discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/244294934
CITATIONS READS
37 38
2 authors:
All content following this page was uploaded by Claudio Airoldi on 05 January 2015.
The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
Polyhedron 20 (2001) 929 936
www.elsevier.nl/locate/poly
Abstract
The silylant precursor agent 3-aminopropyltrimethoxysilane (APTS) reacted with ethylenesulfide to yield 2-{2-{3-(trimethoxysi-
lyl)propylamino}ethylthio}-ethanethiol, which was anchored on silica gel by using the sol gel process. The new synthetic silylant
agent displayed a chelating moiety containing one nitrogen and two sulfur basic centers, which are potentially favored for
adsorbing divalent cations from aqueous solution. Thus, the similar chemisorption isotherms for all cations were obtained by
batchwise method and the data were adjusted to a modified Langmuir equation to give the sequence of the maximum retention
capacity as Cu \Co\Ni. The same adsorption was followed by calorimetric titration and the enthalpic values of 7.4090.01,
1.5090.10 and 0.9890.02 kJ mol 1 for copper, nickel and cobalt respectively, were obtained. From the calculated Gibbs
free energy 25.8 90.1, 35.190.1 and 30.890.1 kJ mol 1, the variation in entropy were also obtained as 62 9 1, 4291
and 100 9 1 J K 1 mol 1 for the same above sequence. All thermodynamic values are in agreement with the spontaneity of the
proposed cation-basic center interactions for these chelating processes. 2001 Elsevier Science Ltd. All rights reserved.
0277-5387/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 1 ) 0 0 7 4 3 - 4
930 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
solvent [11,12] and seawater [13], beside this, these metric titration with standard EDTA solution. All
materials exhibit wide applicability in many areas such other chemicals have a reagent grade.
as high-performance liquid chromatography [8,14],
catalysis of enzymatic reactions [15,16], and also for
rubber reinforcement [17]. Novel properties have been 2.2. Synthese of 2 -{2 -{3 -(trimethoxysilyl)propylamino} -
obtained by the combination of organic and inorganic ethylthio}ethanethiol (NSSH)
elements, especially when are mixed at a molecular
level. For example, the mechanical strength of organic This new silylant agent was synthesized in anhydrous
polymers can be improved by incorporation of inor- condition by mixing 20.0 cm3 (57.28 mmol) of the
ganic segments [10]. High transparency is another im- precursor 3-(trimethoxysilyl)propylamine (APTS) with
portant property of the polymer hybrids and is an 7.0 cm3 (114.56 mmol) of ethylenesulfide, maintained in
indispensable factor for development of optical waveg- a slightly refluxed in sand bath at 373 K in a sealed
uides [10], optical biosensors [18,19], potentiometric tube for 24 h to give the final product of reaction
sensor [20], non-linear optical materials [10] and other NSSH.
applications such as contact lenses [10].
The present investigation reports the immobilization 2.3. Immobilization of silylant agent NSSH onto silica
of ethylenesulfide on silica gel surface using solgel gel
process. In this coating a low-temperature process is
required and the organosilicate matrix is usually The synthesized silylant agent NSSH was anchored
formed, which comprises the hydrolysis of tetra- on silica surface by hydrolysis of alkoxydes by using
ethoxysilane (TEOS) and immediately condensation of ammonium hydroxide 8.0 10 2 mol dm 3 solution,
the free silanol groups is formed. The silylant agent as catalyst [21]. In a typical immobilization, 24.0 cm3 of
produces a colloidal suspension of the sol, which causes TEOS and 17.0 cm3 of NSSH were mixed at room
a gelation due to the polycondensation of the sol. As temperature (r.t.). To this solution ethanol and water in
the interconnection between these particles increases, a 2:1 molar ratio were added. Finally, an amount of 3.0
the viscosity of the sol starts to increase and leads to cm3 of basic catalyst was added dropwise to the re-
the formation of a solid gel [12,18,21,22]. sulted solution under stirring at 333 K. After 0.5 h the
Immobilization of sylilant agent by sol gel process gel was formed, which was aged for 48 h at 323 K, and
seems very promissing specially due to the mild condi- was maintained for another 48 h at r.t. The white solid
tions that are used, as well as the simplicity of the was filtered, washed with water, ethanol and dried in
procedure involved and the most important is that vacuo at r.t. for another 8 h.
provides a high concentration of funcional groups,
which moreover, are linked to the matrix via carbon
silicon bonds that are stable towards hydrolysis [12,21]. 2.4. Physical measurements
On the other hand, the sol gel method provides an
elegant way to obtain solid-state materials with variety The functionalized silica were characterized by the
of organofunctional molecules [21] determination of surface area through BET method [23]
One nitrogen and two sulphur basic centers of each by using Flowsorb II 2300 Micrometrics apparatus.
