Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-019-02324-7

Covalently linked porphyrin‑graphene oxide nanocomposite:

synthesis, characterization and catalytic activity
Altaf Ahmed1 · Gita Devi1 · Ashu Kapahi1 · Sujata Kundan2 · Sapna Katoch1 · Gauri D. Bajju1 

Received: 7 July 2019 / Accepted: 9 October 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
The work presented in this paper illustrates a synthetic endeavour devoted to the design and modification of an important
donor–acceptor porphyrin-graphene oxide (Por-GO) nanocomposite. The resulting novel Por-GO architecture was thoroughly
characterized with respect to their spectroscopic and catalytic properties. The functionalization of GO is mediated by an
axial ligand on the respective metalloporphyrin having an amide linker between the graphene oxide and the porphyrin moi-
ety. The successful functionalization of GO with axial ligand modified Ni(II)-porphyrin forming covalently linked Por-GO
nanocomposite with good dispersion stability in organic solvents was confirmed by various spectroscopic techniques viz.,
Fourier Transform Infrared Spectroscopy, Ultraviolet Visible Absorption Spectroscopy, Powder X-ray Diffraction, Scanning
Electron Microscopy and High-resolution Transmission Electron Microscopy. Finally, the catalytic reduction of 4-Nitrophenol
to 4-Aminophenol by sodium borohydride (­ NaBH4−) as reductant and synthesized nanocomposite as a catalyst was monitored
spectrophotometrically. The aqueous solution of 4-Nitrophenol is yellow in color and shows intense absorption in the visible
range. The completion of reduction reaction was confirmed by the change of yellow color to completely colourless solution
corresponding to the reduced product (4-Aminophenol). Furthermore, the complete disappearance of the absorption peak
related to 4-Nitrophenolate and emergence of a new peak exhibiting large hypsochromic shift corroborate the formation of
4-Aminophenol. The whole process of reduction completes within an hour as evident by time-dependent UV–Vis spectra.
The Por-GO nanocomposite exhibit excellent catalytic activity.

1 Introduction hydrophilic and water-soluble [6], and provides a handle for

Graphene, an allotrope of carbon, is one of the thinnest and
strongest materials in the universe and considered as the
most stunning nanomaterial owing to its fabulous physical
and chemical properties [1]. It consists of a two dimensional
one atom thick sheet of graphite having a honeycomb lattice
of ­sp2-carbon atoms [2]. Graphene is an excellent electron
acceptor [3] which can be easily functionalized with other
molecules and therefore, presents a set of properties like
mechanical rigidity, optical transparency, high chemical and
thermal stability and electrical transport [4]. The presence
of oxygen-containing groups like epoxides, hydroxyl and
carboxylic acid [5] in graphene oxide renders it strongly
* Gauri D. Bajju
gauribajju@gmail.com
1
Department of Chemistry, University of Jammu, Jammu,
Jammu and Kashmir 180006, India
2
Department of Chemistry and Chemical Sciences, Central
University of Jammu, Jammu and Kashmir 180011, India
the chemical modification of graphene using known carbon
surface chemistry [7]. Moreover, graphene oxide (GO) has
large π-electron network and edges provide additional cata-
lytic sites ideal for electrocatalytic applications. However,
GO is electrically insulating because of the discontinuous
­sp2 bonding network and is thus unfavorable for the building
of optoelectronic devices [5, 8]. The electrical conductivity
and electron transfer properties of graphene can be partly
reinstated on moving from GO to reduced graphene oxide
(RGO). RGO has comparatively more electrochemical activ-
ity than GO because of the fewer oxygen functionalities on
the edges. Implanting organic framework onto the surface
of RGO proceed with retention of the structural integrity
of the RGO framework, thereby purging the problematical
loss of electronic structure [9]. The unique two dimensional
structures with its high specific surface area have made gra-
phene an attractive photocatalyst as well as ideal support
for constructing new type of graphene-based photocatalysts
for photocatalytic reactions [10]. Graphene sheets can be
decorated with different functional groups or nanomaterial

