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Mechanistic evaluation of heterocyclic aromatic

Cite this: DOI: 10.1039/c8pp00580j
compounds mineralization by a Cu doped ZnO
photo-catalyst
Bharat Kumar Mahajan,a Navneet Kumar, a Rohit Chauhan, a

Vimal Chandra Srivastava *a and Siddhant Gulati b

In this study, Cu doped ZnO photo-catalysts were used for the degradation of the heterocyclic com-
pounds, pyridine and quinoline. Three ZnO based photo-catalysts with different amounts of Cu doping
(1%, 5% and 10%) were synthesized by precipitation method. The characterization of the catalyst was
done using field emission scanning electron microscopy (FE-SEM), transmission electron microscopy
(TEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET), diffuse reflectance spectroscopy (DRS)
and photo-luminescence (PL) techniques. The band gaps of the pure ZnO, and 1%, 5% and 10% Cu
doped ZnO photo-catalysts were found to be 3.27 eV, 3.21 eV, 3.17 eV and 2.91 eV, respectively. The
effects of pH, photo-catalyst dose and irradiation time were studied. Under optimum conditions (5% Cu
doped ZnO, dose of 1.2 g L−1 for pyridine and 1.6 g L−1 for quinoline, pH = 11 and time = 5 h), the
maximum pyridine and quinoline mineralization efficiencies were found to be 92.4% and 74.3%,
respectively. The mineralization process followed first-order kinetics. The in situ formation of singlet
oxygen, hydroxyl radicals and superoxide radicals was confirmed by reactive oxygen species (ROS) sca-
venger studies. Catalyst reusability studies showed excellent mineralization up to four consecutive
Received 18th December 2018, cycles. The enhanced photo-catalytic mechanism was studied by comparing the band structure with
Accepted 5th April 2019
respect to the potential of highly reactive species (•OH and O2•−). A possible mineralization pathway was
DOI: 10.1039/c8pp00580j proposed on the basis of the intermediates detected by gas chromatography coupled with mass spec-
rsc.li/pps trometry (GC-MS) analysis.

1. Introduction such as coal processing generate wastewater contaminated

with pyridine and its derivatives like quinoline.3,4 Pyridine and
Global industrialization has led to the generation of a huge quinoline are heterocyclic nitrogenous pollutants which have a
amount of toxic compounds which are polluting water bodies. complex ring structure with the nitrogen atom being within
Effluents generated in numerous industries like the pharma- the ring. This makes them highly difficult to mineralize. In the
ceutical, coal processing, herbicide–pesticide and many other past, various methods like ultrasonic, microwave, and biologi-
chemical industries contain organic heterocyclic aromatic cal techniques and the advance oxidation process (AOP) have
compounds such as pyridine (C5H5N) and quinoline been explored for the degradation/removal of these com-
(C9H7N).1,2 These compounds can have adverse effects on pounds.4 Biological degradation is not very effective due to the
human health, e.g. nausea, insomnia, abdominal discomfort toxic nature of pyridine and quinoline.1 Recently the photo-cat-
and cancer.3 Several man-made products and/or compounds alysis technique has gained more importance because of its
like pharmaceuticals, pesticides, dyes and industrial solvents ability to mineralize organic pollutants into products like CO2,
contain N-heterocyclic structures. In addition, many industries NH3 and H2O.5,6 However, limited research studies are avail-
able into the mineralization and degradation of pyridine and
quinoline by photo-catalytic processes.
a
Department of Chemical Engineering, Indian Institute of Technology Roorkee, In photo-catalytic studies, TiO2 nanostructures have been
Roorkee 247667, Uttarakhand, India. E-mail: vimalcsr@yahoo.co.in, studied widely due to their suitable properties like band gap,
vimalfch@iitr.ac.in, bharat8215@gmail.com, navneetrsh@gmail.com,
morphology, and surface area.7 However, Ti is an expensive
rohitchn18@gmail.com; Fax: +91-1332-276535; Tel: +91-1332-285889
b
Department of Chemical Engineering, National Institute of Technology Hamirpur,
metal. Compared to TiO2, lower priced ZnO has the advantage
Hamirpur 177005, Himachal Pradesh, India. that a large fraction of the UV spectrum can be absorbed over
E-mail: siddhantgulati1997@gmail.com its surface.8 Also, ZnO shows a higher rate of degradation of

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organic pollutants than TiO2 in both acidic and basic 2.2. Synthesis of Cu doped ZnO photo-catalysts
mediums. ZnO based catalysts have shown magnificent Cu doped ZnO photo-catalysts were synthesized using the pre-
thermal and chemical stability as well as exhibiting properties cipitation method. For the preparation of the Cu doped ZnO
like non-toxicity and easy reusability.9 One of the major con- photo-catalyst, 0.5 M NaOH and 0.5 M CuNO3 solutions were
cerns with the use of ZnO is the recombination of electrons added simultaneously to 0.5 M ZnNO3 solution at room temp-
(e−) and holes (h+).10 This drawback can be overcome by erature (27 °C) along with continuous stirring. 0.5 M NaOH
doping of some other metal ion into the ZnO material.11,12
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solution was added until the pH stabilized at 9. The whole

