Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588

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Journal of Photochemistry & Photobiology A: Chemistry

journal homepage: www.elsevier.com/locate/jphotochem

Facile synthesis and extended visible light activity of oxygen and sulphur co- T
doped carbon nitride quantum dots modified Bi2MoO6 for phenol
degradation
Abhinandan Kumara, Pankaj Raizadaa,b,*, Pardeep Singha,b, Ahmad Hosseini-Bandegharaeic,d,
Vijay Kumar Thakure
a
School of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan HP, 173229, India
b
Himalayan Centre for Excellence in Nanotechnology, Shoolini University, Solan HP 173229, India
c
Department of Environmental Health Engineering, Faculty of Health, Sabzevar University of Medical Sciences, Sabzevar, Iran
d
Department of Engineering, Kashmar Branch, Islamic Azad University, PO Box 161, Kashmar, Iran
e
Department of Engineering, Science and Technology Scotland's Rural College (SRUC), Edinburgh, United Kingdom

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

Keywords: A novel one-pot solvothermal route was employed to construct O and S co-doped graphitic carbon nitride
O and S co-doped graphitic carbon nitride quantum dots (OSCNQDs) hybridized with Bi2MoO6 (BMO) photocatalyst and utilized to catalyse aqueous
quantum dots phenol from simulated wastewater under extended visible light exposure. The photodegradation analysis de-
Bi2MoO6Z-scheme nanohybrid picted that the (OSCNQDs/BMO) nanohybrid exhibited incremented photocatalysis of phenol (98 %) under
Extended visible light absorption
visible light illumination which is due to the effective coupling and formation of Z-scheme heterostructure which
Phenol degradation
rendered superior space isolation and retained high redox abilities. The OSCNQDs might contribute to the ex-
tended absorption of visible light as well as increased adsorption of phenol on the surface of photocatalyst. As a
result, the nanohybrid displayed prominent absorption in visible region, improved space charge isolation and
superior photoactivity which can be utilized as an effective approach for the photo-assisted degradation of
organic pollutants.

1. Introduction the treatment of simulated wastewater [12–15]. Thus, it is highly de-

The current scenario involving the discharge of untreated phenolic
compounds from various industrial effluents requires serious attention
because of their carcinogenic nature, toxicity, inertness and endocrine
disrupting abilities [1–3]. Presence of phenol and its derivatives in
water at a very less concentration range of 1 mg L−1 is harmful for the
public health as well as for aquatic bodies [4]. As per reports, the En-
vironmental Protection Agency of US and the Canadian National Pol-
lutant Release Inventory has declared phenol as a primary pollutant
[5]. Moreover, stringent discharge limits for phenols (< 1 ppb) have
been set to avoid serious consequences [6,7]. Off note, various research
reports have mentioned that due to the highly recalcitrant and persis-
tent nature of phenolic compounds, they are difficult to remove through
conventional techniques [8,9]. For the effectual removal of such
harmful contaminants from water, advanced oxidation processes have
been considered as a vital strategy [10,11]. Specifically, visibly driven
photocatalysis has been widely opted advanced oxidation process for
sirable to design efficient semiconductor photocatalysts with superior
features of visible light harnessing and optimal redox abilities.
Recently, up-converted quantum dots (QDs) material with size
below 10 nm has become an intensively perused topic in photocatalysis
owing to their unique features like bright luminescence, low or negli-
gible toxicity, and excellent biocompatibility [16–19]. It was observed
that the robust quantum confinement and edge effects induced by
lowering the particle size to less than 10 nm endows excellent optical
properties, which is significantly useful in photocatalysis [20]. Con-
sidering that, significant efforts have been made to synthesise promi-
nent metal-free graphitic carbon nitride quantum dots (CNQDs) which
can convert near infra-red (NIR) light to visible region. As a result, the
harnessing of solar light can be significantly boosted due to the ex-
ploitation of NIR region. For instance, when CNQDs are coupled with a
visible-light active photocatalyst, the CNQDs after absorption of NIR
light will emit visible light having high energy and shorter wavelength
which can be utilized by the nanohybrid for photocatalytic activity.

⁎
Corresponding author at: School of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan HP, 173229, India.
E-mail address: pankajchem1@gmail.com (P. Raizada).

