Sustainable Materials and Technologies 23 (2020) e00140

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Sustainable Materials and Technologies

journal homepage: www.elsevier.com/locate/susmat

Photocatalytic application of spinel ferrite nanoparticles

and nanocomposites in wastewater treatment: Review
Kebede Keterew Kefeni a,⁎, Bhekie B. Mamba a,b,⁎
a
University of South Africa, College of Science, Eng. and Technology, Nanotechnology and Water Sustainability Research Unit, Florida Science Campus 1710, South Africa
b
State Key Laboratory of Separation Membranes and Membrane Processes, National Centre for International Joint Research on Membrane Science and Technology, Tianjin 300387, PR China

a r t i c l e i n f o a b s t r a c t

Article history: This review shade light on the recent advances in a photocatalytic application of spinel ferrite nanoparticles and
Received 25 May 2019 their nanocomposites towards pollutant degradation capacities in wastewater, with more emphasis on their nov-
Received in revised form 13 November 2019 elties. Furthermore, the possible recovery and reuse of spinel ferrite nanoparticles being used as a photocatalyst
Accepted 15 November 2019
in wastewater treatment are addressed. Innovative techniques needed for surface modification and improving
photocatalytic efficiency of spinel ferrite nanoparticles, nanocomposites and their selectivity towards different
Keywords:
pollutant degradation are briefly reviewed. Finally, challenges, gaps and future research needs in order to im-
Spinel ferrite nanoparticle prove the photocatalytic application of spinel ferrite nanoparticles and their nanocomposites are addressed.
Spinel ferrite nanocomposite © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
Photocatalyst creativecommons.org/licenses/by-nc-nd/4.0/).
Photodegradation
Wastewater
Organic pollutant

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Commonly used spinel ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Photocatalytic application of SFNPs and SFNCs for wastewater remediation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Mechanism of contaminant degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Organic pollutant degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. Dye degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2. Phenol and phenol derivatives degradation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.3. Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3. Photo-corrosion reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Improving catalytic efficiency and selectivity of SFNPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.1. Surface immobilisation with metal or semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2. Surface functionalisation with organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3. Doping rare earth metals into SFNPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.4. Increasing surface area and crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Comparison of photocatalytic efficiency of SFNPs with their NCs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Gaps and research needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

⁎ Corresponding authors at: University of South Africa, College of Science, Eng. and Technology, Nanotechnology and Water Sustainability Research Unit, Florida Science Campus 1710,
South Africa.
E-mail addresses: kefenkk@unisa.ac.za (K.K. Kefeni), mambabb@unisa.ac.za (B.B. Mamba).