Doping results in a Schottky junction, creating an electric field solution was kept under stirring for an additional 12 h at room
close to photo-generated electrons, making holes and electrons temperature. At this pH, the formation of uniform and fine
travel in different directions and preventing recombination.13 solids of metal hydroxide occurred. The same solution was
Many researchers have synthesized CuO/ZnO photo-catalysts kept in an oil-bath arrangement at 90 °C for a 12 h period to
for their photo-catalytic activity and utilized them for their develop thermal stability of the metal hydroxide particles.
environmental remediation.14 There are different types of After completing this step, the solid particles were separated
specific doping methods that have been used previously, like by centrifugation and washed 3 times with ethanol to remove
the co-precipitation method, thermal decomposition, sol–gel, any metal impurity, if present. In the final step, the solid par-
chemical vapor deposition, the wet impregnation method and ticles were kept in a programmable furnace for 6 h at 600 °C.
complex-directed hybridization.15 This step of calcination led to the formation of a 1% Cu doped
In this manuscript, the co-precipitation method has been ZnO photo-catalyst. To prevent moisture regaining entry and
used for Cu doping of ZnO. Doping of Cu inhibits e−–h+ any other contamination, the prepared photo-catalysts were
recombination, which results in enhanced separation of kept in a desiccator until they reached room temperature. The
charge carriers and promotes the photo-catalytic activity of same methodology was adopted for the preparation of 5% and
ZnO. The prepared photo-catalysts have been characterized by 10% Cu doped ZnO photo-catalysts.
a field emission scanning electron microscope (FE-SEM), X-ray
diffraction (XRD), transmission electron microscope (TEM),
differential reflectance spectroscopy (DRS) and Brunauer– 2.3. Characterization and analytical measurements
Emmett–Teller (BET) techniques. The photo-catalyst was A powder X-ray diffraction (XRD) unit (Bruker D8-advance
further applied for the degradation of pyridine (C5H5N) and XRD, with operating parameters 30 mA/40 kV with λ = 1.5406 Å
quinoline (C9H7N) at different pH values and doses to find the Cu Kα radiation source at room temperature and an angle
best parametric conditions. Pseudo-first-order reaction kine- range of 5–90° with step size 0.02°) was used for the quantitat-
tics and an reactive oxygen species (ROS) scavenging study ive and qualitative crystallographic phase analysis of the
have been performed for the degradation of pyridine and photo-catalyst. The ICDD-JCPDS library was used for the study
quinoline in aqueous solution. The enhanced photo-catalytic of the crystalline phase of the photo-catalyst. Surface mor-
mechanism for the degradation of pollutants over Cu/ZnO phology along with elemental composition was studied by
photo-catalyst was studied by comparing band structure using FE-SEM (Quanta 200 FEG, FEI Netherlands). During
with respect to potential of in situ generated highly reactive EDAX analysis, spot and area mode methods were used on
species (•OH and O2•−) which was confirmed by ROS and different points of the samples. Transmission electron mor-
photo-luminescence (PL) experiments. The reaction pathway phology (TEM) was done using digital TEM (FEI Tecnai G2 20
for the degradation of pyridine and quinoline has been S-Twin) where the TEM point resolution was 0.24 nm whereas
suggested on the basis of reaction intermediates detected with the TEM line resolution was set at 0.14 nm at an applied accel-
the help of gas chromatography coupled with mass eration voltage of 200 kV.
spectroscopy (GC/MS). Textural properties such as the surface area of the calcined
photo-catalysts were obtained by multi-point nitrogen adsorp-
tion–desorption isotherms, which were determined by a
2. Materials and methods Micromeritics ASAP 2020 at −197 °C. Photo-catalyst samples
were degassed for around 6 h at 220 °C followed by overnight
2.1. Materials drying at 105 °C in a hot air oven. The BET method was used
Zinc nitrate hexahydrate AR (Zn(NO3)2·6H2O, 99.0% pure), to determine the specific surface area of the photo-catalysts
sodium hydroxide pellets AR (NaOH, 98.0% pure), and quino- and the Barrett–Joyner–Halenda (BJH) method was used to
line (C9H7N, purity >97.0%) were purchased from S D Fine- determine the distribution of pore sizes with the help of the
Chem Limited. Copper(II)nitrate trihydrate (Cu(NO3)2·3H2O) adsorption part of the isotherm.
and ethanol (CH3CH2OH, purity >99.0%) were obtained from Optical properties and the band gap of the photo-catalysts
Loba Chemie Pvt. Ltd, India. Pyridine (C5H5N, purity >99.5%) were measured by diffuse reflectance spectroscopy (DRS)
was purchased from RFCL Limited. Photo-catalysts were syn- (SHIMADZU, model no.: UV-2450) in the wavelength range
thesized using de-ionized water (DI water, Millipore) and tap from 200 to 800 nm. The reference material was BaSO4. In the
water was used throughout the study for the preparation of DRS study, the ratio of photo-catalyst to BaSO4 was 1 : 100
synthetic wastewater. (weight by weight) for sample preparation. A FluoroMax-4 spec-

