Journal of Colloid and Interface Science 541 (2019) 269–278

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Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

Regular Article

Stabilization of oil-in-water emulsions with graphene oxide and cobalt

oxide nanosheets and preparation of armored polymer particles
Katelynn Edgehouse a, Maria Escamilla a, Louisa Wang b, RhayAuna Dent c, Kevin Pachuta d, Lee Kendall d,
Peiran Wei a, Alp Sehirlioglu d, Emily Pentzer a,⇑
a
Department of Chemistry, Case Western Reserve University, 10900 Euclid Ave, Cleveland, OH 44106, United States
b
Hathaway Brown High School, 19600 N Park Blvd, Shaker Heights, OH 44122, United States
c
John Hay School of Science and Medicine, 2075 Stokes Blvd, Cleveland, OH 44106, United States
d
Department of Materials Science and Engineering, Case Western Reserve University, 10900 Euclid Ave, Cleveland, OH 44106, United States

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o a b s t r a c t

Article history: Pickering emulsions are emulsions stabilized by particles instead of small molecules or polymers, and
Received 27 November 2018 commonly consist of oil droplets dispersed into a continuous water phase with particles lying at the
Revised 13 January 2019 fluid-fluid interface. New particle surfactants are important for tuning the composition and properties
Accepted 22 January 2019
of assemblies and enabling advanced applications, such as energy harvesting and management.
Available online 23 January 2019
Although most particle surfactants are spherical, graphene oxide (GO) nanosheets and clay platelets have
garnered recent attention as 2D (i.e., planar) particle surfactants. Herein, we report the preparation of
Keywords:
Pickering emulsions stabilized by a composite of GO nanosheets and cobalt oxide (CoOx) nanosheets,
Pickering emulsion
Graphene oxide
and illustrate the impact of GO:CoOx ratio, oil identity, and flocculating agent (i.e., salts) on emulsion for-
Cobalt oxide mation and stability. Distinct effects were noted for salt concentration and identity, as well as GO: CoOx
2D particles ratio. We further illustrate the applicability of these GO-CoOx-stabilized emulsions in dispersion polymer-
Dispersion polymerization ization, preparing polystyrene particles armored with both nanosheets. This work provides a method for
facilitating oil-in-water emulsions with composite particle surfactants that are stable for at least a week
and offers the foundation for using the fluid-fluid interface to architect structures of dissimilar materials.
Ó 2019 Elsevier Inc. All rights reserved.

1. Introduction

Emulsions are mixtures of two or more immiscible liquids,

often of substantially different polarity (e.g., oil-water). These
⇑ Corresponding author. systems are of vital importance to a number of daily and
E-mail address: ebp24@case.edu (E. Pentzer). specialized applications, including in food, cosmetics, medicine,

