Research Article

pubs.acs.org/journal/ascecg

Green Fluorescent Onion-Like Carbon Nanoparticles from Flaxseed

Oil for Visible Light Induced Photocatalytic Applications and Label-
Free Detection of Al(III) Ions
Kumud Malika Tripathi,† Tuan Sang Tran,† Yoon Jin Kim,‡ and TaeYoung Kim*,†
†
Department of Bionanotechnology, Gachon University, 1342 Seongnam-daero, Sujeong-gu, Seongnam-si, Gyeonggi-do 461-701,
South Korea
‡
Energy Nano Materials Research Center, Korea Electronics Technology Institute, 25 Saenari-ro, Bundang-gu, Seongnam-si,
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Gyeonggi-do 463-816, South Korea

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*
S Supporting Information

ABSTRACT: Onion-like carbon nanoparticles (CNOs) were synthesized via

traditional pyrolysis of flaxseed oil. Oxidative treatment of as-synthesized carbon
soot introduced numerous carboxyl (−COOH) functionalities, rendering them
hydrophilic and stable in aqueous phase. The water-soluble onion-like carbon
nanoparticles (wsCNOs) were 4−8 nm in size and exhibited stable green
photoluminescence (PL) emission. CNOs were explored as efficient photocatalysts
for the degradation of methylene blue (MB) as model organic pollutant dye under
visible light irradiation. The wsCNOs exhibited photocatalytic efficiency ∼9 times
higher than CNOs for MB degradation. Enhanced photocatalytic efficiency of
wsCNOs was attributed to their surface functionalities and nanostructure. The
unique morphology (concentric nanographene shells) with considerable surface
defects, increased the physisorption of MB on the wsCNOs surface and significantly
enhanced the photocatalytic efficiency of wsCNOs. Furthermore, the wsCNOs
enabled specific detection of Al(III), even with interference from high
concentrations of other metal ions, with a detection limit of 0.77 μM, which compares favorably to other reported fluorescent
probe. Altogether, the wsCNOs showed a significantly enhanced photocatalytic activity and were used as highly selective
fluorescent probes for Al(III) ion detection, suggesting a potential use in environmental wastewater treatment.
KEYWORDS: Carbon nanoonions, Green emissions, Enhanced photocatalysis, Fluorescence sensor, Sensing of Al(III)

■ INTRODUCTION
Nanostructures of carbon in all of its forms have been the focus
of interdisciplinary research and have proved to be extremely
useful. Among them, carbon nanoonions (CNOs) are one of
the latest and least popular carbon nanostructures, although
they exhibit unique physicochemical properties due to the
pronounced edge effects.1−4 CNOs consist of concentric
nanographene shells around a solid or hollow inner core and
morphologically are in between fullerenes and multiwall
nanotubes.3 This peculiar onion-like structure results in
CNOs possessing small graphitic sp2 carbon domains with
highly localized π electrons and peripheral defects in the form
of dangling bonds.5 Consequently, CNOs exhibited unique
optical, mechanical, and electrochemical properties that render
them a potential candidate for myriad applications, including
bioimaging,4,6,7 electrochemical energy storage devices,3,8
hydrogen storage,9 immunotherapy,10 drug delivery,11 sens-
ing,12,13 plant productivity,14,15 and environment remedia-
tion.16,17 So far, a variety of methods have been developed
for the synthesis of CNOs including arc discharge, annealing of
nanodiamonds, chemical vapor deposition, flame pyrolysis, ion
implantation, and microwave synthesis.1,4,18 However, the facile
fabrication of homogeneous water-soluble onion-like carbon
nanoparticles (wsCNOs) with unique surface properties and
aqueous stability is still in its infancy, while appropriate carbon
precursors and synthetic routes are considerable factors in
establishing targeted synthesis and characteristics of CNOs.
