Composites: Part B 37 (2006) 7480 www.elsevier.

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Synthesis and characterization of nanosized metals embedded in polystyrene matrix*

Devinder Mahajana,b,*, Amruta Desaia, Miriam Rafailovichb, Min-Hui Cuic, Nan-Loh Yangc
a b

Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11973-5000, USA 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 2004 Available online 25 July 2005

Abstract Thermal treatment of a solution containing iron pentacarbonyl and styrene monomer in hexadecane resulted in a high yield (O90%) of nanoparticles of iron encapsulated in a polystyrene matrix (Fe-PST). The freshly prepared off-colored Fe in polystyrene (Fe-PST) material consisted of black particles that were attributed to zero-valent iron. On exposure to air, the black Fe particles slowly turned dark brown due to conversion into iron oxide. The observed oxidation phenomenon was conrmed by electron paramagnetic resonance (EPR) spectroscopy: the freshly prepared Fe-PST was EPR silent but after exposure to air, a strong signature EPR signal for iron oxide was recorded. The infrared data conrmed 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 an enhanced glass transition temperature to 120 8C 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 from those in bulk and their applications range from semiconductors to catalysis [1]. Facile agglomeration, oxidation, and limited-quantity production are some of the challenges to synthesize nano materials in the desired form. New methods are sought to facilitate synthesis of supported nano materials for potential applications in catalysis, gas separation and storage. Polymers provide better structural exibility than well-studied inorganic frameworks such as zeolites. There is recent interest in preparing
*

Zero-valent iron nano particles encapsulated in polystyrene matrix are produced by thermal treatment of a solution containing iron pentacarbonyl and styrene monomer in hexadecane solvent. * Corresponding author. Address: Energy Sciences and Technology Department, Advanced Fuels Group, Brookhaven National Laboratory, Building 815, Upton, NY 11973-5000, USA. Tel.: C1 516 344 4985; fax: C1 516 344 7905. E-mail address: dmahajan@bnl.gov (D. Mahajan). 1359-8368/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesb.2004.12.005

dendrimers-encapsulated metal nanoparticles because dendrimers are unique globular-shaped entities that result from their uniformly branched architecture and their monodisperse nature [2]. The dendrimers-encapsulated metal nanoparticles are prepared by sequestering metal ions within dendriemrs [3]. But the nano metals in the metal dendrimer complex are in higher oxidation state that must be chemically reduced to obtain the desired zero-valent metal for application in catalysis. The metal-organic framework synthesis is another approach that offers builtin exibility due to the presence of an organic framework [4] but these moieties could not maintain uniform porosity due to their collapse in the absence of guest molecules [5]. However, synthesis of highly porous metal-organic frameworks that remain stable when fully desolvated and heated up to 300 8C [6] was recently reported. The stability of these materials was attributed to the crystalline supertetrahedron clusters when capped with monocarboxylates. Another approach for the synthesis of supported metals is the use of polymers as a support to stabilize colloidal iron dispersions [7]. In the synthesis of supported colloidal iron dispersions, it was postulated that the well-characterized polybutadiene and various styrene-based functional

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polymers act as catalysts to facilitate decomposition of Fe(CO)5 at 140160 8C to yield Fe particles of 515 nm size. The prepared materials are typically described as metal particles that reside on a polymer support. For particular application to catalysis, CO-breathing Ru and Rh clusters have been reported that exhibit high CO uptake for potential enhancement of high activity during CO hydrogenation [8], a pathway to synthesis of clean fuels. Our interest is in developing a convenient method to synthesize nano materials in which: (1) the nano metal is in zero-valent state, (2) the product purity is high and (3) several gram-quantity of the desired material is produced. We report herein a facile synthesis and characterization of supported Fe nanoparticles that are embedded in the polystyrene matrix. A preliminary account of this work has been recently reported [9].