https://doi.org/10.1016/j.susmat.2019.e00140
2214-9937/© 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
1. Introduction
Spinel ferrite nanoparticles (SFNPs) are metal oxides with spinel
structure of general formula AB2O4, where A and B are representing var-
ious metal cations situated at tetrahedral (A site) and octahedral (B
site), at least with ferric in the chemical formula. The metal cations at
both sites are tetrahedrally and octahedrally coordinated to oxygen
atoms, respectively. The physicochemical properties of ferrites are
highly dependent on the types, amounts and positions of the metal cat-
ions in the crystallographic structure [1–3], a representative structure
for spinel ferrite is shown in Fig. 1. They have wide applications in var-
ious fields, which range from biomedical to industrial. In the former
case, the major applications of SFNPs include cancer diagnosis, cancer
gene therapy and drug delivery [4–7], while in the latter case, they
could be used as catalyst and pollutant removal via adsorption or
photodegradation [8–13], as gas sensor [14], in high-frequency device
[15], for water splitting [16], and for membrane modification [17,18].
When SFNPs are used as catalyst, they aid in facilitating the rate of
chemical reactions in a number of organic and inorganic synthesis and
photodegradation of organic waste pollutants. After treatment is over,
SFNPs can be easily separated from the solution mixture using an exter-
nal magnetic field [19–21]. They are particularly important in improving
reaction yield, reducing the required reaction temperature and promot-
ing specific chemical reactions. In addition, their photodegradation ca-
pacity for organic pollutants is another important aspect, where their
nanoparticles, as well as their nanocomposites are utilised for wastewa-
ter treatment. Several research reports confirmed that SFNPs based cat-
alysts have strong photodegradation capacities, consequently, they are
very useful for the complete removal of contaminants. Incomplete re-
moval or degradation of pollutants may result in the formation of
more toxic by-products than the parent pollutants [22]. Therefore, in
order to limit such incidence, looking for nanoparticles (NPs) and nano-
composites (NCs) with strong photodegradation capacity is inevitable.
At the same time, SFNPs could be used as antibacterial agents during
wastewater treatment. Particularly, partial substitution of transition
metals in commonly used SFNPs improves the antibacterial properties
of the NPs [23]. Recent studies also confirmed that zinc substituted co-
balt ferrite has shown high efficiency against drug resistance bacteria
relative to Mn(II) and Cu(II) substituted cobalt ferrite [24,25]. This addi-
tional advantage of SFNPs may open an interesting area of study apart
from their application in industrial and biological areas.
Catalysts are mainly divided into two groups, namely heterogeneous
and homogeneous [26]. On relative bases, the former catalyst is easily
separated from the reaction mixture and can be reused but the reaction
Fig. 1. Schematic diagram of spinel ferrite structure showing oxygen (red), tetrahedral
(yellow) and octahedral (blue) sites “image generated using CrystalMaker®: http://
crystalmaker.com”
rate is lower due to limited surface area, while it is more difficult to sep-
arate the latter from the reaction mixture after the reaction is complete,
and this limits its further utilisation. On the other hand, due to the ex-
pensive nature of catalysts, recovery and reuse of the catalyst is very im-
portant. In addition, NPs with high surface areas are very important for
catalytic purposes, for many industrial applications. Thus, even with NPs
of heterogeneous photocatalysts, especially when the photocatalysts
are nonmagnetic such as semiconductors (TiO2, ZnO, and ZnS), their
separation and recovery after treatment is difficult, expensive and also
time-consuming due to their small sizes [27]. Consequently, the prob-
lem of insufficient recovery not only leads to loss of the photocatalyst
but also the residual photocatalyst become an additional environmental
pollutants. These problems reduce the practical application of nonmag-
netic photocatalytic semiconductors. In order to reduce the aforesaid
limitation, incorporating SFNPs into semiconductors recently emerged
as possible solutions [28–30]. Furthermore, incorporating SFNPs into
nonmagnetic photocatalysts improve the degradation rate of pollutants,
ease the recovery of photocatalysts from the reaction mixture after
being used and enhance their relative stability in acidic and basic condi-
tions, particularly when a pH N 3 [31,32].
The SFNPs have good adsorption capacity for both anions and cat-
ions, which is one of the important preconditions for NPs to act as pho-
tocatalytic materials. This is because below their pH of zero point charge
(pHzpc) their surfaces are positively charged and easily adsorb anions,
while above pHzpc negatively charged and responsible for cation
adsorption (Fig. 2). For example, on ascorbic acid surface-modified
Fe3O4 NPs of pHpzc 7, the higher removal of arsenate (AsO3− 4 ) and arse-
nite (AsO3− 3 ) were exhibited (45%) for solution pH less than 7, and de-
creased to 15% as pH rose above 7 [33]. In another study, increased
arsenic removal was exhibited when MnFe2O4, CoFe2O4 and Fe3O4 NPs
used as an adsorbent in acidic media, where the surface of the afore-
mentioned NPs are positively charged relative to the higher pHs [32].
For (Ni,Mg)Fe2O4 synthesised from steel pickling with pHzpc 4.35,
high adsorption for Pb2+ in aqueous solution was observed at a pH
5.8, where (Ni,Mg)Fe2O4 surface is negatively charged [34]. Similarly,
CoFe2O4-rGO with pHzpc 4, higher adsorption capacity of Pb2+ (87%)
and Hg2+ (88%) were achieved at pH 5.3 and 4.6 in aqueous solution, re-
spectively [35].
It is also very important to highlight why there is a need for SFNPs
based photocatalysts than the commonly used photocatalysts such as
TiO2, ZnO, and ZnS. These commonly used photocatalysts have similar
problems such as large energy band gap, limited visible light harvesting
capacity, rapid e− and h+ pair recombination and difficulty of recovery
after being used [36,37]. In fact, despite all the aforementioned prob-
lems, particularly TiO2 is considered among the best photocatalyst of
choice. Currently, many research works revealed that incorporation of
SFNPs with these semiconductors in order to alleviate the previously
mentioned drawbacks. Similar to the aforementioned semiconductors,
organic based photoactive materials such as graphitic carbon nitride
(g-C3N4), biochar and carbon quantum dots have low visible light har-
vesting capacity and not easily recovered after being used as
photocatalyst. Recently, the incorporation of SFNPs gained great atten-
tion of several researchers and found to be a promising method in im-
proving their photocatalytic activities and magnetic separation
[38–41]. However, resistance to step out from a well-established TiO2
research area seems the problem in the commercialisation of SFNPs
based photocatalysts.
2. Commonly used spinel ferrites
There are a number of SFNPs and their derivative composites which
could be used as a photocatalyst, and the most common are Fe3O4,
CoFe2O4, CuFe2O4, MnFe2O4, NiFe2O4 and ZnFe2O4. These SFNPs could
be coupled to commonly used photocatalyst to induce magnetic proper-
ties into it, and aid for ease of separation by an external magnetic field as
well as enhance photocatalytic degradation of contaminants and
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140 3