https://doi.org/10.1016/j.jcis.2019.01.092
0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
270 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
etc. [1,2]. Typically, a mixture of two immiscible fluids is agitated,
yielding droplets of one dispersed in a continuous phase of the
other (e.g., oil-in-water emulsions). Most emulsions are kinetically
unstable, and thus upon standing the two phases separate from
each other, yielding, for example, an oil phase atop of water [3].
Addition of an amphiphilic small molecule such as sodium dodecyl
sulfate (SDS) can render emulsions kinetically stable, although
polymers and particles can also be used to lower interfacial tension
between the two fluids [4]. Of particular interest are Pickering
emulsions in which particles reside at the fluid-fluid interface, as
these systems have stability and applications distinct from emul-
sions stabilized by small molecules or polymers [5]. Further, Pick-
ering emulsion platforms have been used to template novel
architectures, such as armored polymer particles and both hollow
and filled capsules [6-9].
A sub-class of Pickering emulsions are those which make use of
2-dimensional (2D) particle surfactants. Provided high aspect ratio
particles are utilized, the platelets are expected to lie at the fluid-
fluid interface, with multiple nanosheets forming a barrier between
the two fluids, assembling side-by-side and overlapping into multi-
layers. Common 2D particle surfactants include clay platelets and
graphene oxide (GO) nanosheets. Clay platelets are layered struc-
tures of aluminum, silicon, and other elements with the faces of
many clay platelets possessing a negative charge, compensated by
simple cations [10]. Alternatively, GO nanosheets are composed of
a carbon framework bearing alcohol, epoxide, and alkene function-
alities throughout the surface and carboxylic acids on the edges (and
thus negatively charged on the edges in solution of appropriate pH)
[11]. Clay platelets can assemble at the fluid-fluid interface when
flocculated prior to emulsion formation. Upon flocculation with salt,
the electrostatic repulsion between neighboring clay platelets is
reduced allowing their assembly at different oil-water interfaces
[10,12]. GO nanosheets act as particle surfactants in a similar vein,
however ionic strength, oil identity, pH, GO concentration, and oil:
water ratio also impact the system. Specifically, low pH and high
ionic strength yield better emulsion stability [13]. Of note, GO is
chemically heterogeneous as well as reactive [14], and thus the
extent of oxidation and functionalization impact interfacial activity.
Indeed, chemical modifications affect the dispersibility of GO and
have been exploited to tailor emulsion identity [15,16]. Recently,
the Pentzer group modified GO to access octane-in-dimethyl for-
mamide (DMF), DMF-in-octane, ionic liquid (IL)-in-oil, IL-in-water,
water-in-IL, and oil-in-IL emulsions [7,8,17,18].
GO nanosheets and clay platelets are the most widely explored
2D particle surfactants for Pickering emulsions, leaving a variety of
2D particles under-explored. Similar to GO, cellulose nanocrystals
(CNCs) are garnering much recent attention for use in Pickering
emulsions [19]. Tam and coworkers report chemically modifying
sulfated CNCs with polystyrene to stabilize toluene-in-water and
hexadecane-in-water Pickering emulsions [20]. More recently,
Rojas and coworkers reviewed cellulosic and lignin colloidal parti-
cles at the oil/water interface and their abilities to stabilize Picker-
ing emulsions [21]. Miele and coworkers reported the use of 2D
hexagonal boronitride to stabilize water-in-ethyl benzoate Picker-
ing emulsions, and used this emulsion platform to template porous
membranes [22,23]. Another interesting class of 2D materials is
transition metal dichalcogenides (TMDs), including MoS2, WS2,
and MoSe2 [24-26]. TMDs have been widely explored in digital
electronic and optoelectronic devices [27], but not studied as par-
ticle surfactants. More recently, MXenes have emerged as a class of
attractive 2D materials; these are accessed by exfoliation of ternary
carbide and nitride ceramics [28]. Huang and coworkers reported
using Ti3C2-MXene to stabilize neutral and basic oil-in-water high
internal phase emulsions (HIPEs), and then used these assemblies
to prepare a solid porous monolith [29]. Like TMDs and MXenes,
transition metal oxides (TMOs) are 2D materials attractive as par-
ticle surfactants in Pickering emulsions, but rarely utilized. One
class of TMOs consist of sheets of transition metal atoms and oxy-
gen that are negatively charged and held together by cations (e.g.,
LiCoO2, LCO) [30]. Such nanosheets of TMOs can be exfoliated from
bulk crystals via removal of the cation with strong acid and treat-