Among various top-down and bottom-up synthetic approaches,
traditional pyrolytic techniques have attracted considerable
attention in recent years due to their simplicity, versatility, and
high yield.5,19 The synthesis of fluorescent, homogeneous
CNOs with outstanding aqueous stability from natural
materials is important in biomedical applications because it is
environment-friendly, less toxic, and compatible with mass
production.5,7,15 From this perspective, we chose flaxseed oil as
the green carbon precursor for the fabrication of homogeneous,
hydrophilic, and fluorescent CNOs. Flaxseed oil, with an
average global production of approximately 2.52 million metric
tons (MMT), is mainly used in nutraceuticals and functional
foods due to its structural characteristics.20,21
Received: December 27, 2016
Revised: March 22, 2017
Published: March 30, 2017

© 2017 American Chemical Society 3982 DOI: 10.1021/acssuschemeng.6b03182

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ACS Sustainable Chemistry & Engineering
To address the issue of scarcity of safe water with the rise in
global population and associated environmental consequence is
a topmost global concern. Organic pollutants such as textile
dyes are a major factor that affects water bodies worldwide
because of their release into water resources and low
biodegradability.22 Because of their complex chemical nature,
organic dyes can block both sunlight and oxygen dissolution in
water bodies and are hard to treat with a biological
technique.23,24 Therefore, a facile, economic and eco-friendly
technique is needed to degrade organic dyes into nonhazardous
compounds. Photocatalytic treatment of wastewater is advanta-
geous over various physical and chemical techniques for water
decontamination since it offers almost negligible or no harmful
byproducts.25 In addition, it is an energy efficient, clean, and
sustainable process. In recent years, carbon nanomaterials have
been investigated for the photocatalytic treatment of waste-
water and other pollutants since they offer band gaps tunable
with visible spectrum.23,26−28 CNOs are particularly attractive
for photocatalysis applications because of their high chemical
stability, environmentally friendly nature, and large specific
surface area with a high degree of curvature.29 To the best of
our knowledge, CNOs have not been explored for photo-
catalytic applications. This led us to investigate the character-
istic electron transfer properties of wsCNOs as a photocatalyst
for dye degradation.
Contamination of water with heavy metal ions has been
another serious global concern for decades. Aluminum, the
third most abundant element in the Earth’s crust after oxygen
and silicon, widely exists in water as a result of acid rain.30 In
addition, the increasing use of aluminum compounds in
industry, water treatment, cosmetics, pharmaceuticals, anti-
perspirants, and food additives further increases its content in
drinking water and foodstuffs.31 Aluminum in water has been
found to be lethal to plants30 and a potential risk factor in
elderly cognitive impairment.32 Furthermore, in humans,
increasing exposure to aluminum is recognized as a significant
cause of Alzheimer’s disease (AD), Parkinson’s disease (PD),
dialysis encephalopathy, down syndrome,33 and even breast
cancer.34 Therefore, the detection of Al(III) is crucial to control
its concentration in the biosphere and limit human exposure
levels. Several standard techniques have been established for
the detection of Al(III), such as atomic absorption spectros-
copy (AAS), hydride generation atomic fluorescence spectrom-
etry (HG-AFS), inductively coupled plasma mass spectrometry
(ICPMS), and square wave anodic stripping voltammetry
(SWASV-CV).30,32 Although SWASV-CV and ICPMS meet the
sensitivity and selectivity demands, their on-site and practical
application is hampered by lengthy, complicated sample
preparation steps, the requirement of trained manpower, and
costly equipment. In recent years, fluorescence-based detection
methods have attracted extensive attention due to their ease of
operation, high sensitivity, rapid implementation, and low
cost.35 The “off−on” fluorescence properties of carbon
nanostructures have been exploited for the development of
PL sensors for a diverse range of molecules.5,19,36,37 Carbon
nanostructures are both electron donors and acceptors,38 and
their fluorescence can be quenched (turned off) upon
absorption of electron acceptor molecules, such as metal ions
or conjugated systems,39,40 while PL emissions are further
enhanced (turned on) upon absorption of electron donor
molecules.39 Various factors direct the PL turn on/off and
selectivity of ions or molecules, such as π−π interactions, H-
bonding, adsorption affinity, metal−catechol interactions,
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surface functionalities of carbon nanostructures, and oxida-
tion−reduction following a photoinduced electron transfer
(PET).39 So far, few reports on the fabrication of fluorescent
probes for selective detection of Al(III) have been pub-
lished.32,41−43 Those probes generally require complex
synthetic protocols, fluorophores, and long incubation times,
and suffer from photobleaching. Hence, it is still challenging to
develop specific, simple fluorescence probes for the detection of
Al(III). To our knowledge, no report exists on the detection of
Al(III) using green fluorescent wsCNOs.
In this work, we aimed to synthesize wsCNOs through a
facile technique via traditional pyrolysis of flaxseed oil using a
cotton wick, as a potentially valuable low-cost and green
precursor. The synthesized wsCNOs exhibited good stability in
aqueous phase and strong green fluorescence. CNOs were
explored for the photocatalytic degradation of methylene blue
(MB) as model pollutant dye under visible light illumination.
The catalytic activities of CNOs were improved ∼9 times by
simple acid oxidation. Moreover, the wsCNOs showed highly
sensitive and selective detection of Al(III) in aqueous media
based on fluorescence quenching effects and thus can serve as a
fluorescent probe for label-free detection of Al(III).
