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Synthesis of Carbon Nanomaterials from Different Pyrolysis Techniques:

A Review
To cite this article before publication: Muhammad Umer Zahid et al 2018 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/aac05b

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Page 1 of 19 AUTHOR SUBMITTED MANUSCRIPT - MRX2-100442.R3

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Synthesis of Carbon Nanomaterials from Different Pyrolysis Techniques: A

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5 Review
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8 Muhammad Umer Zahida, Erum Pervaiza*, Arshad Hussaina, Muhammad Imran Shahzadb and
9 Muhammad Bilal Khan Niazia

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11 a
Chemical Engineering Department, School of Chemical & Materials Engineering (SCME),
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National University of Sciences & Technology (NUST), Sector H-12, Islamabad 44000, Pakistan
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National Center for Physics (NCP), Islamabad 44000, Pakistan
15 Corresponding Author Email*: erum.pervaiz@scme.nust.edu.pk
16 Tel: +92-51-90855113

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19 Abstract
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21 In the current age, the significance of carbon-based nanomaterials for many applications has
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made the efforts for the facile synthesis methods from abundantly available wastes in a cost-
effective way. Pyrolysis in a broad spectrum is commonly employed for the synthesis of carbon
nanostructures by thermally treating the organic waste. The mechanism of growth of the
nanoparticles determines the functional distribution of nanoparticles based on the growing size,
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30 medium, and physio-chemical properties. Carbon nanomaterial’s growth is a complicated
31 process which is profoundly influenced by temperature, catalyst, and type of precursor.
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33 Nowadays, significant progress has been made in improving nanomaterial’s growth techniques,
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35 opening new paths for commercial production of carbon-based nanomaterials. The most
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promising are the methods involving hydrocarbon-rich organic waste as the feed source. In this
38 review, synthesis of carbon-based nanomaterials, specifically carbon nanotubes (CNTs), Carbon
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40 nanofibers (CNFs) and Graphene (G) are discussed by different pyrolysis techniques.
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42 Furthermore, the review explores recent advancements made in the context of pyrolysis.
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Keywords: carbon nanotubes, Graphene, nanomaterials, pyrolysis, organic waste
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49 1. Introduction
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51 Nanomaterials have revolutionized all major industrial areas, from drug delivery to agriculture
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53 and food industry [1]. Chemical synthesis methods for nanomaterials include emulsion solvent
54 extraction method, double emulsion, evaporation, salting out method, emulsion diffusion
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56 method, and solvent displacement/precipitation method. However, industrial-scale production of
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3 nanomaterials has familiarized a new kind of pollution into the environment. It is highly
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5 desirable to reduce loads of chemical contamination on the environment by developing new and
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7 convenient methods to overcome the drawbacks of chemical techniques while at the same time
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improving the yield, and reducing cost [2].

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10 There are various nanostructures of carbon materials among which fullerenes, graphene, carbon
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12 nanofibers and carbon nanotubes have most important applications [3]. The importance of multi-
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14 wall carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs) have increased by many folds
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due to their remarkable applications in aerospace, transportation, and energy [4-6]. Carbon
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17 nanotubes made up of graphite, are tubular with diameters of nanometer order and are several
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19 micrometers in length [7]. CNFS possess cylindrical structures with different stacking
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21 arrangement of the graphene sheets like stacked platelet, ribbon or herringbone. The main
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difference between CNF and CNT is in hollowness and growth structure, In CNF the graphite
sheets can be parallel to growth axis while in CNTs the graphene sheets are necessarily
perpendicular to growth axis in the form of rolled tubes. CNFs are mostly conductors while
CNT’s can be conductor or semiconductor depending upon the orientation of hexagonal carbon
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29 structure with respect to tube axis which is so-called chirality [8]. These nanostructured materials
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31 possess exceptional properties such as high mechanical strength and high thermal and electrical
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33 conductivity [9, 10]. These properties have promising applications in conductive and high
34 strength composites, energy storage and energy conversion devices, sensors, field emission
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36 displays and radiation sources, direct methanol fuel cells (DMFCs), and various fields such as
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38 biotechnology and nanoelectronic devices, aerospace technology, solar panels, and construction
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industry [11-14]. These materials have also found application in automotive industries for
41 developing highly efficient engines by enhancing the thermal efficiency using carbon
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43 nanostructures [15, 16].
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46 Graphene the two dimensional (2D) is another allotrope of carbon has also attracted a lot of
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attention due to its exceptional properties; finding applications in transistors, thermal
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49 applications, sensors and one of most important is transparent conductive films [17]. Graphene
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51 Oxide (GO) has its importance as it provides a route to the large-scale synthesis of reduced
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53 graphene oxide (RGO) which is a type of graphene. However physical properties of graphene
54 depend upon the method of preparation. With this background, the current review explores one
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3 of the most common, environmentally friendly and promising method, i.e., pyrolysis of
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5 hydrocarbon-rich wastes for synthesizing carbon-based nanomaterials.
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8 2. Production of carbon nanomaterials (CNMs) by different Pyrolysis
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10 Techniques
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13 Pyrolysis is one of the thermochemical processes in which matter is degraded into smaller
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components at a high temperature in the absence of oxygen; it was used to produce valuable
16 fractions from heavy petroleum feedstock’s decades ago. In recent times, this technique has

