Accepted Manuscript

Title: Magnetically recoverable graphitic carbon nitride and

NiFe2 O4 based magnetic photocatalyst for degradation of
oxytetracycline antibiotic in simulated wastewater under solar
light

Authors: Anita Sudhaik, Pankaj Raizada, Pooja Shandilya,

Pardeep Singh

PII: S2213-3437(18)30284-7
DOI: https://doi.org/10.1016/j.jece.2018.05.039
Reference: JECE 2404

To appear in:

Received date: 20-2-2018

Revised date: 20-5-2018
Accepted date: 21-5-2018

Please cite this article as: Anita Sudhaik, Pankaj Raizada, Pooja Shandilya,
Pardeep Singh, Magnetically recoverable graphitic carbon nitride and NiFe2O4
based magnetic photocatalyst for degradation of oxytetracycline antibiotic in
simulated wastewater under solar light, Journal of Environmental Chemical
Engineering https://doi.org/10.1016/j.jece.2018.05.039

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Magnetically recoverable graphitic carbon nitride and NiFe2O4 based magnetic
photocatalyst for degradation of oxytetracycline antibiotic in simulated wastewater under
solar light

Anita Sudhaika, Pankaj Raizadaa,b*, Pooja Shandilyaa and Pardeep Singha,b

a
School of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan (HP) India-173229

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b
Himalayan Centre for Excellence in Nanotechnology, Shoolini University. Solan (HP) India-
173229

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Corresponding Author

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Tel: +91-1792-308000,

Fax: +91-1792-30800
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A
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Email: pankajchem1@gmail.com

Graphical abstract
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 Highlights

 Graphitic carbon nitride (GCN) was coupled with NiFe2O4.

 GCN/NiFe2O4 was effectively used to mineralize oxytetracycline antibiotic.

 Photocatalysis was substantially affected by adsorption process.

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 GCN/NiFe2O4 was magnetically separated in 2 minute from reaction solution.

 GCN/NiFe2O4 has significant stability for ten catalytic cycles.

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Abstract

In this work, we report the applicability of NiFe2O4 loaded graphitic carbon nitride (GCN/

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NiFe2O4) as a magnetic photocatalyst for wastewater treatment. Herein, GCN was prepared by
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thermal condensation of urea and successfully loaded with NiFe2O4 nanoparticles. . GCN/NiFe2O4
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was characterized by FESEM, HRTEM, IR, XRD, VSM and UV visible spectral analysis. High
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surface area of GCN/NiFe2O4 was suitable for adsorption coupled photocatalysis. The
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GCN/NiFe2O4 exhibited significant photocatalytic activity for mineralization of oxytetracycline

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(OTC) antibiotic under solar light. The OTC was completely mineralized in 8 h during

simultaneous adsorption and photocatalysis process. The rate of OTC degradation was optimal at
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pH 5. GCN/NiFe2O4 possessed ferromagnetic behavior and could be easily separated by external

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magnetic field from waste water. The excellent activity of GCN/NiFe2O4 was due to efficient

separation of photogenertaed electron and hole pair. GCN/NiFe2O4 exhibited significant recycle
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efficiency for ten catalytic cycles.

Keywords: GCN; NiFe2O4; Nanocomposite; Photocatalysis; Antibiotic mineralization; Magnetic

recovery.

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1. INTRODUCTION

Antibiotics are most prescribed medicines which easily enter into aquatic system. Non-

biodegradability and persistence nature of antibiotics pose major threat to quality of natural water

sources [1, 2]. The conventional physico-chemical methods such as chemical oxidation

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coagulation, flocculation, photocatalysis and aerobic biological treatments have been generally

applied to remove antibiotics in wastewater [2]. Among all these methods, semiconductor based

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photocatalytic processes have shown great potential due to successful utilization of renewable

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solar energy [3, 4]. Recently, graphene family based carbonaceous semiconductors are regarded

as potential photocatalysts due their abundance, non-toxic nature, chemical stability and low cost

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[5-7]. In this context, graphitic carbon nitride (GCN), a π-conjugated polymeric semiconductor

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has attracted scientific community all over the world [8, 9]. The narrow band gap (~2.7 eV), two-
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dimensional structure and facile synthesis route make GCN a stable visible-light active
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photocatalyst [10 ,11]. The CB minimum of GCN (−1.12 eV vs. NHE) is responsible for high

reduction of photogenerated electrons [12-15]. However, GCN suffers from high recombination
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rate of photogenerated electron hole pair and low specific surface area. The bulk GCN has stacked
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polymeric layers causing overall decrease in photocatalytic efficiency of GCN [16-18].

