Evolution of Graphene Oxide and Graphene: From

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Hummers et al. published excellent work in JACS titled with “Preparation of Graphitic oxide” which was the first alternative ...... Communication, Sendai, Japan. 10. ...... graphene on a template and doing so greatly overpowers the actual ...

DOI: 10.1002/cnma.201800089 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57

Focus Review

Carbon Nanomaterials

Evolution of Graphene Oxide and Graphene: From Imagination to Industrialization Santosh K. Tiwari,[a] Raghvendra Kumar Mishra,[b] Sung Kyu Ha,[a] and Andrzej Huczko*[c]

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applications of graphene and its derivatives. The current progress in graphene research output of renowned scientists around the globe is also evaluated based on the Scopus and Web of Science databases. However, a particular emphasis is focused on the current technological innovations (2010– 2017) based on graphene, as well as mostly prototype devices fabricated using graphene as a key material along with discussing the recent challenges in graphene nanotechnology, and a recommendation of the ways to advance the commercial readiness of the products based on graphene and their derivatives. In addition, we have also briefly discussed the limitations of graphene, future prospects and present global market trends of graphene-based products.

Abstract: During the past 32years, more than 103000 research articles with term graphene in the title or in manuscript have been recorded in the Scopus database. This exceptional reputation of graphene is due to numerous reasons; the most significant one appears to be its incomparable physical properties, resulting in real-time application in many fields of science and technology. That’s why it seems to be absolutely justified that “graphene possesses everything’s what you want”. This article is a tribute to the researchers who contributed to the background of the current face of graphene. In this short paper we are presenting the contributions of initial research articles on graphite that are responsible for the present status of graphene and led the research interests of materials scientists toward the potential

1. Introduction

the oxidation of graphitic sheets to graphite oxide was performed much earlier by a German chemist C. Schafhaeutl around 1840 and recently it was a matter of debate regarding original credit for the first oxidation of graphite.[3] Initial literature on graphite very clearly indicates that it was P.R Wallace who first predicted electronic properties of single layer of graphite (nowadays, it is graphene) in 1940s (Table 1). At present the predictions of Wallace about graphene is not only confirmed accurate, but it also has many exceptional properties. Thus discoveries and potential applications of graphene oxide and graphene is closely associated with the structure of graphite. Nowadays, graphene belongs to a unique class of nanomaterials with zero band gap and often treated as semimetal is a very wonder material in terms of nano and micro structuring and commercial applications.[4–5] In a decade, graphene and their derivatives have demonstrated extraordinary performance for the several prototype applications, including advanced manufacturing, biomedical engineering, medicine, space science and sustainable energy.[2–5] At present graphene and interrelated 2D (two dimensional) materials constitute the material basis of one of the most auspicious and multipurpose enabling nanotechnologies, in particular for flexible electronics. The 2D layer of graphene combine a huge surface area and exceptionally high electrical conductivity, making it extremely appropriate for the storing electrical charge, gas storage (especially for H2, which considered as future energy), and solar cell devices.[5] Therefore, in the area of graphene utilizations for the next generation technologies, researchers around the globe are proactive and actions are chiefly motivated towards the consumption of graphene and interrelated materials to solve present issues like energy crisis and environmental pollutions.[6] It implies that evaluating various scientific methods that are safe, ecofriendly, and scalable in a commercial environment while remaining profitable for the producers. To do so, several start-up businesses as well as established industries have thus pursued graphene and its derivatives on a scale of tons, or hundreds of thousands of square meters of GR films obtained using CVD technologies.[6–7] Many well-known material indus-

The 19th century saw many unbelievable findings, from elemental discoveries to new materials, from electromagnetic phenomena to electrodynamics and many more.[1–2] In this line, chemist Benjamin Collins Brodie focused on the extremely layered morphology of reduced graphite oxide as early as 1859 having testified the atomic weight of graphite in an article of the Royal Society of London (Table 1). However, an attempt for

Table 1. Contributions of the top ten countries to graphene nanoscience and technology.

[a] S. K. Tiwari, S. K. Ha Department of Mechanical Engineering, Hanyang University, Korea [b] R. K. Mishra Director BSM Solar and Environmental Solution, A-348, Awas Vikas Colony, Sitapur, Unnao, India [c] A. Huczko Laboratory of Nanomaterials Physics and Chemistry, Department of Chemistry, Warsaw University, Warsaw, Poland Phone No. + 48-508221506 E-mail: [email protected] Supporting information for this article is available on the WWW under https://doi.org/10.1002/cnma.201800089 ChemNanoMat 2018, 4, 1 – 24

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tries have also started processing of graphene and related materials as commercial products.[5–6] In this short review, we aim to provide a brief summary of the graphene based market products and related industrial applications. So, along with booming graphene research brief we are concerned about application of graphene in the real world and some marketable products for the common people. Moreover, on the basis of recent progress and investigations implemented within the technological framework of the graphene, a number of roadmaps for application of graphene have been evaluated.[5–7] The leader status of graphene in nanoscience and technology can be observed on the basis of research articles published on graphene and their derivatives in the reputed international journals. Till the date (19/12/2017) nearly ~ 102879 articles in Scopus and ~ 762274 articles in Web Science data base with word ‘graphene’ in title of documents were recorded (Table 1). Herein, our determination is to confer and assess the potential of graphene in light of various real time applications on the basis of granted US patents during the years 2010 to 2017. Keeping this in mind, the practical challenges still to be addressed will be emphasized, but, prominently, we will see how some graphene based technologies advanced for specific applications can maximize the benefit taken from various like materials. moreover, a comprehensive information about the prehistory of graphene and their derivatives is presented on single platform. Along with the prehistory we tried our best to incorporate all the ground breaking discoveries after year 2004 concerning to the graphene in a single review paper with proper citations. On the basis of Scopus and Web Science data base we have also presented quite interesting statistical data regarding the graphene based nanotechnologies around the globe (see Table 4 below). Finally, we have concluded this review with author’s viewpoints about the pristine graphene (GR), graphene oxide (GO) and reduced graphene oxide (rGO).

Prof. Andrzej Huczko is a full professor at Dept. of Chemistry, Warsaw University, Poland with specialization in ceramics and composite materials. In 1977 he defended his doctoral thesis on plasma synthesis of silicon nitride. And continuing further work at the University of Warsaw as a lecturer. In the years 1979–1992 he spent five years working scientifically in Canadian universities in the field of thermal plasma physics and chemistry, worked on plasma chlorination and fluorination of niobium and uranium ores. In 1996 he was awarded with D.Sc. from Warsaw University on the thesis devoted to heterogeneous reactions in thermal plasma. Since 1993 he’s been a head of the Laboratory of Plasma Chemistry (now Laboratory of Physical Chemistry of Nanomaterials), while since 2010 he’s has become a full professor at Warsaw University. He worked with many nano materials including fullerenes, carbon nanotubes, Nano capsules and ceramic. He published more than 200 very scientifically sounded articles as well as 7 books and monographs. He is currently editor of the monograph series “The World of Nanotechnology” published by the Warsaw University Publishing House. Prof. Sung Kyu Ha is a professor in Department of Mechanical Engineering in Hanyang University, and the director of Ha Structures and Composites Laboratory. He received a B.Eng. (1983) in Mechanical Engineering from Hanyang University, an M.S. (1985) and a Ph.D. (1988) in Mechanical Engineering from Stanford University. Before joining the faculty of Hanyang University in 1991, Professor Ha had been included in the faculty of Mechanical Engineering of Stanford University as a research associate. Dr. Ha, is a renowned researcher in mechanics of composite materials and has authored or co-authored of several books. His books has been extensively used as a textbook in solid mechanics for students majoring in engineering in Korea. He is also the author of more than 80 technical articles in the reputed academic journals. His research interests include design of flywheel energy storage system, development of finite element analysis tools, optimal design of innovative applications of composite materials, prediction of static, fatigue failure behavior of composite materials and presently he is working on graphene based composites for the real time applications. Dr. Santosh K. Tiwari completed his M.Sc in organic chemistry in 2011. In 2012, he qualified CSIR-UGC JRF/NET Exam (one of the top most PhD entrance examination in India), IIT(ISM) all India entrance examination for PhD & GATE Exam (organized by IITs & HRD ministry of India) with very good all India rank. In 2013 he, joined Dept. of Applied Chemistry as a PhD student and completed his PhD on bulk synthesis of graphene and its application for polymer blend nanocomposites. During his PhD, he published 24 research articles (in ACS, RSC, Springer, Taylor & Francis and Elsevier), including two review articles, three book chapters related to the graphene and graphene based polymer composites and presently he is a postdoctoral fellow at Hanyang Structure & Composite lab, Hanyang University, Seoul.

2. Initial Incarnations of Graphene Oxide and Graphene (1840–1970) Reviewing history of materials is very essential because it allows scientists to understand origin and earlier contribution of materials for our civilization, which in turn allows to understand further development and innovation in materials science and engineering. Therefore, if we want to know how and why our innovations is the way it is nowadays, scientist have to look to prehistory of materials for the decisive replies. Instead of this, history of science and technology is very exigent to provide a heartiest tribute to the scientist and inventors for his/her work in the past. Some outstanding review articles were published by the renowned researchers including Prof. A. Geim and Prof. Rodney S. Ruoff to explore initial works on graphene and graphene oxide.[8–10] However, herein we are presenting revolutionary contributions of the scientists regarding the graphite and graphene derivatives since year 1840 to 2010 in more comprehensive manner with proper citations.

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Mr. Raghvendra Kumar Mishra has received India’s most prestigious Visvesvaraya Research Fellowship (Department Information and Electronics, Govt. of India), and he is currently serving as Visvesvaraya Senior Research Fellow at the International and Interuniversity Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, India. He has completed his M. Tech. in Materials science and Technology at Indian Institute of Space Science and Technology (Indian Space Research Organization, India). He has edited 10 books, 15 original research articles and several book chapters. He has work as well research experience in Mechanical engineering, Materials science and Technology, and Nanoscience and Nanotechnology.