2.3. Analytical The evolved gas was analyzed on Gow-Mac Model 580 gas chromatographs tted 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 spectrophotometer. Sample preparation involved either using a pure solid or dissolving the material in toluene. Gel permeation chromatography (GPC) was used to calculate the molecular weight of the polymer. Differential scanning calorimeter (DSC) was used to measure the glass transition temperature of the prepared materials. Samples were prepared by sonication in ethanol and transmission electron microscopy (TEM) images were recorded on a JEOL 2000FX, 200KV model to determine particle sizes and scanning electron microscopy (SEM) measurements utilized LEO 1500. For electron paramagnetic resonance (EPR) studies, a sample was loaded into an EPR tube and the X-band spectra were recorded on a Bruker ESP380E spectrometer equipped with a HP 5361 frequency counter. The spectrometer was equipped with a variable temperature option.

2. Experimental 2.1. Materials Pentacarbonyl iron (99.5%), styrene monomer (99% and containing w15 ppm 4-tert-butylcatechol as an inhibitor), hexadecane (99C%, anhydrous), and hexanes (98.5C%, ACS reagent grade) were purchased from Aldrich Chemical Co. Ar and N2 gases were obtained from Scott Specialty Gases. Since, Fe(CO)5 is a toxic and ammable liquid, all manipulations were carried-out in a fume hood with appropriate precautions that conformed to the Material Safety and Data Sheet (MSDS). The styrene monomer was puried by vacuum distillation at 308 K to remove the inhibitor, poured in an argon-lled glass ask that was stored in a refrigerator. 2.2. Synthesis of Fe nanoparticles in polystyrene Puried styrene (50 ml) monomer and 50 ml hexadecane were dispensed into a 250 ml glass ask, purged with argon for 0.5 h, 1.2 ml of Fe(CO)5 was added, and the mixture was then stirred and heated to 100 8C in an air-tight ask at an ambient atmosphere. A gas evolved during heating was collected and periodically analyzed. The colorless solution turned dark and viscous due to gradual solidication of the solution. The black solid was taken out by breaking the ask and transferred under argon to a glove box. Small samples of the black solid were taken for spectroscopic analysis. Typical product yield was O90%.

3. Results and discussion The strategy used to produce Fe nanoparticles in polystyrene involved mixing Fe(CO)5 and styrene monomer in hexadecane solvent under argon to yield a yellow homogeneous solution that upon heating allowed concurrent generation of nanosized Fe particles and polymerization to polystyrene (Scheme 1): The use of hexadecane, a non-reactive hydrocarbon solvent, helps to better control the reaction though, in principle, the styrene monomer could serve as a solvent. The reaction progress could be followed by monitoring changes in color and viscosity of the solution. The formation of a black slurry within a few minutes of heating was indicative of Fe particle formation, an observation consistent with a previous study in which it was shown that an almost quantitative decomposition of Fe(CO)5 to Fe nanoparticles (!30 nm) could be achieved by heating the metal carbonyl complex in hexadecane in less than 24 h [10]. The darkening of the solution was followed by gradual solidication. The rate of Fe(CO)5 decomposition was greater than styrene polymerization as we observed the solution viscosity to increase slowly with time over a period of four days till the contents of the ask could not be stirred further. Since no

Scheme 1.

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initiator was added to the reaction solution, it is inferred that the produced Fe nanoparticles act as polymerization initiators. Such Fe dispersions consisting of 515 nm particles have been prepared by thermal decomposition of Fe(CO)5 in the presence of functional polymers selected from the type, poly(styrene-butadiene), poly(butadiene), copoly(styrene-butadiene) [7]. In the same study, their formation was explained by locus control formalism of particle nucleation and growth. Furthermore, the functional polymer was thought to enhance decomposition of Fe(CO)5 via classical surface-catalyzed reaction. A facile decomposition of Fe(CO)5 catalyzed by nucleophiles such as pyridine, N-methylpyrolidone has been suggested [7,11] to proceed via Reaction 1: FeCO5 C Nu 0 FeNuFeX COy Nu Z nucleophile (1)

