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Manuscript_7e71b087e53bc5fca6c771085b5c1463

Polyvinylpyrrolidone (PVP) Effects on Iron Oxide Nanoparticle Formation

Kyungah Seo1, Kaustav Sinha2, Ekaterina Novitskaya1, and Olivia A. Graeve1,2,*

1
Department of Mechanical and Aerospace Engineering
University of California, San Diego
9500 Gilman Drive – MC 0411
La Jolla, CA 92093-0411
2
Chemical and Materials Engineering Department
University of Nevada, Reno
1664 N. Virginia Street – MS 388
Reno, NV 89557

* Corresponding author: (858) 246-0146, ograeve@ucsd.edu, http://graeve.ucsd.edu/

Abstract

The effects of polyvinylpyrrolidone (PVP) on the formation of iron oxide

nanoparticles during polyol synthesis are described. The addition of PVP during synthesis

changes the particle morphology from compact to porous with chains of small iron oxide

nanocrystals at the surface of the particles due to the steric repulsion of PVP ligands. The

addition of PVP also reduces average particle size from 857 nm to 225 nm by preventing

agglomeration. In addition, the presence of PVP restricts crystal growth of iron oxide and

limits oxidation. The high-surface areas achieved for the powders can be useful for catalytic

applications.

Keywords: Iron oxide, polyol synthesis, polyvinylpyrrolidone, particle size, dynamic light

scattering

1. Introduction

Iron oxide nanopowders are of technological interest because of their use in

information storage, catalysts, biosensors, magnetic resonance imaging (MRI), and drug and

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© 2017 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
gene delivery. They have been used as catalysts for many technologically relevant reactions

such as the removal of carbon monoxide, decomposition of industrial dyes, desulfurization of

natural gas, and oxidation of various organic compounds. In particular, it has been reported

that porous iron oxide particles with large surface area and good surface crystallinity can

drastically improve catalytic ability for water treatment applications, such as decomposition

of hydrogen peroxide and removal of heavy metal ions and organic compounds.

Among the many available synthesis methodologies, including colloidal synthesis,

electrochemical methods, and laser ablation, the polyol process has attracted attention due to

its ability to produce iron oxide nanoparticles of hydrophilic surfaces, high magnetization, as

well as the capacity for self-assembly of the synthesized primary nanoparticles into

compacted clusters, which can have ultra-high magnetization properties. The polyol process

involves an organic medium, such as ethylene glycol or diethylene glycol, which acts as a

solvent as well as a reducing agent. The formation of iron oxide nanoparticles during the

polyol process depends on several parameters such as type of precursors, reflux temperature,

heating rate, reaction atmosphere, as well as use of surfactants or stabilizers. Several

surfactants/stabilizers such as sodium citrate, NaOH, PVP, and PVA have been used for the

synthesis [1-3]. For example, Cheng et al. [1] reported that a variation in concentration of

sodium citrate during polyol synthesis tuned the final iron oxide cluster size to values

between 40 nm and 300 nm, while also resulting in a change in cluster morphology from

porous to dense. This cluster size tuning effect was explained by a variation in the

electrostatic repulsion force between neighboring nanocrystals due to a change in the

concentration of OH-, resulting in a disruption of the balance between electrostatic repulsion

and the surface tension of the cluster. Also, Zhu et al. [2] reported that PVP molecules

attached to the surface of iron oxide particles prevented random agglomeration of particles

and facilitated the cluster formation. Finally, Ruiz-Baltazar et al. [3] reported that a change

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in the amount of PVP during chemical reduction synthesis of iron/iron oxide nanoparticles

can control the oxidation of the final nanoparticles as well as change the final morphology.

It has also been reported that PVP can control not only the size and agglomeration of the

clusters, but the reaction speed during synthesis of ultrafine silver nanoparticles via both the

polyol process and chemical reduction [4-6].

It is believed that surface area and crystallinity of iron oxide nanoparticles have a

critical role in catalytic reactions. However, as the particle size decreases, it is more

difficult to prevent agglomeration of the particles, which decreases the surface area and

thereby reduces the catalytic effect. Here, an optimization of PVP additions during the

polyol synthesis of iron oxide nanoparticles is achieved, which prevents random

agglomeration and changes the final particle morphology from compacted particles with hard

agglomerates (857 nm) to porous particles with soft agglomerates (225 nm), thus achieving

larger surface areas. Also, the PVP addition restricts crystal growth, resulting in smaller

crystallite sizes, as well as limiting the oxidation of the iron oxide nanoparticles.