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displayed most of the data and information in the form of table for the sake of clarity. From the tabulated information it is evident that previous workers (1840–1970s) were mainly focused on structure of graphite, oxidation of graphite (but not with a clear motive to separate monolayers of graphene) via intercalation of suitable small molecules to produce thin graphitic fragments (Figure 1). However, few of them were also trying for the separation of single layer of graphene and for the properties of free standing graphene.[30] In this line few path breaking theoretical works are credited to Wallace, Semenoff, DiVincenzo and Mele regarding

There has been a powerful surge in interest in graphitic layer based nanotechnology during recent years owing to its huge industrial potential. However, concept of pure graphene was in scientific realm since 1900s. In this article we are tabulating (Table 2) a scientific expedition of graphene from stone to star for the carbon nanotechnology. In the Table 2, authors have incorporated most of the key achievement and role of prominent researchers related to the synthesis, purification and characterization of graphite oxide (if single layer, now it is called as graphene oxide), reduced graphite oxide and pristine graphene. In this review article we have

Table 2. Scientific development of graphene from stone to star for carbon nanotechnology. Years

Initial work on Graphite, GO, GR and notable achievement

Scientist(s)

1840

C. Schafhaeutl, first reported intercalation of tiny chemical species like alkali metal, acid in between the carbon lamellae. It was an exceptional attempt for oxidation of graphite (it happened unwillingly) using concentrated HNO3 and H2SO4. However, C. Schafhaeutl did not concentrated on structural information of oxidized graphite and he even did not much clear about the type of graphitic oxidation. In the same period few other researchers tried the oxidation of graphite and they popularized word ‘graphitic acid’, for the graphite oxide on the basis of solubility in the acids and bases. Brodie was much aware about the oxidation of graphite and he used term “Graphon” for the product obtained after the treatment of graphite with the mixture HNO3 and H2SO4. To produce Graphon, he treated graphite with strong oxidation mixture containing KClO3 and fuming HNO3. Nowadays, Graphon observed by the Brodie, is called as graphene oxide. It is notable that Brodie was mainly concerned to the chemical formula of graphite and its discrete molecular weight. Therefore he did not focused much on molecular structure of Graphon. The author tried to improve Brodie’s method of oxidation by adding the KClO3 stepwise during the reaction rather than in a single addition as performed by Brodie. Due to the stepwise and slow addition of KClO3, he noted much better oxidation of graphite into graphite oxide. First well established oxidation of graphite. P. Debije et al. first used XRD technique to elucidate structure of pure graphite. In the same line, Bernal et al. used single crystal XRD to determine exact crystalline pattern of graphite. It was the path breaking discovery toward the separation of single layer graphene in the following days. Frenzel et al. first used to XRD analysis to examine intercalation of sulfuric acid into the graphite lattice in the presence of a strong oxidizing mediator. However, they just got a broad idea about the same. During this period term Graphitic oxide or Graphitic acid was quite popular on the basis of its solubility in various solvents. However, these researchers did not focus much on structural features and reactivity of Graphitic oxide. But they have just tried to produce graphitic oxide in good quantity by using strong oxidizing mixtures containing at least one concentrated mineral acid. The theoretical analyses for the single layer of graphite (now graphene) was first developed by P. R Wallace. It was initial systematic theoretical understanding of electronic properties for 3D graphite and 2D graphene layers as well Hummers et al. published excellent work in JACS titled with “Preparation of Graphitic oxide” which was the first alternative oxidation method by reaction of graphite powder with a mixture of KMnO4 and conc. H2SO4. Hummers et al. first used resinous anion and cation exchangers and vacuum drying techniques for the purification of graphite oxide. We assume that it was the first well fully organized oxidation of graphite for the production of pure graphite oxide. However, they also did not focus much on the structural aspect of graphite oxide. G. Ruess and F. Vogt first performed systematized TEM analysis of graphite oxide, by drying single droplet of graphite oxide suspension on a transmission electron microscopy (TEM) grid. On the basis of TEM observation they reported thickness of graphene oxide down to a few nanometer. The first TEM image of graphite oxide is shown in the Figure 1. Boehm et al. first reported chemical reduction of graphite oxide in dilute alkaline media with hydrazine and hydrogen sulfide in a suitable condition. This work opened a door for separation few and single layer graphitic sheets from bulk graphite. In the same year Hofmann and Boehm first observed single layer reduced graphene oxide (thinnest materials ever) along with reduced graphite oxide using TEM instrument. Morgan et al. first successfully obtained Low-energy electron diffraction (LEED) patterns of adsorbed gaseous organic molecules (C2H4, CO) onto the surface of platinum (100) at elevated temperature. This research was not directly connected to the separation of graphene layers from graphite but it provided a very strong experimental and theoretical support for the existence of free standing 2D single layer atomic sheet in our 3D universe. It was a sensation research output. In the next year May et al. verified the work of Morgan regarding the adsorption of gaseous organic molecules on suitable substrate and he carefully interpreted data collected by the Morgan then he stated that “the first monolayer of graphite minimizes its energy of placement on each of the studied faces of platinum” It was another strong support regarding the free existence of graphene which was further supported by Blakely et al.

C. Schafhaeutl, German chemist

1859

1899

1913– 24 1935

1940

1940– 47 1958

1948

1962

1962 1968

1969– 70

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Ref. [11–12]

[13]

Benjamin Brodie, British chemist

L. StaudenmaierGerman Chemist

P. Debije et al., W. Friedrich et al., J. D. Bernal et al.

[15–17]

[18]

A. Frenzel et al.

B. R. Brown and O. W. Storey and many other researches

[19–21]

[22]

P. R Wallace

W. S. Hummers and R. E. Offeman USA

G. Ruess and F. Vogt

[23]

[24]

[25]

H. P. Boehm et al. German chemist Hanns-Peter Boehm and Ulrich Hofmann Morgan and Somorajai

J. W. May et al.

[14]

[26]

[27]

[28–29]

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individual layers discussed”.[32] In this way, we can see that till 1985 there were no much importance of graphene and graphene oxide production. However, some very outstanding theoretical work were carried out on graphite and various 2D materials which later became a fundamental pillar for the rise of graphene.[42–47]

3. Real Rise of Graphene (1986–2004) Interestingly, within 19 years (1985–2004) nearly 850 original articles (including reviews) were published on graphite and their derivatives. This number is approximately 4–5 times greater than the total number of research articles, which were published on graphite and their derivatives since 1840 to 1985 (Figure 2). It is notable that up to 1998 most of graphite

Figure 1. One of the earliest well-characterized TEM micrograph of few layer graphitic flakes obtained after reduction of graphene oxide (Reproduced with permission from Ref. [26] Copyright 2018 John Wiley and Sons).

the electronic properties of graphene and three dimensional (3D) graphite. These contributions are deep theoretical work on emergent massless Dirac equation and anomalous integer quantum Hall effect in graphite and graphene. These studies on graphite/graphene were later played a vibrant role to understand exceptional physical properties of pristine graphene/ graphene oxide and are still a matter of further research.[31–33] It seems that up 1975 scientist working on various expects of graphite became very confident that single or few layers of graphite one day could be separated out beyond the Van Der Waal forces. However, some theoretical physicists working on graphene had doubt about the restacking and edge deformation of layers on the basis of Badami’s X-ray diffraction results for C C distance in the case of single layer, two layers and for multilayers graphene.[32–34,35] In 1975 Boehm et al. had taken a U-turn in production of graphene and they reported epitaxial sublimation of silicon from single crystals of silicon carbide (0001) for the production of monolayer flakes with the graphene structure under very high temperatures and vacuum (< 10 10 Torr). Boehm et al. used LEED pattern and Auger electron spectroscopy to provide crystal clear evidence about the formed single layer, few layer and multilayers carbon under different experimental condition during his sublimation experiment. But due to the hidden properties of graphene and their limited real time applications, this method was also unable to attract proper attention of scientific community on uniqueness of graphene. The work of Boehm et al. boosted theoretical research on graphene and their derivatives.[36–39] Around 1975–1986 Boehm et al. and few other groups dominated graphene research in term of separation and chemical transformation of individual or few layered graphene.[40–41] It was Boehm (1986) whose suggestion has later made great impact on the present IUPAC (International Union of Pure and Applied Chemistry) definition of graphene. According to Boehm’s term graphene is only applied for single layer graphite like structure. IUPAC accepted Boehm’s definition for graphene with little modification. Exact IUPAC (1997) definition of graphene is “term graphene should be used only when the reaction, structural relations or other properties of ChemNanoMat 2018, 4, 1 – 24

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Figure 2. Number of research articles containing the search term “graphene” by year (Scopus and Web Science databases).

research either concerned with the peculiar features of graphitic layers or about separation of graphitic layers via intercalation of small molecules from bulk graphite.[48–56] Therefore, we believe the real rise of graphene started after the evaluation 13 C-NMR chemical shift (Figure 3)for the carbon atoms of a

Figure 3. (a) 13C-NMR spectrum showing chemical shift of highly oriented pyrolytic graphite (b) charcoal and (c) highly graphitized carbon fiber (Reproduced from Ref. [57] Copyright free).

