Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861

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Journal of Photochemistry & Photobiology A: Chemistry

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Sunlight mediated improved photocatalytic degradation of carcinogenic T

benz[a]anthracene and benzo[a]pyrene by zinc oxide encapsulated
hexacyanoferrate nanocomposite
⁎
Rachnaa, Manviri Ranib, Uma Shankera,
a
Department of Chemistry, Dr B R Ambedkar National Institute of Technology Jalandhar, Punjab, 144011, India
b
Department of Chemistry, Malaviya National Institute of Technology Jaipur Jaipur, Rajasthan, 302017, India

A R T I C LE I N FO A B S T R A C T

Keywords: Polycyclic aromatic hydrocarbons (PAHs), pervasive plus priority emerging pollutants have the potential to
Encapsulated ZnHCF@ZnO nanocomposite destruct the bionetwork. Therefore, photocatalytic decay of toxic 4- and 5-ring membered PAHs, namely benz[a]
Photo-catalysts anthracene (BaA) and benzo[a]pyrene (BaP), was explored in water. The nanocomposite of zinc hex-
Polycyclic aromatic hydrocarbons acyanoferrate encapsulated with zinc oxide (ZnHCF@ZnO) was synthesized by Azadirachta indica mediated co-
Water
precipitation under normal conditions. Sunlight exposure caused a quick downfall in the concentration of PAH
Removal
with composite exposing its eminent photo-activity. Encapsulation resulted in enhanced surface area
(113 m2 g−1) and lesser band gap energy (2.2 eV) of nanocomposite owing to the synergism of semiconducting
stuff of zinc oxide and intercalative properties of ZnHCF. At neutral pH, photo-degradation of PAHs (2 mg L−1)
by optimum dose of catalyst followed first order kinetics and Langmuir isotherms (R2≥0.98; p ≤ 0.05). Slightly
lower elimination of BaP (90%) than BaA (93%) might be due to its higher molecular weight and conjugation.
Mechanism exploration revealed the involvement of “cation- π” interaction effectively between nanocomposite
and PAHs (Xm =25.6 mg/g of BaA and 21.7 mg/g of BaP) than bared (ZnO and ZnHCF). Besides, it compacts the
t1/2 value of BaA(0.35 h) and BaP (0.49 h) up to manifolds than its constituents (13–26 h). Smaller by-products
like prop-2-en-1-ol, propionic acid and acrylic acid identified in GCeMS, clearly supported electron excitement
from encapsulated nanocomposite followed by %OH (active species)based oxidation of PAHs. Particularly, the
mineralization evaluation of PAHs through TOC analysis confirmed its conversion into H2O and CO2. Inclusive of
the present study provides promising photo-catalyst with greater surface activity, low quantum yield with charge
separation and reusable for ten cycles deprived of substantial loss of its action. Similar studies can be promoted
to build up methods that can accurately predict the acceleration in the environment clean up strategies.

1. Introduction transformed into biologically active chemicals [8]. Lipophilic nature of

Polycyclic aromatic hydrocarbons (PAHs), a hefty collection of
fused aromatic rings, are persistent semi-volatile contaminants of
human and ecological anxiety derived from incomplete combustion of
fossil fuels, oil spills and other organic sources [1–3]. Moreover, PAHs
with their photo-oxidation products are found ubiquitously in all nat-
ural compartments and often considered responsible for the acute
toxicity of oil spills in the naval environment [4]. PAHs containing four
or more rings like Benz[a]anthracene (BaA) and benzo[a]pyrene (BaP)
have been classified priority chemicals based on high chemical stabi-
lities and known or suspected carcinogenicity [5–7]. The physiochem-
ical properties of these PAHs are listed in Table 1S. On metabolic ac-
tivation by microsomal and hydrolases enzymes, these PAHs were
PAHs makes quick adsorption of these into human body through in-
halation, direct intake and dermal contact [9]. Metabolites of PAHs
bound with the body proteins, nucleic acids covalently and cause per-
manent damage to various parts of body including respiratory system
[10]. Relatively unmanageable BaA (14–312 mg kg−1) is typically de-
tected in mud from susceptible areas containing leftover of wood
treatments, creosote and industrial gas [11]. BaP is one of the most
potent carcinogenic PAHs, and priority compounds highlighted by Food
and Drug Administration and Tobacco Product Regulation with a
narrow edge of 5 μg kg−1 d. wt of smokeless tobacco [12,13]. In ad-
dition to BaP, its reactive enzymatic metabolite called BaP-7,8-diol-
9,10-epoxide is also liable for the carcinogenic effects [2,14]. The
World Health Organisation and the European Union has set the

⁎
Corresponding author.
E-mail addresses: shankeru@nitj.ac.in, umaorganic29@gmail.com (U. Shanker).

