Sie sind auf Seite 1von 59

Accepted Manuscript

Title: High efficient catalytic degradation of tetracycline and


ibuprofen using visible light driven novel Cu/Bi2 Ti2 O7 /rGO
nanocomposite: Kinetics, intermediates and mechanism

Authors: S. Shanavas, A. Priyadharsan, I. Gkanas, R.


Acevedo, P.M. Anbarasan

PII: S1226-086X(18)31305-4
DOI: https://doi.org/10.1016/j.jiec.2019.01.008
Reference: JIEC 4350

To appear in:

Received date: 5 November 2018


Revised date: 31 December 2018
Accepted date: 8 January 2019

Please cite this article as: S.Shanavas, A.Priyadharsan, I.Gkanas, R.Acevedo,


P.M.Anbarasan, High efficient catalytic degradation of tetracycline and
ibuprofen using visible light driven novel Cu/Bi2Ti2O7/rGO nanocomposite:
Kinetics, intermediates and mechanism, Journal of Industrial and Engineering
Chemistry https://doi.org/10.1016/j.jiec.2019.01.008

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
High Efficient Catalytic Degradation of Tetracycline and Ibuprofen Using Visible Light

Driven Novel Cu/Bi2Ti2O7/rGO Nanocomposite: Kinetics, Intermediates and Mechanism

S. Shanavasa, A. Priyadharsana, I. Gkanasb, R. Acevedoc and P.M. Anbarasana*

PT
a
Nano and Hybrid Materials Laboratory, Department of Physics, Periyar University, Salem- 636

RI
011, India.

SC
b
Hydrogen for Mobility Lab, Institute for Future Transport and Cities, Coventry University,

Priory Street, CV1 5FB, Coventry, UK.

U
c
Facultad de Ingeniería y Tecnología. Universidad San Sebastián, Bellavista 7, Santiago

8420524, Chile. N
A
M

*Corresponding author.
D

Email address: profpmanbarasan@gmail.com (Prof. P. M. Anbarasan)


TE

Phone: +91-0427-2345766, 2345520


EP

Fax No: +91-0427-2345565, 2345124


CC
A

1
Graphical abstract

PT
RI
SC
U
N
A
M

Highlights
D

 The enhanced trapping of photoexcited charge carriers were successfully obtained by


TE

constructing a novel Cu/Bi2Ti2O7/rGO nanocomposite.


 The trapping of electrons were confirmed by the observed suppression of e--h+ pair
EP

recombination by Photoluminescence analysis


 The photoexcited charge transfer and trapping mechanism in ternary photocatalyst was
discussed in detail with the help of UV-Vis DRS, PL and XPS analysis
CC

 The degradation pathways of tetracycline and ibuprofen were proposed by identifying the
degradation intermediates using LC-TOF/MS analysis.
A

 The obtained ternary nanocomposite showed were ~8.7 times enhanced photocatalytic
degradation ability comparing to P25-TiO2.

2
Abstract

The photoexcited charge carriers trapping was an effective way to generate a large number

of active species like O•− •


2 and OH radicals to oxidize pharmaceutical molecules. In ternary

Cu/Bi2Ti2O7/rGO composite Cu nanoparticles and rGO sheets act as charge carrier trappers and

PT
the suppression of e--h+ pair recombination was confirmed by Photoluminescence analysis. The

Cu/Bi2Ti2O7/rGO composite exhibited higher photocatalytic degradation efficiency for

RI
degradation of ibuprofen and tetracycline molecules under visible light irradiation within 90 min.

SC
Therefore, this research designates a promising strategy for higher photoexcited charge carrier

trapping photocatalyst design for efficient degradation of pharmaceutical molecules.

U
N
Keywords: Nanocomposite; Hydrothermal; Visible light-driven; Charge carrier trappers;
A
Pharmaceutical contamination.
M

1. Introduction
D

The extensive use of antibiotics and anti-inflammatory drugs has grabbed attention because
TE

of its possible direct damages to living organisms and agriculture[1–5]. The antibiotics and anti-
EP

inflammatory drugs were usually used to treat bacterial diseases, fever and used as painkillers, a

huge amount of antibiotics and anti-inflammatory drugs were produced and consumed in day to
CC

day life. Among them, tetracycline (TC) and ibuprofen (IBP) is the most important pharmaceutical

molecules which are widely used in veterinary and human medicines for disease control and
A

growth promotion due to its high efficiency[6]. But, TC and IBP can be easily entered into our

aqueous environment because of its poor absorption, lower metabolism, exploitation and

overuse[2]. The TC and IBP in aqueous environments could cause several direct toxicity effects

3
and potential risks to human health. Over the past decades, these antibiotics and anti-inflammatory

drugs are attracted much attention in rapidly increasing water environments [1]. To eradicate these

challenges, various researches were targeted to deal with pharmaceutical molecules condemned

water, like biological degradation, chemical reactions and physical absorption[7]. The huge

PT
challenges in these methods are poor efficiency at low concentrations and biochemical rate[8,9].

While compared with these traditional methods, photocatalytic technology is considered as a

RI
promising method of degrading pharmaceutical contaminations in an aqueous environment due to

SC
its low energy consumption, very high mineralization ability, no secondary pollution and simple

practical application[10].

U
The photocatalytic process of semiconductors mainly depends on the absorption of photons

N
from the sun and the separation of photo-excited charge carriers. Unfortunately, the photocatalytic
A
activity of most photocatalyst is still low due to some drawbacks such as the lack of active sites,
M

utilization of photons from the sun and the limited fast photoinduced charge carrier

recombination[11,12]. The catalytic degradation performance of photocatalytic materials can be


D

increased by suppressing the charge carrier recombination on the photocatalyst. It is possible to


TE

trap the charge carriers excited in the photocatalytic materials using noble metals and rGO sheets
EP

as charge carrier trappers[13–15]. However, rGO is a single layer of sp2 hybridized carbon atoms

arranged in a 2D honeycomb structure with high surface area, excellent mechanical, thermal and
CC

electrical properties. It is an excellent material which excellently supports the metal oxide

nanoparticles used in a wide range of environmental and energy applications. The combination of
A

rGO with metal oxide nanoparticles results in the novel functional materials with enhanced

performance[16–18]. Hence, rGO based nanocomposites showed huge enhancements in

photocatalytic performance. The excellent surface properties of rGO sheets support it to accept

4
and transfer electrons which are excited on the photocatalytic semiconductors and helps to decline

the recombination rate of photoinduced electron-hole pairs. In addition, the π-π conjugation

between the aromatic regions of graphene and pharmaceutical molecules allows the adsorption of

pharmaceutical molecules on the rGO surface[10,13,19]. Among different semiconductor

PT
photocatalysts, pyrochlore bismuth titanate (Bi2Ti2O7) is one of the new visible light driven

photocatalytic material owing to its moderate band gap energy of about 2.88 eV[20,21]. Due to

RI
the considerable band edge positions of Bi2Ti2O7 for oxidation and reduction process to generate

SC
active species like hydroxyl and superoxide radicals, Bi2Ti2O7 has been confirmed towards the

photocatalytic activity for pollutants removal and water splitting applications[22,23]. However,

U
there are few practical difficulties while using pristine Bi2Ti2O7 photocatalysts, such as low

N
catalytic activity due to higher recombination rates of photo-excited carriers and it results with low
A
quantum efficiency. In general, it is proved that the binary Bi2Ti2O7/noble metal and Bi2Ti2O7/rGO
M

can efficiently promote the photo-excited charge carrier separation and transfer[20]. A large

number of binary semiconductor/noble metal and semiconductor/rGO nanocomposites have been


D

prepared and attained improvement in photocatalytic efficiency[15,20]. However, the quantum


TE

efficiency of such photocatalytic materials can be enhanced furthermore by introducing trappers


EP

like noble metal and rGO on the pristine Bi2Ti2O7 structures as ternary nanocomposites[24,25].

The metal ions incorporation in semiconductor photocatalysis has been conventionally used as an
CC

effective photo excited charge trapping sites to restrict the recombination of charge carriers. More

specifically, introduction of Cu metal ion in Bi2Ti2O7 nanostructure can rapidly create the oxygen
A

vacancy sites and the electronic behaviors of metal oxide semiconductors will be effectively

changed to extend the light absorption edge. The redox potential level of Cu nanoparticles is well

below to the conduction band of Bi2Ti2O7 nanostructures this lead with the effective trapping of

5
photo excited charge carriers. In addition, Cu is one of the abundant metals in the earth and low in

price with eco-friendly nature [13,24].

In the present work, a simple electrostatic approach has been carried out to synergistically

couple rGO with Cu/Bi2Ti2O7 (CBT) nanocomposite to produce Cu/Bi2Ti2O7/rGO (CBTG) and

PT
the properties of obtained ternary nanocomposite were examined through several complementary

characterization techniques. The main objective of current work is to develop highly efficient

RI
separation and transmission of photo-induced charge carriers to enhance the reactive species

SC
production by photocatalytic materials, and it is achieved using Cu and rGO as trappers for photo-

induced charge carriers. The suppression of charge carrier recombination rate is analyzed and

U
confirmed by PL analysis. The PL analysis of CBTG ternary nanocomposite shows the effective

N
decrement in PL intensity which corresponds to the lower recombination rate of charge carriers.
A
The photocatalytic ability of CBTG ternary nanocomposite to degrade aqueous pharmaceutical
M

contaminations was investigated in detail by using ibuprofen (IBP) and tetracycline (TC) as a

target pollutant under visible light irradiation. Furthermore, the possible photocatalytic mechanism
D

and possible degradation pathways of TC and IBP molecules have been examined and proposed
TE

in detail. Not only the degradation of pharmaceutical contaminations are enhanced in presence of
EP

rGO and Cu as charge carrier trappers in Bi2Ti2O7 photocatalyst, cyclic runs indicating higher

stability of CBTG composite, highlighting its real-time utilization. The novel findings reported in
CC

this work are anticipated to assist as an effective strategy in the construction of such high photo-

excited charge carrier trapping photocatalyst to develop the catalytic performance towards the
A

degradation of pharmaceutical contaminations.

2. Experimental Procedure

2.1 Materials

6
All the raw materials used in the current study are the following: Graphite flakes, copper

sulphate pentahydrate (CuSO4.5H2O), bismuth nitrate pentahydrate (Bi(NO3)3.5H2O),

titanium(IV) isopropoxide (Ti[OCH(CH3)2]4), sodium nitrate (NaNO3), hydrochloric acid (HCl),

potassium permanganate (KMnO4), sulfuric acid (H2SO4), nitric acid (HNO3) hydrogen peroxide

PT
(H2O2), cetyltrimethylammonium bromide (CTAB), sodium hydroxide (NaOH), hydrazine

hydrate (N2H4.H2O), ethanolamine (C2H7NO), ammonium hydroxide (NH4OH), ethanol

RI
(C2H5OH), terephthalic acid, benzoquinone (BQ), isopropyl alcohol (IPA), triethanolamine

SC
(TEOA), tetracycline (TC), ibuprofen (IBP) and glacial acetic acid (CH3COOH). All the above

mentioned analytical grade chemicals were purchased from Merck Chemical Company and used

U
directly without any further purification.

2.2. Synthesis of photocatalyst N


A
2.2.1 Synthesis of graphene oxide (GO)
M

GO was prepared by strong oxidation of graphite flakes through modified Hummer’s

method[26,27]. In a typical modified Hummer’s method, graphite flakes, NaNO3, and


D

concentrated H2SO4 were stirred together at a low temperature in an ice bath for 30 min.
TE

Subsequently, KMnO4 was slowly added in a controlled manner to it resulting in the formation of
EP

a dark green colored solution. Due to the addition of H2SO4 and KMnO4, the temperature of the

solution will increase rapidly but the ice bath was maintained to restrict the temperature as below
CC

20°C. After 5 min of constant stirring, the ice bath was removed and the temperature of the reaction

solution was increased to 40°C under stirring for 30 min. The reaction solution converted in a thick
A

paste and then deionized water was added slowly to it. This reaction is exothermic and hence the

temperature of the solution is increased. The solution was further slowly heated up to 90°C and

constantly maintained at this temperature for 40 min. At that time, deionized water was added

7
followed by dropwise addition of 30% H2O2 solution to reduce the presence of excess KMnO4.