Fig. 2. Schematic diagram of SFNPs surface charge and possible pollutant adsorption in acidic and basic media. In general, SFNPs and SFNCs can serve as one of the most useful
photocatalysts due to their lower energy band gap, high surface area to volume ratio, ease of separation from the solution mixture after being used for wastewater treatment by an
external magnetic field and reusability. In addition to the facile separation of the catalyst by an external magnetic field, the SFNCs are more stable than the bare SFNPs, do not
aggregate easily and also have increased lifetime relative to bare SFNPs [42,43]. In this work, a brief background information about commonly used SFNPs will be provided. This will be
followed with a brief review of recent advances of the photocatalytic applications of SFNPs and their NCs for the removal of recalcitrant pollutants, particularly organic pollutants via
photodegradation route from wastewater. Finally, possible means of improving photocatalytic efficiency, comparisons of bare SFNPs with their SFNCs and research gaps are presented.
The synthesis methods of SFNPs and their NCs have been well-reviewed by a number of researchers [44–47]. Therefore, alternative synthesis techniques are not included in this
review. However, any recent advances in the synthesis of photocatalytic SFNCs could be discussed whenever necessary. It is also worthy to note that the numbers of articles published
with respect to SFNPs based photocatalysts are extremely huge and this review will not do justice to all the relevant published papers.

