Applied Energy 191 (2017) 287–310

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Advanced nanomaterials in oil and gas industry: Design, application and

challenges
Munawar Khalil a,⇑, Badrul Mohamed Jan b, Chong Wen Tong c, Mohammed Ali Berawi d
a
Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Indonesia, Depok, West Java 16424, Indonesia
b
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
c
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
d
Center for Sustainable Infrastructure Development (CSID), University of Indonesia, Depok, West Java 16424, Indonesia

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

Synthetic protocols for nanoparticles

used in oil and gas industry.

Surface functionalization for
nanoparticles used in oil and gas
industry.

Application of nanoparticles in
enhancing hydrocarbon exploration
and production.

The potential of nanoparticles in
refining and fuels production.

Challenges and prospects of
nanomaterials in oil and gas industry.

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

Article history: The increase of global energy consumption and the growing demand of fossil fuels as predominant energy
Received 4 April 2016 resources have greatly improved the advancement of new technologies in hydrocarbon recovery pro-
Received in revised form 25 January 2017 cesses. New class of materials, such as nanoparticles has been widely studied in an effort to ensure sim-
Accepted 27 January 2017
pler and more economical oil exploration and production processes, especially in challenging and harsh
reservoirs environments. The unique physical and chemical properties of nanomaterials have lead to
their application in almost all oil and gas aspects, such as exploration, reservoir characterization, drilling,
Keywords:
cementing, production and stimulation, enhanced oil recovery (EOR), refining and processing. This review
Nanomaterials
Nanoparticles design
article presents comprehensive discussion on the most recent development of nanomaterials and their
Functional nanoparticles roles in new or enhanced applications in oil and gas industry. Here, the synthetic strategies and function-
Oil and gas industry alization of some of the most common nanomaterials used in oil and gas industry, i.e. metallic and metal
oxide nanoparticles, carbon nanotubes and magnetic nanoparticles are summarized. Their applications in
different types of oil and gas processes are also discussed. Finally, an outlook on the current challenges
and some prospects for the future applications is also highlighted.
Ó 2017 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: mkhalil@sci.ui.ac.id (M. Khalil).

http://dx.doi.org/10.1016/j.apenergy.2017.01.074
0306-2619/Ó 2017 Elsevier Ltd. All rights reserved.
288 M. Khalil et al. / Applied Energy 191 (2017) 287–310

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
2. Nanomaterials design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
2.1. Synthetic protocols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
2.1.1. Metallic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
2.1.2. Metal oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
2.1.3. Carbon nanotubes (CNTs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
2.1.4. Magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
2.2. Functionalization, stabilization and modification of nanomaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
2.2.1. Ligand incorporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
2.2.2. Biomolecule conjugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
2.2.3. Polymer coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
3. Application of nanomaterials in oil and gas industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
3.1. Exploration and reservoir characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
3.2. Drilling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
3.3. Cementing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
3.4. Production and stimulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
3.5. Refining and fuel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
4. Outlook and future challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