13
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to form graphene composites. The incorporation of gra-
phene into the composite can offer versatile characteristics
providing a new opportunity for designing and developing
next-generation catalyst. Chemical functionalization of RGO
may therefore potentially pave the way for their utilization
in various realistic applications.
Porphyrins on the other hand are regarded as one of
the most investigated group of macrocycles owing to their
exceptional photochemical and photophysical properties [11,
12]. Porphyrin consists of an 18 π-conjugated electronic
system moving in a square-planar circuit, giving rise to the
aromatic character of the ring and consequently for its stabi-
lization. Porphyrins are particularly amenable to the design
of complex and robust architectures because of their rigid
framework. In addition, porphyrin has an affinity to accom-
modate with almost all the metals of the periodic table to
form various metalloporphyrins and subsequently used for
numerous purposes ranging from solar energy harvesting
to photodynamic therapy (PDT), etc. [13]. The extensive
18 π-electron conjugated porphyrins have been widely stud-
ied for the functionalization of graphene oxide on the basis
of π–π interactions between them. Linking porphyrins to
material systems can improve the photochemical and redox
properties of the systems [14]. Axial coordination of metal-
loporphyrins however, offers a more versatile approach to
the rapid preparation and photophysical characterization of
self-assembled porphyrin-graphene oxide nanocomposites
[15]. Anchoring graphene with porphyrin through covalent
or non-covalent bonds can result in effective heterogeneous
interfacial electron transfer and long-distance transport at the
surface junction and therefore, it is expected that the cata-
lytic activity of the resultant nanohybrid can be tailored. The
coordination chemistry of axially ligated metalloporphyrins
with polydentate salicylic acid derivatives has provided a
vast field for the building of supramolecular entities [16].
There is a paucity of reported work consisting of covalently
linked Ni(II)-porphyrin to the graphene oxide-mediated by
axial ligands, although reports of various metalloporphyrins
linked through peripheral groups can be found in the litera-
ture [14]. Ni(II)-porphyrins have received attention as recep-
tors for various oxygen donors and their subsequent linking
to carbonaceous materials. Porphyrin-based graphene oxide
(GO) nanocomposites are fascinating since they merge the
exceptional properties of two unique materials. Porphyrin
itself exhibit excellent catalytic chemistry [17]. Combination
of the unparalleled properties of graphene and the porphy-
rin on its surface led to improvement the composite perfor-
mance. In fact the use of graphene as a support for porphyrin
led to a measureable enhancement of the electronic proper-
ties and synergistic interactions between the porphyrin and
the graphene. Many reports of graphene oxide functional-
ized with porphyrins and their metal complexes are available
in literature [7, 18–20].
13
Journal of Materials Science: Materials in Electronics
Herein, we report an approach for covalent grafting of a
metalloporphyrin over graphene oxide surface. The amino
group (–NH2) present on the axial salicylate ligand of the
porphyrin was used to covalently link onto RGO surface by
the amide reaction between the amino group of porphyrin
complex and carboxyl (–COOH) group of RGO. The result-
ing nanocomposite was well characterized by various spec-
troscopic techniques. The catalytic activity of the resulting
porphyrin-graphene oxide nanocomposite was also evalu-
ated spectrophotometrically for the catalytic reduction of
4-Nitrophenol. Furthermore, we discuss here the possible
mechanism of the reduction reaction.
2 Experimental sections
2.1 Materials
All reagents used in the experiment were of analytical
grade. Pyrrole was used as received and chloroform was
first dried over C
­ aH2 and then distilled. Nickel(II) acetate
[Ni(OAc)2·4H2O] was procured from Sigma Aldrich, para-
chlorobenzaldehyde ­(C7H5OCl) and ortho-nitrobenzalde-
hyde ­(C7H5NO3) were purchased from Himedia Labs and
used as received. 5-Aminosalicylic acid was procured from
SISCO Research Laboratories Pvt. Ltd. Mumbai-India.
Silica gel (60–120 mesh) procured from Merck, Germany,
was used for column chromatography. Graphite flakes and
potassium permanganate (­ KMnO4) were purchased from
Alfa Aesar and were used as received without further puri-
fication. Ethanol, sulphuric acid, phosphoric acid, hydrogen
peroxide, hydrazine hydrate, thionyl chloride ­(SOCl2) and
triethylamine ­(Et3N) were all supplied by Himedia Chemical
Reagent Company.
2.2 Synthesis
The synthesis process involves the following three steps.
2.2.1 Synthesis of graphene oxide and its derivatives
2.2.1.1  Preparation of  graphene oxide (GO) from  graph‑
ite flakes Graphite flakes were used for the synthesis of
graphene oxide (GO) following Hummers and Offeman’s
method with modification [21, 22]. The technique involves
the mixing of concentrated ­H2SO4/H3PO4 in 9:1 (81:9 mL)
ratio to a mixture of 1.25 g of graphite flakes and 9.0 g of
­KMnO4, producing a small exotherm (35–40  °C). Subse-
quently, the reaction mixture was stirred for 12 h at 50 °C,
cooled to room temperature and poured into ice-cold water
(100  mL) containing 30% H ­ 2O2 (1.25  mL) and finally fil-
tered. The filtrate was centrifuged (3000 rpm for 2 h) and the
supernatant was decanted away. The residual solid material
Journal of Materials Science: Materials in Electronics
was then washed twice in succession with 50 mL of water,
50  mL of dilute 30% HCl, and 50  mL of ethanol. Finally
washed with diethyl ether and the solid so obtained were
dried in vacuum overnight at room temperature yielding the
desired product.
2.2.1.2  Preparation of  reduced graphene oxide (RGO)
from graphene oxide  In a 250 mL round-bottom flask con-
taining 100 mL of distilled water, graphene oxide (1.0 mg)
was added and kept on a magnetic stirrer. After sonication
for 30 min, 10 mL of 50% hydrazine-hydrate was gradually
added to the resulting reaction mixture and refluxed for 4 h
at 100  °C. The solution mixture so obtained was filtered,
washed thoroughly with anhydrous THF and dried under
vacuum for 24 h.
2.2.1.3  Acylation of  reduced graphene oxide; (GO‑COCl)  NO2H3,6), 8.16 (6H, d, ­ArH2,6), 8.80 (2H, d, βHa), 8.87 (4H,
Thionyl chloride ­(SOCl2) was added in reduced graphene
oxide (1.0 g) under an inert ­(N2) atmosphere in a fuming
hood. After 5 min, 10 mL of DMF was added into the result-
ing mixture and refluxed at 70 °C for 24 h. The solution was
then filtered and washed thoroughly with anhydrous THF
and dried under vacuum for 24 h. At the end of the reaction,
excess ­SOCl2 and solvent were removed by distillation.
Scheme 1  Synthesis of Axially ligated Ni(II)-porphyrin
2.2.2 Synthesis of axially ligated metalloporphyrin
­[NH2SA‑NiPor]
A brief outline of the procedure is summarized in Scheme 1.
The procedure consists of first preparing metal-free porphy-
rin precursor followed by metalation and subsequent axial
ligation in three successive steps as below;
2.2.2.1  Step‑(i) Synthesis of  5,10,15‑Tris(4‑Chlorophenyl)
‑20‑(2‑Nitrophenyl)porphyrin (Por) The synthesis and
characterization of ­A3B-type unsymmetrical free-base por-
phyrin were carried out according to our previously pub-
lished procedure [23].
Characterization Anal. calcd. for C44H26N5Cl3O2 (%): C
69.26, H 3.43, N 13.94. Found: C 69.59, H 3.70, N 14.12,
UV–Vis ­(CHCl3): 460, 580, 623, 657 and 729 nm. 1H NMR
(400 MHz, ­CDCl3): δ (ppm) = − 2.70 (2H, s, NH), 7.29
(2H, d, Ar-NO2H4,5), 7.75(6H, d, A ­ rH3,5), 8.11 (2H, d, Ar-
s, βHc), 8.91 (2H, d, βHb). ESI–MS ­(CH3OH): m/z calcd. for
C44H26N5Cl3O2: 763.07; found 764.01 ([M + H]+), Rf = 0.71.
2.2.2.2  Step‑(ii) Synthesis of  5,10,15‑Tris(4‑chlorophenyl)
‑20‑(2‑nitrophenyl)nickel(II)‑porphyrin (NiPor) The syn-
thesis of the corresponding metalloderivative of free-base
porphyrin was carried out by treating Por with the Ni(II)-
acetate dissolved in methanol and chloroform [24].
13