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years 2004 to 2010. The competition between CNTs and graphene research can be observed in the Figure (4 a&b). The sensational approach (Scotch tape method) for the separation of monolayer graphene from the bulk graphite developed by Prof. Geim and co-workers is very dull in term of scalable production of graphene for a particular application.[62] It is a very tedious and time consuming process and one could not produce even 0.5 g of graphene in a day by this technique. So, that during the 2004 to 2007 pure and bulk amount graphene production was the main bottleneck for its potential applications. At that time there were no any facile route for the production of graphene and their derivatives in a gram scale. This is why well established CNTs were quite predominant on graphene even after the superior properties of graphene (Figure 4 a&b). Material chemists around the globe accepted challenges about scalable graphene production and as a result after 2007 nearly 100 methods (Scopus and Web Science data base) were developed for the graphene and graphene oxide synthesis. The advantages and disadvantages of major synthetic routes for the graphene are listed in the Table 3. All these method mainly based on chemical exfoliation (oxidationreduction), chemical vapor deposition (CVD), SiC processing, electrochemical expansion and arc discharge techniques and having their own advantages and disadvantages.[69–72] Till the 2018 nearly 60–65% graphene and their derivatives are produced via oxidation-reduction route owing to the sake of simplicity, economical, and simple path toward the bulk production of graphene for the commercial utilizations.[69–73] Top twenty methods (merit based on google Scholar Citation) which have widely been accepted for the production of graphene and their derivatives are listed in the Table 4.

graphene plane present in graphite and like materials by H. A. Resing, et al.[57] Similar, contribution due to J. R Gaier of National Aeronautics and Space Administration (NASA) on intercalation study of graphite fibers based on the bromination dynamics (via bromination and de-bromination reactions).[58] In the same research article J.R Gaier very clearly presumed the application of graphene for the fabrication of electrically and mechanically reinforced novel composites.[57] In this section ofreview, we are again tabulating facts regarding the discoveries and advances in graphene nanotechnology. We assume that it was the real growing time of graphene because most of the fundamental pillars (Fermi energy of graphitic layer, exceptional quantum Hall phenomenon in graphene, calculation of Van Der Waal faces between adjacent graphitic layers and many crucial theoretical aspects) for the graphene and its derivatives were formulated and established during (1986–2004) this period only.

4. An Overview of New Synthetic Routes for Graphene and Graphene oxide and their Potential Applications (2010–2017) As well discussed in the previous sections that earlier efforts to make atomically thin graphitic layers employed exfoliation via intercalation procedures was similar to work carried out by the Brodie et al.[13–17] But neither of the any earlier interpretation was adequate to promote the “graphene gold rush” that anticipated macroscopic samples of exfoliated atomic planes (graphitic layers). However, in 2004 Prof. A. Geim and Novoselov extracted pure single layer graphene from bulk graphite through scotch tape method and it was the greatest boost in graphene research. Prof. A.Geim et al. worked a lot on the various theoretical aspects of graphene for which Sir A.Geim and Sir K.S Novoselov were awarded with Nobel Prize.[62&ESI*] Nobel Prize to Prof. Geim and co-workers on graphene created a huge attention of scientific community. The well-established CNT’s exceptional properties and potential applications, however, was giving very tough competition to graphene. So, that even after the high recognition of single layer graphene, CNT was a biggest star of the carbon nanotechnology during the

5. The Game-changer Technological Patents on Graphene and Related Materials: A Commercial Aspect of Graphene Nanotechnology In the previous sections of this article we have concentrated mostly on the prehistory and scalable synthesis of graphene and their derivatives. In this section, we are presenting prosper-

Table 3. Advantages and disadvantages of major synthetic routes for graphene. Methods

Advantages

Disadvantages

Mechanical exfoliation Chemical Approach

Very much time consuming Poor scalability in real-world application. Very Hazardous

CVD method

Ultrapure SLGR Quick oxidation, most effective for bulk production of GO and rGO High quality, SLGR and FLGR

Epitaxial Growth

Large quantity, van der Waals heterostructure

Electrochemical exfoliation Pyrolysis Sonication

Very less defect, pure FLGR Bulk production Very less defect, pure FLGR/FLGR

Ref.

Very expensive, hard to take care of equipment and time consuming High Temperature, Inconsistent Uniformity, Effects of substrate bonding Time consuming and not applicable for bulk amount GR production Only FLGR with huge defects Time consuming and not applicable for bulk amount GR production

[62] [76–77,80]

[83,90]

[68–82]

[85]

[72,81] [73,78]

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Figure 4. Number of research articles containing the search term “graphene/CNTs” in the defined time period (Scopus and Web Science databases). Graphs (a&b) showing competition between newly invented single layer graphene and well-established CNTs during 2004–2010.

granted on the various technological aspects of graphene and it is impossible to incorporate all of them in a single review paper. So, that in this paper we have noted only selected patents on graphene which have created great scientific innovations for the modern technologies. The functionality, as well as cost of the “preparation of the graphene”, triggered a considerable level of scientific interest, and also graphene research began to take off at a mindblowing rate. The game-changing technologies influenced by the graphene seem to be amazingly worthwhile, it is probably unsurprising that graphene-related enthusiasm has significantly amplified world widely. As presented in the pie chart (Figure 5), values are determined on a scale from 0 to 100, in which 100 is the place with the large amount global recognition in form of total internet searches in this particular place, a value of 50 implies a place that is fifty percent as in graphene-related inquiries, and a value of 0 shows a place in which the graphene-related inquiries was under 1% as popular as the

ous applications of graphene and related materials for the real times utilization to solve various scientific and technical challenges. In this trend, many review articles related to the graphene for the different applications have been published time to time by active researches of renowned groups.[5–6,69,72] But most of the published review articles were related to the various aspects of graphene either based on research articles or research articles along with few patents on the same.[69–72] For example, review articles related to synthesis of graphene, application of graphene for energy storage, composites materials, solar cell application, carbon capture and many more has been extensively explored by the many active researchers.[5–6,69,72] Because, technology based patents always give an accurate and comprehensive details about the commercial applicability of an intellectual idea therefore, herein we have considered only granted patents to explore prospectives of graphene and their composites for real time applications. Since 2004 approximately ~ 17000 patents (Google Patent) have been ChemNanoMat 2018, 4, 1 – 24

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On the basis of google patent database, it is found that at least 51,519 patent applications based on the graphene have been filed in the year 2004 to 17-12-2017 worldwide. From Figure 6, the bar chart shows that the total number of 259 patents based on the graphene was granted worldwide in 2004. The graphene was the primary focus of 4655 patents granted in 2014, which reached maximum number till now on other hand in this year (17-12-2017), only 440 patents were granted. However, the drop in recent years is mostly due to the fact that many patent applications is under scrutiny. Though, edge cutting research on graphene was started from UK USA and Europebut after a short period of time China, South Korea, India, Iran, Taiwan and Singapore have emerged as big players in graphene nanotechnology. This reflect that graphene research has been well recognized worldwide even in developing countries in spite of highly developed counties like USA, UK and Israel. It is also notable that most of the patent on graphene were granted from Japan, South Korea and China. The majority of the leading industries of the world hold patents regarding 2D graphene during the year 2004–2017. International Business Machines Corporation (IBM), Samsung Electronics Co. (SE), Ltd., Nanotek Instruments, Inc., Lockheed Martin Corporation (LMC), Hon Hai Precision Industry Co. Ltd. and Kabushiki Kaisha Toshiba are all rank among the best ten graphene patent assignees during the year 2004–2017. Due to the fact, graphene is a comparatively emerging technological innovation; consequently, research and development (R&D) institutions, as well as universities, are the owners of an astonishing percentage of graphene-related patents. Korea Advanced Institute of Science and Technology (KAIST), Sungkyunkwan University (SKKU), Korea Institute of Machinery & Materials (KIMM), University of California (UC), Korea Institute of Science & Technology (KIST) as well as Rice University are the research institute, which are among the top ten patent assignees in the two-dimensional graphene during the year 2004–2017. Aruna Zhamu, B. Z. Jang, Jae-Young Choi, Hyunjong Chung, Hyeon-jin SHIN, Jin-SeongHeo, PhaedonAvouris, Christos D. Dimitrakopoulos, Yu-Ming Lin, Alfred Grill are the leading ten inventors in the area of graphene technological innovation. The proportion of patents owned by the top ten academic/research institutes as well as inventor is presented in the bar chart of Figure 7. Nowadays, the promising graphene technologies are employed in the broad spectrum and we are trying to point out the graphene-related progress in the light of granted patents during the year 2002–2017 as a nascent report. Since, the beginning of growth and development of graphene era, Yihong Wu et al. developed equipment for two-dimensional nano-sized structures such as such as carbon, boron nitride, SiC, MoS3, MoSe2, GaN, ZnO, TiO2 as well as mixtures and additionally approaches for their production.[91] The processing of a 2D, nano-sized structure was accomplished by a CVD method, the procedure composed of directing a stream of precursor material to the first surface of a target plate for a suitable time period to allow a nano-sized structure.[91] A low-temperature chemical method to effectively generate nanomaterials was developed by Julia Mack et al.[91] In such a technique, the

Table 4. Twenty path-breaking techniques for the facile synthesis of graphene and its derivatives which have changed the face of graphene. S.N

Title of article for GO-rGO and graphene synthesis

Path

Year

1.

Toward the synthesis of wafer-scale single-crystal graphene on copper foils Hydrazine-reduction of graphite-and graphene oxide Improved synthesis of graphene oxide Wafer-scale synthesis and transfer of graphene films Reducing sugar: new functional molecules for the green synthesis of graphene nanosheets Reduced graphene oxide by chemical graphitization Ultrafast, dry microwave synthesis of graphene sheets Synthesis of high-quality graphene with a pre-determined number of layers A green approach to the synthesis of graphene nanosheets Synthesis of graphene sheets with high electrical conductivity and good thermal stability by hydrogen arc discharge exfoliation Gram-scale production of graphene based on solvothermal synthesis and sonication Large-area synthesis of high-quality and uniform graphene films on copper foils Synthesis of water soluble graphene Processable aqueous dispersions of graphene nanosheets One-step ionic-liquid-assisted electrochemical synthesis of ionic-liquid-functionalized graphene sheets directly from graphite Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide rGO Preparation and characterization of graphene oxide paper A chemical route to graphene for device applications Planarnano-graphenes from camphor by CVD

CVD

2012

Chemical

2011

Chemical CVD

2010 2010

Chemical

2010

Chemical

2010

microwave

2010

Chemical

2009

Chemical

2009

arc discharge

2009

Chemical

2009

CVD

2009

Chemical Chemical

2008 2008

Chemical

2008

Chemical

2008

Chemical

2007

Chemical

2007

Chemical

2007

CVD

2006

2. 3. 4. 5.

6. 7. 8. 9. 10.

11.

12. 13. 14. 15.

16.

17.

18. 19. 20.