https://doi.org/10.1016/j.jphotochem.2020.112588
Received 15 February 2020; Received in revised form 20 April 2020; Accepted 21 April 2020
Available online 04 May 2020
1010-6030/ © 2020 Elsevier B.V. All rights reserved.
A. Kumar, et al.
Interestingly, 0D CNQDs possess significantly more active catalytic sites
due to the presence of graphitic as well as pyridinic N and edge amine
groups which boosts the photoactivity of CNQDs [21]. Liu et al. syn-
thesised fluorescent CNQDs via recrystallization and ultrasonic ex-
foliation of dicyandiamide and evaluated its potential for the detection
of trace copper (II) [22]. Tang et al. utilized one-step microwave as-
sisted route for the synthesis of highly fluorescent CNQDs by using
EDTA and guanidine hydrochloride as starting materials [23]. The as-
fabricated CNQDs system was utilized to detect free residual chlorine
with a disclosure limit of 0.01 μM. Although, CNQDs exhibit good
photocatalytic activity yet quantum confinement hinders the visible
light absorption due to apparently smaller size of QDs and higher
HOMO-LUMO (H–L) gap. Moreover, with a significant lowering in the
size of QDs, the H–L gap decreases optimally which causes absorption
of light higher than the visible region (400−700 nm) [24,25]. In order
to overcome this hurdle and to tune the wide band gap of CNQDs,
controlled introduction of the foreign non-metal dopant is an effective
strategy [26]. Precisely, doping CNQDs with n-type dopants like S, O
and P atoms, is more favourable due to their somewhat similar atomic
radii which don’t disturb the doped network structure [25]. Moreover,
introduction of n-dopants induce optimal midgap states in the energy
spectrum which substantially tune the band structure. Of note, it was
observed that due to significant electronegativity difference, S and P
atoms replace graphitic or pyridinic C and N atoms, respectively [27].
For instance, Wu et al. modified the band gap of CNQDs by P-doping
through simple hydrothermal route [28]. The involvement of P atoms
in the network structure of CNQDs resulted in significant lowering of
band gap energy by p electrons. Chun Lu et al. fabricated O and S co-
doped CNQDs (OSCNQDs) by treating thiourea and citric acid thermally
[29]. The as-fabricated OSCNQDs sample displayed significant blue
photoluminescence (PL) which is utilized to detect Hg (II) ions
(0.001–20.0 μM) with a detection limit of 0.37 nM.
Among diverse bismuth-based semiconductor photocatalysts,
Bi2MoO6 (BMO) is prominently attractive photocatalytic material due
to its captivating physicochemical features, suitable bandgap (2.5
eV – 2.8 eV), cost effectiveness and significant resistance to photo-
corriosion [30,31]. Typically, BMO is an Aurivillius oxide consisting
[Bi2O2]2+ layers sandwiched between the uniform slabs of MoO42−,
making it a fascinating 2D layered semiconductor material for efficient
harnessing of solar light [32]. However, some inherent drawbacks of
BMO like; poor isolation of photocarriers, less quantum yield, sub-
stantially less surface sites and poor response towards desired reaction
limits its practical applicability. Hybridizing BMO with metal-free
CNQDs to form a heterologous system is found to be an excellent
technique to overcome the aforementioned bottlenecks associated with
it. For instance, Chen et al. reported the effectual hybridization of BMO
and CNQDs through in situ coupling and observed the excellent pho-
tocurrent intensity of the system [33]. The as-designed system dis-
played remarkable performance in the detection of Cu (II) ions due to
effective isolation of charge carriers. Lin et al. reported in situ route for
effective decoration of CNQDs and Ag NPs on BMO surface and utilized
its potential for the 100 % RhB discolouration under visible light ex-
posure [34]. The up-conversion behaviour of CNQDs expended the
absorption in visible range as well as improved the space isolation of
photocarriers. Thus, hybridizing these two fascinating materials seem
as an appropriate technique to achieve the amended photocatalytic
efficacy. Moreover, construction of coupled heterostructures with su-
perior migration and space isolation of photocarriers through Z-scheme
mode is considered as a fascinating approach to increment the overall
photo-efficacy [10]. Typically, in Z-scheme photocatalytic systems, the
two semiconductor materials are either in direct contact with each
other or they are connected by an electron mediator (shuttle redox
mediator and solid-state mediators) which foster the migration of
electrons. The former system known as direct Z-scheme with tightly
coupled semiconductors avoiding any electron mediator is in limelight
because of its superior ability in transportation of electrons from one
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Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
semiconductor system to another. Also, due to intact interface junction,
the built-in electric field boost the recombination of CB electrons of one
semiconductor with the VB holes of another. As a consequence, spa-
tially separated charge carriers with superior redox abilities are ob-
tained for improved photocatalytic abilities [10,12,14].
Herein, we report the efficacious decoration of O and S co-doped
CNQDs (OSCNQDs) onto the surface of BMO via a facile one-pot sol-
vothermal route. The resulted intact junction between OSCNQDs and
BMO displayed extended visible light absorption and incremented
photoactivity for the photodegradation of phenol. The improved photo-
efficiency of the photocatalyst was due to the effectual isolation of
photocarriers through the formation of Z-scheme heterostructure. The
Z-scheme OSCNQDs/BMO nanohybrid not just fostered the migration of
photocarriers but also rendered superior redox potential ability to the
system. To the best of our knowledge, there is no study which depicted
the coupling of OSCNQDs with BMO in Z-scheme mode for the photo-
degradation of phenol. Besides, the photodegradation pathway through
the formation of active species by the composite photocatalyst remains
far from clear. The experimental analysis inferred that the as-designed
OSCNQDs/BMO Z-scheme photocatalyst displayed superior photo-
activity for the degradation of phenol. Additionally, the plausible
photocatalysis mechanism of OSCNQDs/BMO under the exposure of
visible light is also discussed in detail.
2. Experimental
2.1. Chemicals
All the reagents and chemicals were of analytical grade and em-
ployed further as received without any further purification. Typically,
thiourea (SC(NH2)2), citric acid (C6H8O7), bismuth nitrate penta-hy-
drated (Bi(NO3)2.5H2O), ammonium molybdate ((NH4)6Mo7O24.4H2O)
and nitric acid (HNO3) are the chemicals used in the experiment.
Double distilled water was used throughout this study.
2.2. Preparation of OSCNQDs
The OSCNQDs was synthesised by a facile microwave assisted route
[35]. Briefly, 0.5 g of citric acid and 0.5 g of thiourea were taken as
precursors for the typical synthesis of OSCNQDs. The precursors were
mixed thoroughly in 25 mL of distilled water under stirring for 30 min.
After constant stirring, the mixture was subjected to the domestic oven
(700 W) treatment for 5−7 min until the dark brown coloured solution
was obtained which demonstrated the carbonization of the reactants.
The mixture was allowed to cool naturally at room temperature. Fur-
thermore, the mixture was re-purified with 25 mL distilled water and
centrifuged at 10,000 rpm for 5 min. The as-obtained particles were
filtered through 0.45 μm membrane filter before employing further.
2.3. Preparation of OSCNQDs/BMO composite
Typical synthesis of OSCNQDs/BMO composite was inspired from
the previously reported one-pot solvothermal route [34,36]. Firstly,
0.24 g of Bi(NO3)2.5H2O and 0.06 g of (NH4)6Mo7O24 was dissolved
respectively into 5 mL ethanol glycol (EG) solution. The two solutions
were mixed under vigorous stirring followed by further addition of
10 mL EG into the mixture which was subjected to 30 min of stirring.
After that, the as-fabricated OSCNQDs (2 wt%) were added into the
mixture and sonicated until a homogeneous suspension was attained. In
the last step, the suspension was autoclaved (25 mL Teflon-lined) at
160 °C for 24 h. The autoclaved sample was placed without disturbing
until it cooled down to room temperature. The as-obtained samples
were re-purified with distilled water and ethanol, dried in hot air oven
at 60 °C.
A. Kumar, et al. Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588