Characterization Anal. calcd. for C 44H 24N 5Cl 3NiO 2
(%): C 64.47, H 2.95, N 12.97. Found: C 64.19, H 3.10, N
13.23, UV–Vis ­(CHCl3): 445, 618 and 675 nm. 1H NMR
(400 MHz, ­CDCl3): δ (ppm) = 9.37 (d, βHa), 8.97 (s, βHc),
9.01 (d, βH b), 7. 73 (6H, d, Ar-H 3,5), 7.28 (2H, d, Ar-
NO2H4,5), 8.15 (6H, d, Ar-H2,6), 8.09 (2H, d, Ar-NO2H3,6).
ESI–MS ­( CH 3 OH): m/z calcd. for C 44 H 24 N 5 Cl 3 NiO 2 :
819.75; found 821.03 ([M + H]+), Rf = 0.52.
2.2.2.3  Step‑(iii) Synthesis of  5″‑Aminosalicylato‑5,10,1
5‑tris(4‑Chlorophenyl)‑20‑(2‑Nitrophenyl)nickel(II)‑por‑
phyrin (NH2SA‑NiPor)  The synthesis of axial salicylate
ligated NiPor was carried out according to our previous
work [25, 26].
Characterization Anal. calc. for C 51 H 30 N 6 Cl 3 NiO 5
(%): C 63.03, H 3.11, N 8.65. Found: C 62.89, H 2.97,
N 8.27, UV–Vis (­CHCl 3 ): 450, 570 and 673  nm. 1 H
NMR (400 MHz, C ­ DCl3): δ (ppm) = 9.55 (d, βHa), 9.09
(s, βH c), 9.17 (d, βH b) 8.01 (6H,d, Ar-H 3,5), 7.75 (2H,
d, Ar-NO 2H 4,5), 8.78 (6H, d, Ar-H 2,6), 8.43 (2H, d, Ar-
NO2H3,6), 7.07 (d, H ­ 4″), 7.39 (d,H3″), 7.41 (s,H6″). ESI–MS
­(CH3OH): m/z calc. for C51H30N6Cl3NiO5: 971.88; found
971.03 ([M + H]+), Rf = 0.67.
2.2.3 Synthesis of covalently linked porphyrin‑graphene
oxide nanocomposites (Por‑GO)
Carboxylic acid groups situated at the periphery of
GO were utilized to covalently graft porphyrin through
amide linkages [27]. This is achieved by the function-
alization of acylated graphene oxide with axially ligated
Ni(II)-porphyrin. In this method, GO-COCl (60 mg) and
­NH2SA-NiPor (60 mg) was taken in a 250 mL round bot-
tom flask. The reaction mixture was dissolved in 30 mL
of N, N-dimethylformamide (DMF) in the presence of tri-
ethylamine ­(Et3N, 3 mL) and was allowed to react under
reflux at 100 °C for 72 h in an inert atmosphere. Conse-
quently, the mixture was sonicated, producing a uniform
black dispersion. The reaction mixture was then cooled to
room temperature and poured into 300 mL of diethyl ether
to precipitate the product. The precipitates were separated
by centrifugation (5000 rpm) and the supernatant contain-
ing unreacted porphyrin as impurities were discarded. The
precipitates were rinsed thoroughly over and again in five
washing successions. Each time sonication, filtration and
re-suspension of the precipitates in THF (60  mL) was
done. Finally, the product was washed several times with
­CHCl3 and water to remove the excess ­Et3N·HCl and dried
under vacuum. TLC was used to ensure the absence of any
unreacted porphyrin in the final product. The procedure
adopted for the synthesis of covalently-linked GO-porphy-
rin composites is outlined in Scheme 2.
13
Journal of Materials Science: Materials in Electronics
2.3 Catalytic activity determination
The catalytic activity testing of porphyrin-graphene oxide
(Por-GO) nanocomposite was carried out by first preparing
an aqueous solution of both the reactants; 4-Nitrophenol
and sodium borohydride (­ NaBH4) in the molar concentra-
tion of 1 mM and 0.3 M respectively at room temperature
and neutral pH conditions. Two separately prepared fresh
solutions of both the reactants (each 1 mL) were mixed by
magnetic stirring and transferred to a quartz cuvette/cell.
In one of the solution, 5 mg of prepared catalyst (Por-GO)
was loaded into the resulting reaction mixture placed in the
cuvette to start the reaction and immediately placed in the
cell holder of the spectrophotometer. From the second blank
solution of 4-Nitrophenol and N ­ aBH4, 5 mL of the solu-
tion was taken and the absorption spectrum was recorded
on UV–Vis spectrophotometer which is taken as read-
ing at 0 min. After every 4 min absorption spectra were
recorded by taking 5 mL of reactant solution containing Por-
GO catalyst. The same procedure was repeated until one
hour, in order to measure the residual concentration of the
4-Nitrophenol. The absorbance at λ = 400 nm in the UV–Vis
absorption spectra was used to monitor the progress of the
reduction reaction i.e. the conversion of 4-Nitrophenol into
4-Aminophenol by recording the time-dependent absorption
spectra at ambient temperature.
2.4 Characterization
Thin layer chromatography was performed on pre-coated
TLC Silica ­gel 60 on aluminium sheet, purchased from
Merck. UV–Vis spectra were recorded on a T90 + UV–Vis
spectrophotometer in the range 350–700 nm. Column chro-
matography was carried out on silica gel (100–200 mesh)
purchased from Merck. The FTIR spectra were recorded
on a Fourier Transform Infrared (FTIR Shimadzu Pres-
tige-21) spectrophotometer. X-ray diffraction patterns of
prepared samples were recorded by using an XPERT-PRO
diffractometer system with monochromatic Cu K ­ α radiation
(λ = 1.54060 Å), at a scanning rate of 12 °C/min in the 2θ
range of 10° to 70°. The SEM imaging of the prepared sam-
ples was carried out by using Nova Nano SEM-450 (JFEI
Company of USA). The TEM imaging of the synthesized
complexes was carried out by using Tecnai G2 20 S-TWIN
(FEI Company of USA).
3 Results and discussion
The coordination of 5″-Aminosalicylic acid to Ni(II)-por-
phyrin occurs through the carboxylic oxygen via depro-
tonation leaving behind the aromatic –OH and an amino
group (–NH2) at 2″ and 5″-Carbon respectively, free to
Journal of Materials Science: Materials in Electronics
Scheme 2  Schematic representation for the synthesis of covalently-linked axially ligated porphyrin-GO (Por-GO) nanocomposite
interact with other ligands. Since the aromatic –OH is steri-
cally hindered and –NH2 spatially more oriented for further
coordination, therefore, it is expected that a combination of
oxyphilic Ni(II)-porphyrin would be suitable for construc-
tion of supramolecular architectures with graphene oxide
via amide-linkages. Axial ligation of the metalloporphyrins,
therefore, affords an additional means for assembly or organ-
ization. Thus, the linking of 5″-aminosalicylato-5,10,15-
tris(4-chlorophenyl)-20-(2-nitrophenyl)nickel(II)-porphyrin
­(NH2SA-NiPor) (electron donor) to the reduced graphene
oxide (electron acceptor) via an amide linkage results in
a perfect donor–acceptor nanohybrid. The attachment of
organic molecules to graphene oxide has made the Por-GO
soluble in DMF and other polar solvents. The characteri-
zation of the synthesized Por-GO nanocomposite has been
discussed in subsequent sections.
3.1 FTIR spectroscopy
FTIR spectrum was used to investigate the structure and
nature of functional groups on the surface of GO. The FITR
spectrum shown in Fig. 1 reveals that GO has many oxygen-
containing groups such as hydroxyl, epoxide and carboxyl
groups [28]. Majority of the oxygen-containing groups on
the surface of GO will disappear after reduction. The most
prominent absorption band displayed by GO is a broad and
intense band at 3178 cm−1 that can be assigned to O–H
stretching vibration. Another characteristic band in the FTIR
spectra of GO at 1730 cm−1 is attributed to the stretching
vibrations of C = O of carbonyl and carboxyl groups [29].
Band appearing at 1624 cm−1 is assigned to the bending
vibration of OH-group whereas, ν(epoxy) band appears at
1170  cm−1. A band attributed to stretching vibration of
C–O–C (epoxy group) appears at 1054 cm−1. The bands at
1407–1330 cm−1 are the C–O absorption of carboxyl. From
the FTIR analysis, it can be assumed that the presence of
carboxyl, hydroxyl, epoxy and carbonyl groups in GO lead
to an increase of interlayer distance.
FTIR measurement results of different samples are shown
in Fig. 2 for the rationale of characterizing the difference
between reduced graphene oxide and Por-GO nanocompos-
ites. It can be seen that the RGO still contains some oxygen
functionalities as evident from the peak around 1720 cm−1.
The less intense peak corresponding to carbonyl or car-
boxyl group indicates that only fewer oxygen functionali-
ties still remains on the surface of graphene oxide even after
13