Ref. [73]

[74]

[66] [75]

[76]

[77]

[78]

[79]

[80]

[81]

[82]

[83]

[84] [85]

[86]

[87]

[65]

[88]

[89]

[90]

maximum. A greater value signifies a better percentage of all inquiries about graphene and its derivatives. The assessment demonstrates that academic/research institutes from around the globe are trying to do a meaningful duty on the graphene, and it is remarkable that South Korea is the most dynamic location with 100 (34%) inquiries. Some other active places are Singapore 41 (14%), China 24 (8%), Iran 26 (9%), Taiwan 23 (8%), and Hong Kong 23 (8%). Additional places in this manner are United Kingdom 17 (6%),India 16 (5%), Malaysia/Australia 12 (4%) and Ireland 12 (4%). It is noteworthy that a small country South Korea accomplished max 100 (34%) as well as properly secured top place among the others. Thus, we can say at present South Korea paying much attention on materials science and engineering research (especially on green energy, fuel cells, supercapacitors, energy storage, carbon capture, water filtration etc.) for the betterment of our planet. ChemNanoMat 2018, 4, 1 – 24

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Figure 5. The distribution of interest related to graphene and its percentage interest in top ten countries (Worldwide from 2004 to 17-12-2017 from Google database).

exfoliating the graphite crystallites in the polymeric carbon, and c) finally, exposing the polymeric carbon having exfoliated graphite crystallites to a mechanical attrition to create the nano-scaled graphene sheet material.[93–94] An innovative graphite-like 3D configuration which contains a finite structure bentup with sort of a steeper curvature compared to that noticed for a carbonaceous material possessing a regular nano size 3D configuration, for example fullerene and even nanotube.[96] This graphite-like 3D arrangement with light in weight as well as superior mechanical durability was created by Yoshiyuki Miyamoto et al.[94–95] The nanometer-sized graphene sheet containing the manipulated extent of desired orientation along with nano-composite fiber carries essential role in a composite application. Jiusheng Guo et al. conceived a technique for developing nano-scaled graphene sheet-reinforced composite.[95] The composites were made up of a matrix materials including distributed as well as dispersed reinforcement nanoscaled graphene sheet which is significantly aligned along at least one defined direction or even axis.[96] Highly conductive nano-scaled graphene platelets containing nanocomposites are a good choice for the fuel cell flow field plate (commonly called as bipolar plate), battery power electrode, automobile friction plates as well as planes braking parts functions. Lulu Song et al. documented a nano-composite material including completely separated nano-scaled graphene platelets distributed in a matrix material, in which each of the platelets entails a sheet of graphite plane or even multiple sheets of graphite plane in addition to bulk graphite has developed a thickness absolutely no more than 100 nm along with the platelets possess a regular length, width, or diameter no higher than 500 nm.[93–96] Typically, the pure graphene based nanocomposites are electrically conductive with bulk conductivity approximately 10 S/cm and more generally at minimum 100 S/cm.[96–97] Low-temperature procedure for forming nano-scaled graphene platelets

Figure 6. Total number of patent applications filled in each year (Worldwide from 2004–2017 from Google patent).

nanomaterials were prepared by intercalating ions into layered compounds, exfoliating to produce separate layers after which sonicating to develop nanotubes, nanorods, nanoscrolls and/or nanosheets.[92] The expanded graphite is especially employed for batteries, anodes as well as fuel cells. Lawrence Drzal et al. accomplished graphite nano platelets of expanded graphite together with composites. The expanding of the graphite was completed by microwaves or even the other sorts of radiofrequency wave treatment of intercalated graphite.[91–92] The expanded graphite was found ideal after the broken up to few nanometers.[93] In the progression of graphene, B. Z. Jang et al. firstl developed a nano-scaled graphene sheet along with a method of preparation. The material encompasses a sheet of graphite or even multiple sheets. The method for developing nano-scaled graphene has composed the several protocols: a)partially or even completely carbonizing a precursor polymer or perhaps heat-treating petroleum or coal tar pitch to create a polymeric carbon including micron- and/or nanometer-scaled graphite crystallites with each and every crystallite that contain an individual sheet or multiple sheets of graphite plane; b)ChemNanoMat 2018, 4, 1 – 24

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Figure 7. Percentage of patents related to graphene for the top 10 a) industries/research institutes, b) inventors (Worldwide from 2004–2017 from Google patents).

called few layers graphene). Nano-scaled graphene platelets are lower-cost options to carbon nanotubes or alternatively carbon nano-fibres.[100] The nano-scaled platelets are likewise a choice in the form of reinforcement fillers for polymer nanocomposites.[100–101] A film article is referred to as a thin film with a thickness less than 50 mm, in fact, the platelets hold a typical thickness below the 10 nm. Thin-film can be employed for thermal management in micro-electronic gadgets and for current-dissipating on an aero plane skin against lightning attacks.[100–101] This kind of real times experiment may be very significant for the future aircraft but it need deep investigation and big funding for a long time. Z. Jang et al. developed a nano-scaled graphene consisting a non-woven aggregate of nano-scaled graphene platelets in which each of the platelets entails a graphene sheet or multiple graphene sheets and the platelets possess a thickness no more than 100 nm.[102] A procedure of inexpensively making a large-area graphene sheet containing a preferred thickness and a preparation method was formulated by Jae-Young Choi et al.[103] A method of efficiently

and additionally their nanocomposites has impressive importance.[96] Aruna Zhamu et al. designed a low-temperature procedure for creating nano-scaled graphene platelets as well as their nanocomposites.[98] Apart from, Aruna Zhamu et al. likewise developed a way of exfoliating as well as splitting up graphite, graphite oxide, and other laminar compounds to establish nano-scaled graphene sheet and also re-compressed elastic graphite.[99] An additional procedure for developing nano-scaled graphene platelets or graphite nano-platelets was introduced by Aruna Zhamu et. al in the same years.[96–97] The technique entails an approach of electrochemically intercalating a layered graphite material, for example, natural graphite, graphite oxide, as well as other laminar graphite compounds, to create a graphite intercalated systems.[96-97] This step is accompanied by exfoliation of the graphite intercalation compound and separation of the exfoliated graphite flakes to develop nano-scaled graphene platelets, especially nano-scaled graphene platelets with a typical thickness of approximately 2 nm or 5 layers (for example 5 graphene sheets commonly ChemNanoMat 2018, 4, 1 – 24

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parent films of exfoliated graphite nanoparticles(graphene sheets) along with additional nanoparticles (for example, metals, metal oxides) hold the potency to generate transparent conductors as an alternative for indium tin oxide (ITO) and also fluorine tin oxide (FTO) in optoelectronics purposes. An approach for manufacturing electrically conductive, optically transparent films of exfoliated graphite nanoparticles (graphene sheets) was introduced by L. T. Drzal et al. The strategies make it possible for the regulated deposition of exfoliated graphite, graphene sheets and other nanoparticles (for example, metals, metal oxides) in portable monolayer, few and multilayer film architectural structure.[111] The portable films offer superior electrical conductivities combined with optical transparencies in the visible spectrum of electromagnetic radiation.[112] Aruna Zhamu et al. built solid graphene nanocomposite particles for lithium metal or lithium ion battery electrode operations.[113] Robert K. Prudhomme et al. developed a technique for preparing nanocomposite having functional graphene and a polymer that can be employed for barrier membranes, for example, gas diffusion membranes and also for the similar applications.[114] A suitable way for developing lubricants such as nanographene layers or particles was formulated by Xingcheng Xiao et al.[115] Aruna Zhamu et al. devised a method for tailoring a lubricant or grease by use of graphene nanosheets or graphene nanoribbons.[112–115] In comparison with graphite nanosheets or carbon nanotube-modified lubricants, graphene nanosheets or graphene nano ribbons-modified lubricants offer significantly better thermal conductivity, friction-reducing capability, antiwear functionality, as well as viscosity constancy.[116] An approach for tire or tire lining composed of a rubber composite consisting a minimum of one rubber or elastomer matrix together with pristine nano graphene platelets was produced by Aruna Zhamu et al. The pristine nano graphene-modified tire or tire lining provides an appreciably improved thermal conductivity.[117] A metal matrix composite consisting of graphene nanoplatelets distributed as well as dispersed in a metal matrix was developed by Namsoo Paul Kim et al. The composite offers better thermal conductivity. This type of composites can be applied into the heat spreaders or supplementary thermal management products to allow better cooling to electronic as well as electrical device and also semiconductor products.[117–118] Hongjie Dai et al. developed large-scale creation of pristine few-layer graphene nanoribbons by means of unzipping of mildly gas-phase oxidized, and also, optionally, metal-assisted oxidized, multi walled as well as fewwalled carbon nanotubes.[118] The technique additionally encompasses sonication in an organic solvent. High-resolution transmission electron microscopy pointed out almost atomically smooth edges for thin graphene nanoribbons (2–3 nm).[119] A hybrid composite consist of tubular carbon as well as graphene was made with the aid of pyrolysis of a milled solid carbon source under an unoxidizing condition.[119] This kind of graphene based composites was developed by Khe C. Nguyen. When examined through X-ray diffraction, the hybrid composite shows peaks at 2q values of approximately 26.58, roughly 42.58, and/or around 54.58.[120] Sometimes ago, a beneficial

