Synthesis of Metal Ion and Metal Oxide Nanoparticles Using the Reflux Method of Heating

Lauren Thompson Dr. Brian Tissue Virginia Tech Undergraduate Research Abstract A similar study done by Grace and Pandian compared two heating processes: the reflux method and microwave dielectric heating12. In this comparative study, silver ion (Ag+), copper (II) ion (Cu2+), silver oxide (Ag2O), and Copper (II) oxide (CuO) metal nanoparticles were synthesized using the reflux method of heating without the stabilizing agent polyvinylpyrrolidone (PVP). Glycerol will serve as the reducing agent as well as the solvent for the metal nanoparticles. UV-vis spectroscopy characterized the metal nanoparticles. The UV-vis results for the silver nanoparticles were comparable to Grace and Pandians study. This study also proved the need for PVP as a stabilizing agent in the synthesis of metal and metal oxide nanoparticles.

Introduction The chemical industry studies metal and metal oxide nanoparticles for their small size as well as large surface to volume ratio. Nanoparticles also have increased surface area offering several potential applications1. This size confinement creates massive changes in physical properties of substances2. Kan and group believe that the shape of the nanoparticle controls its properties3. Nanostructures have several unique spectroscopic, electronic, and chemical properties. They also display distinct optical properties, not seen in the individual molecules or in large quantities of the metals1, 3-4. An example is the optical property effects in metal

nanoparticles and nanowires due to size restrictions. Crystals of metal nanoparticles produce stunning changes in color when light enters the crystal5. Metal nanoparticles also contain valuable catalytic properties 2. Hydrogen fuel cells use copper oxide nanoparticles for their catalytic properties6. With the presence of a second metal, there is an increase in catalytic rate, allowing a bimetallic nanoparticle. The two metals form an alloy due to the co-reduction of metal ions while mixing the individual solutions. This also increases the stability of the nanoparticle2. Metal nanoparticle studies use polymers to stabilize the aggregation of the metal atoms while in solution. Common polymers used for metal nanoparticle studies include polyvinylpyrrolidone (PVP) and polyaniline1. PVP remains the more common polymer used in polyol synthesis because of its distinct shape and PVP can be thermodynamically and kinetically controled3. PVP consists of repeating chains of polar groups, which help dissolve metal salts and facilitate transport. Without PVP, the metal nanoparticle is unstable. This instability causes rapid destruction of the membrane7. One study conducted by Xu and group utilized sodium carbonate (Na2CO3) to increase the stability of the nanostructure and amplify the formation of nanoflowers. Na2CO3 used in combination with a lower concentration of PVP allowed for more distinctly shaped nanoclusters8. PVP used in combination of platinum (Pt) seeds, called seeded growth, facilitated nucleation and growth of metal nanoparticles in other studies9-10. Seeded growth supports the formation of spherical metal nanostructures with rod, wire, and tube shapes. Figure 1 displays these shapes as provided using transmission electron microscopy (TEM)11.

Fig. 1. TEM images, TEM patterns, and crystal structures of the various shaped silver nanocrystals synthesized with the microwave (MW) heating method (Tsuji, 2008).

Synthesis of these metal compounds sometimes requires small stable reducing agents due to the extremely small size and unique properties of nanoparticles1. Previous studies used citrate salts, alcohols, polyols, NaBH4, and even organoborohydrides as reducing agents; however, Grace and Pandians utilized glycerol as the reducing agent in their comparative studies12. Selvaraj and colleagues conducted a similar study on the reducing ability of metal nanoparticles with ethylene glycol, a deviation of pure glycerol, as a reducing agent15. Metal nanoparticle studies using ethylene glycol need PVP as a stabilizing agent because ethylene glycol is less stable than glycerol. However, in combination, ethylene glycol and PVP successfully control the size and shape of the metal nanostructures16-17. Glycerol is very viscous matrix which enables

