A facile strategy to fabricate nanoscale zero-valent iron decorated graphene oxide composite for dechloridation of trichloroacetic acid in water

Article abstract of DOI:10.1166/jnn.2018.16374

In this study, nanoscale zero-valent iron decorated graphene oxide (NZVI/GO) composite was fabricated through a reduction process in the presence of sodium borohydride (NaBH₄) solution. Subsequently, physicochemical properties of the NZVI/GO composites were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), N₂ adsorption/desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR) and Raman spectra. Results indicated that Fe species existed in the form of Fe0, which uniformly dispersed on the surface of GO. Furthermore, the performance of NZVI/GO was evaluated by the degradation of tichloroacetic acid (TCAA). TCAA can be rapidly degraded by NZVI/GO. This paper provides a promising strategy to synthesize versatile catalyst which would be potentially applied in sewage treatment to degrade chlorinated organic compounds.

Full text of DOI:10.1166/jnn.2018.16374

Article
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Nanoscience and Nanotechnology
Vol. 18, 8252–8257, 2018
Copyright © 2018 American Scientific Publishers
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Printed in the United States of America
A Facile Strategy to Fabricate Nanoscale Zero-Valent
Iron Decorated Graphene Oxide Composite for
Dechloridation of Trichloroacetic Acid in Water
Huixuan Zhang1, Xinyi Zhang1, Ruonan Guo1, Qingfeng Cheng2, and Xiuwen Cheng1ꢀ∗
1Key Laboratory of Western China’s Environmental Systems (Ministry of Education), College of Earth and Environmental Sciences,
Lanzhou University, Lanzhou 730000, P. R. China
2College of Resources and Environment, Chengdu University of Information Technology, Chengdu 610225, P. R. China
In this study, nanoscale zero-valent iron decorated graphene oxide (NZVI/GO) composite was fab-
ricated through a reduction process in the presence of sodium borohydride (NaBH4) solution. Sub-
sequently, physicochemical properties of the NZVI/GO composites were characterized by scanning
electron microscope (SEM), transmission electron microscopy (TEM), N2 adsorption/desorption,
X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared
spectroscopy (FT-IR) and Raman spectra. Results indicated that Fe species existed in the form of
Fe0, which uniformly dispersed on the surface of GO. Furthermore, the performance of NZVI/GO
was evaluated by the degradation of tichloroacetic acid (TCAA). TCAA can be rapidly degraded by
IP: 185.13.33.15 On: Mon, 17 Sep 2018 15:06:44
NZVI/GO. This paper provides a promising strategy to synthesize versatile catalyst which would be
Copyright: American Scientific Publishers
potentially applied in sewage treatment to degrade chlorinated organic compounds.
Delivered by Ingenta
Keywords: Nanoscale Zero-Valent Iron, Graphene Oxide, Tichloroacetic Acid, Degradation.
1. INTRODUCTION
for TCAA since it has being the most recalcitrant among
them in water.4
Trichloroacetic acid (TCAA), as one of the chlorinated
organic compounds (COCs), is a non-biodegradable pollu-
tant detected in aquatic ecosystem throughout the world,
including surface and ground water.1 So it has become
a focus which attached much attention in environmental
research in recent years. Also, due to the high solubil-
ity and different natural sources as well as anthropologi-
cal sources, the presence of TCAA and other chloroacetic
acids (CAAs) which are in water and soil causes a serious
risk to human beings.2 As one of disinfection by-products
(DBPs), the exposure to TCAA and other CAAs are very
wide. Cardador and Gallego evaluated the exposure of
swimmers and workers to haloacetic acids (HAAs) in
indoor and outdoor pools through the analysis of urine
samples, finding that TCAA and DCAA might reach
the maximum concentration level set by the U.S. EPA
for haloacetic acids (HAAs).3 Traditional bioremediation
method has been applied in the degradation of HAAs,
including CAAs. However, it is unsuccessfully especially
Apart from these methods, phase-transfer techniques
such as adsorption also are promising technologies, which
can result in good effects. Among traditional conventional
adsorbents for the removal of TCAA, graphene oxide
(GO) has attached much attention due to its properties
such as large specific surface areas, superior mechanical
properties, strong adsorption capacity and special physic-
ochemical properties.5ꢀ6 As a novel carbon nanomate-
rial, graphene oxide has many functional groups such as
hydroxyl, carboxyl and epoxy groups. These functional
groups not only improve the dispersibility of graphene
oxide, but also play a very important role in the adsorp-
tion of various contaminants.7 However, adsorption simply
transfers contaminants from one phase to another while
the pollutants themselves are not degraded.8 Therefore,
finding an environmental-friendly approach to degrade
the C-Halogen bond which is toxic in nature, is very
urgent.