■ EXPERIMENTAL SECTION
Materials and Reagents. Cold-pressed and unrefined flaxseed oil
was obtained from a local market. All chemicals and solvents were of
analytical reagent grade and used as obtained without any further
purification. All metal ions were chloride salts, except K2Cr2O7 and
Al(NO3)3·9H2O, and purchased from Alfa Aesar (South Korea).
Methylene blue(MB) was purchased from Sigma-Aldrich (South
Korea). Deionized (DI) water was used throughout for the
preparation of solutions, unless stated otherwise.
Instrumentation. Transmission electron microscopy (TEM) and
high resolution TEM (HRTEM) images were taken with Tecnai G2 at
a 200 kV operational voltage. Samples for TEM were prepared by
casting droplets of an aqueous solution of wsCNOs onto a carbon-
coated copper grid, followed by drying under vacuum at 25 °C for 12
h. Imaging of wsCNOs was done with a DM 2500 inverted
microscope (Leica, Heerbrugg, Switzerland). Samples for fluorescence
microscope imaging were prepared by drop-casting an aqueous
solution of wsCNOs on a glass slide, followed by drying under
vacuum at 25 °C for 12 h. Fourier transform infrared (FTIR) spectra
were determined in solid state using KBr pellets on a Bruker Vector 22
IR spectrometer in the range of 400−4000 cm−1. Raman analysis was
done with a WITec Raman spectrometer at 532 nm laser excitation.
Thermogravimetric analysis (TGA) was performed under nitrogen
atmosphere with a Mettler thermal analyzer at a heating rate of 10 °C
min−1, starting from room temperature up to 900 °C. Fluorescence
spectra of aqueous solutions were recorded at room temperature with
a Varian fluorescence spectrometer. The UV−vis absorption spectra of
wsCNOs were analyzed with a Varian 50 Bio UV−vis spectropho-
tometer. The powder X-ray diffraction (XRD) patterns were acquired
for 2θ values from 10 to 80° on a Rigaku model D X-ray diffractometer
using Cu−Kα radiation. X-ray photoelectron spectroscopy (XPS)
measurements for surface analysis were done with a ULVAC-PHI X-
tool XPS spectrometer with an Al Kα X-ray source. Zeta potentials
were measured by a zeta potential analyzer version 5.72 (Brookhaven
instruments).
Synthesis of Water-Soluble Carbon Nanoonions (wsCNOs).
The wsCNOs were prepared following a recently reported method,19
using flaxseed oil as carbon source. An earthen pot was filled with
flaxseed oil, which was then pyrolyzed in a traditional way using a
cotton wick in stable air conditions. The as-synthesized soot was
collected on a clean inverted borosilicate glass beaker to avoid any
metal contamination. Control oxidation of as-obtained carbon soot
under acidic conditions resulted in its water-soluble version, as
wsCNOs.44,45 In brief, 1 g of soot was oxidized in 100 mL of nitric acid
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Scheme 1. Representation of the Synthesis of Green Fluorescent Water-Soluble Carbon Nanoonions (wsCNOs) from Flaxseed
Oil
Figure 1. (a,b) TEM images of wsCNOs; the inset shows the size distribution of wsCNOs; (c) HRTEM image of single wsCNO; (d) HRTEM
image of wsCNO showing the lattice spacing with marked surface defects.
(65%) by refluxing for 10 h. The resulted mixture was centrifuged
(8000 rpm, 10 min), and water was decanted. The excess nitric acid
was removed through repetitive solution evaporation in a water bath
until pH reached 7. The resultant wsCNOs were dissolved in 200 mL
of DI water, subsequently purified by filtration on a 0.2 μm
microporous membrane, and finally vacuum-dried at room temper-
ature.
Photocatalytic Activity Measurement. The photocatalytic
efficiency of CNOs and wsCNOs were evaluated by the decolorization
of MB in aqueous solution under direct visible light illumination. MB
solution (5 × 10−5 M/L) was prepared in DI water for photocatalysis
measurements. Ten milligrams of CNOs and wsCNOs were separately
added to 50 mL of MB solutions, and both solutions were stirred for
30 min in the dark to achieve an absorption equilibrium. Both MB
solutions containing CNOs and wsCNOs were then sealed in a glass
vial and exposed for visible light illumination from a 60 W tungsten
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lamp placed 25 cm away. Aliquots were taken at a set 10 min time
interval in a quartz cell for UV−vis absorbance measurements. The
heat effect was minimized by employing air conditioning of the room.
