Journal of Colloid and Interface Science 566 (2020) 211–223

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Journal of Colloid and Interface Science

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

Resurrection of boron nitride in p-n type-II boron nitride/B-doped-g-C3N4

nanocomposite during solid-state Z-scheme charge transfer path
for the degradation of tetracycline hydrochloride
Lopamudra Acharya, Susanginee Nayak, Sambhu Prasad Pattnaik, Rashmi Acharya ⇑, Kulamani Parida ⇑
Centre for Nano Science and Nano Technology, Siksha ‘O’ Anusandhan Deemed to be University, Bhubaneswar 751030, Odisha, India

g r a p h i c a l a b s t r a c t
The current study involves BN modified BCN nanocomposite for the effective photocatalytic degradation of TCH under solar light irradiation. This inves-
tigation emphasises on type-II p-n heterojunction with solid-state Z-scheme charge transfer pathway for the enhanced photocatalytic performance of BN/
BCN heterostructure towards TCH degradation.

a r t i c l e i n f o a b s t r a c t

Article history: Antibiotic contaminants have received much attention due to the increasing serious environmental con-
Received 4 December 2019 cerns. In this work, for the first time, we have fabricated a series of significant type-II p-n heterostructure
Revised 13 January 2020 with Z-scheme charge transfer between p-type B-doped g-C3N4 with different proportion of n-type BN
Accepted 19 January 2020
through a simple in-situ growth process. PXRD, FTIR, UV–Vis, FESEM, HRTEM and EIS analysis were
Available online 24 January 2020
applied for the detailed characterization of the as-prepared composites to study the crystal phase, struc-
tural features, optical and electrical properties. The photocatalytic behaviour of BN/BCN photocatalyst
Keywords:
was investigated by the degradation of tetracycline hydrochloride under solar light illumination.
B-doped-g-C3N4
Nanocomposite
Experimental results revealed that about 88.1% of TCH was degraded by the BN/BCN composite contain-
Z-scheme ing 4 wt% BN in the BN/BCN matrix, in 60 min of solar light irradiation. Reduction in recombination rate of
Tetracycline hydrochloride photo generated electron-hole pair’s and enhanced visible light absorption ability is credited to the
p-n heterostructure enhanced photocatalytic performance of BN/BCN composite. Trapping experiment for the scavenging
agents has confirmed that superoxide (O2) and hydroxyl (OH) radicals are the main reactive species

⇑ Corresponding authors.
E-mail addresses: rashmiacharya@soa.ac.in (R. Acharya), kulamaniparida@soauniversity.ac.in (K. Parida).

https://doi.org/10.1016/j.jcis.2020.01.074
0021-9797/Ó 2020 Elsevier Inc. All rights reserved.
212 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

during the TCH degradation process. The high stability shown by the BN/BCN composite opens a new
path for designing of significant BN based Z-scheme photocatalyst for prevention of environmental
issues.
Ó 2020 Elsevier Inc. All rights reserved.

