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Wednesday, 6 January 2021

Graphene -A miracle material of the 21st century: A review

Incessant researches are being carried out to ensure a beautiful, vibrant and improved life. And as a result of the non-ending researches, many strange things are being discovered and various mysterious unknowns are being revealed. Likewise, graphene is one of the amazing discoveries of the 21st century and attracted tremendous research interest. Today graphene with its unique properties is being used in a wide range of important areas from biomedical to wearable textiles. Information found from the researches done on graphene till today has been consolidated in this review paper though studies on graphene are still ongoing for its booming properties. It is obvious that graphene is certainly one of the most important discoveries in the Twenty-First Century. In the current research, it is observed that graphene is persistently revealing a new horizon in every single day. And that is why graphene has been mentioned as a miracle material in this review paper.

Due to the relentless study of scientists, different kinds of unknowns are being known today and new wonders are being revealed. Today, People are starting to think that in this age of science, nothing is really impossible. It seems everything is within our hands. And that is being possible as a result of the ceaseless journey of rigorous researches on materials science. Likewise, graphene is one of the most remarkable discoveries of the 21st century. Graphene is a carbon allotrope consisting of tightly packed carbon atoms arranged in a 2D honeycomb lattice. It is a thin layer of graphite and this laminar material is usually used in pencil lead. Although some scattered attempts on graphene can be traced back to about 1899, two physicists named Andre Geim and Konstantin Novoselov from the University of Manchester, brought a major breakthrough in the field of material science by discovering the new process of graphene production in 2004. [1]

Hexagonal structure of graphene
Figure 1: Honeycomb lattice structure of Graphene reprinted with permission [2]

Graphene for its very amazing properties has become the pioneer in modern material science and technology. Graphene has drawn significant attention due to its exceptional electronic, mechanical, thermal and optical properties. [3]–[7] And all these properties are derived from the unique electrical band structure of graphene. Still different types of researches on graphene and its properties are being carried out. It has gifted and still gifting us so many dazzling applications in a wide range of fields. It is wise to employ these useful properties of graphene and its derivatives in various functional materials.[8] To date, graphene-based composites have been successfully made with inorganic nanostructures,[9][10] organic crystals,[11] polymers,[12][13] metal-organic frameworks (MOFs),[14][15][16] biomaterials,[17][18] and carbon nanotubes (CNTs)[19][20] and are intensively explored in applications such as batteries,[21][22] super-capacitors,[23] fuel cells,[24] photovoltaic devices, photocatalysis, sensing platforms.[25] These marvellous graphene properties along with their applications have been tried to be comprehensively presented in this review study.

Graphene has been invented by a playful experiment done by two Russian scientists at the University of Manchester, named Andrei Geim and KostyaNovoselov. The main theme was to make the graphite films ‘as thin as possible’ and investigate their electronic properties. Sticky scotch tape was used to flake off a graphite layer from its body. Scientists did this peeling process repeatedly and finally succeeded to get down to a thin layer of about a few atoms.[26][27][28][29] Although there has been a significant advance in the study of graphene so far, no controlled method of getting crystalline and defects free graphene at large scale has been discovered yet. Many factors of graphene synthesis are under observations. It has been found that high-quality graphene can be synthesized by improving various parameters like temperatures, pressures, cooling rates, catalysts as well as the thickness of the catalysts etc.[30]–[33] 

Graphene is the miracle material in the 21st century and that is why it could gather unbelievable research interests. As a consequence of rigorous research, various methods are now being developed and used to produce graphene. Some mostly used methods are Mechanical Exfoliation, Epitaxial Growth on Silicon Carbide, Chemical Vapour Deposition, Arc Discharge Method, Reduction of Graphite Oxide, intercalation methods in graphite, unzipping of CNTs, electrochemical and chemical methods, micromechanical cleavage method. [34] [35] [36] [2] [37] 

3.1 Electrical Transport Properties
Graphene is a 2-Dimensional and 1-Atom thick crystal consisting of sp2 hybridized carbon atoms which are arranged in a hexagonal lattice. Properties like High Charge Carrier Mobility, Ambipolar Field Effect, Anomalous Quantum Hall Effect, Ballistic Transport, Chirality and Weak Antilocation have made the graphene unparallel. Due to the electronic structure graphene has very high charge mobility. Generally, the mobility of graphene lies in between 2000–15000 cm2 v−1s−1. Very recently it has been found that graphene with a clean surface shows carrier mobility up to 200 000 cm2 v−1s−1.[37] Ambipolar field-effect is another crucial graphene property which has instigated its huge applications in electronics. Furthermore, the electronic structure of graphene results anomalous hall effect, chirality and weak antilocation properties.[38][39] The quantum anomalous Hall effect is an unorthodox demonstration of the topological structure of graphene and can be observed even at room temperature due to the high charge mobility.[40] 