establishing a graphene shell possessing in a variety of 3D arrangement was introduced by Jae-Young Choi et al.[104] For the practical application perspective, an approach for graphene-based transistors was devised by the Brent A. Anderson et al. A graphene layer is produced on a surface of a silicon carbide substrate. A dummy gate arrangement is created over the fin, in the trench, or on a segment of the planar graphene layer to insert dopants into source and drain areas. Then, the dummy gate structure is wiped out to offer an opening over the channel of the transistor. The finished graphene-based field effect transistor possesses excellent carrier mobility because of the graphene layer in the channel, minimal contact resistance to the source as well as drain region, and consequently optimized threshold voltage together with leakage as a result of the threshold voltage insertion zone.[105] A supercapacitor that includes such type of a nanocomposite, which manifests an amazingly superior capacitance value, is vital for practical application.[105–106] A procedure for manufacturing mesoporous nanocomposite electrode including nano-scaled graphene platelets was produced by Aruna Zhamu et al.[106] A specific pattern of a graphene design on a substrate was devised by Jae-Young Choi et al. This graphene design is generally created by developing a graphitizing catalyst pattern on a substrate, contacting a carbonaceous material along with the graphitizing catalyst as well as heat-treatment.[107] The conductive inks can be imprinted to develop a variety of electrically or thermally conductive objects. A nano graphene platelet-based conductive ink was developed by B. Z. Jang et al.[107] The inks contained a binder or matrix material and/or may be as a surfactant. The graphene platelets ideally had a typical thickness no more than 10 nm and more ideally no higher than 1 nm.[108] Conductive nano graphene platelets are also able to be employed in the role of a conductive additive in transparent electrodes for solar cells or flat panel displays (for example, to replace costly indium-tin-oxide and other similar materials), battery as well as supercapacitor electrodes, and consequently polymer nanocomposite for electromagnetic wave interference (EMI) shielding and static charge dissipation, and so forth. An additional method for designing pristine graphene platelets was generated by Aruna Zhamu et al. and it was found that produced pristine graphene platelets tremendously conductive and can be used as alternative of silicon.[109] In the continued innovation, a dispersible, as well as electrically conductive nano graphene platelet material consisting at least a single-layer or multiplelayer graphene sheet, was designed by B. Z. Jang et al.[109] Nano graphene platelet possesses an oxygen content no more than 25% by weight and no lesser than 5% by weight. Conductive nano graphene platelet is able to apply for applications in transparent electrodes for solar cells or flat panel displays, nano additives for batteries and also supercapacitor electrodes, conductive nanocomposite for EMI shielding and static charge dissipation, and so on.[110] Moreover, a graphene nanocomposite material to be used in an electrochemical cell electrode, for example, an anode of the secondary batteries, especially a lithium-ion battery, and also an electrode of a supercapacitor was also produced by Aruna Zhamu et al.[111] Electrically conductive, optically transChemNanoMat 2018, 4, 1 – 24

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radiation sensor possesses low power and the higher sensitivity, a flexible configuration, along with a broad temperature range, which enable it to be used in a number of applications, especially in space missions for human venture.[132] In the same line, Yiru Qin et al. created a strategy for creating graphene quantum dots with a mono disperse size distribution.[130–132] The graphene quantum dots were made, through one-pot synthesis, from a graphene source as well as a strong oxidizing mixture at an elevated temperature.[133] Zhihong Chen et al. formulated an unique electronic gadget consisting of an insulator (with graphene derivatives), a local first gate inserted in the insulator with a top surface of the first gate becoming noticeably coplanar with a surface of the insulator, a first dielectric layer created over the first gate channel, insulator, along with a channel.[134] Michael Scott Arnold et al. developed graphene nanoribbon arrays, ways of developing graphene nanoribbon arrays as well as electronic and photonic gadgets. The graphene nanoribbons in the arrays were created via a scalable, bottom-up, CVD approach.[135] Recently, Hyoyoung Lee invented an approach for generating reduced graphene oxide. The procedure for creating reduced graphene oxide entailed the forming a graphene oxide-dispersed solution consisting of graphene oxide along with a surfactant that encompassed at least two aromatic functional groups.[136] Byung Jin Cho et al. invented a technique of production of N-doped graphene and consequently an electrical component by utilizing ammonium fluoride.[137] Aruna Zhamu et al. invented a nano-graphene enhanced particulates in a lithium-ion battery in the role of an anode active material (as an solid electrode).[137] A lithium-ion battery containing an anode having these types of grapheneenhanced particulates shows a stable charge-discharge cycling response, an excellent specific capacity per unit mass, substantial first-cycle efficiency, a good capacity per electrode volume, and a prolonged cycle life.[138] In further development, Aruna Zhamuet al. built a way of making an integral 3D graphene-carbon hybrid by a) blending multiple particles of a graphitic material and also multiple particles of a solid polymer, b) transferring the graphene sheets to surfaces of solid polymer carrier material particles to generate graphene-coated polymer particles, c) conversion of graphene-coated polymer particles into a preferred pattern of graphene-polymer composite structure, d) pyrolyzing the pattern of graphene-polymer composite structure.[139] Aruna Zhamu et al. developed a lithium-ion battery anode layer, consisting of an anode active material inserted in pores of a solid graphene foam comprised of multiple pores and pore walls.[140] Stuart D. Hellringet et al. introduced lithium-ion battery electrodes, which include graphenic carbon particles. The application of graphenic carbon particles in the cathodes leads to enhanced overall performance of the lithium-ion batteries.[141] Perforated graphene sheets can be employed in developing separation membranes. Separation membranes are used in gas separation methods. Procedures for separating a gas mixture include physical contact of a gas mixture with the separation membranes. Steven W. Sinton et al. introduced separation membranes having graphene.[142] Alexander A. Baland in designed a graphene sensor and also technique for particular

framework to shield electromagnetic radiation is composed a thin layer of graphene, as well as the flexible substrate, was developed by Phaedon Avouris et al.[121] To take into account the impact of chemicals on the environment, Aruna Zhamu et al. developed a technique of generating graphene materials, which include pristine graphene, graphene oxide, graphene fluoride, together with functionalized graphene.[121] The technique had an inter-graphene expansion, intercalation, exfoliation, in addition to separation of graphene sheets in a single step, which significantly reduce the time to develop graphene and considerably minimize the quantities of chemicals applied.[122] Combinations as well as procedures for polishing, hardening, protecting, and lubricating moving and stationary components in equipment and systems for engines, turbos, turbines, tracks, races, wheels, bearings, gear systems, armour, heat shields, as well as other physical and mechanical systems is very important aspect for machine component life.[121–122] Richard S. Shankman conceived strategies for in situ synthesis of graphene, graphene oxide, reduced graphene oxide, supplementary graphene derivative arrangements and nanoparticles for nano-polishing ingredients.[123] David Joseph Burton et al. developed a procedure for generating graphene materials, such as virgin graphene, graphene oxide, graphene halogenide, hydrogenated graphene, nitrogenated graphene, and also functionalized graphene.[124] A graphene/nano filament-based hybrid film with a pair of exceptional optical transparency as well as superior electrical conductivity was accomplished for transparent conductive electrodes for the solar cell, photo-detector, lightemitting diode, touch screen, in addition to display device applications.[125] A graphene, in addition to doped graphene sheets designed to reflect and/or absorb the electromagnetic waves influenced by the amount of dopant was achieved.[126] A graphene-based heat dissipation framework for an electronic gadget was formulated by Aruna Zhamu et al.[127] The integrated graphene film, either a graphene film was obtained from a graphene oxide gel or a graphene composite film was formed of graphene oxide gel-bonded nano graphene platelets. This system exhibits highest thermal conductivity and highest effectiveness in reducing hot spots in various kinds of display devices. This kind of graphene film-enhanced display device, was invented by Mingchao Wang et al.[128] An approach for forming an extremely oriented graphitic film, comprise of GO or chemically functionalized graphene (CFG) dispersed in a liquid to create a liquid crystal phase was formulated by Aruna Zhamu et al.[129] Aruna Zhamu et al. developed a procedure for constructing a supercapacitor electrode. This method contributes to a supercapacitor possessing a large electrode thickness, excessive active mass inserting, higher tap density, and outstanding energy density.[130] She has found that an integrated graphene system is appropriate for basically all electrolytes generally employed in batteries as well as for the other energy storage devices. Aruna Zhamu et al. manufactured a unitary graphene-based current collector in batteries or even capacitor.[131] A field effect transistor-based radiation sensor (graphene based) to apply in a range of radiation identification purposes, such as manned spaceflight missions. Mary J. Li et al. created a graphene field effect transistor-based radiation sensor. The ChemNanoMat 2018, 4, 1 – 24

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sensing of vapors, gases as well as biological agents.[141–142] The graphene sensor includes a substrate; a dielectric substrate on an upper layer of the substrate; a layer of graphene on an upper layer of the dielectric substrate, a source and drain contact on an uppermost surface of the graphene layer.[143] In the same way, a touch screens comprising one or more graphene layers was invented.[144] Zhenning Yu et al. designed a flexible, asymmetric electrochemical cell for the various applications. This asymmetric supercapacitor cells with distinct nano graphene platelets -based electrodes display an extraordinarily high capacitance, specific energy, as well as stable as well as prolonged cycle life.[145] The patents and technologies are products of fundamental scientific research.[145] Thus, through this review article, we want to give many thanks as well as heartiest congratulations to top most innovative modern scientist working on graphene and interrelated 2D nano materials around the globe (Table 5).[146] The hard works of

graphene.[147] The strategy intended to encourage high-risk scientific studies in the area of high technologies. Almost all the estimated discoveries are going to be an invention in Cloud Computing as well as the Internet of Stuff. Nokia, that is an important part of the Graphene Flagship Consortium and also owned by Microsoft company, was the Corporation to collect the above-mentioned grant from the FET.[148] So, this supermaterial which can, in fact, offer an innovative concept as well as worth to anything that advanced extraordinary technologies own nowadays.[148] Graphene, in comparison with silicone (the present leader of electronic devices but we hope next is graphene and its derivatives), graphene doesn’t have an “energy gap”, and therefore cannot be switched on/off. Latest scientific studies in the area are going to undoubtedly provide brand new opportunities for advanced technology concerning all spheres of work as well as life. In the near future, we may receive an amazing possibility to have remarkably thinner high tech products with incomparable potentials.[149] This may be correct for super-light conductors together with exceptionally powerful world’s processors.[148] Graphene market size was evaluated over USD 20 million in 2016 along with the industry will increase by a compound annual growth rate (CAGR) of around 35% up to 2024 (Figure 8).[150] As above mentioned, graphene is a transparent 2D carbon allotrope that was figured out in 2004.[151] It is an excellent electrical and also thermal conductor which is considered to be 200 times stronger in comparison with steel. Products capabilities which include high electron mobility, permeability and also heat resistance has triggered its increasing application in flexible radio frequency gadgets, electronic components, supercapacitors, sensors, conductive inks, coatings, composites, and so forth.[152] Because its invention, the range of scientific studies literature on the goods has raised from over 125 in 2005 to higher than 9000 in 2013. The worldwide graphene market is estimated to achieve USD 278.47 Million by 2020, with a rate of 42.8% from 2015 to 2020.[150] The graphene marketplace in Asia-Pacific is expected to record the most rapid growth rate on the globe.[153] This is principally related to the high economic growth rate, increasing production industrial sectors, low-cost labor, and also raising graphene-based application patents.[153–154] In addition, the participation of leading research institutes-industry collaborations for graphene R&D efforts is couple of aspects resulting in the development of graphene within this place in the growing economies, for example, China, India, and Japan.[155–156] China is the key contributor in addition to the primary source of graphite together with other materials employed for graphene extraction to the graphene marketplace in Asia-Pacific.[156] The prominence of China considering graphene in the location is owing to its swiftly growing cross-industry collaborations, moreover, key R&D activities for the commercialization as well as the deployment of graphene is being implemented by a number of educational institutions as well as research institutes.[156–157] North America is covered topmost share in 2014 which is supposed to continue topmost throughout 2015– 2021, as shown in (Figure 9).[155,157]

Table 5. All-time top ten (based on published articles and patents) scientist/inventors working on graphene around the globe and their current affiliation (Scopus and Web Science database). S.N

Scientist

Present Affiliation

1.