ment with a bulky counterion, for example tetramethylammonium
hydroxide (TMAOH). Sehirlioglu and coworkers recently reported
the chemical exfoliation of cobalt oxide nanosheets (CoOx = sheets
of CoO
2 repeat units bearing some oxygen and cobalt vacancies)
from LCO, thoroughly evaluating changes to the nanosheets upon
exfoliation and giving ready access to 2D CoOx particles [31].
Herein, we report the use of GO and CoOx nanosheets as surfac-
tants for oil-in-water Pickering emulsions, and evaluate the impact
of GO:CoOx ratio, oil identity, flocculating agent identity (inorganic
and organic salt), and concentration. The use of GO and CoOx
nanosheets as Pickering emulsion co-surfactants gives access to
novel hybrid structures that can leverage the electrical conductiv-
ity of GO (once reduced), and the redox activity of CoOx for appli-
cations in energy storage and catalysis. For all particle surfactants,
nanosheets were flocculated by addition of salt, then oil was added
and the system agitated to form emulsions (Scheme 1). In general,
the most effective particle surfactant system with the highest load-
ing of CoOx was 1:1 GO:CoOx, and the best flocculating conditions
utilized LiCl, KCl, or 1-ethyl-3-methylimidazolium hexafluo-
rophosphate ([Emim][PF6]). Emulsions with different oils were also
examined. We illustrate that styrene-in-water emulsions stabilized
by GO-COx can be used to prepare GO-CoOx-armored polymer par-
ticles by thermally induced free radical dispersion polymerization.
Optical microscopy shows individual particles, indicating that GO
and CoOx are suitable particle surfactants. Further, X-ray photo-
electron spectroscopy (XPS) reveals the presence of cobalt. This
work illustrates that GO and CoOx together can stabilize oil-in-
water emulsions, thereby yielding composites of intimately associ-
ated nanoparticle structures.
2. Materials and methods
2.1. Materials
All inorganic salts (>98% purity), oils, and NBu+4Br
(1643-19-2,
Alfa Aesar, 98%) were purchased from commercial sources
(>97% purity) and used as received without further purification.
1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF6])
(155371-19-0, 99%), 1-ethyl-3-methylimidazolium dimethyl
phosphate ([Emim][DMP]) (945611-27-8, 98.0%), and 1-butyl-
3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) (174501-
65-6, 98.0%) were purchased from Iolitec and used as received.
2,20 -Azobis(2-methylpropionitrile) (AIBN, 78-67-1, 98%) was pur-
chased from Sigma-Aldrich and purified via recrystallization in
hot methanol (67-56-1, Fisher Scientific, 99.8%) and dried under
reduced pressure before use. Before dispersion polymerization,
styrene (100-42-5, Sigma-Aldrich, 98%) was passed through a basic
alumina column to remove inhibitor. Graphite flakes (7782-42-5)
and sulfuric acid (7664-93-9, 95-98%) were purchased from Sigma
Aldrich, and hydrogen peroxide (7722-84-1, 35 wt% in water) was
purchased from Acros Organics. Potassium permanganate (KMnO4,
7722-64-7, 99.0%) was purchased from Alfa Aesar. Bulk lithium
cobalt oxide (LCO, 12190-9-3) was purchased from MTI Corpora-
tion, and tetramethylammonium hydroxide (TMAOH, 75-59-2,
25 wt% in water) was purchased from Alfa Aesar.
2.2. Instrumentation
XPS data was collected using a PHI Versaprobe 5000 scanning
X-ray photoelectron spectrometer. The data was processed using
 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
Scheme 1. Overview figure illustrating the formation of oil-in-water emulsions stabilized by graphene oxide (GO), cobalt oxide (CoOx), or GO and CoOx (GO/CoOx), as well as
representative photographs and optical images of the resulting emulsions.
Origin 2018 64bit and the counts per second (CPS) normalized
using the Z scores (standardized to N(0.1)). Centrifugation was per-
formed with an Eppendorf 5804 centrifuge. Ultrasonication was
done with a Branson M3800 bath sonicator, and vortex mixing
was achieved with a Fisher Model 9454FIFSUS vortex mixer.
Atomic force microscopy (AFM) was performed using a NX-10 Park
System in tapping mode for GO and contact mode for CO and
imaged in topography mode. Samples for AFM analysis were pre-
pared by drop casting from solution onto mica. Fourier transform
infrared (FTIR) spectroscopy was performed using an Agilent Cary
630 FTIR with a diamond/ZnSe crystal in ATR mode. Zeta potential
measurements were performed on a Mobius, Wyatt Technology.
Scanning electron microscopy (SEM) measurements were taken
on a VEGA3 TESCAN instrument. For imaging of GO-CoOx coated
polystyrene (PS) particles, the voltage was 20.5 kV and for imaging
of GO-CoOx nanosheets 11.0 kV. Optical microscopy images were
taken using an AmScope M150C Microscope with an AmScope
MD35 camera. Samples for optical microscopy were prepared by
drop casting emulsions on a glass slide and spreading with a pip-
ette tip, then application of a top slide. Optical microscopy images