2.4. Characterization of photocatalysts

The surface morphology, crystal structure and fundamental com-

ponents were scrutinized by scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) analysis. The SEM micro-
graphs were attained through Nava Nano SEM-45 system while TEM
analysis were carried out using FP/5022-Technai G2 20 S-TWIN (USA)
model operated at 200 kV accelerating voltage. The X-ray diffraction
(XRD) study was carried out through Panalytical’s X’Pert
Prodiffractrometer operated at 45 kV/100 mA and FTIR study was in-
spected by using Perkin-Elmer Spectrometer by employing KBr pellet.
The X-ray photoelectron spectroscopy (XPS) analysis was performed on
PHI Vers Probe II with AES by applying Al Kα radiations (24.63 W). The
BET surface area of AV/PSGCN was analysed using nitrogen adsorption-
desorption isotherms on Coulter SA3100 instrument. The photo-
luminescence (PL) studies of the samples were investigated through
F4500 (Hitachi, Japan) photoluminescence detector having 325 nm
excitation wavelength. The UV–vis diffuse reflectance spectroscopy
(DRS) were analysed through UV–vis spectrophotometer (UV-2550).

2.5. Analysis of the photocatalytic activity of OSCNQDs/BMO

nanocomposite

The photoactivity of the OSCNQDs/BMO nanocomposite was as-

sessed for the photodegradation of phenol. The photocatalytic experi- Fig. 1. XRD patterns of CN, OSCNQDs, BMO and OSCNQDs/BMO samples.
ment was performed in a photo-reactor comprising double walled pyrex
container lamp with height 7.5 cm and diameter 6 cm having 300 W Xe
lamp as a visible-light source. To filter UV light, a 420 nm cut-off filter
was employed between the sample and the lamp. Before visible light
exposure, the phenol sample containing photocatalyst was subjected to
magnetic agitation for the establishment of adsorption/desorption
equilibrium. To further analyse the photoactivity, 2 mL of the suspen-
sion was sampled and removed the photocatalyst for subsequent spec-
trophotometric analysis at 270 nm. The degradation efficiency was es-
timated using the formula:

Degradation (%) = (C0-C)/C0 × 100 (1)

Where C0 represents initial concentration of phenol in solution and C

depicts residual concentration of phenol at a given illuminated time.