Takashi Taniguchi

2.

5.

Kenji Watanabe Rodney S. Ruoff Franc¸ois Maria Peeters Martin Pumera

6.

K. S. Novoselov

7.

Xinliang Feng

8. 9.

Pulickel M. Ajayan Taiichi Otsuji

10.

Klus Mllen

National Institute for Materials Science Tsukuba, Research Center for Functional Materials, Tsukuba, Japan National Institute for Materials Science Tsukuba, Advanced Materials Laboratory, Tsukuba, Japan Institute for Basic Science, Center for Multidimensional Carbon Materials, Daejeon, South Korea Universiteit Antwerpen, Department of Physics, Antwerpen, Belgium Nanyang Technological University, School of Physical and Mathematical Sciences, Singapore City, Singapore University of Manchester, School of Physics and Astronomy, Manchester, United Kingdom Technische Universitat Dresden, Department of Chemistry and Food Chemistry, Dresden, Germany Rice University, Department of Materials Science and NanoEngineering, Houston, United States Tohoku University, Research Institute of Electrical Communication, Sendai, Japan Max Planck Institute for Polymer Research, Mainz, Germany

3. 4.

these scientists are behind the mentioned groundbreaking patents and technological innovation that now really exist in our real world.[146]

6. Graphene Market by Product: Status and Prospect Due to the vast applications many manufacturing hubs and small industries related to the graphene production are raising day by day.[147] In 2013, the European Union’s Future together with Emerging Technologies (FET) declared its $1.3 billion grant for the same.[146–147] The objective of the program was to improve innovative technological alternatives influenced by ChemNanoMat 2018, 4, 1 – 24

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Table 6. Ten key research works responsible for the real rise of graphene nanotechnology. Years 1985

1986

1986– 95

1998

1999

2002

2004

2004

2005– 8 2007

2007

2010

2010– 17

Remarkable achievement

Scientist(s)

Resing et al. pointed out graphene planes present in the different carbon materials (Pyrolytic graphite, charcoal and highly graphitized carbon fiber) and showed different kind of 13C-NMR spectrum (Figure 3). This work was a direct information about the spacing between the two adjacent layers in graphitic materials. This study also provides clue about the magnetic properties of graphene planes with respect to their orientation. However, H. A. Resing et al. did not focus much on the same. Gaier provided a very strong support about the effect of orientation of graphene planes on the intercalation (on the basis of bromination reaction dynamics). This work indirectly presented a link between thickness and size of graphitic layers with rate of bromination reaction. During this period nearly 35 original research papers were published related to the intercalation of different small molecules between the graphitic layers. It seemed that during 90s scientist were trying much for the single layer of graphene than ever. We assume it was golden period for the carbon based nano allotropes. In the same period Iijima established reality of single wall carbon nanotubes (CNTs). The discovery of (fullerenes (1985–1990) and CNT seems to diminish somehow the growth of graphene research which can be seen in the Figure 2. Andersson published a unique work on graphitic nanoparticles. In this article he discussed molecular structure and electronic majesty of graphite nanoparticles produced by heat treating of diamond nanoparticles. This article again attracted researcher’s attention on graphene instead of CNTs. For the graphite nanoparticles they pointed out that the Fermi energy has an extra band superimposed on the bonding p and antibonding p* bands around the Fermi energy region. Ruoff et al. developed micromechanical approach for the production of graphene. In this work they reported partially exfoliated monolayers of carbon lamellae. We assume that it was first great idea to produce pure graphene layer using lithographic technique. B. Z. Jang et al. filed one of the initial US Patents related to the production of graphene. This invention was related to the production of nano scaled graphene, and a procedure for producing the mono/few layer graphene. However, this patent was granted in 2006 only. A. Geim, S. Novoselov and co-workers first isolated well characterized single layer graphene via Scotch tape method (a mechanical approach) in 2004. This was the first time in graphene history when a group of scientists compared properties of single layer pristine graphene theoretically and experimentally. In the Scotch tape technique Geim et al. pulled monolayer graphene from bulk graphite and relocated instantly them on thin silicon dioxide onto a silicon wafer. They used SiO2 which very easily electrically isolated the single graphitic sheets and weakly interacted with it, providing approximately charge-neutral graphene layers. Therefore they used SiO2 as a back gate electrode to vary charge density in the pristine graphene over a wide range. In the same year C. Berger et al. on the basis of his study predicted novelty of graphene as a potential candidate for electronic device applications. They found that graphene exhibits Shubnikov-de Haas oscillations that correspond to nonlinearities observed in the Hall resistance, indicating a potential new quantum Hall phenomenon. It was one of the few first fundamental works on graphene showing its brilliant utility for the next generation electronic device. In this period KS Novoselov and AK Geim performed a series of exceptional work on graphene especially on its electronic properties, gas of massless Dirac fermions and on Raman spectrum of graphene. I.W. Frank et al. reported exceptional mechanical properties of suspended nano graphene sheets using AFM instrument. This articles attracted researchers for the use of graphene in various composites where mechanical stability is needed in priority. In the same year S. Stankovich of Ruoff’s research groups reported a very efficient method for the scalable reduced graphene oxide production. We are treating this work as the one opening the mind of researcher for the bulk amount graphene synthesis via chemical routes. Marcano et al. developed a quite impressive method for bulk amount GO synthesis by removing the sodium nitrate, increasing the amount of KMnO4, and carrying out the reaction in a 9 : 1 mixture of conc. sulfuric acid and ortho phosphoric acid enhancing the effectiveness of the oxidation procedure. This alteration provided a greater amount of hydrophilic oxidized graphene material as compared to conventional methods. They stated that improved synthesis of GO can be important for gram scale synthesis of GO as well as the fabrication of devices containing of GO. In this period many outstanding work regarding the bulk amount of graphene production and their applications in different filed were carried out. Few notable one are cited here for the further reading (Table 3).

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J. R Gaier, NASA

[48–55]



O. E. Andersson Japan

R. S. Ruoff et al., USA

Jang et al., Nanotek Instruments, Inc. A. Geim et al., UK

C. Berger, USA

A. K. Geim et al. I. W. Frank et al.

S.Stankovich et al. USA DC Marcano et al. USA



[58]

[56]

[59–60]

[61]

[62&ESI]*

[63]

ESI* [64]

[65]

[66]

[67–72]

which is anticipated to achieve by a CAGR of 34.3%.[158] Monolayer graphene is applied in the role of atomic scaffolding to produce supplementary materials (Figure 10). Columbia University experts are in a position to produce mono-layer graphene filters of five-nanometer pore dimension.[158–159] Bi-layer graphene material features such as a semiconductor and also are employed in sensors in which offers excellent sensitivity, beneficial repeatability, swiftly response as well as stable specificity.[159] Raising investigation & development with this product group will probably boost its utility in a variety of areas

This may augment the graphene market development from 2013 to 2024 because it is going to improve product functionality in different industrial sectors.[157] The worldwide graphene market is classified into four main goods sectors such as graphene oxide, graphene nano platelets, and mono/ bi layer graphene, in addition to other goods including few-layer graphene as well as multi-layer graphene. Graphene nano platelets are the main item segment which accounted for much more than 30% of the total business in 2016. Mono-layer & bilayer graphene item market of the worldwide graphene market subscribed an income of greater than USD 2.4 million in 2016 ChemNanoMat 2018, 4, 1 – 24

H. A. Resing et al. USA

Ref. [57]

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Figure 8. Present status and future expectation about global graphene market, 2014–2022.[153]

Applied Graphene Materials plc, AMO Gmbh, Graphenea S.A., Graphene Laboratories, Inc., XG Sciences, Inc., Grafoid Inc., Angstron Materials, Inc., and Graphene Frontiers LLC and so on.[167–168] The market place for the GO is much better that the pure GR and reduced graphene oxide and it is very clear from the Figure 10. This trend is due to the easy production and variety of applications of GO.[169–171] For example GO has been used extensively for the polymer composites as nanofiller for energy storage, for biomedical application, for water purifications, for drug delivery, for the fabrication of flexible insulators and many more.[168–171] But pure graphene have fewer applications in comparison to GO. In addition to this production of pure GR in bulk amount is very tedious and expensive and this is why GO have much global popularity.[169–171] It is interesting to note we can produce very high quality of GO in a very ordinary lab through chemical exfoliation and after reduction we can produce rGO but we can’t produce pristine single layer GR without any defects in an ordinary lab. These things again make GO much adorable for the scientists in contrast to GR.[77–78,83] Graphene Oxide also referred to as GO, is the most significant derivative of the graphene and has a big current market value. It possesses huge amount of oxygen functional groups, which make it very suitable candidate for dispersibility in water along with other organic solvents.[169–171] However, due to the superior electrical conductivity and very high surface area, pure graphene (GR) and reduced graphene oxide are commonly used in electronic gadgets. On other hand due to the special surface morphology, GO is very frequently used as catalytic oxidation, biotechnology, and also in the role of a surfactant in commercial applications.[172] In North America, GO is the major element, because of its low price, effortless manufacturing operation, and also accessibility to huge production features in comparison with other forms of graphene.[167–168] The energy application is the fastest growing

which is able to drive the worldwide market in the course of predicted time as shown in Figure 10. The current worldwide graphene market is grouped into six client groups such as electronic devices, automobile, aerospace & security, medical care, energy, while others including coating inks, water filtrations, and so on, as shown in Figure 11.[159–166] Electronic components were the most important client market and also accounted for greater than 30% of the total graphene business in 2016. Automobile client market accounted for nearly 20% of the worldwide graphene business in 2016.[158,167] The worldwide graphene business is substantially fragmented as a result of the existence of several companies that produce the merchandise. The best participants in the market consist of