pendant chain of the new silylant agent were explored Mass loss determination were performed on DuPont
in extracting divalent cobalt, nickel and copper from thermogravimetric instrument, model 951, using 515
aqueous solution, and this property is applied to obtain mg of sample under argon atmosphere, with a pro-
the thermodynamic of cation basic centre interactions grammed heating rate of 0.17 K s 1. Infrared spectra
by using calorimetric titrations. of all compouds were obtained in a FTIR spectropho-
tometer MB-Bomem, using KBr pellets in 4000400
cm 1 region, with a resolution of 4 cm 1. The com-
2. Experimental pounds have the elements analyzed through a Perkin
Elmer 2400 Series II microelemental analyser
2.1. Chemicals instrument. 13C and 29Si nuclear magnetic resonance
spectra for solid samples were obtained on an AC/300P
Ethyleneamine, ets, (Aldrich) was distilled before use. Bruker spctrometer with cross polarization and magic
Tetraethoxysilane, TEOS, (Aldrich) and 3- angle spinning at a frequency of 75.47 MHz with
(trimethoxysilyl)propylamine, APTS, (Aldrich) were acquisition time of 0.311 s, pulse repetition time of 4 s,
used without previous purification. Hydrated divalent contact times 1 ms and the number of scans were 20480
copper (Carlo Erba), nickel (Carlo Erba) and cobalt for 13C, and 59.62 MHz with acquisition time 0.110 s
(Vetec) nitrates were also used without purification and pulse repetition time at 4 s contact time 1 ms and the
the concentration was determined through complexo- number of scans were 1303 for 29Si.
C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936 931
The thermal effect evolved from the interaction of The current method to anchor a silylant agent on
the cations with pendant groups attached to the suport silica gel surface consists of exploring the ability of the
in the solidliquid interface was followed by an LKB- available alkoxide group attached to the agent interact-
2277, heat-flow microcalorimeter [24,25]. Samples of ing with the free silanol group on a silica surface,
functionalized silica, varying from 15.0 to 50.0 mg were establishing a covalent bond between the inorganic
suspended in 2.0 cm3 of water and vigorously stirred at backbone and the pendant organic chain. These synthe-
298.159 0.02 K. After equilibrium, the thermostated sized materials have advantages over organic resins due
solutions of the cation varying in the range of 3.0 to the fact that they have good thermal and hydrolytic
10 3 to 0.10 mol dm 3 were added into the calorimet- stability and do not swell in organic solvents [28].
ric vessel through a microserynge. For each increment A direct reaction of the synthesized silylant agent
of solution a correspondent thermal effect of the titra- with activated silica gel in non-aqueous solvent yields
tion (DtitH) was recorded until saturation was reached, the immobilized compound. When the objective is to
indicating a constant thermal effect. Thus, in the same expand the organic chain, in order to include a series of
experimental conditions, dilution of the cation solution desirable functions, two main routes are followed: (i)
were done in the absence of the support (DdilH). A null heterogeneous the previous anchored silica gel re-
thermal effect was observed when water was added to
acts to another molecule or (ii) homogeneous the
the calorimetric vessel containing the suspension of the
silylant agent is firstly prepared before immobilizing
modified support. By combining those effects, the re-
[27,28]. However, in situ immobilization through a
sulting integral thermal effect of adsorption (DrH) can
hydrolysis process an inorganic backbone can be
be determined through the expression: DrH =DtitH
formed, by using an alkoxysilane compound, which
DdilH. The change in enthalpy associated to cationma-
causes a considerable increase in the anchored pendant
trix interaction can be determined by adjusting the
adsorption data to a modified Langmuir equation groups, due to the solgel process.
[24,25]. In attempting to increase in size the precursor silylant
molecule in homogeneous condition, the reaction of the
2.6. Isotherms of adsorption agent APTS with cyclic three member molecule con-
taining sulfur, ethylenesulfide (etn) was performed. The
The isotherms of adsorption were obtained by using final obtained product conducted to the new agent
the batchwise method, which consisted in suspending 2 - {2 - [trimethoxysilyl)propylamino]ethylthio} - ethane-
thiol (NSSH), as is illustrated by the reaction:
defined bands at 2937 and 2839 cm 1 assigned to CH Carbon NMR spectrum of the anchored surface gave
stretching vibrations [27,28]. a series of peaks as shown in Fig. 1. A large expected
This new silylant agent NSSH reacted with TEOS peak around 55 and 52 ppm, could be attributed, in
and the copolymerization occurred due to the silica principle, to the presence of ethoxy groups. This possi-
backbone formation, caused by the basic catalyst. The bility was negleted due to the fact that the reaction was
new material combines the stability of the inorganic done in aqueous medium so all ethoxy groups should
matrix, which is associated with the chemical proprierty be hydrolyzed. The main reason to confirm such an
of the organic molecule [12,21,30], as represented by the assumption is owing to 29Si NMR spectroscopy. This
reaction:
29
Fig. 2. Si CP/MAS NMR spectra of Sil NSSH synthesized through basic catalysis.
AS(solv) + M(NO3)2(solv) ? AS.M(NO3)2(solv) +solv The maximum adsorption capacity of modified sur-
face n s, listed in Table 1, showed that the sequence is in
When the adsorption remains constant, a monolayer good agreement with experimental nf values. Copper
is supposed to form and the chemical interaction in- cation showed a large adsorption capacity of 1.46 mmol
volving metallic ion-surface may be followed by apply- g 1, followed by cobalt and nickel with 1.17 and 1.11
ing the modified Langmuir equation that defines the mmol g 1, respectively. Based on these values, the
isotherm as represented by Eq. (1): sequence of adsorption gives the order Cu\ Co \Ni.