Nanoscale zero-valent iron (NZVI) material, as a kind of
strong reducing agent who’s standard electrode potential is
−0.43 V, has been successfully used to eliminate a variety
∗Author to whom correspondence should be addressed.
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doi:10.1166/jnn.2018.16374

Zhang et al.
A Facile Strategy to Fabricate NZVI/GO Composite for Dechloridation of Trichloroacetic Acid in Water
of organic and inorganic pollutants in environment, such as
chlorinated solvents,9 the dye effluents,10 polychlorinated
biphenyls11ꢀ12 and heavy metals13–15 due to its large spe-
cific surface area, strong surface activity and relatively low
price. However, owing to the high surface energy and mag-
netism among particles of NZVI, it suffers strong aggrega-
tion and fast oxidation in air. This can lead to a decrease
both in adsorption sites and reactive sites, so the effective
contact areas between target pollutants and NZVI become
smaller, resulting in a low reactivity of NZVI.
2.2. Synthesis of NZVI/GO Composites
Normally, GO was synthesized by using chemical oxida-
tion process. First, 25 mL concentrated sulfuric acid was
added into 1.0 g graphite powder and 0.5 g sodium nitrate
under stirring in ice-water bath. Second, in order to con-
trol the temperature which was 293 K of the suspension,
3.0 g potassium hypermanganate (KMnO4ꢁ was dropwise
added. After these, the mixture obtained was transferred to
a water bath whose temperature is 308 K under mechanical
stirring for 90 min. Subsequently, 10 mL 30 wt% hydrogen
peroxide (H2O2ꢁ was added slowly. Next, 50 mL 5 wt%
hydrochloric acid was used to purify the mixture. Then,
the as-obtained mixture was washed by 200 mL MQ-water
and then filtrated to form a neutral solution. Eventually,
the powder was dried for 24 h at 333 K.
Apart from the properties described above of the
graphene oxide, it also can be considered as a con-
venient support material for the nanoparticles. In order
to overcome agglomeration and passivation of NAVI,
NZVI could be fixed on the surface of GO. On the
one hand, GO can effectively inhibit the aggregation
of metal nano-particles.16 Magdalena et al.17 prepared
reduced graphene oxide with metal or metal oxide nano-
particles by using various methods, finding that GO can
be successfully used as a template for direct synthesis of
metal or metal oxide nano-particles on its surface with
a homogenous distribution.18ꢀ19 Zhang et al.20 synthesized
silver phosphate/graphene oxide (Ag3PO4/GO) composite
by ultrasound-precipitation processes, which can degrade
tetrabromosphenol A (TBBPA) successfully. On the other
hand, the GO-supported nanometer iron material can be
recycled due to the magnetic properties of NZVI. What’s
In order to obtain the NZVI/GO composite, further
experiment needs to be performed. In detail, 0.5 g GO was
dispersed in MQ-water (250 mL) under ultrasound for 2 h
so that GO can be fully peeled off. Afterwards, the above
solution was placed in a three-necked flask. Next, 0.92 g
FeSO4 ·7H2O was added to the solution stirring for 15 min.
Then, 0.2 g NaBH4 was added to the mixture under the
condition of 80 ꢀC water bath. After 4 h reaction, the prod-
uct was washed twice or 3 times with absolute ethanol
ꢀ
and then dried at 60 C. Finally, the product was sealed
and stored. NZVI immobilized in the surface of GO was
prepared according to Eq. (1).
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more, the price of NZVI materials is cheaper while the
Copyright: American Scientific Publishers
Fe2+ +2BH4− +6H2O → Fe0 +2BꢂOHꢁ3 +7H2 ↑ (1)
price of graphene oxide is more expensive. ThereDfoereli,vfiexre-d by Ingenta
ing NZVI on GO can reduce the cost of materials and
improve its economy.