Figure 9. Schematic presentation of countries in global graphene manufacturing.[157] ChemNanoMat 2018, 4, 1 – 24

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Figure 10. Global graphene market by product.[158]

together with inexpensive graphene-based materials for several applications. Accordingly, world graphene sector is forecasted to achieve 151.3 million dollars by 2021. Energy storage application is recognized as one of the one of most developing areas for the graphene consumption.[168,174] From the market scenario discussion, it is very clear that graphene has tremendous potential to be a leader of nanomaterials and also for many real times applications. However, the challenge for the graphene is its band gap, bulk production of free standing graphene and their applications without any substrate. Thus we can say the foremost problem; we must overcome is up-scaling GR and rGO production along with challenge which lies in conserving the high quality during the bulk production as well. Materials scientist around the world are working hard for the same and optimistic for the possible solutions to push graphene research from the patents to the common people. According to authors viewpoints there is need of further intense research to make graphene technologies cheaper and affordable. The present technologies and methods were used for graphene related patents either very costly or not suitable for the commercial applications. So, in one sentence we can say; there is need of affordable technologies and we are hoping within 5 years most of graphene products will be in market. The more about graphene limitations is discussed in the next sections.

Figure 11. Global market of graphene in the different industrial sectors.

sector for graphene in addition to this trend is estimated to maintain over time in consideration of the accelerating requirement of light and portable, flexible, and alternative innovative materials with durability and long life.[158,167] In Asia-Pacific, the energy sector is the third-largest customer of graphene. The raising requirement of cost-efficient energy-storage materials, lithium ion (Li-ion) batteries, and advancement of ultra-efficient solar panels are the important aspects of the development of the graphene-based energy sector in the Asia-Pacific graphene industries.[168] The worldwide graphene industry is a spread and unorganized marketplace due to the sheer number of manufacturers as well as customers around the world. Additionally, the rising competition among the competitors to receive the largest number of the patents for graphene-based applications has performed a significant role in increasing the degree of rivalry.[158] Leading competitors, for example, CVD Equipment Corporation (U.S.), Haydale Graphene Industries Plc. (U.K.) and also research institutions such as the University of Manchester (U.K.), and University of Waterloo (Canada) have implemented a variety of organic as well as inorganic developmental techniques. These types of techniques majorly consist of merger & acquisitions, joint ventures, contracts & collaborations, and product innovations to accomplish growth in the graphene sector.[173] They primarily concentrate on offering good quality ChemNanoMat 2018, 4, 1 – 24

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7. Limitations of Graphene As we knew the graphene’s beehive-shaped molecular structure provides it strength and flexibility along with the capability to conduct heat as well as electricity effectively.[175] Though graphene, offers outstanding strength, great flexibility, light in weight in and excellent conductivity but it also have a variety of complications that have to be resolved before its various real applications.[176] Because, excellent quality graphene is a costly material, due to the fact manufacturers cannot presently provide graphene in bulk amount. Because the majority of graphene consist at least a defects, its particular strength is probably to be considerably less than the inherent strength of

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Consequently, throughout the development of the Stone-Wales defects, absolutely no atoms are usually eliminated or even included. The defects are basically produced due to the reconstruction of the graphene lattice.[184] For example, four hexagons are converted into two pentagon-heptagon pairs (two pairs of imperfections or Stone-Wales defects) by revolving the C C bond 908, as presented in Figure 12a.[185] An additional basic defect type is a vacancy, a losing atom in the graphene lattice (Figure 12b and c). The mono- and also di-vacancies are experimentally visualized as well as identified for the graphene systems. When thinking about a stable graphene with an ideal carbon lattice, each and every carbon atom is coordinated to three different carbon atoms.[186] When numerous atoms are absent from the perfect graphene lattice, the defect structure can turn out to be more complex, along with the graphene can be energetically unstable. When the variety of absent atoms is even, the carbon atoms are completely reconstructed, eventually resulting in no dangling bonds. By difference, in the event that an odd number of atoms are omitted, there may be dangling bonds that make the graphene additional unstable as well as reactive.[187] These types of dangling bonds can be applied as helpful sites to dope with impurities or even functionalize with distinct atoms or perhaps molecules for supplementary applications.[187–188] The alignment of mono- and also di-vacancy arrangements in graphene can create one-dimensional imperfections (Figure 12d), which is a line defect.[188] These types of line defects are borders splitting up two independent domains of the various lattice orientation (Figure 12e), which often seems in graphene produced on metal surfaces because of its concurrent nucleation at various regions.[189] The line defects comparable to grain boundaries in graphene may seem if two grains with

a perfect sheet of the atom-thick carbon material. The investigations render a more intense perception of how imperfections are going to influence the handling, processing as well as fabrication of the materials.[177] In another exploration, scientists additionally analyzed the drawbacks of graphene in real-world situations. The bonds between carbons atoms are recognized to be the most effective in character, also it entails that a perfect sheet of graphene would certainly show this property. However, in real times utilizations, graphene sheets do not reside about their theoretical certainty.[178] Typically, experts manufacture graphene via the “Scotch Tape” technique, wherein they use sticky tape to peel off layers of graphite until definitely a layer with the thickness of one atom is piled, however, this laborious method generates only limited quantities of graphene as mentioned in the previous section.[179] The researchers measured the fracture toughness of graphene, they found the brittle nature of graphene sheets [180]. In contrast to imperfections in bulk materials which have a dissimilar dimensionality (say 0-D, 1-D, 2-D and 3-D), graphene carries decreased dimensionality, which diminishes the variety of possible defects which is, point defects, line defects as well as imperfection in grain boundaries.[178] Due to the sp2-hybridizing character of the graphene which enables the attachment of a different variety of closest neighbor carbons, the carbon atoms themselves are able to develop various polygon arrangements, mostly in hexagons but also inform pentagons, heptagons as well as octagons.[181–182] This characteristic of graphene contributes to the development of non-hexagonal arrangements of carbon, which is, the most basic point defects (often called as Stone-Wales imperfections).[183] The Stone-Wales imperfections are a result of C C bond rotation that enables carbon polygons to turn between pentagons, hexagons as well as heptagons.

Figure 12. Limitations of graphene and their derivatives in term of recently discovered defects. (a) Stone-Wale type defect in graphene, (b) mono-vacancy in graphene sheets, (c) di-vacancy in pristine graphene layers, (d) line defect formed by aligned vacancy structures in graphene, (e) grain boundary mapping of polycrystalline CVD graphene, (f) flaw generated by partial surface coverage of the CVD graphene, (g) macroscopic defect created in graphene layers during the transfer processes (Reproduced with permission from Ref. [192] Copyright 2018 Elsevier). ChemNanoMat 2018, 4, 1 – 24

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various orientations coalesce.[188–189] It has been found that line defect in graphene demised badly electronic and mechanical properties of graphene sheets.[189] Usually, graphene domains produced through CVD, develop nontrivial shapes, which mostly rely on the growth situations and can be hardly expected in advance.[190] Consequently, in some instances, graphene grown on metal surface demonstrates only limited surface coverage and therefore with growing several areas which overlaps as well as small gaps (Figure 12f). Furthermore, graphene is generally affected and also torn in the course of the transfer process, which may produce macroscopic imperfections and consequently efficiency of the fabricated devices (Figure 12g).[177] On a molecular level, the band gap is the minimal level of energy needed for an electron to escape.[191] As soon as it happens, the electron is able to take part in conduction.[191] Due to the lack of a band gap, the electrons in graphene movement continuously, resulting graphene to behave the same as a metal in comparison with a semiconductor.[191] In contrast to metals, semiconductors provide on/off switching behavior. The band gap hinders scientists from managing electron flow and consequently employing graphene in transistors as an important element of electronic products.[192–193] Graphene-based transistors can operate at speeds a hundred to one thousand times swifter than silicon transistors. However, the band structure of graphene is its one of the most important drawback in comparison with the silicon chips.[192–193] In contrast to silicon that is switched off graphene persists to a considerable amount of electrons flow during its “off” condition.[194] A chip composed of billions of this kind of transistors are going to waste a huge quantity of energy thereby be unrealistic. But, it may be achievable to significantly enhance these on/off ratios by carving graphene sheets into extremely narrow ribbons just a couple of nanometers wide.[192,194] There had already been earlier confirmation promoting these types of concepts from researchers, nevertheless, the ratios developed were still much lesser than those in silicon and their analogs.[194] More suitable lithography techniques are established to design these sheets into slim ribbons and also circuits; this may offer an effective method of producing sophisticated graphene-based electronics.[195] Perfect graphene may be employed to develop a quantum computer which may hold infinitely faster computer speed.[195–196] However it must be systematically of high purity, therefore, the entire level of chemistry may possibly be complicated. This can direct to more attention in establishing graphene for next-generation computers.[196] In order to analyze thermal conductivity, the thickness of graphene on a substrate is increased, thermal conductivity is an essential asset as electronics elements go to the nanoscale.[195] When graphene is within its perfect state (freely placed in a vacuum without any substrate), it provides outstanding thermal conductivity. Whenever we produce devices making use of graphene, we need to support the graphene on a substrate and also accomplishing this; this inhibits the high thermal conductivity of graphene.[197] The heat transfer, as well as its administration is a significant issue for any technological innovation that relates to high power together with compact ChemNanoMat 2018, 4, 1 – 24

