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Materials Today: Proceedings 5 (2018) 22063–22068 www.materialstoday.com/proceedings

The 3rd International Conference on Green Chemical Engineering Technology

(3rd GCET_2017): Materials Science

Influence of precipitating agent on catalytic activity of Fe3-xCoxO4

catalyst
Nor Aida Zubira,b, Rasyidah Alrozia,b*, Nur Syaherra Paisana,
Mohammad Khairul Azam Selamata, Anees Nurzalikha Zakaryaa,
Nur Alwani Ali Bashaha, Siti Aminah Md Alia, Norliza Ibrahimc
a
Faculty of Chemical Engineering, Universiti Teknologi MARA, Cawangan Pulau Pinang, 13500 Pulau Pinang, Malaysia
b
Hybrid Nanomaterial, Interfaces & Simulation (HYMFAS), Faculty of Chemical Engineering, Universiti Teknologi MARA, Cawangan Pulau
Pinang, 13500 Pulau Pinang, Malaysia
c
Faculty of Chemical Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia

Abstract

Cobalt ferrite catalysts (Fe3-xCoxO4) were synthesized by substituting cobalt into the structure of iron oxide via oxidation-
coprecipitation method. Two types of precipitating agent (strong and weak base) were utilised at different molarity (1M, 3M and
5M) during the synthesis. NaOH and NH4OH were used as strong base and weak base, respectively. The resultant catalysts were
further tested for its catalytic activity in the oxidative degradation of acid orange 7 (AO7). It was found that 43% of dye removal
was obtained for the catalyst synthesized using 1M NaOH solution. Meanwhile on 20% of dye removal was observed for weak
base at the similar concentration. Such differences could be corresponded to the differences in structural formation of resultant
Fe3-xCoxO4 catalyts. The pore volume of catalyst synthesized by strong base comprised of 18% higher compared to the weak
base; which may lead to better accessibility of pollutants directly to the active sites during the catalysis. In addition, the formation
of synthesized catalyst from the strong base exhibited with crystalline phase; whilst amorphous for the weak base. Hence, it can
be concluded that the used of strong base precipitating agent provides modest influence during the catalyst’s formation which
directly affecting the overall catalytic performance of the Fe3-xCoxO4 catalyst during the Fenton-like reaction.

© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of The 3rd International Conference on Green Chemical Engineering and Technology (3rd
GCET): Materials Science, 07-08 November 2017.

Keywords: Precipitating agent; strong base; weak base; Fe3-xCoxO4; Fenton-like

* Corresponding author. Tel.: +604-3822545; fax: +604-3822812.

E-mail address: rasyidah.alrozi@ppinang.uitm.edu.my

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of The 3rd International Conference on Green Chemical Engineering and Technology (3rd
GCET): Materials Science, 07-08 November 2017.
22064 Zubir et al. / Materials Today: Proceedings 5 (2018) 22063–22068

1. Introduction

Precipitating agent is a causative substance that influences the formation of resultant’s suspension in solution
[1,2]. Precipitating agents are divided into two types of base which are strong and weak bases. The examples of
strong bases that commonly used as precipitating agents are NaOH and KOH while for the weak bases are K2CO3,
Na2CO3, NH4OH, NH4HCO3. Strong base will completely be dissociated in the solution at low concentration due to
greater concentration of OH- ions whereas for weak base will not completely dissociated in the solution at low
concentration due to less concentration of OH ions [3].
Previous researches claimed that structural properties as well as its catalytic performances of resultant’ catalysts
prepared via coprecipitation method were significantly affected by type of precipitation agent that have been used
during the synthesis. Spiridigliozzi et. al [4] reported that precipitating agent has a crucial role in co-precipitation
process where it will influence the morphology of the resultant precipitant. Tarka et. al [5] observed the materials
obtained with the use of K2CO3 have better textural parameters (smaller Co3O4 crystallites) than the KOH.
Meanwhile, Dong et al. [6] found that the catalytic activity of CuO–CeO2–ZrO2 catalysts using with different type of
precipitating agents were decreased in the order of Na2CO3> NH4OH > (NH4)2CO3> NaOH. The usage of Na2CO3
during the synthesis resulted to the formation of smaller grains of CuO–CeO2–ZrO2 catalyst with uniform
distribution. On contrary, Tangale et al. [7] claimed that the use of tetraalkyl ammonium hydroxide (TAAOH) as
precipitating agent showed 2.6% and 0.4% higher of cyclohexanol conversion and cyclohexanone selectivity,
respectively than those prepared using Na2CO3 and urea. On the other hand, several research works [6,8] reported
that the use of NaOH as precipitant agent during the catalyst synthesis were profoundly affecting the
physicochemical properties, which exhibited the highest activity and stability in glycerol hydrogenolysis than those
by other precipitants (Na2CO3, NH4OH and NH4HCO3).
Hence, in brief; utilization of different types of base will lead to unique physicochemical properties as well
catalytic activity of the synthesised catalyst [3]. However, detailed investigations on the effect of precipitating agents
in relations to the physico-chemical properties as well as the catalytic activity of cobalt ferrite catalyst (Fe3-xCoxO4)
has not been addressed. Therefore, this work investigates the influence of precipitation agents (NaOH and
ammonium hydroxide NH4OH) at varying strength on the synthesised Fe3-xCoxO4 catalyst. The catalytic activity of
resultant catalysts were evaluated using a model reaction of AO7 oxidative degradation in the heterogeneous Fenton-
like reaction.

