Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
a r t i c l e
i n f o
Article history:
Received 8 July 2008
Received in revised form 26 August 2008
Accepted 26 August 2008
Available online 30 August 2008
Keywords:
Goethite
Linde type A zeolite
Nanocomposite
Phosphate adsorption
Pb adsorption
a b s t r a c t
Linde type A zeolite (LTA)goethite nanocomposite was synthesized by adding sodium orthosilicate solution to goethite, followed by addition of sodium aluminate and NaOH solutions at 100 C. Optimum
condition at the Si addition step required for nanocomposite formation was pH 10.0 and Si/Fe = 2.7. The
nal product composed mainly of LTA and goethite crystals. Formation of LTAgoethite nanocomposites
in the nal product was suggested by differences in IR spectra and SEM images between the nal product
and a mixture of LTA and goethite. The mixture separated into LTA and goethite components after washing
with water, but the nal product did not show such separation. Precipitation of silica on the surface of
goethite and subsequent formation of SiOFe bonds at the Si addition step contributed to formation of
the LTAgoethite nanocomposite. The amount of adsorption of phosphate on the nal product was more
than 1.6 times the amount adsorbed on the mixture, indicating generation of synergistic effect in the
LTAgoethite nanocomposite.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Various pollution remediation techniques such as adsorption,
precipitation, ion exchange and ltration have been employed.
Most of these techniques concentrate on removal of only one type
of pollutant, which may either be positively charged or negatively
charged. Currently, combinations of cation and/or anion exchangers with inorganic cohesion precipitants are generally used for
simultaneous removal of both species of pollutants. However, these
materials are expensive; and they release huge amounts of counter
anions such as Cl and SO4 2 ions into the treated system [1]. This
may require further treatment. There is an increasing need, therefore, to develop adsorbent materials that are not only economically
effective at removing both types of pollutants, but that can also be
easily synthesized from natural and waste materials [1].
Zeolites, with their permanent negative charges as well as the
interconnection of channels and cages that run through their secondary framework structure, are efcient adsorbents for positively
charged pollutants such as heavy metals [2]. Zeolites are easily synthesized from industrial wastes such as coal y ash and
paper sludge ash [3,4]. On the other hand, iron minerals such as
goethite (-FeOOH) are common constituents of soils, sediments
and aquifers, and are known to be efcient adsorbents for negatively charged pollutants such as phosphates [5]. If zeolite and
goethite are mixed, it could be used for the removal of both positive
and negatively charged pollutants in the environment. However, a
simple mixture of the two components results in separation into
zeolite and goethite components in aqueous solutions: hence does
not effectively adsorb the two types of pollutants at the same point
in time. A nanocomposite of zeolite and goethite, on the other hand,
could be used in remediation of environments without the separation problem. In addition, nano-level composition of zeolites with
other materials has resulted in tremendous increase in useful characteristics [610]. For example, Fukugaichi et al. [6] found that the
amount and rate of decomposition of acetaldehyde under UV irradiation was much higher on a nanocomposite of faujasite type zeolite
and anatase type TiO2 , than on a mixture of the two components.
Synthesis of zeolitegoethite nanocomposite has not been
reported in literature: one reason is that coexisting Si and Al inhibit
the formation of goethite [11,12] when zeolite and goethite were
simultaneously synthesized. The aim of this study was, therefore, to
synthesize stable zeolitegoethite nanocomposites as fundamental
study for syntheses of the nanocomposite from natural and waste
materials. In the synthesis procedure, silica was rst precipitated
on the surface of synthesized goethite. An Al source was then added
to form Linde type A zeolite (LTA, NaAlSiO4 ) on the surfaces of
goethite crystals to obtain the LTAgoethite nanocomposite. The
nanocomposite was not obtained by simultaneous syntheses of LTA
and goethite. Neither was it obtained by synthesis of goethite in the
presence of LTA. LTA was selected as a zeolite species, because it is
readily synthesized from a wide range of Si and Al sources under a
wide range of synthetic conditions [13].
930
931
932
Fig. 3. SEM images. Low magnication images of (a) synthetic LTA, (b) nanocomposite sample and (c) LTAgoethite mixture: high magnication images of (d) nanocomposite
sample and (e) LTAgoethite mixture.
intensity of peaks of goethite in the nanocomposite sample, as compared to that in the LTAgoethite mixture, indicates incorporation
of goethite into LTA body, or covering of goethite by LTA in the
nanocomposite sample.
