DRAFT REPORT

Graphene Based
Nanotechnology
Abstract
During the relatively short time since the discovery of
fullerenes in 1985, carbon nanotubes in 1991, and graphene
in 2004, the unique properties of carbon-based
nanomaterials have attracted great interest, which has
promoted the development of methods for large-scale
industrial production. The continuously increasing
commercial use of engineered carbon-based nanomaterials
includes technical, medical, environmental and agricultural
applications. Regardless of the application field, this is also
associated with an increasing trend of intentional or
unintended release of carbon nanomaterials into the
environment, where the effect on living organisms is still
difficult to predict. This review describes the different types
of carbon-based nanomaterials, major production techniques
and important trends for agricultural and environmental
applications. The current status of research regarding the
impact of carbon nanomaterials on plant growth and
development is summarized, also addressing the currently
most relevant knowledge gaps.
Introduction
Some chemical elements are able to compose a rangeof
different molecular structures from the same type ofatoms—
a unique feature known as “allotropy”. Differentchemical and
physical properties of those materials aredetermined by the
structural geometry of the atoms andthe type of chemical
bounds within the molecules. In thiscontext, carbon is one of
the most interesting elements,with the ability to form a wide
range of structures, frequentlywith fundamentally different
properties. Classicalexamples of carbon allotropes comprise
“hard” diamondand “soft” graphite used in science and
technology and ina wide range of products, including
consumer goods invarious areas of human activity .The list of
known carbon allotropes has expanded duringthe last
decades of the 20th century after the discoveryof several
new low-dimensional carbon forms. Thenovel materials
comprised carbon nanotubes (CNTs),fullerenes and graphene
and attracted high interest fromscience and industry, since
these materials exhibited awide range of outstanding and
novel features as promisingmaterials for numerous
application fields. Based onthese properties, they were
repeatedly termed as “wondermaterials” in the scientific
literature.Natural carbon-based nanoparticles exist only in
negligiblequantities, and the overwhelming majority
areengineered, or artificially synthesized. Therefore,
theiravailability does not depend on natural reserves (suchas
diamonds), and theoretically production can be performedin
unlimited quantities as long as raw materialsfor synthesis are
available. According to latest forecasts, aconstant increase of
production volumes is expected duringthe next decade [6, 7].
However, despite the fact thatcarbon-based nanomaterials
promote industrial progressthere are concerns about a
potential release into the environmentand interactions of
released nanomaterials with
living organisms and incorporation into food chains
withyetunknown consequences.In the face of the increasing
importance of practicalapplications, this review will focus on
two major aspectsassociated with the handling of carbon-
based nanomaterials
considering:
1. Production and potential applications, with specialfocus on
the environmental and agricultural sectors,and the
significance for the improvement and developmentof novel,
efficient products and technologies;
2. Potential impact on living organisms with a specialfocus on
plants, as a fundamental component offood chains in natural
and agricultural ecosystems,where increased input of carbon
nanomaterials canbe expected as a consequence of
intentional use inagricultural and environmental applications
or byaccidental release as unintended contamination.
Classification of carbon‑based nanomaterialsCarbon is one of
the few chemical elements (includingalso silicone) with the
ability to polymerize at the atomiclevel, thus forming very
long carbon chains. Due to thefour electrons in the outer
electron layer . carbon atoms have a valence of four and can
be linked via single, double or triple covalent bonds, or also
withother elements. These properties of carbon atoms canbe
attributed to their special electron structure and thesmaller
size compared with other elements of group IV.For the
reasons specified above, carbon can exist in arange of
different molecular forms, composed by thesame type of
atoms but due to different structures, possessingdifferent
properties. These forms are termed as“allotropes” or
“allotropic modifications” of a certainchemical element. Until
recently, only two natural carbonallotropes were known:
diamond and graphite. Meanwhile,various new allotropic
forms have been described, including carbon nanomaterials.
In general, nanomaterials are defined as materials containing
particles with atleast one dimension between 1 and 100 nm
in size.All nanomaterials composed of carbon atoms are
termedas carbon-based or carbon nanomaterials.
Classificationof carbon-based nanomaterials is most
commonly performedaccording to their geometrical
structure. Carbonnanostructures include particles which can
be tubeshaped,horn-shaped, spherical or ellipsoidal.
Nanoparticleshaving the shape of tubes are termed as carbon
nanotubes; horn-shaped particles are nanohorns and spheres
or ellipsoids belong to the group of fullerenes.In the
meantime, carbon nanomaterials have numerous technical
applications including micro- and nanoelectronics, gas
storage, production of conductive plastics,composites,
displays, antifouling paints, textiles, batterieswith improved
durability, gas biosensors and others.