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trofluorometer recorded the PL spectrum of the photo-catalysts corresponding to the highest one recorded at λ = 256 nm. To
at a wavelength of 360 nm. The degradation efficiency for pyri- study the reusability of the photo-catalysts, the degradation of
dine and quinoline was monitored by a UV-spectrophotometer pyridine and quinoline was performed using 30 mg L−1 pyri-
(UV-1800, Shimadzu, A114548) with λmax = 256 nm for pyridine dine and 40 mg L−1 quinoline solutions each with a 50 ml
and 281 nm for quinoline. PL spectra of Cu doped ZnO photo- volume, and the pH of the solution was kept at 11. The dose of
catalysts were recorded in a FluoroMax-4 spectrofluorometer catalyst was taken to be 1.2 g L−1 for pyridine and 1.6 g L−1 for
with an excitation wavelength of 360 nm. quinoline. The experiment was performed four times and each
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Gas chromatography coupled with mass spectroscopy time the same 5% Cu–ZnO catalyst (duly separated from the
(GC-MS) was used to identify in situ generated intermediates earlier solution by centrifugation) was used.
for the degradation of pyridine and quinoline. For the analysis,
a 1 : 2 ratio (v : v) of sample and dichloromethane (DCM) was
utilized for the extraction of pyridine and quinoline as well as 3. Results & discussion
the generated intermediates. Extraction was done 3 or 4 times
and then Na2SO4 (anhydrous) was used to dehydrate the 3.1. Characterization of photo-catalysts
aqueous sample. The gas chromatograph was equipped with a 3.1.1. X-ray diffraction (XRD). The XRD patterns of Cu
capillary column (DB-5 MS, 30 × 0.25 mm, 0.25 m) and the doped ZnO particles are shown in Fig. 1a. The diffraction
mass-spectrometer (MS, Saturn 2100 T) was coupled with a pattern exhibits peaks at 2θ values of 36.18°, 36.21°, 36.25°
source of electron ionization (EI). The following GC-MS and 36.29°, corresponding to the (1 0 1) plane of 1%, 5% and
program was applied for intermediate identification: split ratio 10% concentration, respectively. The obtained patterns
of 15/1, solvent delay of 3 min, scanning range from 50 to 500 matched well with JCPDS file number 34-1451, which corres-
with 3 scan per s, the oven temperature was increased from 50 ponds to the wurtzite structure of ZnO. Some peaks observed
to 300 °C, the ramp rate was set at 8 °C min−1. The NIST in the photo-catalyst matched with JCPDS file number 800-
library was applied for intermediate identification, and 0076, corresponding to the monoclinic end-centered structure
matches >70% were utilized to propose the degradation of CuO. Also, no significant shift in the peak positions was
mechanism for pyridine and quinoline. observed with an increase in dopant (Cu) concentration.
This is due to the fact that Cu2+ and Zn2+ both have almost
2.4. Enhanced photo-catalytic activity similar ionic radii (Zn2+ = 0.60 Å, Cu2+ = 0.57 Å).11 However,
A multi-chamber photo reactor was used for this study. This the intensity of the peaks decreased with an increase in Cu
photo reactor was equipped with 125 W mercury tungsten concentration, indicating a decrease in crystallinity of ZnO.16
lamps and a magnetic stirrer. Aluminum paint was spread all The Debye–Scherrer formula D = 0.9λ/β cos θ17 was used to
over the inner walls to provide a highly reflective surface. calculate the crystalline size of the photo-catalysts, where λ =
Cooling fans were also installed in order to exhaust the heat incident X-ray wavelength (1.54 Å), β = full width at half
generated during the photo-catalytic activity. A lab-scale glass maxima (FWHM) of the most intense peak, and θ = diffrac-
reactor of 250 mL volume was used to perform the degradation tion angle commensurate with the most intense peak. The
of pyridine and quinoline. This glass reactor was kept inside average crystalline sizes came out to 28.47 nm, 24.74 nm,
the photo reactor. The distance between light source and glass 21.55 nm and 18.80 nm (Table 1) for pure ZnO, and 1%, 5%
reactor was maintained at 20 cm. The Cu doped ZnO catalyst and 10% Cu doped ZnO photo-catalysts, respectively.
was poured into a 50 mL solution of pyridine (0.379 mM L−1) Thus, the crystallite size decreased as the Cu concentration
and quinoline (0.309 mM L−1) at different concentrations increased.
(40–120 mg L−1). Dispersion of catalyst into pollutants was 3.1.2. Optical band analysis. DRS studies provide infor-
done by keeping the mixture in an ultra-sonication unit for mation about the optical band of photo-catalysts in the solid
10 min. After complete dispersion, the solution with continu- form as they behave as semiconductors. The DRS for the as-
ous stirring was kept under a mercury lamp, which emitted UV synthesized batches of photo-catalysts are shown in Fig. 1b,
radiation. 3 mL of decomposed pollutant was taken out at which shows graphs of (αhυ)2 against band gap (eV), where α =
regular intervals (60, 120, 180, 240, 300, 360 and 420 min) and absorbance, h = Planck’s constant and υ = frequency. The band
subjected to centrifugation to separate the photo-catalyst and gaps of pure ZnO, and 1%, 5% and 10% Cu doped ZnO photo-
analyzed for residual pyridine and quinoline concentration. catalysts were found to be 3.27 eV, 3.21 eV, 3.17 eV and 2.91 eV
by extrapolation of the straight-line part of the Tauc plot. As
2.5. Scavenger and reusability study the concentration of doped metal increased, the band gap
For the scavenger study, 60 mg of 5% Cu–ZnO photo-catalyst energy decreased. It was previously reported that when Cu
was poured into a 50 mL batch of pyridine and they were doping on ZnO increased from 1% to 5%, the band gap
further treated with 1 mM of ROS scavengers for 5 h in the decreased from 3.24 eV to 2.73 eV,17 and when Cu doping
presence of UV light. Samples were collected at regular inter- increased from 2.5% to 10%, the band gap decreased from
vals. Centrifugation was done to settle the suspended photo- 3.20 eV to 3.08 eV.14 As a consequence of doping in semi-
catalysts and then monitoring was undertaken using a UV conductor, the energy levels of the valence or conduction band
spectrophotometer. The intensities of the peaks decreased get altered. This happens either due to widening or narrowing

