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Synthesis and characterization of nanosized metals embedded in polystyrene matrix

Synthesis and characterization of nanosized metals embedded in polystyrene matrix

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Published by Rachel Pincus
Mahajan 2006
Mahajan 2006

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Published by: Rachel Pincus on Aug 28, 2013
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08/28/2013

 
Synthesis and characterization of nanosized metals embeddedin polystyrene matrix
*
Devinder Mahajan
a,b,
*
, Amruta Desai
a
, Miriam Rafailovich
b
, Min-Hui Cui
c
, Nan-Loh Yang
c
a
Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11973-5000, USA
b
 Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794-2275, USA
c
 Department of Chemistry, City University of New York at Staten Island, NY 10314, USA
Received 20 August 2004; accepted 28 December 2004Available online 25 July 2005
Abstract
Thermal treatment of a solution containing iron pentacarbonyl and styrene monomer in hexadecane resulted in a high yield (
O
90%) of nanoparticles of iron encapsulated in a polystyrene matrix (Fe-PST). The freshly prepared off-colored Fe in polystyrene (Fe-PST) materialconsisted of black particles that were attributed to zero-valent iron. On exposure to air, the black Fe particles slowly turned dark brown due toconversion into iron oxide. The observed oxidation phenomenon was confirmed by electron paramagnetic resonance (EPR) spectroscopy: thefreshly prepared Fe-PST was EPR silent but after exposure to air, a strong signature EPR signal for iron oxide was recorded. The infrared dataconfirmed changes in intensity of characteristic bands of PST in Fe-PST. The TEM image of the oxidized Fe-PST material consisted of discrete Fe particles that were distributed throughout the polymer matrix. The differential scanning calorimetric data of Fe-PST showed anenhanced glass transition temperature to 120
8
C owing to the presence of Fe nanoparticles.
q
2005 Elsevier Ltd. All rights reserved.
Keywords:
Nano metal particles
1. Introduction
Nanosized materials exhibit properties that differ fromthose in bulk and their applications range from semi-conductors to catalysis[1]. Facile agglomeration, oxidation,and limited-quantity production are some of the challengesto synthesize nano materials in the desired form. Newmethods are sought to facilitate synthesis of supported nanomaterials for potential applications in catalysis, gasseparation and storage. Polymers provide better structuralflexibility than well-studied inorganic frameworks suchas zeolites. There is recent interest in preparingdendrimers-encapsulated metal nanoparticles because den-drimers are unique globular-shaped entities that result fromtheir uniformly branched architecture and their monodis-perse nature[2]. The dendrimers-encapsulated metalnanoparticles are prepared by sequestering metal ionswithin dendriemrs[3].But the nano metals in the metal– dendrimer complex are in higher oxidation state that mustbe chemically reduced to obtain the desired zero-valentmetal for application in catalysis. The metal-organicframework synthesis is another approach that offers built-in flexibility due to the presence of an organic framework [4]but these moieties could not maintain uniform porositydue to their collapse in the absence of guest molecules[5].However, synthesis of highly porous metal-organic frame-works that remain stable when fully desolvated and heatedup to 300
8
C[6]was recently reported. The stability of thesematerials was attributed to the crystalline supertetrahedronclusters when capped with monocarboxylates. Anotherapproach for the synthesis of supported metals is the useof polymers as a support to stabilize colloidal irondispersions[7]. In the synthesis of supported colloidaliron dispersions, it was postulated that the well-character-ized polybutadiene and various styrene-based ‘functional’
Composites: Part B 37 (2006) 74–80www.elsevier.com/locate/compositesb1359-8368/$ - see front matter
q
2005 Elsevier Ltd. All rights reserved.doi:10.1016/j.compositesb.2004.12.005
*
Zero-valent iron nano particles encapsulated in polystyrene matrix areproduced by thermal treatment of a solution containing iron pentacarbonyland styrene monomer in hexadecane solvent.
*
Corresponding author. Address: Energy Sciences and TechnologyDepartment, Advanced Fuels Group, Brookhaven National Laboratory,Building 815, Upton, NY 11973-5000, USA. Tel.:
C
1 516 344 4985; fax:
C
1 516 344 7905.
E-mail address:
dmahajan@bnl.gov (D. Mahajan).
 