3. Results and discussions

3.1. Structure and morphology analysis

In order to discern the crystal structure and an insight into the

formation of heterostructure, XRD patterns were examined and pre-
sented in Fig. 1. It is clearly evident that pristine CN displayed two
characteristic peaks at 27.40° and 13.0°, indexed to (002) and (100)
planes, respectively. The diffraction peak at 27.40° signified the inter- Fig. 2. FT-IR spectra of the synthesised samples.
planer graphitic stacking and packed motif of aromatic units corre-
sponded to 0.33 D-spacing. These two peaks in the XRD pattern of pure
812 cm−1 corresponded to breathing modes of triazine units in hapta-
CN fits well with the previously reported literature [37]. In case of
zine rings indicating the formation of CN [39]. The strong absorption
OSCNQDs, the broad peak at 27.40° reflected the presence of graphite
bands that emerged at 1200−1500 cm-1 were credited to either C]N
like stacking in the as-fabricated QDs which was indexed to (002) plane
or CeN stretching vibration modes [40]. The smaller peaks at
[38]. In the diffraction pattern of BMO, diffraction peaks at 10.93,
3370 cm−1 and 3460 cm−1 corresponded to OeH vibration modes and
23.52, 27.40, 32.50, 47.20 and 55.50° corresponded to (020), (111),
NeH stretching modes, respectively [41]. For OSCNQDs the peaks
(131), (002), (062) and (133) planes, respectively. This indicated the
emanated at 3350 and 3195 cm−1 attributed to the NeH/O-H
formation of pure orthorhombic BMO. For the OSCNQDs/BMO nano-
stretching modes, indicating the significant hydrophilic features of
hybrid, the diffraction spectra displayed all the characteristic peaks of
OSCNQDs [42]. Moreover, the peak at 2054 cm−1 was attributed to the
BMO, specifying that the solvothermal method did not affect the
stretching vibrations of SeH group. The peaks at 1704 and 1409 re-
structural motifs of BMO. Moreover, the (002) peak of CN as well as of
presented the vibrational absorption of C]O and COO group in COOH.
OSCNQDs intersects with the (131) peak of BMO.
Also, the peak of 1180 cm−1 credited to C]S vibration modes sug-
To further elucidate the characteristic structure and chemical
gesting the successful doping of O and S in CNQDs. The FTIR of pure
bonding, FTIR analysis of bare CN, OSCNQDs, BMO and OSCNQDs/
BMO displayed a broad band at 3236 cm−1 which was assigned to OeH
BMO nanohybrid is depicted in Fig. 2. For pristine CN, a keen peak at