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18 found renewed attention for its application in the conversion of organic wastes into useful and
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20 advance application products. Several studies have shown that valuable products like char, bio-
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oil and fuel grade pyrolysis gas can be obtained from feeds such as waste tyres [18-24], wheat
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straw [25], sugarcane bagasse [26], waste wood sawdust [27, 28] and rice husk [29]. In some
cases, bio-oil obtained from pyrolysis could be further processed and used in diesel engines [30,
31]. Even greater application of pyrolysis technique was realized once the production of
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advanced application materials such as CNTs was demonstrated [32]. Use of several types of
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30 waste material has been demonstrated for carbon nanomaterials synthesis including styrene
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32 butadiene rubber (SBR) [33]. Although synthesis of carbon-based nanomaterials such as CNT
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was shown as early as 1958 [34], they were truly classified in 1991 by Ijima et al. when they
35 synthesized MWCNTs and Single-wall carbon nanotubes (SWCNTs) using an arc discharge
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37 process [35]. The difference between SWCNT and MWCNT is that SWCNT consists of a single
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tube made of rolled graphene sheets whereas MWCNT consists of multiple tubes in which sheets
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of graphene are arranged in concentric cylinders like in Russian doll model. The possibility of
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42 converting all the products of pyrolysis including black char [36], pre-condensation fumes [37]
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44 and post-condensation gas [38, 39] to carbon-based nanomaterials makes this process even more
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46 promising. Although commercialization of such a process requires further investigation, there are
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47 reports [40-49] about the production of carbon nanotubes by using pyrolysis technique. This
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49 process shows the great benefit regarding the manufacturing of valuable resources from the
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51 waste materials. Unlike the commercial production of CNTs using CVD reaction in which
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mostly methane or acetylene gas is used [50] as feed, this technique is still in developing stage
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54 and is usually a two-stage process. In the first step, precursors for nanomaterials are generated
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56 via pyrolysis while in second stage these precursors are deposited over catalyst usually nickel
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3 [19, 39], iron [51-56], and cobalt [38]. Moreover, these catalysts are deposited over support
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5 material such as alumina; the purpose is to allow enough dispersion of catalyst particles generate
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7 few nanometer size nucleation sites during the growth phase. Many researchers have
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experimentally proved that nucleation sites should be only in few nanometer ranges, in fact, 3-4

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10 nm for SWCNT [57] growth and larger for MWCNT. Additionally, a study carried out by
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12 Acomb et al. [58] showed that iron-based catalyst showed maximum activity for CNT growth
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14 compared with nickel, cobalt, and copper-based catalysts. In this study, low-density polyethylene
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(LDPE) plastic was used as feedstock in a two-stage process; pyrolysis and catalytic chemical
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17 vapor deposition (CCVD). Iron-based catalyst shows greater activity compared with other
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19 catalysts, the main reason for this is that iron produces smallest particles on support surface [54],
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21 furthermore it was reported that support itself also plays an important role. A study carried out
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by Takenaka et. Al. demonstrated that iron supported on alumina showed greater activity as
compared to iron supported on silica. The main explanation for this phenomena was effective to
increase the catalyst size during carbon loading in case of silica support whereas in alumina
support the catalyst size remained same [51]. In research by Mahanandia and team [59] aligned
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29 MWCNT were synthesized in single step pyrolysis and carbon deposition process. This process
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31 was advantageous as it allowed growth of CNTs without using carrier gas and prepared catalyst
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33 particles making the process straightforward. Another study by the same group [60] was
34 conducted to study the effect of temperature on MWCNT growth it was revealed that
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36 temperature had great effect on structure and iron catalyst filled CNTs were obtained at 9500C
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38 while normal CNTs were synthesized at 7000C. The detail of this one step process was discussed
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elsewhere [61]; it was shown that good quality MWCNT’s were obtained after gas phase
41 oxidation and subsequent acid treatment of the as-synthesized material. The process was carried
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43 out in single hot zone quartz tube reactor with 500mm length and 10mm diameter. One end of
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45 the tube was closed while another end was attached to rubber bladder to collect residual reaction
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gases. The whole setup was placed in the furnace.
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49 2.1. Fixed Bed Pyrolysis
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52 Though at commercial scale fluidized bed CCVD reactors are mostly used for CNT growth, at
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54 lab scale, fixed bed proves to be convenient since they can be easily designed and operated while
55 being effortlessly scaled up into fluidized bed operation. There are reports of performing
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3 pyrolysis and nanomaterials growth in a single stage as well as in two stages. Yang [21] and
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5 team performed study on CNTs growth employing two-stage horizontal fixed bed reactor, scrap
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7 tyre rubber was used as feedstock which was placed in pyrolysis section while powdered catalyst
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having composition Co:Mg:Mn:Al; 2.5:0.5:0.5:0.5 was placed in ceramic boat in CCVD section