Detection of Al(III) Ions. Detection of Al(III) was performed at
room temperature in DI water. A 0.001 M stock solution of Al(NO3)2
was prepared. Fluorescence intensity of 2 mL of wsCNOs solution (5
× 10−3 mg/mL) was measured at 390 nm excitation wavelength,
denoted as Io fluorescence intensity of the starting point. Following
that, 10 μL of Al(NO3)2 solution was added to the wsCNOs solution,
and fluorescence intensity was measured after 1 min. The excitation
and emission slits were kept at 15 throughout the experiment. The
sensitivity and selectivity for Al(III) and Fe(III) were measured in
triplicate under identical experimental conditions. The effect of metal
ions (Co2+, Ag+, Cr2+, Cr3+, Cr6+, Mg2+, Ca2+, Na+, K+, Ba2+, Fe2+, Cu+,
Cu2+, Ni2+, Hg+, Hg2+, Cd2+, Mn2+, and Zn2+) on fluorescence sensing
of Al(III) were also analyzed under identical experimental conditions.
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Figure 2. Comparative analysis for the structural characteristics of as-synthesized CNOs (black line) and wsCNOs (blue line). (a) FTIR spectra of
as-synthesized CNOs and wsCNOs; (b) Raman spectra of as-synthesized CNOs and wsCNOs; (c) thermograph of as-synthesized CNOs and
wsCNOs as obtained under an inert atmosphere; (d) X-ray diffraction patterns of as-synthesized CNOs and wsCNOs.
■ RESULTS AND DISCUSSION
The wick pyrolysis of flaxseed oil initially formed channel-type
carbon clusters possessing graphitic domains, which further
assembled to form CNOs. The oxidation of as-obtained CNOs
with nitric acid rendered them water-soluble as wsCNOs with
no precipitation for several months, thus making them suitable
for various biological and environmental applications. In
addition, acid treatment oxidized the defective sites of larger
particles into smaller ones with spherical shape and high
crystallinity.46 The formation of wsCNOs via carbonization and
fragmentation of carbon clusters during traditional pyrolysis is
depicted in Scheme 1. The present synthetic method has the
advantages of gram-scale fabrication at considerably lower costs.
Structural and Morphological Characterization. TEM
images, shown in Figure 1a and b, indicate the homogeneous
and monodisperse nature of wsCNOs. The wsCNOs exhibited
relatively narrow size distribution in a range of 2−10 nm in
diameter, as evaluated statistically through the measurement of
about 100 particles. Most of the wsCNOs are 4−8 nm in size.
The structure of wsCNOs was further examined with HRTEM.
The HRTEM image in Figure 1c reveals the well-defined
spherical shape with concentric nanographene shells.47 Figure
1d shows the crystalline structure of wsCNOs with obvious
surface defects and an in-plane lattice spacing of 0.26 nm.15,48,49
The surface functionalization with hydrophilic moieties was
confirmed with FTIR. Figure 2a shows the FTIR spectra of
CNOs (black line) and wsCNOs (blue line) with distinguish-
able features of a carboxylic group in wsCNOs. The broad peak
at 3430 cm−1 in the as-synthesized CNOs (Figure 2a black line)
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is due to adsorbed water. A strong peak around 1607 cm−1
arose due to CC stretching vibrations5 and a broad band at
550 cm−1 due to C−H bending.45 In the IR spectrum of
wsCNOs (Figure 2a blue line), the sharp peak at 1720 cm−1 is
attributed to stretching vibrations of the carboxyl groups on the
carbon surface. A main absorption band characteristic of − O−
H stretching appears at 3430 cm−1 and a −C−H stretching
band at 3017 cm−1.7 A sharp band at 1595 cm−1 is attributed to
vibrational stretching of CC, and a peak at 1236 cm−1 to
−C−O stretching. A high density of −COOH on the surface of
wsCNOs is likely due to the breaking of CC and C−C
carbon clusters by −OH during oxidation, which were
simultaneously oxidized into −COOH groups. Raman spec-
troscopy was used for characterization of the intrinsic
properties and quality of wsCNOs. The Raman spectra in
Figure 2b show two prominent peaks, corresponding to
characteristic D and G bands. The G band of wsCNOs (Figure
2b, blue line), which indicates the in-plane vibration mode of
sp2 carbons, is centered at 1591 cm−1. Existence of a well-
defined sharp G band in both CNOs and wsCNOs
corroborates the high quality of material.50 The D band,
which corresponds to disruptions in sp2 bonding, such as
dangling bonds, sp3 bonding, vacancies, and carbon rings other
than hexagon, is located at 1335 cm−1.51,52 The existence of a
broad and intense D band results from surface oxidation of
CNO’s heptagon and pentagon rings, known to produce bent
or curved shapes from flat two-dimensional graphene (2D-
graphene) sheets as found in carbon nanoparticles.37,53 From
Figure 2b, it is evident that the peak position of the D band for
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Figure 3. XPS full scan spectra of (a) CNOs and (d) wsCNOs. Corresponding C 1s short scan of (b) CNOs and (e) wsCNOs. O 1s scan of (c)
CNOs and (f) wsCNOs.