https://doi.org/10.1016/j.jphotochem.2019.111861
Received 18 January 2019; Received in revised form 3 May 2019; Accepted 12 May 2019
Available online 14 May 2019
1010-6030/ © 2019 Elsevier B.V. All rights reserved.
Rachna, et al.
Fig. 1. Possible synthesis mechanism of ZnHCF@ZnO nanocubes, FESEM, EDX and PXRD pattern of nanocomposite.
indicative limit value of BaP at 1 ng m-3 [15]. BaP containing 5-benzene
ring is bio-accumulative and resistance to self-degradation and hence,
considered as persistent organic pollutant [16,17]. The volatility of BaP
is lower with very slow degradability, i.e. 2–66 months [18,19]. A large
portion of tobacco smoke constitutes of BaP, it creates abnormal im-
mune responses and ultimately develops cancers [20]. Therefore, the
rising concern towards the global environment purity, occurrence to-
gether with the toxicity of PAHs and their oxidative derivatives need
the superior removal strategy. The time consuming biological systems
have been the earlier procedures to get rid of PAHs from highly filthy
environs [11,21,22]. The high molecular weight of BaP and BaA bound
their degradation in contrast to PAHs of low molecular weight (phe-
nanthrene and naphthalene) [23]. Heterogeneous catalysis based on
semiconductor being exhibited most successful recital in water pur-
ification methods by degradation (oxidation/reduction) of con-
taminants with high efficiency, low cost and utilization of clean solar
energy [24–26]. Recently, iron oxides, zinc oxide and TiO2 nano-
particles utilised degradation of PAHs have been reported [27–29].
Conversely, the application of ZnO in engineering industry is restricted
due to combination of photo-generated charge carriers, wide band gap
and narrow spectral response [30].
Synergistic effect in nanocomposites of Zn, Fe or Ti oxides (having
band gap 3.3, 2.23 and 3.2, respectively) are of great significance as it
can improve the photo-catalytic activity of the existing composite
technology to the huge amount [31–33]. Zinc oxides doped with other
metal ions overpower the recombination of charge carriers [34–36].
This results in the improved surface activity and amplified excitation of
electron-hole pairs [37,38]. Recently, photo-catalysis has attracted
huge attention due to its effectiveness in converting pollutants to H2O
and CO2 [39]. Such concerns have recommended the photocatalytic
enhancement, and thus, the elimination of pollutants by nanocompo-
sites depends upon its surface, dimensions and optical property [40,41].
However, the photo-catalytic activity of the catalyst depends upon the
method of fabrication involved along with particle size, morphology
and band gap energy [24,42]. ZnS and Cu nanomaterials loaded on
activated carbon [43], zinc ferrite spinels [44], metal doped ZnO [34]
and nanocomposite of silver, silver oxide, zinc oxide and graphene
oxide [45] which, came out to be an excellent photo-catalyst for photo-
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Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861
degradation of organic contaminants are being synthesized with co-
precipitation. Copper doped ZnO nanostructures were able to degrade
90% of anthracene and 50% of phenanthrene [46]. Habibi-Yangjeh and
co-workers found ZnO/Bi2MoO6/AgBr and ZnO/NiWO4/Ag2CrO4 na-
nocomposites as efficient photo-catalysts [35,36]. Addition of TiO2 and
Fe2O3 lowered the t1/2 photo-decay of BaP from ˜15 days to 3 and 4
days, correspondingly, signifying efficacy of semi-conducting materials
[47]. Collected works showed the good performance of TiO2 and ZnO
only under UV source because of the high straight band gap (˜3.2 eV)
[48–50]. Nevertheless, zinc oxide nano-sheet (2D) is interesting to
construct and enhanced photo-catalytic material due to the modifiable
coating space for the amassing of Zn2+ ions and the better ion ap-
proachability to redox-active sites. Better findings through the sy-
nergistic effect; suggest such fabrication of semiconducting nano-
composites could be an effective approach in expanding the application
and to overcome the shortcomings of bare materials, hence creating
novel possessions. Furthermore, to shirk accumulation of organics and
restrict the exaggeration of an exact metallic structure, a substitute
should be promoted. In sight of this, the ZnO doped zinc hex-
acyanoferrate (ZnHCF) was inspected for photo-catalytic removal of
targeted PAHs. Metal hexacyanoferrates (MHCFs) have acquired huge
attention in the photo-catalytic discharge of organic toxic wastes due to
their large surface area, significant band gap (1.31–2.52 eV) and
semiconducting properties [51–56]. ZnHCFs with large surface activity
and definite morphology are economical, biocompatible [57–59].
ZnHCF@ZnO was synthesized using natural plant extract (Azadirachta
indica). A. indica is one of the potential promising biogenic plant for the
synthesis of nanoparticles, the parts of the plants are, easily accessible
and storage of plant is very simple [60–62]. Benzoquinones of this plant
extract (cyperoquinone, dietchequinone and remirin), decrease the
element size and the proteins incorporate stabilization [63]. Synthe-
sized nano-catalyst was examined with the parent metal oxide and
ZnHCF nanoparticles. Compared to the parent catalyst, the photo-cat-
alytic activity of the synthesised catalysts at different dose was opti-
mised for pH for varying concentration of target PAHs. Employment of
green route for the synthesis under room temperature without the
employment of any hazardous chemical and exploration of water as a
matrix increases the significant value of the present work. It has been
Rachna, et al. Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861

Fig. 2. Degradation efficiency of photocataysts at different parameters: concentration, catalytic dosage and pH.

Fig. 3. Time dependent kinetics studies of PAHs degradation over photocatalysts.