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Till date different approaches such as metal/non-metal doping, surface sensitization,

semiconductor coupling, band gap bending and heterojunction formation have been utilized to
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enhance the photocatalytic activity of GCN [19, 20]. Among these strategies, heterojunction

formation between GCN and metallic semiconductors having well-matched band gap and redox
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potential is regarded as promising strategy to improve the efficiency of GCN based photocatalytic

systems. The heterojunction formation results in effective separation of photogenerated electron

and hole pair. The magnetic photocatalysts have been effectively used to overcome time

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consuming and tedious separation of photocatalyst from reaction solution due to quick magnetic

separation using external magnetic field [21, 22]. Nickel ferrite (NiFe2O4) is an inverse spinel

with equal number of Ni2+ and Fe3+ locates on octahedral sites and remaining Fe3+ locates on

tetrahedral sites with band gap of 2.19 eV [23, 24]. Due to suitable optical band gap and

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appropriate positioning of CB and VB with respect to redox potential, NiFe2O4 is emerging as a

promising visible-light active photocatalyst [25, 26]. Xu et al. prepared magnetic photocatalyst

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TiO2/NiFe2O4 with typical ferromagnetic hysteresis and used it for the photodegradation of methyl

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orange dye in water [27]. Naeri et. al. synthesized NiFe2O4-NiO photocatalyst via a facile

precipitation method using agents such as starch, glucose, gelatin, salicylic acid and

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polyvinylpyrrolidone and green in the water. NiFe2O4-NiO exhibited significant recycle

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efficiency for acid blue, acid violet and acid black removal form aqueous phase [28].
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Owing to small size and magnetic interaction, nanosized ferrites tend agglomerate in
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reaction leading to reduction in photoactive volume [21]. Moreover, preliminary adsorption of

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aqueous phase pollutants on photocatalyst surface is essential for efficient photodegradation of

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pollutants in aqueous phase [29]. Sourav et al. fabricated magnetic NiFe2O4/GSC and NiFe2O4/BT

nanocomposites using simple hydrothermal methods. NiFe2O4/GSC and NiFe2O4/BT displayed

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significant photocatalytic activity for antibiotics degradation and quick separation from reaction

solution due to magnetic nature of photocatalyst [30]. In precedent work, we report magnetically
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separable and visible-light driven GCN/NiFe2O4 nanocomposite for the photodegradation of

oxytetracycline antibiotic in aqueous phase. GCN/NiFe2O4 nanocomopsite was characterized

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employing various spectral analysis viz. scanning electron microscope (SEM), transmission

electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy

(FTIR), vibrating spin magnetometer (VSM) and energy-dispersive X-ray spectroscopy (EDX)

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analysis. The effect reaction parameter such as catalyst dose, OTC concentration and pH of

reaction was also investigated. The mineralization of OTC was investigated in term of COD and

CO2 estimation. Lastly, recyclability and mechanistic view of OTC degradation using

GCN/NiFe2O4 were also explored.

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2. EXPERIMENTAL

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2.1. Synthesis of GCN

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In this work, all used chemical were of analytical grade. Urea, nickel chloride (NiCl2.6H2O),

ferric chloride (FeCl3.6H2O), sodium hydroxide (NaOH) were procured from Sigma Aldrich

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Company and used without further purification. GCN was synthesized by thermal

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polycondensation of urea . Typically, 5 g of urea was heated in a muffle furnace at 550 oC for 4 h
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with heating rate of 10°C min−1. Finally, yellow colored GCN was obtained and preserved for
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further use.