Cs Cs 1 The extension of adsorption depends not only on the
= s+ s (1) solubility of the adsorbent, but also on the degree of
nf n nb
the pendant groups anchored on surface. The ratio
were Cs is the concentration of supernatant cations between the amount of ions adsorbed with that of
(mol dm 1) in the equilibrium, nf is defined previously available sites to bond on immobilized silyant agent,
and n s is the maximum amount of solute adsorbed per which were 2.50 mmol of nitrogen or 5.97 mmol of
gram of the silica surface, which depends on the sulfur per gram of silica, gave values for cations in
amount of adsorption sites and b is a constant. From agreement that two pendant groups are used as ligands
angular and linear coeficients of the linearized form of
the adsorption isotherms, n s and b values are obtained Table 1
by plotting Cs/nf versus Cs. Number of moles adsorbed (nf), maximum adsorption coefficient (n s),
volume of hydration (Vhyd) and correlation coefficient (r) for the
In present case, the anchored molecule contains three
interactions of divalent cations (M) with modified surface, SilNSSH,
centers composed by one nitrogen and two sulfur atoms at 298 9 1 K
that are potentially available as chelating basic atoms
to complex cations. The ability of this surface to extract Metal(II) nf (mmol n s (mmol Vhyd (cm3 r
divalent cations such as copper, nickel and cobalt from g1) g1) mol1)
aqueous solutions was evaluated by measuring the
Cu(NO3)2 1.46 90.01 1.66 9 0.01 147.8 0.9983
sorption isotherms [6,7,27,28,36,37]. A summary of the Ni(NO3)2 1.11 9 0.10 1.42 9 0.10 147.8 0.9911
results involving adsorption of these cations on Co(NO3)2 1.17 90.02 1.26 9 0.02 169.6 0.9995
modified surface are presented in Table 1.
934 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
X X 1
= + (2)
DrH DmonH DmonH(K 1)
References
[18] B.C. Dave, B. Dunn, J.S. Valentine, J.I. Zink, Anal. Chem. 22 [30] C.J. Brinker, G.W. Scherer, Sol Gel Science The Physics and
(1994) 1120A. Chemistry of Sol Gel Processing, Academic Press, New York,
[19] C.M. Ingersoll, F.V. Bright, Chemtech 1 (1997) 26. 1990.
[20] A.A.S. Alfaya, Y. Gushiken, J. Colloid Interface Sci. 209 (1999) [31] C. Bresson, M.J. Menu, M. Darliguenave, Y. Dartiguenave, J.
428. Chem. Res. M (1998) 1919.
[21] C.R. Silva, C. Airoldi, J. Colloid Interface Sci. 195 (1997) 381. [32] C.A. Fyfe, Y. Zhang, P. Aroca, J. Am. Chem. Soc. 114 (1992)
[22] A.A. El-Nasser, R.V. Parish, J. Chem. Soc., Dalton Trans. 3252.
(1999) 3463 [33] G.E. Maciel, D.W. Sindorf, J. Am. Chem. Soc. 102 (1980) 7606.
[23] S. Brunauer, P. Emett, E. Teller, J. Am. Chem. Soc. 60 (1938) [34] D.W. Sindorf, G.E. Maciel, J. Am. Chem. Soc. 105 (1983) 3767.
309. [35] A.R. Cestari, C. Airoldi, J. Thermal Anal. 44 (1995) 79.
[24] S. Roca, C. Airoldi, J. Chem. Soc., Dalton Trans. (1997) 2517. [36] A.S. Gonc alves, C. Airoldi, Polyhedron 8 (1989) 2901.
[25] L.M. Nunes, C. Airoldi, Thermochim. Acta 328 (1999) 416. [37] C. Airoldi, A.S. Gonc alves, Colloids Surf. 28 (1987) 199.
[26] H.A. Flaschka, EDTA Titration, An Introduction to Theory and [38] C. Airoldi, L.M. Nunes, Langmuir 16 (2000) 29.
Practice, 2nd edn., Pergamon Press, Oxford, 1967. [39] Y. Marcus, Ions Solvation, Wiley, UK, 1985.
[27] M.R.M.C. Santos, C. Airoldi, J. Colloid Interface Sci. 183 [40] C. Airoldi, E.F.C. Alcantara, J. Chem. Thermodyn. 27 (1995)
(1996) 416. 623.
[28] L.N.H. Arakaki, C. Airoldi, Polyhedron 19 (2000) 367. [41] O.A.C. Monteiro Jr., C. Airoldi, J. Colloid Interface Sci. 212
[29] J.G.P. Espnola, J.M.P. Freitas, S.F. Oliveira, C. Airoldi, Col- (1999) 212.
loids Surf. A 87 (1994) 33. [42] C. Airoldi, A.P. Chagas, Coord. Chem. Rev. 119 (1992) 29.