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Rachna, et al.
Fig. 4. Time dependent disappearance profile of total organic carbon (TOC)
content of PAHs with ZnHCF@ZnO nanocomposite.
Fig. 5. Variation in the degradation efficiency of photocatalysts under sunlight
and dark conditions.
observed by the various researchers around the globe that coupling or
mixing of metal oxides with different metallic frameworks can be done
for their exploitation under sunlight. Mixing of ZnO with the ZnHCF has
significantly enhanced its properties such as surface area, band gap,
stability and semi-conducting behavior. This helped in activation of
molecules under the sunlight and makes it a easily applicable natural
scenario. The coupling of ZnO and ZnHCF enable the successful sup-
pression of recombination of charge carriers. Moreover, such nanoma-
terials have their own importance in breaking the limitation of bio-
enrichment of a particular metal in environment. Its application in the
removal of PAHs was done by creating natural condition faced by the
water (sunlight exposure). Various reaction parameters were studied
under the PAHs removal including concentration, dose, pH, irradiation
source, time and reaction kinetics. The decrease in the band gap energy
of the nanocomposite shifts the absorption into the visible range and
hence, improves its activity under sunlight. The reusability of the na-
nocatalysts upto 10 times has confirmed its applicability with higher
efficiency in waste water treatment. The distinctive construction of
ZnHCF coated with zinc oxide nano-sheets, enables to a synergistic
consequence for refining photocatalytic recital in degradation of ha-
zardous PAHs. To the best of our knowledge, ZnHCF@ZnO nano-
composite has not been reported for the degradation of BaA and BaP.
Since in recent time world has faced huge demise of aquatic life due to
the oil spilling and accumulation of PAHs in the living body. This work
has engineering importance in degradation of various emerging con-
taminants causing threat to the life and environment.
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Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861
2. Materials
2.1. Reagents
K4Fe(CN)6, Zn(NO3)2, NaOH, benzo(a)anthracene and benz(a)
pyrene standard and acetonitrile (HPLC grade) were acquired from
Merck, Germany. Distilled water was used in all the experiment. A.
indica leaves (5 g) collected from the locally found tree were thoroughly
washed, crushed, mixed in distilled water to prepare plant extract
(10 mL), filtered and stored at 4 °C.
2.2. Preparation of photo-catalysts (encapsulated ZnHCF@ZnO
nanocomposites)
The procedure involved the synthesis of ZnO followed by en-
capsulation of ZnHCF as already reported by Rani and Shanker [64].
2.2.1. ZnO nanosheets
Zn(NO3)2 having 0.05 M concentration and 2 mL of the plant extract
(A. indica) were initially stirred for 1 h at room temperature. In order to
make immediate precipitates, pH of the above solution was maintained
at 9 using 0.1 M NaOH solution. The colourless precipitates were fil-
tered, washed with distilled water and finally dried in muffle furnace at
300 °C for 4 h.
2.2.2. Encapsulated ZnHCF@ZnO nanocubes
Initially suspension of ZnO nanoparticles was prepared by gradually
suspending the as synthesized nanoparticles into 100 mL of distilled
water with the help of an ultra sonicator. After this, the above sus-
pension was added in to the 100 mL of 0.1 M aqueous solutions of Zn
(NO3)2. Mixture of suspension and metal salt were drop-wise added into
the K4[Fe(CN)6] solution having 4 mL of A. indica in it with continuous
stirring for 2 h at room temperature. The product obtained was washed,
filtered, dried (at 70 °C) and stored.
For comparison ZnHCF was also synthesized by pouring K4[Fe
(CN)6] into Zn(NO3)2 solution containing plant extract and stirred for
2–3 h. The product formed was filtered, washed and dried.
2.3. Characterization
The details of instrumentation of Powder X-ray diffraction (PXRD),
Field-Emission Scanning Electron Microscopy (FE-SEM), Brunauer-
Emmett-Teller (BET), UV–vis absorption spectrophotometer (Shimadzu
UV-2401PC), Fourier transform infrared, Zetasizer (Zetasizer Ver.
7.11), gas chromatograph interfaced with mass selective detector has
been presented in the supplementary information file.
2.4. Analytical procedure for photo-catalytic activity
Photo-catalytic degradation of BaP and BaA was carried out in the
presence of the as synthesised catalysts in simulated water. Procedural
blank (10 mL of each PAH without catalyst) were examined to know the
exact potential of nanocatalysts. Experimental conditions like con-
centration (2–10 mg L−1), amount of nanocatalyst (5–35 mg), pH (5–9)
and time were inspected with and without sunlight. For making water
of different pH, citrate and borax buffer were used.
The final experiment consisted of 15 mL of water spiked with 2.5 mL
of the PAH (2–10 mg L−1) and ZnHCF@ZnO nanocomposite or parent
nanoparticles. At that time, the reaction mixture was exposed to non-
stop sunbeams for 24 h without disturbing in the night. The usual
temperature (°C) and light-strength (W/m2) were 32.3 ± 4.2 (range:
22.0–36.0) and 463 ± 181 W/m2 (range: 150–823). Further, the su-
pernatant was examined for extent of degradation, absorbance by UV-
Spectrophotometer and the by-products were identified through
GC–MS. The % degradation of PAHs was calculated using the equation
(Ci – Ct/Ci) ×100. Here Ci is the initial concentration of the sample and
Rachna, et al. Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861

Fig. 6. Schematic representation of charge separation mechanism for degradation of PAHs over photocatalysts.