1. Introduction reservoir managements and drilling processes, to the production

Nanotechnology has revolutionized the perspective of today’s
scientists and engineers towards smart materials. The study and
application of very small materials (1–100 nm) has become one
of the fastest growing research areas in wide variety of science
and engineering fields. Advancement in nanotechnology has
enabled researchers to fabricate collection of various unique and
enhanced nanomaterials, nanodevices and nanotools that can be
used in many fields including electronics, aerospace, medical and
biomedical, smart materials and manufacturing, pharmaceutical,
photography, energy, etc. [1–10]. This is generally due to their
unique size-dependent physical and chemical properties that are
often not observable in their bulk counterparts [11]. In bulk mate-
rials, the number of atoms at the surface is significantly smaller
than the number of atoms in the bulk. Therefore their physical
and chemical properties are mostly constant regardless of their
sizes. However, when the size of a particle is reduced to near or less
than the wavelength of conduction electrons, several properties
such as magnetism, optical behavior, thermal resistance, chemical
and catalytic activities, melting point and internal pressure are
altered. This is due to the surface/volume ratio becomes exponen-
tially larger and the number of atom on the surface becomes signif-
icant with regards to the amount of atoms in the bulk [12]. This
allows researchers to utilize these unique properties for many dif-
ferent applications. In addition, nanotechnology also offers not
only cost-effective and cost-efficient industrial processes but also
a precise design and manipulation of atoms and molecules as well
the as full control on their unique properties [6].
In the past few decades, rapid advancement of nanotechnology
has lead to the application of various nano-sized materials and
nanoparticle-based devices and tools for oil and gas industry. In
addition, the high global demand for energy and the remaining
major challenges in the application of current conventional proce-
dures have forced researchers to embark on the search for more
economical, efficient and environmentally sound techniques to
extract more hydrocarbons. In a recent review article by Kong
and Ohadi, a summary of major challenges in petroleum industry
has been comprehensively discussed [12]. These challenges lie
from the early stage of exploration such as reservoir mapping,
and post-production processes such as refining and processing.
Recent advancement of nanotechnology enables researchers and
engineers to potentially solve industrial problems in almost all
aspects of oil and gas industry, from upstream to midstream to
downstream. For instance, new nanoparticles based sensor tech-
nology can be used to probe key valuable information about deep
reservoir properties which enables one to solve the complex struc-
ture and the nature of reservoir rocks and their interaction with
trapped fluids. This is important in many different aspects of pet-
roleum engineering field since it can be used to design suitable
exploration and production plans. In a work by Wang et al., metal-
lic nanoparticles have been used in geochemical exploration to
delineate ore deposition [13]. In drilling processes, drilling equip-
ments and platforms can be made with better resistance towards
water and corrosion, better durability, wear- and shock-resistant,
and enhanced thermal conductivity by coating them with a special
type of nanoparticles [12]. Furthermore, another emerging applica-
tion of nanotechnology in oil and gas industry called ‘‘nano-fluid”
has also been reported. According to literatures, nanofluids can
be used in a wide range of applications such as drilling, cementing,
and enhanced oil recovery (EOR) [14–18]. Recently, nano-sized sil-
ica particles were used to stabilize the formation of liquid CO2
foam for CO2 EOR processes which can facilitate the improvement
of oil production [19]. Moreover, iron oxide based nanocatalyst for
in-situ aquathermolysis process to upgrade the quality and
improve the productivity of heavy and extra heavy oil [20]. Various
types of nanocatalysts have also been used in this regard [21–23].
Because of these great technological and industrial potencies,
considerable efforts and innovations have been applied to the
design and characterization of nanomaterials, particularly for oil
and gas applications. Therefore, the development of nanotechnol-
ogy and its contribution in oil and gas industry will be highlighted
and discussed in this review article. In the first part of this review,
synthetic protocols for nanomaterials that are commonly used in
oil and gas application as well as their functionalization strategies
are briefly discussed. This study will greatly serve to underscore
the key role of chemistry on the fabrication of suitable nanomate-
rials and their applications in petroleum industry. Furthermore,
recent progress on relevant nanotechnological studies and their
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
applications on different major areas in oil and gas processes will
be summarized. Finally, future challenges, perspectives, imple-
mentations and directions will also be discussed.
2. Nanomaterials design
2.1. Synthetic protocols
Over the last several decades, tremendous efforts have been
conducted in the development of reliable synthetic protocols for
nano-sized materials with full control on size, shape and other spe-
cial characteristics. In general, nano-sized particles can be pre-
pared either by physical, chemical, or biological methods
depending on the nature of the materials and involvement of
chemical reactions [24]. Furthermore, the synthesis of nanoparti-
cles can also be categorized as either a ‘‘top-down” or a ‘‘bottom-
up” method [25–27]. In top-down synthetic method, nano-sized
particles are usually produced by size reduction via various phys-
ical and/or chemical treatments. Several common top-down syn-
thetic methods include mechanical milling/ball milling, chemical
etching, thermal ablation, laser ablation, explosion process and
sputtering [25,28]. Meanwhile, in bottom-up method, the nanopar-
ticles are formed by smaller entities such as atoms, molecules, and
smaller particles as building blocks that are assembled to form the
final particle [29,30]. Commonly, this method is based on either
chemical or biological mechanisms. Several examples of bottom-
up synthetic methods are chemical/electrochemical precipitation,
vapor deposition, atomic/molecular condensation, sol-gel pro-
cesses, spray pyrolysis, laser pyrolysis, aerosol processes, and
chemical or biological reduction [25]. In this article, synthetic pro-
tocols for four types of nanomaterials that are commonly used in
oil and gas application, i.e. metallic nanoparticles, metal oxide
nanoparticles, carbon nanotubes, and magnetic nanoparticles, are
discussed.
2.1.1. Metallic nanoparticles
Due to their unique chemical and physical characteristics, dif-
ferent types of metallic nanoparticles have been used in wide vari-
ety of oil and gas applications, from exploration to production. In
most cases, both noble and transitional metal nanoparticles are
mainly used as catalyst in many petroleum-related processes such
as catalytic reforming, in-situ aquathermolysis, hydrocracking and
hydro-desulphurization [20,31]. This is mainly due to their large
surface area-to-volume ratio in comparison to their bulk counter-
parts, which significantly improves their catalytic activities and
selectivities [32]. Because of these vast potential applications, a
Fig. 1. Schematic mechanism of metallic nanoparticles formation in metal salt reduction process.
289
controlled synthetic strategy of metallic nanoparticles has received
enormous attentions. During the past several years, numerous syn-
thetic methods for different types of metallic nanoparticles have
been widely studied. Depending on the type of the metal, oxidation
states, shape, functionalities, and other characteristics, various
synthetic methods can be used. They can be synthesized with
either physical approaches or chemical reactions [33]. These
methods have been extensively discussed in many review articles
[34–40].
In general, there are four most common methods to synthesize
metallic nanoparticles, i.e. reduction of metal salt precursors, elec-
trochemical synthesis, reduction of organic ligands in
organometallic precursors, and metal vapor chemistry [41]. Among
these methods, metal salt reduction is considered as one of the
simplest and the most common methods to produce metallic
nanoparticles. Different types of metallic nanoparticles such as
Ag, Au, Pd, Cu, Pt, Os, Rh, and Ir have successfully been synthesized
using this method [42–45]. In this approach, the metal salt precur-
sor is typically mixed with reducing agent in the presence of stabi-
lizing agent to prevent particle aggregation. The overall reaction
mechanism of this process can be expressed as the following
equation [41]:
xMnþ þ nxe þ stabilizing agent ! M0nðclusterÞ ð1Þ
In this process, the metallic nanoparticles are generally formed
in stepwise processes involving nucleation, growth and agglomer-
ation [46]. Fig. 1 presents the schematic mechanism of the metallic
nanoparticles formation synthesized via metal salt reduction. Ini-
tially, the metal cations (Mn+) in the solution are reduced to metal
atoms (M0) using reducing agents. Several reducing agents that can
be used are including hydrogen, carbon monoxide, hydrazine,
hydrides or salts such as sodium borohydride and sodium citrates,
different types of solvents such as alcohols, and most recently a
reducing agent obtained from natural sources (plant extracts)
[34,47]. Following the reduction process, the metal atoms are
rapidly clustered to form small metallic nanoparticles nuclei or
commonly called ‘‘seed” particles which will then slowly grow
and aggregate together to form more stable and bigger metallic
nanoparticles as the final product. At this step, stabilizing agent
is commonly added to control the particle growth and aggregation.
Here, various size, shape and morphologies of the final nanoparti-
cles can easily be controlled using various types of stabilizing
agents such as surfactants, polymers, or organic ligands [41]. The
ability of stabilizing agent to control such parameters is due to
its ability to alter surface energy of the particles and thus changes
the growth habit of different facet in the metal surface and induces
290 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Fig. 2. Schematic mechanism of electrochemical synthesis method of metallic nanoparticles; (a) oxidative dissolution of metal bulk at anode, (b) ion migration, (c) electron
transfer from cathode, (d) reductive formation of zerovalent ad-atoms, and (e) particle growth and stabilization.
the growth into certain direction. Moreover, stabilizing agent can
also prevent metal atoms deposition on the surface of metal
nanoparticles [8]. As a result, particles with different anisotropic
characteristics such as nanoplates, nanocube, nanowires, and
nanorods can be obtained depending on the type and amount of
stabilizing agent [48–50].
The second general method to synthesize metallic nanoparticles
is electrochemical synthesis. This method was initially introduced
by a research group at Max Planck Institute in 1994 [51]. In this
approach, nanoparticles are generated via electrochemical redox
reaction between cathode and sacrificial anode that consists of the
bulk metal. Both schematic and reaction mechanisms of this process
are shown in Fig. 2. In general, this process is initiated by the oxida-
tion of bulk metal at the anode to form metal ions. These metal ions
will then travel to the cathode where the ions are reduced to form
zerovalent metal atoms (ad-atoms) as seed particles, which further
grow to form stable metallic nanoparticles (Fig. 2). In literatures,
various collection of both noble and transitional metals nanoparti-
cles such as Pd, Co, Fe, Ag, Au, Ti, and Ni, as well as bi-metallic alloy
nanoparticles such as Fe-Ni, Pd-Ni, and Fe-Co have been successfully
synthesized using this methods [51–55]. It is reported that this
method allows an easy control for size-selective particle formation
by simply adjusting the current density (higher current density for
small NPs, and vice versa) [41]. In addition, particles with different
shapes and morphologies can also be obtained by introducing dif-
ferent type of capping or stabilizing agents. For example, uniform
Au nanoparticles with dumbbells-like structure can be obtained
when two surfactants, i.e. cetyltrimethylammonium bromide
(CTAB) and tetradecyltrimethylammonium bromide (TTABr) are
used [53]. In another approach, different Au particle shapes such
as spherical and plate-like can also be obtained using poly(N-
vinylpyrrolidone) (PVP) as protective agent [52].
Another method for metallic nanoparticles synthesis is
organometallic reduction. In general, the principle mechanism of
this method is very similar to the reduction of metal salt precursor.
However, organometallic precursor is used as the metal source
instead of metal salt. It is used to prevent passivation of excess salt
and water on the surface of the particles during the particles
growth which can alter metal precursor’s reactivity by producing
thin layer of oxides or hydroxides [56]. In the literature, several
metallic nanoparticles have been successfully synthesized from
their organometallic precursors [56,57], for example, Ni nanoparti-
cles from Ni(C8H12)2 [58], In nanoparticles from [In(g5-C5H5)]
([InCp]) complex [59] and Ru nanoparticles from Ru(C8H10)
(C8H12) [60]. Moreover, organometallic can also be used as precur-
sors in several other synthetic methods, such as high temperature
decomposition process like chemical vapor deposition (CVD) [61],
inorganic support deposition process [62], UV radiation [63],
sonolysis [64], and thermal treatment [65].
Furthermore, metallic nanoparticles can also be fabricated using
another common method called metal vapor chemistry or com-
monly known as chemical vapor synthesis (CVS). In this method, a
wide range of materials such as organometallics, carbonyls,
hydrides, chlorides and other type of volatile compounds are used
as precursors to produce their corresponding metallic nanoparticles.
The practical procedure for this vapor-phase synthesis and its recent
advancements has already been reviewed comprehensively in the
literature [66]. In general, this method is initiated by rapid evapora-
tion of metal precursors to form the atomic vapor of the metal. The
metal vapor is then condensed into a cold liquid containing stabiliz-
ing agent to form the corresponding metallic nanoparticles [41,66].
In comparison to the previous synthetic methods, fabrication metal-
lic nanoparticles via CVS offers several benefits such as the applica-
tion of wide range of precursors materials in the form of solid, liquid,
or gas. Moreover, the ability to form doped or multi-component
nanoparticles is another key feature of this method.
2.1.2. Metal oxide nanoparticles
Metal oxide nanoparticles is considered as one of the most
emerging nanomaterials in many areas due to their unique
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Fig. 3. General schematic mechanism of CVD process; (a) transport and adsorption of metal source precursors on the substrate, (b) desorption of metal precursors, (c) surface
diffusion and reaction, (d) particle growth, and (e) release of volatile byproducts.
physical and chemical properties, such as thermal conductivity and
heat transfer [67–69]. In oil and gas industry, a wide variety of
metal oxide nanoparticles have been used in almost every aspect
of hydrocarbon E&P such as filler or additive in drilling/completion
fluid [70], for trapping and fine particles mobility control [71], wet-
tability agent [72], enhanced oil recovery [73], reservoir imaging
[74], and catalyst [20]. Among different type of metal oxide
nanoparticles, the most commonly used are including Fe2O3,
SiO2, Al2O3, MgO, ZrO2, CeO2, TiO2, and ZnO [75]. Generally, fabri-
cation of metal oxide nanoparticles can be divided into two cate-
gories based upon the nature of the phase transformation, i.e.
liquid-solid and gas-solid [76]. Between the two, the former is con-
sidered as the simplest and the most common due to its ability to
easily control morphological features such as size and shape. In
liquid-solid transformation approach, synthetic methods that can
be used are including co-precipitation [77–79], sol-gel processing
[80–82], microemulsion [83–86], solvothermal methods [87,88],
template/surface derivated methods [89–91], hydrothermal [92–
95], and sonochemical method [96,97]. Here, both metal salts
and organometallics can be used as metal precursor. Various types
of surfactants and polymers are frequently used to control particle
growth, aggregation and to induce self-assembly system. It can be
done in either aqueous and/or organic solvent system [98,99].
Recently, a new solvent-deficient method can also be used for
the synthesis of a wide variety of metal oxides nanoparticles from
group 3–4 and 6–12 (ZrO2, MoO3, Mn2O3, Fe2O3, CuO, Ag2O, Fe3O4,
CoO, TiO2, PdO, Co3O4, NiO, Y2O3, ZnO) and semi-metal oxide
groups (In2O3, SnO2 Al2O3 and Bi2O3) [100].
The second approach to fabricate metal oxide nanoparticles is
via gas-solid transformation. Unlike the former approach, gas-
solid transformation is only limited to the chemical vapor deposi-
tion (CVD) and pulsed laser deposition (PLD). In CVD, several tech-
niques can be used on the production of ultra fine metal oxide
particles, i.e. pyrolytic or thermally activated method, plasma-
assisted, and photo CVD processes [75]. In principle, the mecha-
nism of CVD is very similar to chemical vapor condensation
(CVS). In both cases, a wide variety of precursors such as metal
salts (chlorides), metal organics (MOCVD), hydrides, and carbonyls
in the form of gas, liquid or solid can be used. Generally, the prin-
ciple of nanoparticles production can be divided into three key
steps, i.e. introduction of metal precursors gas and vapor into the
reaction chamber, reaction step, and condensation. Fig. 3 shows
the general schematic CVD mechanism. It is reported that one
can easily manipulate the particle size and distribution of the
nanoparticles by simply controlling growth temperature, flow rate
of the metal precursor, and the deposition rate [76].
291
Gas-solid transformation can also be done by laser evaporation
or commonly known as pulsed laser deposition (PLD). Here, target
sample (metal source precursors) is initially heated with high
power pulsed laser beam inside a vacuum chamber which lead to
the instantaneous evaporation, ionization and decomposition of
the sample. As a result, the gaseous formed acquire radiation
energy from the incoming pulses and collect kinetic energy which
then condensed into the heated substrate to allow the crystalline
particle to grow [76]. PLD is much faster method to fabricate nano-
materials and nanofilms directly from their bulk precursors com-
paratively to CVD. Nevertheless, large particle size and wide
particle size distribution still limit this method on the extensive
usage for the large-scale production. One way to minimize this
problem is by using matrix-assisted pulsed laser evaporation
(MAPLE) [101,102]. Unlike PLD, MAPLE uses mixture of precursor
and frozen matrix consisting of polymeric compound dissolved in
a volatile solvent as target sample. The comparison between PLD
and MAPLE has been comprehensively summarized and reviewed
in the literature [103]. Many metal oxide nanoparticles such as
TiO2 and SnO2 with unique electrical and semiconducting proper-
ties have been successfully fabricated using MAPLE [104,105].
2.1.3. Carbon nanotubes (CNTs)
In comparison to nanomaterials discussed earlier, CNTs are con-
sidered as newer generation of nanomaterials. The discovery of
CNTs is firstly known and described in 1952 and further described
in 1976 [106,107]. In 1991, Iijima was considered as the first scien-
tist to describe the preparation process of multi-walled CNTs after a
random even during arc evaporation of C60 and other fullerenes
[108]. Since then, CNTs have attracted many research interests
due to their very distinct unique physical and chemical properties.
Their mechanical flexibility and strength along with their unique
electrical features offer great potential in many applications, includ-
ing in oil and gas industry. In the past decade, the potential applica-
tion of CNTs in many oil and gas processes has been widely studied.
For instance the application of CNTs as emulsion/foam stabilizer in
enhanced oil recovery (EOR) and as contrast agent in rock matrix
[109–111], as composite cables and electronics for extreme condi-
tion such as at ultra-deep water oil and gas fields [112,113], wetta-
bility alteration agent [114], cement reinforcement [115], oil spilled
remediation [116,117], and as an additive for drilling fluid [118].
Structurally, CNTs are simply tube-shape carbon-made material
with diameter in the scale of a few nm to about 50 nm. The length
is ranging from about several micrometers to a few centimeters. It
can be viewed as ‘‘rolled up” one-atom-thick sheet of graphene
[106]. Based on their physical structure, CNTs can be divided into
292 M. Khalil et al. / Applied Energy 191 (2017) 287–310

