Journal Pre-proofs

Electrically conductive honeycomb structured graphene composites from natu-

ral protein fibre waste

Rechana Remadevi, Md Abdullah Al Faruque, Jizhen Zhang, Maryam Naebe

PII: S0167-577X(20)30016-1
DOI: https://doi.org/10.1016/j.matlet.2020.127311
Reference: MLBLUE 127311

To appear in: Materials Letters

Received Date: 18 October 2019

Revised Date: 2 January 2020
Accepted Date: 4 January 2020

Please cite this article as: R. Remadevi, M.A.A. Faruque, J. Zhang, M. Naebe, Electrically conductive honeycomb
structured graphene composites from natural protein fibre waste, Materials Letters (2020), doi: https://doi.org/
10.1016/j.matlet.2020.127311

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover
page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will
undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing
this version to give early visibility of the article. Please note that, during the production process, errors may be
discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2020 Published by Elsevier B.V.

Electrically conductive honeycomb structured graphene
composites from natural protein fibre waste
Rechana Remadevi, Md Abdullah Al Faruque, Jizhen Zhang, Maryam Naebe*
Deakin University, Institute for Frontier Materials (IFM), Geelong, Victoria 3216,
Australia
*Corresponding author: maryam.naebe@deakin.edu.au

Abstract
A large amount of short and waste protein fibres, including silk and wool generated

during fibre processing that is not spinnable, eventually ends up in the landfill. Here we

are reporting on using these waste materials for fabrication of conductive composite.

We prepared Nickel (Ni) doped textile-based conductive composites from silk, and wool

waste fibres in powder forms and graphene oxide (GO), for the first time, by bulk

synthesis method. The infrared spectroscopy revealed that the silk and wool formed

composites with graphene oxide and Ni. The obtained Ni-doped graphene/protein fibres

composites after carbonisation showed a honeycomb structure with high surface area

and pore volume. The conductivity of the Ni-doped composites was higher than the

undoped composites. Considering the surface area, pore volume and conductivity

results, there is a huge potential for the fabricated material from biobased to use as an

electrode material.

Keywords: Biomaterials; Composite materials; Honeycomb morphology; Conductive

1. Introduction
Due to the global growth of luxurious textile, protein fibre consumption has increased,

resulting in a high amount of post-industrial and post-consumer fibre waste. Among all

protein fibres, wool and silk fibres are high in demand because of their luxurious look,

comfort and high market value [1]. A large amount of short and waste fibres generated

during fibre processing that are not spinnable eventually ends up in the landfill. There

are some studies conducted on the use of protein short fibres composites for thermal-

mechanical applications [2, 3]. However, there is no report on the fabrication of waste

protein fibres composites in their powder form through a bulk synthesis method for

electrode material applications. Furthermore, currently, biomaterial-based composites

have drawn more interest because of their nontoxicity. Additionally, the majority of the

preparation of electrochemical materials and processing routes are not user-friendly

and produce a large amount of toxic waste. The present work aimed to utilise silk and

wool waste fibres and graphene oxide to fabricate a protein fibre composite material

and study its conductivity. Graphene is a promising material in the electronics industry

due to its unique one-atom‐thick two‐dimensional (2D) structure, an ability to form

composites with high electrical-thermal conductivity and large surface area. Moreover,

the presence of oxygen-containing groups on the graphene surface forms strong

interactions with the protein fibre materials. Given that Nickel (Ni) doping on the

composites will enhance the electrical properties of the materials, we have trialled Ni

doping in this work. It has been reported that Ni can act as a catalyst for CNT (Carbon

nanotube) or CNF (Carbon nanofiber) growth on the material after subsequent

carbonisation [4]. Therefore, this current work also investigates if the Ni doping and
carbonisation of the as-prepared protein fibre composites affect their conductive

properties.

2. Experimental procedure

The waste silk/wool powders were fabricated by milling (S1). The nickel doped/un-

doped graphene oxide (GO) composites using silk and wool powder were prepared by

the bulk synthesising method (S3, S4). The morphology (scanning electron microscopy

(SEM), S7), fine structural analysis (Fourier Transform Infrared (FTIR), S9) and the

porosity (Brunauer–Emmett–Teller (BET), S10) analysis on the powder samples were

performed. The DC electrical resistance of the compressed powders was measured by a

two-point method, using an in the house built two-point resistance measure device

(Figure S6).

3. Results and discussion

The physical appearance of the samples was similar (Figure S8). The ecru colour of the

natural wool and silk powder turned to grey colour in Go and Ni-doped composite, and

all the carbonised samples appeared black (S8). The SEM images showed graphene

layers wrapped around the powders on the silk-GO and wool-GO composites (Fig.1a,b).

The carbonised nickel doped composites (Fig.1c,d) showed an altered morphology; a

porous honeycomb structure compared to the un-doped carbonised (Figure: f, g S7).