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Fig. 1 (a) XRD pattern of ZnO and Cu doped ZnO photo-catalysts, (b) complete DRS analysis of pure ZnO, and 1%, 5% and 10% Cu–ZnO photo-cat-
alysts, (Tauc plot) to mark the band gap (eV) of synthesized photo-catalysts, (c) N2 adsorption/desorption isotherms, (d) pore size distribution for Cu
doped ZnO photo-catalysts.

Table 1 Crystallite size, textural properties and composition of photo-catalysts

Composition of photo-
catalysts (from EDX) Textural properties
XRD
Photo-catalysts Crystallite size (nm) Metals (%) Oxygen (%) Specific surface area (m2 g−1) Pore sizea (nm)

ZnO 28.47 — — 4.89 —

1% Cu–ZnO 24.74 80.28 19.72 5.46 15.90
5% Cu–ZnO 21.55 90.67 9.33 18.33 20.22
10% Cu–ZnO 18.8 85.15 14.84 11.79 23.92
a
Average pore diameter (BJH desorption).

of the band gap.16 Naseri et al.5 also calculated the band gap 3.27 eV and 1.32 eV, respectively. Also, the band gap decreased
for CuO modified ZnO photo-catalysts with CuO varying in the from 2.93 eV to 1.94 eV as CuO wt% increased in the CuO/ZnO
range of 0.1–50%. The band gaps of pure ZnO and CuO were photo-catalyst. Hence, the band gaps obtained in the present

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study are in good agreement with those previously reported in (Fig. 4a). Similarly, under the same parametric conditions, qui-
the literature.5 noline degradation efficiency was observed to be 19.4%, 49.0%
3.1.3. Textural properties. The textural analysis of the and 45.0% with 1%, 5% and 10% Cu–ZnO, respectively
photo-catalysts was done using the liquid nitrogen adsorp- (Fig. 4b). It was found that after 300 min, the degradation
tion–desorption isotherm. Fig. 1c and d show the N2 adsorp- efficiency becomes constant both in pyridine and quinoline.
tion–desorption isotherm and BJH pore size distribution, The concentration of pollutants and amount of Cu doped ZnO
respectively. The curves of the N2 adsorption–desorption iso- photo-catalysts are constant, but the amounts of •OH and O2•−
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therm seemed to be of type-IV with H3 hysteresis loops free radicals increase with an increase in irradiation time, so
(Fig. 1c), adopted from the IUPAC classification. This also the pollutants are nearly completely degraded in the aqueous
suggests that all the photo-catalysts have a mesoporous struc- solution.22
ture. BJH analysis shows that the photo-catalysts have a defi- This is mainly due to some of the active sites becoming
nite pore size distribution (5–40 nm), as shown in the inset to blocked and saturated.22 Consequently, no more pollutant was
Fig. 1d (observed from the distribution of pore volume to pore adsorbed on their surface. The photo-catalytic oxidation of pyr-
diameter). The specific surface area of the photo-catalysts was idine and quinoline occurs at the active surface of Cu doped
measured by using the BET method, whereas the pore volume ZnO where •OH and O2•− free radicals get trapped by the holes
with pore size of the photo-catalysts was calculated by using of the reactive pollutant species. The •OH free radicals have
the BJH method, as listed in Table 1. Pure ZnO had a specific sufficient oxidation potential to break the bonds of the pyri-
surface area of only 4.9 m2 g−1. The specific surface areas of dine and quinoline molecules which were adsorbed on the
1% and 10% Cu doped ZnO were 5.5 and 11.8 m2 g−1; the surface of Cu doped ZnO.
cumulative pore volumes were 0.019 and 0.034 cm3 g−1; and The degradation kinetics of pyridine and quinoline degra-
the average pore diameters were 15.9 and 23.9 nm, respect- dation was modelled by a pseudo-first-order kinetic model rep-
ively. The specific surface area of the 5% Cu doped ZnO resented by the following equation:23
photo-catalyst was found to be 18.3 m2 g−1 and the cumulative
½C0 
pore volume was found to be 0.094 cm3 g−1 which was the ln ¼ kt ð1Þ
½Ct 
largest among all the synthesized photo-catalysts. However, the
average pore diameter of 5% Cu doped ZnO was found to be where, C0 is the initial concentration of the pollutant (mg L−1),
20.22 nm. Saravanan et al.18 reported 8.6 m2 g−1, 15.4 m2 g−1 Ct is the respective concentration (mg L−1) at treatment time
and 9.7 m2 g−1 for pure ZnO, 5% Cu/ZnO and 50% Cu/ZnO, (t ), and k is the pseudo-first-order kinetic constant. Fig. 4c and
respectively, which are quite similar to our study. In d show the pseudo-first-order rate kinetics plots. For 1%, 5%
the case of 10% Cu doped ZnO, the fall in specific area is and 10% Cu doped ZnO photo-catalysts, values of k for pyri-
due to the blockage of some ZnO pores by high Cu dine degradation were found to be 0.149, 0.156 and
concentration.19 0.155 min−1, respectively; whereas for quinoline degradation,
3.1.4. Morphology. For the surface morphology analysis, the respective values were: 0.018, 0.058 and 0.052 min−1. For
both FE-SEM and TEM techniques were used. The SEM images both pollutants the value of k was a maximum with 5% Cu
along with EDX analysis of 1%, 5% and 10% Cu doped ZnO doped ZnO; therefore the overall degradation of pyridine and
photo-catalysts are shown in Fig. 2a, b and c, respectively. Cu quinoline was best for 5% Cu–ZnO. Subbaramaiah et al.24
doped ZnO showed coagulated cut shaped crystals with used Cu/SBA-15 for the degradation of pyridine and reported a
uneven size. A similar type of morphology has also been k value of 0.009 min−1. Subbaramaiah et al.25 used nFe0/GAC
reported in various pieces of literature.17,20 EDX analysis for the degradation of pyridine and calculated a k value of
showed that along with oxygen, only copper and zinc are 0.008 min−1. Pachupate and Vaidya26 reported a k value of
present in the composition. No trace of any other element was 0.00437 min−1 for quinoline degradation by an Ru/C catalyst.
found. The ratio of copper and zinc was also found to be
almost the same as that used during synthesis. TEM images of
5% Cu doped ZnO catalyst particles are shown in Fig. 3. This 3.3. Influence of solution pH
illustrates that the photo-catalysts are spherical and have an Since the 5% Cu–ZnO catalyst performed best and its perform-
average size of 22 nm. The observation unveils that the par- ance matches its characteristics among all Cu–ZnO photo-cata-
ticles are mainly crystallized granules with an almost spherical lysts well, 5% Cu–ZnO was used for the optimization of pH.
shape.21 The results of the effect of pH (range 4–12) are shown in
Fig. 5a. As the solution pH increased from 4 to 12, the degra-
3.2. Effect of irradiation time and lumped degradation dation efficiency also increased. It was observed that the degra-
kinetics dation efficiency was higher when the pH was basic. This is
Before optimizing other parametric conditions, the time for because, with the agglomeration of ZnO particles at low pH,
maximum degradation of pyridine and quinoline was evalu- the adsorption of pollutants gets reduced. Although acidic pH
ated (Fig. 4). At natural pH and using a catalyst dose of 1 g L−1, decomposes H2O2 because of the scavenging effect of •OH by
the degradation of pyridine was found to be 77.3%, 82.5% and H+ ions ( protons) which results in the formation of H2O and
79.0% after 5 h using 1%, 5% and 10% Cu–ZnO, respectively O2. The increase in the degradation efficiency on the basic side