1. Introduction hetero-structure like BN/g-C3N4 [41], BN/Zn2SnO4 [42], BN/TiO2

[43], BN/Ag3PO4 [44], and BN/Bi4O5Br2 [14].
The flying increase in the world population will need huge In this work, BN modified BCN was designed to form a hetero-
amount of industrialization and water resource to fulfil their structure via a simple in situ method at room temperature for
requirement. But with the rapid development of industrialization, the first time and the photocatalytic efficiencies of the composite
organic pollutants in water and environment are increasing day examined by the degradation of antibiotic TCH. BN/BCN compos-
by day creating hazardous threats to ecological system [1–4]. To ites were characterized by PXRD, UV–Vis DRS, FTIR, SEM and
overcome these serious obstacles for green and pure society, semi- HRTEM in order to study the structural view, morphological con-
conductor photocatalysts are now receiving a lot of attention cept and also to verify the functional groups present in the as syn-
because of their low cost and reusability qualities [5–7]. In recent thesized materials. The BN/BCN composite having 4 wt% BN
area of research, degradation of antibiotics is becoming a hot topic showed better photocurrent response as compared to pristine BN
for researchers [8,9]. Tetracycline hydrochloride (TCH) is the most and BCN and exhibited best TCH degradation. A complete mecha-
widely used antibiotics in animal and human medication for nism for the study of photocatalytic behaviour of BN/BCN compos-
growth promotion and prevention of disease. As the antibiotics ite towards degradation of TCH is described through type-II p-n
are not completely absorbed by the organism and released through heterojunction and Z-scheme mechanism path.
its urine and faeces resulting in the contamination of soil and
water bodies. The comprehensive use of TCH antibiotics has also
2. Results and discussion
given rise to risky health issues such as liver toxicity, allergic reac-
tions, chronic poisoning and gastrointenstinal reactions. Therefore,
2.1. Physical characterization
degradation of antibiotics is dragging attention of researcher’s
now-a-days [10–15]. Large number of semiconductor photocata-
Crystallographic properties of all the composites were evalu-
lysts that have been utilized in the field of photocatalysis towards
ated by powdered XRD technique on a Rigaku Miniflex X-Ray
redressal of environmental issues, include MOF [16], CuInS2 [17],
diffractometer using a Cu Ka source (I = 1.54 Å, 40 kV, 100 mA).
ZnO [18], g-C3N4 [19], and Fe2O3 [20].
The structural information of the compound was investigated by
Among them, graphitic carbon nitride (g-C3N4) is a metal free
studying Fourier transform infra-red spectrum in a JASCO FTIR
visible light active low cost semiconductor material of 2.7 eV band
4600 spectrophotometer. SEM images of BN/BCN composite were
gap possess remarkable properties like non-toxicity and high
observed by ZeissSupra 55 SEM at 20 kV accelerated voltage and
chemical stability for wider interest in photocatalytic application
the microstructure detected by HRTEM images using transmission
[21–26]. Various approaches were developed to achieve further
electron microscope (TEM) JEOL JEM-2010. The optical properties
development in the photocatalytic performance of g-C3N4, which
of the samples were investigated by the UV–Visible spectra with
includes morphology adjusting [27], forming heterojunction with
(JASCO-V-750). The photoluminescence (PL) spectra were analysed
other semiconductor [28], and metal-nonmetal doping [29,30].
on JASCO FP-8300 spectrofluorometer with an excitation wave-
Doping of foreign elements such as boron into the framework of
length of 350 nm using xenon lamp as light source. X-ray photo-
g-C3N4 has been proven to be a better solution for the improved
electron spectroscopy (XPS) was investigated with the help of
visible light absorption and dye adsorption ability [31,32]. In spite
monochromatic X-ray source (Mg Ka X-ray) by a VG Microtech
of having such advantages, the photocatalytic activity of B doped g-
Multilab ESCA 3000 surface analyzer and all of the X-ray photo-
C3N4 (BCN) is retarded because of its high recombination rate of
electron spectroscopy spectra were plotted by taking C1s peak as
photo-induced electron-hole pairs and low specific surface area.
reference body with binding energy at 284.8 eV.
Hence, coupling with other semiconductor is considered to be a
superior solution to further improve the charge transfer efficiency
and photocatalytic performance of BCN. Especially, coupling BCN 2.2. Photoelectrochemical experiments
with layered materials to form a p-n heterojunction with
Z-scheme charge transfer path can reduce the interfacial charge The photoelectrohemical analysis of the samples was evaluated
transfer resistance, thus improving the separation of photogener- by electrochemical analyzer (IVIUM STAT) connected to a 300 W
ated charge carriers and enhancing photocatalytic ability of BCN. Xenon lamp as the source of visible-light. The three electrode sys-
Hexagonal boron nitride (h-BN), a metal free material with tem used for the electrochemical experiment constituted Pt as
structure similar to graphite, is constituted of covalently bonded counter electrode, Ag/AgCl as reference electrode and composite
boron and nitrogen atoms [33,34]. Boron nitride, because of its material coated fluorine-doped tin oxide (FTO) as working elec-
excellent qualities of high chemical inertness, thermal stability, trode, respectively. 0.1 M Na2SO4 (pH = 6.8) was used as the elec-
oxidation resistance, nontoxicity, large specific surface area and trolyte solution. The working electrodes were prepared as per the
wide band gap has been studied extensively in the last few decades following procedure. 0.02 g each of BCN, BN and BN/BCN compos-
[35–37]. Moreover, BN can serve as a large platform for the move- ite along with 0.02 g of Iodine was mixed with 40 ml of acetone fol-
ment of charge carrier species and plenty of active sites for adsorp- lowed by sonication for 10 min. The FTO electrodes were cleaned
tion of organic pollutants [38,39]. Thus by coupling layered BN repeatedly with acetone, distilled water and isopropanol and
with other semiconductor will encourage the separation of dipped in to the prepared Iodine solution. The photocatalyst mate-
electron-hole pairs by reducing the charge transfer resistance rial was coated on the FTO electrode through the electrophoresis
leading to enhanced photocatalytic activity [40]. Investigation on method, then, these FTOs were dried in an oven at 90 °C for 12 h
modifying semiconductor with BN photocatalyst includes before use.
 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223 213

