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Bougainvillea
Bougainvillea
Bougainvillea
Herein, we demonstrated a green approach for the synthesis of high surface area (850 m2 g−1) meso-
porous perforated graphene (PG) from Bougainvillea flower for the first time using a template free single-
step method. The existence of PG was confirmed by XRD, Raman spectroscopy, FESEM, and FETEM.
Surprisingly, FETEM clearly showed 5–10 nm perforation on the graphene sheets. More significantly, these
mesoporous perforated graphene sheets can be produced in large scale using the present green
approach. Considering high surface area and unique perforated graphene architecture, these PGs were
studied for supercapacitor applications in detail without any chemical or physical activation. The nano-
porosity and high conductivity of PG derived from Bougainvillea flower exhibited excellent supercapacitive
performance. According to the supercapacitor study, the synthesized perforated graphene sheets
conferred a very high specific capacitance of 458 F g−1 and an energy density of 63.7 Wh kg−1 at the
power density of around 273.2 Wh kg−1 in aqueous 1 M Na2SO4. Significantly, the areal capacitance of PG
was observed to be very high, i.e. 67.2 mF cm−2. The cyclability study results showed excellent stability of
synthesized perforated graphene sheets up to 10 000 cycles. Note that the specific and areal capacitance
Received 24th January 2017, and the energy density of the synthesized PGs are much higher than the earlier reported values. The high
Accepted 10th March 2017
supercapacitive performance may be due to high surface area and mesoporosity of PG. The present
DOI: 10.1039/c7nr00583k approach has a good potential to produce cheaper and high surface area PG. These PGs are good candi-
rsc.li/nanoscale dates as an anode material in the lithium-ion battery.
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capacitors were designed based on electrochemical double- has been achieved up to 400 F g−1 at 0.5 A g−1 in 1 M aqueous
layered capacitors (EDLCs). The EDLCs store energy through H2SO4 as an electrolyte,4 whereas the supercapacitance for
the adsorption of both anions and cations of the electrolyte at carbon as an electrode material derived from the animal waste
the interface between the electrode and the electrolyte. has been achieved up to 349 F g−1 at 1 A g−1 in 1 M aqueous
Nowadays, the scientific community is motivated to consider- H2SO4 as an electrolyte.32 Beside natural waste, scientists have
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ably improve the energy and power density of supercapacitors also focused their attention on the manmade waste manage-
by developing new electrode materials. For the fabrication of ment through the production of value-added products.
electrodes of EDLCs, carbon materials have been extensively Activated carbon has also been synthesized using carboniz-
studied as an electrode material due to its eco-friendly nature, ation of the scraped tires, plastic etc. This carbon material
easy availability, high surface area, and moderate cost.4–7 exhibits a super capacitance of 100 F g−1 at 10 A g−1 in 6 M
However, commercially available carbon materials have some KOH aqueous solution.33,34 Considering the demand for
limitations as supercapacitor materials due to their low con- energy storage devices, there is enormous scope to increase
ductivity, low ion-transport, and insufficient ionic diffusion the efficiency of these devices by developing new carbon
within the complex micropores; hence, high energy and power materials with a high surface area as well as to investigate new
density cannot be achieved. Presently, activated carbon is pro- sources of activated carbon via waste management. Carbon
duced using diminishing natural products such as petroleum materials such as graphene has a high theoretical surface area,
coke, pitch, and coal.8,9 Recent studies on carbon-based super- substantially higher than the more common electrode active
capacitors concluded that micro and mesoporous nanocarbon material, activated carbon, thus potentially allowing the
produces excellent supercapacitor results.10,11 Hence, there is storage of more electrostatic charge.35,36 However, it is very
an urgent need to explore novel two and three-dimensional difficult to synthesize these 2D graphene materials with a con-
nanostructured porous carbon materials for high performance trolled morphology, structure, and property. It is urgent task to
supercapacitors. To improve the properties of carbon-based identify a method to develop these 2D graphene-like materials
electrodes, highly porous morphologies should be developed. for supercapacitor applications. Graphene has been produced
In view of this, as activated carbons,12 templated carbons,13 by the reduction of graphene oxide (GO) prepared by the
carbon nanofibers,14 carbon nanotubes,15 carbide-derived Hummers and Offeman method37 and other modified
carbon16 and graphene17 have been extensively studied. The methods.38 Graphene materials have been extensively used for
activated carbon and nanoporous carbon has an advantage in EDLC supercapacitors; however, the maximum capacitance
the controllable synthesis and acceptable properties.18 was observed to be 250 F g−1.39 Very few reports are available
However, the poor conductivity and abundant micropores in on the synthesis of perforated graphene from biomass.