Now, the color of the reaction solution was changed from dark brown to yellow. The mixture was

kept under constant stirring for 3h and filtered out from the hot acidic solvent. The obtained

material was washed several times with warm water. Then the recovered material was well

PT
dispersed in cold water by sonication followed by centrifugation several times. The separated black

colored material was dried and used for further characterization and composite preparation.

RI
2.2.2 Preparation of pristine Cu

SC
The Cu nanoparticles were prepared via typical experimental procedure, 0.01 M of

CuSO4.5H2O were well dissolved in 50 mL of deionized water and stirred for 30 min to obtain a

U
homogeneous solution. Then, 0.1 M NaOH aqueous solution was added quickly until pH of the

N
solution reached 10. Finally, 1 ml of M of hydrazine hydrate was added dropwise into the solution
A
under constant stirring. The reduction reaction was performed in a single step under reflux
M

treatment at 80 °C for 1 h. The shiny brown colored particles were precipitated and it was separated

by centrifugation and washed using deionized water and anhydrous ethanol several times. The
D

obtained final shiny brown product was collected and dried in vacuum at 80 °C for 6 h[24].
TE

2.2.3 Synthesis of pristine Bi2Ti2O7 and binary CBT nanocomposite


EP

The pristine Bi2Ti2O7 particles were synthesis through a simple co-precipitation method.

Initially, Titanium isopropoxide and bismuth nitrate stock solutions were prepared for the synthesis
CC

of pristine Bi2Ti2O7. To produce stock solution A, 0.1 M of Titanium isopropoxide was hydrolyzed

in deionized water to form a white precipitate of titanium hydroxide/oxyhydroxide. The obtained


A

white precipitate was dissolved in concentrated nitric acid with sonication for 10 min in closed

container followed by the addition of deionized water to maintain an acid concentration at 1 M.

bismuth nitrate stock solution was prepared by dissolving 0.1 M of solid bismuth nitrate in nitric

8
acid of 1 M concentration and labeled as solution B. Equal volumes of solution A and solution B

were well mixed by stirring at 400 rpm for 15 min followed by the addition of strong ammonium

hydroxide solution until the pH of the solution reached 10. The formation of metal hydroxides

precipitated was observed. The obtained precipitated was collected and washed several times with

PT
deionized water and ethanol and dried at 120 °C. The obtained dried material was finely ground

using mortar and pestle followed by the calcination at 600 °C for 6 h. The binary CBT

RI
nanocomposite was prepared by adding 1 M of Cu nanoparticles after the addition of strong

SC
ammonium hydroxide solution and subsequent washing and heating process was done as same as

the above reaction process

U
N
A
M

2.2.4 Synthesis of ternary CBTG capsules

The ternary CBTG capsules was prepared by a simple hydrothermal assisted self-assembly
D

process (Scheme. 1). The as-prepared CBT nanocomposite were well dispersed in 150 ml of
TE

deionized water by constant sonication until a uniform dispersion was observed. The surface of
EP

CBT composite was tuned as positively charged by adding acetic acid (dropwise) and the pH of

the suspension is maintained at ~3. Then, rGO was well dispersed in deionized water by sonication
CC

and the pH of rGO dispersion is maintained at ∼8 using ammonium hydroxide. The tuned surface

charge of rGO and CBT is examined by the Zeta potential analysis and shown in Fig. S1. The basic
A

medium results to the deprotonation of the carboxylate groups in rGO surface and it becomes

negatively charged. Then 0.5 wt% of rGO suspension (with respect to CBT) was added to the

surface tuned CBT dispersion. The mixing of positive and negative charged suspension causes an

9
instant flocculation due to self-assembly of oppositely charged components and also results in a

transparent supernatant[15]. The obtained flocculated matrix with supernatant was quickly

transferred to an autoclave and maintained at 160 °C for 4 h and after that, the reaction mixture

was allowed to cool slowly until it attains room temperature. The hydrothermally treated

PT
flocculated matrix was well centrifuged to separate supernatant, followed by drying and annealing

of the sample at 120 °C for 6 h and the obtained black sample is labeled as CBTG.

RI
2.3 Characterization techniques

SC
The crystalline phase and structure of as-prepared photocatalyst were examined by powder

X-ray diffractometry (XRD) using a (Rigaku Miniflex X-ray diffractometer equipped with Cu Kα

U
(λ = 1.54 Å) radiation source operating at 40 kV with 30 mA. The X-ray diffraction patterns were
N
recorded for 15 min with the continual scanning rate of 4° min-1 in the wide range of 2θ = 20–80°.
A
The chemical states of as-prepared photocatalyst were analyzed by X-ray photoelectron
M

spectroscopy (XPS) measurement was analyzed by Krotas analytical Instrument, Shimadzu

Corporation, ESCA 3400, Japan, with Dual Mg/Al anodes and operating voltage at 12 kV with 25
D

mA under ultra-high vacuum condition. The functional groups in catalytic materials were analyzed
TE

by recording Fourier transform infrared (FTIR) spectra using Brucker Tensor 27


EP

spectrophotometer in the range of 4000–400 cm-1 at solid KBr phase. Raman analysis was carried

out using a LabRAM HR Horbia Micro Raman spectrometer. The morphological characteristics
CC

of the as-prepared nanostructures were characterized by field emission scanning electron

microscope (SEM, Zeiss18 Evaluation) and transmission electron microscopy (Jeol/JEM 2100).
A

The high-resolution transmission electron microscopy (HR-TEM) was performed by LaB6 electron

gun with an acceleration voltage of 200 kV and was analyzed by digital micrograph software. The

optical characteristics of as-prepared catalyst were analyzed by UV-Vis diffuse reflectance

10
spectrometer (DRS) (SHIMADZU-UV 1800) in the wavelength range λ=200–800 nm. The

photoluminescence (PL) properties were examined by with Perkin Elmer LS-45 fluorescence

spectrophotometer at room temperature (excited at λ = 330 nm). The total organic carbon (TOC)

in the photocatalytic degradation reaction was scrutinized by TOC analyzer (Aurora 1030, O-I

PT
Analytical).

2.4. Photocatalytic performance analysis, reactive species identification and degradation

RI
intermediates analysis.

SC
The photocatalytic degradation ability of as-prepared samples was evaluated by the

photocatalytic degradation of pharmaceutical molecules like TC and IBP in aqueous solution under

U
visible light irradiation. In a typical photodegradation process, 0.5 g of catalyst was added to 100

N
mL of 50 mg of pollutant solution. The catalytic reaction mixture was stirred in the dark for 30
A
min to attain an adsorption-desorption equilibrium between catalyst particles and pollutant
M

molecules before visible light illumination. Then the reaction solution was irradiated by the visible

light using a Xenon lamp with 100 W and a visible filter was equipped in front of the light source
D

to avoid irradiation of UV spectrum. The photocatalytic reaction suspension was stirred


TE

continuously during the photocatalytic degradation process. In regular periodic intervals of


EP

irradiation, about 2.5 mL sample solution was collected, centrifuged and then analyzed through

UV-Vis spectrometer. In order to find the stability and reusability of the photocatalyst, several
CC

cycles of pollutant-degrading were implemented. In addition, the reactive species responsible for

the photocatalytic degradation of pollutants were effectively determined by the trapping


A

experiments. Superoxide radicals (O•− • +


2 ), hydroxyl radicals ( OH) and holes (h ) were examined by

adding BQ (O2•− -suppressor), IPA (•OH-suppressor) and TEOA (h+-suppressor), all the above

substances were taken in the concentration of 0.1 mmol/100mL[28]. The procedures of active

11
species trapping experiment were similar to the above discussed photocatalytic pollutant

degradation process. The suppressors were added separately into the aqueous tetracycline and IBP

solution before the addition of catalyst. The degradation intermediates produced during the

photocatalytic degradation process of TC and IBP was monitored using liquid chromatography-

PT
time-of-flight mass spectrometry (LC-TOF/MS) and the analysis was carried out in API 4000

Triple TOF 5600 LCQ Advantage MAX instrument. A mixture of water: methanol (70:30, v/v,

RI
2% formic acid present in water) was used as transportable phase and the sample was injected with

SC
flow rate of 1ml/min. The volume of injection of the sample is about 20 µl, with a vaporizer

temperature of about 300 °C. The MS spectra were obtained in the scanning range from m/z = 50

U
to 600 in the positive ion mode.

2.5. Analysis of hydroxyl radical productions N


A
The production of hydroxyl radicals by the prepared nanostructures was analyzed by
M

employing terephthalic acid (TA) as a probe molecule. The reaction process between terephthalic

acid (TA) and hydroxyl radicals occurs to produce 2- hydroxyterephthalic acid (HTA) (a
D

fluorescent molecule)[29]. In the current set of experiments, 0.1 mM of TA solution was dissolved
TE

in 100 ml of deionized water. Furthermore, 0.5 g of catalyst was well dispersed by sonication in
EP

dark for 30 min. Then, the reaction solution was exposed to a xenon lamp. The photon-irradiated

solution in the presence of catalyst was collected and centrifuged to remove the catalyst and the
CC

PL spectrum of the solution was recorded at an excitation wavelength of 315 nm. The PL spectrum

of the solution was recorded periodically with regular interval of time.


A

3. Results and discussion

3.1 Structural Analysis

12
The crystalline phase and structural analysis of the as-prepared rGO, Cu, Bi2Ti2O7, CBT

and CBTG nanostructures were carried out by XRD analysis (Fig. 1a,b). The strong peaks in XRD

diffractogram of as-prepared pure and composite nanostructures show that the obtained products

are highly crystallized in nature. In Fig. 1a, the typical XRD diffractograms of pure Cu and

PT
Bi2Ti2O7 nanostructures where shown, all diffraction peaks of Bi2Ti2O7 can be represented to its

pure cubic phase. The characteristic peaks at 2θ = 14.97°, 30.2°, 32.32°, 34.63°, 38.37°, 48.26°,

RI
52.53°, 58.23° and 62.35° can be indexed to (222), (444), (642), (800), (662), (1042), (1062),

SC
(1244) and (888) planes of cubic phase of Bi2Ti2O7 (JCPDS no. 32- 0118)[1,22,23]. The XRD

diffractogram of Pure Cu nanoparticles shows typical diffraction peaks at 36.35°, 43.09° and

U
50.20° can be indexed to (110), (111) and (200) planes of cubic Cu nanoparticles (JCPDS no. 04-

N
0836)[30–32]. The diffractograms of the CBT nanocomposite shows that all the characteristic
A
diffraction peaks are in good arrangement with the cubic Cu and cubic Bi2Ti2O7 crystallite phases.
M

From the above analysis, it can be extracted that binary nanocomposite is a good composition of

Cu and Bi2Ti2O7 nanoparticles. In Fig. 1b, XRD pattern of as-prepared graphite oxide shows a
D

strong diffraction peak at 2θ = 10.3°, corresponding to the (001) plane of graphite oxide. In the
TE

XRD pattern of RGO nanosheets, the peak at 2θ = 10.3° was disappeared that confirms that GO is
EP

successfully reduced into rGO nanosheets[15]. The presence of Cu, Bi2Ti2O7 and rGO XRD peaks

in nanocomposite confirms the good formation of a ternary nanocomposite. In CBTG


CC

Nanocomposite the characteristic peak of rGO was not clearly visible. It is due to the merging of

Bi2Ti2O7 peak with a characteristic peak of rGO and also due to lower mass percentage
A

composition (5%) of rGO in the ternary nanocomposite. The XRD diffraction peaks on ternary

nanocomposite are significantly widened this is due to the formation of small-sized particles as a

composition of a ternary nanocomposite. The d-spacing of Cu and Bi2Ti2O7 was calculated as 0.21

13
nm and 0.298 nm for pristine Cu and pristine Bi2Ti2O7 from there high intense peak at 2θ= 30.2°

and 43.09° respectively by using Bragg’s law[33,34]. The obtained d-spacing values were

correlated with HRTEM results of respective pristine nanostructures.