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Fig. 2 FE-SEM and EDAX images showing the morphology and elemental composition of (a) 1% Cu–ZnO, (b) 5% Cu–ZnO, (c) 10% Cu–ZnO.

could also be attributed to an increase in the generation of and obtained an enhanced degradation efficiency for tetra-
radical oxidant species like •OH on the basic side.27 Similar cycline from 47% to 68%. Isari et al.7 synthesized an Fe–TiO2/
results have been reported in various studies for the photo- rGO photo-catalyst and studied rhodamine B dye degradation
catalytic degradation of other pollutants.12 The pKa values of under a pH range of 2 to 10 and reported an increase in dye
pyridine and quinoline are 5.2 and 4.92, respectively.1 Pyridine degradation from 73% to 90% when the pH was varied from 2
is present in aqueous solution in the form of C5H5N and to 6; however, dye degradation efficiency declined to 55% and
C5H6N+ whereas quinoline is in the form of C9H7N and 43% at pH = 8 and 10, respectively.
C9H8N+. The solution pH value of 11 is optimal for the photo-
catalytic degradation process because at higher values of pH, 3.4. Effect of photo-catalyst dose
the degradation efficiency shows a negligible increment. This The dose of photo-catalyst is also a very important parameter
is because the self-decomposition of H2O2 generates O2 as well for the photo-catalytic degradation of pollutants. Different
as the charge neutralization reaction occurring at the active amounts of catalyst dose were added in order to determine
surface of the photo-catalysts.2 At pH 11, the degradation optimum dose when all other operating parameters were kept
efficiencies for pyridine and quinoline were observed to be constant ( pH = 11, 5% Cu doped ZnO). The study was carried
89.7% and 62.6%, respectively, as shown in Fig. 4c. Tiwari out using a catalyst dose in the range of 0.8–2.4 g L−1 (Fig. 5b).
et al.28 studied the photo-catalytic degradation of tetracycline It can be seen that as the photo-catalyst dose increases (up to
in the pH range from 4 to 10 using an Au/TiO2 photo-catalyst 1.2 g L−1 for pyridine and 1.6 g L−1 for quinoline), degradation

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Fig. 3 TEM images of prepared 5% Cu–ZnO photo-catalyst: (a) Image showing average diameter size of 22.64 nm, (b) coagulated structure as also
confirmed by FE-SEM, (c) selected area electron diffraction (SAED) image showing perfectly crystalline structure, (d) Cu doping in ZnO crystal
defects.