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10 of horizontal quartz tube reactor, multi-walled carbon nanotubes were successfully synthesized at
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12 650oC which were characterized by Raman spectra and thermogravimetric analysis (TGA). In a
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14 study conducted by Zhang [22] and others, truck tyres along with car tyres were used as
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feedstock in two-stage pyrolysis (CCVD) vertical stainless steel fixed bed reactor which was
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17 externally heated. The process was mostly as stated in the previous study; however, in this case,
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19 nickel-alumina catalyst was used. The authors reported a high yield of hydrogen production up to
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21 68.3 vol% and carbon deposition as high as 14 wt% however; in this case, a large amount of
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amorphous carbon was also produced along with CNTs. In another study by same group
different catalyst were considered for carbon deposition and it was found that Ni/Al 2O3 gave the
highest quality of CNT production along with highest H2 generation as compared with Co/Al2O3,
Cu/Al2O3 and Fe/Al2O3 [23]. Single stage pyrolysis and MWCNTs growth were performed by
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29 Zhu et. Al. [36]. In this study, a fixed bed horizontal tube furnace was used where fresh bamboo
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31 cubes were placed. The reactor was purged with argon then sealed and allowed to heat at
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33 1oC/min heating rate to 1000oC – 1500oC. At a required high temperature between 1000oC –
34 1500oC, argon and ethanol purging was done which also acted as the promoter. It was shown
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36 using TEM images that silicates present in sample played an important role in nucleation and
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38 subsequent growth.
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2.1.1. Fixed Bed Hydrous Pyrolysis
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43 Hydrous Pyrolysis is the name given to pyrolysis process when steam is injected. Multiple
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45 authors had reported a significant increase in quality and yield of CNT when the steam injection
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was employed. The basic principle remains same; pyrolysis is performed to generate precursors
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while they are deposited over the catalyst in the second stage; however, water is injected in the
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50 process either by direct steam injection along with carrier gas or by transferring carrier gas
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52 through water bubbler before pyrolysis section.
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3 Extraordinary ultra-high purity SWCNT forest was grown by a group of Iijima [55] who is also
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5 known as the father of carbon nanotubes. Exceptional growth of SWCNTs was made possible by
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7 the introduction of water vapors to CVD reaction. In this process, ethylene was deposited over
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iron-based catalyst using argon or helium as carrier gas while the controlled amount of water

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10 vapors were also introduced. The effect of water was further studied in another research
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12 conducted by Amama et. Al. [57]; acetylene decomposition was performed over an iron catalyst
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14 in CVD chamber with and without water. It was shown that presence of water greatly enhanced
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CNT growth; moreover, the effect of water presence was also studied in catalyst preparation and
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17 the annealing step. It was demonstrated that presence of water hindered Ostwald ripening a
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19 process in which bigger particles grow at the expense of smaller ones until later are diminished.
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21 As a result, greater numbers of smaller catalyst particles were obtained with narrow size
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distribution; this along with water presence during CVD process helped the super growth of CNT
forest since the presence of water also diminishes amorphous carbon deposits during CVD.
Using this study, several more experiments were conducted to analyze the effect of steam/water
introduction to pyrolysis/CVD process. One such study was carried out by Acomb and team [40].
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29 Three different kinds of plastics for instance like polypropylene (PP), Low-density polyethylene
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31 (LDPE) and polystyrene (PS) were studied in two staged pyrolysis CVD reactor. The pyrolysis
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33 of plastic in nitrogen gas was carried out at 600oC and produced gaseous stream was then passed
34 over nickel-alumina catalyst at 800oC. Steam was injected at different rates to observe the effect
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36 of it. It was demonstrated that filamentous carbon deposits decreased by increasing steam
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38 injection rate. Results showed that LDPE had the highest carbon yield with 0g/h steam injection
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rate while PP and PS had given the highest yields with 0.25 g/h injection rate. The overall
41 production of CNTs was 32 wt. %. Therefore it was concluded that introduction of steam
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43 reduced formation of carbon nanomaterials in this case but hydrogen production increased
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45 showing the flexibility of process in terms of products. In a different study, increased graphitic
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structure growth was reported by water introduction in pyrolysis/CVD process in which coconut
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48 coir dust was used as feed. Carbon yield as high as 80% was shown [62, 63]. Though positive
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50 results with the introduction of water are well proven for CVD reaction, further studies are
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52 required for its effect in two-stage pyrolysis CVD process.
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54 2.1.2. Microwave Pyrolysis in Fixed Bed
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3 The concept of microwave pyrolysis is similar to thermal pyrolysis, just that in this case, heat is
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5 generated by microwave irradiation. This process is advantageous in some cases i.e. whole waste
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7 tyres could be pyrolyzed efficiently at one time [64]. Synthesis of carbon materials such as CNFs
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and CNTs from renewable sources i.e. biomass using microwave radiation is intricate process