Similar morphology changes were reported in Ni-doped graphene composites [5], where

Ni acted as a catalyst for the structural modification. The porous structure provided a
large accessible surface area, suitable for active material decoration for electrochemical

applications [5]. This can be concluded that the natural fibre composites in the current

study are capable of arranging themselves into porous structures similar to the

electrochemical composite materials (Eg: MOF-reduced graphene composites).

(a) (b)

(c) (d)

Fig. 1. Scanning electron microscopy image of (a) Wool–GO composite. (b) Silk-GO
composite. (c) Silk-GO Ni-doped: carbonised. (d) Wool-GO Ni-doped: carbonised.

Figure 2 represents the FTIR spectra of wool (Figure 2a) and silk ( Figure 2b) and their

corresponding composites and carbonised samples. As protein fibres, wool and silk have

relatively similar characteristics. Both wool and silk powder showed the characteristic of

methyl, methylene and amide peaks at 1630-1660 cm-1 (amide I), 1520-1550 cm-1 (amide

II), 1240-1265 cm-1 (amide III). Additionally, the peak at 3250 and 3300 cm-1 confirmed

the presence of -OH groups of silk and amide-A of wool, respectively [6].
Fig. 2. (a) FTIR spectra of wool and composites. (b) FTIR spectra of silk and composites.

While similar peak positions of wool (or silk) alone were found in the composite

structure of wool- GO ( Silk-GO), the typical GO peaks were also visible at 1400 cm-1 and

1700 cm-1 (carboxyl –C-O and –C=O, respectively) and 3170-3300 cm-1 (hydroxyl –OH

group) [7]. Similarly, wool-GO Ni-doped and silk- GO Ni-doped composites spectrum

showed nickel’s characteristic peaks at around 1092 cm-1, 1386 cm-1, 1645 cm-1 and 3250

cm-1, those stand for C-O stretching, C=O group’s stretching vibration, cross-linked C-C

stretching and O-H stretching, respectively [8]. From Figure 2, it was evident that the

functional groups of both wool and silk were present in the other composites structures.

As in wool-GO Ni-doped composite structure, all of these three components possess -

OH groups, it showed the maximum intensity in this peak position. A similar effect was

also found for peaks between 1640 and 1700 cm-1. The peaks corresponding to hydroxyl

–OH groups between 3170-3300 cm-1 were diminished because of the carbonisation

process, as shown for all wool and silk based carbonised samples. Moreover, the wool

and silk alone carbonised sample showed a small shoulder peak in the amide peak

regions. However, the other two carbonised samples (Wool (or silk)-GO carbonised and
wool (or silk)-GO Ni-doped carbonised) amide peaks getting less significant after

carbonisation.

The carbonised samples had a higher surface area and pore volume than the

uncarbonised samples for both wool and silk materials (particularly the carbonised Ni-

doped samples) as shown by BET measurements (Fig.3). The observation was in

agreement with the results reported in increased surface area with nickel doping for

carbon aerogels [9]. During the carbonisation process, nickel acted as a catalyst and

created more honey-comb porous structures. Increased in cumulative pore volume was

also reported where nickel promoted the creation of more porous structures in carbon-

inorganic oxide composites [10].

 (a)

Wool-GO Ni doped: carbonised

Wool-GO composite
Wool-GO Ni doped: Carbonised
(b) Silk-GO Ni doped carbonised
Wool alone carbonised
Silk-GO Ni doped
Silk alone carbonised
0.020
Silk-GO
Wool-GO carbonised
Silk-GO carbonised
Cumulative Pore Volume (cc/g )

0.015

0.010

0.005

0.000

0 5 10 15 20 25 30 35 40
Half pore width( Å)

Fig. 3. (a) Surface area analysis for silk and wool composites. (b) Cumulative pore
volume-half pore width comparison

Table 1. Conductivity of carbonised samples.

Name Pressure (KPa) Conductivity (S m-1)
Samples Wool-GO Silk –GO Wool Silk GO-Wool Silk-GO
(Carbonised) Ni-doped Ni-doped alone alone
1 200 3.12 3.1 1.02 1.10 1.96 2.21
2 500 129.45 123.11 84.49 71.61 105.09 94.79
3 1000 256.62 243.74 179.37 169.07 225.72 217.99
4 1500 356.64 333.47 233.05 220.17 292.27 276.80
5 2000 430.92 413.29 261.37 253.65 351.49 341.19
6 3000 523.23 500.45 295.24 287.52 397.84 379.82
7 5000 582.05 554.13 338.62 323.17 451.52 418.05
Conductivity measurement (Table 1) demonstrated that by increasing the pressure, the

conductivity increased and the carbonised nickel doped composites showed a higher

conductivity value compared to its un-doped counterpart. Because of the catalytic

activity of nickel, the conductivity of the material increased. It was reported that metal

dopant has a positive correlation with conductivity [11]. Overall, it can be stated that

nickel doped protein fibre composites have the potential to be used as an

electrochemical material.