2.3. Characterization
Apparent morphology of GO and NZVI/GO was recorded
by scanning electron microscopy (SEM) at 20 kV. The
particle size of the catalyst was analyzed by transmission
electron microscopy (TEM). X-ray diffraction (XRD) mea-
surements were performed using a Rigaku D/Max IIIB
diffractometer with Cu Kꢃ radiation (ꢄ = 0ꢅ15418 nm).
The X-ray photoelectron spectroscopy spectra were carried
out at 10 kV and 5 mA under 10–8 Pa residual pressure
using a thermo ESCALAB 250 electron spectrometer
(Al Kꢃ X-ray source, 1486.6 eV) with multidetection ana-
lyzer. Raman spectrum was carried out by using a Jobin
Yvon HR800 Raman spectrophotometer (equipped with Ar
laser excitation wavelength of 457.9 nm). Fourier trans-
formed infrared spectroscopy (FT-IR) was measured on
Spectrum One apparatus, in which KBr standards were
used as reference.
In this study, GO was firstly prepared by ultrasonic
method, then the NZVI/GO composites were fabricated
via liquid-phase reduction methods with borohydride
salt. Afterwards, physicochemical properties of GO-NZVI
composites were systematically investigated through series
of characterizations. Furthermore, the performance of
NZVI/GO was evaluated by degradation of TCAA. The
results showed that NZVI/GO exhibited higher degradation
performance. Besides, the possible degradation pathways
of TCAA by identifying the corresponding degradation
intermediates were further elucidated.
2. MATERIALS AND METHODS
2.1. Materials and Reagents
Ferrous sulfate hepta-hydrate (FeSO4 · 7H2O), sodium
nitrate (NaNO3ꢁ, graphite powder (purity, >99.5%),
concentrated sulfuric acid, potassium hypermanganate
(KMnO4ꢁ, ethanol (C2H5OH), hydrogen peroxide (H2O2ꢁ,
sodium borohydride (NaBH4ꢁ, and trichloroacetic acid
(TCAA) were analytical grade and purchased from
Sinopharm Chemical Reagent Co. Ltd. All these chemi-
cals were used as received without any further purification.
MQ water was used throughout this experiment.
2.4. Dechlorination of Trichloroacetic
Acid by NZVI/GO
TCAA dechlorination was conducted in 50 mL glass vials
with some dose of NZVI/GO. And the glass vials allowed
for about a 10 mL headspace. The vials were sealed with
Telfon-lined rubber septa and aluminum cap immediately
and then placed on an orbital shaker under stirring at room
J. Nanosci. Nanotechnol. 18, 8252–8257, 2018
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A Facile Strategy to Fabricate NZVI/GO Composite for Dechloridation of Trichloroacetic Acid in Water
Zhang et al.
temperature. This process ran through the dechlorination
experiment. At selected time intervals, duplicate sample
vials were sacrificed and liquid samples were taken with
a gas-tight syringe and then filtered through a 0.22 mm
Millipore syringe filter for subsequent analyses. All exper-
iments were performed in triplicate. If there was not any
special instruction, the solution used in this study was pre-
pared by deionized water.
3. RESULTS AND DISCUSSION
3.1. SEM and TEM Analysis
The microstructures and morphologies presented in the
prepared GO and NZVI/GO composite were inves-
Figure 2. The TEM image of NAVI/GO samples.
tigated by SEM, and the results were shown in
Figures 1(a) and (b), respectively. From Figure 1(a), GO
had irregular layer or sheet structure, and its surface had
some folds owing to the outer layer of the oxidation pro-
cess in the peeling off part of the formation of a large
number of different sizes of graphite sheet. As seen from
Figure 1(b), a large number of small zero-valent iron nano-
particles evenly dispersed on the surface of GO. But there
was still a small amount of nanoscale zero-valent iron
aggregated particles due to magnetic interaction. Figure 2
showed the TEM image of NAVI/GO samples. Similar to
the SEM of NZVI/GO composite, GO showed a trans-
parent, wrinkled structure and folding back of the edges.
oxygen containing functional groups on the surfaces of
the GO sheets. Besides, the diffraction peak at 2 theta =
46.5 degrees, corresponding to the formation of iron as
the form of zero-valent (Fe0 state 110), suggesting Fe2+
was reduced by the potassium borohydride. Furthermore,
the peak at 2 theta = 65.1 degrees represented Fe2O3 pro-
duced. What’s more, the peak of the reduced graphene
oxide (rGO) was not found, indicating that the graphene
oxide was only used as a carrier in the process and did not
participate in the reaction.