Fig. 4. Three types of common structure for carbon nanotubes (CNTs).

three general categories, i.e. single-walled carbon nanotubes pulsed laser deposition (PLD). It is considered as one of the supe-
(SWNT), double-walled carbon nanotubes (DWNT), and multi- rior methods for large-scale production of high-purity SWNTs at
walled carbon nanotubes (MWNT) (Fig. 4). During the past several high yield. Since its discovery in 1995 by a research group at Rice
years, different types of systematic methods for CNTs synthesis University [127], laser ablation technique has been extensively
have been extensively reported. These methods have been compre- studied due to its ability to have a greater control on tip tempera-
hensively discussed and reviewed in many articles [106,119–124]. ture, continuity of nanotubes growth and the formation of defect
Depending on the type of CNTs, their application, and their charac- free tube structure than arc discharge method. In addition, SWNTs
teristics, each method has its own advantages and disadvantages. grown using laser ablation give rises to higher purity (90%) and
In developing a systematic synthesis method, it is always impor- better graphitize than arc discharge method [128–130]. However,
tant to consider the relationship between the weight and density this method requires the utilization of small carbon deposit and
of CNTs with their geometrical features such as inner/outer diam- special reaction condition for the fabrication of MWNTs [124].
eters, length, and the number of walls which plays a key role on the
overall physical and chemical properties of the tubes [125]. In
addition, separation and purification is also one of the important
steps during the synthesis of CNTs. For instance, a recent investiga-
tion by Duque and his co-worker found that the diameter of
SWNTs can greatly influence their solubility in aqueous solution
[126]. Based on their result, it is found that SWNTs with smaller
diameter were more soluble in aqueous solution than larger diam-
eter as they can easily be protonated.
In a recent review article by Prasek et al., general methods for
synthesizing sizeable quantities of CNTs is classified into several
categories, i.e. arch discharge, laser ablation, chemical vapor depo-
sition (CVD), sonochemical, hydrothermal, and electrolytic method
[106]. In the early development of CNTs, the first two methods
were widely used due to their ability to produce CNTs with fewer
structural defects in comparison to other techniques. In arch dis-
charge method, high temperature (>1700 °C) is commonly used
to grow CNTs. Here, the production of CNTs is commonly carried
out in a chamber filled with inert and/or reactant gas (helium,
hydrogen or methane) at subatmospheric pressure (30–130 torr
or 500 torr) where two water-cooled high-purity graphite elec-
trodes (anode can be either pure graphite or contains metal) are
momentarily brought into contact and create an arc. The detail
on the synthetic mechanism of nanotubes via arch discharge
method and the factors affecting its growth can be found in the
recent review article by Arora and Sharma [119]. In arch discharge,
size and yield of CNTs are significantly influenced by type of
catalyst, type of electrode, temperature, atmospheric gas used in
the chamber, grain size of precursor, arc current, and pressure.
Furthermore, it is also known that the arc current is considered
Fig. 5. Schematic illustration of (a) size-dependent magnetic coercivity relationship
as the most significant factors in the formation of CNTs, although
of magnetic nanoparticles [165] and a typical of hysteresis loop of (b) single-
the relationship between the two is still unclear. Another high domain superparamagnetic nanoparticles and (c) single-domain ferromagnetic
energy method is laser ablation. This method is very similar to nanoparticle [164].
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Recently, several low-temperature methods such as CVD, sono-
chemical, hydrothermal, and electrolytic methods can also be used
to produce CNTs. In electronics application, CVD is considered as
the most common methods due to its ability to allow nanotubes
to directly grow on a substrate via grow-in-place technique
[131]. This allows the integration of CVD as a stage in chip fabrica-
tion which is essential for the fabrication of CNTs embedded in a
specific substrate. In many reports, it has been shown that the
growth mechanism of CNTs in CVD is extremely sensitive to vari-
ous parameters such as the type and particle size of catalyst, car-
bon precursor, temperature and pressure [132–135]. With the
utilization of suitable catalyst, the CVD-temperature can be low-
ered down to room temperature [133]. Furthermore, it is also pos-
sible to control the diameter and chirality of the nanotubes by
correctly determining the growth-limiting steps during the reac-
tion [132]. Other widely known low-temperature methods are
hydrothermal and sonochemical methods. These two methods
are usually integrated in order to obtain better yield and greater
control on CNTs growth [136]. Unlike CVD, these methods can be
done at moderately low temperature (160–175 °C) to ambient con-
ditions [137–140]. In addition, the utilization of hazardous gas
such as H2 as carrier can also be avoided.
2.1.4. Magnetic nanoparticles
Another class of unique advanced nanomaterials that received
special attention in this review is magnetic nanoparticles. In gen-
eral, magnetic nanoparticles are commonly made of magnetic ele-
ments such as iron, cobalt and nickel and/or their oxides for
instance magnetite (Fe3O4), cobalt ferrite (Fe2CoO4) and chromium
dioxide (CrO2) [141,142]. In recent years, there have been a grow-
ing number of investigations on the fabrication, characterization of
properties and potential application of magnetic nanoparticles.
Currently, a wide variety of applications have been reported for
this class of nanoparticles which include ultra high density mag-
netic storage [143,144], magnetic vectors and probes for biosepa-
ration[145–148], chemical catalyst and separation [149,150],
biosensor [151,152], magnetic-based imaging for various diseases
such as cancer and Alzheimer’s diseases [153–155], and for wide
variety of processes in petroleum E&P [156–159]. In general, these
applications have always been associated with their unique quan-
tum size effect phenomena [160]. One of the most interesting fea-
tures of these phenomena is their size-dependent magnetic
properties [161–163]. This occurs due to the comparability
between the size of the particle and its magnetic domain that
enables one to obtain two important types of magnetic properties,
i.e. ferromagnetism (FM) and superparamagnetism (SPM) in one
individual particle (Fig. 5) [164]. In a typical magnetic nanoparticle,
magnetic coercivity (Hc) is very sensitive to the size variation
[165]. In most cases, the coercivity tends to increase initially due
to the reduction of size to a maximum value at specific size called
critical diameter (Ds). Here, magnetic nanoparticles posses a
single-domain (SD) magnetism instead of multi-domain (MD)
where all magnetic spins are in unidirectional fashion [148]. At this
condition, the particle behaves as single-domain ferromagnetic
(FM) and it is usually difficult to reverse its magnetization due to
the high coercivity value. At the region below critical diameter
(Ds), further size reduction will rapidly reduce the coercivity value
until it reaches zero coercivity. The size where the coercivity
reaches zero is called zero-coercivity diameter (Dp). Here, the par-
ticle is in the superparamagnetic state and behaves as superparam-
agnetic (SPM) in which the magnetization can randomly flip
direction under the influence of temperature [148]. In many
applications, superparamagnetic nanoparticles are usually pre-
ferred due to their zero net magnetization at room temperature
which reducing the risk of particle aggregation [141]. However,
293
superparamagnetic systems often requires relatively high external
magnetic field to obtain magnetic response.
During the past several years, syntheses of different types of
magnetic nanoparticles have been reported. In most cases,
ferrite-based particles such as magnetite (Fe3O4) and maghemite
(c-Fe2O3) are preferred due to their biocompatibility and
biodegradability [166–168]. In general, fabrication of magnetic
nanoparticles can be divided into three categories, i.e. physical,
chemical and biological methods [166]. Among many different
types of physical methods, electron beam lithography [169,170]
and CVD [171–173] are the most widely used techniques. In prin-
ciple, physical methods offer an easy way to produce high yield of
magnetite nanoparticles and suitable for the fabrication of
magnetic-based hybrid materials like bi-metallic based magnetic
nanoparticles [174] or graphene-coated magnetic nanoparticles
[175]. However, the applicability of these methods is still hindered
by several factors such as their inability to fully control morpho-
logical features of the resulting particles, the need for high energy
and high temperature process, and the requirement of expensive
instrumentation [167]. In chemical methods, it is possible to pro-
duce high yield of magnetic nanoparticle with full control on their
morphological features by simply adjusting the involved reaction
parameters like reaction temperature, concentration of precursors,
mixing rate, reaction time, etc. Several chemical methods that are
commonly used are sol-gel [176,177], hydrothermal [178,179],
microwave-assisted method [180,181], solvothermal [182–184],
redox method [185,186], chemical coprecipitation [187,188],
microemulsion [189,190], flow injection synthesis [191,192], elec-
trochemistry [193,194], sonochemistry [195,196], and supercritical
fluid [197,198]. Furthermore, biological synthetic approaches offer
greener way to obtain high yields good reproducibility, and good
scalability fabrication of magnetic nanoparticles in considerably
low production cost [199]. The synthesis can be achieved via the
utilization of microorganisms such as metal reducing bacterium
like Thermoanaerobacter [200] and Clostridium sp. [201] or using
reduction agent extracted from natural resources such as seaweed
(Sargassum muticum) [202].
2.2. Functionalization, stabilization and modification of nanomaterials
In nanomaterials engineering, one of the main challenges in
nanomaterials design is to control colloidal stability of the parti-
cles, such as prevention of aggregation and damaging-interaction
with the surroundings. In general, very small particles with diam-
eter in the range of nanometers tend to aggregate together to form
bigger particle clusters. This is mainly due to the high surface
energy as a result of its high surface area. In some cases, this
may also lead to the adsorption of other particles or molecules
on the surface of the particles. Consequently, it may also change
their physical and chemical properties. Therefore, surface function-
alization, stabilization and modification of nanoparticles play a key
role in this regard. In many reports, modification and functional-
ization of nanomaterials is commonly done in order to obtain sev-
eral benefits, i.e. to prevent particle agglomeration and improve
their colloidal stability [203–207], to render particles with compat-
ibility in different phases such as particles that soluble in aqueous
and/or organic solutions [7,208,209], to enable self-organization
[210–212] and to obtain specific functionalities such as for cat-
alytic activities [213,214], biocompatibility [215,216] or for speci-
fic binding capabilities as in biomedical applications [217,218].
Furthermore, in oil and gas application, nanoparticles are often
injected into oil and gas wells and are subjected to reservoirs con-
ditions such as high pressure, high temperature, high salinity and
the presence of various contaminants. Therefore, surface modifica-
tion and functionalization of the nanoparticles play a key impor-
tant role in ensuring the success of nanoparticles-assisted oil and
294 M. Khalil et al. / Applied Energy 191 (2017) 287–310