were collected at the center of the sample. Emulsion stability was
tested by letting the emulsions stand unagitated for a period of
time and then taking optical microscopy images.
2.3. Preparation of Graphene Oxide (GO)
GO was synthesized following a method previously reported
[11]. Briefly, graphite flakes (1.0 g) were dispersed in concentrated
271
H2SO4 (150 mL) and the solution stirred at room temperature
using a magnetic stir bar. Then, an aliquot of KMnO4 (1.0 g,
63 mmol) was carefully added to the graphite/H2SO4 mixture and
stirred for 24 h. This procedure was repeated three more times
until a total of 4 g of KMnO4 had been added. The solution was
quenched by transferring to an ice-water solution (0.75 L), fol-
lowed by the addition of aqueous H2O2 until the color changed
from pink to yellow, indicating that excess KMnO4 was quenched.
Crude GO was isolated as a yellow-brown solid via centrifugation.
The supernatant was discarded, and the solid GO washed repeat-
edly with 2-propanol (67-63-0, Fisher Scientific, 99.9%) until the
supernatant achieved a neutral pH. GO was then dried under
reduced pressure at room temperature. To prepare a stock GO solu-
tion, solid GO was vortexed and sonicated in water at a concentra-
tion of 1 mg/mL.
2.4. Preparation of Cobalt Oxide (CoOx)
CoOx was synthesized following a previously reported method
[31]. LCO powder (3.30 g) was dispersed in HCl (7647-01-0, VWR
Analytical, 36.5%–38%) (330 mL, 1.0 M) and magnetically stirred
for 24 h at room temperature. The solid was isolated by gravity fil-
tration, then washed with water (650 mL) and allowed to air dry
overnight. The dried solid (0.15 g) was then dispersed in aqueous
TMAOH (15 mL of 1.25 vol%). This mixture was then agitated using
a mechanical stir bar at room temperature for 5 days. The solution
was then centrifuged at 4000 rpm for 5 min and then the super-
natant was separated and again centrifuged for 10 min. The super-
272 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
natant was decanted, and the pellet dried under reduced pressure
at room temperature. To prepare a stock CoOx solution, the dried
solid was dispersed in water at a concentration of 1 mg/mL
(agitated by vortex).
2.5. Preparation of Oil-in-Water Pickering Emulsions Stabilized by GO,
CoOx, and GO- CoOx
Standard oil-in-water emulsions were prepared by dispersing
GO in distilled water (1.0 mg/mL) and CoOx in distilled water
(1.0 mg/mL). A total of 4 mL of aqueous nanosheet solution was
placed in a 2 dram vial with the following GO:CoOx ratios – 1:0,
2:1, 1:1, 1:2, 1:5, and 0:1. This solution (0.75 mL) was then placed
in a 2 mL vial. Oil (0.50 mL) was added to the vial, and then the vial
was vortexed for 5 s and bath sonicated for 30 s [8]. All emul-
sions were prepared in triplicate.
2.6. Preparation of Oil-in-Water Pickering Emulsions Stabilized by GO,
CoOx, and GO and CoOx with Salt
A given amount of salt was weighed into a 2 dram vial, then the
nanosheet solution (4.0 mL) was added to the vial, and the vial vor-
texed for 10 s. Next, this solution (0.75 mL) was transferred to a
2 mL vial, and oil (0.50 mL) was added. The vial was vortexed for
5 s and sonicated for 30 s. For CaCl2 (10043-52-4, Merck) and
MgCl2 (7786-30-3, Alfa Aesar, 99%), the salts were added to the
nanosheet solutions as a saturated aqueous solution until floccula-
tion was observed; the method was altered because dissolution of
these salts in water is highly exothermic. To evaluate reproducibil-
ity, all emulsions were prepared in triplicate.
2.7. Preparation of GO-CoOx Armored Polystyrene Particles via
Dispersion Polymerization
GO-CoOx armored PS particles were synthesized via dispersion
polymerization of styrene-in-water with a GO:CoOx ratio of 1:1
[32]. LiCl (0.15 g), GO stock solution (3 mL), and CoOx stock solu-
tion (3 mL) were added to a 25 mL round bottom flask,. The flask
was swirled until the salt dissolved. Then, AIBN (0.3 g, 1.8 mmol)
was dispersed in styrene (3 mL), and then this solution was added
to the round bottom flask. The mixture was sonicated for 30 min in
cold water, and then degassed by bubbling nitrogen through the
solution. The resulting emulsion was placed under nitrogen gas
and heated to 70 °C without stirring. After 24 h, the reaction was
cooled to room temperature to yield a milky gray solution. The
styrene:water ratios used were 1:2, 1:3, and 1:5, with 1:3 yielding
discrete particles.
3. Results and discussion
Graphene oxide (GO) and cobalt oxide (CoOx) nanosheets were
prepared as previously reported, and thoroughly characterized by a
number of techniques (see Fig. S1, S2, and Table S1). Briefly, GO
nanosheets were prepared by the chemical oxidation of expanded
graphite using a modified Hummer’s method [11]. The FTIR
spectrum of GO nanosheets revealed the characteristic stretching
