III) was done by the addition of 5.0
silica sol-gel matrices can be used as catalysts for the de- mL of an aqueous solution of 3×10-2 M NaBH4. 5.0 mL of 2.8% NH3 was
halogenation of halo-organic compounds and not only for the added to the mixture for the conversion of the sol to gel. The final
reduction of p-nitrophenol.[22,23,26] Thus a process for removal of solution was then stirred for another 15 minutes for complete gelation.
The solid gel was kept for 7 days for ageing and drying. After one week,

4
This article is protected by copyright. All rights reserved.
European Journal of Inorganic Chemistry
COMMUNICATION
the solid matrix was well crashed and washed with water for several
times. The washed matrix was then dried and used for the catalytic
processes. Blank matrix with same composition was prepared as
explained in case of Au-cat. Here, 10.0 mL of ice-cold water was added
in place of the 5.0 mL of the solutions of HAuCl4.3H2O and NaBH4.
Catalytic tests: TBAA, DBAA, MBAA and TCAA were taken as model
substrates to study the catalytic activity of our purposely synthesised Au°
materials towards reductive de-halogenation. In a typical catalytic run,
3.5 mL of 0.010 M halo-acetic acid was added to the suspension of 0.50
g (0.054 mol %) of the Au-cat taken in 18 mL of deionised water in a 50
mL beaker kept at room temperature. The mixture was then stirred for
few minutes. 3.5 mL of 0.040 M of aqueous NaBH4 (for MBAA) or 0.060
M of aqueous NaBH4 (for TBAA) was then added. The resulting solution
was stirred for 5 h. After completion of the reaction the catalyst was
recovered by filtration and the filtrate was analysed by HPLC. HPLC
chromatogram highlighting acetic and succinic acid are presented in the
supporting information file (Figures S3-S4). The catalyst was washed
extensively with water, dried in a desiccator and reused as such in
subsequent reaction runs under the same conditions. The yields in each
cycle were not significantly different, implying the stability of our catalyst
(Figures S5).
Under the same reaction conditions, no de-halogenation was
detected without added catalyst (blank test). Also in absences of NaBH4
but in the presence of catalytic amount of Au-cat no reduction was
observed (blank test).
Acknowledgements
This study was supported in part by a grant from the Pazy
Foundation.
Keywords: Sol-gel processes . gold nanoparticle .
dehalogenation . radicals . succinic acid
[1] D. L. Sedlak, U. von Gunten, Science 2011, 331, 42-43.
[2] S. W. Krasner, P. Westerhoff, B. Y. Chen, B. E. Rittmann, G. Amy, Environ.
Sci. Technol. 2009, 43, 8320-8325.
[3] O. A. Ali, S. J. Tarek, Desalin. Water Treat. 2009,1, 229-289.
[4] A. K. Adamantia, G. S. Euripides, Water Res. 2012,36, 2596-2606.
[5] M. T. Yang, X. G. Zhang, Environ. Sci. Technol. 2013, 47, 10868-10876.
[6] J. Q. Liu, X. R. Zhang, Water Res. 2014, 65, 64-72.
[7] S. D. Richardson, M. J. Plewa, E. D. Wagner, R. Schoeny, D. M. DeMarini,
Mutat. Res. - Rev. Mut. Res. 2007, 636,178-242.
[8] a) R. Mao, N. Li, H. Lan, X. Zhao, H. Liu, J. Qu, M. Sun, Environ. Sci.
Technol. 2016, 50, 3829-3837; b) A. Z. Li, X. Zhao, Y. N. Hou, H. J. Liu, L. Y.