polymers act as catalysts to facilitate decomposition of Fe(CO)
5
at 140–160
8
C to yield Fe particles of 5–15 nmsize. The prepared materials are typically described as metalparticles that reside on a polymer support. For particularapplication to catalysis, CO-breathing Ru and Rh clustershave been reported that exhibit high CO uptake for potentialenhancement of high activity during CO hydrogenation[8],a pathway to synthesis of clean fuels.Our interest is in developing a convenient method tosynthesize nano materials in which: (1) the nano metal is inzero-valent state, (2) the product purity is high and(3) several gram-quantity of the desired material isproduced. We report herein a facile synthesis andcharacterization of supported Fe nanoparticles that areembedded in the polystyrene matrix. A preliminary accountof this work has been recently reported[9].
2. Experimental
2.1. Materials
Pentacarbonyl iron (99.5%), styrene monomer (99% andcontaining
w
15 ppm 4-tert-butylcatechol as an inhibitor),hexadecane (99
C
%, anhydrous), and hexanes (98.5
C
%,ACS reagent grade) were purchased from Aldrich ChemicalCo. Ar and N
2
gases were obtained from Scott SpecialtyGases. Since, Fe(CO)
5
is a toxic and flammable liquid, allmanipulations were carried-out in a fume hood withappropriate precautions that conformed to the MaterialSafety and Data Sheet (MSDS). The styrene monomer waspurified by vacuum distillation at 308 K to remove theinhibitor, poured in an argon-filled glass flask that wasstored in a refrigerator.
2.2. Synthesis of Fe nanoparticles in polystyrene
Purified styrene (50 ml) monomer and 50 ml hexadecanewere dispensed into a 250 ml glass flask, purged with argonfor 0.5 h, 1.2 ml of Fe(CO)
5
was added, and the mixture wasthen stirred and heated to 100
8
C in an air-tight flask at anambient atmosphere. A gas evolved during heating wascollected and periodically analyzed. The colorless solutionturned dark and viscous due to gradual solidification of thesolution. The black solid was taken out by breaking the flask and transferred under argon to a glove box. Small samplesof the black solid were taken for spectroscopic analysis.Typical product yield was
O
90%.
2.3. Analytical
The evolved gas was analyzed on Gow-Mac Model 580gas chromatographs fitted with a molecular sieve column(9
00
!
1/8
00
) with He as the carrier gas. The infrared (IR)spectra were recorded on an ATI Mattson FTIR spectro-photometer. Sample preparation involved either using apure solid or dissolving the material in toluene. Gelpermeation chromatography (GPC) was used to calculatethe molecular weight of the polymer. Differential scanningcalorimeter (DSC) was used to measure the glass transitiontemperature of the prepared materials. Samples wereprepared by sonication in ethanol and transmission electronmicroscopy (TEM) images were recorded on a JEOL2000FX, 200KV model to determine particle sizes andscanning electron microscopy (SEM) measurements uti-lized LEO 1500. For electron paramagnetic resonance(EPR) studies, a sample was loaded into an EPR tube andthe X-band spectra were recorded on a Bruker ESP380Espectrometer equipped with a HP 5361 frequency counter.The spectrometer was equipped with a variable temperatureoption.
3. Results and discussion
The strategy used to produce Fe nanoparticles inpolystyrene involved mixing Fe(CO)
5
and styrene monomerin hexadecane solvent under argon to yield a yellowhomogeneous solution that upon heating allowed concurrentgeneration of nanosized Fe particles and polymerization topolystyrene (Scheme 1):The use of hexadecane, a non-reactive hydrocarbonsolvent, helps to better control the reaction though, inprinciple, the styrene monomer could serve as a solvent. Thereaction progress could be followed by monitoring changesin color and viscosity of the solution. The formation of ablack slurry within a few minutes of heating was indicativeof Fe particle formation, an observation consistent with aprevious study in which it was shown that an almostquantitative decomposition of Fe(CO)
5
to Fe nanoparticles(
!
30 nm) could be achieved by heating the metal carbonylcomplex inhexadecane in less than 24 h[10].The darkening of the solution was followed by gradual solidification. Therate of Fe(CO)
5
decomposition was greater than styrenepolymerization as we observed the solution viscosity toincrease slowly with time over a period of four days till thecontents of the flask could not be stirred further. Since no
Scheme 1.
 D. Mahajan et al. / Composites: Part B 37 (2006) 74–80
75
 