3.2 FT-IR Analysis

PT
The chemistry of all the functional groups and surface characteristics of as-prepared

pristine Cu, by pristine Bi2Ti2O7, CBT and CBTG, were further investigated and clarified using

RI
FT-IR spectroscopy and the obtained results were shown in Fig. 2. The catalytic oxidation of

SC
pharmaceutical molecules is highly governed by the functional groups presented on the surface of

catalytic materials. The surface behavior and surface characteristics of the catalytic materials are

U
highly affected by the carboxyl functional groups[12]. The FT-IR spectrum of Pristine Bi2Ti2O7

N
shows the strong absorption peak between 450 cm-1 and 750 cm-1, it confirms the formation of
A
metal-oxygen bonding such as Bi-O-Bi and Ti-O-Ti. The stretching peak of -OH bond vibration,
M

stretching vibration peaks (1000–800 cm−1) of C-O and C-O-C bonds, as well as the symmetric

stretching vibration peak (1384 cm−1) of O-C-O, still can be observed[35,36]. The FTIR
D

spectrograph of Cu nanoparticles and all other as prepared nanostructures shows the wider
TE

absorption peak at 3400 to 3800 cm-1, it corresponds to the N-H stretching vibration of amino
EP

groups and the hydroxyl stretching vibrations of water molecules adsorbed on the surface of

nanoparticles[10]. Besides, no peak of Cu nanoparticles is observed in FTIR analysis because Cu


CC

is inactive for infrared spectra. In the case of CBTG ternary nanocomposite, the peaks at 939 and

811 cm-1 are observed with less intense than the pristine nanostructures it is due to the binding of
A

pristine nanoparticles with the surface of rGO[28]. The band at 1632 cm-1 is developed due to the

metal-O-C vibration of Bi and Ti atoms, they are suggesting the effective atomic interaction

between Bi and Ti with carbon atoms of rGO[15]. In addition, the absorption peak signals in the

14
range between 450 and 700 cm-1 can be attributed to the metal-oxygen bonding such as Ti-O-Ti

and Bi-O-Bi bonding resulting on the surface of rGO[15]. The most of the oxidized functional

groups are disappeared in CBTG nanocomposites and the presence of metal-oxygen bonding

groups shows the successful incorporation of both Bi2Ti2O7 and Cu nanoparticles on the surface

PT
of rGO sheets. The chemical bonding in the as-prepared nanostructures were further studied by

Raman spectroscopic analysis (Fig. S2). In Fig. S2a, two typical peaks of GO was observed at

RI
1358 cm-1 is attributed to the D band which is A1g symmetry’s defect-mediated breathing mode

SC
and 1576 cm-1 is attributed to the G band which is E2g mode’s first-order scattering. The little shift

of D and G bands in CBTG (Fig. S2d) was observed after the thermal treatment clearly shows the

U
formation of additional graphene domains. The Raman spectrum of Bi2Ti2O7 nanostructure is

N
shown in Fig. S2b. The two vibration bands at 197 cm-1 and 630 cm-1 attributes to the Eg
A
vibrational modes of Ti-O. The Vibrational modes at 123 cm-1 and 232 cm-1 are attributes to the
M

stretching vibrations of of Ti-O in Bi2Ti2O7. The apparent peaks at 421 cm-1 and 295 cm-1 are

assign to the Bi-O vibrational modes [22,34]. The vibration mode at 154 cm-1 is due to the
D

formation of Bi2Ti2O7 nanostructures. The little peak shift towards lower wavenumber is occurred
TE

in the CBTG nanostructures when compared with Bi2Ti2O7 and it is due to the electrostatic
EP

interaction and assembly between rGO and Bi2Ti2O7 nanostructures. The combination results of

FTIR and Raman reveals the formation of electrostatically assembled rGO with CBT
CC

nanostructures.

3.3 Morphological characterization and elemental analysis


A

The detailed morphological properties of as-prepared pristine Cu, Bi2Ti2O7, CBT and

CBTG capsules were revealed by using SEM and High-resolution TEM (HR-TEM)

characterization techniques. The formation of crumpled sheet-plike rGO with folding and wrinkles

15
on its surface were obtained in both SEM and HR-TEM images Fig. 3(a,b) and Fig. 4(a,b). The

SEM images of the pristine Bi2Ti2O7 as present in Fig. 3(c,d) reveals the formation of spherical

shaped nanoparticles with uniform size and homogeneous agglomeration. The pristine Cu

nanoparticles are shown in Fig. 3(e,f) are found to have a spherical structure with freely dispersed

PT
with each other, this freely dispersing ability of Cu nanoparticles will results with good attachment

of Cu nanoparticles with Bi2Ti2O7 nanostructures and shown in Fig. 3(g,h) .The SEM and TEM

RI
images of CBTG capsules are shown in Fig. 3(i,j) and Fig. 5 respectively, revealed the formation

SC
of well agglomerated spherical and ellipsoidal shaped CBTG capsules with the size of about ̴150

nm. Formation of such inorganic oxide with graphene or graphene-like material has been also

U
reported in similar studies[13,15]. The difference between the TEM images of Cu and Bi2Ti2O7

N
nanoparticles with CBTG capsules are presented in Fig. 4 and Fig. 5. The size of CBTG capsules
A
is comparatively larger than the pristine Cu and Bi2Ti2O7 particles due to the binding between the
M

Cu and Bi2Ti2O7 nanostructures with the rGO sheets. Furthermore, the results showed that the Cu

nanoparticles and the pyrochlore Bi2Ti2O7 nanostructures are well encapsulated in the rGO
D

nanosheets. Such a tight contact between the surface of Cu and Bi2Ti2O7 nanostructures with the
TE

rGO sheets is desired for the reasons Introduced and is expected to support the photocatalysis
EP

process. The encapsulation of the nanoparticles is mainly due to the electrostatic interaction

between the nanoparticles and rGO sheets[37]. The surface contact between nanoparticles and rGO
CC

sheets was highly increased due to the enrichment of surface charges of pristine nanoparticles and

rGO sheets during synthesis. The obtained results indicate that electrostatic self-assembly
A

approach assisted the encapsulation of Cu and Bi2Ti2O7 nanostructures with the rGO sheets.

During the electrostatic self-assembly process, the wrapping of the rGO sheets can be expected to

continue until the attainment of charge neutralization between the positively charged CBT surface

16
and the negatively charged rGO surface[15,38]. If the rGO loading is higher, the excess rGO sheets

are expected to remain in the reaction solution without wrapping around the nanostructures, due

to the lack of positively charged CBT surface. From the HRTEM images of pristine Bi2Ti2O7, CBT

and CBTG capsules the presence of Cu and Bi2Ti2O7 nanoparticles can be clearly identified from

PT
the respective lattice fringes. The fringe lines with a spacing of about 0.298 nm are due to the

formation of cubic Bi2Ti2O7 particles and that of 0.21 nm corresponds to the Cu nanoparticles. The

RI
purity of as-prepared pristine nanomaterials and nanocomposites were further confirmed by energy

SC
dispersive X-ray analysis (EDX) and the results show that the materials were highly pure in nature.

The presence of Cu and Bi2Ti2O7 particles in CBTG capsules were confirmed by using EDX

U
analysis as presented in Fig. 6.

N
A
3.4 Chemical state analysis
M

The XPS spectra of CBTG and Bi2Ti2O7 nanostructures were show in Fig. 7 and Fig. S3,

and the survey spectrum of CBTG and Bi2Ti2O7 sample was displayed in Fig. 7a and Fig. S3a,
D

respectively. The survey spectrum reveals the presence of Cu, Bi, Ti, O and C. The high-resolution
TE

XPS analysis of the Cu-2P, Bi-4f, Ti-2p, O-1s and C-1s for this CBTG capsule was also studied
EP

and represented in Fig. 7(b-f). The high-resolution XPS spectrum of Bi-4f region shown in Fig. 7b

is dominated by Bi-4f7/2 and Bi-4f5/2 components with the peaks observed at 157.02 and 158.08
CC

eV for Bi-4f7/2 whereas, 162.4 and 164.4 eV for Bi-4f5/2[39,40]. The XPS spectra of Bi-4f region

for pristine Bi2Ti2O7 nanostructure is shown in Fig. S3b. It is dominated by Bi-4f7/2 and Bi-4f5/2
A

components with the peaks observed at 157.8 and 159.5 eV for Bi-4f7/2 whereas, 163.3 for Bi-4f5/2.

The peaks at 158.8 and 164.4 eV with little peak shift of about 1 eV from the XPS analysis of pure

Bi2Ti2O7 can be attributed to the interaction between pyrochlore bismuth titanate and rGO sheets.

17
The binding energy of the Bi-4f7/2 component 157.02 and 158.08 eV has an intermediate value

between bismuth metal (156.85 eV) and typical Bi(III) oxides (159.0 eV to 159.8 eV)[1]. In Fig.

7c, two peaks were observed at the binding energies of about 464.8 eV and 459.1 eV, which are

attributed to the Ti-2p1/2 and Ti-2p3/2 states for CBTG nanocomposite, respectively and in case of

PT
Bi2Ti2O7 the peaks of Ti-2p1/2 and Ti-2p3/2 states were observed at 464.6 and 458.9 eV, respectively

[41,42]. A characteristic Ti-2p spin-orbit splitting of 5.6 eV ascribes to a normal state of Ti4+ in

RI
CBTG capsules. The peak at 464.8 eV is also due to the partially overlapped Ti-2p1/2 and Bi-4d3/2

SC
peaks. The XPS spectra of Cu-2p is illustrated in Fig. 7d with two peaks at 933.4 eV and 953.1 eV

for Cu-2p3/2 and Cu-2p1/2, respectively, with the splitting of about 20 eV which evidence towards

U
the producing metallic Cu by reducing CuSO4 during the hydrothermal process. The high-

N
resolution O-1s spectra of CBTG capsules is presented in Fig. 7e. The two peaks identified at 530.5
A
eV and 531.68 eV are attributed to Bi-O lattice oxygen and Ti-O lattice oxygen bonds,
M

respectively. More specifically, the existence of the peak at 531.05 eV is credited to the surface

adsorbed -OH group and chemisorbed oxygen-containing species and may be in favor of the
D

enhancement in photocatalytic properties[15,43]. The interface between CBT and rGO was further
TE

probed by high-resolution XPS analysis of element C1s and is presented in Fig. 7f. The
EP

deconvolution of the obtained C-1s XPS spectra shows two peaks at 284.4 eV and 287.5 eV

corresponding to graphitic −C−C and –O–C=O functionalities respectively. The –O–C=O


CC

functionalities are will be formed during the strong oxidation of the graphene sheets using

modified hummers method[38]. The deconvoluted peak presented between 286 eV to 289 eV is
A

comparatively less intense than that of GO. The significant decrement in oxygenated carbon

species in CBTG capsules is due to the reduction of GO into rGO during the hydrothermal reaction.