Fig. 3 shows SEM images of the nanocomposite sample and the
LTAgoethite mixture. In both samples, long acicular, needle-like
goethite crystals were found with multidomain structure along
their needle axis (Fig. 3b and c). The acicular goethite crystals
formed aggregations in the LTAgoethite mixture (Fig. 3c), but they
appeared to be arranged in an order on the surface of LTA crystals in the nanocomposite sample (Fig. 3b). Higher magnication
images showed two types of arrangements of goethite and LTA
in close proximity. The goethite crystals in the LTAgoethite mixture appeared to be held with their acicular ends stacked on the
LTA crystal to form the regularity in their surface arrangement
on the LTA crystal (Fig. 3e). On the other hand, formation of ner
LTA crystals on the surfaces of goethite crystals was noticed in the
nanocomposite sample (Fig. 3d): leading to the formation of undulations, on goethite crystal surfaces, which were not observed in
the LTAgoethite mixture (Fig. 3e). The SEM observations together
with the FT-IR results indicate that LTA and goethite particles in the
nanocomposite sample were closely attached to each other to form
LTAgoethite nanocomposites. As a result, after shaking treatment
with water, the nanocomposite sample did not separate into LTA
and goethite components, but the LTAgoethite mixture separated
easily into the two components.
3.2. Mechanism of nanocomposite formation
To clarify the LTAgoethite nanocomposite formation mechanism, chemical state of Si after the rst Si coating step was
examined by FT-IR spectroscopy. Fig. 4a shows FT-IR spectrum of
the sample just after the rst Si coating step at the optimum conditions (pH 10.0, Si/Fe = 2.7). The spectrum was compared with that
933
weaker for the sample than for the mixture: this may be due to the
covering effect of goethite by silica in the sample.
The mechanism of LTAgoethite nanocomposite formation
appears to have involved the adsorption and bonding of Si onto surfaces of goethite; together with precipitation and polymerization of
Si, during the Si coating step, onto synthetic goethite. Subsequent Al
treatment caused substitution of trivalent Al for tetravalent Si in its
tetrahedral framework and rearrangement of Al and Si tetrahedra
to form regular lattice of LTA crystals on the surfaces of synthetic
goethite, resulting in formation of the LTAgoethite nanocomposite.
3.3. Adsorptive properties of the nanocomposite
Merit for synthesis of LTAgoethite nanocomposite is to generate synergistic properties as an adsorbent for pollutants in addition
to solving the separation problem which occurs in LTAgoethite
mixtures. Adsorption experiments of water, Pb and phosphate were
therefore carried out to examine whether synergistic properties
were generated in the nanocomposite sample as compared to the
LTAgoethite mixture.
Fig. 5 shows adsorption isotherms for water adsorption by
the nanocomposite sample and the LTAgoethite mixture. The
isotherm for the nanocomposite sample was similar to that for
the LTAgoethite mixture. BET specic surface area of each sample
was calculated from the data within monolayer adsorption region
of relative humidities between 0.15 and 0.45. Calculated specic
surface areas were 157 m2 g1 for the nanocomposite sample and
160 m2 g1 for the LTAgoethite mixture: similar values for both
samples indicates that synergistic effect was not generated in the
nanocomposite sample in view of the specic surface area and
water adsorption. Fig. 6 shows adsorption isotherms for Pb, a representative of heavy metals, on the nanocomposite sample and the
LTAgoethite mixture. The two isotherms were similar, and both
tted to the Langmuir equation:
C
1
C
=
+
X
Xm K
Xm
934
Fig. 6. Pb adsorption isotherms of nanocomposite sample and LTAgoethite mixture. 50 mg of sample was mixed with 30 mL of 0, 2 5 mM Pb(NO3 )2 , and shaken at
20 1 C for 24 h. pH was maintained at 5.00 0.02 throughout the experiment.
Nanocomposite
Mixture
LTA
Goethite
0
1
2
3
4
9.7
8.7
8.1
7.6
7.4
9.9
8.6
7.8
7.4
7.3
9.8
8.6
7.8
7.4
7.3
8.8
7.1
6.8
6.6
6.2
935