Wu, J. H. Qu, Appl. Catal. B 2012, 111-112, 628-635; c) J. Zhou, Y. X. Han, W.
J. Wang, Z. Y. Xu, H. Q. Wan, D. Q. Yin, S. R. Zheng, D. Q. Zhu, Appl. Catal.
B 2013, 134-135, 222-230; d) Y. P. Li, H. B. Cao, Y. Zhang, Water Res. 2007,
41, 197-205; e) L. Altamar, L. Fernández, C. Borras, J. Mostany, H. Carrero, B.
Scharifker. SensorsActuators B 2010,146, 103-110; f) X. Li, J. Ma, G. Liu, J.
Fang, S. Yue, Y. Guan, L. Chen, X. Liu, Environ. Sci. Technol. 2012, 46, 7342-
7349; g) O. Scialdone, A. Galia, S. Sabatino, D. Mira, C. Amatore,
ChemElectroChem 2015, 2, 684-690.
[9] a) X. Zha, L. Ma, Y. Liu, RSC Adv. 2016, 6, 16323-16330; b) L. Zhang, W.
Arnold, R. Hozalski, Environ. Sci. Technol. 2004, 38, 6881-6889; c) Z. He, Q.
5
This article is protected by copyright. All rights reserved.
10.1002/ejic.201700069
Wang, J. Sun, J. Chen, S. Song, Int. J. Electrochem. Sci. 2011, 6,2932-2942;
d) L. L. Lifongo, D. J. Bowden, P. Brimblecombe, Chemosphere 2004, 55,
467-476; e) X. Li, J. Ma and S. Yue, Adv. Mat. Res. 2012, 518-523, 2939-2943.
[10] a) A. K. Patra, A. Dutta, A. Bhaumik, ACS Appl. Mater. Interfaces 2012, 4,
5022−5028; b) D. Wang, S. Chen, J. Wang, D. Astruc, B. Chen, Tetrahedron,
2016, 72, 6375-6379; c) B. Nakhjavan, M. N. Tahir, F. Natalio, M. Panthöfer, H.
Gao, M. Dietzsch, R. Andre, T. Gasi, V. Ksenofontov, R. Branscheid, U. Kolb,
W. Tremel, Nanoscale, 2012, 4, 4571–4577; d) J. Yang, S. Cui, J. Qiao, H.
Lian, Journal of Molecular Catalysis A: Chemical 2014, 395, 42–51; e) X. Yuan,
G. Sun, H. Asakura, T. Tanaka, X. Chen,Y. Yuan, G. Laurenczy, Y. Kou, P. J.
Dyson, N. Yan, Chem. Eur. J. 2013, 19, 1227 – 1234; f) H. Zhong, C. Liu, H.
Zhou, Y. Wang, R. Wang, Chem. Eur. J. 2016, 22, 1 – 10; g) C. D. McTiernan,
S. P. Pitre, H. Ismaili, J. C. Scaiano, Adv. Synth. Catal. 2014, 356, 2819 –
2824; h) Y. Huang, S. Liu, Z. Lin, W. Li, X. Li, R. Cao, Journal of Catalysis,
2012,292, 111–117; i) H. Göksu,Y. Yıldız, B. Çelik, M. Yazıcı, Benan Kılbaş, F.
Şen, ChemistrySelect 2016, 5, 953 –958; j) B. Y. Kara, M. Yazici, B. Kilbas, H.
Goksu, Tetrahedron 2016, 72, 5898-5902.
[11] a) J. Gong, Chem. Rev. 2012,112, 2987-3054; b) C. D. Pina, E. Falletta,
M. Rossi, Chem. Soc. Rev. 2012, 41, 350-369; c) P. Zhao, X. Feng, D. Huang,
G. Yang, D. Astruc, Coord.Chem.Rev. 2015, 287,114-136; d) R. Rajesh, S. S.
Kumar, R. Venkatesan, New J. Chem. 2014, 38,1551-1558; e) S. K.
Beaumont, G. Kyriakou, R. M. Lambert, J. Am. Chem. Soc. 2010,132, 12246-
12248; f) B. Karimi, F. K. Esfahani, Chem. Commun. 2011, 47, 10452-10454;
g) C. Wang, L. Salmon, Q. Li, M. E. Igartua, S. Moya, R. Ciganda, J. Ruiz, D.
Astruc, Inorg. Chem. 2016, 55, 6776-6780; h) C. Wang, R. Ciganda, L.
Salmon, D. Gregurec, J. Irigoyen, S. Moya, J. Ruiz, D. Astruc, Angew. Chem.,
Int. Ed. 2016, 55, 3091-3095; i) M. S. Ide, R.J. Davis, Acc. Chem. Res. 2014,
47, 825-833; j) Y. Guo, D. Gu, Z. Jin, P. Du, R. Si, J. Tao, W. Xu, Y. Huang, S.
Senanayake, Q. Song, C. Jia, F. Schüth, Nanoscale 2015, 7, 4920-4928; k) S.
M. Ansar, C. L. Kitchens, ACS Catal. 2016, 6, 5553-5560; l) Y. Wang, B.
Chen, M. Crocker, Y. Zhang, X. Zhu, C. Shi, Cat. Comm. 2015, 59, 195-200.
[12] a) G. Maduraiveeran, R. Ramaraj, J. Electroanal. Chem. 2007, 608, 52-