Table 1 PXRD pattern confirmed the crystalline nature of nanocomposite. Fur-

Rate constant and half-life values of PAHs with nanoparticles at optimised ther the encapsulation of ZnHCF with the ZnO was affirmed through the
conditions. minor alteration of parameters (Fig. 1S). The peaks formed in ZnHCF
Catalyst BaA BaP and ZnO nanoparticles were in accordance with the ICSD card number
98-000-8248 and 79-2205, respectively. The details of the PXRD
−1
k (h ) t1/2 (h) R 2
k (h−1) t1/2 (h) R2 parameters of the photo-catalysts are listed in the table 2S. The FE-SEM
and EDX image of ZnHCF@ZnO showed the uniform distribution of
ZnHCF@ZnO 1.96 0.353 0.98 1.4 0.49 0.99
ZnHCF 0.05 13.86 0.99 0.033 20 0.99 nanoflowers of ZnO upon the nanocubes of ZnHCF and size within the
ZnO 0.03 23.1 0.99 0.027 26 0.99 nanorange (below 100 nm). The ZnHCF were perfect cubes while ZnO
Blank 0.006 115.5 0.99 0.0019 364.73 0.99 nanoparticles were flowery sheets (100 nm each) (Fig. 2S). FTIR ana-
lysis revealed the presence of various functional groups and bonds
formed in nanocomposite (Fig. 3S). In order to reveal the semi-
Ct is the final concentration. conducting properties of nanocomposites band gap energy analysis was
performed (Fig. 4S). The ZnHCF@ZnO nanocomposite had lower band
2.5. Statistical analysis gap (2.2 eV) than the parent nanoparticles (ZnO-3.3 eV, ZnHCF-2.3 eV)
favouring the belief of its enhanced semiconducting property. Based on
The statistical plots of reaction and kinetics for the degradation of the actuality of photo-catalysis involving adsorption as a central phe-
PAHs over the nanocomposites were performed factually from an nomena, BET surface area analysis of the nanoparticles was performed
asymptotic examination by SPSS software. Results stood reproducible (Fig. 5S). Encapsulation of ZnHCF by ZnO increased the surface area of
for triplicate analysis. The standard deviation of the triplicates were ZnHCF (108.70 m2 g−1) to 113.491 m2 g−1, attributed to the synergistic
calculated through Microsoft excels program. Significance of results effect of parent components.
was compared through regression of coefficient (R2) and p-values (≥
0.05). Several adsorption models data were scrutinized. Linear curves 3.2. Photo-catalytic degradation of PAHs
(Y = mX + c) for adsorption and concentration dependent study have
been obtained while exponential graphs attaining maxima were ob- The encapsulated ZnHCF@ZnO nanocomposites were examined for
served for adsorption. the photocatalytic degradation of selected BaP and BaA (Toxic PAHs)
under daylight.
3. Results and discussion
3.2.1. Effect of concentration
3.1. Characterization of photo-catalysts The degradation was found to differ with concentration
(2–10 mg L−1) whilst the catalyst dosage (25 mg) and pH (7) were kept
The phase composition, structure, size and geometry of photo-cat- constant (Fig. 2a). Highest degradation was obtained at least con-
alyst were investigated using PXRD and FE-SEM (Fig. 1). The sharp centration (2 mg L−1) of the PAHs. Sufficient active sites of ZnHCF@