2.3. Photocatalytic experiments coloured compound of B-doped g-C3N4 (BCN) was allowed to cool
to room temperature and then thoroughly ground into powder
The photocatalytic activity of BCN and BN/BCN composite was with an agate mortar and pestle for further use.
investigated by the degradation of TCH under the irradiation of
solar light. 20 mg of BCN and BN/BCN composites (2 wt%, 4 wt%, 3.3. Synthesis of BN/BCN composite
6 wt% and 8 wt%), each were taken in 100 ml conical flasks contain-
ing 20 ml of TCH aqueous solution (10 ppm). To achieve The synthesis procedure for BN/BCN composite is as follows:
adsorption-desorption equilibrium, the samples underwent 1.0 g of BCN was dispersed in 150 ml of deionized water by ultra-
30 min magnetic stirring under dark condition before solar light sonication for 30 min. After 2 h of magnetic stirring of the BCN dis-
illumination. After the adsorption-desorption experiment, the sus- persion, 0.02 g of BN was added. The stirring continued for 4 h
pensions were kept under sun light for 60 min. Subsequently the more to get 2 wt% BN/BCN product. The as-prepared product was
samples were centrifuged at speed of 7000 rpm for 7 min to then centrifuged and dried in an oven at 90 °C for 12 h to form
remove the photocatalyst particles and the decrease in concentra- the BN/BCN (2 wt%) composite. Similarly, by adding different
tion of TCH measured by JASCO V-750 UV–vis spectrophotometer. amounts of BN, namely 0.04 g, 0.06 g and 0.08 g to each of 1.0 g
The reactive species responsible for the TCH degradation were of BCN dispersion BN/BCN (4 wt%), BN/BCN (6 wt%) and BN/BCN
determined from the scavenger tests, for which citric acid (2 mg), (8 wt%) composites respectively were prepared. The flow-chart of
dimethyl sulfoxide (DMSO, 7.1 ml), 1, 4-benzoquinone (PBQ, synthesis steps involved in the preparation of BN/BCN composites
11 mg) and isopropanol (IPA, 7.64 ml) were taken as scavenging are given in Scheme 1.
agents in 20 ml TCH solution for h+, e, O2and OH, respectively.

3.4. Characterization
3. Experimental section
3.4.1. Structural analysis
3.1. Chemicals X- ray diffraction study was performed to examine the crystal
structure, phase purity and interlayer stacking distortion of BN,
Boron nitride was purchased from Sigma-Aldrich, USA. Mela- BCN and BN/BCN composite. As shown in Fig. 1, diffraction peaks
mine, boric acid and all other chemicals were purchased from Mer- at 2h = 26.6°, 41.8°, 43.8° and 55° are the characteristic peaks
ck, India. All of the chemicals were of analytical grade and directly belong to (0 0 2), (1 0 0), (1 0 1) and (0 0 4) planes of hexagonal
used without further purification. boron nitride respectively in accordance with (JCPDS card no.34-
0421) [45,46]. The XRD pattern for BCN displayed two diffraction
3.2. Synthesis of B-doped g-C3N4 (BCN) peaks at 13.0° and 27.5°, while the former peak represents the
(1 0 0) plane which was ascribed to in-planar structural units of
B-doped g-C3N4 was synthesized by calcination of boric acid tris-triazine, the latter corresponding to the (0 0 2) plane denoted
and melamine mixture according to Babu et al. [32]. The synthesis the interlayer stacking of the aromatic rings [47,48]. After intro-
method is similar to the conventional preparation method of g- ducing BN to BCN, peaks appeared at 13.0° and 27.5° in the XRD
C3N4 by polymeric condensation of melamine. First, 1.24 g of boric pattern of BN/BCN composites were ascribed to the characteristic
acid and 20 g of melamine were dispersed in 500 ml of deionized peaks of pure BCN, indicating that the introduction of BN doesn’t
water and heated at 60 °C for about 24 h till water evaporated to significantly affect the crystal structure of BCN [49]. In BN/BCN
provide a white crystalline powder, which was then placed in an composite, intensity of the peak at 26.6° corresponding to (0 0 2)
alumina crucible, covered partly and calcined for 2 h at 550 °C plane of BN increases with increase in the amount of BN as
(at a ramp rate of 5 °C per minute). The obtained light yellow displayed in Fig. 1(b). The above results showed the well

Scheme 1. Schematic representation of synthesis steps of BN/BCN composite.

214 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

Fig. 1. (a) PXRD pattern of BN, BCN and BN/BCN composites and (b) enlarged (0 0 2) plane of BN/BCN composite.