Fig. 1  FTIR spectra of graphene
oxide (GO)
Fig. 2  FTIR spectra of RGO, NiPor, ­
NH2-SA-NiPor and Por-GO
nanocomposite
reduction. The absorption intensity of the O–H band of GO
is stronger than corresponding RGO and Por-GO nanocom-
posites, it is proposed that the graphene oxide contains a
greater number of O–H groups on the surfaces due to oxida-
tion. Although the graphene oxide gets reduced during the
process of reduction, the FTIR spectrum of RGO even shows
some characteristic bands of GO such as stretching vibra-
tions due to OH and C = O. The main characteristic bands of
RGO are located at 1339, 1581, and 1632 cm−1, which are
attributed to stretching/deformation of C–OH and aromatic
C = C stretching, respectively. It has been reported that the
FT-IR spectra of reduced graphene oxide is very similar to
that of graphite. Some peaks observed around 2900 cm−1 are
13
Journal of Materials Science: Materials in Electronics
attributed to the stretching vibrations of C–H of GO, RGO
and Por-GO nanocomposite. The NiPor and N ­ H2SA-NiPor
spectrum shows many characteristic bands. The presence of
a band around 2900 cm−1 corresponding to the stretching
vibrations of C–H bonds of the phenyl. Moreover, the band
at 1550 cm−1 is attributed to C–C stretching. A broad band
at 3400 cm − 1 is attributed to the N–H bond stretching of
the axial 5-Aminosalicylate ligand [30].
The covalent functionalization of GO with porphyrins
results into the appearance of a new peak ~ 1600 ­cm−1
related to the C = C vibrations of porphyrins along with the
shift of peak at 1730–1640 c­ m−1 for Por-GO nanocompos-
ites corresponding to the C = O stretching vibration of the
amide group. The peak of the amide C–N stretching vibra-
tion appears at 1250 c­ m−1. The peak present at ~ 1707 cm−1
is assigned to the bending vibration of the C = N of the por-
phyrin ring. These results clearly point out that in graphene
oxide–porphyrin composites, the porphyrin molecules are
covalently linked to the graphene oxide via amide-linkages.
Moreover, all other frequencies corresponding to GO-free
porphyrin complex i.e. NH-2SA-NiPor are also presented by
the nanocomposite as well.
3.2 UV–Vis absorption spectroscopy
The electronic absorption spectra of the free base porphy-
rin (Por) exhibit two characteristic types of bands [31]; an
exceptionally intense Soret (B-band) band molar absorp-
tivities, ε, on the order of ­105 M−1 cm−1, can be found in
the near-UV or shorter-wavelength regions (400–450 nm)
and four weak bands, the Q-bands with one order of mag-
nitude lower molar absorbance, assigned to the π–π* transi-
tion between bonding and anti-bonding molecular orbitals
Journal of Materials Science: Materials in Electronics
­(S0 → S1), appear in the visible region of the spectrum or
longer-wavelength range (500–700 nm). However, the
UV–Vis spectra of NiPor exhibited blue-shifts in B-band
which is attributed to the metal d­ π ­(dxz and ­dyz) to porphy-
rin π* (M → L) back-bonding and the four Q-bands of free-
base porphyrin collapse to two bands. This dramatic effect is
ascribed to the enhancing of the D ­ 2h symmetry of the free-
base porphyrin to D­ 4h on metalation (Fig. 3a). Moreover, the
Por display ‘etio-type’ Q-band spectrum in which the rela-
tive intensities of these bands are such that IV > III > II > I
as shown in Fig. 3a (Por x 10). The extremely low intensity
of Q–I band may be due to the unsymmetrical nature of the
porphyrin causing distortion.
The optical absorption spectra recorded in DMF for
graphene oxide (GO), reduced graphene oxide (RGO)
before and after its covalent interactions with porphyrin
molecule are shown in Fig. 3b. Graphene oxide displays
a broad absorption signal [32, 33] at 265 nm decreasing
(a)
(b)
Fig. 3  a UV–Vis absorption spectra of Por, NiPor and Q-Bands of
Por (x 10) in ­CHCl3. b UV–Vis absorption spectra of GO, RGO,
­NH2SA-NiPor and Por-GO nanocomposites
monotonically from the UV to the visible region and a small
shoulder band around 315 nm. These bands are attributed
to the π–π* transitions of aromatic C = C band and n–π*
transitions of C = O band [22], respectively. However, the
reduced graphene oxide (RGO) exhibit a red-shifted UV–Vis
absorption spectrum (λmax = 276 nm) compared to GO, the
shoulder band at 315 nm disappears and the absorbance in
the whole spectral region decreases. The bathochromic shift
indicates that the GO was efficiently reduced. Certainly, the
reduction in oxygen functionalities led to slight diminishing
in the absorption intensity, thus the electrons can easily be
excited at lower energy and a slight shift is noted after the
reduction of GO sheets.
Conversely, the absorption spectrum of free porphy-
rin complex ­(NH 2SA-NiPor) in which the delocalized
π-electrons shows very strong π–π* absorption and exhibit
a strong soret absorption at 419 nm and two weak Q-bands
at 518 and 549 nm. The nanocomposite (Por-GO) exhibits
a broad absorption at 283 nm, which is the corresponding
RGO peak with a red-shift of 7 nm. Moreover, in the Por-GO
nanocomposites, a similar band is also observed at 425 nm,
which corresponds to the soret band of the porphyrin moiety
and obviously a red-shift of 6 nm is observed which is attrib-
uted to the covalently grafted porphyrin moiety. However,
the Q-bands as displayed by the free porphyrin complex at
518 and 549 nm get shortened, red-shifted and flattened to
the baseline in the corresponding nanomaterial [34] and only
a broader hump is observed at 550 nm.
The red-shifts in the soret band [35] from 419 to 425 nm
for the nanocomposites can also be ascribed to the adsorp-
tion of porphyrin complex on GO induced by π–π stack-
ing interactions between the porphyrin moiety and the GO.
These results corroborate not only the linkage of porphyrin
with the GO sheets but also indicate that attachment of the
porphyrin moiety has perturbed both the ground state elec-
tronic state of the graphene oxide as well as of the porphyrin
part.
3.3 Powder X‑ray diffraction
The structural characterization of the nanoparticles has been
carried out by Powder X-ray diffraction technique using Cu
Kα radiation [36]. The powder X-ray diffraction (PXRD)
pattern of graphene oxide is shown in Fig. 4. A sharp peak
(2θ) at 10.15° (001) and a weak peak at 42.05° (002) cor-
responding to layer-to-layer distance (d–spacing) spacing of
8.27 and 3.47 Å respectively, are characteristic diffraction
peaks for graphene oxide. The diffraction peak at 2θ = 10.15°
is indistinct, which suggests that the graphite is exfoliated to
graphene oxide and reduced graphene oxide; the sectional
oxygen-containing groups were removed during reduction
treatment. Some weak and broad peak in the range of (2θ)
20° corresponds to (100) with the d-spacing 3.17 Å indicates
13