efficiency increases. As the dose was further increased, it dose increased from 0.2 to 0.6 g L−1. Soltanabadi et al.31 found
started to hinder the UV radiation and the degradation that rhodamine B dye degradation efficiency increased from
efficiency began to decline.29 It was also reported that the rate 20% to 75% as the CuO(50%)/LaFeO3 nanocomposite photo-
of removal of pollutants gets reduced because the higher dose catalyst dose increased from 0.5 to 1.5 g L−1.
of photo-catalyst shows an effect of self-scavenging for •OH.
3.5. Reusability of photo-catalyst
M2þ =M3þ þ • OH ! M3þ =M4þ þ  OH ð2Þ
The reusability of any catalyst is very crucial for practical appli-
Also, blockage of the active sites of the photo-catalysts may cations. Fig. 5c shows the reusability studies of the photo-
occur because of the agglomeration of the high dose of photo- catalysts with pyridine and quinoline. The experiments for re-
catalysts, which reduces the rate of removal of pollutants at an usability analysis were performed four times and each time
increased dose of photo-catalysts.30 Under optimum con- the same 5% Cu–ZnO photo-catalyst (duly separated from the
ditions, the degradation efficiencies of pyridine and quinoline earlier solution by centrifugation) was used. Fig. 5c elaborates
were observed to be 92.4% and 74.3%, respectively. Isari et al.7 that for pyridine, the degradation efficiency of the first and
reported that rhodamine B dye degradation increased from fourth runs showed a difference of 26.0% as it declined
59% to 91% as the Fe–TiO2/rGO nanocomposite photo-catalyst from 92.3% to 66.2%. Similarly, for quinoline, the

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Fig. 4 Degradation efficiency of (a) pyridine and (b) quinoline with time, using 1% Cu–ZnO, 5% CO–ZnO and 10% Cu–ZnO photo-catalysts.
Kinetic analysis of (c) pyridine and (d) quinoline degradation under optimum conditions, using 1% Cu–ZnO, 5% Cu–ZnO and 10% Cu–ZnO
photo-catalysts.

catalyst lost efficiency from 74.2% to 49.6% in the last applying significant radiation light (UV light, solar radiation,
run. Due to the complex ring structure of quinoline, the etc.) which has an appropriate wavelength to excite the semi-
degradation efficiency was comparatively low in every run than conductor materials. This results in the transfer of electrons
pyridine. The catalyst showed relative inertness in later runs from the valence band (VB) to the conduction band (CB) and
due to the photo-corrosion effect (for both pollutant generates electron–hole (e−–h+) pairs. This mechanism can be
solutions).32 enhanced by doping with metal ions that can significantly
enhance electron–hole pair generation, charge dissolution,
and interfacial e− transfer rate and finally enhance the photo-
4. Possible mechanism for enhanced lytic mineralization of organic pollutants.33
photo-catalytic activity Nethercot Jr34 proposed the concept of electronegativity to
predict the Fermi level energies (Fermi energy is directly
It is well known that during photo-catalysis, the semi- related to the semiconductor-junction) and photo-electric
conductor materials or the photo-catalysts are activated by threshold of simple binary compounds. It was assumed that

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Fig. 5 Degradation efficiency of pyridine and quinoline with (a) pH and (b) different doses of photo-catalyst using 5% Cu–ZnO photo-catalyst; (c)
Reusability check of 5% Cu–ZnO photo-catalyst for degradation of pyridine and quinoline procured under optimum conditions of degradation like
time (min), pH and photo-catalyst dose (mg L−1).

there is an analogy between bond energies and atomic elec- and the HOMO–LUMO energy level of the targeted compounds
tronic energies. Therefore, electro-negativities derived from ( pyridine and quinoline) being photo-degraded.
bond-formation energies were used to develop spectroscopic
information about compounds. This spectroscopic infor- ECB ¼ χ  0:5Eg þ EH2 ð3Þ
mation can be used for the prediction of bond-formation ener-
EVB ¼ ECB þ Eg ð4Þ
gies very accurately. To understand photo-generated e−–h+
pairs over the photo-catalyst, it is necessary to analyze the con-
χ ¼ ½χðAÞa χðBÞb χðCÞc 1=ðaþbþcÞ ð5Þ
venient energy levels ( potential) of the semiconductor conduc-
tion band (ECB) and valence band (ECB) edges with respect to where ECB and EVB are the CB and VB potentials of the semi-
potential of the reactive species O2/O2•− and •OH/H2O. The conductors, respectively; Eg is the band-gap energy for the
energy levels of ECB and EVB were calculated using eqn (3)– semiconductor and EH2 is the energy of free electrons vs. H2
(5).34,35 These equations help in calculating the energy gaps of (−4.5 eV); χ is the absolute electronegativity (AE) of the semi-
different semi-conductors, and plotting them for comparison conductor (geometrical mean of the constituent elements);
with standard elements like O2/O2•− and •OH/H2O (vs. NHE) χ(A), χ(B) and χ(C) are the AE of element A, B and C, respect-

