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Materials Today: Proceedings 22 (2020) 1885–1892 www.materialstoday.com/proceedings

ICMMM 2019

Enhanced Photocatalytic Activity of Ag-CoFe2O4 Over NixCo1-x

Fe2O4 Catalyst Under Visible Light: A Comparative Study
Srinivas M a*
a
Department of Chemistry, REVA University, Kattigenahalli Yelahanka, Bangalore-560064

Abstract

NixCo1-x Fe2O4 (x=0.5%) catalyst was prepared by sol-gel method and Ag-CoFe2O4 (0.5%) catalyst was prepared by photo-
reduction method. These catalysts were characterized by various analytical techniques. UV-Visible spectra of NixCo1-x Fe2O4 and
Ag-CoFe2O4 samples show wide absorption in the visible region. PL spectra of NixCo1-x Fe2O4 show higher emission than the Ag-
CoFe2O4 sample. This indicates that Ag-CoFe2O4 catalyst possesses lower recombination rate. Cyclic voltametry (CV) of Ag-
CoFe2O4 electrode observed enhanced oxidation and reduction peak. Langmuir adsorption isotherm model was calculated by
using Langmuir equation and in which the Ag-CoFe2O4 sample shows higher adsorption than NixCo1-x Fe2O4. Langmuir
adsorption model best fits the Ag-CoFe2O4 sample towards fast red (FR) dye degradation. This indicates Ag-CoFe2O4 sample
generates more number of adsorption sites than NixCo1-x Fe2O4. Ag-CoFe2O4 catalyst exhibits higher photocatalytic activity than
the NixCo1-x Fe2O4 catalyst could be due to the well known phenomena of surface plasmon resonance (SPR) which allows more
electrons to be available on the surface of Ag-CoFe2O4 catalyst, and these electrons react with atmospheric oxygen to generate
additional number of super-oxides radical.
© 2019 Elsevier Ltd. All rights reserved.
Peer-review under responsibility of the scientific committee of the 2nd International Conference on Materials Manufacturing and
Modelling, ICMMM – 2019.

Keywords: Spinel structure; Adsorption; Photocatalysis; semiconductor

* Corrsponding author. Tel.: +91-0000000000

E-mail address: author@institute.xxx

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Peer-review under responsibility of the scientific committee of the 2nd International Conference on Materials Manufacturing and Modelling,
ICMMM – 2019.
1886 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892

1. Introduction

Preparations and properties of transition metal ferrites with the molecular formula MFe2O4 (M = Zn, Cd, Ni, Mn,
Co etc.,) have been largely studied as they are important semiconducting materials due to low-cost and chemically
stable. Photocatalysis has been proven to be effective in treating wastewater pollution and hydrogen generation has
received much attention [1-8]. Cobalt ferrites have narrow band gap and could be potential photocatalyst for
degradation of pollutants due to their superiority in full utilization of natural sunlight [9-10]. The introduction of
nickel in the cobalt ferrite lattice leads to an interesting cation distribution over tetrahedral A-sites and octahedral B-
sites. Noble metal nanoparticles such as Ag and Au have received much attention in many new applications [11-15].
Ag nanoparticles improve the charge carrier separation and lesser recombination [16-17]. In this study, NixCo1-
xFe2O4 sample was prepared by sol-gel method and Ag-CoFe2O4 sample is synthesized by photoreduction method
and to probe its Langmuir adsorption isotherm model and photocatalytic activity by taking fast red as a model
pollutant under visible light irradiation.

2. Experimental section

2.1. Materials

FR, Ni(NO3)2.6H2O, Fe(NO3)3.9H2O, and Co(NO3)2.6H2O are analytical grade provided by Sigma Aldrich.
AgNO3, K4Fe(CN)6, K3Fe(CN)6, KCl, silicone oil, graphite powder sodium hydroxide (NaOH), hydrochloric acid
(HCl) were obtained from Sisco-chemical industries. All reagents were used without further purification.

2.2. Synthesis of NixCo1-xFe2O4 by sol-gel route method

The procedure adopted for the preparation of CoFe2O4 in the present research work is similar to the method
adopted by James wang et al., [18]. The citric acid (CA) is used as chelating agent and a solution of it was prepared
by dissolving 5% w/v and the solution was heated at 70 0C to obtain clear solution.
To this clear solution Co(NO3)2.6H2O, Fe(NO3)3.9H2O and Ni(NO3)2.6H2O were added in accordance with the
formula NixCo1-xFe2O4 (x=0.5). The solution was evaporated by stirring and heating for 4 hours at 70 °C until it
turns into a solid gel. Finally, the product was calcined in a furnace for 2 hours at 800 °C.