activated carbons are a hurdle for ion and electron transport, Perforated graphene has been synthesized using cost-effective
which deteriorate capacitance performance at high current routes from renewable biomass waste such as waste food
rates.19 Carbon nanotubes have good electric conductivity and items, dead insects, etc.40 Today, the economics of super-
unique pore channels, alleviating ion diffusion and charge capacitor is totally dependent on the cost of carbon. It is
propagation; however, they have poor surface area that affects possible to achieve high porous perforated graphene using
the resulting capacitive performance of the supercapacitor.20 natural waste (free source) at lower cost, which ultimately
To improve the capacitive performance of the carbon-based reduces the cost of supercapacitors. Hence, we demonstrated
EDLC, the dispute between their specific surface area and elec- the preparation of mesoporous perforated graphene using
tric conductivity should be balanced. In view of this, graphene dead waste Bougainvillea flowers for supercapacitors for the
has attracted significant interest as an electrode material for first time.
supercapacitors because of the large surface area and porous In the present investigation, perforated graphene was syn-
layered structure. This will also confer the good conductivity of thesized by the one-step carbonization of dead Bougainvillea
the electrode, which can provide low-resistant pathways for flower (natural waste) without any chemical or physical acti-
electron transport.21,22 vation. Further, their supercapacitive performance was tested.
Herein, natural waste was utilized for the synthesis of active A detailed study of the synthesis of mesoporous perforated gra-
electrode materials for supercapacitors. Activated carbons can phene materials derived from dead flowers of boganvel
be typically prepared by the carbonization of easily available (Bougainvillea) was performed. To the best of our knowledge,
natural biomass wastes.23,24 The synthesis of porous carbon there are no reports on the synthesis of high surface area
from natural waste has received wide attention. Waste mesoporous perforated graphene from waste dead flowers.
materials such as waste coffee grounds,25 cow dung,26 human Using mesoporous perforated graphene derived from the dead
hair,27 a tea-leaf,28 peat moss,29 and fruit shells and seeds30,31 flowers, we achieved a specific capacitance of 458 F g−1 and a
have been extensively employed as raw materials for carboniz- very high energy density of 63.7 Wh kg−1 at the current density
ation to synthesize porous carbons as active electrode of 2.28 A g−1. These superior properties may be due to the
materials in supercapacitors. Nitrogen and oxygen-activated high surface area and high conductivity of the carbon material.
carbon materials were also synthesized via carbonization of These properties are superior to those of the commercially
these natural raw materials. The supercapacitance for carbon available material as well as other materials reported in the
as an electrode material derived from the horticulture waste literature.
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N-methyl-2-pyrrolidone (NMP), and PVDF ( polyvinylidene drops of NMP were added and thoroughly ground to make a
fluoride) were purchased from a reputed source. viscous slurry. This slurry was coated on the carbon paper sub-
strate area. The loaded electrodes were dried at 100 °C for
2.2. Synthesis of perforated graphene (PG) driven from
6 hours. Electrochemical cyclic voltammetry was performed
dead flowers
in an aqueous 1 M Na2SO4 solution in the potential range of
The dead boganvel flowers were obtained in large quantity, 0–1 V at various scan rates.
thoroughly washed, and dried at 80 °C in an oven. The dried
flowers were crushed to a fine powder. For the synthesis of per- 2.5. Electrochemical impedance spectroscopy measurements
forated graphene, 10 g boganvel flower powder was pyrolyzed Electrochemical impedance spectroscopy (EIS) was performed
in a quartz crucible at 600 °C and 800 °C for 5 hours in an for a symmetrical supercapacitor cell consisting of the bogan-
argon atmosphere at the heating rate of 10 °C min−1 and the vel (Bougainvillea) flower-derived PG-PG electrodes in aqueous
samples were marked as RC-A and RC-B, respectively. Fig. 1 1 M Na2SO4 electrolytes. The frequency range used for the
shows the process algorithm used for the synthesis of perfo- study was from 10 kHz to 10 mHz and an AC amplitude of
rated graphene from dead flower powder and subsequent 10 mV without an external DC applied voltage was utilized.
supercapacitor measurements.