initiator was added to the reaction solution, it is inferred thatthe produced ‘Fe nanoparticles’ act as polymerizationinitiators. Such Fe dispersions consisting of 5–15 nmparticles have been prepared by thermal decomposition of Fe(CO)
5
in the presence of ‘functional polymers’ selectedfrom the type, poly(styrene-butadiene), poly(butadiene),copoly(styrene-butadiene)[7]. In the same study, theirformation was explained by ‘locus control’ formalism of particle nucleation and growth. Furthermore, the functionalpolymer was thought to enhance decomposition of Fe(CO)
5
via classical surface-catalyzed reaction. A facile decompo-sition of Fe(CO)
5
catalyzed by nucleophiles such aspyridine, N-methylpyrolidone has been suggested[7,11]toproceed via Reaction 1:Fe
ð
CO
Þ
5
C
Nu
0
½
Fe
ð
Nu
Þ½
Fe
X
ð
CO
Þ
y
ð
Nu
Z
nucleophile
Þ
(1)The mechanism in Reaction 1 invokes the formation of an intermediate polymer-bound metal carbonyl (both multi-and mono-nuclear) species. The concomitant and steadyevolution of stoichiometric CO in our study discounts thepathway suggested in Reaction 1 in which styrene monomercould serve as a nucleophile. Moreover, the initial
P
-bonded Fe-styrene moiety would cleave as the polym-erization reaction proceeds. Our results were furtherconfirmed by a control experiment in which no polymeri-zation of styrene monomer in hexadecane was noted afterseveral hours in the absence of Fe(CO)
5
under argon. Theobserved changes in our study are indicative of nanoFe metal formation and styrene polymerization via theReactions 2 and 3:Fe
ð
CO
Þ
5
0
D
Fe
C
5CO (2)
Styrene
0
Fe
Fe
ÿ
Polystyrene (3)where Fe-Polystyrene (Fe-PST) represents a polymericmaterial in which nano Fe particles are incorporated in thepolystyrene matrix. The Fe nanoparticles, produced byReaction 2 appear to initiate polymerization of styrene thatleads to incorporation of nano Fe particles withinthe polystyrene matrix (Reaction 3). The present study isthe first example of concurrent polymerization that wasinitiated by generation of zero-valent metal in situ. Thetypical yield of Fe-PST was high (
O
90%) suggestingproduct specificity. The product was a slightly brownishsolid in which black Fe particles could be distinctly seen.The air-sensitivity of the prepared Fe-PST sample couldbe monitored simply by observing accompanying colorchanges.Fig. 1a shows freshly polymerized styrene.Fig. 1b shows Fe-PST material immediately after exposure to air.The light brown color at the top shows the oxidizedmaterial.Fig. 1c represents a block of Fe-PST that wasexposed to air for several hours. Most of the material, exceptat the center that appears as a black spot, has been oxidized.Therefore, proper precautions were taken to protect Fe-PSTfrom air oxidation during the entire study.We carried out time-resolved concurrent formation of Fenanoparticles and styrene polymerization in an EPR tube toestablish the spin-state of the encapsulated Fe particles. 5 mlfreshly distilled styrene was mixed with 5 ml hexadecanesolvent, degassed, and 0.1 ml pure Fe(CO)
5
was added in aN
2
-filled glove box. The resulting solution was transferredto an EPR tube that was sealed under N
2
,heated at 80
8
C andthe X-band EPR spectra were recorded. The initial yellowhomogeneous solution turned viscous and darkened within2 h but no EPR signal was observed. On continued heating,the solution solidified overnight at 80
8
C but no EPR signalwas not observed (Fig. 2a).The Fe-PST material obtained by such procedure afterexposure to air and purification by re-precipitation wasexamined using GPC and quantitative EPR. The samplesshowed a strong EPR signal with
g
value
Z
2.2399 (fromDPPH), peak-to-peak of 
D
 H 
pp
Z
1071 G and a spin densityof 2.4
!
10
20
spin per gram of sample (Fig. 2b). The
g
valueand line width are characteristic of Fe
2
O
3
. GPC of theFe-polystyrene material yielded the weight averagemolecular weight,
w
, of 5.95
!
10
4
and number averagemolecular weight,
n
, of 1.93
!
10
4
with the highestpopulation at
p
Z
4.99
!
10
4
(Fig. 3). The polydispersity,
 M 
w
 / 
 M 
n
, of the sample is about 3, a value higher than normallow conversion radical polymerization. Assuming spindensity originating from paramagnetic Fe
2
O
3
, it is
Fig. 1. Monitoring air-sensitivity of the Fe-PST material. (a) Freshly polymerized styrene, (b) Fe-PST sample after exposure to air, and (c) several hours afterexposure to air.
 D. Mahajan et al. / Composites: Part B 37 (2006) 74–80
76

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