incorporation of BN with BCN and formation of no new character- electron transfer between BN and BCN in BN/BCN (4 wt%), binding
istic peaks in the diffraction pattern confirmed the high purity of energies of both the neat materials had been compared with the
the composite. binding energy of the BN/BCN (4 wt%) composite [55]. For pure
BN, the B1s peak appeared at 190.4 eV, represented the binding
3.4.2. FTIR analysis energy of B-N stretching vibration as shown in Fig. 3(a) [56]. The
To further study the chemical interaction between BN and BCN, B1s peak for neat BCN obtained at 189.5 eV was assigned to
Fourier transform infrared spectroscopy (FT-IR) analysis was used. CANAB group as reported before [52]. It may be seen that for
The peaks appeared at 790 cm
1 and 1408 cm
1 were correspond- BN/BCN (4 wt%) composite, the B1s revealed a red shifted primary
ing to B-N-B out of plane bending vibration and in-plane BAN binding energy from 190.4 eV to 188.3 eV corresponding to B-N
stretching mode of BN, respectively. The broad peak observed at bond of BCN and another peak at 187.3 eV referring to CANAB
3430 cm
1 was corresponding to the OAH stretching vibration bonding shifted from 189.5 eV [57].
band obtained due to the absorption of water molecules during In BN, the C1s peak appeared at 284.8 eV is ascribed to the
synthesis process [37,50]. In the spectrum for pure BCN, the tri- adventitious carbon species. As displayed in Fig. 3(b), in case of
s-triazine vibration peaks observed at 807 cm
1 and the corre- BCN, two peaks with different binding energies were observed.
sponding peaks at 1200–1700 cm
1 represented the CAN and The less intense peak placed at 284.8 eV is attributed to the adven-
C@N stretching vibration. The broad peaks at 3000–3500 cm
1 titious (CAC) bond and the large intense peak at 287.9 eV is related
were ascribed to NAH stretching modes of pristine BCN [51,52]. to the sp2 hybridized (CANAC) bond [58]. After amalgamation of
As presented in Fig. 2(b), the interaction between BN and BCN BN with BCN, the C1s peak for sp2 hybridized (CANAC) bond of
resulted in the slight shifting of in plane B-N stretching band at neat BCN appeared at 287.8 eV and CAC bond at 284.8 eV remains
1408 cm
1 to higher frequency 1390 cm
1. Also FTIR spectrum unchanged.
for BN/BCN composite presented that the intensity of absorption As can be sighted from Fig. 3(c), the N1s XPS spectrum of BN
band at 1390 cm
1 increases with increase in content of boron was found at 398.0 eV as a result of BAN bond [8]. The N1s XPS
nitride. The above results indicated that boron nitride has been spectrum for BCN splitted in to three main peaks detected at
successfully consolidated with BCN [53,54]. 397.8 eV, 398.8 eV and 399.5 eV. The peak at 397.8 eV was
assigned to graphitic N atom. The sp2 hybridized nitrogen pyridinic
3.4.3. XPS analysis bridge (CAN@C) group appeared at 398.8 eV, while 399.5 eV orig-
To elucidate the chemical states and elemental information of inated for tertiary N-bonded NA(C)3 [25]. In BN/BCN (4 wt%) com-
the as-synthesized BN/BCN (4 wt%) composite, X-ray photoelec- posite, the binding energy for the sp2 hybridized B-N bond is
tron spectroscopy (XPS) was studied. In order to explain the placed at 398.0 eV, indicating there is no change in BN after merger

Fig. 2. (a) FTIR spectra of BN, BCN and BN/BCN composites and (b) magnified FTIR spectra of BN, BCN and BN/BCN composites showing slight shifting of in-plane B-N
stretching mode of BN in BN/BCN composites.
 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223 215

Fig. 3. Comparison of XPS deconvoluted peak between BN, BCN, and BN/BCN (4 wt%) composite for (a) B1s, (b) C1s, and (c) N1s.