This results revealed that the GO is considerably reduced after the hydrothermal reaction process

18
to form rGO and it’s composite with CBT. The existence of –O–C=O shows the formation of

metal-oxygen binding as Ti-O-C=O through the reduction of Ti-OH in Bi2Ti2O7 and COOH groups

at the surface of the graphene[15].

3.5 Valence band analysis

PT
The energy band edge positioning is the predominant parameter for developing excellent

photocatalytic materials. The adjustment of the band edges towards the desired potential levels

RI
will effectively enhance the light harvesting efficiency and will promote the utilization of charge

SC
carriers for oxidation and reduction cycles during photocatalytic activity[10]. The band edge

adjustments can be greatly succeeded by introducing new energy levels and narrowing the band

U
gap energy during nanocomposite formation[44]. The introduction of metal nanoparticles and

N
graphene sheets can effectively bend the band edges of materials due to their band energy
A
levels[45,46]. The XPS valence band spectra of Bi2Ti2O7 and CBTG nanostructure is shown in
M

Fig. 8. The extrapolated dominant edge of the valence band spectra can provide the valence band

value of material and it was found to be 1.75 eV and 2.25 eV for CBTG and Bi2Ti2O7
D

nanostructure, respectively. The obtained valence band potential of the Bi2Ti2O7 nanostructure is
TE

higher than the redox potential of O2/H2O (1.23 eV) and hence Bi2Ti2O7 nanostructure can
EP

effectively split H2O molecules to generate active species[12]. The shifting of valence band

towards conduction band could decrease the band separation energy thereby it results with the
CC

improved production of active species during the photocatalytic process. The XPS valence band

spectrum of Bi2Ti2O7 nanostructure is shown in Fig.8b. The valence band edge of the Bi2Ti2O7
A

capsule is found to be 2.39 eV. The obtained valence band edge value is well matching with the

calculated valance band edge value of Bi2Ti2O7 capsules.

3.6 Optical Investigation

19
The photon absorbing ability of a semiconductor is inseparably linked to its electronic

structure and it is considered as the predominant factor responsible for its photocatalytic

activity[14]. The optical properties of the as-prepared Cu, Bi2Ti2O7, CBT and CBTG

nanostructures were characterized by UV-Vis DRS spectroscopy and is presented in Fig. 9. From

PT
Fig. 9a, it is extracted that all the as prepared nanostructures show strong absorbance in the visible

light region. Predominantly, the absorption spectra of CBT and CBTG capsules shows distinctly

RI
improved visible-light absorption compared to other photocatalysts. While comparing with

SC
pristine Bi2Ti2O7, ternary nanocomposite showed the shift towards the red on photon absorption

edge at 460 nm. The photon absorption band edges of Bi2Ti2O7 and CBT were found to be 452

U
and 470 nm respectively. The characteristics absorption peaks of Cu nanoparticles were observed

N
around 570 nm, this could be attributed to the surface plasmon resonance occurred in the
A
conduction bands of Cu nanoparticles. The surface plasmon resonance effect is due to the
M

generation of strong electromagnetic fields at the surface of metal particles when a wavelength of

incident light coincident with surface plasmonic optical absorption. In previous research
D

endeavors, the surface plasmon resonance of Cu nanoparticles was in the absorption range between
TE

550-590 nm because free electrons present in the conduction bands were persuaded and oscillated
EP

by photons[47]. In addition to that, another optical absorption peak at 500 nm was observed for

the prepared Cu nanoparticles. This variation of optical absorption can be ascribed due to the
CC

negligible difference in geometry from particles to sheets and it will affect the scattering of photons

to a diverse extent[48]. When Cu nanoparticles composites with the metal oxides it enhances the
A

absorption of photons in visible region due to surface plasmon resonance. The improvement in

photon absorption ability of CBT is due to either improvement in charge transfer from electrons

excited from plasmon resonance in Cu to conduction band of Bi2Ti2O7 or due to the enhancement

20
of the local electric field, where electron-hole pair generation rate becomes much faster[49]. When

the Cu and Bi2Ti2O7 nanostructures were encapsulated with rGO the absorption spectra of CBTG

capsules shows very close absorption edge with CBT nanocomposite. The encapsulation of pristine

Cu and Bi2Ti2O7 nanostructures slightly decreases the light absorption ability, this may be due to

PT
the complete encapsulation of nanostructures within the rGO sheets[37]. But the composition of

CBT and the encapsulation of these nanostructures with rGO shows better photonic absorption

RI
than the pristine Bi2Ti2O7. According to the above observation, it can be extracted that CBTG

SC
capsules can absorb visible light on a more effective way. In general, the photon absorption ability

of photocatalyst is often associated with its band gap energy. The band gap energy of the as-

U
prepared nanostructures can be determined by using Tauc plot[28]. The plots of (αhν)2 vs hν of as-

N
prepared samples are presented in Fig. 9b. The intercepts of an extrapolated linear line of the curves
A
at x-axis allow the calculation of the band gap energies of Bi2Ti2O7, CBT and CBTG
M

photocatalysts. By applying this equation the band gap energies of pristine Bi2Ti2O7, CBT and

CBTG was found to be 2.88, 2.75 and 2.79 eV, respectively, suggesting that the CBT and CBTG
D

photocatalysis does not have huge difference in photon absorption ability but decrement in
TE

recombination rate of (e- - h+) will effectively increase the photocatalytic ability and it is discussed
EP

in the next section.

3.7 PL analysis
CC

The photocatalytic performance of nanostructures was closely associated with the

separation and recombination dynamics of photo-induced electrons and holes. The PL spectra of
A

the as-prepared nanostructures, as well as the CBTG capsules, can provide the information about

their photo-induced electron-hole (e--h+) pair separation efficiency[12]. The (e--h+) pair

recombination rate can be directly measured by the intensity of the PL spectrum of the respective

21
materials. If the PL spectrum of the nanostructure is more intense, then recombination of (e--h+)

pair is expected to be higher. Otherwise, the lower PL intensity indicates that the more

photoexcited electrons were trapped and firmly transferred through the interface of catalyst[10].

As presented in Fig. S4, a strong and wide emission band was observed between 370 to 420 nm in

PT
the PL spectra of Bi2Ti2O7 it is corresponds to the bound excitons[1]. When the Cu nanoparticles

are incorporated with pristine Bi2Ti2O7, the PL intensity was highly decreased. It is due to the

RI
existence of Schottky barriers at Bi2Ti2O7 and Cu interface, the Cu nanoparticles will act as an

SC
electron trap to preventing recombination of (e--h+) pairs[13,50]. The PL intensity was decreased

further when rGO is introduced with the binary composite. The reason for the decrement in PL

U
intensity is due to the rapid delocalization of photo-excited electrons to the rGO sheets and

N
reducing the (e--h+) pair recombination probability[16]. In addition, little red-shifts were observed
A
in the PL spectra, after incorporating rGO with the CBT nanocomposite. It may be attributed to
M

molecular conjugation between Bi2Ti2O7 with Cu nanoparticles and rGO sheets. These results

clearly state that the as-prepared CBTG capsules not only enhances the light absorption ability but
D

also constrains the photoinduced (e--h+) pair recombination which is more responsible for
TE

enhancing its photocatalytic performance.


EP

3.8 Photocatalytic examination and degradation kinetics of pharmaceutical contaminations


CC

The photocatalytic pharmaceutical contamination degradation potential of the as-prepared

materials was examined by using TC and IBP as a target model pharmaceutical molecule under
A

visible light irradiation for 90 min. The temporal concentration of TC and IBP molecules were

found by UV-Vis analysis with the difference in their peak intensities in regular periodic time

intervals and the degradation rates of TC and IBP was shown in Fig. 10. The Figure shows that the

22
photocatalytic degradation rate of both TC and IBP was higher when using CBTG ternary

nanocomposite than the pristine Bi2Ti2O7, and binary nanostructure as the photocatalyst. The self-

stability of TC and IBP molecules were tested by dissolving them in deionized water and the results

reviled that the TC and IBP molecules were highly stable in the aqueous solution, it is due to self

PT
photodegradation of TC and IBP molecules are very slow. The photodegradation TC was found to

be 49%, 74% and 92% and in the case of IBP, the photodegradation rate was found to be 41%,

RI
66% and 84%% in presence of pristine Bi2Ti2O7, CBT and CBTG, respectively. To analyze the

SC
self-degradation property of TC and IBP, the photocatalytic degradation examination was

performed in absence of a photocatalyst. The catalytic ability of CBTG was also analyzed in

U
absence of visible light irradiation. In both TC and IBP degradation it is observed that the

N
photocatalytic ability of CBTG is much higher than the pristine and binary nanocomposite.
A
Additionally, to examine the practical assessment of CBTG, the comparative photocatalytic
M

experiment with P25-TiO2 was also carried out. The results showed that the photocatalytic activity

of P25-TiO2 is much lower than that of CBTG composite. From the obtained results it was found
D

that the composition of rGO with CBT was able to enhance the photocatalytic performance and
TE

the due to the presence of an oxygen-containing groups like ketonic (C=O) groups with several
EP

zig-zag edges in rGO, it is catalytically active towards organic element degradation. More

specifically, these zig-zag ketonic groups are highly active due to the presence of the surplus
CC

amount of electrons and this behavior results to the great ability towards co-ordination of redox

reaction process[13,38]. Consequently, the addition of rGO to the CBT enhances the synergetic
A

effect in the photocatalytic activity and the reactive species generation. The enhancement in

chemical reactions at active sites and relative mass transfer rates is analogous to some other

photocatalytic systems like TiO2-rGO[46], MnFe2O4-rGO[51], CoFe2O4/rGO[52], and Co3O4-

23
rGO[37]. Furthermore, the photocatalytic degradation kinetics of TC and IBP were studied in

presence of as-prepared photocatalyst and P25-TiO2 photocatalyst. The results suggest that

𝐶
degradation of TC and IBP follows the pseudo first-order kinetics as following ln (𝐶𝑡 ) = 𝑘𝑎𝑝𝑝 𝑡,
𝑜

where, Ct and C0 are the temporal concentration at time t and initial concentration of

PT
pharmaceutical molecules respectively and kapp is the apparent first order photoreaction rate

constant per minute[12]. From Fig. 10 (e &f) it can be extracted that CBTG shows enhanced

RI
photocatalytic degradation ability than CBT, P25-TiO2 and Pristine Bi2Ti2O7 nanostructures

SC
towards both TC and IBP degradation. The photocatalytic degradation rate constant of CBTG is

kapp= 3.08×10-2 and 2.68×10-2 for TC and IBP degradation respectively. The degradation rate

U
constant of CBTG is 7.7 times greater than P25-TiO2 and 1.8 times greater than CBT towards TC
N
degradation and 8.9 times greater than P25-TiO2 and 1.9 times greater than CBT towards IBP
A
degradation. The reduction of total organic carbon in the photocatalytic degradation reaction
M

solution of TC and IBP in presence of P25-TiO2 and as-prepared nanostructures under visible light
D

irradiation is shown in Fig. S5. The P25-TiO2, Bi2Ti2O7, Cu, CBT and CBTG nanostructures
TE

exhibits 22.4, 41.3, 7.2, 70.5 and 92.6 % of TOC removal in TC degradation reaction and 13.4,

32.1, 4.7, 59.2 and 72.6% of TOC removal in IBP degradation reaction, respectively. These
EP

obtained results suggest that photocatalytic degradation ability is highly improved when rGO and

Cu are composited with Pristine Bi2Ti2O7.