5
Rachna, et al.
Fig. 7. Adsorption isotherm (a) and Langmuir adsorption model (b) for adsorption of PAHs on ZnHCF, ZnO and ZnO@ZnHCF nanoparticles.
ZnO nanocomposite (113.491 m2 g−1) caused the 93% and 90% de-
gradation of BaA and BaP, respectively followed by ZnHCF (70%; 65%)
and ZnO (46%; 38%). Nonetheless, upon gradually increasing the
number of molecules of PAHs in the reaction mixture, the distance
between photons of light and catalyst increases. Ultimately the
screening by the PAH molecules limited the photo-degradation ability
(electron hole formation) as displayed by negative slope [65–68]. In the
absence of catalyst, little change in the PAHs adsorption was observed.
Slower degradation of BaP in comparison to BaA could be attributed to
the more ring (high molecular weight) leading to more conjugation and
hence, higher persistence (log Kow: 6.06) (Table 1S).Similar trends in
PAHs degradation has been reported in other studies [54,55,69].
Overall, it can be concluded that, when the concentration of PAHs ex-
ceeds a certain value, the number of active species causing the de-
gradation is lower than the PAH molecules. Hence, higher concentra-
tion is not benefitting the PAHs degradation.
3.2.2. Effect of dose
All through investigated suitable dose (5–35 mg) of photo-catalysts,
degradation plot rose to maxima at 25 mg and then declined (Fig. 2b).
Early rise in the graph with dose was because of huge number of surface
active sites causing the absorption of considerable amount of photons
[51,53,54]. Yet, the decline obtained in degradation on additional in-
crease of the dose of the catalyst could be due to the limited surface
area (due to aggregation) and collision of the activated charge particles
with the ground state molecules. Moreover, a large amount of photo-
catalyst in limited reaction vessel might cut-off the entrance of light-
rays to PAHs [66,67,70]. The reason of variation after a particular dose
can also be described as further rise can cause the gathering of the
catalysts particles. Eventually under such conditions contact area of
nanocatalysts with the water molecules was lowered, thus fall in its
performance.
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Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861
3.2.3. Effect of pH
The degradation of PAHs (2 mg L−1) was investigated over a range
(5–11) of pH (Fig. 2c). Highest degradation ability of nanocomposites
was observed at neutral pH due to the lessening in electrostatic inter-
action [71,72]. Moreover, the encapsulation of ZnHCF by ZnO elevated
the acidic character of ZnHCF@ZnO nanocomposites indicated by its
negative zeta potential value at neutral pH (ZnHCF@ZnO: −41.6 eV:
ZnHCF: −40.3 mV; ZnO: -13.4 mV) (Fig. 6S). However, the presence of
hydronium and hydroxyl ion caused the ion screening effect in acidic
and basic pH and hence reduced the photocatalytic [58]. Due to the
stability of the resonance ring structure, PAH containing high π-elec-
tron density were believed to form “cation-π” complexes upon inter-
action with the positive surface of nanocomposite [55]. The similar
event has also been observed upon the photolysis of PAHs on Fe3+-
montmorillonite surface [69]. The use of HCl and NaOH to make so-
lution acidic and basic, respectively, can also initiate secondary inter-
actions (chlorate ion-catalyst and hydroxyl-hydroxyl interaction) and
hence limit the desired interaction [73]. Overall, the highest degrada-
tion at neutral pH was due to its acidic character, highest surface ac-
tivity, synergistic effect (production of large e–h pairs) and reduced
charge carriers recombination [58,59].
The results suggest formation of a naturally acting catalyst which
can perform well at environmental conditions with almost valuable
results at all pH conditions.
3.2.4. Reaction kinetics
The rate of photocatalysis, reaction kinetics of BaP and BaA, were
studied with 25 mg of ZnHCF@ZnO nanocomposite at neutral pH
(Fig. 3). Degradation followed first-order kinetic which included quick
initial downfall along with slow or no degradation with time. This
phenomenon resulted from the semiconducting behaviour that in-
creases in the life span of energized electrons upon introduction to
sunlight. Consequently, an instant generation of massive hydroxyl ra-
dicals may oxidize the colossal rings of the PAHs into smaller by-
Rachna, et al. Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861

Fig. 9. Degradation efficiency variation of photocatalysts upon introduction of

hydroxyl radical scavenger.

Fig. 10. PL spectra of different photocatalysts.

products. The steady state in the degradation outline could be due to a

Fig. 8. Proposed degradation pathway for the degradation of (a) BaA and (b)
BaP over ZnHCF@ZnO nanocubes (Concentration; 2 mg/L−1; pH:˜7; catalyst
dose: 25 mg; natural sunlight.
minute change in concentration or use of %OH by additional pathway
products. The assumption of rapid degradation with the encapsulated
nanocomposite has also been supported by the 50% degradation of the
PAHs within 5 h only. Moreover, the highest k-value and least half-life
was obtained with ZnHCF@ZnO as shown in Table 1.The PAHs (BaA;
BaP) concentration remaining after 5 h was (0.90 ± 0.028;
1.1 ± 0.023), (1.6 ± 0.032; 1.73 ± 0.029) and (1.8 ± 0.031;
1.9 ± 0.023) mg L−1 with ZnHCF@ZnO, ZnHCF and ZnO, respec-
tively. The potential of the nanocomposite was greater than ZnO in
PAHs degradation under sunlight. Total organic carbon (TOC) analysis
also confirmed the complete removal or mineralization of both the
PAHs. Results indicated that 57% and 38% TOC was left in treated
reaction mixture water after 5 and 24 h, respectively (Fig. 4). Similar
results based on TOC analysis have also been reported [71,72].
Results clearly show the better activity of the nanocatalysts in the
degradation of carcinogenic PAHs. Moreover, deficiency in studies of
nanoparticles as photocatalysts for the degradation of several other
contaminants under sunlight lifted the importance of present work. In
order to safe guard the environment, plant based synthesis of materials
should be promoted. All in all, A. Indica based ZnHCF@ZnO nano-
composite (2.2 eV) came out to be an efficient agent in almost complete
and quick removal of PAHs under sunlight. These facts make it a va-
luable and safe catalyst than the usual metal oxides and other ad-
sorbents.
3.2.5. Effect of irradiation source
Under optimized parameters (PAHs: 2 mg L−1; neutral pH; 25 mg
catalyst), PAHs were treated with ZnHCF@ZnO and constituents under

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Rachna, et al. Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861

Table 2
Comparison data of PAHs degradation reported by other studies.
S. No. Name Method & Properties Degradation Reference

1 BaA Mycobacterium vanbaalenii 15% in 12 days [8]

2 BaA (0.5 mg/flask) Irpex lacteus 70% in 14 days [17]
3 BaA Indigenous Strains Reduced to 0.02 mg/l in 56 days [18]
4 BaA (0.1 mg g−1) Fe3+-modified montmorillonite 17% in 6 hours [60]
5 BaA ZnHCF@ZnO (distorted nanocubes ˜100 nm; 113 m2 g−1) 93% in 24 hours Present study
6 BaA ZnHCF 70% in 24 hours Present study
(nanocubes, 108.70 m2 g−1)
7 BaA ZnO (Flower shaped, 12 m2 g−1) 46% in 24 hours Present study
8 BaP (50 mg L−1) FeHCF (69 m2 g−1) 70% in 48 hours [46]
9 BaP (50 mg L−1) ZnHCF (108 m2 g−1) 70% in 48 hours [45]
10 BaP (2 mgL−1) ZnHCF@ZnO 90% in 24 hours Present study
11 BaP (2 mgL−1) ZnHCF (108 m2 g−1) 65% in 24 hours Present study
12 BaP (2 mgL−1) ZnO 38% in 24 hours Present study