And NZVI had a low degree of aggregation. This indi-
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3.3. XPS Analysis
cates that GO sheets could not only act as supports for the
growth of the NZVI but also function as stabilizing agent
Copyright: American Scientific Publishers
Figure 4 exhibited the results from the X-ray photoelec-
Delivered by Ingenta
tron spectroscopy (XPS) characterization of the NZVI/GO,
which presented spectra of Fe 2p. A feature peak around
706.7 eV could be observed, corresponding to the 2p3/2
peaks of zero-valent iron (Fe0ꢁ,22 which indicated that Fe0
did exist on the surface of GO. Besides, the peaks at
720.5 eV suggested the presence of ꢆ-Fe2O3, indicating
that a part of NZVI had been oxidized on the surface
of GO. This might be due to the existence of graphene
oxide, inhibiting the aggregation of zero-valent iron nano-
particles, making the contact area between zero-valent iron
for preventing the agglomeration of the as grown NZVI.
The specific surface areas (SSA) of NZVI were measured
by using a BET-N2 surface area analyzer. Hardiljeet et al.21
measured that the freshly prepared NZVI had a specific
surface area of 26.3 m2 ·g−1. However, the specific surface
area measured in this study was 65 m2 ·g−1. This might be
due to the presence of GO, inhibited the accumulation of
nanoscale zero-valent iron to a certain extent, which were
in accordance with the SEM and TEM results.
3.2. XRD Analysis
In order to confirm the existence of NZVI on the sur-
face of GO, XRD patterns were measured and showed in
Figure 3. Noted, GO showed a strong diffraction peak at
2 theta = 11ꢅ8 degrees ascribed to the presence of abundant
2400
2200
2000
1800
1600
1400
1200
a
b
10
20
30
40
50
60
70
80
2 theta/degree
Figure 3. XRD pattern of NZVI/GO composite.
J. Nanosci. Nanotechnol. 18, 8252–8257, 2018
Figure 1. The typical top-view SEM image of GO (a) and NAVI/GO
(b) samples.
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Zhang et al.
A Facile Strategy to Fabricate NZVI/GO Composite for Dechloridation of Trichloroacetic Acid in Water
functional groups in the GO were effectively reduced
in the NZVI/GO. These results above confirmed that
NZVI/GO were well prepared via this method.
720.5eV
4500
4400
4300
4200
4100
4000
Fe2p
706.7eV
3.5. Raman Analysis
Figure 6 showed the Raman spectra of GO and NZVI/GO
composite. As shown in Figure 6, the presence of the
intense D-band at 1362.5 cm−1 (the band referring to lat-
tice distortion) and the normal G-band at 1582.8 cm−1
were both Raman characteristic peaks of C atoms. Among
them, the D-band was attributed to the high level of oxi-
dation which resulted in defects on GO nanosheets sur-
face and lattice distortion. According to the Raman spectra
of NZVI/GO composite, it was noticed that D band and
G band have a little blue shift to a certain degree, which
could be attributed to the synergistic effect between GO
and NZVI. What’s more, we found that the value of ID/IG
ratio (the intensity ratio of D-band and G-band, as an indi-
cator of structural defects) increased from 0.785 for GO to
0.937 for NZVI/GO composites, which may be due to the
change in the microstructure of graphitized structures.27ꢀ28
690
700
710
720
730
740
Binding energy/eV
Figure 4. XPS spectrum of Fe 2p of the GO/NZVI composite.
nano-particles and the outside become larger, thus making
NZVI easier to be oxidized.