interaction with the metal nanoparticles18. The general mechanism for the reduction of a metal ion in glycerol is: CH2OHCH(OH)CH2OH CH2OHCH(OH)CHO + H2 CH2OHCH(OH)CH2OH CH2OHCOCH2OH + H2 3CH2OHCH(OH)CHO + metal ions metal(0) + 3CH2OHCH(OH)COOH 3CH2OHCOCH2OH + metal ions metal(0) + 3CH2OHCOCOOH Grace and Pandian conducted a study for the reduction of monometallic nanoparticles. In the study they synthesized PVP polymer protected platinum (Pt), palladium (Pd), silver (Ag) and ruthenium (Ru) monometallic nanoparticles using reflux and microwave dielectric heating processes. They used a domestic oven for one method of synthesis of the monometallic nanoparticles to simulate microwave dielectric heating because it allows for rapid synthesis and quick results. Microwaves use frequencies ranging between 300 MHz and 300 GHz and allow for dipole-dipole interactions between polar molecules and the electromagnetic field to provide the energy source. This creates a more even heat distribution as well. Other advantages include an increase in reaction crystallization kinetics by as much as two orders of magnitude as well as the development of novel phases and morphologies, which allow for improved and smaller size requiring less energy since the initial heating is so fast12. In a similar study completed by Liao and colleagues, synthesis of nanocrystalline CeO2 powders required microwave heating. They found that microwave heating allowed for fast homogeneous nucleation of their solution; however, they could not determine the exact interaction between the reactants during synthesis. Additionally, they observed a large quantum size effect due to the quick method of heating13. Grace and Pandian discovered another way to synthesize metal nanoparticles, which was used in this comparative study to prove its beneficial products over microwave dielectric heating. This

method of heating produced larger crystals as well as both triangular and spherical crystal shapes. Their second method heated the monometallic nanoparticle solution at a constant rate of 5C/minute for 1 hr to the boiling point of glycerol (290C) using the reflux method of heating12. The reduction of each monometallic nanoparticle displayed color changes and measurable wavelength peaks on the Ultraviolet-visible (UV-vis) spectrometer as shown in Figure 2.

Fig. 2. UVvis spectrum for (a) Pt, (b) Pd, (c) Ag and (d) Ru(0) with the reflux method (where x1, y1 and z1 show the initial absorptions of Pt, Pd and Ru metal ions) (Grace and Pandian, 2007).

Pt (transparent) and Pd (dark brown) nanoparticles showed peaks at 270 and 438 nm respectively. Ag formed yellow colored particles and peaked at 418 nm. While Ru ions reduced to Ru nanoparticles, the color changed from red to yellow, then green and ended at dark brown.

The Ru ions had a peak at 349 nm, which began to disappear as the color, turned dark brown. Xray diffraction (XRD) studies confirmed the formation of crystallized nanoparticles in Grace and Pandians experiments and the Scherrer formula calculated their sizes more precisely. The Scherrer results showed that the reflux method of heating provided greater reduction of the monometallic metal nanoparticles, allowing for a larger average particle size of 6nm. With the reflux mode of heating, nucleation and growth of the nanoparticles occurred separately because sufficient time to divide the two phases. The microwave method of did not allow for the separation and growth of the particles due to the short 2 min heating time. The metal nanoparticles formed spherical crystals under both methods of heating; however, under the MW process, Pd nanoparticles formed triangular prismatic nanoprisms as well. The reason remains unclear why only Pd formed triangular nanoprisms, but Grace and Pandian believe that PVP only had enough time to attach along the planes of the metal nanoparticle. The length of reflux heating however, allowed time for PVP to attach to all planes and axis12. Pastoriza-Santos and group confirmed Grace and Pandians findings. Table 1 compares the reflux method to the microwave method and the size of the silver nanoparticles is significantly larger under the reflux method1.

Table 1. Summary of Silver Nanoparticle Sizes Under Reflux and Microwave Methods of Heating (Grace and Pandian, 2007)

Glycerol and glycerol variations such as ethylene glycol serve as excellent reducing agents for Pt, Pd, and Ru metal nanoparticles12. The reflux method of heating proved more successful than microwave dielectric heating for the synthesis of the monometallic nanoparticles. It allowed for the formation of larger and different shaped crystals. When the metal nanoparticles were synthesized using the reflux method of heating and studied under UV-vis spectroscopy and XRD, all monometallic nanoparticles formed spherical crystals; however, Pd nanoparticles formed triangular prismatic nanoprisms as well12. The monometallic nanoparticles proved successful in the oxidation of glycerol.