Fig. 11. Degradation efficiency variations of photocatalysts with the subsequent degradation cycles (a) ZnHCF, ZnO and ZnHCF@ZnO nanoparticles; (b) XRD pattern
of photocatalyst upto 10 cycle.

sunlight and dark exposure (Fig. 5). The PAHs were degraded to 90%,
70% and 40% under sunlight exposure, while ˜40%, 30% and 25%
degradation were obtained in the dark with ZnHCF@ZnO, ZnHCF and
ZnO, respectively. The energy provided by the natural sunlight excited
the electrons to higher energy levels, which caused the advanced de-
gradation of PAHs [2,54,55]. This excitation was fast in nanocompo-
sites having lower band gap energy ZnHCF@ZnO (2.2 eV), than ZnHCF
(2.34 eV) and ZnO (3.3 eV). Further, the interactions of charge carriers
(e–h+ pairs) with H2O/O2 produce dynamic groups which degraded the
bulky structure of PAHs into less toxic by-products. The photo-catalytic
activity of the catalyst was also justified by the slightest degradation in
the blank (8 and 5% in sunlight and dark). Encapsulation or doping
increased the charge separation and hence limited the recombination of
e- and h+ as shown in Fig. 6. Expansion of light spectrum towards
visible light of nanocomposites was also confirmed by the small band
gap of encapsulated nanocomposites [74,75].