with BCN. Again, the N-bonded NA(C)3 bond was slightly shifted to 3.6. Optical properties
399.3 eV from 399.5 eV in BN/BCN (4 wt%) compound.
XPS spectra displayed in Fig. 3, validated that the as- 3.6.1. UV–Vis DRS
synthesized sample BN/BCN (4 wt%) composite consists of both The optical properties i.e. band gap energy and light absorption
BN and BCN. After the combination of BN with BCN, the percentage region of BN, BCN and BN/BCN composite was determined by
of B centered sites attained importance as may be seen from the UV–Vis DRS analysis in region of 200–800 nm. As it may be seen
intensity of the B1s peak in BN/BCN (4 wt%) composite. from Fig. 5(a), pure BN showed absorption in the UV region
between 200 nm and 270 nm which is because of the wide band
3.5. Morphology characterization gap of BN. However, neat BCN shows strong absorption from UV
to visible light region up to 625 nm [57,62]. It could be noticed
3.5.1. FESEM and HRTEM from the spectrum that BN/BCN composite exhibited bathochromic
Fig. 4(a) depicted the FESEM image of BN/BCN (4 wt%), which shift to a longer wavelength of 660 nm (as shown in inset of
shows that the composite exhibits an aggregated sheet like mor- Fig. 5a). Hence it is expected that as a result of coupling of BN to
phology and the surface of sheet appears to be coated with broken BCN in BN/BCN composite could enhance its photocatalytic activity
slate like crystallites [45]. The Fig. 4(a) also revealed the porous in visible light region [63,64].
heterogeneous structure of the composite. HRTEM analysis was The band gap energies of the samples were calculated from
used for the high resolution examination of the structure of BN/ Schuster-Kubelka-Munk function and Tauc plots
BCN (4 wt%) composite. The thin layered sheet like structure of
aht ¼ Cðht
Eg Þn ð1Þ
BN/BCN (4 wt%) composite was confirmed by HRTEM image anal-
ysis. Fig. 4(b) shows the clear lattice fringes having d-spacing of where a, h, t, C, Eg and n are absorption coefficient, Plank’s con-
about 0.33 nm. Incidentally both BCN and BN have near identical stant, light frequency, a constant and band gap respectively. The
crystal structures and hence exhibit d-spacing value of 0.33 nm direct band gap of neat BN and BCN were determined from the
corresponding to their respective (0 0 2) planes. The d-spacing graph of (aht)2 vs Eg by extrapolating straight line to Eg axis as
value of about 0.33 nm for (0 0 2) planes corroborates the same shown in Fig. 5(b) and (c). The band gap energies for the pure BN
obtained from PXRD measurements. The d-spacing value of about and BCN are calculated to be 5.4 eV and 2.5 eV respectively
0.21 nm for (1 0 0) plane of BN could be found from lattice fringes [65,66]. After modification of BCN with BN, the band gap of BN/
indicating the presence of BN phase in the composite (Fig. 4(c)). BCN (4 wt%) composite narrower to 2.3 eV (Fig. 5(d)). The decreased
The SAED pattern of (0 0 2) plane of BCN in BN/BCN (4 wt%) com- band gap of BN/BCN (4 wt%) composite enhances its visible light
posite is depicted in Fig. 4(d). The clear lattice fringes indicate the absorption ability, thus making it more favourable for improved
crystalline nature of the BN/BCN (4 wt%) composite. The existence photocatalytic performance in comparison to pristine BCN.
of the elements B, C and N in the BN/BCN (4 wt%) composite has
been confirmed from the HRTEM- elemental mapping as displayed 3.6.2. PL analysis
in Fig. 4(e)–(h). All the elements were found to be well distributed Photoluminescence spectra are one of the most effective analyt-
throughout the BN/BCN (4 wt%) composite [60,61]. ical tools for the investigation of separation of photo-induced
216 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

Fig. 4. (a) FESEM image,(b-c) lattice fringe showing the crystal plane, (d) SAED patteren of BCN and (e–h) elemental mapping images of BN/BCN (4 wt%).

electron-hole pair of the photocatalysts. From the Fig. 6, it may be But, in case of BN the slope was found to be of positive nature sug-
seen that the emission peaks of samples ranges from 450 nm to gesting that the graphite analogue BN as n-type material and by
550 nm [67]. From PL spectroscopy, it may be concluded that lower extrapolating the curve to the potential axis, the band edge
the peak intensity, lower is the recombination rate of photo- potential is calculated to be
0.43 eV [69]. The conduction band
excited electron-hole pairs and hence, higher is the photocatalytic minimum of the n-type BN and the valence band maximum of
activity [68]. BN being a wide band gap material shows an insignif- the p-type BCN on a NHE scale may be evaluated by applying the
icant intensity peak as it couldn’t be excited [60]. BCN showed formula [70].
emission peak at around 460 nm upon excitation at 320 nm [52].
After the introduction of BN to BCN, the intensity peak for BN/ EðNHE;pH¼7Þ ¼ EAg=AgCl
0:059ð7
pH of the electrolyteÞ þ 0:198
BCN (4 wt%) composite was lowered as compared to the pure ð2Þ
BCN and all other BN/BCN composites, indicating the lower recom-
The CB position of BN and VB position of BCN were determined
bination rate of photo-induced electron-hole pairs and therefore
to be
0.65 eV and 0.97 eV respectively. Now, the corresponding
expected to enhanced photocatalytic activity of the composite.
VB position of n-type BN and CB position of p-type BCN were cal-
culated to be 4.75 eV and
1.53 eV respectively by using the Eq.
(3).
3.7. Photoelectrochemical measurements
EVB ¼ Eg þ E71
CB ð3Þ
3.7.1. Mott-Schottky plots
Mott-Schottky plots were used to investigate the band edge
potential and the formation of heterojunction. As shown in Fig. 7, 3.7.2. Electrochemical impedance spectroscopy (EIS) analysis
the MS plot of BCN showed a negative slope indicating that BCN The study of charge carrier transfer resistance was carried out
is a p-type semiconductor with band edge potential +1.2 eV [32]. from the arc radius of Nyquist plot acquired for BN, BCN and
 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223 217

Fig. 5. (a) UV–Vis absorption spectra of BN, BCN and BN/BCN composites and UV–Vis absorption spectra of BCN and BN/BCN (4 wt%) composite (inset). (b–d) Direct band gap
of BN, BCN and BN/BCN (4 wt%) from the (aht)2 vs Eg plots, respectively.