2.2. Preparation of GCN/NiFe2O4 nanocomposite

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GCN/NiFe2O4 nanocomposite was prepared in accordance with scheme 1. Briefly, 1.0 g

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of graphitic carbon nitride was dispersed into 150 mL water and ultrasonicated for 20 min. To this
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solution 0.2M (25 ml) of NiCl2·6H2O and 0.4M (25 ml) of FeCl3·6H2O solution was added and

stirred continuously. The solution was heated at 80 0C for 3 h to obtain GCN/NiFe2O4 composites.
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The precipitates were filtered, washed with double distilled water and ethanol for 3 times and oven

dried at 700 oC for 3 h. The resultant final product was labelled as GCN/NiFe2O4 composite. Same
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methodology was used for NiFe2O4 preparation without addition of GCN to reaction solution.

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2.3. Photocatalytic activity test

The photocatalytic activity of GCN/NiFe2O4 was evaluated for antibiotic degradation from

aqueous solution and explored in a double walled borosilicate beakers with thermostatic water

circulation arrangement (25±0.3°C). The solar light intensity was measured using digital lux-meter

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(35 x 103± 1000lx). Typically, 0.50 g powdered photocatalyst was added to 50 mL antibiotic

solution. The solution was placed under solar light and stirred continuously. At certain time

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intervals, 2 mL aliquot was withdrawn and magnetically separated from aliquot. The resulting

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clear aliquot was analyzed on UV–Vis spectrophotometer to record change in OTC concentration

at 260 nm. Photocatalytic experiments were conducted between April to June 2017 (10 am to 2

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pm). The chemical oxygen demand (COD) was measured by closed reflux method. The unreacted
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oxidant was determined by titrating sample with ferrous ammonium sulphate using ferroin
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indicator. The CO2 was estimated by titrating sample with NaoH using phenolphthalein as
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indicator. The inorganic ions were detected using TDS bench top ion analyser. The removal
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efficiency was calculated using Eq.(1).

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𝐶0 −𝐶𝑡
% 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = (1)
𝐶0
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Where, C0 is the initial concentration of sample/COD and Ct/COD is instant concentration of

sample/COD. The rate constant (k) and half-life period (t1/2) were calculated using Eq.(2) and (3)
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respectively.
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𝑘 = 2.303 × 𝑠𝑙𝑜𝑝𝑒 (2)

0.693
𝑡1 = (3)
2 𝑘

Where slope was obtained from the plot of ln (c) versus‘t’.

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3. Results and discussion.

3.1. Characterization of GCN/NiFe2O4

The morphology of GCN and GCN/NiFe2O4 was investigated by scanning electron

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microscopy (SEM) and transmission electron microscopy (TEM) . The representative SEM images

of GCN and GCN/NiFe2O4 are shown in Figure 1(a-f). Figure 1(a-c) revealed quite rough and

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irregular sheet like structure of GCN with thickness of 50-70 nm. The loading of NiFe2O4 was

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clearly seen in GCN/NiFe2O4 [31]. TEM micrographs displayed non-uniform curled sheet like

structure of GCN (Black portion in TEM images) (Figure 2a and b). The deposition of NiFe2O4

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was clearly seen in Figure 2c and d. The loading NiFe2O4 nanoparticles onto GCN with good

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dispersion is vital for effective separation of photogenerated electron hole pairs [32].
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XRD patterns of GCN, NiFe2O4 and GCN/NiFe2O4 are shown in Fig. 3. The
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characteristics peaks of CN were recorded at 12.8˚ and 27.2˚ [33, 34]. The peak at 12.8˚ was

assigned to in-plane structural packing motif of tri-s-triazine units (100) and dominant peak at
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28.2˚corresponded to inter-planer stacking reflection of aromatic segments (002) planes of

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tetragonal phase of GCN (JCPDS 87-1526) [35, 36]. XRD pattern of NiFe2O4 exhibited diffraction
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peaks at 18.1◦, 32.3◦, 36.5◦, 38.3◦, 43.8◦,54.2◦, 57.8◦, 63.0◦ and 74.2◦ with reflection planes at (111),

(220), (311), (222), (400), (422),(511),(440) and (533). These diffraction peaks confirmed spinel
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cubic structure of NiFe2O4 (JCPDS 10-0325) [37]. In GCN/NiFe2O4, the major characteristic

diffraction peaks of NiFe2O4 and GCN were observed [38].