CC

3.9 Effect of operational parameters


A

3.9.1 Effect due to initial pH of the solution

The organic pharmaceutical molecules usually have a wide-spread range of pH value and

hence pH of the reaction will play an important role in the characteristics of pharmaceutical

molecule and also it influences on the surface charge properties of photocatalyst, the charge of

24
pharmaceutical molecules, the size of catalytic aggregate formation, adsorption of pharmaceutical

molecules onto catalytic surface and the concentration of hydroxyl radicals (•OH)[38]. The

photocatalytic efficiency of CBTG for degradation of TC and IBP in different initial pH of the

reaction solution varies from acidic to alkaline condition by using CBTG as photocatalytic material

PT
is presented in Fig. S6. From the obtained results it is found that the photodegradation of IBP and

TC molecules depends on the pH levels of the reaction solution. The results showed that an

RI
increase in the pH level of the reaction solution from 3 to 10, the photocatalytic degradation

SC
efficiency is also parallel for both TC and IBP. The photocatalytic degradation of both TC and IBP

molecules were gradually decreasing when the pH of the reaction solution increased above 10. But

U
the degradation rate of both the pharmaceutical molecules is slightly similar at pH values of 7-10.

N
From the obtained results it is found that the optimum pH for efficient photocatalytic degradation
A
of TC and IBP molecules by CBTG photocatalyst is 7. The photocatalytic degradation efficiency
M

of catalyst depends on the ability of adsorption of TC and IBP. The adsorption of pharmaceutical

molecules is influenced by the ionic nature of pharmaceutical molecules and the surface ionic
D

nature of photocatalyst. The TC and IBP molecules are highly cationic nature and hence they will
TE

exist as positive ions at neutral pH and the surface charge of the photocatalyst can be easily
EP

modified by changing the pH of the reaction solution[28]. The photocatalytic surface will become

more anionic if the pH of the reaction solution is increased above 7. The electrostatic force of
CC

attraction between negatively charged CBTG photocatalyst and positively charged pharmaceutical

molecules may lead to sturdy adsorption of pharmaceutical molecules on the surface of CBTG
A

photocatalyst. The higher adsorption of pharmaceutical molecules on the photocatalytic surface

leads to higher photocatalytic degradation.

3.9.2 Effect due to the initial concentration of pharmaceutical contaminations

25
The effect of the initial concentration upon the photocatalytic degradation of TC and IBP

by CBTG photocatalyst is illustrated in Fig. S7. The photocatalytic degradation of both TC and

IBP was examined in their various initial concentration (25, 50, 75, 100 and 125 mg/L) while all

the rest parameters were maintained as explained in typical photodegradation reaction. The

PT
obtained results from Fig. S7 shows that the photocatalytic degradation rates of both TC and IBP

were slowly decreased when increasing the pharmaceutical molecule concentration. The

RI
decrement in photocatalytic degradation of pharmaceutical molecules at higher initial

SC
concentration is due to the insufficient amount of reactive species generation by the photocatalytic

materials to degrade such a higher amount of pharmaceutical molecules[38]. The photon

U
penetration ability through the reaction solution also plays a major role in the activation of the

N
photocatalyst to generate the reactive species results in the degradation of pharmaceutical
A
contamination [27,53–55]. But in a higher initial concentration of pharmaceutical contamination,
M

the incident light gets screened by the pharmaceutical molecules and thus screening effect

decreases the possibility of light to reach the photocatalyst and results to the shrinkage of
D

photocatalytic performance.
TE

3.10 Reaction pathway of Tetracycline degradation


EP

The photocatalytic degradation pathways of TC molecules was studied by identifying the

degradation intermediates formed during photocatalytic degradation process and the formation of
CC

degradation intermediates of TC molecules was scrutinized by LC-TOF/MS (Fig. S8). In the basis

of previous research studies the two possible degradation pathways during photocatalytic
A

degradation process, several intermediates are formed.

Initially, the peak with m/z of 445 was detected by LC-TOF/MS analysis and it corresponds

to TC molecules. In the period of time with photocatalytic degradation of TC, several additional

26
peaks were appeared along with TC degradation (they are m/z = 461, 434, 394, 375, 172, 208, 416,

171, 402, 357, 191). By combining these detected results through LC-TOF/MS analysis and

previous research literatures the degradation process of TC molecules could be anticipated as two

major pathways[1,2]. The schematic diagram of first and second possible TC degradation pathway

PT
is shown in Fig. 11a,b. The first possible TC degradation pathway showed that the intermediate

molecule (T1) with the m/z of 461 appeared from a cycloaddition of •OH radical to the 11C-12C

RI
double-bond. Due to the incessant visible light irradiation, several active species such as •OH,

SC
•O2−, and h+ are formed by photocatalyst and continuously attacks the TC molecules and its

intermediates. Due to the unremitting attacking of intermediates by reactive species several

U
secondary degradation products of TC is formed with lower molecular weight. The molecular

N
compound (T2) with m/z of 434 was formed by removal of two methyl groups from a tertiary
A
amine of T1. Subsequently, the product (T3) with m/z of 394 was detached off a formamide. The
M

hydroxyl group from T3 was removed to produce the intermediate product T4 and it was detected

by m/z of 375. In further, the degradation products with m/z of 172 (T5) and 209 (T6) formed by
D

the contravention of 5C-6C bond and 11C-12C bond of T4. The second possible degradation
TE

pathway of TC molecules was should be occurred as a couple of methyl groups were initially
EP

detached from the TC molecule and produces the intermediate m/z of 416 (T7). The removal of an

amino group connected on the 5C was removed and it was detected with m/z of 402 (T8), Followed
CC

by the formamide deductions with m/z of 358 (T9). Consequent attacking of reactive species to

the reaction intermediates results to the formation of two additional ions at m/z of 173 (T10) and
A

191 (T11). These T10 and T11 intermediates were formed by the breaking of 5C-6C and 11C-12C

bonds. From obtained above results it can be seen that TC molecules were gradually degraded and

the relevant degradation intermediates were formed and then decomposed. At last these substances

27
were converted into carbon dioxide, water, NH4+ and other organic degradation products. During

the photocatalytic degradation process, these TC intermediate products predominantly stopped

from the degradation of TC molecules after breaking down of some active groups from the

collision of bridge ring[6]. The remaining positions were unfit to be attacked by the reactive

PT
species frequently locating at the hydroxyl, methyl, formamide, third amine and the band of 5C-

6C and 11C-12C. Still, the photocatalytic degradation of TC molecules was a highly complicated

RI
process, and further studies should be carried out to understand the degradation process clearly.

SC
3.11 Reaction pathway of ibuprofen degradation

The photocatalytic degradation pathway of IBU molecules was studied by identifying the

U
intermediate molecules formed during the photocatalytic degradation process and the formation of

N
degradation intermediates of IBU molecules was examined by LC-TOF/MS. The identification of
A
organic molecules present in the photocatalytic degradation reaction solution was carried out
M

initially at 0 min and finally at 90 min of degradation reaction and the obtained MS spectra is

shown in Fig. S9. The MS spectra of the initial reaction solution show the presence of IBU with
D

m/z = 205. The MS spectral results of the reaction solution after 90 min of catalytic degradation
TE

shows the efficient removal of IBU with the formation of intermediate products like aromatic
EP

carboxylic acids and Phenolic compounds. By combining the obtained MS analysis and previous

literature survey the possible degradation pathway of IBU molecules was proposed in Fig. 12.
CC

The MS spectra of the reaction solution after 90 min of catalytic degradation shows the

presence of hydroxy-ibuprofen as an intermediate molecule with m/z = 221 (B1) and another peak
A

at m/z = 177 (B4) corresponds to the presence of 1-(4-isobutyl-phenyl)-ethanol[56]. The formation

of B4 is due to the decarboxylation of B1 intermediate. The direct decarboxylation of IBU

molecule is occurred to form with m/z = 175 (B2). The peak formed at m/z = 177 (B3) is

28
corresponds to 1-(4-ethyl-phenyl)-2-methyl-propan-1-ol. The intermediate B3 is formed by the

reaction of B2 intermediates with hydroxyl radicals. Thus produced B3 and B4 intermediates

during the photocatalytic degradation process further losses C3H9 to produce 4-ethylbenzaldehyde

with m/z = 134 followed by the opening of benzyl rings due to the rapid reaction of reactive species

PT
with 4-ethylbenzaldehyde and produces CO2 and H2O[57].

3.10 Hydroxyl radical production analysis

RI
The production of •OH radicals from the as-prepared CBTG photocatalyst under visible

SC
light irradiation was analyzed by terephthalic acid (TA) as a probe molecule as described in the

experimental section. The absence of an absorbance peak in PL graphs represents no emissions

U
from the TA solution. When CBTG photocatalyst was added to the TA solution, the broad peaks

N
with emission at 425 nm represents the formation of 2-hydroxyterepthalic acid (HTA)[29]. The
A
HTA molecules are formed by the reaction of hydroxyl radicals with TA molecules which are
M

generated by the CBTG photocatalyst and it is confirmed by PL spectrographs as shown in Fig.

S10. The increasing peak intensity with the visible light irradiation in presence of photocatalyst
D

indicates the formation of a large number of HTA molecules and it results from the increase in
TE

production rate of the •OH radicals in the solution. The obtained results clearly showed that the
EP

CBTG photocatalyst can produce •OH radicals in a more efficient way. In the general pathway of

photocatalytic reaction, when the photocatalytic material is irradiated by photons with the
CC

appropriate wavelength, it excites the electrons from the valence band (VB) to the conduction band

(CB) and leaving the equivalent holes in the valence band (VB). When this electron charge
A

separation is continued in photocatalytic material, the pharmaceutical molecules either oxidized or

reduced through the acceptance or donation of electrons. The redox reaction is the key aspect of

the photocatalytic process and they are mainly determined by the band edge position of

29
photocatalytic materials[36]. In the case of CBTG photocatalyst, the electrons excited from VB to

CB of Bi2Ti2O7 are trapped by the Cu nanoparticles and the graphene sheets. Thus the trapping of

electrons will restrict the recombination of e--h+ pairs and in parallel the redox process will occur

rapidly. The reaction of holes with OH‾ ions leads to the generation of •OH radicals. When the

PT
electrons are trapped by Cu and rGO sheets, more amount of holes will react with OH‾ ions to

produce a higher amount of •OH radicals. In further, these •OH radicals react with the

RI
pharmaceutical molecules and leads to the effective degradation of pharmaceutical molecules. In

SC
addition, the holes have a capability to react directly with pharmaceutical contaminations and

degrade the molecules[28]. Hence, the observed net enhancement in photocatalytic degradation

U
efficiency of CBTG photocatalyst is attributed to the effective charge carrier separation which is

N
achieved by trapping excited electrons in photocatalyst[58]. The delocalization of electrons in CB
A
restricts their recombination with holes. So, these trapped electrons and separated holes were
M

effectively reacted with surrounding medium and results to the effective photocatalytic

degradation of pharmaceutical molecules.


D

3.11 Stability and recyclability analysis


TE

The catalytic stability is a significant parameter that describes the effectiveness of a


EP

photocatalytic material and can lead to a significant cost reduction of the pharmaceutical

contamination removal treatment if it is used for longer time slots. The reusability and stability of
CC

CBTC composite can be verified by performing a series of cycling experiments performed with

optimal CBTG and the curves for 5 cycles of photocatalytic degradation of TC and IBP is shown
A

in Fig. S11a,b. This stability verification experiment was carried out for a protracted period of time

(460 min) under typical photocatalytic reaction conditions. From the recycling experiments very

small reduction in photocatalytic performance of CBTG was observed after 5 cycles of

30
photocatalytic pharmaceutical molecule degradation. This reduction of ~4% and ~5% in TC and

IBP degradation respectively after 5 cycles of photocatalytic degradation revealed that the as-

prepared CBTG composite can present high stability for practical photocatalytic applications.