Fullerenes
Fullerenes are an allotropic modification of carbon, often
termed as a molecular form of carbon, or carbon
molecules.Fullerenes were discovered in 1985 by H.W. Kroto,
R.F. Curl and R.E. Smalley who were later awardedwith the
nobel prize for chemistry in 1996. The fullerenefamily
includes a number of atomic Cn clusters (n > 20), composed
of carbon atoms on a pherical surface. Carbonatoms are
usually located on the surface of the sphere at the vertices of
pentagons and hexagons. In fullerenes,carbon atoms are
usually present in the sp2-hybrid formand linked together by
covalent bonds. Fullerene C60 isthe most common and best-
investigated fullerene. Thespherical molecule is highly
symmetric and consists of 60carbon atoms, located at the
vertices of twenty hexagons and twelve pentagons. The
diameter of fullerene C60 is 0.7 nm.

Carbon nanotubes (CNTs)

Among other carbon-based nanomaterials, CNTs are oneof
the carbon allotropes with exceptional properties suitablefor
technical applications. They were discovered in1991 by the
Japanese researcher S. Iijima. Carbon nanotubesare
characterized by cylindrical structures with adiameter of
several nanometers, consisting of rolled grapheme sheets.
Carbon nanotubes may vary in length, diameter, chirality
(symmetry of the rolled graphitesheet) and the number of
layers. According to theirstructure, CNTs may be classified
into two main groups:single-walled nanotubes (SWCNTs) and
multi-wallednanotubes (MWCNTs). Some researchers
additionallyisolate double-walled carbon nanotubes
(DWCNTs) as a separate class of CNTs. Generally SWCNTs
have a diameteraround 1–3 nm and a length of a few
micrometers.Multi-walled CNTs have a diameter of 5–40 nm
and alength around 10 μm. However, recently synthesis of
CNTs with a length of even 550 mm has been reported. The
structure of CNTs leads to exceptional propertieswith a
unique combination of rigidity, strengthand elasticity
compared with other fibrous materials.For instance, CNTs
exhibit considerably higher aspectratios (length to diameter
ratios) than other materials,and larger aspect ratios for
SWCNTs as compared withMWCNTs due to their smaller
diameter. Additionally, CNTs show high thermal and electrical
conductivitycompared to other conductive materials.
Electrical propertiesof SWCNTs depend on their chirality or
hexagonorientation with respect to the tube axis.
Accordingly,SWCNTs are classified into three sub-classes: (i)
armchair(electrical conductivity > copper), (ii) zigzag
(semiconductiveproperties) and (iii) chiral (semi-conductive
properties). By contrast, MWCNTs consisting ofmultiple
carbon layers, frequently with variable chirality,can exhibit
extraordinary mechanical properties insteadof outstanding
electrical characteristics.

Graphene
Graphene is a two-dimensional allotropic form of
carbon,formed by single layers of carbon atoms (Fig. 1f). In
graphene,carbon atoms exhibit sp2-hybridization
connectedby σ- and π-bonds in a two-dimensional hexagonal
crystallattice with a distance of 0.142 nm between
neighboringatoms of carbon hexagons. Graphene also
representsa structural element of some other carbon
allotropes,such as graphite, carbon nanotubes and
fullerenes. Theoretical studies on graphene began a long
time before the real material samples were obtained.
TheCanadian theoretical physicist P. R. Wallace first
exploredthe theory of graphene in 1947, while the first
grapheme samples were described 57 years later (in 2004) by
A.Geim (Dutch-British physicist) and K. Novoselov (Russian-
British physicist), awarded with a nobel prize in 2010. Despite
the long history of theoretical investigation,the fact that the
real material has been obtained onlyrecently, implies that
comprehensive studies on the properties of graphene are still
ongoing. Graphene has many unique physical properties,
such as extremely high mechanical rigidity and a high thermal
stability. Also theelectric properties of this carbon allotrope
are fundamentallydifferent from the roperties of three-
dimensionalmaterials.