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size in the presence of graphene.[197] Increasing energy requirements, accuracy manufacturing, miniaturization, nuclear police as well as crucial economies request extreme efficient coolants and also lubricants. Application of nanofluids to deal with these problems has been topic of great interest by the several researchers all over the world. Oftentimes, a nanofluid is formed to suit a specific requirement which enables it to work as a flexible cooling approach, customizing to the demands of a particular system.[198] Basically, some nanofluids hold the potency to turn into a very smart and efficient coolant. The heat transfer functions straightly or other way influence people’s everyday life and call for an extra investigation in an effort to enhance their efficiencies. Together with an improvement in manufacturing strategies, the goods which have a compact size, excessive heat flux and also non-uniform heat flux have engaged a considerable part in several sectors. Additionally, with minimum thermal conductivity and also the high viscosity of typical heat transfer fluids consisting of water, ethylene glycol ammonia, and also mineral oil are the primary concerns in heat transfer applications.[199] The convective thermal effectiveness was frequently ineffective and added obstacles in developing compact heat rejecting equipment. Therefore, a modern coolant such as nanofluid with enhanced heat transfer characteristics is preferred over the traditional coolants.[199] Benefits of graphene nanofluids over supplementary nanofluids are advantages of graphene nanofluids over other nanofluids are longer suspension time period greater thermal conductivity, lesser erosion, corrosion as well as clogging, for working power, decrease in the stock of heat transfer fluid, considerable energy efficient.[200] Drawbacks of graphene nanofluids with regards to alternative nanofluids are substantial Processing expense, agglomeration at more pH value as well as at high temperatures due to the potential of the particle to conquer thermal energy hurdle resulting in an intensification in Van der Waals forces and therefore leading to decrease of conductivity, application of surfactants for stability which leads to reducing of conductivity because of the creation of a thermal boundary layer around the particles.[201] The two primary strategies presently have been applied in water filtration: 1) multi-stage flash distillation, which flashes heats a segment of the water into steam via a number of heat exchanges, 2) reverse osmosis, which employs a high-pressure pump to force seawater through reverse osmosis membranes to eliminate ions as well as contaminants from drinkable water, possess a number of crucial problems.[202] Present desalination strategies are energy demanding and also generate unfavourable environmental consequence. Aside from that, energy generation burns up large volumes of water and consequently produces wastewater that ought to be handled with added energy input.[200] Graphene oxide membranes exhibit assure the role of a comparatively affordable substitute, and also water conveniently flows through them, salts will not. Nevertheless, if immersed in water on large-scale, graphene oxide membranes are likely to rapidly swell.[203] As soon as swollen, the membranes not only water to go through but additionally sodium as well as magnesium ions, reducing the efficiency of

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electricity.[209–201] Graphene will probably be a vital material in the future of electronic components as well as large-scale energy storage.[211–212] The main limitations with graphene and their derivatives pointwise summarized below for the sake of convenience of reader: i. Graphene produced via chemical methods have very limited applications because of various defects.[71–72] ii. Zero band gap: Graphene is an excellent conductor of electricity, but it doesn’t have a specific band structure. Researchers around the globe are working to resolve the same.[191–193] iii. Scalable synthesis of single layer graphene is still a big issue, which is a main obstacle for the commercial products of graphene.[69–72] iv. Producing defect free large area graphene is very difficult (because larger the layer, the greater will be probability of defects.) and costly and not possible in an ordinarily labs and therefore results currently in low number of commercial products.[71–72] v. Graphene as a catalyst is much susceptible to the oxidative environments and therefore it is not a good candidate for drugs and pharmaceuticals industries.[206] vi. Very recently researchers have confirmed that graphene displays some toxic potentials. This again make it a bad candidate for the biological applications. vii. It has been confirmed that graphene in its ideal state (freely suspended in a vacuum) shows amazing thermal conductivity. However, when one wants to produce a device using graphene, then you have to support the graphene on a template and doing so greatly overpowers the actual thermal conductivity of graphene. In this way use of graphene for the real times applications without substrate is a big issue.[206] viii. Restacking of pristine graphene in polymer matrices is also a drawback for the production of high quality graphene based composites.

the purification. However, Rahul Nair together with his coworkers invented that by putting walls composed of epoxy resin on both sides of the graphene oxide, they are able to prevent the expansion by minimizing the membranes with resin.[204] Claims by Nair et al., Kim et al. and Li et al. on gas as well as vapour transportation throughout GO membrane has been viewed as most important technical contributions to the science and technology of membranes.[205] The framework of the GO membranes is altered to modify the pore size or even the interlayer spacing between the GO layers to employ this kind of membranes for realistic applications. The crucial criteria for example durability as well as constancy of membranes require enhancement for practical functionality. The membranes using single layers with good quality purification characteristics and also boosted water flow are supported by issues linked to durability, scalability as well as reproducibility.[206] While the multilayer dependent membranes have the potency for effective utilization under fixed thickness, however, the practical application may have certain restrictions linked to the thermal stability of GO due to presence of oxygen functional groups.[206] The primary drawback of pristine graphene in the role of a catalyst is its susceptibility to oxidative conditions. Studies have confirmed that graphene shows certain toxic features as well. Researchers have shown that graphene capabilities sharp edges which can easily pierce cellular membranes, which enables it to insert the cell and consequently interrupt regular functions.[207–208] As it is very thin and also light in weight, it can be produced into a paper-like material and consequently can be employed to produce flexible or even rollable batteries. But production of large area big graphene paper is quite expensive and therefore further innovation is necessary. Graphene may also be employed to create solar panels due to its good conductivity but cost and optimization still a big issue for the commercialization. In spite of its several satisfactory aspects, the most significant problem for graphene-based supercapacitors and batteries is the fact that there are absolutely no mass production strategies of good quality batteries right now.[209–210] The expense of manufacturing ranges from tens to thousands of dollars per kilogram, that is considerably more than the expense of developing activated carbon. Furthermore, the thickness of graphene-based materials is usually restricted to micrometers which restricts the total battery capacity considerably.[211] Researchers have reported 3D interconnected foam arrangements of graphene and ultrathin graphite, and even hexagonal boron nitride that have a crystal structure identical to graphene. Germanane is an additional material that exhibits assure to be used in electronics or thermoelectric energy conversion products.[212] Although, graphene provides amazing attributes as well as powerful properties, more deeply research is needed to figureout the practical functionality of this material. Mass production methods continue to be a high concern of research if graphene can actually be viewed for industrial applications. In the future, composite materials may be the most positive application prospect for graphene. Researchers have confirmed that mixing small amounts of graphene with polymers are able to produce tough, light and portable materials that provide ChemNanoMat 2018, 4, 1 – 24

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8. Conclusion and Viewpoints In this short focus review, authors have summarized the current advancements in the graphene and related materials in term of selected US patents granted during the years 2004–2017 in different arena of industrializations. To evaluate the performance of graphene based materials and their marketplace for different applications and also for the fabrication for next generation devices, we have presented year wise advancement in graphene based nanotechnology since 2004 to 2017 where required. In this article, we have decorated contribution of top twenty researchers working on graphene based 2D materials around the globe along with contribution of top ten counties for the graphene nanoscience. For the readers convenience we have collected titles of widely recognized research article for the bulk amount of graphene/graphene oxide in the last section of this review article. Moreover, the most of the key achievement and role of prominent researchers related to the

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Keywords: commercialization of graphene · graphene · graphene oxide · graphite oxide · history of graphene · carbon nanomaterials

graphene nanotechnology has also been added in this article as prehistory. At present graphene and interrelated materials have been appealing much consideration as an emerging 2D, layered nanostructure in the fields of nanoscience, nanotechnology material science, chemistry, biomedical engineering, and physics owing to their tunable physical properties especially mechanical properties, very high surface area, noteworthy electronic and thermal properties, as well as easy functionalization. The graphene nanotechnology have shown tremendous real time applications in nanoelectronics, bioimaging and nanomedicines. Graphene and their derivatives have revealed brilliant interface and adhesive properties for mammalian cells, protein and microbials, which make graphene based nanocomposites for the next generation multifunctional bioengineering applications. However, cost effective pure graphene separation still suffers with some shortcomings therefore much easier route for graphene production is still a matter of deep consideration. The stability and interactions of graphene and their derivatives in in vivo and in vitro conditions is one of the most challenging tasks for the researchers working on different aspects of graphene. And to solve such challenging issues scientists are working continuously around the globe. Though graphene and their derivatives showed very high competency in the aforementioned branches of science and technologies, a big funding and time is required from the governments and industries for the further research to utilize full potential of graphene for tissue engineering, bioimaging, optoelectronics, frequency multiplier, Hall effect sensors, conductive ink, spintronics, ultraviolet lens, charge conductor, thermo-electrics, condenser coating, radio wave absorption, catalyst, sound transducers, waterproof coating, coolant additive, structural material nanoantennas and piezoelectric application. To solve funding problems, govt. organizations of different countries are showing very positive interest. For example, Department of Science and Technology (DST), India, a main competent authority for scientific development and innovations funding of India, asked recently for definite proposals of main challenging topics to be addressed through nanoscience and technology.

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Acknowledgement Authors are very grateful to scientific communities cited directly or indirectly in this review. The first authors Dr. Santosh K. Tiwari is very grateful to Prof. G.C.Nayak of Dept. of Applied Chemistry, IIT (ISM) Dhanbad, India for his cooperation and help during the preparation of this article. We are also very grateful to Scopus and Web Science database for the various statistical information regarding the published research articles and patents.

Conflict of Interest The authors declare no conflict of interest. ChemNanoMat 2018, 4, 1 – 24

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Manuscript received: February 28, 2018 Version of record online: &&&, &&&&

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FOCUS REVIEW The big picture for a small material: The capabilities of graphene in a variety of realistic applications are evaluated based on approved US patents. The primary drawbacks of graphene that hinder the commercialization of graphene-based products are also discussed along with detailed information about the early history of graphene and its derivatives.

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Carbon Nanomaterials S. K. Tiwari, R. K. Mishra, S. K. Ha, A. Huczko* 1 – 24 Evolution of Graphene Oxide and Graphene: From Imagination to Industrialization

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