Figure 4. (a) Ultraviolet−visible (UV−vis) absorption spectrum and digital images of an aqueous solution of wsCNOs under (1) daylight and (2)
385 nm excitation wavelength. (b) Photoluminescence (PL) emission spectra at different wavelengths; (c) PL excitation spectrum at a 523 nm
emission wavelength; (d) fluorescence image of wsCNOs at 488 nm band-pass filter; scale bar = 20 μm.

wsCNOs downshifted from 1341 to 1335 cm−1, while that of shifting of peak positions is induced by the strain of curved
the G band shifted upward from 1586 to 1591 cm−1. The graphitic layers in spherical wsCNOs.18 The ratio of the D and
3986 DOI: 10.1021/acssuschemeng.6b03182
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Figure 5. Extent of (a) MB photodegradation at different visible light irradiation times with CNOs and wsCNOs; inset change in color of MB (1)
before and (2) after photodegradation. (b) Plot of ln(C/Co) for MB photodegradation with CNOs and wsCNOs under visible light irradiation.
G band intensities (ID/IG) was used to quantify oxidation since
they are directly related to the extent of defects in the form of
sp3 carbons. The higher ID/IG for the oxidized CNOs (1.66)
than for as-synthesized CNOs (1.40) reflects their higher
degree of surface functionalization in terms of carboxylic acid
groups.5,54 Subsequently, the functionalization of CNOs was
determined by TGA. The comparative thermal stability of as-
synthesized CNOs and wsCNOs, based on their respective
decomposition, is shown in Figure 2c. The as-synthesized
CNOs exhibited the weight loss of ∼12% at 900 °C due to the
loss of incorporated oxygenated species, while the wsCNOs
loses 27.51% of its total weight, ascribed to the thermal
decomposition of surface functional groups.19 A higher density
of oxygenated functional groups on the surface of wsCNOs
resulted in a larger weight loss as compared to that of the
CNOs. The structure of CNOs was further examined by XRD.
In Figure 2d, the CNOs showed a broad diffraction peak
centered at 2θ = 23°, corresponding to (002) reflections of
graphitic carbon, and a peak at 44°, indexed to the (100)
reflections of the hexagonal graphite crystal structure. The XRD
patterns of as-synthesized CNOs and wsCNOs were similar.
X-ray photoelectron spectroscopy (XPS) was performed on
CNOs and wsCNOs to examine their composition. In Figure
3a, two prominent peaks for C 1s and O 1s were clearly
observed in the full survey spectrum of CNOs, with a C/O
ratio of 12.27. The C 1s XPS spectrum of CNOs showed
distinct peaks for CC (284.5 eV), C−C (285.4 eV), and
three small peaks for C−O (286.2 eV), CO (287 eV), and
COO− (287.9 eV) (Figure 3b).55 Three oxygen signals for C
O (531.7 eV), C−O (532.5 eV), and COO− (535.2 eV) were
observed in a short survey scan for O 1s as shown in Figure 3c.
In Figure 3d, the wsCNOs exhibited two clear peaks for C 1s
and O 1s in full scan spectrum, showing an increased oxygen
content (C/O ratio = 4.63). The C 1s XPS spectrum of
wsCNOs was deconvoluted into CC (284.4 eV), C−C
(285.4 eV), C−O (286.2 eV), CO (287 eV), and COO−
(287.9 eV), as shown in Figure 3e.40 The O 1s XPS spectrum of
wsCNOs was fitted to CO (531.7 eV), C−O (532.5 eV), and
COO− (535.2 eV), with three carbon−oxygen bindings modes
(Figure 3f). Taken together, the CNOs are carbon-rich
nanoonions, which contain aromatic and aliphatic carbon
cores with surface adsorbed moisture, while wsCNOs are
oxidized with carboxylic and hydroxyl groups present on the
surface. The zeta potential was measured to assess the stability
and solubility of wsCNOs in aqueous solution. The negative
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zeta potential value of −77.91 mV at pH 7 indicates excellent
stability without any sign of coagulation or precipitation for
months.