Fig. 6. Schematic representation of interaction modes of (a) phosphonic acid-based ligands via (1) monodentate, (2) and (3) bridging bidentate, (4) bridging tridentate, (5)
chelating bidentate; and (b) carboxylic acid-based ligands via (1) monodentate, (2) chelating bidentate and (3) bridging bidentate; (c) surface functionalization of CNTs via
various chemical reactions [234].

gas processes. In this current review, strategies for surface modifi-
cation and functionalization of different group of nanomaterials
are discussed. Some of which might not directly related to the oil
and gas application, but the technology is worth to be highlighted.
2.2.1. Ligand incorporation
Ligand incorporation is considered as one of most widely used
approaches in modification and functionalization of nanomaterials.
Different types of ligands have been successfully grafted on the
surface of nanoparticles for a wide variety of purposes, such as par-
ticles stabilization and enabling them to be dispersed in various
solvents [219,220]. In general, organic ligands are among the most
widely used modifiers for nanoparticles modification [221].
Depending on their functional groups, ligands that are commonly
used include thiols [222,223], carboxylic acids [224,225], amines
[226,227], phosphonic acids [228,229] and silanes [230,231]. Many
different strategies have been widely reported for the incorpora-
tion of these ligands onto the surface of nanoparticles. One
approach is via chemical reaction. In this approach, the ligand is
anchored on the surface of nanoparticles via the establishment of
chemical bonding. Depending on the reaction condition, ligand’s
functional group can form various types of interaction modes with
nanoparticle surface. For instance, ligands with phosphonates
group can be anchored onto metal oxide surfaces via the formation
of five different types of interaction modes, while carboxylic acid-
based ligands can only form three types of interaction modes
(Figs. 6a and 7b) [224,232,233]. In the case of CNTs, surface modi-
fication via ligand integration can be achieved via various chemical
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
reactions, such as cycloaddition, halogenations, reductive and
oxidative coupling (Fig. 6c) [234].
Another approach that can be used to integrate ligands on the
surface of nanomaterials is via the formation of non-chemically
bonding interactions. Here, ligand is not covalently bonded to the
nanoparticle host, but rather forms a weakly bonded complex via
electrostatic interaction, van der Waal force or p-p stacking inter-
action for the case of CNTs. Several types of ligands have been suc-
cessfully anchored on the surface of different types of
nanoparticles using this approach such as the attachment of proto-
nated alkylamines [235] and positively/negatively charged short
alkanethiols [236] on the surface of Au nanoparticles. Since the
ligand is not strongly and chemically bounded to the nanoparticles,
this method is often used for ligand exchange. Here, the ligand
molecule can be replaced by other ligands that can possibly give
new functionalities and properties to the particles. Generally, the
new ligand has more affinity and binds more strongly to the
nanoparticle. Furthermore, this approach can also be utilized for
the purpose of charged particles self-organization. For instance,
Kolny and co-workers can easily control the self-assembly of CdS
and Au nanoparticles to form a superlattice arrangement by utiliz-
ing particles electrostatic interactions [237]. Similar approach was
also used by Hiramatsu and Osterloh to induce self assembly of
CdSe-SiO2 and Au-SiO2 nanoparticles clusters [238].
2.2.2. Biomolecule conjugation
Surface modification of nanomaterials with biomolecules is
often done to obtain specific functionalities in biomedical applica-
tions, such as allowing them to be used as biosensors [239,240],
drug delivery [241], diagnosis of diseases [242], cytotoxicity reduc-
tion and intracellular delivery [243,244]. Studies on the application
of nanoparticles-biomolecules conjugates in oil and gas related
processes are very limited. Nevertheless, owing to their benefits
such as low resulting nanoparticles toxicity, high colloidal stability,
their simple, low cost, and eco-friendly modification processes,
such technology can be a great potential for the application in oil
and gas industry. Similar to the aforementioned method, the
attachment of biomolecule ligands can be achieved by the forma-
tion of chemical (covalent) bonding or non-covalent interactions
(through electrostatic interaction or van der Waals force). Different
types of biomolecules have widely been used as nanoparticles
modifiers, such as protein, vitamins (B, C, D, and K), lipids and
amino acids [245–247]. Recently, it has also shown that secondary
metabolites extracted from natural products may also be used for
surface modification of nanoparticles. For example, Maurya and co-
workers used pure plant extracts of Bauhinia variegata and Tinos-
pora in surface modification of TiO2 nanoparticle to improve its
antibacterial activity [248]. Furthermore, Kanipandian et al. have
also successfully used leaf extract of Cleistanthus collinus as surface
modifier for Ag nanoparticles [249]. Based on their experimental
result, it was observed that several organic nitrates phosphorous-
oxy compounds and some proteins from the leaf extract were
attached on the surface of Ag nanoparticles and gave additional
high antioxidant activity and low cytotoxicity features to the
particles.
2.2.3. Polymer coating
Encapsulation of nanoparticles with polymer or polymer coat-
ing has been considered as one of the most common methods to
achieve specific nanoparticles features in many oil and gas applica-
tions, especially in EOR [250]. To ensure a successful implementa-
tion in the oil and gas industry, nanoparticles must have two
important characteristics, i.e. the ability to withstand the harsh
condition of oil reservoirs and the ability to migrate through por-
ous media. In terms of particles stability, surface modification via
295
polymer coating offers more benefits than the integration of small
molecule ligands. Even though some small ligand molecules such
as thiols bind relatively strong to various types of metals, they still
tend to be desorbed at extreme conditions (high temperature and
high salinity). As a result, nanoparticle colloidal stability could sig-
nificantly be diminished when injected into the oil well. Alterna-
tively, stabilization of nanoparticles at harsh reservoir conditions
can easily be achieved with the use of a specific type of polymers
such as polyelectrolyte and polyampholyte [251]. Furthermore,
polymer coating can provide additional advantages by imparting
the properties of macromolecular systems to the nanoparticle sur-
face [8]. For example, some polyelectrolytes such as poly(acrylic
acid), poly(vinyl pyrrolidine) or poly(styrene sulfonate) can be
used to provide electrostatic repulsion between nanoparticles
and stabilize them in high salinity brine [252,253].
In general, encapsulation of nanoparticles with polymer can be
achieved in two ways, i.e. ‘‘grafting to” or ‘‘grafting from” methods
[254]. In the former method, encapsulation is usually done by
grafting the preformed polymer onto the surface of nanoparticles
via electrostatic interaction or coordination. For the later method,
encapsulation is done by firstly immobilizing an initiator onto
the surface of nanoparticles then followed by polymerization of
the corresponding monomer(s). In most cases, the former is con-
siderably easier to conduct than the later. For the oil and gas appli-
cation, most of the polymer coatings are done with ‘‘grafting to”
method [250]. In this method, polymers with functional groups
that react with the complementary group on the nanoparticle sur-
face are usually used. These functional groups include alcohol,
amine, thiol, silane, carboxylic acid or phosphonic acid [254,255].
In literatures, various classes of polymers have been explored in
the application of nanoparticles stabilization in subsurface applica-
tions. For instances, different types of polymers such as poly(ethy-
lene glycol) (PEG) [256], polyacrylamide (PAM) [257], poly(acrylic
acid) (PAA) [258], and various sulfonated copolymers [259,260]
have been used as colloidal stabilizing agent for metal oxide
nanoparticles at extreme salinity and temperature. Recently, it is
also reported that encapsulation of nanoparticles with sulfonated
and zwitter ionic polymers such as poly([3-(methacryloylamino)
propyl]dimethyl(3-sulfopropyl)ammonium hydroxide) (PMPDSA)
may be used to achieve high particle stability and low silica
absorption in extreme oil field applications [261].
In the case of CNTs, polymer modification may be achieved
either by covalent or non-covalent attachment method. Like inor-
ganic metallic and metal oxide nanoparticles, covalent attachment
of polymers can be achieved via ‘‘grafting to” and ‘‘grafting from”
methods. In general, covalent attachment via ‘‘grafting to” method
is achieved in several ways such as through oxidation CNT’s surface
using strong acids (nitric acid and sulfuric acid) to form carboxylic
group and forming amide or ester linkage with polymers [262],
radical attachment [263], cycloaddition [264], condensation
[265], and creation of surface defects using ultrasonication [266].
Furthermore, several chemical reactions as previously presented
in Fig. 6c can also be used to obtain the corresponding functional
groups for polymer anchoring. Meanwhile in the ‘‘grafting from”
approach, several applicable methods include atom transfer radical
polymerization (ATRP) [267], reversible addition-fragmentation
chain transfer (RAFT) [268], ring opening polymerization (ROP)
[269], free radical polymerization [270], cationic/anionic polymer-
ization [271], condensation polymerization [272], reduction/oxida-
tion polymerization [273], metallocene catalysis polymerization
[274], electrochemical grafting [275] and nitroxide-mediated radi-
cal polymerization [276]. Furthermore, the non-covalent polymer
attachment is commonly achieved through the establishment of
weak interactions such as p-p stacking and van der Waals interac-
tion between the polymers and CNT’s surface [277].
296 M. Khalil et al. / Applied Energy 191 (2017) 287–310
3. Application of nanomaterials in oil and gas industry
3.1. Exploration and reservoir characterization
One of the most essential yet expensive and high-risk activities
in oil and gas industry is hydrocarbon exploration. The objective of
this process is simply to find hydrocarbon accumulations beneath
the earth’s surface. However, it often presents many unique chal-
lenges such as the unexpected geology and unanticipated hazard,
which may greatly increase the total cost of production. It is
reported that many conventional sensing methodologies, with
exception of seismic techniques, can only provide little informa-
tion about reservoir as they can only penetrate a few inches from
the wellbore [12]. Current sensing technologies are still unable to
obtain high-resolution reservoir imaging and lacking on the ability
to penetrate deeply into reservoir to get key information about
reservoir characteristics. Furthermore, many sensing techniques
like conventional electrical sensors are often unable to provide reli-
able information at certain extreme reservoir conditions. Despite
the advancement of recent state-of-the-art exploration techniques
such as 3D and 4D seismic surveys, new, simple, low-cost, non-
damaging and sensitive sensing technologies that can accurately
locate hydrocarbon accumulation are still desired. The integration
between new reservoir mapping and computational strategies is