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10 due to some challenges such as the choice of precursors, catalyst, and source gases thereby
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12 making the development of large-scale production and usage difficult. However, there is a report
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14 of good quality MWCNT production using microwave pyrolysis [65]. In a study conducted by
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Shi and team; gumwood was used as feedstock, and silicon carbide was added as microwave
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17 receptor in 20:1 ratio. The pyrolysis mechanism is quite different than conventional thermal
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19 pyrolysis. It is believed that localized hotspots are created as a result of microwave irradiation
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21 which has much higher temperature than bulk of material, these hotspots on carbon char act as
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nucleation sites and with the help of minerals present in feed material the process is catalyzed.
Omoriyekomwan et al. [5] synthesized hollow carbon nanofibers (HCNFs) during microwave
pyrolysis of palm kernel shell at 500oC and 600oC. The formation of HCNFs was only observed
during microwave pyrolysis and not the fixed-bed pyrolysis, indicating that microwave played a
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29 key role in the formation of HCNFs. It was proposed that during microwave irradiation highly
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31 confined hotspots were created which became nucleation sites for nanofibers growth. The
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33 pyrolysis volatiles self-extruded from active site and underwent re-solidification this might be
34 due to secondary pyrolysis or because of lower outside temperature than core of active site. As a
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36 result, carbon nanofibers with bamboo-shaped morphology were formed. For nanomaterials such
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38 as CNTs growth, the surrounding temperature has to be in 800oC – 900oC range combined with
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other factors as discussed earlier. X-ray diffraction (XRD) analysis of microwave bio-chars
41 showed typical carbon diffractions at ϴ = 26.30 and 43.20, indicating a good graphitic structure
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43 of HCNFs, especially for bio-chars prepared at 600oC. High-resolution transmission electron
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45 microscope (HRTEM) results revealed multiwall nature of the HCNFs with carbon layer spacing
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of 0.34 nm. Two major tubular and bamboo-shaped structures were observed for HCNFs. With
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48 increasing microwave pyrolysis temperature from 500 to 600oC, the yield of HCNFs increased
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50 from 5.85 wt. % to 9.88 wt. %. Raman spectroscopy analysis showed that with increasing
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52 pyrolysis temperature to 600oC, the ID/IG ratio decreased from 0.95 to 0.86, indicating the
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53 higher order of the carbon layers of the HCNFs. Energy dispersive X-ray spectroscopy (EDS)
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55 showed the presence of Fe, K, and Ca in HCNFs structure which may have played a catalytic
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3 role during their formation and growth. The HCNFs-coated bio-char has great potential for
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5 removal of heavy metals from wastewater. In a research conducted by Debalina and team,
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7 microwave-assisted pyrolysis of bagasse was performed in the presence of powder metal
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susceptors [66]. The experiments were performed by irradiating bagasse sample loaded with