Optical Properties. The optical properties of wsCNOs
were examined by UV−vis and PL spectroscopy. Aqueous
solution of wsCNOs exhibited bright green fluorescence under
illumination with 365 nm UV light (Figure 4a inset). The
wsCNOs exhibited broad optical absorption at 246 nm with a
long tail toward the visible light region (Figure 4a), assigned to
the overlapping of aromatic polycyclic hydrocarbon backbone
and oxygenous functional groups.56,57 The fluorescence emitted
from the aqueous solution of wsCNOs was recorded at
different excitation wavelengths, and the corresponding PL
spectra are shown in Figure 4b. Fluorescent emission peaks
were red-shifted with an increase in excitation wavelengths. The
maximum emission peak was centered at 523 nm on excitation
with the 380 nm wavelength. The corresponding full width at
half-maximum (FWHM) was ∼56 nm, which suggests a
relatively narrow size distribution of particles consistent with
the TEM results.56 Green emissions correspond to the previous
reports and are assigned to the large number of surfacial
carbons with −CO functional groups.57 The excitation
spectrum at a 523 nm emission wavelength shows a broad band
at 335 nm (Figure 4c), revealing the presence of one emission
species. The quantum yield, measured using quinine sulfate as
the standard was ∼5%. The fluorescence image of an aqueous
solution of wsCNOs obtained with a 488 nm band pass filter is
shown in Figure 4d. The PL mechanism of CNOs has been
extensively studied but remains controversial and debatable due
to the existence of several synthetic routes and diverse size
distributions. As CNOs have no defined band gap, surface
functional groups on CNOs have a significant impact on tuning
of the surface energy traps and the formation of localized
electronic states. The most accepted mechanism for tunable
emissions is radiative recombination of electron−hole pairs/
quantum confinement effects.6,58−60 A recent study by Sun and
co-workers argued that edge functional groups affected the
electron trapping states to compete with the radiative
fluorescence emission states.57 Some studies have argued that
variations in surface energy states, chemical defects, and surface
functionalities significantly contribute to the emissive properties
of CNOs.5,56,61,62 One often stated conjecture is that CNOs act
as electric dipoles and that recombination of photogenerated
charges on defect centers leads to their emission.63 A strong
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coupling between the electronic transition and collective
vibrations of the lattice contributes to tuning of the emission.
Photocatalytic Dye Degradation under Visible Light
Illumination. The photocatalytic behavior of as-prepared
CNOs and wsCNOs was studied by measuring photo-
degradation of model organic pollutant dye (i.e., MB).
Absorption changes from the initial concentration (C0) to the
final concentration (C) of the dye were analyzed at a set time
interval of 10 min under visible light irradiation. The rate
constants (k) of MB degradation in the presence of CNOs and
wsCNOs were calculated using the Langmuir−Hinshelwood
model formula26
k = ln(C /C0)/t
where C0 and C represent the concentrations of organic dye at
0 and t minutes of irradiation times, respectively. Figure 5a
showed a variation in the concentration of MB versus visible
light irradiation time. Drawing assessment between photo-
catalysis activity clearly shows that wsCNOs exhibited
enhanced degradation efficiency than CNOs, as demonstrated
in Figure 5a. The intensity of the characteristic MB absorbance
peak (663 nm) was decreased to 14.5% from its initial
measured value (100%), after 120 min of exposure to visible
light in the presence of wsCNOs (Figure S1 a). This indicates
the photodegradation of MB by 85.5% (5 × 10−3 M/L) from its
initial concentration. In sharp contrast, a 78.6% decrease in MB
absorbance intensity was observed for CNOs (Figure S1b)
from its initial measured values (100%). No significant
photodegradation of MB was observed even after 120 min of
visible light irradiation in the absence of CNOs and wsCNOs,
as shown in Figure 5b. These results suggest that wsCNOs play
a vital role in the photocatalytic process. The whole catalytic
experiment was repeated in dark conditions to confirm the dye
degradation via photocatalysis instead of the adsorption
process. Figure S2 demonstrates a variation in the concen-
tration of MB in the presence and absence of light with CNOs
and wsCNOs. In the absence of visible light irradiation, the
degradation of MB was significantly diminished, and only
∼31.1% degradation was observed by wsCNOs after 120 min.
These results give direct evidence that wsCNOs facilitate the
degradation of MB in the presence of visible light.