2.3. Preparation of Ag-CoFe2O4 catalyst

Surface silver metallization on CoFe2O4 was done by photoreduction method [19]. 0.478g of AgNO3 (0.5%) and
0.5g of oxalic acid is dissolved in 1L of distilled water. 1.5 g of CoFe2O4 was suspended in the above solution. The
pH of the suspension was adjusted to 6.8-7.0 by the addition of 0.1 N NaOH solutions. The above suspension was
irradiated with UV light for 40-50 min to get silver deposited CoFe2O4. After the irradiation, the solution containing
Ag-CoFe2O4 was allowed to stand for 6h. The colour of the reaction mixture changed under the UV light irradiation
indicating the process of reduction of Ag+ to Ago and confirming the deposition of Ago on CoFe2O4 surface. The
solid is filtered, washed, dried and was heated at 120o C for 2h and colour of the solid catalyst changes from black
to pale greyish black. The absence of silver in the aliquot sample was checked by chloride precipitation method
which confirms the complete silver deposition on CoFe2O4 surface.

2.4. Catalyst characterization

The catalyst is characterized by the following techniques: powder X-ray diffraction (PXRD), Fourier transform
infra red (FTIR) spectroscopic technique, UV-Vis absorption spectroscopic technique, Scanning Electron
Microscope (SEM) equipped with Energy-Dispersive X-ray analysis (EDX), surface area measurements by
Brunner–Emmet–Teller (BET) technique and X-ray photoelectron spectroscopy (XPS) techniques. The detail of the
experiment and instrumentation is given elsewhere [20].
 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892 1887

2.5. Photochemical reactor

The detail pertaining to photocatalytic degradation experiments are given elsewhere [20]. The solar light
experiments were performed under the direct sunlight between 11 a.m. to 2 p.m. The experiments were conducted at
Bangalore, India. The latitude and longitude of the place are 12.58 N and 77.38 E respectively. The average solar
intensity was measured by using solar radiometer and the intensity was found to be 0.761 KW/m2. The solar light
was focused through a convex lens. The solar radiation as a function of wavelength was measured by photometer,
which shows a maximum at 450 nm.

3. Resultant and discussion

3.1. PXRD

PXRD pattern of NixCo1-xFe2O4 shows peaks at 2θ values 18.39º (111), 30.27º (220), 35.56º (311), 36.85º (222),
42.86º (400), 53.89º (422), 57.31º (511), 62.90º (440) 71.48º (622) 74.63º (533) and for Ag-CoFe2O4 peaks at 2θ
values 18.30º(111), 29.91º (220), 35.26º (311), 37.78º (222), 43º (400), 53.15º (422), 56.74º (511), 62.31º (440)
70.82º (622) 73.59º (533) and it is in accordance with spinel structure with space group Fd3m which is in agreement
with JCPDS standard card (22-1086) as shown in the Figure 1a and 1b. The crystallite size was calculated by using
the Debye-Scherrer’s equation D=K λ/ β Cos θ. The crystallite size of NixCo1-xFe2O4 and Ag-CoFe2O4was found to
be 58.46 nm and 55.06 nm respectively.

600 311 1000 311

a) NixCo1-xFe2O4
500
800 b) Ag-CoFe2O4
400
Intensity

600
Intensity

300
400
440 400
200 220 222 511 440
220
511
100 533 400
111 422 200
622 111 422
222 533
0 622
0
10 20 30 40 50 60 70 80 10 20 30 40 50 60 70
2θ 2θ

Fig 1. PXRD pattern of a) NixCo1-xFe2O4 and b) Ag-CoFe2O4

3.2. UV-visible absorbance spectra

UV–Vis absorbance spectra of NixCo1-xFe2O4 and Ag-CoFe2O4 show the broad absorption band in the visible
region (Figure 2 a and b). Characteristic SPR peak of Ag particle is merged into CoFe2O4. Band gap values were
calculated for NixCo1-xFe2O4 and Ag-CoFe2O4 by using Kubelka-Munk function and band gap were found to be 2.21
and 2.19 eV respectively (inset Figure 2).
1888 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892