8
Rachna, et al.
Photo-catalysis begins first with the adsorption of PAHs over the
catalysts surface. In order to confirm this fact various adsorption iso-
therms were tried (Fig. 7S and 8S). However, the photo-catalysis of
PAHs was most compelling to the Langmuir isotherms (Fig. 7) as in-
dicated by their highest R2 values (Table 3S). Out of the five models,
Temkin was not applicable (negative lnCe values) while, D-RK, Sips and
Freundlich were not accepted statistically (Table 3S).
Consequently, the Langmuir adsorption equation (refer to sup-
porting information) was utilized to determine the constant kL (dm3/
mol) and Xm (maximum amount of PAH adsorbed; mg/g).
Xm, kL and R2 values for BaA were perceived in the succeeding
order: ZnHCF@ZnO(25.57; 0.23; 0.991) > ZnHCF (14.79; 0.26;
0.993) > ZnO (6.27; 0.28; 0.992) for BaA. In case of BaP, these values
were found to be: ZnHCF@ZnO (21.73; 0.21; 0.98) > ZnHCF (10.52;
0.25; 0.987) > ZnO (5.17; 0.27; 0.99). The maximum PAH adsorption
obtained with ZnHCF@ZnO nanocomposite than the parent nano-
particles supported the maximum degradation with nanocomposite
(surface area: 113.491 m2 g−1).
3.3. Proposed photocatalytic degradation pathways
In order to identify the various products formed and understand the
degradation pathway, GC–MS analysis was carried out under optimized
conditions (PAH: 2 mgL−1; pH˜7.0; catalyst loading: 25 mg). The by-
products of original reaction mixture (Fig. 10S) corresponding to the
peaks were identified through previously stated works besides NIST
library integral with GC–MS [54,55,76,77]. Based on real results, de-
gradation mechanisms involving the function of %OH (main reactive
oxidative species) have been drawn (Fig. 8a and 8b). In BaA (mol.
wt. = 228), a small peak corresponds to m/z of 281 was identified as
(E)-2-hydroxy-3-(2-hydroxyanthracen-1-yl)acrylic acid (1) that pro-
duced by an unstable intermediate named tetraphen-2-ol formed by
initial attack of %OH to parent. It is believed to be formed through
oxidation and ring opening of mono-hydroxy BaA intermediate. Further
oxidation of this compound was identified by 3 crests in total ion
chromatogram (TIC). The first one was recognized as naphthalene-2,3-
dicarboxylic acid (2; m/z = 218), this could have produced by perva-
sive oxidation of terminal rings. Other two products named naphtha-
lene-1,4-diol (3; m/z = 161) and (E)-2-(2-carboxyvinyl)benzoic acid (4;
m/z = 192) may form by the hydroxylation followed by terminal ring
cleavage. The product named naphthalene-1,4-diol (3; m/z = 161) may
further undergo oxidation to form phthalic acid (3a; m/z = 166). The
compound (E)-2-(2-carboxyvinyl)benzoic acid (4; m/z = 192) via
dealkylation and decarbonylation may result into 2-hydroxybenzoic
acid (4a; m/z = 138).These products (3a and 4a) upon further oxida-
tion led into formation of smaller products called as but-3-ene-1,1,2-
triol (3b; m/z = 105), acrylic acid (3c; m/z = 73),(Z)-3-hydroxyacrylic
acid (4b; m/z = 133) and prop-2-en-1-ol (4c; m/z = 59).The identified
by-product but-3-ene-1,1,2-triol (3b; m/z = 105) and acrylic acid (3c;
m/z = 73) might have formed by di, tri hydroxylation and decarbox-
ylation of phthalic acid (3a; m/z = 166). The other two smaller pro-
ducts (4b and 4c) were formed by oxidation of 2-hydroxybenzoic acid
(4a; m/z = 138).
Being highly stable, photo-oxidation of BaP (mol. wt. = 252) was
slower and resulted in three by-products of relatively higher weight.
Those small peaks were respectively identified as pyrene-2-carboxylic
acid (1; m/z = 246), (Z)-3-(pyren-2-yl)acrylic acid (2; m/z = 273) and
chrysene-4,5-dicarboxylic acid (3; m/z = 316) believed to form through
oxidation of terminal rings of intermediates named benzo[pqr]tetra-
phene-9,10-diol and benzo[pqr]tetraphene-4,5-diol. Further, oxidation
of compounds (1 and 2) expected to form naphthalene-1,2,6,7-tetraol
(2a; m/z = 193) and 1-hydroxy-2-naphthoic acid (2b; m/z = 190)
tentatively known based on the mass spectra. These two compounds
might have formed through terminal ring cleavage and extensive hy-
droxylation of (Z)-3-(pyren-2-yl)acrylic acid (2; m/z = 273). On the
other hand, metabolite (3) undergo decarboxylation followed by
9
Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861
oxidation to form (E)-2-(3-carboxy-3-oxoprop-1-en-1-yl)benzoic acid
(3a; m/z = 220). Moreover, the synergistic effect of %OH radicals and
repulsion caused by two −COOH groups in by-product led to its ex-
tensive ring cleavage. The products 2a and 2b undergo oxidation and
led into formation of one cyclic and two acyclic products called as 2-
hydroxybenzoic acid (2d; m/z = 138), 2-hydroxypropanoic acid (2c; m/
z = 91) and (Z)-2,5,5-trihydroxypent-3-enoic acid (2e; m/z = 149). The
monocyclic ring compound2-hydroxybenzoic acid further oxidised into
smaller acyclic product propionic acid (2f; m/z = 75). These smaller
products upon attack of extensive %OH may undergo mineralization.
The comprehensive degradation trails for BaA and BaP have been seen
by Fig. 8a and b, respectively. The TOC analysis of the optimized
sample at various time intervals was investigated. Almost 60% (BaA)
and 59.5% (BaP) TOC was lost after 24 h indicating the conversion of
PAHs into CO2 and H2O through reaction intermediates (Fig. 4).
However, the small amount of TOC left might be due to presence of
smaller by-products. Effect of scavenger (ethanol) on the degradation of
PAHs was also investigated. Upon addition of scavenger the degrada-
tion % of PAHs decreases with all the catalysts at neutral pH under
sunlight (Fig. 9). Therefore, the results justified that the radical species
causing the degradation of PAHs are hydroxyl radicals and the process
involved is not only adsorption but also degradation.
The targeted PAHs were successfully ruined into non-toxic plus
smaller products with intense peak as compared to the bigger products
(Fig. 9S). Previous reports told about the safety and non-toxicity of
these products [54,78]. All-encompassing indicated that degradation of
PAHs involved the initial addition of OH group to terminal rings led to
oxidation, breaking of cyclic-ring, decarboxylation and to end with
elements. Different degradation by-products were formed in both the
PAHs (Fig. 10 S). It might be due to presence of more condensed rings
in the BaP as compared to BaA. In case of BaA degradation was initiated
though the hydroxyl attacks on terminal ring. However, because of
large structure of BaP, large number of hydroxyl radicals might attack
on the lesser hindered site. Degradation pathway on similar trail of BaA
and BaP has been reported [21,28,77].
3.3.1. Investigation of photo-catalytic degradation mechanism
To further investigate the charge separation and understand the
possible mechanism of photo-degradation, the photoluminescence (PL)
spectra were recorded as shown in Fig. 10. The emission spectra of
nanocatalysts were obtained at 350 nm excitation wavelength keeping
in view that wavelength setup should be greater than band gap energy.
As clearly shown in the figure, there was a slight difference between the