2. Experimental procedure

The iron oxide powders were synthesized by the following route. A total of 3.98 g

of FeCl2•4H2O (99%, Alfa Aesar) were dissolved in 200 mL of ethylene glycol (>99%,

Sigma Aldrich), in a protected N2 environment, followed by the addition of PVP (MW 10000,

Alfa Aesar) (PVP:Fe=1:1), resulting in a green solution. Next, 80 g/L of NaOH were added,

resulting in a darker solution. The solution was placed in a hot plate for heating. At

around 100°C, N2H4 (H4:Fe=3:1) was added as a reducing agent, resulting in a color change

from grayish to black within a few seconds. The solution remained black thereafter, and

was maintained at 140°C for 2 hours with mechanical stirring. Once the reaction was

complete, the heat was turned off, and the system was allowed to cool. The stable colloidal

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solution was drained in a vessel and transferred to a glove box for cleaning. In order to

isolate the iron oxide powders, 50 mL of methanol were added to the solution. The black

precipitate was collected by applying an external magnetic field (0.4 T) in the form of a bar

magnet. After the precipitate was obtained, it was washed with 50 mL of methanol three

times in a glove box with an inert atmosphere to remove any impurities. The precipitate

was then dried overnight in a desiccator. The synthesis process for iron oxide nanoparticles

without the capping agent was the same as above, except for the exclusion of the PVP.

Powders were characterized by X-ray diffraction (XRD) on a Philips 3100

diffractometer with CuK radiation. Scans were conducted over the range 20 to 80 degrees

2 using a step size of 0.02 degrees and a dwell time of 1 s. The average crystallite size was

calculated using TOPAS software (Bruker AXS, Madison, WI). Thermogravimetric

analysis (TGA) was performed on a 2960 SDT V3.0F TA instrument in air. The

temperature was increased from room temperature to 350°C with a heating rate of 10°C/min.

Imaging was completed using a Hitachi S-4700 scanning electron microscope (SEM). The

samples were coated with platinum in order to enhance imaging. The powder particle size

distribution was measured using dynamic light scattering (DLS) on a Microtrac (Microtrac

Inc., Montgomeryville, PA) Nanotrac ULTRA dynamic light scattering (DLS) instrument.

The powders were dispersed in ethanol and exposed to ultrasonic energy for 5 minutes before

each measurement. Each measurement was taken using a 45 s run time.

3. Results and Discussion

The polyol synthesis methodology can be used for reduction of a variety of metal ions

due to the polarity and high boiling point of the reactants used during the process. The

following chemical process is proposed for the synthesis procedure [1, 7]:

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 2HOCH 2 CH 2 OH  2CH 3 CHO  2H 2 O
3FeCl 2  Fe3  6Cl 
NaOH  Na   OH 
Fe3  3OH   FeOH3
2FeOH3  2CH 3 CHO  CH 3 COCOCH 3  2FeOH2  2H 2 O
FeOH2  2FeOH3  Fe3 O 4  4H 2 O

The crystalline phase of the powders prepared without PVP [Figure 1(a)] was

confirmed to match the Fe3O4 phase (PDF 01-076-2948) except for one significant peak at

around 50 degrees 2θ (marked with a star), which is associated with the Fe2O3 phase (PDF

01-072-6229). Three other minor peaks of Fe2O3 are also found in the pattern and labeled

as such. In contrast, the powders with PVP [Figure 1(b)] show a significantly reduced

presence of the Fe2O3 phase, with only one noticeable peak at 50 degrees 2θ. The crystallite

size of the samples was found to be approximately 30 nm for the uncoated powders [Figure

1(a)] and 10 nm for the coated powders [Figure 1(b)], determined from X-ray line

broadening. Thus, the PVP protects the Fe3O4 powder from further oxidation (to Fe2O3) and

restricts crystal growth.

TGA measurements [Figure 2(a)] show that the powders without PVP had a weight

loss of approximately 3% in the temperature range from 20 to 200°C, due to the removal of

surface-adsorbed water, methanol and evaporation of ethylene glycol. The weight increase

of the uncoated powder in the range between 200 and 350°C is believed to be associated with

absorption of oxygen in transitioning from Fe3O4 to Fe2O3. The PVP-coated powder had a

weight loss of approximately 25% in the range between 25 and 300°C, which is a cumulative

effect of evaporation of surface-adsorbed water and volatilization of PVP. Moreover, the

powder with PVP showed a weight increase in the range of 320 to 400°C, which is slightly

higher than the oxidation temperature range of non-PVP powder. From this, it can be

derived that the residual PVP coating protects Fe3O4 from oxidation during the heating

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process, and only after the PVP coating burns off at about 300°C, the Fe3O4 can be oxidized

to Fe2O3.