3
A. Kumar, et al.
Fig. 3. XPS spectra confirming the existence of S, O, C, N, Bi and Mo in OSCNQDs/BMO nanocomposite.
vibrations. The bands emerged in the 700−850 cm−1 region ascribed
to Mo-O stretching vibrations in BMO [8]. For OSCNQDs/BMO nano-
composite, the typical band around 820 cm−1 was ascribed to the
aromatic haptazine unit, the band at 1423 cm−1 corresponded to the
characteristic stretching modes in CN heterocycles [43,44]. The broad
bands at 3060 and 3182 cm−1 were credited to either NeH or OeH
stretching vibrations of carboxylate anions, suggesting the bonds be-
tween hydroxyl groups and carboxylate groups on the surface of
OSCNQDs.
The elemental and chemical composition of the synthesised nano-
composite was assessed by XPS analysis. The results confirmed the
existence of S, O, C, N, Bi and Mo elements in OSCNQDs/BMO nano-
composite. Fig. 3a shows XPS spectrum of S 2p and two peaks were
recorded at 161.58 eV and 168.19 eV binding energies. The peak at-
tained at 161.58 eV is recognized with eSH and another peak at
168.19 eV is related to -C-SO3- which indicated partial doping of S
elements into CNQDs [45]. XPS spectrum of O 1s is shown in Fig. 3b,
possessing a characteristic peak at 532.37 eV originated from C]O
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Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
bands and confirmed oxygen doping [46]. XPS spectrum of C 1s is
presented in Fig. 3c and exhibited two distinctive peaks at 284.51 eV
and 288.13 eV binding energies which resembled to sp2 C]C bonds and
sp2-bonded carbon (NeC]N), respectively [47]. N 1s XPS spectrum is
revealed in Fig. 3d in which specific peak at binding energy 398.09 eV
was credited to pyridinic N [48]. XPS spectrum of Bi 4f exposed two
sharp peaks at 158.67 eV and 164.53 eV Fig. 3e, which were ascribed to
Bi 4f7/2 and Bi 4f5/2 binding energies, respectively and were allocated
to Bi4+ or Bi5+ [49]. In Fig. 3f, XPS spectrum of Mo 3d peak exhibited
two distinctive peaks at 232.73 eV and 235.45 eV which were accre-
dited to Mo 3d5/2 and Mo 3d3/2 of MoO42−, respectively [50].
In order to scrutinize the microstructure of as synthesised
OSCNQDs/BMO nanohybrid SEM and TEM analysis were performed
and represented in Fig. 4. The SEM morphology of OSCNQDs and
OSCNQDs/BMO nanohybrid is shown in Fig. 4a and b, respectively
suggested the uniform decoration of OSCNQDs onto the surface of BMO
sample. To further investigate the formation of OSCNQDs and suc-
cessful coupling of OSCNQDs with BMO, HRTEM analysis was
A. Kumar, et al.
Fig. 4. SEM images of (a) OSCNQDs and (b) OSCNQDs/BMO nanocomposite. HRTEM images of (c) OSCNQDs (inset image showing formation of OSCNQDs) (d)
OSCNQDs/BMO nanohybrid. (e) SAED pattern representing different planes and (f) Lattice fringes present in OSCNQDs/BMO nanocomposite.
examined. From Fig. 4c, the spherical shape of OSCNQDs is clearly
visible [35,51]. In case of OSCNQDs/BMO nanohybrid the BMO sur-
rounded by OSCNQDs can be clearly seen. Many uneven particles of
OSCNQDs aggregate at the surface of BMO can be observed clearly in
Fig. 3d suggesting the formation of intact junction. Furthermore, the
SAED patterns as shown in Fig. 4e, suggested the semi-crystallinity of
OSCNQDs/BMO nanocomposite. The well-defined lattice fringes were
distinctly observed indicating the inter-fringe distance (d) of 0.33 nm
for OSCNQDs corresponded to (002) plane. While for BMO the D-spa-
cing was found to be 0.32 and 0.19 nm indexed to (131) and (062)
planes, respectively which is similar to the previously reported data
[35,52]. Fig. 5a–g depicts the existence of C, N, O, S, Bi and Mo in the
OSCNQDs/BMO nanohybrid which is in accordance with XPS analysis.
3.2. Optical properties
The optical properties of the OSCNQDs, BMO and binary OSCNQDs/
BMO nanohybrid were analysed with UV–vis diffuse reflectance spec-
troscopy (DRS) as depicted in Fig.6a. The optical absorption edge of
pure OSCNQDs and BMO was observed at less than 450 nm and 485 nm,
respectively. Intuitively, the heterologous hybrid of OSCNQDs/BMO
showed substantial red-shift towards the longer wavelength. This sug-
gested the photo-absorption ability from UV-light to visible region
5
Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
corresponded to typical absorption patterns of photocatalyst, i.e. the
nanohybrid could exploit longer wavelength visible light. The band-gap
energy of the samples was estimated through Tauc’s plots utilizing the
formula given as below [53]:
αhv = A (hv − Eg ) n/2 (2)
where α is absorption coefficient, hv is energy of photon, A is constant,
Eg represents the absorption bandgap energy and index (n) destined
direct and indirect values based on the absorption process. In light of
this, the bandgap energy of the samples was calculated from the in-
flection point between the tangent at the point of inflection on (αhv)2
and the horizontal line (hv). As shown in Fig. 6b, the bandgap energies
of OSCNQDs and BMO were assessed to be 2.65 eV and 2.48 eV, re-
spectively which were close to the known values in previous literature
[54,33].
Photoluminescence (PL) emission spectra resulting from the re-
assembly of photocarriers are useful to exploit the transfer, migration
and separation of photoinduced carriers. Fig. 6c illustrated the PL
spectra of OSCNQDs, BMO and OSCNQDS/BMO samples. The lumi-
nescence intensity of nanohybrid was lowest indicating the effectual
space isolation and reduced recombination of photocarriers.
A. Kumar, et al. Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588

Fig. 5. Corresponding elemental mapping of OSCNQDs/BMO nanocomposite.

3.3. BET surface area analysis
To analyse the textual properties, mesoporosity and pore volume of
OSCNQDs/BMO photocatalyst, N2 adsorption-desorption isotherm was
utilized (Fig. S1). The plot obtained from BET isotherm suggested that
the samples displayed a classical type-IV isotherm and confirmed the
mesoporous surface of the photocatalysts [54]. Moreover, the calcu-
lated specific surface area and pore volume of OSCNQDs/BMO nano-
hybrid were found to be 61.107 m2 g−1 and 0.1852 cm3 g−1, respec-
tively (Table S1). The incremented specific surface area (SBET) of
OSCNQDs/BMO nanocomposite can provide sufficient active sites
which facilitated the adsorption of phenol molecules on the surface of