frequencies of GO associated with OAH, C@C, and C@O bonds;
X-ray photoelectron spectroscopy (XPS) revealed an overall C:O
ratio of 2:1 and Raman spectroscopy showed the signature D and
G bands of GO at 1350 cm
1 and 1600 cm
1 respectively (2:1,
AD/AG). The CoOx nanosheets were prepared by the chemical exfo-
liation of commercially available LCO by treatment with aqueous
HCl then TMAOH. XPS was used to monitor this exfoliation process,
specifically by following the Co 2p peak at 780 eV. Atomic force
microscopy (AFM) images reveal GO nanosheets are 2 nm thick
and a few microns in diameter whereas CoOx nanosheets are
0.8 nm thick and 1 mm in diameter. GO and CoOx both have a
negative Zeta potential, showing that both nanosheets had a nega-
tive charge. Both GO and CoOx were dispersed in water at a con-
centration of 1 mg/mL. As a dispersion, GO was more stable than
CoOx upon standing, as the latter precipitated after 5 h.
First, the ability to form toluene-in-water Pickering emulsions
with only GO, only CoOx, or different ratios of the nanosheets as
particle surfactant was evaluated using a 2:3 toluene:water ratio
(a similar system has been reported for GO). As expected, GO
nanosheets formed emulsions (Fig. 1A), however CoOx nanosheets
did not, and simply aggregated (Fig. 1F). Further studies revealed
the GO:CoOx ratio dictated the ability to form an emulsion, with
2:1, 1:1, and 1:2 GO:CoOx ratios leading to the formation of dro-
plets (Fig. 1B–D), but a higher content of CoOx leading again to
aggregation of nanosheets (1:5 GO:CoOx, Fig. 1E). Although the
presence of enough GO led to emulsion formation for GO:CoOx sys-
tems, nanosheets remained in the continuous phase, emulsion dro-
plets varied in size, and the emulsions were dramatically less
stable than emulsions stabilized by GO only. The inability of CoOx
and 1:5 GO:CoOx to stabilize toluene-in-water emulsions suggests
that CoOx nanosheets do not have a suitable affinity for the oil-
water interface and cannot act as particle surfactants. Whereas
GO and CoOx both have net negative charge (see above), the nega-
tive charge of GO is attributed to carboxylic acid groups present
only at the nanosheet edges, and thus inter-sheet repulsion can
be overcome by offset GO nanosheets when assembled at the oil-
water interface. In contrast, the negative charge of CoOx
nanosheets is likely distributed throughout the faces and edges,
which renders them more dispersible in water.
Flocculation of negatively charged nanosheets can facilitate
their assembly at the oil-water interface and use as surfactants.
For example, the groups of Bon and Bourgeat-Lami illustrated that
addition of salt improves the ability of clay platelets (e.g., Laponite)
to stabilize oil-in-water Pickering emulsions [12,33,34]. Addition
of NaCl compresses the double layer, lowering the electrostatic
repulsion between nanosheets, causing flocculation, and leading
to the formation of multiple layers of clay at the oil-water interface
[10]. Thus, in an effort to facilitate the formation of Pickering emul-
sions stabilized by GO-CoOx and CoOx, the nanosheets were floccu-
lated with readily available inorganic and organic salts. Salt was
added to an aqueous suspension of nanosheets to induce floccula-
tion, then toluene was added and the resulting mixture agitated by
vortex and sonication to yield opaque, milky emulsions. This
approach dramatically facilitated the formation of emulsions. The
quality of emulsions was determined by droplet uniformity (spher-
ical shape and diameter heterogeneity) and lack of nanosheets in
the continuous phase, whereas stability was tested by letting the
emulsions to stand unagitated for 10 weeks and comparing pho-
tographs and optical microscopy images.
The inorganic salts used to flocculate GO, GO-CoOx, and CoOx
prior to emulsion formation were LiCl, NaCl, KCl, CsCl, MgCl2, and
CaCl2; a variety of salt concentrations were evaluated, as well as
different GO:CoOx ratios. Figs. S3–S8 shows the impact of salt con-
centration and GO:CoOx ratio for each inorganic salt evaluated;
Fig. 2 shows photographs and optical microscopy images of the
best emulsions for each salt. For each system, 1:1 GO:CoOx yielded
the best emulsions, though the optimum concentration was differ-
ent for each salt. The addition of monovalent chloride salts (LiCl,
NaCl, KCl, CsCl, Fig. 2A–D) all improved emulsion formation, as
indicated by more homogenous droplet diameters and a clear con-
tinuous phase, indicating no nanosheets remained in the water and
suggesting all are associated with the oil-water interface. In con-
trast, neither the addition of MgCl2 nor CaCl2 led to improved
emulsion formation (heterogeneous droplet sizes, compare
Fig. 1C, Fig. 2E and F).
 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278 273