SYNTHETIC STRATEGY OFGRAPHENE-NANOPARTICLE

(G-N)COMPOSITES
Chemical structure of graphene, GO, RGO and G-N
compositesare shown in Figure 1. High quality graphene
isgenerallysynthesized by micromechanical exfoliation on
silicon substrate or chemical vapour deposition on
transitionmetal surfaces but these methods have low
productionefficiency. In addition insufficient functional
groups generatedon graphene surfaces limits preparation of
grapheme based nanocomposites.1662–64 Thus colloidal GO,
preparedby Hummer’s method or modified Hummer’s
method, arecommonly used for large scale synthesis of
graphene basedcomposites.6566 Figure 2 summarized
different synthetic178 Rev.approaches. At first colloidal GO is
synthesized fromgraphite flakes by modified Hummer’s
method. G-N compositesare then synthesized by in-situ
reduction of metalions in presence of colloidal graphene
oxide. Alternatively,preformed colloidal solution of
nanoparticles is mixed withcolloidal GO and then GO is
reduced to prepare G-Ncomposites. Different surfactants and
polymers have beenused to improve the dispersion of G-N
composites. Inaddition different reducing agents (e.g.,
hydrazine, sodiumborohydride, ascorbic acid, ethylene glycol,
ammonia,alkali solution) and different reaction condition
(temperature,reaction time) have been used to control the
propertyof G-N composites.6768 In these processes
metalions or pre-functionalized metal nanoparticles attach
with GO surfaces through electrostatic interactions,
covalentor by week interaction to form nanocomosites.6970
Next,reduction of metal ion and/or GO is performed to
produceG-Ncomposites.71 72 The GO-based composites are
mainly used in sensing, photocatalysis and water purification
applications where as graphene-based composites areused
for all types of applications.
PROPRIETIES OF GRAPHENENANOPARTICLE(G-N)
COMPOSITES
The UV-visible absorption spectrum of GO clearly
representthe n- * transition at around 300
nm whereas transition is not observed due to lower
percentage of conjugateddouble bonds. (Fig. 3) The chemical
reduction ofgraphene oxide by hydrazine leads to increased
percentageof conjugated double bonds and appearance of
transitionband at 260 nm. Optical property of G-N
compositesshows combined property of both components.
For example G-N composites with plasmonic silver or gold
nanoparticles shows respective plasmonic band alongwith
graphene band. However, plasmonic band is
extensivelydamped by graphene. The plasmonic bands for
silver and gold nanoparticles are observed at ∼400 nm and
∼530 nm, respectively, along with the transitionband at
∼260 nm and n- * transition band at ∼300
nm.In the case of platinum and other nanoparticle based
composites,plasmon band is absent and only graphene band
isobserved.Raman spectroscopy is a non-destructive tool for
theanalysis of order and disorder of the crystallized
carbonsamples.7374 In pure form graphene has ordered
structureshowing intense graphitic bands (G) at 1600
cm−1which arise from the scattering of the E1g phonon of
thesp2 hybridized carbon. (Fig. 4) As the disorder arises
ongraphene surfaces a new defective band (D) at 1300 cm−1
arises from a breathing mode of point photons of A1g
symmetry. Such defects can arise due to chemical oxidation,
doping and thermal annealing and results the disruption of
sp2 domain of graphene surfaces. The disorderingof the
graphene based material can be elucidated by the ratio of
intensity of defective bands to graphitic bands (ID/IG. For
example, the GO and RGO have the defective structure of
graphene which represent the D bandat 1300–1350 cm−1
and the G band at 1600 cm−1 andthe ID/IG ratio is > 1. This
indicates prominent defectivenature of graphitic structure.
Incorporation of nanoparticles on the graphene surfaces
further increases the disorderingof graphitic structure and
thus the ID/IG ratio become in the range of 1.9–2.1.75–
77.Characteristic reflection from both components can be
observed from XRD of G-N composites. (Fig. 5) The RGO has
two broad reflections of graphitic planes of C (002)and C
(100). The number of layers and d spacing betweenthe planes
can be derived from Scherer equation and asthe number of
stacking layers increases the reflection fromcrystalline carbon
becomes sharper. G-N composites show respective
reflections from nanoparticle components alongwith
reflection for graphene component. (Fig. 5) For example,G-N
composites with silver nanoparticle shows reflectionsdue to
silver planes of (100), (200), (220) and (311)as well as
reflection of graphitic (002) planes. The G-Au composites
gives the signature of Au metal planes reflection at (111),
(200), (220), and (311) along with reflectionof graphitic
plane. G-Pt composites shows the broadreflections of
platinum plane at (111), (200), (220), alongwith graphite
plane at (002). When less noble metal isused the reflection of
respective metal oxide dominates.For example copper and
palladium based nanocompositesshow reflection of metal
oxides. The G-Cu compositesshows the reflections of Cu
metal at (111), (200), (220)and reflections of copper oxide at
(200), (111), (220). G-Pdcomposites shows the reflections of
palladium oxide at (101), (110) along with the signature of
graphite. The compositesnature of G-

-Fe2O3 is well elucidated from the appearance of reflection

due to

-Fe2O3 and graphene.