2.3. Characterization
Perforated graphene synthesized from the abovementioned
3. Results and discussion
dead flowers was characterized by X-ray Powder Diffraction Generally, the dry or dead flowers consist of flavonoids, gluco-
(XRD) using a Bruker Advanced D8 diffractometer. Raman sides, sugar esters, terpenoids, sterides, and anthraquinones
spectroscopy using a LabRAM HR800 from JY Horiba and high- enwrapped in the thin petal of the flower and these are a rich
resolution transmission electron microscopy (HRTEM) were source of carbon.41 A pyrolysis treatment can convert these
carried out (IFEI, Tecnai F30, FEG with 200 kV). The surface organic components into carbon. The formation of PG from
area of the samples was determined using the Brunauer– flower is given in Scheme 1. In addition to these organic com-
Emmett–Teller (BET) adsorption method (Quantachrome ponents, traces of Ca and Mg are also present, which have
NovaWin ©1994–2012). Cyclic voltammetry measurements already been reported as porogens to create pores in activated
were performed by Auto Lab (model PGSTAT 30, eco-chemie). carbon.4 After carbonization, thin petals of the flower were
directly converted into graphene and elements such as Ca and
2.4. Electrochemical measurements
Mg were helpful for the generation of porosity after leaching.
The electrodes for electrochemical analysis were prepared on Indeed, PG has been prepared without any graphitic catalyst or
carbon paper. Two carbon paper substrates with a similar area activation agent, as reported earlier.42,43
The TGA results are shown in Fig. S1 (see ESI-I†). In the
TGA curve, the weight loss (2.23%) from room temperature to
200 °C was attributed to dehydration/water loss from the
surface and pores of the powder of dead flowers. From 200 to
450 °C, 48% weight loss was observed, which was attributed to
the degradation of cellulose. Further, there is the possibility of
degradation of lignin between 450 and 800 °C by further
extending the temperature, giving a total weight loss ∼60%.
The as-synthesized PG (RC-A and RC-B) was characterized
by XRD. Fig. 2a shows the XRD pattern of the samples RC-A
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Fig. 2 XRD pattern (a) and Raman spectra (b) of RC-A and RC-B.
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Table 2 Comparison of the properties of graphene synthesized from natural waste and their supercapacitance and energy density
Natural waste material Maximum capacitance (F g−1) Electrolyte Energy density (Wh kg−1) Ref.
−1 −1
Coconate [Editor33]shell 268 at 1.0 A g 6 M KOH 54.7 at 10 000 W kg 42
Fungus 374 at 1.0 A g−1 6 M KOH 22 at 784 W kg−1 43
Bougainvillea flower 458 at 2.28 A g−1 1 M Na2SO4 63.7 at 273.2 W kg−1 Present work
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Fig. 10 (a) Nyquist plot for RC-B in 1 M Na2SO4, and the inset shows
the magnified higher frequency region. (b) Plot of the Bode phase angle
(circle) and plot of the total impedance vs. frequency with frequency
(square).
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flowers of Bougainvillea for the first time. Further, we 18 G. A. Ferrero, M. Sevilla and A. B. Fuertes, Carbon, 2015, 88,
used graphene for supercapacitor applications without any 239–251.
external activation. The perforated graphene synthesized using 19 M. M. Shaijumon, F. S. Ou, L. J. Ci and P. M. Ajayan, Chem.
Bougainvillea flowers at 800 °C demonstrated a very high Commun., 2008, 20, 2373.
charge storage capability with a specific capacitance of 458 20 L. L. Zhang and X. S. Zhao, Chem. Soc. Rev., 2009, 38, 2520–
Published on 15 March 2017. Downloaded by National Institute of Technology - Rourkela on 12/8/2022 5:55:38 AM.
4808 | Nanoscale, 2017, 9, 4801–4809 This journal is © The Royal Society of Chemistry 2017
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43 C. Long, X. Chen, L. Jiang, L. Zhi and Z. Fan, Nano Energy, 57 J. Li, G. Zan and Q. Wu, New J. Chem., 2015, 39, 3859–3864.
2015, 12, 141–151. 58 J. A. Macia Agullo, B. C. Moore, D. Cazorla-Amoros and
44 S. Park, J. An, J. R. Potts, A. Velamakanni, S. Murali and A. Linares-Solano, Carbon, 2004, 42, 1367.
R. S. Ruoff, Carbon, 2011, 49, 3019–3023. 59 M. Sathishkumar, A. R. Binupriya, D. Kavitha,
45 L. Wei, M. Sevilla, A. B. Fuertes, R. Mokaya and G. Yushin, R. Selvakumar, R. Jayabalan, J. G. Choi and S. E. Yun,
Published on 15 March 2017. Downloaded by National Institute of Technology - Rourkela on 12/8/2022 5:55:38 AM.