0.12
0.04 0.008

0.007

0.04 0.10
0.006

0.08
a) NixCoi-xFe2O4 0.005
C) Ag-CoFe2O4

1/2
0.004

[F(R)hv]
[F(R)hv )]1/2

0.06
0.003

0.04
0.002

0.02
0.03 0.001

Absorbance
Absorbance

0.03 0.00
0.000
1 2 3 4 5 6 7
Bandgap(eV)
1 2 3 4 5 6 7
Bandgap (eV)

0.02
0.02

0.01
0.01

300 400 500 600 700 800 400 500 600 700 800

Wavelength (nm) Wavelength (nm)

Fig. 2. UV-Visible spectra of a) NixCo1-xFe2O4 and b) Ag-CoFe2O4

3.3. PL

The PL spectra shows broad peak was observed between 545-565 nm for both the samples. This peak may
correspond to the transition of charges from valence band to conduction band (Figure 3 a and b). It was observed
that AgCoFe2O4 has the lower intensity compared to NixCo1-xFe2O4. These results suggest that trap sites induced by
the dopant prevent the lesser recombination of charge carriers at the bulk when compared to surface deposition of
Ag-CoFe2O4.
40

30
NixCo1-xFe2O4
Ag-CoFe2O4
PL emission

20

10

0
500 600

Wavelength (nm)

Fig. 3. PL spectra of a) NixCo1-xFe2O4 and b) Ag-CoFe2O4

3.4. CV

The chemically deposited NixCo1-xFe2O4 and Ag-CoFe2O4 electrodes, the oxidation and reduction potential were
tested using cyclic voltammetry. Ag-CoFe2O4 electrode shows enhanced and higher redox potential compared to
NixCo1-xFe2O4 (Figure 4a and b).
 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892 1889

0.00020
Bare
0.00015 Ag-CoFe2O4
NixCo1-xFe2O4
0.00010

0.00005

Current (A)
0.00000

-0.00005

-0.00010

-0.00015

-0.00020

-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential (V)
Fig. 4. CV of a) NixCo1-xFe2O4 and b) Ag-CoFe2O4

3.5. Langmuir adsorption isotherm model

Langmuir adsorption isotherm can be represented by the following equation [21]:

Ce 1 C
= + e (1)
q e bq m q m
Where, Ce and qe have the same significance as mentioned earlier. qm (mg/g) is the concentration of the FR dye
required to complete a unimolecular layer of adsorption and b is the Langmuir constant which is ratio of equilibrium
constants for adsorption and desorption. The plot of Ce/qe versus Ce gives a straight line whose slope and intercept
will give the values of b and qm (Figure 5 a and b and Table 1). Langmuir adsorption isotherm model is favourable
for both the catalysts and relatively the strong interaction between the FR and catalyst. Co-relation coefficient of
Ag-CoFe2O4 for Langmuir adsorption isotherm is significantly high than that of NixCo1-xFe2O4 catalyst.

9.25

9.20
a) NixCo1-xFe2O4
2
R = 0.9936
9.15
Ce/qe

9.10

9.05

9.00
3.6 3.8 4.0 4.2 4.4 4.6 4.8
Ce
1890 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892

9.25

9.20 b) Ag-CoFe2O4
2
R =0.9988

9.15
Ce/qe

9.10

9.05

3.6 3.8 4.0 4.2 4.4 4.6 4.8

Ce

Fig.5. The values of Langmuir adsorption isotherm constants for the adsorption of FR dye on the surface of (a) and (b) samples in the aqueous
medium.

Table 1: Langmuir adsorption isotherm constants for the adsorption of FR in an aqueous medium

Catalysts qm (mg/g) b (mgL-1 ) R2

NixCo1-xFe2O4 0.178523 8.377796 0.9936

AgCoFe2O4 0.200679 8.311919 0.9988

3.6. EIS

The electrochemical impedance technique was employed to characterize the electrical conductivity. The Nyquist
plot of NixCo1-xFe2O4 and Ag-CoFe2O4 as shown in Figure 6. Ag-CoFe2O4 has the smallest radius than NixCo1-
xFe2O4 electrode, implying that lowest resistance of the interfacial charge transfer. The smaller charge transfer
resistance is favourable for separation of charge carriers.