Fig. 4  PXRD pattern of graphene oxide (GO)
Fig. 5  PXRD pattern of Por-GO nanocomposite
the presence of some under oxidized graphitic material. The
results obtained are in accordance with the literature [37].
These peaks vary, depending on the preparation method and
the number of layers in the graphite gallery.
However, the parent graphite exhibits a peak at 26.31°
(2θ) [38]. This downshift of XRD-signal from 26.31° (2θ)
to 10.5° (2θ) after oxidation is an indication of decreasing
graphene layer number in graphene oxide (GO) due to exfo-
liation with respect to parent graphite, suggesting the pres-
ence of few-layered graphene sheets [39].
For the Por-GO Nanocomposites (Fig. 5), a comparatively
broader peak is observed at 12.1° (2θ) corresponding to a
d-spacing of 7.52 Å. This indicates that the interlayer spac-
ing was maintained due to the intercalation of porphyrin
and the successful formation of the Por-GO nanocomposites
[40]. The peaks of the nanocomposites are comparatively
13
Journal of Materials Science: Materials in Electronics
broader indicating typically amorphous nature. Moreover, in
the XRD pattern of Por-GO nanocomposites, the presence of
smaller peaks around 2θ = 13o indicates oxygen-containing
groups still exist in the nanocomposites through the oxygen-
containing groups were partly removed during exfoliation.
The presence of crystalline domains could enhance the
charge transport and stabilize the amorphous Por-GO dur-
ing charging and discharging. The PXRD profile confirmed
the amorphous character of cross-linked porphyrin-graphene
oxide nanocomposites. Therefore, the cross-linked Por-GO
is an amorphous and nanoporous polymer bearing covalently
linked porphyrin functionalities in the nanocomposites.
These results corroborate the formation of a new product
as a result of covalent linkage of porphyrin moiety with the
GO surfaces.
3.4 Scanning electron microscopy
Morphology and topography of graphene oxide have been
investigated by scanning electron microscopy (SEM). The
graphite powder is composed of a number of flake-like
layers. However, after the oxidation process, these graph-
ite layers were exfoliated and subsequently intercalated by
epoxy, carbonyl, carboxyl and hydroxyl functional groups of
graphene oxide. The SEM images of synthesized graphene
oxide and its covalently linked Por-GO nanocomposites are
shown in Fig. 6. The SEM micrograph shows that the gra-
phene oxide has a layered structure [41] with a large number
of cavities and free space, which affords ultrathin and homo-
geneous films. It is observed from the images that crumpled
and rippled structures are there which are due to resulting of
deformation upon the exfoliation and restacking processes.
Figure 6 shows that the graphene sheets are entangled with
each other and also the single or few-layer graphene oxide
sheets have lots of wrinkles.
The scanning electron micrographs for the Por-GO nano-
composites reveal the expected sheet morphology over a few
micron length scales. The graphene sheets in the nanocom-
posites appear somewhat more wrinkled compared to the
neat the GO sheets. A stacked lamellar morphology with
graphene sheets was also observed in the Por-GO nanohy-
brid. On account of functionalization, GO exhibits a three-
dimensional network of randomly oriented sheet-like struc-
tures with a wrinkled texture and hierarchical pores with
wide size distribution. The SEM-micrograph for the Por-
GO nanohybrid materials also demonstrates a homogeneous
system. It is clearly seen from the top-view image that the
composites have a uniform and dense surface, composed of
plate-like particles with slightly scrolled edges ranging from
several tens of nanometers to several hundreds of nanom-
eters in the lateral dimension. Some GO flakes of composites
fold together and represent crinkly sheets. The surface is
Journal of Materials Science: Materials in Electronics
Fig. 6  a–b SEM images of graphene oxide c ­NH2SA-NiPor and d Por-GO nanocomposite
much rougher than that of GO which can be attributed to the
covalent linkage of porphyrin to the GO sheet [42].
3.5 Transmission electron microscopy
The morphological and structural features and extent of
covalent linking of Por-GO nanocomposite as investigated
by SEM analysis were further supported by TEM micro-
graphs. Figure 7 shows the selected high-resolution TEM
(HR-TEM) micrographs for GO and free porphyrin with
their corresponding nanocomposites. The HR-TEM image
of GO has few micrometer lengths with fold however, that of
RGO reveals a wrinkled, curled and corrugated morphology
typical of few-layered structure [43]. It has been found that
the graphene flakes have wrinkled surfaces. Furthermore, in
the TEM image GO shows the layer-by-layer stacked struc-
ture and have a wrinkled paper like morphology. Such mor-
phological changes can be attributed to the increased forma-
tion of phenolic and epoxy functional groups on the basal
plane of GO. The curled and overlapped nanosheets can be
clearly observed. The existence of small nanoparticles (dark
spots) [5] distributed on the wrinkled graphene sheets of
Por-GO Fig. 7d confirms the presence of N ­ H2SA-NiPor, and
further supports the presence of covalent bonding between
­NH2SA-NiPor and GO. The images reveal a uniform distri-
bution of porphyrin nanocomposites on the surface of gra-
phene sheets making rough (granular) surfaces.
4 Catalytic activity of Por‑GO
nanocomposite
Nitroaromatic compounds and their derivatives are key
organic pollutants created as by-products or intermediates
in a number of industrial processes [44, 45]. Plentiful of
nitroaromatic compounds have been discharged into the riv-
ers and soil amid the over use of dyes, explosives and pes-
ticides in industry, causing severe water and soil pollution
[46]. Regrettably, among nitro-compounds, 4-Nitrophenol
is the most typical toxin and insurmountable organic pollut-
ant, distressing the eco-systems of both humans as well as
animals and hence promoting a variety of ailments. 4-Nitro-
phenol with other derivatives is a familiar by-product of the
chemical industry. The manufacture of pesticides, herbi-
cides, pharmaceuticals, synthetic dyes, cosmetics, photo-
graphic chemicals, etc. produces 4-Nitrophenol as the side-
product. 4-Nitrophenol notably is well-known to cause lethal
effects in the biological systems particularly it affects the
13

Fig. 7  HR-TEM micrographs of a GO b RGO c ­NH2SA-NiPor and d Por-GO nanocomposites
liver, kidney and blood of both animal and human and dam-
age to the central nervous system owing to their severe tox-
icity in water and soil. Therefore, its degradation into less/
non-toxic small molecules and in turn thwarting mischief
is a crucial task and has become an active area of research
in recent years. Likewise, the reduction of 4-Nitrophenol is
particularly indispensable in pharmaceutical industries for
the manufacture of analgesic, antipyretic and primarily a
key intermediate in the synthesis of paracetamol [47, 48].
Moreover, it also finds relevance as a photographic devel-
oper, corrosion inhibitor, anticorrosion lubricant, drying
agent [49, 50], etc.
In general, the catalytic conversion of 4-Nitrophenol to
4-Aminophenol is a crucial process, using excess sodium
borohydride ­( NaBH 4) as the reducing agent, not only
because 4-Aminophenol is less toxic than 4-Nitrophenol,
but also because 4-Aminophenol is in demand on the market
in many industrial fields [51]. Disappointingly, the reduc-
tion process of 4-Nitrophenol to 4-Aminophenol is very
sluggish by ­NaBH4 alone. Hence, the use of catalysts is
necessary to enable electron transfer from donor ­BH4− to
acceptor 4-Nitrophenol [52]. Many practices have been in
use to solve the pollution problems of 4-Nitrophenol (nitro-
group removal or its conversion to non-toxic form) [53].
13
Journal of Materials Science: Materials in Electronics
Use of semiconductor nanomaterials such as ZnO, ­Cu2O and
­TiO2 and various methods (e.g. photocatalysis and chemical
catalysis) have been reported and even succeeded in its deg-
radation or reduction [54]. But no efficient method has been
developed so far to deal with the problem of slow reduction
of 4-Nitrophenol. The difficulty to degrade 4- Nitrophenol is
due to the high stability and low solubility of the substrate in
water [55]. Most recently, porphyrin-based graphene oxide
nanocomposites have been intensely explored because of
their unique and tuneable electric, thermal, mechanical, opti-
cal properties and high catalytic activities.
4.1 Catalytic reduction of 4‑nitrophenol
To determine the catalytic behaviour of porphyrin-based
graphene oxide nanocomposites, the catalytic reduction of
4- Nitrophenol was chosen as a model reaction. The aque-
ous solution of 4-Nitrophenol is yellow in color that assists
to study the kinetics of the reaction spectrophotometrically.
The nitrophenolate ion at a higher alkaline pH (pH > 12.0)
increases the spectrophotometric sensitivity of the method
that can be gauged by a visible spectrophotometer only.
It has been reported that the original aqueous solution of
4- Nitrophenol has a maximum absorption peak (λmax) at
Journal of Materials Science: Materials in Electronics