6
A. Kumar, et al.
Fig. 6. (a) UV–vis spectrum of OSCNQDs, BMO and OSCNQDs/BMO nanohybrid. (b) Tauc’s plot of OSCNQDs and BMO for bandgap analysis. (c) PL spectra of
OSCNQDs, BMO and OSCNQDs/BMO nanocomposite.
nanocomposite and boosted the photodegradation efficiency sig-
nificantly.
3.4. Photocatalytic activity
3.4.1. Photocatalytic performance of OSCNQDs/BMO nanocomposite
To evaluate the photoactivity of as-designed photocatalysts, phenol
was selected as the target pollutant which was treated under visible
light illumination. The photocatalytic performance of different photo-
catalysts under visible light illumination as well as in dark is depicted in
Fig. 7a and c. From Fig. 7a it can be clearly seen that the OSCNQDs/
BMO nanohybrid displayed maximum phenol removal efficiency of 98
% after 120 min of visible light exposure. However, the results depicted
no apparent removal of phenol in the presence of light only without any
photocatalyst. The phenol removal efficacy over pristine samples of CN,
OSCNQDs, and BMO was found to be 60 %, 65 % and 70 %, respectively
under 120 min of irradiation time. The incremented photoactivity of
OSCNQDs/BMO nanohybrid was due to the effectual spatial isolation of
photocarriers as a result of Z-scheme charge migration mode, which is
consistent with PL analysis. Through Langmuir Hinshelwood model the
photodegradation kinetics of phenol was explicated and the photo-
catalytic analysis was carried out using Eq. 3 and 4;
C
− ln ⎛ t ⎞ = kt
⎜ ⎟
⎝ C0 ⎠ (3)
C0
= kt
Ct (4)
where C0 and Ct depicts the concentration of phenol at illumination
time t = 0 and at time t, respectively. k (min−1) represents the ap-
parent rate constant for phenol mineralization [55]. Moreover, from
previously reported literature, it was evident that the value of regres-
sion coefficient (R2) greater than 0.95 suggested the reaction kinetics to
follow pseudo first order [56]. Therefore, Fig. 7b confirms that the
photodegradation reaction of phenol through as-designed samples fol-
lowed pseudo first order kinetics and Kapp for OSCNQDs/BMO, CN,
OSCNQDs and BMO was calculated to be 6.8 × 10-4 s−1, 5.3 × 10-4
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Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
s−1, 5 × 10-4 s−1 and 4 × 10-4 s−1, respectively. Fig. 7c depicts neg-
ligible photocatalytic removal efficiency of the samples in dark condi-
tions suggesting the importance of visible light to boost degradation
reactions. Furthermore, to evaluate the extent of mineralization, COD
was estimated during photodegradation phenomenon. The results dis-
played 100 % of COD removal efficiency utilizing OSCNQDs/BMO na-
nocomposite under 100 min of visible light exposure. The apparent
improvement in photocatalytic properties could be creditable to the
synergic effect between OSCNQDs and BMO. Precisely, the effective
decoration of OSCNQDs over BMO not just extended the absorption in
visible region but also boosted the adsorption ability, enabling more
adsorption sites for phenol and then accelerating the degradation re-
actions. Moreover, the intact surface junction and appropriate band
alignments of OSCNQDs and BMO facilitated the formation of Z-scheme
mode which stimulated the transport of photocarriers by avoiding their
reassembly.
3.4.2. Evaluation of phenol degradation under different reaction parameters
In order to further evaluate the photoactivity of Z-scheme
OSCNQDs/BMO nanohybrid, phenol degradation phenomenon was
performed under different reaction conditions involving catalyst
loading, effect of H2O2 concentration and pH change as shown in
Fig. 8a–d. During degradation process, the amount of OSCNQDs/BMO
photocatalyst was varied from 30 mg/50 mL to 80 mg/50 mL to check
the effect of photocatalyst dose on phenol degradation (Fig. 8a). It was
observed that the with increase in catalytic dose from 30 mg/50 mL to
50 mg/ 50 mL the value of rate constant increased from 4.2 × 10−4 s-1
to 6.8 × 10−4 s-1. However, by further incrementing the photocatalyst
dose, rate constant decreased significantly suggesting 50 mg/50 mL as
optimal catalytic amount. Thus, optimal amount of photocatalyst is
necessary for effective absorption of light photons as well as to carry
photodegradation process avoiding agglomeration [57]. Similarly, the
degradation process was carried by varying the concentration of H2O2
as depicted in Fig. 8b. The results displayed maximum rate constant of
8.5 × 10−4 s-1 at an optimum H2O2 concentration of 7 × 10−4 mol dm-
3
. The variation in pH plays a significant role in photodegradation
phenomenon of organic pollutants [58]. Generally, the effect of primary
A. Kumar, et al.
Fig. 7. (a) Photocatalytic removal of phenol by different photocatalysts in the presence of light only. (b) Bar graph showing kinetics of phenol degradation. (c)
Photodegradation of phenol by different photocatalysts in dark only. (d) COD removal efficiency during phenol mineralization. Reaction conditions: Initial reaction
pH = 4.0, [Phenol] = 1.0 × 10−4 mol dm-3, [Photocatalyst] =50 mg/100 mL, Reaction time =120 min, Intensity of light =0.750 lx.
pH value of the reaction mixture depends upon the type of target pol-
lutant and the zero point charge (zpc) of the semiconductor material
used in photodegradation process [59]. Moreover, the pH of reaction
mixture significantly affects the surface adsorption ability of the pho-
tocatalyst through electrostatic interaction between the nanohybrid
surface and organic pollutant. Keeping that in mind, the phenol de-
gradation process was performed under varying pH conditions and the
reaction kinetics was observed as shown in Fig. 8c. It can be seen clearly
in Fig. 8c that rate constant decreases significantly at pH values higher
than 7. The best photodegradation kinetics was observed at neutral pH
value as shown in Fig. 8d. The pKa value for phenol was found to be 9.9
and above this peculiar value, phenol releases H+ ions and become
negatively charged [60]. Thus, higher pH hindered the adsorption of
phenol on the active surface sites of photocatalyst and neutral pH was
found to be the optimal condition for maximum adsorption of phenol.