Furthermore, the XRD analysis of CBTG was also carried out after 5 cycles of TC and IBP

PT
degradation and the obtained spectrographs didn’t show any phase change in CBTG photocatalyst

(Fig. S11c). That reveals that the CBTG is stable even after 5 cycles of pharmaceutical

RI
contamination degradation.

SC
3.12 Photocatalytic mechanism

During a photocatalytic process, redox reactions occur on the surface of the photocatalyst

U
which successively produces reactive species such as O•− • +
2 , OH and h , which are involved in the

N
photodegradation process of pharmaceutical molecules. The study on the contribution of these
A
oxidative species is important to elucidate the photocatalytic mechanism of CBTG photocatalyst.
M

Hence, trapping experiments of the active species O2•− , •OH and h+ were carried out under visible

light irradiation in presence of their respective trapping agents (as explained in section: 2.4). As
D

shown in Fig. S12, the photocatalytic degradation efficiency of CBTG photocatalyst was
TE

effectively decreased and the degradation efficiency was found to be 23% while adding BQ (O•−
2
EP

radical suppressor). When adding TEOA (h+ suppressor) and IPA (•OH radical suppressor) the

photocatalytic degradation efficiency of CBTG was affected up to 39% and 65% respectively.
CC

These results indicate that the O2•− radicals have the highest contribution than •OH and h+ species

during the photocatalytic degradation of pharmaceutical molecules.


A

The possible photocatalytic mechanism of CBTG composite is proposed in Fig. 13, based

on the previous experimental results. In general, the photo-excited electrons from valence band

31
(VB) to conduction band (CB) are expended by the oxygen molecules adsorbed on the

photocatalytic surface to generate superoxide radicals (O•−


2 ), at the same time holes generated in

the valence band of photocatalytic material are scavenged by the hydroxyl groups to generate

hydroxyl radicals (•OH)[10,59]. On the other hand, holes generated on the VB of the photocatalyst

PT
can directly oxidize the organic pharmaceutical molecules. These generated radicals are utilized

for degrading pharmaceutical molecules. The photocatalytic degradation rate primarily depends

RI
on the concentration of photo-excited e--h+ pair remains without recombination[19]. In case of

SC
CBTG photocatalyst the photoexcited electrons from VB of CBTG are trapped by the Cu

nanoparticles and the rGO sheets which subsequently decreases the e--h+ pairs recombination and

U
it results to the enhanced generation of reactive species like O•− •
2 and OH radicals. In order to

N
understand the electron charge transfer between pristine Bi2Ti2O7 and electron trappers, such as
A
Cu nanoparticles and rGO sheets, the VB and CB band edge positions of pristine Bi2Ti2O7 were
M

calculated using following equations, ECB = χ − E C − 0.5 Eg and EVB = ECB + Eg . where, χ is

the electronegativity of the semiconductor, EC is the energy of free electrons on the hydrogen scale
D
TE

of 4.5 eV, Eg is the band gap of the semiconductor, EVB and ECB are valence band and conduction

band energy[28]. The electronegativity (χ) of Bi2Ti2O7 can be expressed as an arithmetic means
EP

of electron affinity between individual atoms (Bi-0.942362 eV, Ti-0.079 eV, O-1.4611134 eV)

and there first ionization energy of atoms (Bi-7.2856 eV, Ti-6.8281 eV, O-13.6181 eV)[60]. Based
CC

on the above values the VB and CB of Bi2Ti2O7 are found to be 2.36 eV vs NHE and -0.52 eV vs

NHE, respectively. When the Cu nanoparticles and rGO sheets are loaded with Bi2Ti2O7
A

nanostructures the photo-excited CB electrons of Bi2Ti2O7 will transfer to these Cu nanoparticles

and rGO sheets which causes e--h+ pair separation. The excited electrons of Bi2Ti2O7 can be easily

trapped by the Cu metal particles to prolong their lifetime due to their lower redox potential of Cu

32
(+0.35 eV vs NHE) than the CB of Bi2Ti2O7 (-0.52 eV vs NHE)[61]. At the same time due to the

lower Fermi level of rGO (-0.08 eV vs NHE) than the CB of Bi2Ti2O7 (-0.52 eV vs NHE), the CB

electrons of Bi2Ti2O7 will be successfully trapped by the rGO and it will decline the e--h+ pair

recombination enormously by delocalizing photo-excited electrons on Bi2Ti2O7. The enhanced

PT
trapping/delocalization of electrons by Cu nanoparticles and rGO sheets will effectively reduce

the recombination rate of charge carriers and it will effectively lead to the higher generation of

RI
reactive species for the degradation of pharmaceutical contaminations. Finally, the catalytic

SC
reaction of reactive species with pharmaceutical contaminations will mineralize the

pharmaceutical molecules into CO2, H2O, and other organic ions. The possible photoexcited charge

U
carrier delocalization and transportation pathway on CBTG photocatalyst will occur as the

following equations (1) to (9) N


A
Cu/Bi2Ti2O7/rGO + hν → Bi2Ti2O7 (e- + h+) (1)
M

e- + Cu → e- (trapped in Cu) (2)

e- + rGO → e- (trapped in rGO) (3)


D

e- (trapped in Cu) + dissolved O2 → O•− (4)


TE

e- (trapped in rGO) + dissolved O2 → O•−


2 (5)
EP

h+ + H2O→ •OH + H+ (6)



OH + Pharmaceutical molecules → CO2 + H2O + Mineral acids (7)
CC

O•−
2 + Pharmaceutical molecules → CO2 + H2O + Mineral acids (8)

h+ + Pharmaceutical molecules → CO2 + H2O + Mineral acids (9)


A

The above discussed photocatalytic mechanism clearly shows that both Cu nanoparticles and rGO

sheets are acting as an excellent electron tapper to decrease recombination of e-- h+ pairs and it

33
facilitates generation of a large amount of O2•− radicals with successive degradation of

pharmaceutical molecules.

4. Conclusion

In the current work, a novel Cu/Bi2Ti2O7/rGO hybrid photocatalyst was successfully

PT
prepared by following a simple hydrothermal method. The presence of both Cu nanoparticles and

rGO sheets on Bi2Ti2O7 was clearly observed by XRD analysis. The UV-Vis DRS analysis

RI
revealed that the Cu/Bi2Ti2O7/rGO ternary nanocomposite is highly active within the visible

SC
region. The deposition of Cu nanoparticles on Bi2Ti2O7 nanoparticles was analyzed and confirmed

by HR-TEM analysis. The PL analysis revealed that the presence of Cu nanoparticles and rGO

U
sheets on the Bi2Ti2O7 photocatalyst is effectively decreasing the e--h+ pair recombination. The

N
photocatalytic degradation ability of as-prepared pristine, binary and ternary nanocomposite was
A
investigated in detail by using IBP and TC as reference pharmaceutical contaminations. The
M

photocatalytic degradation results revealed that Cu/Bi2Ti2O7/rGO photocatalyst is highly efficient

than other as-prepared nanostructures. The analysis of the obtained results suggested that the Cu
D

nanoparticles and the rGO sheets are playing a major role in the photocatalytic ability of
TE

Cu/Bi2Ti2O7/rGO photocatalyst. From trapping experiments, it was found that O•−


2 radicals can be
EP

massively generated by Cu/Bi2Ti2O7/rGO photocatalyst. The passage of the photoexcited electrons

and its trapping on Cu nanoparticles and rGO sheets were clearly explained in the photocatalytic
CC

mechanism. The degradation of pharmaceutical contamination was also confirmed by LC-

TOF/MS analysis and the possible degradation pathway of TC and IBP is proposed. In addition,
A

the Cu/Bi2Ti2O7/rGO photocatalyst showed higher stability and recyclability even after five cycles

of pharmaceutical contamination degradation. Our strategy of using CB electron trappers on

34
photocatalytic materials are expected to inspire future development of high efficient photocatalytic

materials for pharmaceutical molecule degradation.

PT
RI
SC
U
N
A
M
D
TE
EP
CC
A

35
Reference

[1] L. Jinhai, M. Han, Y. Guo, F. Wang, L. Meng, D. Mao, S. Ding, C. Sun, Hydrothermal

PT
synthesis of novel flower-like BiVO4/Bi2Ti2O7 with superior photocatalytic activity

toward tetracycline removal, Appl. Catal. A Gen. 524 (2016) 105–114.

RI
doi:10.1016/j.apcata.2016.06.025.

SC
[2] F. Chen, Q. Yang, J. Sun, F. Yao, S. Wang, Y. Wang, X. Wang, X. Li, C. Niu, D. Wang,

G. Zeng, Enhanced Photocatalytic Degradation of Tetracycline by AgI/BiVO4

U
Heterojunction under Visible-Light Irradiation: Mineralization Efficiency and Mechanism,

N
ACS Appl. Mater. Interfaces. 8 (2016) 32887–32900. doi:10.1021/acsami.6b12278.
A
[3] G. Sandin, G.M. Peters, Environmental impact of textile reuse and recycling – A review,
M

J. Clean. Prod. 184 (2018) 353–365. doi:10.1016/j.jclepro.2018.02.266.

[4] S. Shanavas, A. Priyadharsan, K. Dharmaboopathi, I. Ragavan, C. Vidya, and P.M.


D

Anbarasan, Ultrasonically and Photonically Simulatable Bi‐Ceria Nanocubes for


TE

Enhanced Catalytic Degradation of Aqueous Dyes: A Detailed Study on Optimization,


EP

Mechanism and Stability, ChemistrySelect 45 (2018) 12841-12853.

doi:10.1002/slct.201802836 .
CC

[5] Z.-M. Yang, G.-F. Huang, W.-Q. Huang, J.-M. Wei, X.-G. Yan, Y.-Y. Liu, C. Jiao, Z.

Wan, A. Pan, Novel Ag3PO4/CeO2 composite with high efficiency and stability for
A

photocatalytic applications, J. Mater. Chem. A. 2 (2014) 1750–1756.

doi:10.1039/C3TA14286H.

[6] C. Reyes, J. Fernández, J. Freer, M.A. Mondaca, C. Zaror, S. Malato, H.D. Mansilla,

36
Degradation and inactivation of tetracycline by TiO2 photocatalysis, J. Photochem.

Photobiol. A Chem. 184 (2006) 141–146. doi:10.1016/j.jphotochem.2006.04.007.

[7] A. Aretxaga, S. Romero, M. Sarrà, T. Vicent, Adsorption step in the biological

degradation of a textile dye, Biotechnol. Prog. 17 (2001) 664–668.

PT
doi:10.1021/bp010056c.

[8] A. Priyadharsan, V. Vasanthakumar, S. Shanavas, S. Karthikeyan, P. M. Anbarasan,

RI
Crumpled sheet like graphene based WO3-Fe2O3 nanocomposites for enhanced charge

SC
transfer and solar photocatalysts for environmental remediation, Applied Surface Science

470 (2019) 114-128. 10.1016/j.apsusc.2018.11.130.

U
[9] S.W.L. Ng, G. Yilmaz, W.L. Ong, G.W. Ho, One-step activation towards spontaneous

N
etching of hollow and hierarchical porous carbon nanospheres for enhanced pollutant
A
adsorption and energy storage, Appl. Catal. B Environ. 220 (2018) 533–541.
M

doi:10.1016/j.apcatb.2017.08.069.

[10] A. Priyadharsan, S. Shanavas, V. Vasanthakumar, B. Balamuralikrishnan, P. M.


D

Anbarasan, Synthesis and investigation on synergetic effect of rGO-ZnO decorated MoS2


TE

microflowers with enhanced photocatalytic and antibacterial activity, Colloids and


EP

Surfaces A: Physicochemical and Engineering Aspects. 559 (2018): 43-53.

doi:10.1016/j.colsurfa.2018.09.034.
CC

[11] A. Priyadharsan, V. Vasanthakumar, S. Karthikeyan, V. Raj, S. Shanavas, P.M.