2. Material and Methods

2.1. Synthesis of Fe3-xCoxO4 catalyst

A mixture solution of 5 mL of 2 M CoCl2.6H2O in HCl 7.4% solution and 40 mL of 0.5 mM FeCl3.6H2O was
prepared in double distilled water at 50oC. 10 mL of 1M NaOH solution was mixed and decanted into previous
solution under vigorous stirring for 30 minutes. The mixture was rapidly stirred at 50oC and aged for 1 hour. After
the mixture was cooling down, dark brown precipitate formed and collected using magnet and washed prior to
drying process. The resultant suspension was dried in an oven at 100oC for 5 hours. Similar procedures were
repeated by using different molarity of precipitating agent/ base. Strong base NaOH with 1 M, 3 M and 5 M and
weak base NH4OH of 1 M, 3 M and 5 M were used during the synthesis of Fe3-xCoxO4 catalyst, respectively.

2.2. Performance and characterization

An amount of 0.2 g/L of catalyst were mixed into 200 mL of AO7 dye solution at concentration of 35 mg/L with
initial pH of 3. Then, the solution were agitated by orbital shaker at 200 rpm. H2O2 were introduced at 22 mM to
initiate the reaction. Next, the concentration of AO7 were analyzed by using Hach DR 2700 Portable
Spectrophotometer at the maximum wavelength of AO7 dye, 483 nm [9]. The same procedures were repeated using
different molarity of strong/ weak bases for the resultant Fe3-xCoxO4 catalyst. The adsorption test were also
performed using the above-mentioned procedures without the addition of H2O2.
 Zubir et al. / Materials Today: Proceedings 5 (2018) 22063–22068 22065

The surface area, pore volume and pore size distribution of the catalysts were determined using nitrogen sorption
analysis (ASAP 202, Micrometric). The XRD patterns of the catalysts were obtained using X-ray diffraction by
Rigaku MiniFlex 600. The zeta potential was measured using a ZetaSizer (Nano-ZS 90,Malvern Instruments).

3. Results and Discussions

The effect of precipitating agents in both catalytic and adsorption tests certainly shows significant profile on the
removal of AO7 as depicted in Fig. 1. The highest AO7 removal for the Fe3-xCoxO4 catalyst synthesized using
strong base (NaOH, Fig. 1a) was found to be at 1M with approximated removal of 43% and 30% in catalysis and
adsorption, respectively. Moreover, the highest AO7 removal using NH4OH solution was at 3 M (Fig. 1b). Marginal
difference of AO7 removal (±5%) was observed between the process, which infers to the predominance of
adsorption rather than catalysis. On contrary, a notable predominance of catalysis was exhibited for synthesized Fe3-
xCoxO4 catalyst by NaOH solution. Hence, based on the aforementioned inference, it can be suggested that
utilization of strong base at low molarity as the precipitating agent during catalyst’s synthesis is preferred due to
better catalytic performance compared to weak base.

Fig. 1. AO7 removal by adsorption and catalytic Fenton-like reaction using Fe3-xCoxO4 catalysts at varies molarity of (a) NaOH and; (b) NH4OH
solutions.

Such differences were plausible to the textural properties of the synthesized catalysts as summarized in Table 1.
No significant changes of specific surface area of the synthesized Fe3-xCoxO4 catalyst for both precipitating agents.
On contrary, the pore volume of the catalyst synthesized using strong base (1M NaOH) comprised of 18% higher
compared to the weak base; which may lead to better accessibility of pollutant directly to the active sites during the
catalysis. The surface accessibility of the synthesized catalyst is crucial in maintaining their catalytic activity as
reported elsewhere [10]. Good accessibility of AO7 towards the active sites can be achieved by the increase in the
pore volume, which are able to diminish limitations in mass transfer during the reaction.