4. Conclusions

This study establishes a new technique through transition metal doping and subsequent

carbonisation to transform protein textile waste into a highly conductive-porous

material. The nickel doped graphene composites were prepared from the silk and wool

waste fibres. The electron microscopic images showed that the carbonisation of the

nickel-doped composites provided more porous honeycomb-like morphology. The

infrared spectroscopy revealed that the silk and wool formed composites with graphene

oxide and Ni. The hydroxyl groups of the graphene oxide were bonded with the amino

group of the protein fibres while forming the composites. The BET results showed that

carbonised nickel-doped composites had a higher surface area and pore volume in

comparison with their un-doped samples. The increased surface area and porous

morphology were evident from the SEM images. Among the carbonised composites, the

conductivity of the nickel-doped composites was higher. Given the materials with high

conductivity and surface area are used as an electrochemical material for

supercapacitors applications, this study opens up a new method for fabrication of the

conductive composites for electro material applications and tuneable energy storage

materials using the textile waste.

Declaration of Competing Interest

The authors declare that they have no conflicts of interest in this work.

References
[1] M. Naebe, R. Denning, M. Huson, P. Cookson, and X. Wang, "Ageing effect of plasma‐
treated wool," Journal of the Textile Institute, vol. 102, no. 12, pp. 1086-1093,, 2011.
[2] S. M. Lee, D. Cho, W. H. Park, S. G. Lee, S. O. Han, and L. T. Drzal, "Novel silk/poly
(butylene succinate) biocomposites: the effect of short fibre content on their
mechanical and thermal properties," Composites Science and Technology, vol. 65, no. 3-
4, pp. 647-657, 2005.
[3] N. Kim, R. Lin, and D. Bhattacharyya, "Extruded short wool fibre composites: mechanical
and fire retardant properties," Composites Part B: Engineering, vol. 67, pp. 472-480,
2014.
[4] L. Chen, H. Liu, K. Yang, J. Wang, and X. Wang, "Catalytic synthesis of carbon nanotubes
from the decomposition of methane over a Ni–Co/La2O3 catalyst," Canadian Journal of
Chemistry, vol. 87, no. 1, pp. 47-53, 2009.
[5] Y. Chen, N. Wang, W. Hu, and S. Komarneni, "In situ construction of porous Ni/Co-
MOF@ Carbon cloth electrode with honeycomb-like structure for high-performance
energy storage," Journal of Porous Materials, vol. 26, no. 3, pp. 921-929, 2019.
[6] M. A. Al Faruque, R. Remadevi, X. Wang, and M. J. P. t. Naebe, "Preparation and
characterisation of mechanically milled particles from waste alpaca fibres," vol. 342, pp.
848-855, 2019.
[7] S. Park, K.-S. Lee, G. Bozoklu, W. Cai, S. T. Nguyen, and R. S. J. A. n. Ruoff, "Graphene
oxide papers modified by divalent ions—enhancing mechanical properties via chemical
cross-linking," vol. 2, no. 3, pp. 572-578, 2008.
[8] S. Sudhasree, A. Shakila Banu, P. Brindha, G. A. J. T. Kurian, and E. Chemistry, "Synthesis
of nickel nanoparticles by chemical and green route and their comparison in respect to
biological effect and toxicity," vol. 96, no. 5, pp. 743-754, 2014.
[9] A. Abdelwahab et al., "Electrodes Based on Carbon Aerogels Partially Graphitized by
Doping with Transition Metals for Oxygen Reduction Reaction," vol. 8, no. 4, p. 266,
2018.
[10] B. J. J. o. T. A. Charmas and Calorimetry, "Structural and thermal characteristics of Ni-
doped carbosils prepared by mechanochemistry," vol. 120, no. 2, pp. 1347-1354, 2015.
[11] R. A. Araujo, A. F. Rubira, T. Asefa, and R. J. C. p. Silva, "Metal doped carbon nanoneedles
and effect of carbon organization with activity for hydrogen evolution reaction (HER),"
vol. 137, pp. 719-725, 2016.
Highlights

 Bulk synthesis of graphene oxide-waste protein fibres composites

 Formation of carbonised Ni-doped composite with honeycomb

structure

 Carbonised Ni-doped composite with higher conductivity than

other fibre composites
CRediT author statement

Electrically conductive honeycomb structured graphene composites from natural

protein fibre waste

Rechana Remadevi, Md Abdullah Al Faruque, Jizhen Zhang, Maryam Naebe*

Deakin University, Institute for Frontier Materials (IFM), Geelong, Victoria 3216,
Australia
*Corresponding author: maryam.naebe@deakin.edu.au

Rechana Remadevi: Conceptualization, Investigation, Writing- Original Draft, Md Abdullah Al

Faruque: Investigation. Jizhen Zhang: Investigation. Maryam Naebe: Supervision, Writing-
Reviewing and Editing, Funding acquisition