58; b) S. Manivannan, R. Ramaraj, J. Chem. Sci. 2009, 121, 735-743.
[13] R. Ciriminna, A. Fidalgo, V. Pandarus, F. Beland, L. M. Ilharco, M.
Pagliaro, Chemcatchem 2015, 7, 254-260.
[14] R. M. Hozalski, L. Zhang, W. Arnold, Environ. Sci. Technol. 2001, 35,
2258-2263.
[15] J. K. Magnuson, L. L. Lasure in Advances in Fungal Biotechnology for
Industry, Agriculture, and Medicine, Chapter 12 (eds.: J. S. Tkacz, L Lange)
Kluwer Academic/Plenum Publishers, New York, NY, 2004, pp 307-340.
[16] S. J. Lee, H, Song, S. Y. Lee. Appl. Environ. Microbiology 2006 72,1939-
1948.
[17] J. Zhu, Z. Ko´nya, V. F. Puntes, I. Kiricsi, C. X. Miao, J. W. Ager, A. P.
Alivisatos, G. A. Somorjai, Langmuir 2003, 19, 4396-4401.
[18] P.Wu, P.Bai, Z.Yan,G.X. S. Zhao, Sci Rep. 2016, 6, 18817.
[19] a) S. Deol, N. Weerasuriya, Y. Shon, J. Mater. Chem. B, 2015, 3, 6071-
6080; b) D. Bartkowiak, V. Merk, V. Reiter-Scherer, U. Gernert, J. P. Rabe, J.
Kneipp, E. Kemnitz, RSC Adv. 2016, 6, 71557–71566.
[20] A. Fidalgo, R. Ciriminna, L. M. Ilharco, M. Pagliaro, Chem. Mater. 2005,
17, 6686-6694.
[21] (a) C.F. Lo, K. Karan, B. R. Davi, Ind. Eng. Chem. Res. 2007, 46, 5478-
5484.
[22] (a) K. Lamei, H. Eshghi, M. Bakavoli, S. Rostamnia, DOI 10.1007/s10562-
016-1921-4; (b) S. Wunder, Y. Lu, M. Albrecht, M. Ballauff, ACS Catal. 2011,1,
908-916; (c) W. Xu, J.S. Kong, Y.E. Yeh, P. Chen, Nat. Mater. 2008, 7, 992-
996; (d) Y.C. Chang, D.H. Chen, J. Hazard. Mater. 2009, 165, 664-669; (e) S.
Wunder, F. Polzer, Y. Lu, Y. Mei, M. Ballauff, J. Phys. Chem. C 2010, 114,
8814-8820.
European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
[23] S. Fountoulaki, V. Daikopoulou, P. L. Gkizis, I. Tamiolakis, G. S. Armatas,
I. N. Lykakis, ACS Catal. 2014, 4, 3504-3511.
[24] a) T. Zidki, H. Cohen, D. Meyerstein, Phys. Chem. Chem. Phys. 2006, 8,
3552-3556; b) R. Bar-Ziv, I. Zilbermann, O. Oster-Golberg, T. Zidki, G. Yardeni,
H. Cohen, D. Meyerstein, Chem. Eur. J. 2012, 18, 4699-4705; c) T. Zidki, R.
Bar-Ziv, U. Green, H. Cohen, D. Meisel, D. Meyerstein, Phys. Chem. Chem.
Phys. 2014, 16, 15422-15429; d) R. Bar-Ziv, I. Zilbermann, M. Shandalov, V.
Shevchenko, D. Meyerstein, Chem. Eur. J. 2015, 21, 19000-19009.
[25] R. Bar-Ziv, T.Zidki, I. Zilbermann, G. Yardeni, Dan Meyerstein,
ChemCatChem 2016, 8, 1-5.
[26] U. Jeong, J. B. Joo, Y. Kim, RSC Adv. 2015, 5, 55608-55618.
[27] K.-Y. A. Lin, S.-Y. Chen, RSC Adv. 2015, 5, 43885-43896.

6
This article is protected by copyright. All rights reserved.
European Journal of Inorganic Chemistry 10.1002/ejic.201700069

COMMUNICATION
Entry for the Table of Contents

COMMUNICATION
Sol-gel entrapped gold nanoparticles
catalyse the de-halogenation of mono Jaydeep Adhikary, Michael Meistelman,
Ariela Burg, Dror Shamir, Dan
and tribromoacetic acids by NaBH4 via Meyerstein, and Yael Albo*
different pathways and depend on the
rate of addition of the reducing agent. Page No. 1 – Page No.5

The Reductive De-halogenations of

Mono and Tribromo Acetic Acids by
NaBH4 Catalysed by Gold
Nanoparticles Entrapped in Sol-Gel
Matrices Follow Different Pathways

7
This article is protected by copyright. All rights reserved.