3.4. FT-IR Analysis
The FT-IR spectra of the NZVI/GO composites were
shown in Figure 5. As for GO, the characteristic bands
appeared for hydroxyl (ꢁOH) (stretching at 3400 cm−1ꢁ,
alkoxy C–O (vibrating at 1050 cm−1ꢁ, epoxy group (C–O)
at 1137 cm−1, carbonyl (C O) at 1730 cm−1, the bend-
ing vibration peak of unsaturated double bonds (C C)
and C–OH at 1618 cm−1, which may be due to inter-
3.6. The Degradation of TCCA by NZVI/GO
Further experiments were performed to investigate the per-
formance of NZVI/GO composite via trichloroacetic acid
(TCAA) degradation. As shown in Figure 7, the con-
centration of TCAA gradually decreased over time and
its concentration was nearly reduced to zero at about
160 min, which indicated that NZVI/GO composites had
a good degradation effect on TCAA. This may be due
to the impact of pHPZC (pH at point of zero charge)
of NZVI/GO composites. Generally speaking, the surface
charge of NZVI/GO was positive at lower pH value than
the pHPZC and vice versa. Sun et al.29 measured the pHPZC
of NZVI and NZVI/GO composites were 5.1 and 4.66,
respectively. Therefore, acidic condition can result in posi-
tive charges on the surface of NZVI/GO composites, which
will attract TCAA. Furthermore, GO also had a capac-
ity to adsorb TCAA to a certain degree. So TCAA can
be rapidly degraded by zero-valent iron nano-particles.
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stitial water presented in the GO sheet, which was con-
Copyright: American Scientific Publishers
sistent with the fact that the GO cannot be completely
Delivered by Ingenta
dried.23ꢀ24 These oxygen-containing groups resulted in
the increase of the interlayer spacing between graphite
sheets. As for NZVI/GO, the weakening of the peak at
3400 cm−1 for graphene suggested that treatment removed
the oxygen from the hydroxyl groups so that the C–O
peak became weaker compared to graphene oxide.25 The
peak near 1400 cm−1 could be attributed to bands associ-
ated with Fe3O4, Fe2O3 and FeOOH formation surround-
ing Fe0.26 Besides, the C O band disappeared and the
intensity of C–O–C band decreased in the spectrum of
the NZVI/GO, which indicated that the oxygen-containing
80
4000
GO
Fe/GO
3000
GO
70
60
50
2000
1000
0
Fe/GO
1000
2000
3000
4000
1000
1200
1400
1600
1800
2000
Wavenumber/cm–1
Raman shift/cm–1
Figure 5. FT-IR spectra of NZVI/GO composites.
Figure 6. Raman spectra of GO and NZVI/GO composite.
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A Facile Strategy to Fabricate NZVI/GO Composite for Dechloridation of Trichloroacetic Acid in Water
Zhang et al.
TCAA
DCAA
MCAA
nano-particles, so the effective contact area of zero-valent
iron nano-particles and TCAA increased. Besides, the GO
itself had a larger adsorption capacity to adsorb TCAA,
therefore, the composite could adsorb more contaminants.
Subsequently, TCAA was reduced by zero-valent iron
nano-particles which dispersed on the surface of GO.
Zero-valent iron nano-particles released many electrons
while being corroded, corresponding reaction (2) and (3).
The extremely fast conductivity and the unique two-
dimensional planar structure of the graphene oxide could
make electrons which were released by zero-valent iron
nano-particles moving rapidly and thus electrons could
involve in the further reaction quickly. As a result, a part
of TCAA removed chloride ions into DCAA, MCAA or
directly to acetic acid (CH3COOH) under the action of
electrons (reaction (4)). Apart from these, superoxide rad-
icals (Oꢁ2−ꢁ which generated via the combination of elec-
trons and oxygen molecules dissolved in water also had
a positive effect for the degradation of TCAA and other
intermediate products. Noticeably, the low pH conditions
of the system and the iron ions produced by the NZVI
as an effective reducing agent provided sufficient condi-
tions for the Fenton reaction. On the one hand, in the
process of corrosion of zero-valent iron nano-particles,
not only divalent iron ions but also trivalent iron ions
would be produced. On the other hand, trivalent iron ions
could further react with zero valent iron nanoparticles thus
1.0
0.8
0.6
0.4
0.2
0.0
Acetic Acid
-
Cl
0
50
100
150
200
250
Time/min
Figure 7. Decomposition of TCAA, DCAA, MCAA, acetic acid and
Cl− concentration during the TCAA degradation.
At the same time, with time increased, the concentra-
tion of dichloroacetic acid (DCAA) and monochloroacetic
acid (MCAA) showed a first increase and then decreased.