Fig. 1. Optical microscopy images and photographs of toluene-in-water emulsions stabilized by (A) GO, (B) 2:1 GO:CoOx, (C) 1:1 GO:CoOx, (D) 1:2 GO:CoOx, (E) 1:5 GO:CoOx,
and (F) CoOx.

Fig. 2. Optical microscopy images and photographs of toluene-in-water emulsions prepared with GO:CoOx (1:1) flocculated with different inorganic salts: (A) 0.59 M LiCl; (B)
0.43 M NaCl; (C) 0.17 M KCl; (D) 0.74 M CsCl; (E) 0.06 M MgCl2; and (F) 0.34 M CaCl2.

Across the inorganic salts evaluated, all facilitated the forma-
tion of emulsion droplets with all ratios of GO:CoOx, including
CoOx-only and 1:5 GO:CoOx. These data support that the salt helps
shield the negative charges of neighboring nanosheets and facili-
tates their assembly at the oil-water interface. Fig. 3 illustrates
the impact of the addition of LiCl on emulsion formation for differ-
ent nanosheet systems. In contrast to the data discussed above in
which no salt was added, for GO, CoOx, and 2:1, 1:1, 1:2, and 1:5
GO:CoOx, droplets are observed. At lower GO:CoOx ratios (1:2
and 1:5, Fig. 3D and E), nanosheets are apparent in the continuous
phase, and with the CoOx-only system nanosheet aggregates dom-
inate, although some droplets are present (Fig. 3F). Neither lower
nor higher salt concentration led to all CoOx nanosheets associated
with the oil-water interface, and the highest salt concentration led
to nanosheet precipitation (see Fig. S3). These observations suggest
that CoOx-only flocculates are not suitable for stabilizing oil-in-
water emulsions. Similar trends were observed for other inorganic
salts (Figs. S4–S8).
XPS was used to confirm the presence of GO and CoOx in these
composite emulsion surfactants. An emulsion with 1:1 GO:CoOx
flocculated with LiCl was prepared and then the composite
nanosheet mixture isolated by centrifugation, with the clear super-
natant discarded. Fig. 4A–C compare the survey and high-
resolution C 1s and O 1s XPS spectra of LCO (blue spectra), GO
(red spectra), and GO:CoOx (black spectra). The survey spectrum
of GO:CoOx reveals the presence of oxygen (pink box), carbon
(orange box), and chloride salt (blue box, Cl 2p), as well as a small
signal due to cobalt (purple box). The high-resolution C 1s spectra
shown in Fig. 4B support the presence of GO in the GO-CoOx pellet,
with a C:O ratio of 1:1. Fig. 4C shows the high-resolution Co 2p
spectra, illustrating the presence of cobalt in the GO:CoOx compos-
ite (peaks at 780 eV and 795 eV). Characterization of the GO:CoOx
274 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278