3.7.3. Transient photocurrent

In order to study the electron transfer during light-on and light-
off mode, transient photocurrent analysis was carried out. The
photocurrent intensity increased to a noticeable value when the
light is on and then rapidly fall down to lower photocurrent inten-
sity after turn off the light [71]. Weak photocurrent intensities of
0.05 mA and 0.23 mA for BN and BCN respectively were observed
as shown in Fig. 9 [37]. After the combination of BN with BCN,
the photocurrent of the BN/BCN (4 wt%) composite was increased
to 0.69 mA, which is ascribed to lowest recombination efficiency
of charge carriers. This result demonstrated that addition of BN
promote the separation of electron and hole due to the formation
of interface in between BN and BCN which is in accordance with
their photocatalytic activities [72].

3.8. Photocatalytic TCH degradation

Fig. 6. Photoluminescence spectra of BN, BCN and BN/BCN composite. 3.8.1. Kinetics of TCH degradation
To analyze the reaction kinetics behaviour of BN/BCN photocat-
alyst towards the degradation of TCH, kinetic analysis was pursued
BN/BCN (4 wt%) composite as demonstrated in Fig. 8 [52]. Usually, by irradiating catalysts (1.0 g L
1) in 10 ppm of TCH solution at a
in EIS plots, the high frequency region was indicated by a semicir- time intervals of 15 min (i.e. 15, 30, 45 and 60 min duration) under
cle and the low frequency region was represented a straight line solar light using Langmuir-Hinshelwood model. As displayed in
[14]. The smaller diameter of arc radius witnessed the lower Fig. 10, all the as-prepared samples follow the pseudo- first order
charge carrier transfer resistance, thus reducing the recombination kinetics as per Eq. (4):
rate of e/h+ pairs by accelerating the charge carriers movement

dc
[15]. Fig. 8 depicted that the arc radius for BN/BCN (4 wt%) com- r¼ ¼ kc ð4Þ
posite is lower as compared to pure BN and BCN. This suggested dt
that the composite having lower charge transfer resistance and where ‘k’ is the rate constant, ‘c’ is concentration of TCH, ‘t’ is the
higher electron hole separation will show better photocatalytic time spell and in logarithm form the above equation may be
activity than the pristine BCN. represented as:
218 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

Fig. 7. Mott-Schottky plots of (a) BN, (b) BCN and (c) BN/BCN (4 wt%) composite.

Fig. 8. EIS representation of BN, BCN and BN/BCN (4 wt%) composite and a blown
up Nyquist plot of BCN and BN/BCN (4 wt%) composite (inset). Fig. 9. Transient Photocurrent response of BN, BCN and BN/BCN (4 wt%).

lnðC0 =CÞ ¼ kapp t ð5Þ degradation rate towards TCH i.e. 88.1% as compared to BN/BCN
(2 wt%), BN/BCN (6 wt%) and BN/BCN (8 wt%) for which the degra-
where C0 = initial concentration of TCH, C = concentration of TCH dation percentages were found to be 71%, 81% and 65% respec-
after time t and kapp = pseudo 1st order rate constant (min
1). tively. This trend of degradation percentage is in agreement with
The value of kapp is represented by the slope of the ln(C/C0) vs t PL analysis. While trying to check the stability of the photocatalyst
curve. The obtained regression coefficient (R2) and kapp values from throughout the TCH degradation process, the BN/BCN (4 wt%) sam-
ln(C/C0) vs irradiation time plot are presented in Table 1. ple was subjected to consecutive reusability tests towards pho-
As can be seen from the above Table 1 and Fig. 10(a)–(c), the todegradation of TCH. Fig. 10(d) demonstrated that the
highest degradation rate constant value observed for the BN/BCN photocatalytic performance of BN/BCN (4 wt%) composite did not
(4 wt%) composite was (0.03431 min
1), showing highest show significant changes even after 3 cycles of use under solar
 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223 219

Fig. 10. (a) Bar diagram of TCH degradation in BCN, BN/BCN (2 wt%), BN/BCN (4 wt%), BN/BCN (6 wt%) and BN/BCN (8 wt%), (b) plots C/C0 vs irradiation time and (c) pseudo-
first-order plots of BN, BCN, BN/BCN (2 wt%), BN/BCN (4 wt%), BN/BCN (6 wt%) and BN/BCN (8 wt%) during TCH degradation and (d) recyclability test of the photocatalyst.