Adv. Energy Mater., 2011, 1, 356–361. Chem. Eng. J., 2009, 147, 265–271.
46 D.-W. Wang, F. Li, Z.-G. Chen, G. Q. Lu and H.-M. Cheng, 60 S. Song, F. i. Ma, G. Wu, D. Ma, W. Geng and J. Wan,
Chem. Mater., 2008, 20, 7195–7200. J. Mater. Chem. A, 2015, 3, 18154–18162.
47 H. L. Guo, X. F. Wang, Q. Y. Qian, F. B. Wang and X. H. Xia, 61 H. Feng, M. Zheng, H. Dong, Y. Xiao, H. Hu, Z. Sun,
ACS Nano, 2009, 3, 2653–2659. C. Long, Y. Cai, X. Zhao, H. Zhang, B. Lei and Y. Liu,
48 D. Mhamane, W. Ramadan, M. Fawzy, A. Rana, M. Dubey, J. Mater. Chem. A, 2015, 3, 15225–15234.
C. Rode, B. Lefez, B. Hannoyer and S. Ogale, Green Chem., 62 C. Lai, Z. Zhou, L. Zhang, X. Wang, Q. Zhou, Y. Zhao,
2011, 13, 1990. Y. Wang, X.-F. Wu, Z. Zhu and H. Fong, J. Power Sources,
49 Q. Wang, J. Yan, Y. Wang, G. Ning, Z. Fan, T. Wei, J. Cheng, 2014, 247, 134e141.
M. Zhang and X. Jing, Carbon, 2013, 52, 209–218. 63 H. Xu, B. Gao, H. Cao, X. Chen, L. Yu, K. Wu,
50 Y. Zhu, S. Murali, M. D. Stoller, A. Velamakanni, L. Sun, X. Peng and J. Fu, J. Nanomater., 2014, 2014,
R. D. Piner and R. S. Ruoff, Carbon, 2010, 48, 2118–2122. 714010.
51 Y. Shao, J. Wang, M. Engelhard, C. Wang and Y. Lin, 64 A. Ganesan, R. Mukherjee, J. Raj and M. M. Shaijumon,
J. Mater. Chem., 2010, 20, 743–748. J. Porous Mater., 2014, 21, 839–847.
52 C. Mattevi, G. Eda, S. Agnoli, S. Miller, K. Andre Mkhoyan, 65 T. Thomberg, A. J. Nes and E. Lust, Electrochim. Acta, 2010,
O. Celik, D. Mastrogiovanni, G. Granozzi, E. Garfunkel and 55, 3138–3143.
M. Chhowalla, Adv. Funct. Mater., 2009, 19, 2577–2583. 66 Q. Cheng, J. Tang, J. Ma, H. Zhang, N. Shinya and
53 S. Park, J. An, I. Jung, R. D. Piner, S. J. An, X. Li, L. C. Qin, Carbon, 2011, 49, 2917.
A. Velamakanni and R. S. Ruoff, Nano Lett., 2009, 9(4), 67 R. Madhu, V. Veeramani, S.-M. Chen, A. Manikandan,
1593–1597. A.-Y. Lo and Y.-L. Chueh, ACS Appl. Mater. Interfaces, 2015,
54 X.-H. Li, S. Kurasch, U. Kaiser and M. Antonietti, Angew. 7, 15812–15820.
Chem., Int. Ed., 2012, 51, 9689–9692. 68 D. Saha, Y. Li, Z. Bi, J. Chen, J. K. Keum, D. K. Hensley,
55 M. Mitra, C. Kulsi, K. Chatterjee, K. Kargupta, S. Ganguly, H. A. Grappe, H. M. Meyer, S. Dai, M. P. Paranthaman and
D. Banerjee and S. Goswami, RSC Adv., 2015, 5, 31039–31048. A. K. Naskar, Langmuir, 2014, 30, 900–910.
56 W. Tian, Q. Gao, Y. Tan, K. Yang, L. Zhu, C. Yang and 69 J. Lee, J. Kima and S. Kim, J. Power Sources, 2006, 160,
H. Zhang, J. Mater. Chem. A, 2015, 3, 5656–5664. 1495.
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