Fig. 3. Optical microscopy images and photographs of toluene-in-water emulsions prepared with different GO-CoOx composition, flocculated with 0.59 M LiCl.

Fig. 4. Characterization of LCO (blue traces), GO (red traces), and GO-CoOx composites (1:1 ratio, black traces): (A) Survey XPS spectra; (B) High resolution C 1 s spectra; (C)
High resolution Co 2p spectra; (D) SEM of the GO-CoOx composites. (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of this article.)

composite by SEM shows a rough morphology, and possible layer-
ing of the two types of nanosheets (Fig. 4D).
In addition to evaluating inorganic salts as flocculating agents
for GO and CoOx nanosheets, water-miscible organic salts were
examined. In comparison to their inorganic counterparts, the
charge on organic salts is more delocalized, and thus the molecule
softer and more polarizable; furthermore, organic salts are less
hydrophilic than their inorganic counterparts and provide a com-
plimentary system [35]. The flocculated nanosheets and emulsions
were prepared in a similar manner to those discussed above
(1 mg/mL solutions of GO and CoOx, and GO:CoOx ratios of 2:1,
1:1, 1:2, 1:5, GO-only, and CoOx-only, Fig. S9–S12). [Emim][PF6],
1-ethyl-3-methylimidazolium dimethylphosphate ([Emim]
[DMP]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]
[BF4]), and tetra-n-butylammonium bromide (NBu+4Br
) were all
evaluated as flocculating agents. Addition of [Emim][PF6] and
 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
[Emim][DMP] led to the formation of emulsions with relatively
homogenous droplets (Fig. 5A and B), NBu+4Br
led to the formation
of an emulsion with a large distribution of droplet sizes (Fig. 5C),
and addition of [Bmim][BF4] did not lead to emulsion formation,
only nanosheet aggregation (Fig. S9). In comparison to [Emim]
[PF6] and [Emim][DMP], the cations of [Bmim][BF4] and NBu+4Br