The wsCNOs have the ability to act as photosensitizers due
to their broad and extended absorption in visible light.64
Electrons in wsCNOs are excited by visible light absorption to
the conduction band, and electron−hole pairs are generated
(eq 1).23 Photosensitized holes on wsCNOs interacted with
surface adsorbed water molecules (eq 2) or directly oxidized
the dye molecules (eq 3), resulting in hydroxyl or organic
radicals, respectively. Aerial oxygen acts as an electron
scavenger to oxidize the activated organic dyes. This reaction
pathway possessed low or nonexistent barriers for facile
oxidative degradation of organic dyes (eqs 4−6).46 The
proposed photocatalytic mechanism for the degradation of
MB is as follows:65
wsCNOs + h v → e− + h+ (1)
H 2O + h+ → ·OH + H+ (2)
dyes‐H + h+ → dyes‐H·+ ⇌ dyes + H+ (3)
dyes‐H + ·OH → dyes· + H 2O (4)
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H 2O/O2
dyes· + O2 → dyes‐OO· ⎯⎯⎯⎯⎯⎯⎯⎯→ degradation (5)
H 2O/O2
dyes‐H + ·OH → H‐dyes‐OH· ⎯⎯⎯⎯⎯⎯⎯⎯→ degradation (6)
The apparent rate constant of wsCNOs is 0.0175 min−1 for
MB, which is ∼9 times higher than that of the CNOs (Figure
5b). The enhancement in photocatalytic activity of wsCNOs is
attributed to the increased adsorption affinity for positively
charged MB on wsCNOs.46 Effective adsorption of organic
dyes on photocatalysts is a key step to mineralization by visible
light induced electron transfer reactions. The unique
morphology (concentric multilayered shell) of wsCNOs with
considerable surface defects in the form of dangling bonds is
likely to enhance MB adsorption. Additionally, wsCNOs with
negatively charged carboxylic groups present on the surface
provide higher binding affinity for hydrophilic MB molecules as
compared to CNOs. Oxygenated surface functional groups
such as −OH, −COOH, −COO−, and −CO facilitate the
charge transfer between organic dyes and wsCNOs, resulting in
a diminished photoexcited electron−hole pair recombination
and high upward band bending with enhanced hole transport.46
Generation of active oxygen species (·O2) and hydroxyl (·OH)
radicals are supposed to be promoted due to this charge
separation process. The dye molecules could be degraded by
these species.64 In addition, the active sites of wsCNOs also
directed the increased generation of holes, contributing to
photocatalytic activity.65 The possible photocatalytic mecha-
nism for dye degradation is shown in Scheme 2.
Scheme 2. Possible Photocatalytic Mechanism of wsCNOs
under Visible Light Irradiation
Zeta potential measurements were further carried out to
confirm the increased photocatalytic efficiency of wsCNOs. An
increase in zeta potential value from −77.91 mV to −12.08 mV
for wsCNOs before and after photocatalytic degradation of
wsCNOs-MB solution, respectively, was observed. Zeta
potential measurements confirm that the increased physisorp-
tion of positively charged MB on the negatively charged
wsCNOs surface simply boost the photocatalytic efficiency of
wsCNOs.
Detection of Al(III) Ions. Encouraged by the strong
photoluminescence and abundant surfacial oxygenous function-
alities, the feasibility of wsCNOs as a fluorescent probe for the
specific detection of Al(III) ions was demonstrated. The
fluorescence of wsCNOs toward varying concentrations of
Al(III) was analyzed at 390 nm excitation wavelength. With
increasing Al(III) concentration from 10 to 100 μL (1 × 10−3
M), the PL emission of wsCNOs centered at 531 nm was
DOI: 10.1021/acssuschemeng.6b03182
ACS Sustainable Chem. Eng. 2017, 5, 3982−3992
ACS Sustainable Chemistry & Engineering Research Article

Figure 6. (a) Fluorescence quenching of wsCNOs by stepwise addition of 100 μL Al(III) (λex = 390 nm); (b) Stern−Volmer plot for linear fitting of
the values of Io/I at 390 nm versus the concentrations of Al(III). (c) Effect of various anions on the relative PL intensity of wsCNOs. (d) Effect of
various metal ions on the relative PL intensity of wsCNOs. (e) Fluorescence quenching of wsCNOs by stepwise addition of 100 μL of Fe(III) (λex =
390 nm).