Table 1. Specific surface area (SBET) and pore volume of synthesised Fe3-xCoxO4 using different types of precipitating agents.
Precipitating agent Molarity (M) SBET (m2/g) Pore volume, (cm3/g)

NaOH 1 124.03 0.26

NH4OH 1 134.20 0.22

22066 Zubir et al. / Materials Today: Proceedings 5 (2018) 22063–22068

As shown in Fig. 2a, the nitrogen sorption-desorption isotherms of both synthesised Fe3-xCoxO4 catalysts
exhibited Type IV characteristics which associated with mesoporous structures. Interestingly, the Fe3-xCoxO4
catalysts (1 M NaOH) possessed bimodal distribution of pores where the primary and secondary mesopores were
clearly observed at relative pressure of 0.5-0.8 and at a higher relative pressure (P/Po > 0.8), respectively. Similar
observation was obtained for ethanesilica materials synthesis in the presence of cobalt ions [11]. Meanwhile, no
secondary distribution of pores was observed in NH4OH. The presence of bimodal distribution of pores (Fig. 2b)
centered at 6 nm and 19 nm provide higher accessibility of pollutant towards the active sites at the surfaces of
resultant catalyst which is in agreement with the expansion of pore volume (Table 1).

Fig. 2. Nitrogen sorption-desorption isotherms (a) and pore size distributions; (b) of synthesised Fe3-xCoxO4 using 1M of (a) NaOH and; (b)
Na4OH solutions.

The crystalline structure of Fe3-xCoxO4 catalysts were confirmed by XRD measurements as presented in Fig. 3a.
The diffraction pattern of the catalyst precipitated by NaOH exhibited the formation of crystalline phase at 2θ of
35.6° of 311 plane; whilst amorphous for the NH4OH. This value is in agreement with previous literature by
Andrade et al. [12] for cobalt ferrite compounds. Presence of impurities (NaCl) deposited on the Fe3-xCoxO4 was
observed at 2θ of 33° and 25° which contributed by insufficient washing during catalyst preparation. Moreover,
previous researchers [8,13] claimed that crystalline phase of the resultant catalyst precipitated by NaOH possessed
better stability since the residual Na+ in the catalyst enable to retard the leaching of the active iron/cobalt species and
reduce the aggregation of iron/cobalt particles.
A further analysis on the surface properties of the Fe3-xCoxO4 catalyst have been carried out using zeta potential
analysis as illustrated in Fig. 3b. The pHPZC of the catalyst precipitated by NaOH and NH4OH was at 8.4 and 8.8,
respectively. Negligible changes of pHPZC of the catalyst between the strong and weak bases. During the catalysis,
the surface charge of Fe3-xCoxO4 catalysts synthesised by both precipitating agents were in negative charge. The
negative surface charge lead to concurrent adsorption of AO7 dye during the catalysis. Thus, the adsorbed AO7
molecules within the immediate vicinity of active sites were degraded rapidly by the generated interfacial •OH
radicals.
 Zubir et al. / Materials Today: Proceedings 5 (2018) 22063–22068 22067

Fig. 3. XRD patterns (a) and zeta potential; (b) of synthesised Fe3-xCoxO4 at 1M NaOH and NH4OH solutions.

4. Conclusions

Fe3-xCoxO4 catalysts were synthesized using two different precipitating agents via co-precipitation method. The
molarity differences in both catalysts played a crucial role in producing a good formation of catalyst. 43% of AO7
removal was found for the catalyst synthesized using 1M NaOH solution. Meanwhile on 20% of AO7 removal was
observed for the weak base at the similar concentration. Such differences could be corresponded to the differences in
structural formation of resultant Fe3-xCoxO4 catalyts. The pore volume of catalyst synthesized by strong base
comprised of 18% higher compared to the weak base and the Fe3-xCoxO4 catalysts (1M NaOH) possessed bimodal
distribution of pores. These findings may lead to better accessibility of pollutants directly to the active sites during
the catalysis. In addition, the formation of synthesized catalyst from the strong base exhibited with crystalline phase;
whilst amorphous for the weak base. Hence, it can be concluded that the used of strong base precipitating agent
provides modest influence in enhancing the overall catalytic performance of the Fe3-xCoxO4 catalyst during the
Fenton-like reaction due to its unique physicochemical properties.

Acknowledgements

The authors gratefully acknowledges the Ministry of Higher Education Malaysia (MOHE) and
Universiti Teknologi MARA (UiTM) for financial support under Fundamental Research Grant Scheme
(600-IRMI/FRGS 5/3 (110/2016)) as well as Research Acculturation Grant Scheme (600-RMI/DANA
5/3/IRAGS(44/2015)).

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