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FTIR spectrum of pristine GCN depicts typical stretching bands of aromatic C-N heterocycle

in range of 1200–1650 cm-1 [Fig. 4] [39, 40]. The absorption peaks at 807 cm-1 was attributed to

characteristics breathing modes of tristriazine ring units. Another peaks between 3200-3400 cm-1

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was assigned to stretching modes of N–H bonds of primary (–NH2) and secondary (=N–H) amines.

These peaks suggested hydrogenation of some nitrogen atoms in the GCN composite material [41].

In FTIR spectrum of NiFe2O4, peaks at 1057, 712, 636 and 417 cm-1 corresponded to Fe-O and

Ni-O stretching vibrations [42]. In case of GCN/NiFe2O4 composites, the peaks at 609 and 500

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cm−1 were due to tetrahedral site (Fe-O) and octahedral metal stretching (Ni-O) bond, respectively

[43]. These two strong absorption bands were of inverse spinel ferrite NiFe2O4 [44]. The shift in

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IR absorption peaks of GCN towards lower wave number (3178–3174, 1638–1613, 1082–1074

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and 743–730 cm−1) indicated the successful formation of GCN/NiFe2O4 composite.

EDX spectrum of synthesized pristine GCN indicated presence of carbon (C) and nitrogen

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(N) element in GCN (Fig. 5 a and b). The diffraction peaks of GCN/NiFe2O4 obviously ascribed

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to carbon (C), nitrogen (N), nickel (Ni), iron (Fe) and oxygen (O) elements which evidently
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supported the anchoring of NiFe2O4 on GCN surface. UV-visible and optical band gap analysis were
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performed by dispersing GCN and NiFe2O4 in ethanol at concentration of 1 mg/10 mL (Fig. 5 c and d).

GCN and NiFe2O4 had an absorption edge at 460 nm and 470 and its composites displayed increased and
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wider visible light adsorption. Moreover, Tauc’s formula was used to calculate band gaps (Eq. 4):
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𝛼ℎʋ = 𝐵(ℎʋ − 𝐸𝑔 )𝑛 (4)

where 𝛼 = absorption coefficient = 2.303 A/l, Eg= optical band gap, B = band tailing parameter, h
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is the photon energy and n = ½ for direct band gap. The optical band gap is estimated by
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extrapolating the straight line of curve between (𝛼ℎʋ) and ℎʋ when 𝛼 = 0. The respective band

gaps of GCN and NiFe2O4 were calculated as 2.7 and 2.19 eV. The narrowing in band gap of
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GCN/NiFe2O4 increased the absorption in visible region [42]. The high surface area of

photocatalyst is highly needed for efficient adsorption coupled photocatalysis process. Fig. 6 (a

and b) shows N2 adsorption adsorption/desorption isotherm of GCN and GCN/NiFe2O4

photocatalyst. Both GCN and NiFe2O4/GCN exhibited type IV isotherm having mesoporous
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nature. The BET specific surface areas of GCN and NiFe2O4/GCN are 16.6 and 15.5 cm2,

respectively. The mesoporous nature of GCN and NiFe2O4/GCN facilated the adsoprtion of OTC

onto the suarfce of photoctalysts.