3.2 Optical Properties
Graphene has very good optical properties like very high optical transmittance, low optical reflectivity, luminescence, photoluminescence quenching properties and fluorescence quenching capability due to its distinctive electronic structures and energy or electron transfer. Interestingly single-layered and bilayered graphene shows different optical responses; that means graphene shows layer dependent optical transmission properties. It has been found that single-layer graphene has 97.4% optical transmittance and it decreases linearly with the number of layers.[40][41] Furthermore, luminescence and photoluminescence properties of graphene are successfully being utilized in various biological applications. [42], [43][44][45]–[47] All these fascinating graphene properties have made it suitably fit for the advanced optical and optoelectronic applications. 

3.3 Mechanical Properties 
Graphene possesses some significant mechanical properties like high in-plane stiffness, highly versatile Young’s modulus and tensile strength due to the hexagonal 2-dimensional lattice consisting of sp2 hybridized C-C bonds.[48][49] Besides, mechanical properties of graphene are influenced by some other factors like- defects, no. of layers, stitching quality of adjacent boundaries and angle of tilt boundaries.[50] Below table shows a summary of the inherent mechanical properties of different layered graphene.

Table 1: Mechanical Properties of Graphene [51]
Mechanical Properties of Graphene

3.4 Thermal Properties 
Graphene manifests very good heat conveyor properties due to its elastic arrangement of atoms in the honeycomb tight compacted lattice. The thermal conductivity of graphene is about 5 × 103 Wm-1k-1, which is three times as high as diamond and higher than carbon nanotubes (CNT).[27][55] It has been demonstrated that the specific heat of graphene is bifurcated into atoms vibrations in the lattice (phonons) and free electron contributions. Specific heat, C = Cp + Ce; where Cp = Phonons’ contributions and Ce = free electrons’ contributions. Electrons’ contributions can play a significant role in doped materials, though phonons’ contribution is dominant in graphene generally. [56] Furthermore, the in-plane heat flow direction is always greater than the out-of-plane direction in graphene due to the hexagonal 2-dimensional lattice consisting of sp2 hybridized C-C bonds. 

Wide range of polymer composites is available now based on different nanofillers like carbon nanotubes (CNTs), graphite, metal-oxides, nano-clay, nano-cellulose, carbon nanofiber (CNF) and graphene pellets (GPs) etc. both for thermoplastic and thermosetting polymer matrix materials. Commonly used matrix materials are thermoplastic matrix materials (polyethene, polypropylene, polystyrene, polyurethane etc.) and thermosetting matrix materials (epoxy, polyester, phenolic resin etc.).[57][58][59][60]
Commonly used Graphene-based polymer composites
Figure 2: Commonly used Graphene-based polymer composites

Graphene has successfully attracted the researchers’ attention due to its fascinating properties and is being used in a wide range of fields. Very surprisingly it is expanding its territory day by day and has been established as a miracle material. This wonder material is still under research and every new day unlocks a new scope of application.

Versatile Applications of Graphene
Figure 3: Versatile Applications of Graphene

5.1 Biomedical Applications
Researchers are working hard to figure out the existing deficiencies. They are seeking for easy and advanced diagnostics. Graphene has been discovered to use in precise biosensing, stem cell differentiation, cell proliferation & control, cancer treatment, drug delivery system and some other disease diagnostics.[61], [62] Among the successful discoveries, some are really outstanding like- biocompatible hydrogel composite produced via physical cross-linking of PVA chains between graphene oxide (GO) platelets showed a controlled release of Vitamin B12 depending on solution pH, and it could be used in drug delivery, graphene oxide (GO) is used with biopolymers to improve their biocompatibility, mechanical strength, cell adhesion, and proliferation properties, specifically for various tissue engineering applications and very recently Graphene/PEG (Polyethylene Glycol)/Fe3O4 hybrid composite have been studied for applications on Magnetic Resonance Imaging (MRI) and Localized Photothermal Therapy of magnetically guided cancer cells.[63], [64][65], [66][67] 

5.2 Electronics
Graphene has been able to occupy an important position in electronics. A number of electronic devices which are of time demand have been developed with the aid of graphene. Low-cost, easily recyclable display screens have been developed by using graphene instead of the indium-based electrode in OLED (Organic Light-Emitting Diode).[68] As electrons can move faster on graphene compared to silicon, Field Effect Transistors (FET) and High-frequency Transistors based on graphene could be refined. On top of that, in recent years researchers have successfully developed graphene-based transparent electrodes like organic thin-film transistors, touch screen, LEDs, solar cells, and smart windows etc.[69]–[71] 