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10 different percentage of Fe, Co susceptors with 600W power to attain bulk temperature of 500oC.
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12 Formation of CNTs combined with other nanomaterials such as flakes were shown. Additionally,
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14 recovery of up to 31% weight boi-oil was also reported. It can therefore, be concluded that
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microwave pyrolysis proves promising in a sense that it enables one pot formation of carbon
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17 nanomaterials with a simple construction. However, scale-up and optimization of operational
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19 costs requires further investigation.
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22 2.2. Carbon Nanomaterials from Spray Pyrolysis
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Spray pyrolysis has some advantages over fixed bed pyrolysis method; there is a possibility of
continuous operation using this method and sometimes without even using well-prepared
substrate. In this process, gaseous precursors and catalyst particles are sprayed in high-
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temperature reaction zone in presence of inert carrier gas. Hydrocarbons decompose over
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31 catalyst particles into carbon nanomaterial, and hydrogen is released. The deposition can occur
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33 either on tube reactor walls or substrate placed within tube. One drawback of this method is that
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35 mixture of nanomaterials is obtained rather than high percentage of single nanomaterial. In a
36 study by Tapaszto et. Al. [67] spray pyrolysis was performed using 50ml ferrocene-benzene or
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38 ferrocene-thiophene precursor with 500 ml/h argon gas flow rate. Well-aligned MWCNTs were
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40 obtained on quartz tube with temperature being maintained between 800oC to 1000oC. Effect of
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temperature and ferrocene precursor was determined, it was found that increasing temperature
43 decreases diameter of nanotubes while same effect was observed by decreasing ferrocene
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45 concentration. Kamalakaran and team demonstrated synthesis of large flakes of alumina-CNT
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composite material at temperature range of 1000oC + 50oC [68] by spray pyrolysis of γ-alumina
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and ferrocene solution in xylene while argon was used as inert carrier gas. The sprayer consisted
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50 of two concentric tubes, with an outer nozzle having a diameter of 2mm and inner nozzle with
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52 0.5mm diameter. Argon is introduced from outer nozzle while liquid precursors are injected from
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54 inner one. During the process, the precursors decompose and form nanomaterial flakes along
55 with some percentage of nanotubes. It was observed nanomaterial flakes were porous on the
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3 surface and denser near base. At one end of tube, large flakes of aligned nanotubes were formed,
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5 and TEM images revealed that nanotubes were formed with 60nm diameter covered with layer of
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7 amorphous material either carbon or alumina. In another study by Ionescu and team [69] well
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aligned CNT arrays were synthesized by employing spray pyrolysis using ferrocene and xylene

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10 solution as liquid precursor. The experimental setup was similar as in previous author’s report
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12 however in this case oriented n-type Silicon wafers were used as substrate. An aluminum layer of
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14 30nm thickness was sputtered over substrate. Following parameters were studied in this research;
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growth temperature, injection speed and concentration of ferrocene in xylene. As observed in
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17 other nanomaterial growth processes temperature also played an important role here. It was
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19 found that nanomaterials were grown only in temperature range 700oC to 800oC. Maximum CNT
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21 length of 63μm was obtained for 800oC. However, Raman spectra showed that better crystallinity
22 was obtained for CNT synthesized at 750oC. Additionally, the diameter of CNTs decreased
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dramatically from 54nm to 19nm as temperature was increased from 700oC to 800oC. The
precursor injection speed was examined in a range of 0.05 to 1ml/min; it was shown that tube
length decreased from a maximum of 237μm to 48μm as injection rate was increased to a
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29 maximum value in said range. This could be due to thermodynamically unfavorable growth
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31 conditions at higher flow rates. Moreover, effect of ferrocene catalyst concentration in xylene
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33 was also studied in a range of 0.1% to 5%. The average length of CNT increased from 11μm to a
34 maximum of 138μm as ferrocene concentration was increased from 0.1% to 1%, further increase
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36 in concentration decreased the average length of nanotubes. At 5% the average length of
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38 nanotubes was measured to be 103μm. Similarly, Raman spectra revealed that CNTs grown at
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lower concentration showed the higher degree of crystallinity. It is believed that at higher
41 concentrations ferrocene particles are unable to find a spot on substrate, as a result, become the
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43 cause of secondary nucleation sites hence introducing defects and sometimes cause amorphous
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45 carbon deposition. Another study by this same authors group [70] was done utilizing ultrasonic
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spray pyrolysis. The process is necessarily same as stated above with the addition of ultrasonic
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48 system at injection point which causes increased atomization then conventional spray pyrolysis
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50 resulting in even smaller droplets. As we know diameter and growth rate of 1-D nanostructures
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52 depends upon size of nucleation site therefore with introduction of ultrasonic system the CNTs
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53 obtained were smaller in diameter, and denser forest of tubes were obtained. In this study,
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55 mixture of imidazole, ferrocene and acetonitrile was used. N-doped nanotubes were obtained due
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3 to injection of acetonitrile. Effect of concentration of imidazole was studied, and it was found
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5 that by increasing concentration from 0 to 50, 100 and 200mg/l the mean diameter of N-doped
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7 tubes decreased from 89 to 70, 66 and 54nm respectively. It was therefore concluded that use of
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ultrasonic processor and by adjusting the concentration of imidazole in acetonitrile the diameter