Experimental Procedure Synthesis of Ag+, Cu2+, Ag2O, and CuO metal nanoparticles: The synthesis of Ag+, Cu2+, Ag2O, and CuO produced metal and metal oxide nanoparticles. 0.0126 Molar amounts of each metal ion or oxide dissolved in 100 mL of glycerol with continuous stirring. Ten milliliters of the first metal salt dissolved in the glycerol solution. The solution warm to the boiling point of glycerol (290C) at a constant rate of 5C/minute for one hour using the reflux method of heating. Afterwards, the solution cooled to room temperature very quickly under running water. The same procedure synthesized each metal ion and metal oxide. An aliquot of each solution was removed at the initial color change to compare its results of the UV-vis spectra with the same solution when heated fully. Characterization: The metal nanoparticle solutions were centrifuged for 10 minutes at rpm 5 to ensure optimal viewing and then observed using UV-vis spectroscopy. After an additional 10 minutes at a speed of 5 rpm, the speed increased to 8.5 rpm or an additional 10 minutes. There was no change after centrifuging the nanoparticle solutions for 30 minutes. There was still no change after the addition of 0.04995 grams of PVP to each solution and heating to a temperature of 80C. Even after centrifuging the PVP protected solutions for an additional 30 minutes, the solutions were still not clear enough to run a UV-vis spectrum. The metal ion and metal oxide nanoparticle solutions used the Cary UV-vis spectrophotometer for characterization. A quartz cuvette held the solutions and the blank prepared was pure glycerol. The absorbance range was between 200 600 nm. The samples

were compared individually against the blank and the highest peaks were recorded. DI water and kimwipes carefully cleaned the inside of the quartz cuvette between each sample. Results and Discussion For the synthesis of metal ion and metal oxide nanoparticles under the reflux method of heating, glycerol acted as the solvent as well as reducing agent. Unlike Grace and Pandians study, no stabilizing agent utilized. Metal Ions: For the silver ion, a color change from clear to yellow occurred at 173C. The copper solutions were much darker. The Cu2+ ion turned to a dark yellow solution at 180C. Bulk Metal Oxides: Silver oxide turned at 137C from dark grey color to a whitish yellow cloudy solution. At 184C, the copper (II) oxide became a cloudy pink solution. Metal Oxide Nanoparticles: At 85C, the silver oxide nanoparticle transformed from a dark grey color to a lighter grey opaque solution with yellow tint. The copper (II) oxide nanoparticle solution turned a dark opaque purple color at 90C. With further heating, the colors of each solution darkened. These color changes proved the reduction of the metal ions to metal nanoparticles without a charge. The results for the silver ion and silver oxide nanoparticles were comparable to Grace and Pandians study. The results from the UV-Vis spectrometer were: Temperature (C) Ag+ 173 285 Peaks (nm) 271, 274 338

Bulk Ag2O

155 290

271, 274, 277.9, 434 343 297, 396, 439 304, 609, 722 310, 610 302, 609, 722 453, 588

Ag2O Nanoparticle Cu2+

85 225 290

Bulk CuO

184 240

The following nanoparticle solutions do not have UV-vis results yet: silver oxide heated fully, copper (II) oxide heated to 90C, and copper (II) oxide heated to 240C. Conclusion During the synthesis of the metal ion and metal oxide nanoparticles glycerol served as a reducing agent as well as a solvent. The synthesis proceeded by reflux method of heating. This experiment transpired without the use of a stabilizing agent such as PVP. Results that are complete and more precise require a stabilizing agent such as PVP. Solid PVP did not dissolve readily in the metal oxide nanoparticle solution and needed heat in order to dissolve. PVP did not bind with the metal oxide nanoparticle nor did it provide any stabilizing property to the metal oxide nanoparticles for the UV-vis spectra. Without the addition of a stabilizing agent initially, UV-vis is unfeasible. The density of the nanoparticle solutions makes them impossible to gather the appropriate data. However, this comparative study proved successful in repeating Grace and Pandians procedure and obtaining similar results.

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