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3.2. Photocatalytic activity of GCN/NiFe2O4 for OTC degradation

3.2.1. Removal of OTC under different reaction conditions

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The photocatalytic activity of synthesized GCN, NiFe2O4 and GCN/NiFe2O4 was evaluated

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for oxytetracycline degradation under solar light irradiation. Fig. 7a shows OTC removal under

different catalytic systems. Under solar light, OTC degradation was remarkable in presence of

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GCN/NiFe2O4 composites. The efficiency of photocatalysts followed the trend: GCN/NiFe2O4 (97

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%) > NiFe2O4 (65 %) > GCN (59 %). GCN/NiFe2O4 exhibited higher efficiency as compared to
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NiFe2O4 and GCN. During surface assisted photodegradation reactions, adsorption of aqueous
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phase pollutant is a vital factor. In this study, the photodegradation process was explored under

three different reaction conditions i.e. adsorption in dark (DA), equilibrium adsorption followed
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by photodegradation (A-P) and simultaneous adsorption and photocatalysis (A+P). Figure 7(b)
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showed the removal efficiency of GCN/NiFe2O4 in the absence of solar light. During dark
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experiments, 60 % of OTC was removed using adsorption process. Figure 7(c) showed A-P and

A+P process based on removal of OTC using GCN/NiFe2O4. Synergistic adsorption and
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degradation process (A+P) had degraded 94% of OTC in 60 min under solar light. While only 65%

of OTC degradation was observed in 65 min during A-P process. The efficiency of OTC
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photodegradation followed the trend: A+P > DA > A-P. In case of A+P, adsorbed OTC was

simultaneously photodegraded under solar light. However, in case of A-P, excessive adsorption of

OTC acted as a filter for sunlight penetration and photoactive volume was reduced which

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ultimately caused decrease in OTC degradation [45, 46]. So, integration of adsorption and

photocatalysis processes in A+P process enhanced OTC degradation under solar light irradiation

[47].

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3.2.2. Optimization of reaction parameters for OTC removal during A+P process

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In order to optimize reaction conditions, effect of OTC concentration, catalyst loading and pH

was investigated for OTC degradation during A+P process (Fig. 7 c-e). The results were analyzed

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in term of first order rate constant (k) and half life time (t1/2). The initial concentration of OTC was

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varied from 0.7×10-4 mol dm-3 to 9×10-4 mol dm-3 (Fig. 7c). The rate constant increased from

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3.2×10-4 s-1 to 5.4×10-4 s-1 with the increase in OTC concentration from 0.7×10-4 mol dm-3 to
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1.0×10-4 mol dm-3. However, rate constant reduced from 5.4 ×10-4s-1 to 3.6 ×10-4 s-1 with increase
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in OTC concentration from 1.0×10-4 mol dm-3 to 9.0 ×10-4 mol dm-3. The rate constant was

maximal at 1.0×10-4 mol dm-3 of OTC concentration. The availability of OTC molecules increased
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the rate of degradation process [48]. But above optimal concentration, excessive adsorption of
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OTC molecules on the surface of photocatalyst inhibited rate of OH˙ formation [49, 50]. The

amount of GCN/NiFe2O4 photocatalyst was varied from 10 mg/50 mL to 120 mg/50 mL to explore
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the effect of photocatalyst dose on OTC degradation (Fig 7 d). Rate constant increased from 1.3×
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10-4 s-1 to 5.3 × 10-4s-1 with increase in GCN/NiFe2O4 loading from 10 mg/50 mL to 120 mg/50

mL. However, further increment in catalyst loading resulted in reduction in value of rate constant.
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With increase in catalyst loading, availability of active sites on the surface of GCN/ NiFe2O4

composite resulted in increased degradation of OTC. As OTC concentration reached optimal

value, excessive concentration of OTC started acting as a filter for incident light. So, optimal

amount of GCN/NiFe2O4 composite was necessary to avoid excess amount of photocatalyst and to

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ensure the availability of light photons for efficient photodegradation of OTC [51]. With increase

in pH from 1 to 5, rate constant increased from 1.8×10-4 s-1 to 6×10-4 s-1 ( Fig. 7e). However, further

increase in pH from 5 to 13 resulted in reduction in rate constant value. Above pH of zero point

charge (pHzpc), photocatalyst surface was predominantly negatively charged above and the

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positively charged species dominated the surface of photocatalyst. In present study, pHzpc of