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10 N-doped carbon nanotubes could be carefully controlled thus enabling greater application of this
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12 process. Another study was conducted for synthesis of SWCNT using ultrasonic spray pyrolysis
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14 by Khatri et al. [71]. This study was different than spray pyrolysis methods described earlier in a
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sense that catalyst particles were not injected during the process but were dip coated over silicon
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17 substrate. A bi-metallic catalyst solution was prepared to consist of cobalt acetate and
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19 molybdenum acetate dimer which was deposited over silicon substrate by dip coating method.
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21 The prepared substrate was placed within quartz tube provided with an electric furnace.
22 Annealing of catalyst was performed at 400oC before commencing spray pyrolysis; after that
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ultrasonic pyrolysis was done using ethanol solution as feed precursor in presence of nitrogen
purging. The authors reported synthesis of SWCNTs for catalyst particle having diameter up to
nanometer while larger diameter catalyst particles favored MWCNTs. Hence spray pyrolysis
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29 provides a unique alternate path for high quality CNTs growth with possibility of continuous
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31 operation.
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34 2.3. Fluidized Bed Pyrolysis
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36 Though fluidized bed process for MWCNTs synthesis is commercially used few studies are
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38 available for fluidized bed operation at lab scale due to difficult construction and control of
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40 operating parameters. Moreover, very little data is made available from commercial operators.
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42
Nevertheless, there are few studies listed here which give effective detail about the quality of
43 CNTs produced and effect of different operating parameters on it when fluidized bed process is
44
45 utilized. In a research by Son and team [72] comprehensive study of MWCNTs synthesis
46
employing fluidized bed pyrolysis was performed. Effect of different carbon sources such as
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47
48
CH4, C2H2, C2H4, and C2H6 was determined. It was shown that CNTs synthesized from CH4
49
50 showed the highest crystallinity and narrow diameter, but carbon conversion was lower than
51
52 other feedstocks. The process consisted of stainless steel reactor provided with gas distributor at
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54 the bottom. Volumetric flow rates of H2, N2, and different carbon precursors were controlled by
55 mass flow controllers while catalyst particles consisting of Fe/Mo/MgO were loaded over gas
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3 distributor. The catalyst particles were fluidized with H2, N2, and carbon source gas flow with
4

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5 temperatures in range 873K to 1173K. Similarly in a work by Hsieh and coworkers [73] highly
6
7 pure MWCNT were synthesized in stainless steel fluidized bed reactor. The experimental setup
8
9
consisted of vertical tube reactor provided with gas distributor at the bottom. A mixture of gases

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10 N2:C2H2:H2 with ratios 93:6:1 respectively were introduced from bottom causing fluidization of
11
12 catalyst particles bed. Catalyst particles consisted of Iron or Nickel supported on alumina made
13
14 by wet impregnation method. Different growth temperature in range 700 oC, 750oC, 800oC and
15
850oC were studied. High purity MWCNTs were confirmed from TEM images having average
16

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17 diameters in the range of 15 to 30 nm. It was shown that Fe based catalyst showed higher activity
18
19 then Ni-based catalyst, using which maximum growth of MWCNTs was observed at 850 oC.
20
21
22 3. Graphene Synthesis
23
24
25
26
27
28
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Graphene is 2-D single layer of sp2 hybridized carbon atoms which are arranged in a hexagonal
honeycomb structure. Graphite is an allotropic form of carbon necessarily consists of stacked
graphene sheets having weak inter-planar bonds [74]. One of the common methods for graphene
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29
30 synthesis is by oxidation of graphite forming graphene oxide and then reducing it to form
31
32
graphene sheets. However, another method utilizing solvothermal combined with pyrolysis
33 technique was introduced as graphene's chemical synthesis process in the bottom-up technique.
34
35 The molar ratio of ethanol and sodium was 1:1 for this thermal reaction in closed vessel [75]. It
36
37 was possible to separate the graphene sheets after sodium ethoxide’s pyrolysis using sonication.
38 Graphene sheets produced through this method had dimensions of 10nm. The band structure,
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40 number of layers, crystalline structure and graphitic nature, were represented by TEM, SAED
41
42 and Raman spectroscopy. Resultant sheet's Raman spectroscopy illustrated a broad G-band, D-
43
44
band and intensity ratio of IG/ID*1.16. The advantages of this technique were easy fabrication,
45 low cost high-purity and functionalized graphene synthesis in conditions of low temperature.
46
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47
48 3.1. Synthesis of graphene through pyrolysis in thermal plasma
49
50
51 One of the most promising procedures of graphene production with desired characteristics is the
52
use of plasma as a microwave discharge [76, 77]. In a study by Dato and coworkers [78] a novel
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54 method for high quality graphene synthesis was developed. Argon plasma was generated in
55
56 quartz tube, and ethanol droplets were introduced to this plasma. Ethanol droplets dissociated in
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3 vapor phase and were collected over nylon membrane filters located downstream. Two to four
4

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5 layered graphene materials were synthesized which were easily dispersed during sonication.
6
7 Graphene sheets were characterized using TEM and Raman spectroscopy which revealed high
8
9
purity graphene synthesis clearly showing the presence of single and multiple graphene sheets. In