effectively quenched, without change in peak position as shown intensity. Quenching of PL was more significant for Al(III)
in Figure 6a. The binding of Al(III) with surface functional than Fe(III). These results revealed the selectivity of Al(III)
groups of wsCNOs led to the quenching of PL emission. There even in the presence of several metal ions. The higher
is a linear relationship between the concentration of Al(III) selectivity of wsCNOs for Al(III) than for Fe(III) is probably
ions and fluorescence quenching, as shown in Figure 6b, in due to the high affinity of carboxylic groups toward Al(III)
which Io and I are the concentrations of wsCNOs in the (hard acid−hard base interactions).41 The possible mechanism
absence and presence of Al(III), respectively. The detection for the quenching of PL emissions of wsCNOs upon the
limit of Al(III), based on the definition of 3 times the standard
addition of Al(III) is explained on the basis of their ion-
deviation of the blank signal (3σ), was calculated as 0.77 μM
selective chemical nature and charge/energy transfer effects.
from the fitted curve with a correlation coefficient of 0.998.5
This limit of detection is approximately 10 times lower than the The carboxylic groups on the surface of CNOs can interact
maximum permitted level of Al(III) (7.4 μM) in drinking water with Al(III) ions via coordination bonds and form a complex.
by the World Health Organization (WHO).5 The wsCNOs- This complex affects the distribution of surface energy traps and
based fluorescence sensing system could provide a green, rapid, enhances the nonradiative recombination of electrons and
sensitive, and reliable method for Al(III) detection in drinking holes, and the consequences of fluorescence quenching
water. (Scheme 3).66
On account of the complexity of real samples, selectivity is
also crucial for fluorescent probes. The selectivity of Al(III) was Scheme 3. Schematic Representation of the Sensing of
therefore examined with respect to other metal ions and anions Al(III) with a wsCNO Based Fluorescent Probe
under identical experimental conditions. Varying types of
anions did not result in any significant change in the relative PL
intensity (Figure 6c), and no obvious effects were observed
upon the addition of other metal ions either (except Fe3+), as
illustrated in Figure 6d. The selectivity for Al(III) is remarkably
higher than that for Fe(III) or other metal ions. The quenching
effect of Al(III) is more prominent than that of Fe(III), as
shown in Figure 6e. The selectivity toward Al(III) was further
investigated in the presence of several metal ions, as shown in
Figure S3. No remarkable change in the PL intensity was
observed after the addition of several metal ions. However,
further addition of Al(III) and Fe(III) caused a decrease in PL
3989 DOI: 10.1021/acssuschemeng.6b03182
ACS Sustainable Chem. Eng. 2017, 5, 3982−3992
ACS Sustainable Chemistry & Engineering
The absorption spectra of wsCNOs before and after the
addition of 100 μL Al(III) is shown in Figure S4. The
absorption intensity and peak position are significantly affected
by Al(III). A strong and wide adsorption band appears at 298
nm, while the absorption band of wsCNOs at 246 nm
disappears after the addition of Al(III). The UV−vis spectrum
thus considerably changes, which confirms the coordination of
Al(III) with wsCNOs. This suggests that co-ordination of
Al(III) with wsCNOs is responsible for the fluorescence
quenching and hence selective sensing of Al(III).
■
CONCLUSIONS
Herein, an economically viable and facile synthetic route for the
synthesis of wsCNOs by traditional pyrolysis of flaxseed oil as
the carbon precursor is reported. The wsCNOs have a
homogeneous and narrow distribution of particle sizes ranging
from 4 to 8 nm. The wsCNOs exhibited excellent visible light
driven photocatalytic performance toward degradation of
organic dyes. Compared with as-synthesized CNOs, the
wsCNOs exhibited improved photocatalytic performance ∼9
times for MB degradation in water. Furthermore, the stable,
green emissions of wsCNOs are employed as a fluorescent
probe for the sensitive detection of Al(III) ions based upon the
florescence turn-off technique. The wsCNO-based fluorescence
probe of Al(III) is highly specific, even in the presence of other
metal ions and anions, with a 0.77 μM detection limit. The
wsCNO-based PL sensor reported here may lead to a novel
pathway for the specific detection of metal ions by the design of
functional nanomaterials. Altogether, wsCNOs could be a
promising material for sustainable treatment of wastewater and
environmental therapy.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.6b03182.
UV−vis absorbance spectra of MB and photocatalytic
properties of wsCNOs and CNOs (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel: +821071237516. E-mail: taeykim@gachon.ac.kr.
ORCID
Tuan Sang Tran: 0000-0002-0047-9571
TaeYoung Kim: 0000-0001-8156-4438
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Collaborative Research
Program among Industry, Academia and Research Institute
through the Ministry of Science, ICT, and Future Planning
(MSIP) and Korea Industrial Technology Association
(KOITA) (grant no. KOITA-2014-4). This research was also
supported by Nano Material Technology Development
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Science, ICT, and Future
Planning (NRF-2016M3A7B4027712)
3990
Research Article
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