3.4.3. Analysis of possible photocatalytic mechanism
Generally, it is widely considered that the photodegradation phe-
nomenon is induced by photo-illuminated charge carriers. Therefore, it
was meaningful to ascertain the leading reactive radical species gen-
erated in the process of exploring the photodegradation mechanism
[37,61]. Keeping that in mind, various radical capturing tests were
executed to assess the effect of these reactive species on photocatalytic
process as shown in Fig. 9a-c. The experiments were employed by using
benzoquinone (BZQ), isopropyl alcohol (IPA), AgNO3 and KI as %O2−, %
OH, e−, and h+ scavengers, respectively [62]. It was observed that the
8
Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
phenol degradation efficacy was reduced significantly from 65 % to 13
%, 62 %, 61 % and 15 % by adding BZQ, IPA, AgNO3 and KI, respec-
tively for OSCNQDs. The bare BMO sample displayed significantly de-
creased removal efficiency by the addition of IPA suggesting %OH ra-
dicals as leading radical species (Fig. 9b). However, in case of
OSCNQDs/BMO photocatalyst, the addition of BZQ and AgNO3 re-
markably lowered the photodegradation rate from 98 % to 13 % and 15
%, respectively (Fig. 9c) this indicated %O2− and e- as leading reactive
species in the photodegradation of phenol. Thus, the intact junction
formed between OSCNQDs and BMO in OSCNQDs/BMO nanocomposite
boosted the photocatalytic removal of phenol by generating %O2- and e-
as reactive species. This can further be attributed to the superior iso-
lation of photocarriers in OSCNQDs/BMO nanocomposite through Z-
scheme mode. To further evaluate the effectiveness of charge isolation
by hybridizing OSCNQDs with BMO, electrochemical impedance spec-
troscopy (EIS) analysis was performed (Fig. 9d). It is evident from the
Fig. 9d that the EIS Nyquist arc radius plot for OSCNQDs/BMO nano-
hybrid is smaller than that of pristine OSCNQDs and BMO samples. The
smaller EIS arc represented a lesser photocarriers migration resistance
of the photocatalyst. Therefore, in OSCNQDs/BMO nanohybrid, the
photocarriers were effectively isolated and migrated to the surface of
photocatalyst via Z-scheme mode, which was due to the effectual
coupling and interfacial connectivity between OSCNQDs and BMO
[37].
Based on aforementioned experimental analysis, the plausible me-
chanism for the photodegradation of phenols by OSCNQDs/BMO
A. Kumar, et al.
Fig. 8. Reaction kinetics for phenol degradation over different reaction parameters involving: (a) catalytic dosage, (b) Concentration of H2O2 and (c) pH. (d) Optimal
pH conditions for photodegradation of phenol. Reaction conditions: Initial reaction pH = 4.0, [Phenol] = 1.0 × 10−4 mol dm-3, [Photocatalyst] =50 mg/100 mL,
Reaction time =120 min, Intensity of light =0.750 lx.
nanohybrid is presented in Fig. 10. Through intact coupling and com-
plimentary band edge positioning of OSCNQDs and BMO, the Z-scheme
heterostructure was formed which could generate photocarriers after
visible light exposure. The mechanism of incremented photoactivity of
the nanohybrid can be further exploited by the band edge positioning of
the semiconductor photocatalysts. The VB and CB positions of the as-
designed photocatalysts were estimated through the following equa-
tions [52,63];
EVB = X − E e + 0.5Eg
ECB = EVB − Eg
where X represents Mulliken’s electronegativity, Ee depicts the energy
of free electrons (on hydrogen scale) and Eg is the bandgap energy. As a
result, the VB and CB edge potentials of OSCNQDs were found to be
1.53 V (vs. SHE) and -1.12 V (vs. SHE), respectively. And for BMO, the
VB and CB edge positions were estimated at 2.29 V (vs. SHE) and
-0.19 V (vs. SHE), respectively. The semiconductor photocatalyst pos-
sessed suitable redox potential to generate photo-illuminated carriers
which then participate in further reactions. Moreover, the incorpora-
tion of co-doped QDs with BMO extended the absorption of light in
visible region which fostered the reaction kinetics. Under visible light
illumination the photo-induced excitons could be effectively isolated
through Z-scheme mode under the influence of induced field due to the
synergistic coupling of OSCNQDs and BMO. As a consequence, the CB
electrons present in BMO reassemble with the VB holes in OSCNQDs
Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
forming a Z-scheme, which incremented the availability of photo-illu-
minated electrons in the CB of OSCNQDs. Thus, the bulk presence of CB
electrons in OSCNQDs boosted the formation of %O2− radicals after
reacting with dissolved O2 due to its more negative reduction potential
than O2/%O2− (-0.33 V vs. SHE). Consequently, the photo-illuminated
CB electrons in OSCNQDs and %O2− radicals participated in the pho-
tocatalysis of phenol. Whilst, the VB holes present in BMO lacks to
oxidize H2O or OH− into %OH radicals due to their insufficient oxida-
tion potential than OH−/%OH (2.40 V vs. SHE). Therefore, they can
(5) directly participate in the photodegradation reaction of phenol. This
result inferred that the superior CB potential of the OSCNQDs was
(6) maintained and the reassembly of the photocarriers was significantly
decreased which facilitated the photocatalysis of phenol. Obviously, the
typical double charge migration mechanism could not explain the su-
perior reduction potential and maintained VB potential in OSCNQDs/
BMO nanohybrid. Thus, the migration of photo-illuminated carriers
could be better explained through Z-scheme charge transfer mode. It
follows that the approach to design a system which follows Z-scheme
charge migration pathway through the coupling of OSCNQDs and BMO
for the degradation of phenol is positive and promising.
3.4.4. Photocatalytic stability and recyclability
Keeping in mind the viewpoint of wide scale applicability, it be-
comes necessary to assess the stability of OSCNQDs/BMO nanohybrid.
It is a known fact that during photocatalytic process, BMO might be
changed into Bi2O2CO3 after the exposure visible of light [37,64]. To
9
A. Kumar, et al. Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588