317 nm [56] and if no catalyst is added, the peak at 317 nm

in the UV–Vis spectra remains unchanged even after keep-
ing the reaction mixture for a long time. The uncatalyzed
reaction does not proceed favorably well in the forward
direction and hence Por-GO nanocomposite plays its role to
catalyze the reduction process. Upon addition of a freshly
prepared solution of ­NaBH4 solution, the absorption peak at
317 nm undergoes bathochromic shift (red-shift) to 400 nm
due to the formation of 4-Nitrophenolate ions, and mean-
while, the color of the mixture changes from light yellow to
dark yellow. The ­NaBH4 leads to an alkaline pH and the yel-
low solution of 4-Nitrophenolate remains stable for hours if
no catalyst is added. The reduction reaction cannot proceed
in the forward direction without catalyst [57] even in the
presence of excess ­NaBH4 as evident from the almost con-
stant absorbance at 400 nm. However, it has been observed
that upon addition of a catalytic amount (5 mg) of Por-GO
nanocomposite, the yellow color of the solution decolorized
within an hour. After a reaction time of about 50 min, no
4-Nitrophenol could be detected by UV–Vis spectroscopy.
The reaction was carried out at room temperature. Schematic
representation of the procedure is described in Scheme 3.
The time-dependent UV–Vis absorption spectra of the
catalytic reduction process of 4-Nitrophenol by Por-GO
nanocomposites in the presence of excess N ­ aBH4 at a cer-
tain time interval is displayed in Fig. 8. As soon as the Por-
GO nanocomposite (catalyst) is introduced into the reaction
mixture, the intensity of the main absorption peak around
400 nm corresponding to organic pollutant starts diminish-
ing [58]. Simultaneously, a new peak around 300 nm starts
emerging and increases (indicated by arrows) in intensity
as a function of the reaction time. The augment of a new
peak around 300 nm is attributed to the formation of 4-Ami-
nophenol, the subsequent products of the reduction reaction
of 4-Nitrophenol. The peak at 400 nm disappears completely
within 50 min of reaction time. The yellow color of the solu-
tion converted to colorless, demonstrating that the 4-itro-
phenol is completely changed into 4-Aminophenol and no
Fig. 8  UV − Vis spectra of the reduction process of 4-Nitrophenolate
to 4-Aminophenolate catalyzed by Por-GO nanocomposite
more reactant is left behind. The product, 4-Aminophenol
devoid of any chromophore imparts no color to the aqueous
solution and hence does not hamper the spectrophotometric
determination.
4.2 Mechanism of catalytic reduction
It has now been established beyond suspicion that cataly-
sis involving nitroarenes reduction depends not only on
the size but also on the shape and surface of the catalyst
particle as well. Therefore, the catalysts having greater sur-
face area, porosity, facet selection and heterojunction etc.
has been found to change the potential of a catalyst dra-
matically. There exists a number of reported mechanisms
for the reduction of niroarenes [59]. The reduction reaction
of 4-Nitrophenol to 4-Aminophenol occurs in the presence
of a reductant, sodium borohydride (­ NaBH4) and a catalyst.
This reduction is ideally considered to proceed through a
number of stages. Thus, it is corroborating a straight forward
process to produce only 4-Aminophenol without any side
product. Thermodynamically the reduction of 4-Nitrophe-
nol to 4-Aminophenol (Eº = − 0.76 V) at ambient condition
is favourable as borohydride in water is a strong reductant

Scheme 3  Schematic represen-
tation of the catalytic reduction
of 4-Nitrophenol to 4-Ami-
nophenol by ­NaBH4