APPLICATION OF GRAPHENENANOPARTICLE (G-N)

COMPOSITES
Graphene-nanoparticle composites have been used
indifferent area of science. (Fig. 6) In
particulargraphene/GO/RGO has been used as coating
material orstabilizer for nanoparticle, as conducting catalyst
support,for assembling nanoparticle on their surface andFig.
6. Schematic representation of different area of applications
ofgraphene-nanoparticle (G-N) composites. as media for
controlled aggregation of nanoparticle. Similarly, presence of
nanoparticle lowers the aggregationproperty of graphene
and thus it’s high surface areaand other properties are
largely remain intact. As a result G-N based composites have
combined property of both components, suitable for various
applications. In following sections we will discuss some of the
emerging areas where they have been used, highlighting
their advantagesand our own contribution in some of the
areas.

Enhanced Catalytic Property

Metal or metal oxide nanoparticles with or withoutcarbon
support are widely used as heterogeneous catalystin various
organic transformation reactions.78–88GO/RGO/graphene
with semiconductive or conductiveplatform has been utilized
as catalyst support for betterperformance of different types
of organic conversion reactions.(Table I and Fig. 7) In general
G-N compositesoffer high conversion yield and composites
catalysts arestable under repeated use.838586 Silica coated
and positivelycharged iron oxide and silver nanoparticles
havebeen used to electrostatically interact with colloidal
GOfollowed by chemical reduction to produce graphene
basedcomposites.8385 These composites have been used for
clickreaction, A3 coupling reactions and alcohol oxidation
reaction.Similarly, mixture of copper salt andGO are
simultaneously reduced to form G-N compositesand showed
high catalytic activity for O/N-arylation.The TEM study shows
that the copper nanoparticles ofsizes 2–3 nm and silica
coated silver nanoparticles ofsizes 7–8 nm are uniformly
distributed on the grapheme surfaces.8385 (Fig. 7(b)) The
graphene surfaces not onlystabilize the active