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ively; and a, b, c are the number of atoms in the compound ECB position of ZnO and CuO lies above and below the
(AaBbCc). potential of O2/O2•−, respectively. Therefore, CB potential of
It may be noted that the AEs of Cu, Zn and O are 4.48, 4.45 ZnO favors the formation of O2•−. Similarly, the VB potential
and 7.54 eV, respectively.36 The potentials of O2/O2•− and •OH/ of ZnO favors the formation of •OH. Hence, we can say that
H2O are taken from the literature to be 0.13 and 2.68 eV, the formation of •OH and O2•− at the VB and CB (due to the
respectively.37 The calculated values of ECB and EVB for CuO photo-induced charge transfer) are responsible for the
were found to be 0.71 and 1.91 eV, respectively; whereas for degradation of pyridine and quinoline, which is also dis-
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ZnO, the respective values were −0.39 and 2.68 eV, respectively. cussed in the scavenger study. The mechanism analysis
Hence, the calculated energy levels (band gaps) are in good showed that the Cu/ZnO photo-catalyst formed a type-I
agreement with previously reported data.7 The HOMO and heterostructure which achieves facile charge transfer by
LUMO energy levels of pyridine lie at −7.2 and −1.08 eV and active charge separation.40
for quinoline lie at −6.47 and −3.6 eV, respectively.38,39 Soltanabadi et al.31 synthesized CuO/LaFeO3 nano-
Fig. 6 shows a schematic representation of the energy levels composite photo-catalysts and calculated Eg = 2.1 eV and χ =
of CuO and ZnO with respect to potential of O2/O2•− and •OH/ 5.54 eV for LaFeO3 whereas for CuO, it was 1.3 and 5.81 eV,
H2O (vs. NHE) and the HOMO–LUMO energy level of pyridine respectively, using eqn (3)–(5). Therefore, ECB = −0.01 eV and
and quinoline. The electrons diffuse from the CB of ZnO to EVB = 2.09 eV for LaFeO3, and ECB = 0.66 eV and EVB = 1.96 eV
the CB of CuO because the ECB ( potential) of ZnO is −0.39 for CuO were obtained with the help of eqn (3)–(5). They
which is more negative than that of CuO (0.71 eV). Also, the explained the transfer phenomena of photo-induced electrons

Fig. 6 Schematic energy level diagram of CuO and ZnO with respect to potential (vs. NHE) of O2/O2•− and •OH/H2O and the HOMO–LUMO energy
level of pyridine and quinoline.

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by plotting these obtained data. The representation of the sity of emission for the PL spectrum indicates rapid photo-
photo-catalytic mechanism of CuO/LaFeO3 photo-catalyst induced charge separation and subsequent inhibition of the
showed a type-I heterostructure. recombination of e−–h+ pairs, which could result in enhanced
photo-catalytic activity.31 To observe the transfer, migration
4.1. ROS scavenging and PL spectrum experiments and recombination of the photo-induced e−–h+ pairs in the Cu
doped ZnO photo-catalysts, PL studies were conducted. The
Scavenging studies were executed to identify reactive oxidant
intensity of the PL spectra peaks (430–435 nm) decreased
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species (ROS) in situ generated during the photo-catalytic

because of Cu doping, as shown in Fig. 7b, and it was a
degradation process of pyridine and quinoline. Sodium azide
minimum for 5%Cu–ZnO. The modification by Cu on the ZnO
(SA) was used to scavenge singlet oxygen (1O2), whereas 1,4-
photo-catalysts increased the adsorption/activation of O2 and
benzoquinone (BQ) was used to scavenge superoxide radical
thus the consumption of photo-excited electrons, thus improv-
ions (O2−). Similarly, ammonium oxalate (AO) and tert-butyl
ing the electron–hole separation efficiency which has a positive
alcohol (TBA) were used to scavenge photo-generated holes
effect on photo-catalytic activity. Also, the optimum (5%) Cu
(h+) and hydroxyl radicals (OH•), respectively. Fig. 7a elaborates
doped photo-catalyst enhances O–O bond cleavage, and the
the ROS studies, which confirmed the degradation of pyridine
two e− oxygen reduction reaction for the generation of H2O2
due to the induction of ROS. It was witnessed that ROS scaven-
on the active surface of the photo-catalyst, resulting in
gers inhibited photo-catalytic degradation of pyridine assisted
enhanced generation of ROS species.41
by 5% Cu–ZnO up to 35–45%, as compared to the conditions
The possible enhanced photo-catalytic mineralization of
provided during the batch treatment of pyridine. The rate con-
pyridine and quinoline over a Cu/ZnO photo-catalyst is shown
stants were calculated as 25 × 10−4, 6 × 10−4, 5 × 10−4, 6 × 10−4
schematically in Fig. 8. The enhanced photo-catalytic activity
and 4 × 10−4 min−1 for 5% Cu–ZnO, 5% Cu–ZnO + AO, 5% Cu–
of Cu doped ZnO is the result of better separation efficiency of
ZnO + BQ, 5% Cu–ZnO + TBA and 5% Cu–ZnO + SA, respect-
e−–h+ pairs due to the rapid photo-induced charge separation
ively. The reason for the scavenging was the in situ generation
as well as the inhibition of the recombination of e−–h+ pairs;
of ROS species like singlet oxygen, hydroxyl free radicals and
subsequently, the number of participating h+ increases in the
superoxide radicals, which inhibited the degradation of pyri-
photo-oxidation process.42 Wang et al.43 reported that the
dine; otherwise these ROS help in the degradation of nitrogen-
rapid recombination rate of photo-induced e−–h+ pairs inhi-
ous heterocyclic compounds.10
bits the degradation of organic pollutants.
The PL technique is a promising tool to study the photo-
electric and optical properties of semiconductor materials. A
PL peak gets generated because of the recombination of 4.2. Degradation pathway of pyridine and quinoline
photo-excited electrons and holes. Generally, an intense peak The photo-catalytic degradation of pollutants is assumed to
in the PL spectrum elaborates the faster charge recombination follow a given mechanism: when photons have energy equal to
rate and a broad peak in the PL spectrum illustrates enhanced or higher than the band gap of ZnO, electrons of the valence
electron (e−)–hole (h+) separation. In this way, a weaker inten- band are transferred to the conduction band, which results a