The mechanism in Reaction 1 invokes the formation of an intermediate polymer-bound metal carbonyl (both multiand mono-nuclear) species. The concomitant and steady evolution of stoichiometric CO in our study discounts the pathway suggested in Reaction 1 in which styrene monomer could serve as a nucleophile. Moreover, the initial P-bonded Fe-styrene moiety would cleave as the polymerization reaction proceeds. Our results were further conrmed by a control experiment in which no polymerization of styrene monomer in hexadecane was noted after several hours in the absence of Fe(CO)5 under argon. The observed changes in our study are indicative of nano Fe metal formation and styrene polymerization via the Reactions 2 and 3: FeCO5 0 Fe C 5CO Styrene 0 Fe Polystyrene
Fe D

(2) (3)

where Fe-Polystyrene (Fe-PST) represents a polymeric material in which nano Fe particles are incorporated in the polystyrene matrix. The Fe nanoparticles, produced by Reaction 2 appear to initiate polymerization of styrene that leads to incorporation of nano Fe particles within

the polystyrene matrix (Reaction 3). The present study is the rst example of concurrent polymerization that was initiated by generation of zero-valent metal in situ. The typical yield of Fe-PST was high (O90%) suggesting product specicity. The product was a slightly brownish solid in which black Fe particles could be distinctly seen. The air-sensitivity of the prepared Fe-PST sample could be monitored simply by observing accompanying color changes. 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 oxidized material. Fig. 1c represents a block of Fe-PST that was exposed to air for several hours. Most of the material, except at the center that appears as a black spot, has been oxidized. Therefore, proper precautions were taken to protect Fe-PST from air oxidation during the entire study. We carried out time-resolved concurrent formation of Fe nanoparticles and styrene polymerization in an EPR tube to establish the spin-state of the encapsulated Fe particles. 5 ml freshly distilled styrene was mixed with 5 ml hexadecane solvent, degassed, and 0.1 ml pure Fe(CO)5 was added in a N2-lled glove box. The resulting solution was transferred to an EPR tube that was sealed under N2, heated at 80 8C and the X-band EPR spectra were recorded. The initial yellow homogeneous solution turned viscous and darkened within 2 h but no EPR signal was observed. On continued heating, the solution solidied overnight at 80 8C but no EPR signal was not observed (Fig. 2a). The Fe-PST material obtained by such procedure after exposure to air and purication by re-precipitation was examined using GPC and quantitative EPR. The samples showed a strong EPR signal with g valueZ2.2399 (from DPPH), peak-to-peak of DHppZ1071 G and a spin density of 2.4!1020 spin per gram of sample (Fig. 2b). The g value and line width are characteristic of Fe2O3. GPC of the Fe-polystyrene material yielded the weight average molecular weight, Mw, of 5.95!104 and number average molecular weight, Mn, of 1.93!104 with the highest population at MpZ4.99!104 (Fig. 3). The polydispersity, Mw/Mn, of the sample is about 3, a value higher than normal low conversion radical polymerization. Assuming spin density originating from paramagnetic Fe 2 O3 , 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 after exposure to air.

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Fig. 2. Time-resolved EPR spectra resulting from heating Fe(CO)5 in puried styrene monomer at 80 8C: (a) up to 16 h under N2 and (b) after exposure to air; g value 2.2399 (from DPPH), DHppZ1071.4 G and g valueZ2.2399. 1 scan.

Fig. 3. The chromatogram depicts the molecular weight distribution for the Fe-PST sample. MwZ59.6 K; MnZ19.3 K and MpZ49.9 K. The cumulative amount curve is also shown.