-80

Bare
-60 NixCo1-xFe2O4
Ag-CoFe2O4
Z''(ohm)

-40

-20

4 6 8 10 12 14 16 18 20 22
Z'(ohm)

Fig. 6. Impedance spectra of NixCo1-xFe2O4 and Ag-CoFe2O4 electrodes

 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892 1891

3.7. Photocatalytic activity

Photocatalytic activity of NixCo1-xFe2O4 and Ag-CoFe2O4 is evaluated by taking FR as the model pollutant under
visible light illumination. In presence of NixCo1-xFe2O4 and Ag-CoFe2O4 catalyst MB undergoes 83 and 95%
degradation at 90 min respectively which supports the rate constant values (Figure 7 a and b and Table 2). CoFe2O4
shows less photocatalytic activity compared to NixCo1-xFe2O4 and Ag-CoFe2O4 (CoFe2O4 catalyst is not shown in
the present research article). Tetrahedrally coordinated Ni+2 ions create electrically charged lattice defects are
beneficial for the photodegradation process. Doping of Ni+2 in CoFe2O4 an octahedral site becomes enlarged and
difficult to transfer electrons from NixCo1-xFe2O4 catalyst to the aqueous solution of FR dye. The larger crystallite
size of NixCo1-xFe2O4 increase the diffusion path length and hence bulk recombination of charge carriers prevails
over the charge transfer process and decreases the photocatalytic activity. Ag nanoparticle generates electron-hole
pairs under visible light illumination and this collective electron oscillation generates high concentration of energetic
electrons at its surface. Effective movement of electrons from CoFe2O4 to Ag, these electrons are trapped by
dioxygen molecule, generates super oxide radical which involved in the degradation of FR dye. Surface electrons
are greater the lifespan and it easily generates charge carriers. Alternatively, the electrons on reaction with dioxygen
under protonated condition generates H2O2 which can enhance the rate of the degradation process either by
generating hydroxyl radicals or serving as electron trap and hence the rate of the degradation reaction with Ag-
CoFe2O4 drastically increases. The improvement is owing to the electron descend consequence, where Ag particles
capable of operate as a puddle to bring together photoexcited electrons of the CoFe2O4 catalyst. Thereafter, those
photoexcited electrons can be used to trigger the photocatalytic reaction in improving the degradation rate. The
shrink in the electron density in Ag-CoFe2O4 tends to a boost in the hydroxyl group acidity. Hence, Ag-CoFe2O4
catalyst is more photocatalytic activity than the NixCo1-xFe2O4 catalyst. Photonic efficiency is calculated for both the
catalysts. Photonic efficiency depends on physico-chemical properties of the catalysts especially absorption
coefficient, the extent of photogenerated charge carriers etc.,. The Ag deposit particles on the CoFe2O4 surface
changes the original charge carrier concentration equilibrium by drawing the electrons out of the bulk CoFe2O4.
Higher photonic efficiency for Ag-CoFe2O4 catalyst could be due to the higher ability to absorb higher number of
photons.
1.1

1.0

0.9 NixCo1-xFe2O4
Ag-CoFe2O4
0.8

0.7

0.6
C/Co

0.5

0.4

0.3

0.2

0.1

0 20 40 60 80 100
Time (min)
Fig.7. C/Co vs time. Experiment contains 100 mg of photocatalysts dispersed in 250 mL of 10 ppm FR.

Table 2. Rate constant, regression coefficient (R2) values and percentage degradation of FR in the time period of 90 min
Percentage of
Photonic efficiency (Фλ
Catalysts Time (min ) Rate constant x 10-2 min-1 Degradation
x 10-8 mol-1Lm2
(%)
NixCo1-xFe2O4 90 1.5418 5.20 83
AgCoFe2O4 90 2.1335 9.86 95
1892 M. Srinivas / Materials Today: Proceedings 22 (2020) 1885–1892

4. Conclusion

NixCo1-xFe2O4 catalyst was prepared by sol-gel method and Ag-CoFe2O4 catalyst was prepared by photoreduction
method. The PXRD pattern indicates both the samples are the spinel structure. Ag-CoFe2O4 catalyst generates
number of photogenerated electrons and holes due to its lower PL emission intensity. Langmuir adsorption isotherm
model best to the Ag-CoFe2O4 catalyst due to the higher correlation coefficient value towards FR dye adsorption.
Higher the photocatalytic activity of Ag-CoFe2O4 than the NixCo1-xFe2O4 because of Ag nanoparticle generates
electron-hole pairs under visible light and this collective electron oscillation generates the high concentration of
energetic electrons at its surface catalyst which ropes the rate constant and photonic efficiency value.

Acknowledgements

Authors acknowledge Dr. Srivatsa S. K, .Atria Institute of Technology, for some of the illuminating discussions.

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