also needed to attain better discovery, sizing and characterization
of reservoirs.
Implementation of nanotechnology in accurate prediction of
hydrocarbon accumulations and characterization of hydrocarbon
reservoirs has been extensively studied. Owing to the virtue of
their size-dependent optical, magnetic, chemical and electrical
properties, nanoparticles can be used as nano-sensor as they would
easily migrate through pores of the surrounding geological struc-
tures and collect information about the reservoir characteristics.
A new sensing technology based on nanoparticles also enables
one to probe rock properties in deeper reservoir regions and to
obtain data about the complex interaction between reservoir rock
and fluids or distribution of immiscible fluids. One of the most
widely studied technologies is the application of magnetic
nanoparticles for electromagnetic (EM)-based reservoir mapping
and characterization [278,279]. It is believed that magnetic
nanoparticles have the capability to provide high-resolution mag-
netic measurement by changing magnetic permeability of the rock
formation and reservoir fluids at very low frequencies [280]. In
recent study, magnetic nanoparticles were proven to be able to
probe the distribution of immiscible fluids as they can easily be
designed to be preferentially adsorbed at oil-water interface
[278]. Here, the detection is based on the creation of interfacial
Fig. 7. Schematic diagram of the magnetic nanoparticles-based fluid interface movement measurement setup [278].
fluctuation and pressure (sound) wave as the result of the move-
ment of nanoparticles adsorbed at the interface of either oil-
water or air-water due to an external magnetic field. This approach
is often called as magneto-acoustic tomography. Fig. 7 shows the
schematic diagram of the magnetic nanoparticles-based fluid
interface movement measurement setup.
Superparamagnetic iron oxide (SPIO) nanoparticles can also be
used as contrasting agent in NMR (nuclear magnetic resonance)
imaging for the characterization of porous rock formation. In a
recent study by Park and co-workers, it is reported that SPIO
nanoparticles were able to enhance contrast of NMR logging by
shortening NMR T2 relaxation time [281]. Similar to the application
of SPIO nanoparticles in other applications such as in magnetic res-
onance imaging (MRI), estimation on the quantity of the nanopar-
ticles is possible since the concentration of the nanoparticle is
proportional with the change of relaxation rate DR2 (reciprocal of
the relaxation time, 1/T2) [282]. In this approach, the nanoparticles
are expected to act as NMR nanosensor where the NMR relaxome-
try can directly be carried out inside the formation at the wellbore
or in the fluid sample extracted from the well [281]. In addition,
one can also measure the changes in fluid properties as the reser-
voir developed and produced since the nanoparticles are injected
within the reservoir rock and adsorbed in the interface of two
immiscible fluids. Furthermore, several other applications of mag-
netic nanoparticles as contrasting agent for subsurface magnetic
sensing and reservoir characterization have also been reported
elsewhere [157,283–287].
Another example of nanotechnology application in exploration
and reservoir characterization is the development of innovative
nanomaterials-based sensing devices for real-time monitoring of
substances such as pollutant, toxic and hazardous gases. Such
sensing devices can be specifically targeted for the detection of
CO2, H2S and different types of natural gases such as CH4. For
instance, a recent study conducted by Piantanida et al. has success-
fully fabricated a small, low-cost, stand-alone, low-power, highly
selective and sensitive sensing device for the detection of H2S gas
based on WO3 nanoparticles [288]. It is reported that this
custom-made WO3 nanoparticles-based sensor was able to selec-
tively measure the concentration of H2S in the range of 0–
200 ppm with a detection limit as low as 1 ppm. It is also claimed
that this sensor does not require considerably high power con-
sumption as it can be used at below 20 lW for very low duty
cycling. In another study, Turkenburg and co-workers have suc-
cessfully applied a water disperse nanosensor for water flooding
process [289]. Here, they formulated a water-based nanosensor
cocktail containing InP/ZnS quantum dots (QDs) and atomic silver
(Ag) cluster with a bright and visible luminescence to optimize
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Fig. 8. Schematic mechanism for the detection of (a) downhole hydrocarbon [291] and (b) H2S [292] using carbon black nanoparticles-based nanoreporters.
sensor functionalities. Based on the experimental result, it is found
that the sensor was able to show enhanced sensor functionalities
and sensing abilities in simulated reservoir conditions (high salin-
ity, Ca2+, pH, high temperature, the presence of oil and reservoir
solids such as clay and calcium carbonates). In addition, it was also
reported that by the modification of surface coating enabled the
identification of changes in pH, chemical environment, tempera-
tures, and presence of solid within the reservoir. Furthermore, sev-
eral other multifunctional nanomaterials such as sulfated and
unsulfated polyvinyl alcohol functionalized oxidized carbon black
(PVA-OCB) nanoparticles have been also used for downhole hydro-
carbon detection probe [290,291]. It is reported that the non-
covalent attachment of probe molecule, i.e. triheptylamine (THA)
into sulfated PVA-OCB (which then called as nanoreporter) can
be injected into oil reservoir and used to obtain accurate informa-
tion about subsurface oil content. In this approach, the nanore-
porter helps probe molecules (THA) travel trough rock formation
and selectively release them whenever the rock contains oil
[291]. In other word, the information about downhole hydrocarbon
content in a particular rock formation can be accurately obtained
by quantitatively analyzing the amount of probe molecules
remaining on the nanoreporter collected at the production well.
Furthermore, similar concept was also used for the application
on the detection of H2S [292]. Here, H2S detection was done by
attaching polyvinyl alcohol functionalized carbon black with H2S-
sensor moieties called fluorescence probe. By injecting these
hybrid molecules into hydrocarbon reservoir, the H2S content can
be determined based on the fluorescent enhancement of the H2S-
sensor addends. Fig. 8 shows the schematic mechanism for the
detection of both downhole hydrocarbon and H2S content using
carbon black nanoparticle-based nanosensors.
3.2. Drilling
Drilling is one of the most crucial processes in creating access to
reservoir rock. The selection of proper and effective development
of this operation plays a key role in optimizing the productivity
of hydrocarbon. During drilling, various types of drilling fluids such
as water-based fluids, oil- or synthetic oil-based fluids, pneumatic
or air-based fluid are commonly used in various drilling conditions
297
[293]. In general, several types of additives (commonly polymers)
are used to enhance the properties and performances of drilling
fluids such as in thermal stability, salty resistance, filter cake gen-
eration, rheological and filtration properties. However, the uses of
several types of nanoparticles have also been reported in drilling
fluids formulation recently. For example, several studies have
revealed that the presence of nanoparticles in drilling fluid were
able to contribute on the formation of effective, dense, thinner
and impermeable cake as sealing for micro cracks during drilling
operation [294–296]. Therefore, the issue of fluid loss and low well
stability due to formation damage can be significantly reduced.
This is proven in the study reported by Ragab and Noah [297]. In
their study, it is reported that the addition of nanosilica (particle
size: 5–15 nm) with concentration in the range of 20–30 wt% were
able to reduce about 56% of fluid loss comparatively to conven-
tional drilling fluids. Sharma and co-workers have also showed
that the addition of nanosilica was able to significantly improve
wellbore stability by reducing water invasion by 10–100 times,
especially in the case of shale formation [298]. It is believed that
the use of non-toxic nanoparticles such as nanosilica in drilling
fluid may significantly reduce the drilling and disposal cost and
thus it offers great advantages to the environmental benefits.
Several other types of nano-sized materials in drilling fluids
have also been reported elsewhere. For instance, two types of
metal oxides nanoparticles, i.e. CuO and ZnO have been used along-
side with xanthan gum to improve rheological, thermal, and elec-
trical properties of water-based drilling fluid [299]. Based on the
result, it is observed that the addition of CuO and ZnO nanoparti-
cles was able to enhance the fluid’s resistance against high pres-
sure and high temperature (HPHT) condition. In other report,
Sedaghatzadeh and co-workers used multi-walled carbon nan-
otubes (MWCNT) to improve thermal and rheological properties
of water-based drilling fluids [300]. It is found that the addition
of 1 vol% of functionalized CNT at room temperature was able to
enhance thermal conductivity of drilling fluids by 23.2%. In addi-
tion, it is also observed that several rheological properties such
as yield point, filtration properties, and annular viscosity were also
significantly improved. Furthermore, a nanocomposite material
made of TiO2 and polyacrylamide (PA) was used as an additive to
water-based drilling fluid [293]. It is reported that the nanocom-
298 M. Khalil et al. / Applied Energy 191 (2017) 287–310
posite was responsible for the significant improvement on fluid’s
viscosity and reduction in fluid loss and cake thickness. Recently,
Agarwal and co-workers used a combination of hydrophobic
nanosilica and organically modified nanoclay to stabilize invert
emulsion drilling fluids for deep-hole drilling operation [301].
Here, the nanoparticles cocktail was able to stabilize the resulting
Pickering water-in-oil invert emulsion with the desired plastic vis-
cosity and yield stress suitable for drilling operation. Furthermore,
the result from aging experiments at reservoir temperature
(225 °C) also showed that the fluid has good high-temperature sta-
bility and suitable for deep-hole drilling operation.
3.3. Cementing
It has been widely known that wellbore failures and well integ-
rity issues due to cementing and/or cementing stability issues are
considered as one of the major problems in oil and gas exploration
and production. Typically, these problems may occur during pre-
productions such as in drilling operation and during production
processes [302]. During drilling operation, several cementing prob-
lems such as casing centralization (incomplete cementing), forma-
tion damage due drilling operations and cementing, inadequate
cement-formation or cement-casing bond, cement shrinkage,
incomplete cement placements, filtration of cement slurry, con-
tamination of cement by drilling or formation fluids, and fracture
formation with cement can seriously affect well integrity. Simi-
larly, problems during production such as the formation of
micro-annulus at casing, cement failure due to thermal or mechan-
ical stress, corrosion of casing, degradation of cement due to car-
bonation, sulfate or acid may significantly lower the oil
production. Therefore, the selection of cementing materials as well
as cementing procedures play a key role to ensure the success in oil
and gas exploration and production.
Similar to drilling operations, the application of nanomaterials