GCN/NiFe2O4 was found to be 7.8. At lower pH, both absorbent and OTC were positively charged

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and adsorption of OTC was lower but as the pH changed from acidic to basic, ionic species of

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OTC completely changed from positive to negative charge. At pH 5, OTC molecule changed to

zwitter ionic form (H2OTC±) at resulted more adsorption of OTC molecule. At pH 11, OTC existed

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mainly as HOTC- and OTC2- [52]. Due to these factors, photocatalytic degradation of OTC was

maximal at pH 5. N
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3.2.3. Photocatalytic mineralization of OTC using GCN/NiFe2O4/A+P and GCN/NiFe2O4/A-P
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From above discussion, it can be summarized that OTC degradation using

GCN/NiFe2O4/A+P and GCN/NiFe2O4/A-P catalytic systems was influenced by adsorption of

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OTC onto GCN/NiFe2O4 surface. So, the degradation of both OTC was investigated under A+P
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and A-P processes for 10 h to obtain complete mineralization of OTC. The COD removal and CO2
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release were investigated long term photocatalytic process (Fig. 8 a-d). During A+ P process,

During 8 h of exposure, 99, 70 and 65 % of COD removal was obtained for GCN/NiFe2O4, GCN
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and NiFe2O, respectively [53, 54]. While in case of A-P process, GCN/NiFe2O4, GCN and NiFe2O

had respective 50, 40 and 65% of COD removal for OTC mineralization. The similar kind of
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observations was noticed for evolution of CO2 during mineralization process. These findings

clearly indicated that OTC was completely mineralized in 8 h using GCN/NiFe2O4 /A+P catalytic

system [55, 56]. Under solar light, there was generation of valence band (VB) holes (h+) and

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conduction band (CB) electron (e¯) in both GCN and NiFe2O4 [57, 58]. The VB edge of GCN

and NiFe2O4 were found to be 1.02 eV and 1.88 eV, respectively and the CB edge of GCN and

NiFe2O4 were -0.71 eV and -0.57 eV, respectively. The photogenertaed holes (h+) of GCN were

migrated to valance band of NiFe2O4. While photogenertaed electrons (e¯) of NiFe2O4 were moved

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down to conduction band of GCN (Fig 9). This efficient electron-hole pair (EHP) separation was

responsible for improved photocatalytic activity of GCN/NiFe2O4 photocatalyst. The conduction

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band electron reacted with O2 to produce ·OH2 radicals. The holes reacted with OH¯ ions to form

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OH· radicals. The produced hydroxyl radicals completely mineralized OTC into CO2 and H2O

[59].

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3.2.3. Magnetic separation and recyclability of GCN/NiFe2O4

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The quick and easy separation of photocatalyst is highly needed for efficient slurry type
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photoreactors [60, 61]. Fig. 10 (a) displays magnetization hysteresis curve for GCN/NiFe2O4. The
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magnetic remanence (Mr) and saturation magnetization (Ms) values of GCN/NiFe2O4 were

observed as 12.27 and 20.54 emu/g, respectively. These observations indicated the ferromagnetic
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behavior of GCN/NiFe2O4 [30]. GCN/NiFe2O4 was separated from reaction solution in 2 min
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using a permanent magnet and used for consecutive ten catalytic cycles (Fig. 10 b). After ten
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catalytic cycles, 90 % of removal efficiency of GCN/NiFe2O4 was obtained. These findings

indicated the stability of GCN/NiFe2O4 photocatalyst during consecutive catalytic cycles. (Fig. 10
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c) In case of bare NiFe2O4, catalytic efficiency was reduced due to agglomeration of magnetic

nanoparticles and GCN was separated form reaction solution using simple using sedimentation
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process in 8 h. The recyclability experiments clearly indicated significant improved

GCN/NiFe2O4 recycle efficiency as compared to GCN and bare NiFe2O4.