On the contrary, the concentration of acetic acid and
Cl− gradually increased as time went by. These indi-
cated that the complete dechlorination product (acetic
acid) was measured as the only final product during the
degradation of TCAA by using NZVI/GO composites.
Besides, both of MCAA and DCAA were intermediate
products.
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formed divalent iron ions according to reaction (5). Oxy-
gen molecules would be reduced by H+ to generate a
certain amount of H2O2 (reaction (6)) under the action
of zero-valent iron nano-particles. Afterwards, due to the
Fenton reaction between trivalent iron ions and H2O2, a lot
of hydroxyl radicals (ꢁOH) which had strong oxidizing
capacities are generated (reaction (7)). Then trivalent iron
ions produced by Fenton reaction instantly being reduced
to be divalent iron ions (reaction (8)) thus forming a cycle.
Finally, the resulting active species were used to dechlo-
rinate and degrade contaminants. At the same time, the
chlorine atoms from TCCA were present in the aque-
ous solution in the form of chloride ions, maintaining the
charge balance. Therefore, this system did hardly produce
any sludge.
Copyright: American Scientific Publishers
3.7. Degradation Mechanism for TCAA by the
Delivered by Ingenta
NZVI/GO Composites
In order to better understand the degradation process of
TCAA, degradation mechanism for TCAA by NZVI/GO
composites was proposed. As shown in Figure 8, the zero-
valent nano-particles were dispersed on graphene oxide.
The process of TCAA dechlorination was divided into two
stages under the presence of NZVI/GO: firstly, TCAA was
adsorbed on the surface of NZVI/GO. As the graphene
oxide could inhibit the accumulation of zero-valent iron
e–
e–
e–
e–
e
e–
Fe3+
e–
e–
e–
e–
e–
Fe0 → 3e− +Fe3+
Fe0 → 2e− +Fe2+
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
e–
e–
e–
Fe2+
e–
e–
e–
RCln
RCln +e− → RCln−1 +Cl−
2Fe3+ +Fe0 → 3Fe2+
RCln-1
O2 +2H+ +2Fe0 → H2O2 +Fe2+
Fe2+ +H2O2 +H+ → ꢁOH+H2O+Fe3+
Fe3+ +e− → Fe2+
GO
NZVI
O2 +2e− → Oꢁ2−
Figure 8. Reaction mechanism of TCAA by NZVI/GO composite.
8256
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Zhang et al.
A Facile Strategy to Fabricate NZVI/GO Composite for Dechloridation of Trichloroacetic Acid in Water
4. CONCLUSIONS
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A magnetic composite material consisting of zero-valent
iron nano-particles and graphene oxide was synthesized
and used as a catalyst for the degradation of trichloroacetic
acid (TCAA). The results showed that the zero-valent
iron nano-particles were dispersed on graphene oxide
and the specific surface area increased. What’s more,
the GO could serve as a stabilizer to avoid aggre-
gate formation of zero-valent iron nano-particles. Fur-
thermore, NZVI/GO had a good ability to degrade
trichloroacetic acid. Trichloroacetic acid was substantially
completely degraded within 250 min. The final product of
trichloroacetic acid degradation is acetic acid. In addition,
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by NZVI/GO composite. It was presumed that Fenton
reaction may have occurred to produce hydroxyl radicals
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Acknowledgment: This work was kindly supported by
National Natural Science Foundation of China (51508254,
41771341), Nature Science Foundation of Gansu Province
of China (1506RJZA216), Opening Project of State Key
Laboratory of High Performance Ceramics and Superfine
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IP: 185.13.33.15 On: Mon, 17 Sep 2018 15:06:44
Engineering Technology Research Center of Environmen-
Copyright: American Scientific Publishers
tal Cleaning Materials (KFK1502), A Project Funded by
the Priority Academic Program Development of Jiangsu
Higher Education Institutions (PAPD) and Key Laboratory
of Comprehensive and Highly Efficient Utilization of Salt
Lake Resources, Qinghai Institute of Salt Lakes, Chinese
Academy of Sciences.
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Received: 15 December 2017. Accepted: 22 March 2018.
J. Nanosci. Nanotechnol. 18, 8252–8257, 2018
8257