13

(Eº = − 1.33 V). The reduction reaction in absence of Por-
GO catalyst does not proceed in the forward direction under
the experimental time scale because of the kinetic barrier.
This barrier is judiciously by-passed through the deployment
of catalyst and even catalysts with a huge support. In the
reduction process the electron relay takes place irreversibly
[11].
Exactly how Por-GO catalyst flank the surface atoms to
accommodate 4-Nitrophenol to 4-Aminophenol molecules
remain unclear. However, the mechanism of the reaction can
be understood in terms of Langmuir–Hinshelwood model
[60]. The mechanism of catalytic reduction of 4-Nitrophe-
nol to 4-Aminophenol involves the diffusion and adsorption
of both the reactants [61]; 4-Nitrophenol and the reduct-
ant ­NaBH4 to the surface of the Por-GO nanocomposite
[62]. The substrate anchors on the nanocatalyst sheet due
to the presence of –OH and –NO2 groups. The substrate
gets uniformly distributed on the Por-GO hybrid catalyst
surface. The reaction medium is mostly basic as sodium
borohydride in aqueous medium splits to give borohydride
anion and sodium cation which makes the solution basic in
nature. In the direct route of substrate reduction, the reduc-
tion of 4-Nitrophenol to 4-Aminophenol occurs in a step-
wise manner through the formation of 4-Nitrosophenol and
4-hydroxylaminophenol as intermediates by using six elec-
trons and six protons. The electron transfer occurs from the
negatively charged B ­ H4− to 4-Nitrophenol [63]. It is note-
worthy to mention here that the 4-hydroxylaminophenol is
the first stable intermediate of the reduction reaction. Hence,
the compounds that compete to undergo adsorption and des-
orption cycle with the fixed number of sites of the catalyst’s
surface are 4-Nitrophenol, 4-Nitrosophenol, 4-hydroxylami-
nophenol and 4-Aminophenol. The adsorbed species then
reacts and finally the reaction product dissociate from the
surface of catalyst. The diagrammatic representation of the
catalytic process is presented in Fig. 9.
The Por-GO support plays an active part in the cataly-
sis to give a synergistic effect. The RGO increases catalytic
activity of the Por-GO nanocomposite by facilitating elec-
tron transfer to reactant molecule along with the extensive
sites for the attachment. RGO, due to the presence of exten-
sive network of conjugated ­sp2 carbons provides excellent
mobility of electrons. Therefore, the synergistic catalytic
activity of the porphyrin and RGO can be explained in terms
of catalytic nature of Ni(II)-metal inside the porphyrin core
whereas, the RGO provide greater surface area for anchor-
ing the substrate to be reduced. RGO alone was also found
to catalyse the reduction reaction of 4-Nitrophenol but with
greater reaction time (≈ 5 h). Moreover, it is also projected
that the π–π interactions [64] between the 4-Nitrophenol and
Por-GO nanocomposite helps the adsorption of 4-Nitrophe-
nol on nanocomposite surface, offering a high concentra-
tion of 4-Nitrophenol near to the Por-GO surfaces and thus
13
Journal of Materials Science: Materials in Electronics
OH
Por
6H+
Por
NaBH4
Por NO2
e 6e
OH
Por
Por
Por
NH2
Fig. 9  Diagrammatic representation of the catalytic process of reduc-
tion of 4-Nitrophenol to 4-Aminophenol facilitated by Por-GO nano-
composite
enabling efficient contact between them. The schematic
representation of the mechanism of catalytic reduction of
4-Nitrophenol to 4-Aminophenol is shown in Scheme 4.
After completion of the reduction reaction, the recyclabil-
ity and reusability of the Por-GO catalyst was checked by
UV–Vis absorption spectroscopy. The catalyst was recov-
ered by centrifugation followed by washing with metha-
nol and dried at 50 °C. The recovered photocatalyst was
reused without recharging for about four subsequent runs
under described experimental conditions. No significant
loss in activity was observed for the recycled catalyst, and
the reduction reaction time remained almost unchanged
even after four recycling experiments, which confirmed the
true heterogeneous nature of the developed photocatalyst.
The absorption spectra of the Por-GO nanocomposite did
not show any change even after four recycling experiment.
These results corroborate not only that the covalent bonding
between the RGO and porphyrin complex as strong enough
but also the porphyrin complex did not show any leaching
out from the surface of RGO during the reaction.
5 Conclusions
A porphyrin-graphene oxide nanocomposite forming
donor–acceptor system has been reported. The resulting
supramolecular architecture was well characterized by
various spectroscopic studies. The covalent functionali-
zation of GO with porphyrin results into the appearance
of a new peak in the FTIR spectrum. The Soret band in
the UV–Vis spectra of Por-GO nanocomposite, display a
slight redshift (≈ 6 nm) as compared to the free porphy-
rin, whereas the two Q-bands get red-shifted, shortened
Journal of Materials Science: Materials in Electronics
Scheme 4  Mechanism of cata-
lytic reduction of 4-Nitrophenol
to 4-Aminophenol in presence
of ­NaBH4 and Por-GO compos-
ite as catalyst
and flattened to the baseline. These results corroborate
not only the linkage of porphyrin with GO sheets but also
indicate that the attachment of the porphyrin moiety has
perturbed both the ground electronic state of the GO as
well as porphyrin. In the PXRD pattern of Por-GO nano-
composite, a comparatively broader peak is observed at
12.1°(2θ) with a d-spacing of 7.52 Ǻ indicating the inter-
layer spacing was maintained due to the intercalation of
porphyrin and the successful formation of Por-GO nano-
composite. The PXRD profile confirmed the amorphous
and nanoporous character of the cross-linked nanocompos-
ite. The morphology and topography of the nanocompos-
ite appear to have stacked lamellar structure with a large
number of cavities and free spaces as evidenced by SEM.
The graphene sheet surfaces in the nanocomposite appear
somewhat more wrinkled and rough compared to the neat
GO sheets which can be attributed to the covalent linkage
of porphyrin to the GO sheet. The morphological features
and extent of covalent linking are further supported by
TEM analysis. HR-TEM images of RGO reveal a wrinkled,
curled and corrugated sheet typical of a few layered struc-
tures. The existence of small nanoparticles (dark spot)
distributed uniformly on the wrinkled graphene sheets of
Por-GO nanocomposite further supports the functionaliza-
tion of GO by the covalent bonding between N­ H2SA-NiPor
and GO.
After the successful synthesis and characterization, the
Por-GO nanocomposite was further tested for the photo-
catalytic reduction of 4-Nitrophenol as the representa-
tive substrate under the visible light irradiation using
sodium borohydride as reductant. The reduction reaction
of 4-Nitrophenol to 4-Aminophenol catalyzed by Por-GO
nanocomposite results in the color change of the substrate
solution from dark yellow to colourless, associated with a
characteristic hypsochromic shift in the absorption peak
from 400  nm to 300  nm, indicating the conversion of
4-Nitrophenolate to 4-Aminophenol. Therefore, the Por-
GO nanocomposites serve as an efficient nanocatalyst for
the catalytic reduction of organic pollutants in the treat-
ment of contaminated water and help reduction in water
pollution.
Acknowledgments  We would like to acknowledge the Council of Sci-
entific and Industrial Research (CSIR), New Delhi under Grant No.
09/100(0184)/2015-EMR-I for financial assistance. We thank SAIF,
Punjab University Chandigarh for powder X-ray diffraction study,
Indian Institute of Technology Mandi for SEM and TEM studies.
References
1. J. Yao, Y. Sun, M. Yang, Y. Duan, J. Mater. Chem. 22, 14313
(2012)
2. Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff,
Adv. Mater. 22, 3906 (2010)
3. G. Cardenas-Jiron, M. Borges-Martinez, E. Sikorski, T. Baruah,
J. Phys. Chem. C 121, 4859 (2017)
4. M. Kumar, H. Khajuria, H.N. Sheikh, J. Mater. Sci. 28, 9423
(2017)
5. A. Wang et al., Inorg. Chem. Front. 3, 296 (2016)
6. S. Stankovich et al., Nature 442, 282 (2006)
7. B.Y. Xu et al., Adv. Mater. 21, 1275 (2009)
8. P.V. Kamat, J. Phys. Chem. Lett. 2, 242 (2011)
9. B. Zhang et al., J. Polym. Sci. 50(2), 378 (2012)
10. A. Kumar, P. Kumar, S. Paul, S.L. Jain, App. Surf. Sci. 386, 103–
114 (2016)
11. P. Kumar, A. Kumar, C. Joshi, R. Singh, S. Saran, S.L. Jain, RSC
Adv. 5, 42414–42421 (2015)
12. S. Katoch, G.D. Bajju, G. Devi, A. Ahmed, J. Therm. Anal. Calo-
rim. 130, 2157 (2017)
13. P. Dechan, G.D. Bajju, P. Sood, U.A. Dar, J. Mol. Str. 1183, 87–99
(2019)
14. R. Yamuna, S. Ramakrishnan, K. Dhara, R. Devi, N.K. Kothurkar,
E. Kirubha, P.K. Palanisamy, J. Nanopart. Res. 15, 1399–1408
(2013)
15. C.M. Drain, A. Varotto, I. Radivojevic, Chem. Rev. 109, 1630
(2009)
16. J.E. Redman, N. Feeder, S.J. Teat, J.K.M. Sanders, Inorg. Chem.
40, 2486 (2001)
17. Y. Watanabe, H. Fujii, in Metal-oxo and metal-peroxo species
in catalytic oxidations, structure and bonding, vol. 97, ed. by B.
Meunier (Springer, Berlin, 2000), p. 61
18. Z.B. Liu, Y.F. Xu, X.Y. Zhang, X.L. Zhang, Y.S. Chen, J.G. Tian,
J. Phys. Chem. B 113, 9681–9686 (2009)
19. M.B.M. Krishna, N. Venkatramaiah, R. Venkatesan, D.N. Rao, J.
Mater. Chem. 22, 3059–3068 (2012)
20. M.B.M. Krishna, V.P. Kumar, N. Venkatramaiah, R. Venkatesan,
D.N. Rao, Appl. Phys. Lett. 98, 081103–081106 (2011)
21. W.S. Hummers Jr., R.E. Offeman, J. Am. Chem. Soc. 80(6), 1339
(1958)
13