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10 another study by Subrahmanyam and team [79] graphene flakes were synthesized using arc
11
12 discharge method. Water cooled stainless steel chamber was used for arc discharge process
13
14 having graphite anode and cathode being placed at a distance of 2mm from each other. The
15
deposit formed on chamber inner walls was used for graphene as deposits on cathode consisted
16

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17 of some amount of MWCNT. Favorable conditions for graphene synthesis were high current and
18
19 high-pressure hydrogen. Under optimum conditions, this process resulted in 10-20% weight
20
21 graphene yield with respect to weight of anode. The growth mechanism is somewhat similar to
22
23
24
25
26
27
28
an
that of CNT synthesis just in this case absence of catalyst and substrate hinders growth of 1-D
structures and favors 2-D structures. Few layers of graphene were synthesized in a similar
process adapted by Wu et. Al. [80]; in this process however instead hydrogen; carbon dioxide
and helium were used. Different parameters were studied, and optimum conditions for few-layer
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29 graphene syntheses were high buffer gas pressure and high current which are in agreement with
30
31 the previously stated study. It was found that the number of flaws were less as compared to the
32
33 synthesis of graphene through other chemical approaches.
34 However, to scale production of graphene is still a challenge. The thermal plasma’s application
35
36 produced by the plasma torch can be very promising for this issue. The benefits of the proposed
37
38 approach as compared to the electric arc approach of the graphene syntheses are the likelihood of
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40
a significant increase in production through continuous operation; the likelihood of the
41 optimization of procedure through independent control over plasma energy flux, pressure over a
42
43 broad range and plasma gas source.
44
45
46 4. Conclusions
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47
48
49 The investigation of the environment-friendly processes for the carbon nanomaterial’s synthesis
50
has been carried out for several years. Most of the techniques discussed in this review are related
51
52 to the application of pyrolysis techniques which utilized sawdust, organic solid wastes, and
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54 plastic wastes for production of CNMs in range of milligrams. CNMs with considerable
55
56 production yield with the maximum amount of ~85% can be produced by these methods. So it
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3 considerably supports the prospection of sustainable CNM’s synthesis and at the same time
4

pt
5 allows a significant reduction in the solid wastes. As compared to CNTs, the green synthesis
6
7 methods for graphene production employing pyrolysis technique are somehow limited. Biomass
8
9
and plastic wastes have been common resources for the production of CNTs. However, reported

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10 results recommended that the CNMs synthesized from plastic have superior quality as compared
11
12 to CNMs synthesized from the biomass. Most probably, one of the reasons for this is that the
13
14 chemical composition of biomass is much more complicated. Though synthesis of high-end
15
products employing pyrolysis of organic solid wastes is highly promising, the developed
16

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17 methods for the green synthesis require further research to scale up CNMs production. The
18
19 appropriate selection of waste materials is critical. During the process of synthesis, it must be
20
21 confirmed whether the produced gaseous products are hazardous. Some of those products can be
22
23
24
25
26
27
28
an
used in CNMs synthesis as carbon precursors, while others must be given appropriate treatment
before liberation. The described reports suggested that the study of catalyst preparation and the
intermediate chemical reaction is most significant. However, this cannot be denied that the
produced yield through the methods of high temperature has comparatively improved the process
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29 quality. Excellent properties are infatuated by CNMs which are applicable for several
30
31 applications, but at the same time, adverse impacts of CNMs cannot be ignored because of their
32
33 dimensions in nm-range. The residues which are left in the CNMs synthesis can impose
34 environmental problems. Also, there is need to efficiently remove any sulphur in pyrolysis
35
36 products as it was found that most organic wastes contain substantial amounts of sulphur. So,
37
38 there is need to execute the rigorous protection in the process of preparing CNMs. With these
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40
precautions in place pyrolysis process for carbon nanomaterial’s production is one promising
41 path which could fulfill our future needs of this advanced material.
42
43
44
45
46 References
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43
44
45
46
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48 Summary of Main findings
49
50
51 Author Methodology Main Findings Reference
52
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53 M. Synthesis of copper High catalytic activity for the

54 Nasrollahzadeh et nanoparticles (Cu NPs) Huisgen [3+2] cycloaddition of [2]
55 al. using Ginkgo biloba L. leaf azides and alkynes
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1
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3 extract
4

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5
6 HCNFs had the multiwall
7 J. E. Microwave pyrolysis of structure with graphitic layer d-
8 palm kernel shell (PKS) at spacing of 0.34 nm. XRD analysis [5]
Omoriyekomwan
9 500 and 6000C. showed two distinct peaks at 2 ϴ