Anbarasan, Multi-functional properties of ternary CeO2/SnO2/rGO nanocomposites:


A

Visible light driven photocatalyst and heavy metal removal, J. Photochem. Photobiol. A

Chem. (2017). doi:10.1016/j.jphotochem.2017.05.030.

[12] S. Shajahan, P. Arumugam, R. Rajendran, A. Ponnusamy Munusamy, Optimization and

37
detailed stability study on Pb doped ceria nanocubes for enhanced photodegradation of

several anionic and cationic organic pollutants, Arab. J. Chem. (2017).

doi:10.1016/j.arabjc.2017.11.001.

[13] Q. Wei, Y. Wang, H. Qin, J. Wu, Y. Lu, H. Chi, F. Yang, B. Zhou, H. Yu, J. Liu,

PT
Construction of rGO wrapping octahedral Ag-Cu2O heterostructure for enhanced visible

light photocatalytic activity, Appl. Catal. B Environ. 227 (2018) 132–144.

RI
doi:10.1016/j.apcatb.2018.01.003.

SC
[14] B. Subash, B. Krishnakumar, M. Swaminathan, M. Shanthi, Highly efficient, solar active,

and reusable photocatalyst: Zr-loaded Ag-ZnO for reactive red 120 dye degradation with

U
synergistic effect and dye-sensitized mechanism, Langmuir. 29 (2013) 939–949.

doi:10.1021/la303842c. N
A
[15] S. Gupta, V. Subramanian, Encapsulating Bi2Ti2O7(BTO) with reduced graphene oxide
M

(RGO): An effective strategy to enhance photocatalytic and photoelectrocatalytic activity

of BTO, ACS Appl. Mater. Interfaces. 6 (2014) 18597–18608. doi:10.1021/am503396r.


D

[16] B.Y. Xia, H. Bin Wu, J.S. Chen, Z. Wang, X. Wang, X.W. (David) Lou, Formation of Pt–
TE

TiO2–rGO 3-phase junctions with significantly enhanced electro-activity for methanol


EP

oxidation, Phys. Chem. Chem. Phys. 14 (2012) 473–476. doi:10.1039/C1CP23367J.

[17] N. Zhang, Y. Zhang, X. Pan, M.Q. Yang, Y.J. Xu, Constructing ternary CdS-graphene-
CC

TiO2 hybrids on the flatland of graphene oxide with enhanced visible-light photoactivity

for selective transformation, J. Phys. Chem. C. 116 (2012) 18023–18031.


A

doi:10.1021/jp303503c.

[18] Z.-R. Tang, Y. Zhang, N. Zhang, Y.-J. Xu, New insight into the enhanced visible light

photocatalytic activity over boron-doped reduced graphene oxide, Nanoscale. 7 (2015)

38
7030–7034. doi:10.1039/C4NR05879H.

[19] T. Liu, B. Liu, L. Yang, X. Ma, H. Li, S. Yin, T. Sato, T. Sekino, Y. Wang,

RGO/Ag2S/TiO2 ternary heterojunctions with highly enhanced UV-NIR photocatalytic

activity and stability, Appl. Catal. B Environ. 204 (2017) 593–601.

PT
doi:10.1016/j.apcatb.2016.12.011.

[20] K. Qian, L. Xia, W. Wei, L. Chen, Z. Jiang, J. Jing, J. Xie, Construction of

RI
Bi2Ti2O7/Bi4Ti3O12 composites with enhanced visible light photocatalytic activity, Mater.

SC
Lett. 206 (2017) 245–248. doi:10.1016/j.matlet.2017.07.036.

[21] Y. Du, Q. Hao, D. Chen, T. Chen, S. Hao, J. Yang, H. Ding, W. Yao, J. Song, Facile

U
fabrication of heterostructured bismuth titanate nanocomposites: The effects of

N
composition and band gap structure on the photocatalytic activity performance, Catal.
A
Today. 297 (2017) 255–263. doi:10.1016/j.cattod.2016.12.048.
M

[22] Z. Zhang, C. Jiang, P. Du, Y. Wang, Synthesis and characterization of Bi2Ti2O7/TiO2

heterojunction by glycerol-assisted alcoholthermal method, Ceram. Int. 41 (2015) 3932–


D

3939. doi:10.1016/j.ceramint.2014.11.076.
TE

[23] D. Zhou, H. Yang, Y. Tu, Y. Tian, Y. Cai, Z. Hu, X. Zhu, In Situ Fabrication of
EP

Bi2Ti2O7/TiO2 Heterostructure Submicron Fibers for Enhanced Photocatalytic Activity,

Nanoscale Res. Lett. 11 (2016) 193. doi:10.1186/s11671-016-1408-7.


CC

[24] M.B. Gawande, A. Goswami, F.X. Felpin, T. Asefa, X. Huang, R. Silva, X. Zou, R.

Zboril, R.S. Varma, Cu and Cu-Based Nanoparticles: Synthesis and Applications in


A

Catalysis, Chem. Rev. 116 (2016) 3722–3811. doi:10.1021/acs.chemrev.5b00482.

[25] X. Wu, Y. Xing, D.T. Pierce, J.X. Zhao, One-Pot Synthesis of Reduced Graphene

Oxide/Metal (Oxide) Composites, ACS Appl. Mater. Interfaces. (2017) acsami.7b12539.

39
doi:10.1021/acsami.7b12539.

[26] W.S. Hummers, R.E. Offeman, Preparation of Graphitic Oxide, J. Am. Chem. Soc. 80

(1958) 1339. doi:10.1021/ja01539a017.

[27] L. Shahriary, A. a. Athawale, Graphene Oxide Synthesized by using Modified Hummers

PT
Approach, Int. J. Renew. Energy Environ. Eng. 02 (2014) 58–63.

doi:10.1016/j.aca.2014.02.025.

RI
[28] S. Shanavas, A. Priyadharsan, V. Vasanthakumar, A. Arunkumar, P.M. Anbarasan, S.

SC
Bharathkumar, Mechanistic investigation of visible light driven novel La2CuO4/CeO2/rGO

ternary hybrid nanocomposites for enhanced photocatalytic performance and antibacterial

U
activity, J. Photochem. Photobiol. A Chem. 340 (2017) 96–108.

doi:10.1016/j.jphotochem.2017.03.002. N
A
[29] Q. Xiang, J. Yu, P.K. Wong, Quantitative characterization of hydroxyl radicals produced
M

by various photocatalysts, J. Colloid Interface Sci. 357 (2011) 163–167.

doi:10.1016/j.jcis.2011.01.093.
D

[30] Y.T. Prabhu, K. Venkateswara Rao, V. Sesha Sai, T. Pavani, A facile biosynthesis of
TE

copper nanoparticles: A micro-structural and antibacterial activity investigation, J. Saudi


EP

Chem. Soc. 21 (2017) 180–185. doi:10.1016/j.jscs.2015.04.002.

[31] A. Khan, A. Rashid, R. Younas, R. Chong, A chemical reduction approach to the


CC

synthesis of copper nanoparticles, Int. Nano Lett. 6 (2016) 21–26. doi:10.1007/s40089-

015-0163-6.
A

[32] A. Primo, I. Esteve-Adell, J.F. Blandez, A. Dhakshinamoorthy, M. Álvaro, N. Candu,

S.M. Coman, V.I. Parvulescu, H. Garćia, High catalytic activity of oriented 2.0.0

copper(I) oxide grown on graphene film, Nat. Commun. 6 (2015).

40
doi:10.1038/ncomms9561.

[33] H.G. Jiang, M. Rühle, E.J. Lavernia, On the applicability of the x-ray diffraction line

profile analysis in extracting grain size and microstrain in nanocrystalline materials, J.

Mater. Res. 14 (1999) 549–559. doi:10.1557/JMR.1999.0079.

PT
[34] S. Koutsopoulos, R. Barfod, K.M. Eriksen, R. Fehrmann, Synthesis and characterization

of iron-cobalt (FeCo) alloy nanoparticles supported on carbon, J. Alloys Compd. 725

RI
(2017) 1210–1216. doi:10.1016/j.jallcom.2017.07.105.

SC
[35] J. Hou, R. Cao, Z. Wang, S. Jiao, H. Zhu, Chromium-doped bismuth titanate nanosheets

as enhanced visible-light photocatalysts with a high percentage of reactive {110} facets, J.

U
Mater. Chem. 21 (2011) 7296. doi:10.1039/c0jm04374e.

N
[36] Z. Ji, X. Shen, J. Yang, G. Zhu, K. Chen, A novel reduced graphene oxide/Ag/CeO2
A
ternary nanocomposite: Green synthesis and catalytic properties, Appl. Catal. B Environ.
M

144 (2014) 454–461. doi:10.1016/j.apcatb.2013.07.052.

[37] Q. Feng, X. Li, J. Wang, A.M. Gaskov, Reduced graphene oxide (rGO) encapsulated
D

Co3O4 composite nanofibers for highly selective ammonia sensors, Sensors Actuators, B
TE

Chem. 222 (2016) 864–870. doi:10.1016/j.snb.2015.09.021.


EP

[38] Y. Yao, C. Xu, S. Yu, D. Zhang, S. Wang, Facile Synthesis of Mn3O4–Reduced Graphene

Oxide Hybrids for Catalytic Decomposition of Aqueous Organics, Ind. Eng. Chem. Res.
CC

52 (2013) 130226103026006. doi:10.1021/ie303220x.

[39] S. Mahboob, G. Prasad, C.C. Chou, G.S. Kumar, Electrical and X-ray Photoelectron
A

Spectroscopy Study on (Na0. 5-xKxBi0.5-xNdx)TiO3 Ceramics, Ferroelectrics. 445 (2013)

161–171. doi:10.1080/00150193.2013.814353.

[40] J. Hou, S. Jiao, H. Zhu, R. V. Kumar, Carbon-modified bismuth titanate nanorods with

41
enhanced visible-light-driven photocatalytic property, CrystEngComm. 13 (2011) 4735.

doi:10.1039/c1ce05409k.

[41] J. Yi, X. Yuan, H. Wang, H. Yu, F. Peng, Preparation of Bi2Ti2O7/TiO2 nanocomposites

and their photocatalytic performance under visible light irradiation, Mater. Des. 86 (2015)

PT
152–155. doi:10.1016/j.matdes.2015.07.119.

[42] L. Li, J. Yan, T. Wang, Z.-J. Zhao, J. Zhang, J. Gong, N. Guan, Sub-10 nm rutile titanium

RI
dioxide nanoparticles for efficient visible-light-driven photocatalytic hydrogen production,

SC
Nat. Commun. 6 (2015) 5881. doi:10.1038/ncomms6881.

[43] Y. Wang, Y. Tang, Y. Chen, Y. Li, X. Liu, S. Luo, C. Liu, Reduced graphene oxide-based

U
photocatalysts containing Ag nanoparticles on a TiO2 nanotube array, J. Mater. Sci. 48

N
(2013) 6203–6211. doi:10.1007/s10853-013-7417-3.
A
[44] A. Santoni, F. Biccari, C. Malerba, M. Valentini, R. Chierchia, A. Mittiga, Valence band
M

offset at the CdS/Cu2ZnSnS4 interface probed by x-ray photoelectron spectroscopy, J.

Phys. D. Appl. Phys. 46 (2013). doi:10.1088/0022-3727/46/17/175101.


D

[45] R. Ji, W. Sun, Y. Chu, One-step hydrothermal synthesis of Ag/Cu2O heterogeneous


TE

nanostructures over Cu foil and their SERS applications, RSC Adv. 4 (2014) 6055.
EP

doi:10.1039/c3ra44281k.