22. D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun,
A. Slesarev, L.B. Alemany, W. Lu, J.M. Tour, ACS Nano 4, 4806
(2010)
23. A. Ahmed, Ashu, G. Devi, S. Katoch, G.D. Bajju, Ind. J. Heter.
Chem. 27, 255–264 (2017)
24. H.M. Ahn, J.M. Bae, M.J. Kim, K.H. Bok, H.Y. Jeong, S.J. Lee,
C. Kim, Chem. 23, 11969–11976 (2017)
25. G.D. Bajju, Ashu, A. Ahmed, G. Devi, BMC Chem. 13, 15 (2019)
26. G.D. Bajju, S. Katoch, G. Devi, S. Kundan, M. Bhagat, Main
Group Met. Chem. 39, 19–29 (2016)
27. S. Sakthinathan, S. Kubendhiran, S.M. Chen, K. Manibalan, M.
Govindasamy, P. Tamizhdurai, Electroanalysis 28, 1 (2016)
28. Y. Xu, H. Bai, G. Lu, C. Li, G. Shi, J. Am. Chem. Soc. 130, 5856
(2008)
29. A. Bakour, M. Baitoul, O. Bajjou, F. Massuyeau, E. Faul-
ques, Mater. Res. Express. 4, 025031 (2017). https ​ : //doi.
org/10.1088/2053-1591/aa5ad​4
30. O. Bajjou, A. Bakour, M. Khenfouch, M. Baitoul, E. Faulques, M.
Maaza, Synth. Met. 221, 247–252 (2016)
31. O. Bajjou, A. Bakour, M. Khenfouch, M. Baitoul, B.M. Mothudi,
M. Maaza, E. Faulques, J. Mater. Sci. 29, 8594–8600 (2018)
32. Z. Liu, Y. Wang, X. Zhang, Y. Xu, Y. Chen, J. Tian, Appl. Phys.
Lett. 94, 021902 (2009)
33. T. Umeyama et al., J. Phys. Chem. C 111, 11484 (2007)
34. N. Karousis, A.S.D. Sandanayaka, T. Hasobe, S.P. Economopou-
los, E. Sarantopoulos, N. Tagmatarchis, J. Mater. Chem. 21, 109
(2011)
35. Y. Xu, L. Zhao, H. Bai, W. Hong, C. Li, G. Shi, J. Am. Chem. Soc.
131, 13490 (2009)
36. M. Jahan, Q. Bao, K.P. Loh, J. Am. Chem. Soc. 134, 6707 (2012)
37. D. Geng, S. Yang, Y. Zhang, J. Yang, J. Liu, R. Li, T.K. Sham, X.
Sun, S. Ye, S. Knights, Appl. Surf. Sci. 257, 9193–9198 (2011)
38. N.A. Kumar et al., J. Mater. Chem. A 5, 13204 (2017)
39. R. Krishna, E. Titus, L.C. Costa, J.C. Menezes, M.R. Correia, S.
Pinto, J. Mater. Chem. 22, 10457–10459 (2012)
40. B. Yao, C. Li, J. Ma, G. Shi, Phys. Chem. Chem. Phys. 17, 19538
(2015)
41. S. Kulbendhiran, S. Saktinathan, S.-M. Chen, P. Tamizhdurai, J.
Colloid Interface Sci. 497, 207 (2017)
42. R. Rahimi, R. Zare-Dorabei, A. Koohi, S. Zargari, Proceeding of
the 18th International Electronic Conference on Synthetic Organic
Chemistry, Lugo (2014)
13
Journal of Materials Science: Materials in Electronics
43. N.A. Kumar, H.J. Choi, Y.R. Shin, D.W. Chang, L. Dai, J.B. Baek,
ACS Nano 6, 1715–1723 (2012)
44. S. Panigrahi et al., J. Phys. Chem. C 111, 4596 (2007)
45. N. Comisso et al., Electrochem. Commun. 25, 91 (2012)
46. X.F. Zhang, X.Y. Zhu, J.J. Feng, A.J. Wang, Appl. Surf. Sci. 428,
798 (2018)
47. K.B. Narayanan, N. Sakthivel, J. Hazard. Mater. 189, 519 (2011)
48. D. Makovec, M. Sajko, A. Selisnik, M. Drofenik, Mater. Chem.
Phys. 129, 83 (2011)
49. T.L. Lai, K.F. Yong, J.W. Yu, J.H. Chen, Y.Y. Shu, C.B. Wang, J.
Hazard. Mater. 185, 366 (2011)
50. P. Babji, V.L. Rao, Int. J. Chem. Studies 4, 123 (2016)
51. Y. Liu, Y.Y. Zhang, Q.W. Kou, Y. Chen, D.L. Han, D.D. Wang,
Z.Y. Lu, L. Chen, J.H. Yang, S. Xing, RSC Adv. 8, 2209 (2018)
52. M.T. Shah, A. Balouch, A.A. Pathan, A.M. Mahar, S. Sabir, R.
Khattak, A.A. Umar, Microsyst. Technol. 23(12), 5745–5758
(2017)
53. E. Marais, T. Nyokong, J. Hazard. Mater. 152, 293 (2008)
54. X. Zhao, Y. Wang, W.H. Feng, H.T. Lei, J. Li, RSC Adv. 7, 52738
(2017)
55. Y. Chen, Y. Zhang, Q. Kou et al., Nanomaterials 8, 353 (2018)
56. M. Gangarapu, S. Sarangapany, K.K. Veerabhali, S.P. Devi-
priya, V.B.R. Arava, J. Clust. Sci. https​://doi.org/10.1007/s1087​
6-017-1280-3
57. R. Krishnaa et al., Int. J. Hyd. Energy 40, 4996 (2015)
58. R. Krishnaa, D.M. Fernandesb, V.F. Domingosc, E.S. Ribeirod,
J.C. Gild, E. Titus, RSC Adv. https​://doi.org/10.1039/c5ra0​5523g​
59. T. Aditya, A. Pal, T. Pal, Chem. Commun. 51, 9410–9431 (2015)
60. Z.D. Pozun, S.E. Rodenbush, E. Keller, K. Tran, W. Tang, K.J.
Stevenson et al., J. Phys. Chem. C 117, 7598–7604 (2013)
61. P. Zhao, X. Feng, D. Huang, D. Astruc, Coord. Chem. Rev. 287,
114 (2015)
62. T. Aditya, A. Pal, T. Pal, Chem. Commun. 00, 1 (2012)
63. R. Krishna, E. Titus, O. Okhay, J.C. Gil, J. Ventura, R.E. Venkata,
Int. J. Electrochem. Sci. 9, 4054 (2014)
64. S. Bai, X. Shen, G. Zhu, M. Li, K. Chen, A.C.S. Appl, Mater.
Interfaces 4, 2378 (2012)
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