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10
et al.
= 26.3˚ and 43.2˚
11
The geometry of graphenes alters
12
13
Decompositions of (from curved petals to disk with
14 R. K. Amirov et hydrocarbon in the plasma the diameter of 100–700 nm). The
15 jet reactor using the direct quantity of graphenes in the [76]
al.
16 current plasma torch synthesized products also alters

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17 from 58 to 95%.
18
19 Particles had a high aspect ratio,
20 Production of carbon
21
M. G. S. Bernd et with a thickness thinner than 50
nanostructures by wood [28]
22 al. nm. the quality of the CNT/CF
23
24
25
26
27
28
Z. Song et al.
sawdust pyrolysis.

an
Pyrolytic performance of
the tire powder was
assessed under different
specific microwave powers
was satisfactory

Maximum yields of liquid

product (45%) and gas product
(18.5%) were obtained at 15 and [81]
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29 per 1 g sample, (9, 15, and 24 W/g, respectively
30 24 W/g)
31 Characterization of
32 nanomaterials synthesized
33 Catalyst meshes were covered by
in a catalyst system from
34 materials with diameters of 20 to
the effluent of burning
35 J. O. Alves et al. 200 nm and lengths of about 40 [33]
36
waste tire chips in a
μm
37 horizontal two-stage
38 laminar-flow furnace
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39 Carbon nanotubes
40 Conversion of plastic into carbon
produced via low-density
41 nanotubes was 29.1 wt. % when
J. C. Acomb et al. polyethylene feedstock [82]
42 0.5g LDPE was used, but reduced
through a two-stage
43 to 13.1 wt. % with 1.25g LDPE.
44 pyrolysis process
45 High-quality CNTs, as observed
Low-density polyethylene
46 from TEM, TPO and Raman
(LDPE), polypropylene
ce

47 spectroscopy were produced by

48 (PP) and
controlling the steam injection
49 polystyrene (PS) were
rate. The largest yield for LDPE
50 J. C. Acomb et al. studied in a two-stage [40]
51
was obtained at 0 g/h steam
pyrolysis-gasification
52 injection rate, whilst PP and PS
reactor and pyrolysis was
Ac

53 gave their largest yields at 0.25

done at 6000C
54 g/h
55
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Page 19 of 19 AUTHOR SUBMITTED MANUSCRIPT - MRX2-100442.R3

1
2
3 The pyrolytic degradation
4

pt
5
of polypropylene to
6 MWCNT was achieved at Pyrolysis of plastic at 8000C gives
7 N. Mishra et al. 600, 700 and 8000C under the purest form of CNT. [49]
8 argon and hydrogen
9 atmosphere for an hour

cri
10 The synthesis of carbon
11 Conversion of non-
nanomaterials proceeded through
12 condensable pyrolysis
13 the formation of intermediate
gases from plastic
14 products, such as methane,
A. Veksha et al. feedstock into carbon [39]
15 ethylene and condensable oils,
nanomaterials through
16 which reacted with the catalyst

us
17 catalytic chemical vapor
producing carbon nanomaterials
18 deposition
at 500 and 8000C.
19
20
Carbon was composed of largely
21 A two-stage pyrolysis- filamentous type carbon,
22 catalytic reactor system producing 253.7 mg/g of the tyre [19]
23
24
25
26
27
28
Y. Zhang et al.
was used

Methane chemical vapor

an
deposition growth of single
and double-walled carbon
with tire: catalyst ratio of 1:1 and
catalyst temperature of 900 0C
The degree of methane
decomposition, i.e., the C–H bond
dissociation, was closely related
dM
29 H. Ago et al. to the nanotube yield, and the Fe– [52]
nanotubes over metal-
30 Mo binary catalyst exhibited a
31
supported MgO catalyst
high activity.
32 Comparative study of the
33
removal of Pb2+ ions and Maximum adsorption capacities
34
35 Cr3+ to determine the of both Pb2+ ions and Cr3+ ions
36 N. M. Mubarak et efficiency of carbon onto the CNT were 15.34 mg/g [83]
37 al. nanotubes (CNTs) for Pb2+ ions and 24.45 mg/g for
38 produced using microwave Cr3+ ions.
pte

39 heating
40 Mass production of High-quality MWCNTs were
41
42
MWCNTs based on obtained from virgin or recycled
43 U. Arena et al. thermal cracking of polyolefins as well as from [41]
44 polymers in a solid-gas recycled polyethylene
45 fluidized bed reactor terephthalate.
46 Efficient chemical vapor Massive growth of super dense
ce

47 deposition synthesis of and vertically aligned nanotube

48 K. Hata et al. [55]
single-walled carbon forests with heights up to 2.5
49
50 nanotubes millimeters
51
52
Ac

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