in cementing operation for oil and gas applications has also
obtained many attentions recently. The development of smart
cement materials based on nano-sized materials as additives with
desired specific properties that solve or minimize many practical
issues in the field has widely been reported in literatures. For
example, several types of metal oxide nanoparticles such as
nanosilica [303–305], TiO2 [306,307], Fe2O3 [308,309], Al2O3
[310,311], ZrO3 [312,313], CuO [314,315], ZnO2 [316], and several
other types of magnetic nanoparticles [317] have been as additives
in cement modification. These metal oxide nanoparticles are added
mostly to improve several cements and concrete properties such as
strength, resistance to water penetration, accelerate hydration
reaction, control calcium leaching, to provide self-cleaning proper-
ties, and many more. Recently, it is also reported that several other
characteristics of cements such as impact and fracture toughness,
durability, dry shrinkage and permeability resistance properties
can also be enhanced by the addition of multi-walled carbon nan-
otubes (MWCNT) [318,319]. It is very suitable for the application of
offshore oil and gas fields where the cementing processes are car-
ried out in deep oceans. Furthermore, it is also known that the
addition of ultra-low concentration of carbon nanotubes (CNT)
and carbon nanofibers is able to improve the electromechanical
properties of cement paste [320]. This enables one to use such
cement composites as self-sensing concrete [321]. Moreover, other
applications of nanotechnology and nanomaterials in cementing
process have also been comprehensively reviewed elsewhere
[322,323].
3.4. Production and stimulation
One of the greatest challenges in the current oil and gas produc-
tions is the recovery from unconventional resources such as heavy
and extra heavy oil, shale gas and liquid, tight gas and oil, coal bed
methane (CBM), and bitumen hydrocarbons. In the past several
years, many national and multinational oil companies are investing
heavily on the exploration and production of unconventional
resources due to the shortage of conventional oil reserve. Accord-
ing to the literature, there are about 5.6 trillion (more than
1.02 trillion barrels of conventional light oil) of only unconven-
tional heavy oil available in the world [324]. However, it is esti-
mated only about 434.4 and 650.7 billion barrels of heavy oil and
bitumen may be recovered due to the limitation of current tech-
nologies. This is mainly due to the nature of their physical and
chemical properties as well as their geological difficulties.
Recently, the development of nanotechnology has enabled one to
effectively and efficiently harvest hydrocarbon from unconven-
tional resources. For example, several type of nanocatalysts such
as nano-sized transition metals and metal oxide nanoparticles
have been used in aquathermolysis process for the improvement
of heavy and extra heavy oil production [20–23]. In aquathermol-
ysis process, it is believed that the significant improvement of oil
production is mainly due to the reduction of oil viscosity as a result
of degradation of large hydrocarbon molecules such as resin and
asphaltene. It is reported that there is a great possibility that some
chemical reactions such as hydrocracking, hydrodesulphurization
(HDS), hydrodenitrogenation (HDN), and hydrogenation can occur
during the process [31]. In addition, it is also believed that one of
the main reasons for the degradation of these large molecules is
due to the cleavage of CAX (X = S, N, O) bonds. Fig. 9 presents sev-
eral types of chemical reactions that might occur during aquather-
molysis process. Recent investigation revealed that nanocatalysts
such as Ni nanoparticles with mean particle size 6.3 nm, which
was prepared in methylcyclohexane-water-n-octanol-AEO9 sur-
factant, was able to reduce the viscosity of heavy oil sample from
Liaohe oilfield by 98.9% [21]. The experimental result also demon-
strated that the molecular weight of the feedstock was signifi-
cantly decreased due to the reduction of sulfur content by nearly
50% and the amount of resin and asphaltene by 15.83% and
15.33% respectively. A comprehensive review on several other
types of nanocatalysts in aquathermolysis has also been reported
elsewhere [31,324].
Nanotechnology has also been used for optimization in the pro-
duction of another type of unconventional resources such as oil and
gas from shale and tight rock formation using hydraulic fracturing
or fracking technique. For instance, Barati and co-workers has suc-
cessfully used polyelectrolyte complex nanoparticles as an encap-
sulation protector and delayed releasing system for fracturing
fluid and filter cake destroying enzymes at harsh reservoir condi-
tion [325]. It is reported that the nanoparticles were able to encap-
sulate the enzymes and delayed their release for up to 11 h. In
addition, it is also found that the nanoparticles seem to protect
the enzymes from denaturation at elevated temperature and pH.
Several other nanoparticles-based technologies have also been used
to improve fluid loss control and proppant transport [326]. It is
reported that the nanoparticles which pseudo crosslinked to vis-
coelastic surfactant fluid (VES) as hydraulic fracturing and frac-
packing fluid can significantly reduce the amount of polymer resi-
due during fracturing process. In addition, it is also believed that
the nanoparticles-containing VES fluid was able to develop a
wall-building pseudo-filter cake on the face of porous media to
avoid fluid loss. In other report, Huang et al. [327] has also reported
that the addition of nanoparticles in surfactant-based frac fluid can
significantly increase fluid’s thermal stability and enhance its rheo-
logical properties. Recently, several types of nanoparticles such as
nanosilica were also able to improve the CO2 fracturing effect for
gas production in low permeability unconventional gas production
such as shale and tight gas [328]. In another report, Lv and
co-workers reported that the generation of foam using partially
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Fig. 9. Several types of chemical reactions during aquathermolysis process [374].
hydrophobic modified SiO2 nanoparticles and sodium dodecyl ben-
zenesulfonate (SDBS) for fracturing fluid were able to significantly
increase foam stability and thermal stability [329]. Here, it is found
that the surface tension of the SDBS emulsion seems to remain the
same after the addition of SiO2 nanoparticles and the proppant set-
tling velocity is two orders of magnitude lower than those without
the addition of nanoparticles. This shows that the addition SiO2
nanoparticles may be used to enhance foam’s proppant carrying
ability which mainly due to the generation of strong and stable
nanoparticles-stabilized bubbles to support the proppant. Another
application of nanotechnology has also been reported for the recov-
ery of gas hydrate (ice-like crystalline solid formed by a mixture of
water and natural gas such as methane). It is reported that the
injection of air-suspended self-healing bimetallic Ni-Fe based mag-
netic nanoparticles with size 50 nm into a hydrate formation and
the application of magnetic field into the reservoir was able to cause
a significant release of methane from gas hydrates [330]. It is
observed that these magnetic nanoparticles in the presence of mag-
netic field were able to cause a temperature rise up to 42 °C inside
the rock formation and decompose the water cage in the gas
hydrate to release methane.
Furthermore, nanomaterials based technologies such as
nanofluids may also be used for the accelerated recovery of hydro-
carbons during secondary and tertiary recoveries. One of the most
common applications of nanotechnology in this area is the applica-
tion of nanomaterials for enhanced oil recovery (EOR). It is believed
that nanoparticles seems to offer better and more efficient way to
control and improve oil recovery that is unmatched by any current
and previous technologies [12]. Based on core-displacement inves-
tigation, it is found that most of these nanoparticles had a better
performance on changing the rock wettability than surfactant/
polymer. This is due to their significantly small size (particle diam-
eter < 100 nm), which allows the particles to easily flow through
porous medium (pore size  1 lm). In comparison to the types of
EOR techniques such as thermal and microbial recovery, the
299
emerging application of nanoparticles in chemical flooding has
gained much attention. In general, nanoparticles are commonly
added to enhance oil displacement efficiency and to improve push-
ing fluid stability [331]. Here, various collections of nanoparticles
such as SiO2, Al2O3, MgO and Fe2O3 have also reported to have a
potential good EOR application. In addition, these nanoparticles
can also be applied in addition to other types of chemical flooding
such as injection of surfactant and polymer. For instance, an exper-
imental study by Suleimanov and co-workers has proven that
nanofluids containing aqueous suspension of nonferrous metal
nanoparticles (70–150 nm) and sulfonate-alkyl aryl sodium sul-
fonate (an anionic surfactant) were able to increase the oil dis-
placement efficiency by 35% compared to that obtained using
only surfactant solution [332]. In another study, Zargartalebi
et al. reported that hydrophilic and slightly hydrophobic silica
nanoparticles were able to improve surfactant (sodium dodecyl
sulfate) performance during flooding experiment [333]. It is found
that the surfactant adsorption was significantly reduced when
mixed with nanoparticles. In addition, it is also reported that the
addition of nanoparticle may lead to the generation of a piston-
like flow behavior trough porous medium, which ultimately
improve the sweep efficiency. Furthermore, the impact of silica
nanoparticles in polymer flooding was also reported recently in a
study conducted by Maghzi and co-workers [334]. Here, a series
of polymer flooding experiments were performed using solutions
of polyacrylamide and dispersed silica nanoparticles. Based on
the result, it is found that the addition of silica nanoparticles was
able to improve the oil recovery due to the increment of viscosity
of the nanoparticles-augmented polymer solution. Similar incre-
ment of fluid’s viscosity and oil recovery due to the addition of
nanoparticles in polymeric solution containing anionic hydrolyzed
polyacrylamide (HPAM) was also reported by Yousefvand and
Jafari [335].
Nanoparticles can also be used to facilitate the formulation of
Pickering emulsion for EOR application. Unlike classical emulsion,
300 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Pickering emulsion is either oil-in-water (o/w) or water-in-oil (w/
o) or multiple type of emulsion stabilized by solid particles such as
nanoparticles instead of surfactant. It is believed that the stabiliza-
tion of solid nanoparticles in Pickering emulsion brings a new type
of unique emulsion properties such as the high resistance to coa-
lescence, high temperature stability and high pH tolerability
[336]. In the literature, various collection of either organic or inor-
ganic solid particles such as calcium carbonate, barium sulfate,
clay, laponite, carbon black, latex, magnetic nanoparticles, carbon
nanotubes (CNT), cationic nanocrystals and protein have been used
as stabilizer for Pickering emulsion [337–345]. However, silica and
magnetic nanoparticles are among the most common particles
used to formulate Pickering emulsion for EOR application [346].
It is believed that the application of nanoparticles in Pickering
emulsion leads to remarkable improvement on emulsion stability