PL intensity of all the nanocatalysts. The PL spectra of ZnHCF@ZnO had
comparatively lower peak height than the ZnHCF and ZnO. En-
capsulation also caused a slight shift towards lower ends. Two peaks
were observed for each nanomaterial in the UV as well as in the visible
region. Such that the emission peak in UV region was corresponding to
the recombination of free charge carriers during their mutual interac-
tion. While, the emission observed in visible region was due to presence
of structural defects of oxygen vacancies and zinc interstitials in the
lattice structures. Photocatalytic performance of nanocatalysts is linked
with the life time of charge carriers (electrons and holes) and preven-
tion of their recombination. Relatively, lower PL intensity of ZnHCF@
ZnO than the native materials signified the quenching of charge carriers
recombination at the interface of ZnHCF and ZnO. Therefore, the re-
combination and transfer of photo-excited e− and h+ nanocomposites
are indeed in accordance with photo-catalytic degradation process.
Hence, it is definite that the best photo-catalytic activity of ZnHCF@
ZnO is sustained by the exceptional visible light absorption cum de-
gradation process and the superior charge separation across the inter-
face.
Moreover the increased concern of society towards health and hy-
giene makes it an appropriate strategy to remove the other hazardous
contaminants like dyes, large ringed PAHs and phenols.
Rachna, et al.
3.3.2. Comparison with other catalysts
It is noteworthy that very few studies are available for the de-
gradation of BaP and BaA, that too scarcely with iron and titanium
oxides [26,28]. In addition to this, recently two reports credited to
MHCFs (ZnHCF and FeHCF) have been found for PAHs degradation
(Table 2). The extensively used nanocatalysts has been unnoticed for
the removal of toxic PAHs, specifically BaA and BaP. However, mi-
croorganisms may well remove 15–70% of PAHs, but, the procedures
involved were prolonged and uneconomical. Being semiconductor,
MHCF could remove 70% of BaP while Fe3+-modified montmorillonite
was able to degrade 17% of BaA in 6 h. The effectiveness of en-
capsulated ZnHCF@ZnO nanocomposite recline on conversion of 93%
and 90% of investigated PAHs (BaA and BaP respectively) into minor
and invulnerable products, named, as prop-2-en-1-ol, propionic acid
and acryclic acid. Moreover, the synergistic effect of the parent nano-
particles ZnHCF and ZnO, enhanced the electronic excitation and hy-
droxyl radicals formation. Furthermore, deployment of unconventional
nanoparticles should be aided to elude the bio-enrichment of exact
recycled catalyst. The significance of comparison with other removal
methods indicated the importance of present study. Moreover, from
table it is very easy to say that very rare studies are available on de-
gradation of BaA and BaP using nanoparticles, which justified the
newness and effectiveness of the work.
Since for a long time rapid recombination of charge carriers has
lowered the photocatalytic efficiency of catalysts with limited light
response towards visible light. Utilisation of ZnHCF@ZnO in this aspect
can solve these problems as synthesise of such eco-friendly and efficient
catalyst is still a tremendous challenge. Overall, the potential of
Azadirachta indica stabilized ZnHCF@ZnO nanocomposites lies in its
ability to eliminate the PAHs entirely and speedily in natural conditions
favoring its safety than the usual metal oxide. Furthermore, Zn is a vital
trace metal having least harm to human [79]. Like iron hex-
acyanoferrate, their metal substitutes and Zn containing coordination
complexes are harmless as the cyanide groups are tightly bound to the
metal atom, comparatively stable (as indicated in PXRD of multiple
used material), and used as drug in Cs and Tl poisoning [80]. According
to a report a person can daily take 10 g of MHCF without any ill effect
on the health [79].
3.4. Reusability of the catalyst
The reusability of nanocomposite and parent nanomaterials was
checked to ensure its efficiency. The reaction mixtures after carrying
out the studies were separated from the catalyst. The catalysts were
procured, washed several times with acetone as well as distilled water
and dried. The photocatalytic activity was examined upto ten cycles for
PAHs (2 mg L−1) degradation to trial the stability of the catalysts
(Fig. 11a). The results obtained showed that the nanocatalysts stick to
its photo-catalytic activity in all the cycles. Little decay in catalyst ac-
tivity was due to the gathering of PAHs molecules. Results were also
supported by the PXRD patterns of the photo-catalysts having no sig-
nificant change in parameters (Fig. 11b). ZnHCF@ZnO nanocomposite
exhibited 90% of degradation in beginning and 85% after 10 cycles
(Fig. 10a).
4. Conclusion
Nanocomposite of ZnHCF encapsulated with ZnO nanosheets by the
use of simplistic green route (azadirachta indica) was low-cost, eco-
friendly and highly resourceful. Highly crystalline nanocomposite with
very well dispersed ZnO nanoflowers upon the nanocubes of ZnHCF
was formed. Herein, by taking advantage of this nanocomposite de-
gradation of PAHs had been effectively done. Under natural conditions,
synthesized nanocomposites speedily despoiled PAHs through langmuir
adsorption cum first order degradation kinetics. Encapsulated nano-
composite with high surface area (113.491 m2 g−1) and large acidic
10
Journal of Photochemistry & Photobiology A: Chemistry 381 (2019) 111861
character (-41.6 mV) was able to absorb 25.57 mg g−1 of BaA and
21.73 mg g-1 of BaP. Encapsulated ZnHCF@ZnO with low band gap
showed better photocatalytic removal efficiency than native ZnO and
ZnHCF. The enhanced interaction of H2O and O2 with excited pairs (e-
+ h+) formed OH% which eliminated and eventually mineralized the
PAHs under sunrays. Different smaller and safer by-products in GCeMS
for both PAHs revealed the role of their structure and attack of OH% on
the less hindered site. Specifically, the bases of ZnHCF around ZnO
sheets were prominent to a cumulative consequence for prompt zinc
ions incorporated degradation course along with redox reactions. The
results seem to new support for constructing new self-assembly na-
nostructures to develop promising composite nanomaterials. This work
highlights the possible use of encapsulated semiconducting nano-
composite with efficient band gap as highly active sunlight photo-
catalyst. It also suggests that coupling between semiconducting com-
pounds could be a very effective plan to modify the photocatalytic
activity and to conduct photo-degradation of contaminants other than
PAHs too.
Acknowledgement
Authors are thankful to DST-FIST for providing the instruments in
characterization and analysis. One of the authors Ms. Rachna is grateful
to Ministry of Human Resource Development (MHRD), New Delhi for
providing financial support.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jphotochem.2019.
111861.
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