5.3 Energy Storage
Lithium-Ion Battery (LiB) is one of the most potential energy storage system. Its high absolute potential (about -3.04V) and low atomic weight (6.94gm/mol) leads to large energy density (up to ~400Wh/Kg).[72], [73] LiB is very promising for especially portable electronics, power tools, and electric vehicles. Several metal oxides like TiO2, MnO2, CoO, NiO, VO2, V2O5, LiMn2O4, LiCoO2, SnO2, Co3O4, Fe3O4 are hybridized with graphene as an anode material for Lithium-ion Battery (LiB)s to improve its performance.[74][65] Very recently, the high energy efficiency of LiB is being used to improve the quality of energy produced from wind, solar, geothermal and other renewable sources.[75] Another important energy storage device is supercapacitor or electrochemical capacitors or ultracapacitors.[76] High power density (10KW/kg) and short charging-discharging time of these supercapacitors have created a wide range of applications, including load cranes, forklifts, electric vehicles, electric utilities, factory power backup and so on.[77][78] 

5.4 Sensors
Graphene has been established as a potential sensor due to the change in conductance as a function of the extent of surface adsorption and large specific area. It can detect a variety of molecules such as gases to biomolecules.[60][79] It has been demonstrated that graphene and graphene-based polymer composites can also be used as a pH sensor, Pressure sensor and Temperature sensor.[43], [78]–[88] 

5.5 Environmental Applications
Environmental pollution caused by both water and gases is the most issue in this present world. Everyone is seeking for ways to mitigate the environmental hazards and trying to develop new technologies if possible. Among the different approaches discovered to face environmental challenges, using nanomaterial has drawn pretty good interests.[89] Graphene-a 2D nanomaterial- has been used in environmental pollution management with an emphasis on gas adsorption and water remediation. Graphene and graphene-based composites are being used in water treatment membranes as well as pollutants removing electrode materials.[90] Furthermore, if the gasoline power transportations can be replaced by the graphene-based lithium battery (LiB), it would reduce the CO2 emission and thus reduce the environmental pollutions. 

5.6 Automobile Applications 
In this age of awareness, everybody is after ensuring getting safe and comfortable vehicles with minimum energy. Actually energy-efficient and safe vehicle means a lighter, less polluting and more fuel-efficient new generation vehicle.[91][36] It has been demonstrated that for each 10% reduction in weight, lightweight material technology can improve vehicle fuel efficiency by 6–8%.[92] Graphene with its fantastic properties can be used in various parts of the vehicles (shown below).

Potential applications of Graphene-based composite in a car
Figure 4: Potential applications of Graphene-based composite in a car reprinted with permission [92]

5.7 Textile Applications 
In recent years smart textiles (e-textiles) have drawn tremendous research interest and are the most promising especially for sportswear, medical textiles and military applications.[93] There exists a lot of methods of producing e-textiles but unfortunately, none of these is eco-friendly nor cost-effective. Graphene inks have been demonstrated to be the promising candidate to eradicate such kinds of problems. Graphene inks can be applied on textiles by ink-jet printing instead of incorporating various electronic devices on textiles.[94], [95][96], [97] [98] Furthermore, very recently a team from the University of Manchester have discovered a scalable and more importantly cost-effective graphene-based e-textiles manufacturing process which has secured the firm position of graphene in e-textile applications.[99] A pretty good number of researches has been fruitfully carried out to ensure e-textiles as conductive as well as strong, highly elastic, mechanically flexible, wearable, and lightweight.[100]–[104] 

The properties of graphene provide basically vast potential for various applications. Graphene and Graphene-based composites have occupied a huge place in advanced engineering applications including energy conversion, energy storage, transparent electrodes, biological and biomedical, etc. Due to the tremendous consumption of limited energy, the earth is forwarding towards future energy crisis and many environmental imbalances. Graphene, for its outstanding electrical conductivity, high specific surface area, and good structural stability, have taken our focus to mitigate this energy and other environmental challenges. Aforementioned review study reveals that graphene is the most promising potential candidate for next-generation materials as well that are being sought immensely for a smooth future. The structure and associated properties of graphene have proved itself as a miracle material indeed. 

We would like to convey our heartfelt gratitude to Marzia Dulal (Assistant Professor at Bangladesh University of Textiles) and Mr Sudip Dey (Assistant Manager, Sparkle Colors (Agent for Dystar), Bangladesh) who has supported us in literature collection and critical analysis. 

There is no potential conflicts of interest with respect to the research, authorship, and/or publication of this article. 

There is no funding agency used for this research. This is a self-funded work. 

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