Supporting Information for paper:

“Engineering Nanofluid Electrodes: Controlling

Rheology and Electrochemical Activity of γ-Fe2O3
Nanoparticles”
Sujat Sen,1 Elahe Moazzen2, Shankar Aryal,2 Carlo U. Segre2 and Elena. V. Timofeeva1,*
1
Energy Systems Division, Argonne National Laboratory, Lemont, IL, USA, 60439
2
Physics Department & CSRRI, Illinois Institute of Technology, Chicago, IL, 60616

*Corresponding author e-mail: etimofeeva@anl.gov

1.1 Conversion of weight into volume fraction

The weight fraction, w can be converted into volume fraction (φ) as follows:
Weight fraction, w = mp / (mp + mf), expressed as percent
or 1/w = (1 + mf/mp)
or mf/mp = (1-w)/w (1)
and volume fraction, φ = Vp/ (Vp + Vf), expressed as percent (2)
where, subscripts ‘p’ and ‘f’ denote nanoparticle and base fluid respectively. Using density (d =
m/v), we can write equation 2 as
φ = (mp/dp) / (mp/dp + mf/df)
or 1/ φ = 1 + (mf*dp)/(df*mp) (3)
Substituting equation 1 in 3, we get
1/ φ = 1 + [(1-w)/w]* [dp/df)] (4)
At 298K, assuming a density of 4.9 g/cm3 (as per manufacturer) for maghemite, and water as the
base fluid with a density of 0.997 g/cm3, we get
φ = w / (4.915 -3.915w) (5)
or w = 4.915 φ /(1+3.915 φ) (6)
which is graphically shown in figure S1.

Figure S1. Graphical depiction of the relationship between weight and volume fraction for Iron
(III) oxide (Maghemite) nanofluids in water as per equation 5.

1.2 Theoretical calculation of surface coverage of hematite nanoparticles

Radius of maghemite nanoparticle (assumed spherical), r = 20 x 10-9m
Density of maghemite = 4.9 g/cm3
Molecular mass of surface grafting moiety = 202 g/mol
Area of one nanoparticle = 4πr2 = 4 x 3.14 x (20 x 10-9)2 = 5024 x 10-18m2 = 5.02 x 10-11 cm2
Volume of one nanoparticle = 4/3 πr3 = 4/3 π x (20 x 10-9)3 = 33493 x 10-27m3 = 33.49 x 10-18 cm3
Number of nanoparticles in 1cm3 = 1 cm3/33.49 x 10-18 cm3 = 2.98 x 1016 particles
Total surface area of nanoparticles in 1cm3 = 2.98 x 1016 x 5.02 x 10-11 cm2 = 14.95 x 105 cm2
Area occupied by one molecule on the surface ~ 1nm2 = 10-18 m2 = 10-14 cm2
Number of molecules in 1cm3 = 14.95 x 105 / 10-14 = 14.95 x 1019
Number of moles in 1cm3 = 14.95 x 1019 / 6.023 x 1023 = 2.482 x 10-4 mol
Mass of molecules in 1cm3 = 2.482 x 10-4 x 202 = 501.39 x 10-4g = 0.05g
Mass of maghemite in 1cm3 = 4.9 g
Fraction of grafting moiety per gram of the modified maghemite in 1cm3 = 0.05 / (4.9 + 0.05) =
 = 0.05/4.95 = 0.01 = 1%

1.3. EDX elemental mapping of pristine and surface coated -Fe2O3 nanoparticles
EDX elemental mapping at high energy beam had a limited sensitivity for low absorption energy
elements. To increase the resolution for carbon maps (0.28 keV), mapping was conducted at 5V
beam, limiting iron signal to Fe-L edge. Figure S3 shows comparison of the maps obtained for
pristine and modified nanoparticles. Although pristine nanoparticles have some residual carbon
on them, as was also seen on the EDX spectra, the C-K maps for sulfonated sample have a
distinct signature of the carbon atoms correlating with the outline of Fe2O3 nanoparticles.
Organic coatings are also clearly seen as haloes around the particles on regular SEM images. In
our experimental set-up maps for Si atoms were not possible to resolve, as the SEM sample was
prepared by placing the nanoparticles on single crystal silicon wafer.

Figure S2. SEM and EDX elemental mapping of pristine (Fe2O3) and surface modified (Fe2O3-S)
iron oxide nanoparticles indicating the presence of Fe, O and C.

1.4. FTIR characterization of pristine and surface coated -Fe2O3 nanoparticles

Fourier Transform Infrared (FTIR) spectroscopy was performed using a Thermo Nicolet Nexus
470 spectrometer in the transmission mode using the KBr pellet method. Both pristine and
surface modified nanoparticles exhibited characteristic absorption bands of maghemite at 635
and 585 cm-1 corresponding to the (Fe-O) deformations in the tetrahedral and the octahedral
sites.1 In addition, distinct peaks detected at ca.1129 and 1043 cm-1in the surface modified
sample correspond to Si-O and Si-metal stretches indicating the presence of the grafting moiety.
Figure S3. FTIR spectra of pristine maghemite (γ- Fe2O3) nanoparticles, surface modified
nanoparticles (sulfonated γ- Fe2O3) and the grafting agent (3-trihydroxysilyl)-1-propanesulfonic
acid).

References

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