Fig. 9. Effect of radical scavengers on Phenol degradation by using (a) OSCNQDs, (b) BMO and (c) OSCNQDs/BMO photocatalysts. (d) Electrochemical impedance
spectroscopy (EIS) analysis for OSCNQDs, BMO and OSCNQDs/BMO samples. Reaction conditions: Initial reaction pH = 4.0, [Phenol] = 1.0 × 10−4 mol dm-3,
[Photocatalyst] =50 mg/100 mL, Reaction time =120 min, Intensity of light =0.750 lx.

Fig. 10. Mechanistic insight depicting the migration of photocarriers through Z-scheme mode and photodegradation of phenol.

ascertain this phenomenon, XRD and FTIR analysis of the nano-
composite before and after catalytic usage were acquired. As can be
seen from Fig. 11b and C, there is no apparent change in the FTIR and
XRD patterns of OSCNQDs/BMO sample, respectively indicating the
stability of the sample. The stability of the sample was also evaluated by
repeating the photodegradation processes five times as depicted in
Fig. 11a. The experimental analyses indicated that OSCNQDs/BMO
nanohybrid had superior activity and photo-stability for phenol de-
gradation. After five run cycles, the sample did not display any sig-
nificant variation in activity. In present work, the OSCNQDs/BMO

10
A. Kumar, et al.
Fig. 11. Recycle efficiency of OSCNQDs/BMO nanohybrid. (b) FTIR and (c) XRD analysis of nanocomposite after 5 catalytic cycles. Reaction conditions: Initial
reaction pH = 4.0, [Phenol] = 1.0 × 10−4 mol dm-3, [Photocatalyst] =50 mg/100 mL, Reaction time =120 min, Intensity of light =0.750 lx.
nanohybrid could be easily re-collected from the reaction solution
through centrifugation, which was favourable for its reusability.
4. Conclusion
In conclusion, a novel Z-scheme OSCNQDs/BMO nanohybrid was
designed through a facilely accessible route. The experimental evalua-
tions confirmed that the as-designed nanocomposite exhibited im-
proved photocatalytic activity for the removal of phenol. The intact
junction between OSCNQDs and BMO not just boosted the migration of
photocarriers but also rendered efficient space isolation of photo-
carriers. The matched band alignments helped to construct the Z-
scheme system and incorporation of OSCNQDs improved the adsorption
ability as well as incremented the absorption of wide spectrum light.
Consequently, the resulted Z-scheme nanohybrid displayed improved
photo-efficiency by maintaining the superior redox abilities of the
system.
CRediT authorship contribution statement
Abhinandan Kumar: Writing - original draft, Writing - review &
editing. Pankaj Raizada: Conceptualization, Investigation,
Supervision. Pardeep Singh: Conceptualization, Investigation, Writing
- review & editing. Ahmad Hosseini-Bandegharaei: Data curation,
Writing - review & editing. Vijay Kumar Thakur: Data curation,
Writing - review & editing.
Declaration of Competing Interest
The authors do not have any conflict of interest.
11
Journal of Photochemistry & Photobiology A: Chemistry 397 (2020) 112588
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.2020.
112588.
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