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Fig. 4. FTIR of the prepared samples: (a) solid-state pure PST, (b) solid-state Fe-PST (upper trace), and (c) Fe-PST in toluene (lower trace).

concluded that there are ca. 1.5 Fe2O3 molecules on average per polystyrene chain, i.e. not all growing polystyrene chain terminated by recombination. The oxidation of the zerovalent Fe to Fe2O3 is slow that supports our conclusion that the nano Fe particles are protected by the polymer matrix. Further conrmation of the presence of Fe particles in polystyrene was achieved by the infrared (IR) spectral data. The solid-state spectrum of freshly prepared PST is shown in Fig. 4a. Fig. 4b shows the solid-state IR spectrum of the freshly prepared Fe-PST. The IR spectrum of Fe-PST in toluene is shown in Fig. 4c. Two noteworthy observations from the IR data are: (1) the absence of FeCO bands around 2000 cmK1 conrming the absence of the starting Fe(CO)5, the precursor to Fe particles, and (2) a change in relative intensity of the PST peaks suggesting a weak interaction between the Fe and PST in the Fe-PST material. The subtle differences between Fig. 4b and c are attributed to the solid state versus the liquid state, respectively of the material whose IR spectra were recorded.

Fig. 5. DSC data of the Fe-PST material. The Fe in Fe-PST was oxidized.

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recorded by scanning electron microscopy (SEM). The bulk of the surface in the SEM image represents polystyrene based on our GPC analysis (1.5 Fe/polymer chain) in Fig. 3. The surface appears relatively non-porous except for a few spots, where Fe nanoparticles may reside on or within the surface (Fig. 7). To summarize all the characterization data, the synthesized Fe-PST is best described as a material in which Fe nanoparticles are dispersed throughout a rather impermeable polystyrene matrix.

4. Conclusions Nanosized particles of zero-valent Fe in a polystyrene matrix have been prepared by heating a solution containing iron pentacarbonyl and styrene monomer in hexadecane. The method is convenient and several-gram quantity of the material can be prepared in O90% yield. The EPR-silent spectrum of the synthesized Fe-PST material shows a signature EPR signal of iron oxide upon exposure to air for several hours. The FTIR and DSC data indicate the presence of Fe in the PST matrix. The TEM and SEM data show that the mean particle size of Fe particles is 44 nm and these metal particles are embedded in the polystyrene matrix. We are now examining the effect of replacing thermal with sonolysis as a method to synthesize Fe encapsulated materials. The technique is also being extended to synthesize nanoparticles of metals other than Fe. Such materials in which the matrix such as polystyrene is essentially non-reactive but protects the integrity of the encapsulated nano metal particles are likely to have a wide range of applications including selective catalysis and gas separation.

Fig. 6. TEM micrographs of Fe-PST. Slice from the surface (left) and slice taken from the center (right). The dark spots are Fe nanoparticles.

The interaction between Fe and PST in the Fe-PST material was further conrmed by measuring its glass transition temperature. Pure polystyrene exhibits glass transition at 100 8C [12]. The DSC data in Fig. 5 shows an enhancement in the glass transition temperature of Fe-PST to 120 8C. The data are consistent with increased stability of Fe-PST due to the presence of Fe particles. The size and location of encapsulated Fe particles in the prepared Fe-PST were measured by TEM. Samples were microtomed and mounted on a carbon-coated grid to record the TEM images. The presence of Fe particles is seen in the TEM images of slices taken from the surface (Fig. 6a) as well as from the center of the synthesized material (Fig. 6b). The TEM data conrm that the nanoparticles are present not just on the polymer surface but rather distributed throughout the polystyrene matrix. The average size of the Fe particles was calculated to be 44 nm. Complementary to TEM, the surface features of the freshly prepared Fe-PST were

Acknowledgements This work was supported by the U.S. Department of Energy under contract No. DE-AC02-98CH10886 at Brookhaven National Laboratory. Supports of this work by the NSF-MRSEC (DMR 9632525) at both SUNY at Stony Brook and CUNY at Staten Island are gratefully acknowledged.

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Fig. 7. SEM of freshly prepared Fe-PST.

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