Table 1 3.8.2. Trapping experiment

Kinetic rate constants, regression coefficients and t1/2 of BCN, BN/BCN composites To explore the prominent active species which were taking
towards TCH degradation under solar light illumination.
part in the degradation process of TCH, trapping experiments
Sl. No. Photocatalysts k (min
1) R2 t1/2 executed by employing certain scavenging agents, such as 1,
1 BCN 9 * 10
3
0.99784 77 4-benzoquinone (PBQ), isopropanol, dimethyl sulfoxide and citric
2 BN/BCN (2 wt%) 20 * 10
3 0.9951 34.65 acid for superoxide radical (O

2 ), hydroxyl radical (OH ), electron
3 BN/BCN (4 wt%) 34 * 10
3 0.9941 20.38
+
(e ) and hole (h ) respectively [12,16,17]. The higher the change
4 BN/BCN (6 wt%) 26 * 10
3 0.9928 26.65
in the photocatalytic performance of the composite, the greater
5 BN/BCN (8 wt%) 17 * 10
3 0.99705 40.76
was the effect of the scavenging agent. The degradation efficiency
of BN/BCN (4 wt%) towards TCH rapidly descended from 88.1% to
28% after PBQ was added (Fig. 11a). Similar trend was noticed
light irradiation. The above results illustrated that the composite
when isopropanol was added as a scavenger towards TCH degrada-
material exhibited high stability during degradation process which
tion. From the above assessment, it was clear that super oxide (O

2)
is beneficial for its practical application [17,73].
and hydroxyl radical (OH) may be considered as the main active
These experimental results towards photocatalytic degradation
species playing predominant role in the antibiotic TCH degrada-
behaviour of TCH were compared with literature data available for
tion. Furthermore, to endorse the formation of O

2 and OH radicals,
other composites and given in Table 2.

Table 2
Comparison study of different photocatalysts towards TCH degradation under visible light illumination.

Sl. No. Materials Synthesis method Illumination light Illumination time (min) Degradation percentage References
1 CuInS2/g-C3N4 In-situ Visible light 60 83.7 [17]
2 h-BN/g-C3N4 Calcination Visible light 60 79.7 [45]
3 HPW@UiO-66 Impregnation Visible light 60 87.2 [70]
4 S-CQDs/HTCN-C In-situ Visible light 60 82.67 [74]
5 Co3O4/Ag/Bi2WO6 Solvothermal Visible light 60 57.2 [75]
6 r-GO/BWO Hydrothermal Visible light 60 85 [76]
7 AgBr/Bi2WO6 Deposition-precipitation Visible light 60 87.5 [77]
8 In2S3/InVO4 In-situ Visible light 60 71 [78]
9 AgI/Bi2Sn2O7 Deposition-precipitation Visible light 50 83 [79]
10 CdS/SnO2 Hydrothermal Visible light 60 92 [80]
11 BN/BCN In-situ Solar light 60 88.1 Present work
220 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

Fig. 11. (a) Trapping experiment for BN/BCN (4 wt%) composite, (b) NBT test and (c) TA tests for BN, BCN and BN/BCN (4 wt%).

NBT (nitro blue tetrazolium) and terephthalic acid tests were con- BN content, a decrease in the photocatalytic behaviour of the com-
ducted. As reported, in NBT test the smallest absorbance peak in posite was witnessed, which might be due to the fact that too
UV–Vis spectrum stated the maximum development of O
2 radicals much amount of BN covered the active sites of BCN and inter-
and in the exactly opposite manner, the highest intensity peak in rupted the visible light absorption [37,68,81].
PL spectra of terephthalic acid test represented the generation of The enhanced photocatalytic performance of as-prepared BN/
OH radicals. In this way, as depicted in Fig. 11(b), the weakest BCN composite might be as a result of the following factors; firstly
UV–Vis spectrum for BN/BCN (4 wt%) composite indicated the for- the addition of metal free BN having large surface area provides
mation of O
2 radicals and Fig. 11(c) confirmed the generation of wide number of active sites for the adsorption of organic pollutants
OH radicals in BN/BCN (4 wt%) composite with highest PL intensity by enlarging the specific surface area of the composites [82], and
[70]. secondly as given by PL, EIS and transient photocurrent analysis,
the BN/BCN composite shows better photocurrent response than
3.8.3. Possible mechanism for TCH degradation the pristine BN and BCN and thus exhibits smaller charge transfer
Taking inputs from the experimental results, suitable mecha- resistance and lower recombination rate of electron hole pairs [73].
nism for the enhancement in the degradation efficiency of the The CB and VB positions of both BN and BCN play a significant role
composites towards TCH under solar light irradiation was repre- in the reduction of the recombination rate of electron and hole and
sented in Scheme 2. The photocatalytic efficiency of pure BCN enhanced photocatalytic performance of BN/BCN composite. As
towards TCH was found to be 42%. The photocatalytic performance illustrated from Fig. 12, the EVB and ECB positions of pure BCN were
of the as-synthesized BN/BCN composites increased with the evaluated to be 0.97 eV and
1.53 eV respectively, while the com-
increase in BN content of composite. The photocatalytic percentage mercially available BN has band edge positions of EVB = 4.75 eV and
of BN/BCN (2 wt%) escalated to 71% which then rapidly increased ECB =
0.65 eV respectively, indicating that the band edge poten-
to 88.1% for BN/BCN (4 wt%). However, further addition of BN led tials of both the pristine materials (BN and BCN) are capable of
to decrease in photocatalytic activity of BN/BCN (6 wt%) to 81% forming heterojunction which led to reduced charge recombina-
and thus BN/BCN (8 wt%) exhibited the lowest degradation effi- tion efficiency of the composite [49,83].
ciency of 65%. The above study confirmed that the BN/BCN (4 wt Among the various approaches for the separation of e
/h+
%) composite exhibited the highest photocatalytic degradation per- pairs, arrangement of p-n heterojunction between p-type and
centage which is in agreement with the photoluminescence data as n-type semiconductor had been considered to be beneficial. The
shown in Fig. 6. The BN in BN/BCN composite channelizes the p-n heterojunction creates an interface or boundary between
photo-generated charges without recombination, which helps p-type and n-type semiconductors by which photo-induced
electrons move to active sites on surface of photocatalyst and con- electron hole pairs get separated easily which increases the
sequent TCH degradation. Due to this there is an enhancement of photocatalytic performance of the semiconductor [84]. In p-n
photo degradation of TCH when BN content was improved up to heterojunction there exits two possible mechanisms which are
4 wt% in BN/BCN composite. However, with further increase in responsible for the separation of electron hole pairs; (a) double
 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223 221