[46] H.M. El-Bery, Y. Matsushita, A. Abdel-moneim, Fabrication of efficient TiO2-RGO


CC

heterojunction composites for hydrogen generation via water-splitting: Comparison

between RGO, Au and Pt reduction sites, Appl. Surf. Sci. 423 (2017) 185–196.
A

doi:10.1016/j.apsusc.2017.06.130.

[47] P. Liu, H. Wang, X. Li, M. Rui, H. Zeng, Localized surface plasmon resonance of Cu

nanoparticles by laser ablation in liquid media, RSC Adv. 5 (2015) 79738–79745.

42
doi:10.1039/C5RA14933A.

[48] L. Xiong, H. Xiao, Q. Zeng, B. Wang, S. Wen, B. Li, Y. Ding, H. Yu, Direct

transformation of metallic copper to copper nanostructures by simple alcohol thermal

treatment and their photoactivity, RSC Adv. 5 (2015) 98344–98349.

PT
doi:10.1039/c5ra17965c.

[49] A.G. Krasnov, I. V. Piir, M.S. Koroleva, N.A. Sekushin, Y.I. Ryabkov, M.M. Piskaykina,

RI
V.A. Sadykov, E.M. Sadovskaya, V. V. Pelipenko, N.F. Eremeev, The conductivity and

SC
ionic transport of doped bismuth titanate pyrochlore Bi1.6МxTi2O7 − δ(М – Mg, Sc, Cu),

Solid State Ionics. 302 (2017) 118–125. doi:10.1016/j.ssi.2016.12.019.

U
[50] N. Riaz, F.K. Chong, Z.B. Man, M.S. Khan, B.K. Dutta, Photodegradation of orange II

N
under visible light using Cu-Ni/TiO2: Influence of Cu: Ni mass composition, preparation,
A
and calcination temperature, Ind. Eng. Chem. Res. 52 (2013) 4491–4503.
M

doi:10.1021/ie303255v.

[51] Y.S. Fu, P. Xiong, H.Q. Chen, X.Q. Sun, X. Wang, High Photocatalytic Activity of
D

Magnetically Separable Manganese Ferrite-Graphene Heteroarchitectures, Ind. Eng.


TE

Chem. Res. 51 (2012) 725–731. doi:10.1021/ie2026212.


EP

[52] Y. Yao, Z. Yang, D. Zhang, W. Peng, H. Sun, S. Wang, Magnetic CoFe2O4 –Graphene

Hybrids: Facile Synthesis, Characterization, and Catalytic Properties, Ind. Eng. Chem.
CC

Res. 51 (2012) 6044–6051. doi:10.1021/ie300271p.

[53] T.S. Jamil, M.Y. Ghaly, N.A. Fathy, T.A. Abd El-Halim, L. Österlund, Enhancement of
A

TiO2behavior on photocatalytic oxidation of MO dye using TiO2/AC under visible

irradiation and sunlight radiation, Sep. Purif. Technol. 98 (2012) 270–279.

doi:10.1016/j.seppur.2012.06.018.

43
[54] J. Madhavan, F. Grieser, M. Ashokkumar, Combined advanced oxidation processes for

the synergistic degradation of ibuprofen in aqueous environments, J. Hazard. Mater. 178

(2010) 202–208. doi:10.1016/j.jhazmat.2010.01.064.

[55] N. Jallouli, L.M. Pastrana-Martínez, A.R. Ribeiro, N.F.F. Moreira, J.L. Faria, O. Hentati,

PT
A.M.T. Silva, M. Ksibi, Heterogeneous photocatalytic degradation of ibuprofen in

ultrapure water, municipal and pharmaceutical industry wastewaters using a TiO2/UV-

RI
LED system, Chem. Eng. J. 334 (2018) 976–984. doi:10.1016/j.cej.2017.10.045.

SC
[56] Z. dong Lei, J. jun Wang, L. Wang, X. yu Yang, G. Xu, L. Tang, Efficient photocatalytic

degradation of ibuprofen in aqueous solution using novel visible-light responsive

U
graphene quantum dot/AgVO3 nanoribbons, J. Hazard. Mater. 312 (2016) 298–306.

doi:10.1016/j.jhazmat.2016.03.044. N
A
[57] J. Wang, L. Tang, G. Zeng, Y. Deng, Y. Liu, L. Wang, Y. Zhou, Z. Guo, J. Wang, C.
M

Zhang, Atomic scale g-C3N4/Bi2WO6 2D/2D heterojunction with enhanced photocatalytic

degradation of ibuprofen under visible light irradiation, Appl. Catal. B Environ. 209
D

(2017) 285–294. doi:10.1016/j.apcatb.2017.03.019.


TE

[58] Y. Xu, S. Huang, M. Xie, Y. Li, L. Jing, H. Xu, Q. Zhang, H. Li, Core–shell magnetic
EP

Ag/AgCl@Fe2O3 photocatalysts with enhanced photoactivity for eliminating bisphenol A

and microbial contamination, New J. Chem. 40 (2016) 3413–3422.


CC

doi:10.1039/C5NJ02898A.

[59] M. Liu, X. Xue, S. Yu, X. Wang, X. Hu, H. Tian, H. Chen, W. Zheng, Improving
A

Photocatalytic Performance from Bi2WO6@MoS2/graphene Hybrids via Gradual Charge

Transferred Pathway, Sci. Rep. 7 (2017) 1–11. doi:10.1038/s41598-017-03911-6.

[60] M. Benčina, M. Valant, Bi2Ti2O7 -based pyrochlore nanoparticles and their superior

44
photocatalytic activity under visible light, J. Am. Ceram. Soc. 101 (2018) 82–90.

doi:10.1111/jace.15177.

[61] M. Tahir, B. Tahir, Dynamic photocatalytic reduction of CO2 to CO in a honeycomb

monolith reactor loaded with Cu and N doped TiO2 nanocatalysts, Appl. Surf. Sci. 377

PT
(2016) 244–252. doi:10.1016/j.apsusc.2016.03.141.

RI
SC
U
N
A
M
D
TE
EP
CC
A

45
Figure captions

 (b) GO
(a)  Bi2Ti2O7
(001) rGO
 Cu

 CBT
CBTG
Intensity (a.u.)

Intensity (a.u.)
    
  

PT

  
    

RI
 
  (002)
       

SC
10 20 30 40 50 60 70 10 20 30 40 50 60 70
2 (degree) 2 (degree)

Fig. 1: (a,b) XRD spectra of the as-prepared pure and composite nanostructures

U
N Bi2Ti2O7
Cu
A
CBT
CBTG
M
Intensity (a.u.)

D
TE

-1
939 cm
-1
3447 cm

-1
1632 cm
EP

-1
-1

620 cm
811cm
CC

4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )
A

Fig. 2: FT-IR spectrographs of as-prepared nanostructures

46
PT
RI
SC
U
N
A
M
D
TE

Fig. 3: SEM micro graphs of (a-b) rGO, (c-d) Pristine Bi2Ti2O7, (e-f) Pristine Cu, (g-h) CBT

binary nanocomposite, (i-j) CBTG ternary nanocomposite


EP
CC
A

47
PT
RI
SC
U
N
A
M
D
TE
EP
CC
A

Fig. 4: HR-TEM images of (a,b) rGO, (c,d) Pristine Bi2Ti2O7, (e,f) CBT

48
PT
RI
SC
U
N
A
M
D
TE
EP

Fig. 5: HRTEM images of CBTG capsules


CC
A

49
PT
RI
SC
U
N
A
M

Fig. 6: EDX analysis graph of (a) Pristine Cu, (b) Pristine Bi2Ti2O7, (c) binary CBT and (d)

ternary CBTG capsules


D
TE

(a) Cu-2p (b) 158.8 eV Bi-4f


4f7/2
164.4 eV
EP

4f5/2
157.02 eV
4f7/2
Intensity (a.u.)
Intensity (a.u.)

CC

162.4 eV
O-1s 4f5/2
A

C-1s
Ti-2p
Bi-4f

0 150 300 450 600 750 900 1050 156 158 160 162 164 166 168
Binding Energy (eV) Binding Energy (eV)

50
(c) Ti-2p (d) 933.4 eV
Cu-2p
459.1 eV 2p
3/2
2p
3/2

Intensity (a.u.)
Intensity (a.u.)

464.8 eV
2p1/2

953.1 eV
2p
1/2

PT
RI
450 453 456 459 462 465 468 471 930 935 940 945 950 955 960 965 970

SC
Binding Energy (eV) Binding Energy (eV)

(e) 531.05 eV O-1s (f) C-1s

U
531.68 eV

N 284.4 eV
Intensity (a.u.)

Intensity (a.u.)

530.5 eV C-C
A
284.9 eV
M
C-C
533.1 eV

287.5 eV
-o-co
D
TE

525 528 531 534 537 540 543 279 282 285 288 291 294 297 300
Binding Energy (eV) Binding Energy (eV)

Fig. 7: XPS spectra of CBTG: (a) survey spectra, (b) Bi-4f, (c) Ti-2p, (d) Cu-2p, (e) O-1s, (f) C-
EP

1s
CC
A

51
CBTG (a) Bi2Ti2O7 (b)

Intensity (a.u.)
Intensity (a.u.)

PT
RI
-5 -4 -3 -2 -1 0 1 2 3 4 5 -4 -2 0 2 4 6 8
Binding Energy (eV)

SC
Binding Energy (eV)

Fig. 8: XPS valence band spectra of (a) CBTG and (b) Bi2Ti2O7 nanostructures

U
N Bi2Ti2O7 (a)
A
Cu
CBT
CBTG
M
Absorption (a.u.)

D
TE
EP

200 300 400 500 600 700


Wavelength (nm)
CC
A

52
(b)
Bi2Ti2O7
CBT
CBTG

2
(h)

PT
RI
SC
1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50
Photon energy (eV)

U
Fig. 9: (a) UV-Vis DRS graph (b) Tauc plot of as prepared nanostructures.

(a)
N
A
(a) (b)
M

1.0 0 min

0.8
Ct/C0 of Tetracycline

Absorption (a.u.)
D

0.6
TE

0.4
Without catalyst
With catalyst in dark 90 min
P25-TiO2
EP

0.2 Bi Ti O
2 2
Cu
CBT
CBTG
0.0
250 300 350 400 450 500
CC

0 15 30 45 60 75 90
Time (min) Wavelength (nm)
A

53
(c)
(d) 0 min
1.0

0.8

Absorption(a.u.)
Ct/C0 of IBP

0.6

0.4 Without catalyst 90 min

PT
With catalyst in dark
P25-TiO2
Bi2Ti2O
0.2
Cu
CBT

RI
CBTG
0.0
240 245 250 255 260 265 270 275 280
0 15 30 45 60 75 90
Time (min) Wavelength (nm)

SC
U
N
A
M
D
TE

Fig. 10: Photocatalytic degradation rate curves: (a) TC and (c) IBP, and degradation spectral

changes of pharmaceutical molecules: (b) TC and (d) IBP with CBTG photocatalyst and The
EP

pseudo first order kinetics plot: (e) TC and (f) IBP (reaction condition: catalyst dosage = 100 mg,
CC

pharmaceutical molecule concentration = 50 mg/L, pH = 7 and reaction time = 90 min).


A

54
PT
RI
SC
U
N
A
M

Fig. 11: (a,b) The proposed photocatalytic degradation pathway of TC


D
TE
EP
CC
A

55
PT
RI
SC
U
N
A
M

Fig. 12: The proposed photocatalytic degradation pathway of IBP


D
TE
EP
CC
A

56
PT
RI
SC
U
N
Fig. 13: Proposed photocatalytic mechanism of CBTG
A
M
D
TE
EP
CC
A

57
Scheme captions

PT
RI
SC
U
N
A
Scheme. 1: Synthesis of CBTG capsules
M
D
TE
EP
CC
A

58