-Fe2O3/Ag/Cu nanoparticles but it canalso provide a suitable

platforms or medium for reactingmolecules to carry out
reaction smoothly and with higherefficiencies. These
catalysts are highly air stable, inexpensivefor large scale
preparation, easy to recover and are reusable.It is proposed
that large number of reactant moleculescan easily adsorb on
the graphene surfaces due its highsurface area and high local
concentration of electrons on the nanoparticles facilitate the
A3 coupling, arylation and click reactions.85 The presence of
oxygen functionality onthe graphene surfaces can catalyze
the oxidation reactionof alkyl/nitro substituted benzyl
alcohol molecules withhigher percentage of yields (about 70–
97%). It is alsoemphasized that graphene surface not only
acts as supportmaterials but it can also establish interaction
between metaland graphene via functional groups present
on nanoparticlessurfaces. The decoration with smaller size
and uniformlydispersed nanoparticles on graphene surfaces
leadsto increased number of catalytic centres and results in
bettercatalytic conversion. The stabilization of
nanoparticleson graphene surfaces by metal-graphene
interaction andhigh tolerance property of graphene in
different conditionor environment give higher catalytic
performance.
Enhanced Electrochemical DetectionSensitively and
Selectively
Electrochemical technique is an important analytical toolfor
diagnosing different types of biomolecules, toxic
materialsand explosive materials. Recently graphene has
beenused in electrochemical sensing application of
differentbiomolecules.172089–102 Graphene oxidizes at high
positivepotential (2.5 V in 0.1 mM phosphate buffer
solution), sothe molecules having high reduction or oxidation
potential can be detected by electrochemical technique.92
The edges and defects in few layer RGO are considered as
superior part for electrochemical activity. The charge transfer
abilitybetween analyte and graphene modified electrode
isquite higher than unmodified electrode. Different types
ofG-N composites are used for electrochemical
biosensingwhich are summarized in Table II. In general noble
metalnanoparticle based composites are used and various
typesof molecules have been detected. The large surface
area to volume ratio of graphene offers decoration of large
number of nanoparticles or affinitymolecules (e.g., enzymes)
as catalytic centres. Nanoparticles are attached with
graphene through functional groups present on surface of
nanoparticle/graphene or by usingadditional stabilizer. It is
shown that G-N composites areuseful for enhanced
selectivity and sensitivity for detectionof different analyte.
Depending on the requirement,the composites material can
be designed to enhance theselectivity or sensitivity. It is
proposed that selectivity maycomes from the surface charge
present in composites orselective affinity of analyte to any
component of compositesor affinity molecules attached on
composites. Thesensitivity arises from large surface area,
high loadingof nanoparticle and high conductivity of
graphene. Summary of application of G-N composites in
electrochemicalsensing.
Representative example of graphene based compositeswith
gold nanoparticle (G-Au) and their electrochemicaldetection
is shown in Figure 8.101 TEM image shows brightround spot
observed on graphene surface as gold nanoparticlesand
similar morphology is expected when they areused to modify
the working electrode. The differentialpulse voltametric
response of ascorbic acid, dopamine anduric acid can be well
resolved from their mixture whenelectrode is modified by G-
Au. In addition signal intensityhas also been enhanced. In
contrast bare electrode or electrodemodified with only Au
nanoparticle or graphene cannot resolve individual redox
signals. It is also observedthat finer optimization of loading of
Au nanoparticles ongraphene surfaces is important for
resolution of individualredox signals. Following this approach
sensitive and selective detection of ascorbic acid, dopamine,
uric acid or DNA bases can be performed from mixture.101 In
mostof the cases ascorbic acid suppress the redox signals
ofdopamine/uric acid. However, G-Au shifts the
oxidationpeak potential of ascorbic acid towards lower
potentialand thus signal is isolated. In addition, G-Au offers
bothcationic and anionic charge centre that can trap
oppositelycharged analyte and induce selectivity.
New Spacecrafts and Spacesuits Using
Nanotechnology
Anticipated advances in space travel thanks to
nanotechnology
• Ultra-small sensors, power sources, as well as
communication, navigation,andpropulsion systems with very
low mass, volume and power consumptioncouldbe
developed using nanotechnology.
• Developments in electronics at the nanoscale are leading to
autonomous, “thinking” spacecraft.
• Networks of ultra-small probes can investigate planetary
surfaces.
• Micro-rovers should be able to drive, hop, fly, and burrow.
• Micro-spacecraft will be able to make a variety of
measurements.
Materials That Reduce Weight and Cost of Components
It costs about $10,000 per pound to lift anything into
Earth’sorbit, and $100,000 per pound to carry anything when
distant planets are the destination. Space exploration experts
agreethat miniaturization of everything onboard spacecraft
isessential to making space travel affordable, without giving
upanything in terms of functionality. In fact, better
performanceand lower weight is always the goal. Some of
the best-known applications of nanotechnology inspace are
those that deal with this issue. Using materialsconstructed
with carbon nanotubes can reduce the weight ofspace
vehicles significantly while maintaining or evenincreasing
structural integrity.
Nanotechnology-based sensor system in space,was
capable of detecting trace amounts ofnitrogen dioxide.
Compact trace gas sensor system comprised ofa main
nanoparticle-impregnated polymersensor and an auxiliary
CNT-based chemicalsensor on the International Space Station
(ISS).It is anticipated that such sensor systems canachieve
sensitivity in the parts per billion levelwith precise selectivity
through the use ofappropriate chemical functionalization.

Engineered Materials and Structures: Damage tolerant

systems

Schematic of nanostitching from the Wardle laboratory.

In the laboratory of MIT Professor Brian L. Wardle,they are

trying to make more durable materialsthrough a technique
called nanostitching.
• “The advanced materials currently used for many
aerospace applications are composed of layers, or plies, of
carbon fibers that in turn are held togetherwith a polymer
glue. But that glue can crack andotherwise result in the
carbon-fiber plies comingapart.”
• To combat this problem, the Wardle group reinforces the
glue with multiwalled carbonnanotubes that are grown
parallel to each other.These nanotubes “bridge the crack”
between layers of carbon fibers which results in composites
thatare 2.5-3 times tougher.
 Nanotechnologymayholdthekeytomakingspaceflightmor
epractical.Advancementsinnanomaterialsmakelightweig
htsolarsailsandacableforthespaceelevatorpossible.
 Bysignificantlyreducingtheamountofrocketfuelrequired,t
heseadvancescouldlowerthecostofreachingorbitandtrav
elinginspace.
 Inaddition,newmaterialscombinedwithnanosensorsandn
anorobotscouldimprovetheperformanceofspaceships,sp
acesuits,andtheequipmentusedtoexploreplanetsandmo
ons,makingnanotechnologyanimportant part of the
‘final frontier.