and superior control over the viscous fingering effect during EOR
process. In a study conducted by Zhang et al., it is reported that
the application of nanosilica for Pickering emulsion were found
to be very stable at subsurface condition and resulted a 50% effi-
ciency in oil-in-place recovery in Barea sandstone [347]. Sharma
and co-workers also reported that o/w Pickering emulsions formed
by nanoparticles (SiO2 and clay)-surfactant-polymer were able to
recover more than 60% of cumulative oil recovery in comparison
to the conventional surfactant-polymer (SP) flooding [346]. Fur-
thermore, nanoparticles can also be used in the stabilization of
Pickering emulsion generated by CO2 for CO2-foam EOR flooding.
In a recent study by Yu et al., it is found that surface-modified silica
nanoparticles were able to significantly facilitate the generation of
stable CO2 foams [19]. It is also observed that the nanoparticle-
stabilized CO2 foam displayed a significant improvement on CO2
foam mobility and reduction on CO2 mobility in porous media.
Another common application of nanofluids in EOR is in the
alteration of wettability of reservoir rock. In fractured reservoirs,
the wettability of reservoir rock at near-wellbore region plays a
Fig. 10. (a) Wetting abilities of different nanoparticles on the contact angle of decane, (b) performance of SiO2 nanofluid in enhanced oil recovery after secondary water
flooding, (c) performance of CaCO3 nanofluid in enhanced oil recovery after secondary water flooding [114].
key role on the reservoir productivity and oil production. It is
known that by changing the rock wettability from oil-wet to
water-wet it may lead to the improvement of oil recovery [348].
In general practices, rock wettability alteration process may be
achieved through several means, such as chemical injections using
thermal or chemical methods using surfactant or polymer flooding
[349,350]. However, recent studies have suggested that several
types of nano-sized materials may also be used as wettability alter-
ation agents. Because of their sizes, nanomaterials have a very high
surface area, which results in an increase on their surface energy,
and it become strongly attractive to be adsorbed on the surface
of reservoir rock which ultimately alters the wettability. For exam-
ple, Maghzi and co-workers investigated the ability of silica
nanoparticles in wettability alteration process and found that
nanosilica was able to significantly improve the sweep efficiency
during water flooding [351]. Based on the result, it is found that
as much as 26% of oil recovery can be reached with the injection
of 3 wt% of dispersed silica nano particles in water. In another
study, Karimi et al. reported that the addition of zirconium oxide
nanoparticles with particle size of 24 nm in aqueous solution of
nonionic surfactant (ethoxylated nonylphenol) has successfully
improved oil recovery by altering the carbonate rock wettability
from strongly oil-wet to strongly water-wet [348]. Recently, a
comparative study on the impact of different types of nanoparti-
cles such as zirconium oxide (ZrO2), calcium carbonate (CaCO3),
titanium dioxide (TiO2), silicon dioxide (SiO2), magnesium oxide
(MgO), aluminum oxide (Al2O3), cerium oxide (CrO2), and carbon
nanotubes in wettability alteration process have also reported
[114]. Based on the result, it is found that both CaCO3 and SiO2
nanoparticles were found to be the most effective wetting agents
comparatively to the rest of nanoparticles tested. This is proven
by the ability of these nanoparticles to significantly increase the
contact angle of decane (Fig. 10a). In addition, it is also reported
that about 8–9% of enhanced oil recovery after secondary water
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
Fig. 11. (a) Displacement of oily solid and solid substrate due to nanoparticle structural film transient gradient [347], (b) disjoining pressure on the walls of the wedge for
contact angle of 0.5° at the vertex as a function of the radial distance [347], (c) disjoining pressure at the nearest vertex for SiO2 [114].
flooding can be increased after the injection of each of these
nanofluids (Fig. 10b and c).
In addition with regards to rock wettability alteration, several
other experimental studies have also shown that EOR efficiency
improvement may be due to the reduction of interfacial tension
(IFT) between the oil phase and aqueous phase [347,352]. For
example, Suleimanov and co-workers believed that the increment
of oil recovery was due to the reduction of IFT and change in the
flow of characteristic of the nanofluids moving from a Newtonian
to non-Newtonian state [332]. Here, they used a mixture of nonfer-
rous metal nanoparticles (70–150 nm) and sulfonate-alkyl aryl
sodium sulfonate (an anionic surfactant) as the nanofluids. How-
ever, they observed that the oil wettability were practically
unchanged after the injection of the nanofluid. In other study,
Babadagli has also suggested that the reduction of IFT between
oil and the aqueous phase was responsible for the faster and
greater oil recovery [353]. In several cases, it is also suggested that
both wettability alteration and IFT reduction processes are respon-
sible for the improvement of oil recovery [353,354]. Recently, a
new type of mechanism on the oil displacement from solid sub-
strates such as reservoir rock using nanoparticles-containing solu-
tion has also been proposed [355]. Based on the experimental
results and theoretical calculations reported in this study, it is
found that a two-dimensional (2D) layered structure is formed
by the presence of nanoparticles (or surfactant micelle) at the con-
tact region of a wetting wedge film. It is formed at the space
between oily soil and the solid substrate (Fig. 11a). As the result
of the formation of the nanoparticle structure, the disjoining
301
pressure, which is a force normal to the interface at the wetting
wedge, is higher at the wedge tip than in the bulk meniscus
(Fig. 11b). It is known that the magnitude of this pressure greatly
depends on particle size of the nanoparticles, polydispersity, parti-
cle charge, and nanoparticles volume friction [347]. Trokhymchuk
et al. have comprehensively developed a simplified equation to
estimate this disjoining pressure structural and depletion force
for fluids or suspension confined in a film [356]. Because of the
increment of this pressure, the nanofluid interface moves forward
and occupies the solid surface and finally detaches the oily soil
from the solid surface. This near vertex disjoining pressure theory
was recently used by Moghaddam and co-workers to estimate the
increment disjoining pressure due to the presence of SiO2 during
EOR process [114]. Based on their estimation, it is reported that
the disjoining pressure at the nearest point of contact (assumed
to be at one layer or particle thickness, SiO2 particle size: 35 nm)
could be as high as 7 psi (Fig. 11c).
3.5. Refining and fuel production
Unlike in the upstream and midstream sectors, nanotechnology
and nanomaterials has been used for over a decade in downstream
sector of oil and gas industry, mainly in refining and processing
process. One of the most common applications of nanomaterials
in the oil refining and petrochemical industry is in the utilization
of nanoparticle-based catalysts. Over the last several years, the
advancement in nanotechnology has contributed substantially in
the development of more effective and efficient refining and
302 M. Khalil et al. / Applied Energy 191 (2017) 287–310
processing processes in converting crude hydrocarbon into useful
products such as liquefied petroleum gas (LPG), gasoline, kerosene,
jet fuel, diesel, and other valuable chemical feedstock. Nanotech-
nology has allowed researchers to develop catalysts that can sub-
stantially increase refining capacity and speed, improve the
efficiency of hydrocarbon conversion, reduce or even eliminate cat-
alyst poisoning issue, and provide better refining efficiency for
extra heavy and sour crude oils. Furthermore, research in clean
fuels has become a trend to produce more environmentally
friendly transportation fuels, which has lower sulfur and aromatic
content.
In petroleum refinery, recent efforts have been focused on the
development of effective and efficient conversion and upgrading
of crude oils into valuable light fuels. With the increase consump-
tion of fossil fuels, research on conversion and upgrading of uncon-
ventional resources such as heavy and extra heavy crude oils have
become one of the major concerns in the past several years. In
unconventional crude oils, there are large amount of atmospheric
residue (AR) and vacuum-distilled residual (VR) that could be
obtained and transformed into other valuable chemical feedstock
and lighter fuels such as gasoline [357]. These residues are the
heaviest fractions obtained from the fractional distillation pro-
cesses, which mainly consist of large amount of hydrocarbon mole-
cules such as asphaltenes, heteroatoms compounds such as sulfur,
nitrogen and oxygen compounds, and heavy metals. Traditionally,
these oil residuals (AR and VR) can be processed via thermal crack-
ing [358,359], catalytic cracking [360,361], and hydrocracking
[362,363]. However, these processes are still limited primarily
due to catalysts deactivation and coke formation [364]. In addition,
large amount of hydrogen are required to reduce the effect of coke
formation. This is still considered ineffective and costly.
Recently, the application of nanomaterials in conversion and
upgrading process of heavy crude oil and its derivatives have
attracted many attentions since nanocatalysts provide a large sur-
face area for the appropriate catalytic reactions. Over the last few
years, different types of nanocatalysts such as metal oxide
nanoparticles have been used in hydroprocessing of crude oil due
to their good asphaltenes adsorption/oxidation and their high oxy-
gen storage/release capacity. For example, Montoya and co-
workers recently investigated the effect of NiO and PdO supported
on fumed silica nanoparticles catalysts in catalytic thermal crack-
ing of n-C7 asphaltenes [365]. Based on their results, it is found that
the presence of NiO or PdO was able to show a better catalytic
activity than fume silica support alone. Furthermore, it is also
reported that bimetallic (both NiO and PdO) on silica nanoparticles
support showed the highest catalytic activity confirming the ability
of the catalyst to effectively lowered the reaction activation energy
at considerably low temperature. In other study, several types of
metal oxide nanoparticles, including CeO2, Co3O4, MnO2 and both
free a-Fe2O3 and SiO2-supported a-Fe2O3 were used alongside with
supercritical water (SCW) in hydrocracking of heavy petroleum
residue obtained from the vacuum distillation unit [364,366].
Based on the result, it is reported that the metal oxide nanoparti-
cles catalysts were able to substantially reduce the formation of
coke and showed a better asphaltene conversion meanwhile SCW
could significantly reduce coke formation. For the case of a-
Fe2O3, it is suggested that the catalytic reaction mechanism occur
in two steps, which involved the oxidative cracking of hydrocar-
bon, by lattice oxygen of a-Fe2O3 to produce aliphatic compounds.
As the result of this oxidative cracking, a-Fe2O3 is reduced into
Fe3O4, which further converted back to a-Fe2O3, by the oxygen
atom released from SCW. Nevertheless, some nanocatalysts were
found unable to maintain its catalytic properties over several suc-
cessive reaction experiments due to the loss of exposed surface
area as the result of nanoparticles agglomeration.