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4. Conclusions

In summary, we have fabricated magnetically separable and visible light active graphitic

carbon nitride and NiFe2O4 based nanocomposite. GCN/NiFe2O4 was characterized employing

various spectral techniques such as SEM, TEM, FTIR, XRD, VSM and BET spectral techniques.

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GCN/NiFe2O4 exhibited ferromagnetic nature and was magnetically separated from reaction

solution in 2 min. GCN/NiFe2O4 had significant adsorption ability for OTC removal from water.

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Excessive adsorption of antibiotics had retarded photodegradation process in A-P processes, while

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A+P process had synergistically effected of photodegradation of OTC. The effect of reaction

parameters was used to explore degradation of OTC under solar light. The OTC removal was

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maximum at pH 5. The mineralization of OTC was successfully achieved in 8 h using

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GCN/NiFe2O4/A+P catalytic system. The mineralization process occurred via hydroxyl radical
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and as depicted in proposed photocatalytic mechanism its hydroxyl radical (OH.). Due to magnetic
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separation, GCN/NiFe2O4 nanocomposite possessed substantial recycle efficiency for 10 catalytic

cycles. Magnetically separable photocatalyst was recovered from reaction solution using external
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magnet in quick time. From this work, it can be inferred that GCN/NiFe2O4 photocatalyst can be
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efficiently used wastewater treatment containing antibiotics as pollutants.

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Acknowledgment
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The corresponding author, Dr. Pankaj Raizada is grateful to Science and Engineering Research

Board-DST (SERB), Department of Science and Technology (DST) New Delhi, India for financial
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support through Young Scientist Fast Track research project no. YSS/2015/000898.

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Figure 1. SEM images of GCN (a-c), GCN/NiFe2O4(d-f).
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Figure 2: TEM images of GCN (a-c),GCN/NiFe2O4(d-f)

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Figure 3. XRD spectrum of GCN, NiFe2O4 and GCN/NiFe2O4.
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Figure 4: FTIR spectra of GCN, NiFe2O4 and GCN/NiFe2O4 composite.

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Figure 5(a-d). EDX spectra of (a) GCN, (b) GCN/NiFe2O4, (c) UV-visible diffuse reflectance
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spectra of GCN and GCN/NiFe2O4 and band gap analysis of GCN and GCN/NiFe2O4 .
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Figure 6. BET isotherm of GCN and GCN/Fe2O4

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Figure 7 (a). Degradation efficiency of different photocatalysts, (b) Adsorbent in dark and (c)
Photodegradation process using GCN/NiFe2O4 system for OTC degradation under solar light. (d-
f) Effect of reaction parameters on OTC degradation under solar, GCN/NiFe2O4 system. (c) Effect

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of OTC concentration; (e) Effect of catalyst loading. (f) Effect of pH ; Reaction conditions: [OTC]
= 1 ×10-4 mol dm-3 ; [OTC]= 1 × 10-4 mol dm-3 ; [catalyst] = 50 mg/100ml ; pH= 5 .0; Solar
light intensity= 35 × 103± 1000 lx; reaction time = 10 h.

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Figure 8. Mineralization of OTC under solar light using A+P and A-P processes. a and d are
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COD removal graph. b and d are CO2 evolution graph. Reaction conditions: [OTC] = 1x10-4
mol dm-3 ; [OTC]= 1x10-4 mol dm-3 ; [catalyst] = 50 mg/100ml ; pH= 5.0; Solar light intensity=
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35 x 103± 1000 lx; reaction time = 10 h.

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Figure 9. Proposed mechanism for the degradation of OTC using GCN/NiFe2O4.
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Fig. 10 (a-c): (a) Hysteresis curve of GCN/NiFe2O4. (b) Magnetic separation of phtotocatalyst (c)
recycle efficiency of photocatalyst. [OTC] = 1 ×10-4 mol dm-3 ; [OTC]= 1 × 10-4 mol dm-3 ;
[catalyst] = 50 mg/100ml ; pH= 5.0; Solar light intensity= 35 × 103± 1000 lx; reaction time =
10 h.

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Scheme 1: Schematic representation of preparation of GCN/NiFe2O4

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