are more hydrophobic, having longer alkyl chains (butyl vs. ethyl)
which also render them bulkier; these differences may account for
the lack of emulsion formation. As in the case of inorganic salts,
nanosheet ratio impacts emulsion formation: emulsions with more
GO tend to have little-to-no nanosheets remaining in the continu-
ous phase, and emulsions with lower GO:CoOx ratios (1:2, 1:5, and
CoOx-only) had larger and more disperse droplet sizes as well as
nanosheets in the continuous phase.
Fig. 5. Optical microscopy images and photographs of toluene-in-water emulsions
prepared when aqueous solutions of GO:CoOx (1:1) are flocculated with different
organic salts: (A) 0.10 M [Emim][DMP]; (B) 0.20 M [Emim][PF6]; C) 0.20 M NBu+4Br
.
Fig. 6. Stability testing of 1:1 GO:CoOx toluene-in-water emulsions with 0.59 M LiCl, 0.17 M KCl, and 0.20 M [Emim][PF6] as prepared (0 h, 1 day (24 h), 1 week (168 h), and
10 weeks.
275
After evaluating the ability of various inorganic and organic
salts to facilitate the formation of emulsions with GO and CoOx
nanosheets as surfactant, stability of the toluene-in-water systems
was studied by leaving the emulsions unagitated. From the discus-
sion above, flocculation of 1:1 GO:CoOx with LiCl, KCl, or [Emim]
[PF6] led to the formation of the best emulsions and thus these sys-
tems were studied. Fig. 6 shows the optical microscopy images and
photographs of the emulsions as prepared, after 1 day, after
1 week, and after 10 weeks. After 1 week unagitated, the droplets
of all samples appeared to increase slightly in diameter, but
remained spherical, with the LiCl droplets undergoing the most
dramatic change. The difference in droplet size and size distribu-
tion appeared similar for all samples between 1 day and 1 week.
In contrast, after 10 weeks of standing unagitated, the KCl emul-
sion lost integrity, with some nanosheets precipitating from solu-
tion and the [Emim][PF6] emulsion underwent catastrophic
changes, with little-to-no emulsion droplets remaining and a large
amount of precipitation. In contrast, after 10 weeks no changes
were observed for the LiCl emulsion. The emulsion stability
indexes of the LiCl and KCl-flocculated emulsions were determined
by the volumetric method to be 7.1% and 18.8%, respectively,
whereas that of the [Emim][PF6] emulsions was 0% (see Fig. S17)
[36]. These samples indicate that the salt used to flocculate the
nanosheets directly impacts the stability of the resulting emulsion,
as each contained the same amount and ratio of GO:CoOx and
toluene-to-water.
Once the preparation of toluene-in-water emulsions stabilized
by GO-CoOx was established, other oil phases were tested: hex-
anes, dodecane, chloroform, and styrene. A variety of salts were
evaluated for each oil, and the best emulsions formed shown in
Fig. 7. Hexanes-in-water emulsions were remarkably different
from those with dodecane, notable given that both oils are hydro-
carbons and thus of similar polarity. Emulsion droplets for
hexanes-in-water were larger with a broader size distribution than
dodecane-in-water emulsion droplets (compare Fig. 7A and B);
these differences could be attributed to boiling points of the sol-
vents (hexanes b.p. = 68 °C and dodecane b.p. = 216 °C) or viscosity
276 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
Fig. 7. Optical microscopy images and photographs of different oil-in-water
emulsions. The salts used for flocculation were (A) 0.20 M [Emim][PF6], (B)
0.17 M KCl, (C) 0.59 M LiCl, and (D) 0.17 M KCl.
(hexanes = 0.297 cP and dodecane = 1.374 cP). However, it has
been shown that the best oils for GO-stabilized Pickering
emulsions are those that are polar and aromatic [13], which could
explain the poor performance of hexanes due to its low polarity
and lack of aromaticity. Chloroform-in-water and styrene-in-
water emulsions both readily formed without nanosheets in the
continuous phase, though the droplets were larger and more
heterogeneous in diameter compared to toluene-in-water or
dodecane-in-water emulsions. Evaluation of the impact of GO:
CoOx ratio on the formation of chloroform-in-water emulsions
revealed that at increased loading of CoOx, irregular, multi-
emulsions were formed regardless of salt identity (water-in-oil-
in-water, Fig. S13–S16).
Fig. 8. Characterization of GO-CoOx-armored polystyrene particles: (A) (i) optical microscopy images of the styrene-in-water emulsion pre-polymerization, and (ii) post
polymerization; (B) SEM image of GO-CoOx coated PS particle with inset showing single particle; and (C) High resolution Co 2p XPS spectrum.
GO-CoOx-stabilized styrene-in-water emulsions are of interest
for the preparation of armored polymer particles, as styrene is
polymerizable and has been applied to dispersion and emulsion
polymerizations [37-39]. For example, Thickett and Zetterlund
reported the miniemulsion polymerization of GO-stabilized
styrene-in-water emulsions to prepare GO-armored polystyrene
(PS) particles [40]. In a similar vein, Bon and coworkers utilized
this technique to fabricate polymer particles armored with
Laponite clay platelets [10,34,41]. Further, Bourgeat-Lami and
coworkers used the Pickering emulsion platform to make armored
co-polymer particles [42]. Here, we used a GO:CoOx ratio of 1:1,
the nanosheets were flocculated with LiCl, and the oil phase con-
sisted of styrene with 0.1 wt% 2.20 -azobis(2-methylpropionitrile)
(AIBN), a thermally activated radical initiator. For these emulsions,
a 1:3 styrene:water ratio was used. After degassing, polymeriza-
tion was initiated by heating the emulsion to 70 °C for 24 h. This
resulted in an opaque, gray solution, and the solid polymer parti-
cles were isolated by filtration, then characterized by XPS, scanning
electron microscopy (SEM), and optical microscopy.
Optical microscopy images revealed individual GO-CoOx-
armored PS particles, with the particle diameters similar to the
styrene-in-water droplets prior to polymerization (Fig. 8A). This
observation indicates that the GO-CoOx nanosheet composite is a
suitable surfactant to contain the inner styrene phase, preventing
droplet aggregation or coalescence during heating. The particles
were further characterized by SEM, after isolation by gravity filtra-
tion and affixing to carbon tape. SEM images reveal a textured sur-
face of the GO-CoOx-coated PS particles (Fig. 8B), similar to that
observed for GO-or clay-armored polymer particles. Characteriza-
tion of the GO-CoOx-coated PS particles by XPS illustrated the pres-
ence of cobalt, as expected, and as indicated by peaks associated
with Co 2p (Fig. 8C and Fig. S18, 795 and 780 eV, similar to the
GO-CoOx mixture itself). As XPS is a surface sensitive technique,
the detection of Co confirms the nanosheets lay near the surface
of the particle.
 K. Edgehouse et al. / Journal of Colloid and Interface Science 541 (2019) 269–278
4. Conclusion
In summary, we have prepared a variety of oil-in-water emul-
sions stabilized by a combination of graphene oxide (GO) and
cobalt oxide (CoOx) nanosheets. We found that the nanosheets
must be flocculated with salt prior to emulsion formation and that
the best particle surfactant system was 1:1 ratio of GO:CoOx; at
higher CoOx composition, nanosheet aggregates formed, and few
emulsion droplets were realized. Various inorganic and organic
salts were evaluated as flocculating agents, and LiCl was deter-
mined to facilitate emulsion formation, leading to relatively
homogenous droplets, and giving prolonged stability (emulsions
remained after 10 weeks unagitated). Further, a variety of oils were
used, including a monomer that can be polymerized. Dispersion
polymerization of the styrene-in-water system led to the forma-
tion of discrete polystyrene particles armored with GO and CoOx,
illustrating the integrity of the Pickering emulsions using com-
bined particle surfactants. Versatility in oil choice and nanoparticle
surfactants offers a pathway to template new hybrid architectures
including capsules, other armored particles, and HIPEs [43,44]. The
combined use of reduced GO and CoOx will find application in elec-
trochemical devices (such as for energy storage) given the electri-
cal conductivity of the former [45,46] and the redox activity of the
latter [47,48].
5. Notes
The authors declare no competing financial interest.
Acknowledgements
K.E., M.E., P.W., and E.P. thank NSF CAREER Award no. 1551943
for financial support. R.D. thanks the ACS SEED program for finan-
cial support. The work of K.P. and A.S. was supported by the Air
Force Office of Scientific Research (AFOSR FA9550-18-1-0030).
The authors also thank the Swagelock Center for Surface Analysis
of Materials (SCSAM) for XPS and the CWRU Physics Department
for SEM.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2019.01.092.
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