Scheme 2. Schematic representation of charge transfer mechanism of TCH degradation by BN/BCN (4 wt%) composite.

Since, the double charge transfer mechanism did not support

the generation of hydroxyl radical (OH), the second path; Z-
scheme mechanism appeared to be more reasonable for the
enhanced photocatalytic performance of the composite
[17,59,85]. As can be seen from Scheme 2b, the photoinduced elec-
trons at the CB of BN will recombine with holes present in the VB of
BCN and electrons in the CB of BCN were available for the genera-
tion of superoxide radials (O

2 ). Similarly, hydroxyl radicals (OH )
might be easily produced at the VB of BN as the band edge poten-
tial of BN (EVB = 5.20 eV) was sufficient for the potential required to
oxidise H2O to hydroxyl radical (OH/OH
= 1.99 eV vs NHE). This
observation was in reconciliation with the trapping tests that
superoxide (O

2 ) and hydroxyl (OH ) radicals were mainly respon-
sible for the improved photocatalytic TCH degradation [86]. The
detailed mechanism of TCH degradation by BN/BCN composite
under solar light illumination involving p-n heterojunction with
Z-scheme mechanism is elaborated in Scheme 2.

Fig. 12. Band gap structures of pure BCN and BN before contact. 4. Conclusion

In summary, the novel BN/BCN Z-scheme with p-n heterojunc-

tion photocatalyst has been successfully prepared by using a sim-
charge transfer path and (b) Z-scheme mechanism. If the as- ple in-situ method. The surface of BCN nanosheet was well covered
synthesized BN/BCN (4 wt%) composite pursues the double with BN particles forming interface between BN and BCN. When
charge transfer path, after equilibration of the Fermi level and BN content is 4 wt%, the composite exhibited the highest photocat-
band bending (after contact), electrons from the CB of p-type alytic efficiency of 88.1% TCH degradation under solar light irradi-
BCN (
2.20 eV) shall be migrating to the CB of n-type BN ation at time period of 60 min. BN/BCN (4 wt%) photocatalyst
(
0.2 eV) and holes in the VB of n-type BN (5.20 eV) relocated shows adequate photocurrent response in comparison to neat BN
to VB of p-type BCN (0.30 eV). After band bending, BN had insuf- and BCN which is corroborated by EIS and photocurrent studies.
ficient potential for ECB electrons to reduce dissolved oxygen to The enhanced photocatalytic behaviour of the BN/BCN (4 wt%)
form superoxide radials O


2 (O2/ O2 =
0.33 eV vs NHE), and photocatalyst are associated with the reduced recombination rate
inadequate EVB potential of BCN for the generation of hydroxyl of photo-induced e
–h+ pairs resulted by the formation of Z-
radical (OH/OH
= 1.99 eV vs NHE). Hence, formation of hydro- scheme based heterojunction between BN and BCN. From trapping
xyl radical at the VB of BCN was not feasible in this case which experiments it can be confirmed that the O

2 and (OH ) radicals are
contradicts with the results of trapping experiments. the main active species during photocatalytic performance of the
222 L. Acharya et al. / Journal of Colloid and Interface Science 566 (2020) 211–223

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