Fig. 7 (a) ROS scavenging studies for the photocatalytic degradation of pyridine and quinolone, (b) PL spectra of pure ZnO, and 1%, 5% and 10% Cu
doped ZnO.

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Fig. 8 Schematic representation of enhanced photocatalytic degradation of pyridine and quinoline over Cu/ZnO under UV radiation, where Eg (1%),
Eg (5%) and Eg (10%) are the band gaps for 1%, 5% and 10% Cu doped ZnO, respectively.

hole in the valence band that can be assembled by the follow- where h+VB is an electron vacancy (hole) in the valence band
ing photo-catalytic reactions:20 and e−CB is an electron in the conduction band. Yin et al.44
reported that a Cu doped TiO2 photo-catalyst increased the for-
ZnO ! e CB þ hþ VB ð6Þ
mation of •OH free radicals more than TiO2 alone, which
e CB þ O2 ! • O2  ð7Þ enhanced the degradation efficiency for pollutants in aqueous
solution. In the present study, a Cu doped ZnO photo-catalyst
hþ VB þ OH ! • OH ð8Þ enhanced the photo-catalytic removal of pyridine and quino-
• line by the following mechanism:
O2  þ H2 O ! HO2 • þ OH ð9Þ

HO2 • þ H2 O ! H2 O2 þ • OH ð10Þ Cuþ þ H2 O2 ! Cu2þ þ OH þ • OH ð13Þ

Cu2þ þ e ! Cuþ ð14Þ
H2 O2 ! 2• OH ð11Þ
Several intermediates were detected (using GC-MS analysis)
•
OH þ organic compounds ! CO2 þ H2 O þ NH3 etc: ð12Þ in the aqueous samples that were extracted during the photo-

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Fig. 9 Photocatalytic degradation mechanism of pyridine and quinoline.

catalytic degradation of pyridine and quinoline. Fig. 9 shows as with previous literature available on pyridine
different possible pathways for the degradation of pyridine degradation.4,45 There are basically four possible paths for
and quinoline. These photo-catalytic degradation pathways are complete degradation of pyridine with the help of in situ gen-
proposed based upon comparison of the reaction intermedi- erated •OH free radicals (eqn (2)–(10)). In possible path I of
ates detected by GC-MS analysis with the NIST library as well pyridine degradation, the pyridine first converts to pyridine-

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2,3-diol which converts to pyridine-2,3-dione after a ring pyridine and quinoline degradation were found to follow
opening step and further converts into N-(4-oxobut-1-enyli- pseudo-first-order kinetics. The photo-catalytic mechanism of
dene) formide, (3Z,5Z)-5-(carboxymethylimino)pent-3-enoic pyridine and quinoline over a Cu/ZnO photo-catalyst was illus-
acid and (Z)-5-(carboxymethylamino)-5-oxopent-3-enoic acid. trated by calculating the band gap energy of the conduction
Whereas in possible degradation path II, pyridine converts and valence bands of semi-conductors with respect to O2/O2•−
into (Z)-5-(carboxymethylamino)-5-oxopent-3-enoic followed by and •OH/H2O (vs. NHE) and the HOMO–LUMO energy level of
pyridine-2,5-diol, pyridine-2,5-dione, 6-hydroxypyridine-2,5- pyridine and quinoline. Cu/ZnO formed type-I heterostructures
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dione (ring opening) and (Z)-N-formyl-4-oxobut-2-enamide. In that achieved enhanced charge separation and easy charge
degradation pathways III and IV, pyridine converts into pyri- transfer. Photo-luminescence (PL) and ROS scavenger studies
dine-3,5(2H,4H)-dione followed by pyridin-3-ol, pyridin-3(4H)- showed that the in situ generated highly reactive species like
•
one and pyridine-3,5-diol. In all the possible paths discussed, OH, •O2− and h+ play important roles in pyridine and quino-
the generated intermediates undergo ring cleavage and form line mineralization. Overall, the 5%Cu/ZnO photo-catalyst was
many organic acids like carbamic acid, maleic acid, malonic found to be effective in mineralizing heterocyclic organic
acid, acrylic acid, oxalic acid, succinic acid, formic acid and pollutants in aqueous solution.
acetic acid.
There are three possible degradation paths for quinoline, as
shown in Fig. 9, observation of which was supported by the Conflicts of interest
intermediates detected by the GC-MS analysis and literature
reports on quinoline degradation.46,47 In paths I and II, quino- There are no conflicts to declare.
line first converts into quinolin-2-ol and quinolin-5-ol, respect-
ively. Quinolin-2-ol can follow different routes to produce acet-
ophenone via quinolin-2(1H)-one, N-phenylformamide and References
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