A comprehensive study on the adsorption kinetic and catalytic
mechanism of different types of metal oxide nanoparticles namely
TiO2, ZrO2, and CeO2 were also reported for the oxidative decompo-
sition process of Athabasca asphaltenes [367]. Based on theoretical
calculation using Langmuir adsorption isotherm model, it appeared
that the adsorption behaviors such as adsorption capacity and
adsorption affinity of asphaltenes obtained from Athabasca VR
was changed according to the type of nanoparticles. However, all
tested nanoparticles exhibited a very high catalytic activity for post
adsorption oxidation and CeO2 were found to have the lowest value
of Gibbs free energy of activation (DGà). Similar study on the pres-
ence of other types metal oxide nanoparticles i.e. NiO, Co3O4 and
Fe3O4 have also been reported elsewhere [368]. Results showed
that these nanocatalysts were able to enhance the rate of asphal-
tene oxidation reaction by reducing the activation energy, which
leads to a conclusion that thermo-oxidative reaction of asphaltene
is metal oxide specific. Various types of metal oxide supported
bimetallic nanocatalysts have also shown a promising application
in conversion and upgrading process of crude oil residue into valu-
able light fuels. Recently, Nassar and co-workers reported the appli-
cation of two metal oxide supported bimetallic nanocatalysts, i.e.
Ni-Pd/c-Al2O3 and Ni-Pd/TiO2 in steam gasification of n-C7
asphaltenes [369]. Based on the result, it is reported that bimetallic
nanoparticles showed a superior catalytic activity than monometal-
lic nanoparticles regardless the types of metal oxides supports used.
This is mainly due to the synergistic effect of the bimetallic
nanoparticles to improve adsorption affinity and catalytic activity.
Study on the catalytic performance also revealed that Ni-Pd/TiO2
had a better catalytic activity and adsorption capacity than Ni-Pd/
c-Al2O3, presumably due to different metal-support interaction,
geometry and electronic effect on the surface of the catalyst.
Several types of nanomaterials can also be used on desulfuriza-
tion process to remove organosulfur compounds such as thiols, sul-
fides, disulfides, thiophenes, benzothiophenes, and other types of
their alkylated derivatives to produce ultra-clean (ultra-low sulfur)
gasoline, diesel fuels and jet fuels. For example, a-MoO3 nanorib-
bons with uniform morphology and composition were successfully
synthesized and had as good catalytic activity as the common
unsupported MoS2 catalyst as catalyst in hydrodesulfurization
(HDS) of dibenzothiophene (DBT) [370]. Another HDS study for
DBT has also reported a very similar good catalytic performance
of other two new types of catalyst made of trimetallic sulfur nanor-
ods i.e. MoWNiS and MoWSNi [371]. In other report, catalytic
activity, selectivity, and efficiency of fluorine-modified supported
CoMo nanocatalysts on alumina for HDS of thiophene was also
investigated [372]. Based on the catalytic performance study, these
fluorine-modified supported CoMo nanocatalysts showed a very
high HDS catalytic activity and were able to significantly and selec-
tively convert nearly 100% of thiophene. Recently, Mohammed and
co-workers has successfully developed a simple fabrication for a
new type of catalyst by homogeneously implanting CoMo on the
structure of multiwalled carbon nanotubes and its catalytic ability
in HDS reaction was compared with the conventional CoMo/Al2O3
[373]. Based on the experimental data, it was revealed that the
integration of CoMo on multiwalled carbon nanotubes was able
to provide a better catalytic activity than CoMo/Al2O3 catalyst in
removing sulfur from gasoil. It is believed that carbon nanotubes
provides a better metal-support interaction and electronic effect
on the surface of the catalyst and improves its adsorption affinity.
4. Outlook and future challenges
As comprehensively discussed earlier, nanotechnology applica-
tion in oil and gas industry may revolutionize the current practice
in searching and extracting hydrocarbon from underground. With
 M. Khalil et al. / Applied Energy 191 (2017) 287–310
a rapid development in nanotechnology in various applications,
synthesis of smart and unique collection of nanomaterials has been
gradually penetrating every aspect of oil and gas operations. In
discussed previously, many current difficult exploration and
production operations may benefit by the application of nanotech-
nology. Unfortunately, there are still many challenges in the appli-
cation nanotechnology and nanomaterials in the oil and gas
industry. For instance, one of the major challenges in the develop-
ment of nanomaterials for many industrial applications including
for oil and gas industry is the conquest for a simple and low-cost
synthetic method. Even though there have been many studies on
the development of synthetic routes for nano-sized materials, pre-
cise control on nanoparticles size, shape and dispersity are still
challenging. Furthermore, most of the current synthetic methods
are still depending on the cost ineffective equipments and non-
environmentally benign raw materials. With the current technolo-
gies, the cost effectiveness on the application of many types of
nanomaterials is relatively still very low, especially in the
upstream oil and gas applications. In oilfield test, the expected
results may only be achieved with the application of large dosage
of nanomaterials. Unfortunately, excessive dosage of nanomateri-
als may significantly increase the cost of operation. Therefore, a
simple and cost effective production of large quantities of nanoma-
terials will become critical for the realization of extensive applica-
tion of nanomaterials in oilfield industry.
Harsh subsurface conditions may also greatly contribute as one
of the major challenges in future application of nanomaterials in oil
and gas industry. It has been widely known that nanoparticles can
easily agglomerate in extreme conditions such as high temperature
and high salinity. As the result, the grain size of the particles will
greatly increase and ultimately lose their unique properties. In pre-
vious section, it has been mentioned that such problems can be
avoided by the surface modification or coating. This can be done
by attaching other molecules onto the surface of nanoparticles or
coat them with polymers to reduce inter-particles attraction force.
However, most of these practices will reduce or even eliminate
several special characteristic features of the nanoparticles such as
their catalytic activities, sensing abilities and rock altering abilities.
Therefore, a different approach is apparently needed. It is desired
to have a new surface modification or coating method to make
nanoparticles have a good stability at harsh subsurface condition
and prevent them from agglomeration without reducing or elimi-
nating their unique properties. Furthermore, the application of
new type of nanoparticles such as Janus particles, which have
multiple distinct properties, may also be beneficial. Lack of under-
standing on the migration and transport behavior of nanomaterials
across porous medium is also becoming one of major difficulties
for the application of nanotechnology in oil and gas industry.
Nowadays, there are only limited studies on the transport mecha-
nism of nanofluids in the rock formations and some fundamental
aspects are seldom involved. This is mostly due to the poor data
characterization, lack of agreement of results obtained from
different studies, and the lack of clarity of fundamental
mechanisms responsible for such phenomenon. In addition, many
issues such as long term stability of the nanoparticles, uncertainty
in several features such as thermal conductivity and magnetic
properties, the Brownian motion of the particles in the solution,
particles migration, heat transfer, etc. should also be taken
into account. As a result, a breakthrough in the application of nan-
otechnology for oil and gas application may not be made achieved
unless the research on the fundamental aspects is appreciated.
Therefore, future research should not focus solely on how to
improve the productivity of hydrocarbon but rather to focus on
the fundamental aspects in both its chemistry and engineering
aspects.
303
5. Conclusion
A detailed critical review on the design, application and chal-
lenges of nanotechnology in oil and gas industry has been compre-
hensively presented in this paper. In general, nanotechnology has
offered many essential applications in many different aspects of
oil and gas operations and broad application prospects in oilfield
chemistries. Various collections of nano-sized materials such as
metallic nanoparticles, metal oxide nanoparticles, carbon nan-
otubes, and magnetic nanoparticles have been widely used in var-
ious types of oil and gas operations. In the literatures, a great
number of studies on both synthesis and functionalization of these
nanoparticles have widely reported. In this review, we have listed
several common synthetic methods for each type of the nanoparti-
cles and several functionalization strategies for them to be used in
oil and gas applications. It is hoped that it will enable researchers
to obtain quick and concise knowledge on selecting and designing
different types of nanomaterials for their applications. It is, how-
ever, observed that some of the synthetic methods and functional-
ization strategies still require more optimum investigation and
engineering design for large-scale oil and gas industrial applica-
tions. This is mostly due to the inabilities of those methods to pro-
vide a simple and cost effective approach to reduce the capital and
operation costs. However, with the current rapid development of
nanotechnology and its wide variety of application, many promis-
ing solutions for such challenges may emerge and nanomaterials
technology may soon be applied in broader field of oil and gas
industry.
The uniqueness and the nature of nano-sized materials have
also brought revolutionary changes in hydrocarbon production
and development. The application of new nanotechnology has
changed the common practices in many oil and gas operations.
In this review, the application of nanomaterials in oil and gas
industry starting form exploration, reservoir characterization, dril-
ling, cementing, production and stimulation have been compre-
hensive discussed. It is obvious that nanomaterials have played a
major role in improving the successful rate of oil exploration and
reservoir characterization, maintaining borehole stability during
various processes such as drilling and perforation, enhancing the
quality of cementing, remediating damaged formations and
enhancing the efficiency of oil and gas recovery. Even though most
of the investigations are still based on laboratory scale and there
are still lack number of field scale application. Many studies have
presented a very promising result in terms of their performance
and effectiveness. Nevertheless, several issues such as the stability
of nanomaterials in the harsh subsurface condition, particles
aggregation and the lack of fundamental understanding on the
mechanism of the migration and transport behavior of nanomate-
rials across porous medium should be taken into account. It is
desired that the future direction of research should not be aimed
only for the quest for optimum production of hydrocarbon but also
a long-term fundamental research on science and engineering
aspects.
Acknowledgement
The authors would like to acknowledge the financial support
from University of Malaya Research Grant (UMRG) RP031B-
15AFR, UM Post Graduate Grant PG141-2015B, and High Impact
Research Grant, UM.C/625/1/HIR/MOE/ENG/15.
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