Particle size analysis of the powders from dynamic light scattering [8-11], Figure

2(b), reveals a smaller particle size of the PVP-coated powders compared to the powders

prepared without PVP. The average particle size of the non-PVP and PVP samples is 857

nm and 225 nm, respectively. The non-PVP powders exhibit a broad size distribution of

that extends from 300 nm to 3000 nm, whereas the PVP-coated powders exhibit a single large

peak at around 225 nm. Thus, the non-PVP powders formed large agglomerates of various

sizes and the PVP-coated powders formed well-dispersed, monosized, particles. The SEM

images (Figure 3) illustrate that the powders without PVP [Figure 3(a)-(b)] consist of tightly

packed crystallites with minimal porosity. On the other hand, the PVP-coated powders

[Figure 3(c)-(d)] consist of loosely packed surfaces with linear chains of iron oxide

nanocrystals. Thus, the PVP plays a role in changing the particle morphology as well as

preventing hard agglomeration of the powders, as these powders can easily disperse in a

solvent. From Figure 3(c), we can see that the powders are agglomerated, but from DLS

one can see that they can be dispersed and have a smaller size of 225 nm.

Thus, PVP has four effects on the synthesis of these iron oxide powders: (1) change of

the powder morphology, (2) dispersion of the powders, (3) restriction of crystal growth, and

(4) limitations of oxidation. Ruiz-Baltazar et al. [3] reported that a variation in PVP amount,

from PVP:Fe=100:1 to 1.25:1, can change the powder morphology from sphere-like iron

(with very limited oxidation) to branched nanostructures of Fe2O3. Furthermore, they

reported that the Fe2O3 is formed from the oxidation of Fe3O4 colloidal solutions due to a

reduced PVP concentration. The morphology change in our materials (dense to porous

sphere-like) was not as significant as was seen in the samples of Ruiz-Baltazar et al. (sphere-

like to branch/flower like). This can be attributed to the rather small amount of PVP that

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was used for the current study (PVP:Fe=1:1). Instead, we confirm that the addition of a

small amount of PVP can change particle surfaces from compacted to porous, as illustrated in

the SEM micrographs (see Figure 3).

Cheng et al. [1, 12] showed that iron oxide particle size and dispersion can be

controlled by tuning the concentration of sodium citrate and by adjusting the electrostatic

repulsion between particles in the polyol synthesis of iron oxide powders. From their SEM

images, one can see that as the amount of sodium citrate was increased, the particle size

decreased, and the particles became loosely packed. The small amount of PVP in our study

produced an effect similar to the effect of sodium citrate in Cheng et al.'s work. However,

the main source of repulsive force is believed to be from steric forces of long chains of PVP

ligands attached to the surface of the particles [13-14]. This repulsive force enables the

particles to disperse in the solution by balancing the surface tension of the particles, which

results in more porous and well dispersed particles.

4. Conclusions

The effects of PVP on the formation of iron oxide nanoparticles produced by polyol

synthesis were investigated. Iron oxide nanoparticles were synthesized in ethylene glycol,

without PVP and with PVP. The XRD and TGA results showed that the presence of PVP

can result in smaller crystallite size and prevent oxidation of Fe3O4. Electron microscopy

shows that addition of PVP can modify the surfaces of the particles from dense to porous

with chains of iron oxide nanocrystals. This change can be attributed to the steric repulsive

force of the PVP molecules on the surface of the iron oxide nanoparticles. Lastly, PVP can

act as a surfactant to prevent random hard agglomeration of the synthesized particles.

Therefore, the particles can be well dispersed from hard agglomeration (857 nm) to small size

particles (225 nm), which can greatly increase the surface area.

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5. Figure captions

Figure 1. X-ray diffraction pattern of iron oxide powders synthesized in ethylene glycol (a)
without PVP and (b) with PVP as dispersant.

Figure 2. (a) Thermogravimetric analysis and (b) particle size distribution of iron oxide
powders synthesized in ethylene glycol with and without PVP.

Figure 3. Scanning electron micrographs of iron oxide powders synthesized in ethylene

glycol at 140°C for 2 hours (a-b) without PVP and (c-d) with PVP.

6. Acknowledgments

This work was supported by a grant from the National Science Foundation (No. 1334160).

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 We report the preparation of iron oxide powders with PVP as surfactant
 The addition of PVP changes the particle morphology from compact to porous
 Chains of small iron oxide nanocrystals at the surface of the particles are produced
 The addition of PVP also reduces average particle size from 857 nm to 225 nm by
preventing agglomeration

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