stability [48–51]. Among the aforesaid SFNPs, Fe3O4 NPs and its NCs are
frequently used as catalysts in a number of wastewater treatments
[52–62]. The major reasons for the wide application of Fe3O4 NPs and
their NCs are mainly due to its outstanding properties such as
nontoxicity, ease of surface modification, efficient catalytic characteris-
tics and ease of synthesis relative to other SFNPs [63–66]. In fact, the
photocatalyst degradation capacity of bare Fe3O4 NPs towards inorganic
and organic pollutants is poor relative to its composites such as Fe3O4@
TiO2 or Fe3O4@TiO2@SiO2 [9]. For example, about 98.7 and 91.5%
photodegradation of ampicillin over Fe3O4/TiO2/Ag NCs was achieved
under UV and visible light irradiation after 6 h, respectively [67].
While only about 30% of ampicillin was photo-degraded when only
bare Fe3O4 microspheres of average size 350 nm were used.
The best catalytic performances of CoFe2O4 and CuFe2O4 NPs as well
as their corresponding NCs have also been reported by many researchers
[68–70]. The photocatalytic effectives of both NPs when used in bare and
NCs form for wastewater treatment have been documented. For exam-
ple, under ultrasound irradiation of wastewater containing methylene
blue (MB), high photocatalytic activity of CoFe2O4@ZnS was observed
than bare CoFe2O4 NPs and ZnS [71]. The enhanced photodegradation
of MB was also observed in the presence of CoFe2O4/GO than in pure
CoFe2O4 and GO [72]. The enhanced photodegradation is mainly attrib-
uted to improved adsorption capacity and ease of electron transfer
from CoFe2O4 NPs to graphene sheet and hindrance of electron recombi-
nation. In addition, the cobalt ferrite at the core-shell nanostructures aid
for several times recovery and reuse of the nanocomposite, and attri-
butes to values for cost-effective treatment.
The CuFe2O4 NPs are also used in a wide range of industrial applica-
tions such as gas sensing [73], wastewater treatment [74,75], catalyst
[68], anode in lithium battery, colour imaging, bio-processing and mag-
netic refrigeration [76]. Among these, its application as a catalyst gained
more attention for the synthesis of several organic compounds and
other valuable industrial chemicals [77,78]. For instance, CuFe2O4 NPs
have been used as one of the efficient and selective catalysts for
deacetylation of carbohydrate derivatives [79], for synthesis of 2-
substituted benzoxazole using benzylamine and 2-nitrophenol as reac-
tants have been reported [78]. Furthermore, the CuFe2O4 NPs are impor-
tant because they are oxygen carriers, the presence of Cu and Fe metals
in one component improve the overall photocatalytic compared to sin-
gle metal oxide of either CuO or Fe2O3 and had a high possibility to be
used in chemical looping combustion of coal [80]. Comparison of three
ferrite NPs (NiFe2O4, CuFe2O4, and ZnFe2O4) synthesised under similar
condition has also shown the highest photodegradation capacity of
CuFe2O4 towards Malachite green (MG) under visible light irradiation
[81]. Based on the Electrochemical Impedance Spectroscopy (EIS), the
main enhanced photocatalytic activity of CuFe2O4 compared to others
has been related to its higher charge transfer capacity. In another
study, a significant photodegradation of MO and tetracycline hydrochlo-
ride by CuFe2O4/AgBr [82], and Malachite green (MG) dye by Ag-
CuFe2O4 [83], were exhibited relative to pure CuFe2O4. The NCs of
CuFe2O4 are among one of the best catalysts due to their effectiveness,
low cost, magnetically recoverability, reusability and non-toxicity [84].
Therefore, synthesis and evaluation of the photocatalytic activity of
CuFe2O4 based NCs have high industrial importance.
Similar to other SFNPs/SFNCs, MnFe2O4 NPs and its NCs display effi-
cient photocatalytic activity. For example, the solar light irradiation of
solutions containing MO in the presence of MnFe2O4/g-C3N4/TiO2
displayed very high photocatalytic degradation of MO dye than that of
g-C3N4, MnFe2O4 and MnFe2O4/g-C3N4 [85], mainly due to the strong
synergic effects among the three components used for the preparation
of composite. Similarly, biochar supported ternary g-C3N4/BiO2CO3/
CoFe2O4 NCs have shown high photodegradation of pesticide paraquat
under visible radiation and solar light, with very high degradation rate
above 90% within 120 min [86]. It has been also observed that the bio-
char supported ternary NCs performance was manifold faster than ei-
ther the binary or the individual components of the NCs.
In the presence of H2O2, NiFe2O4 and ZnFe2O4 NPs have shown
efficient photodegradation towards the complete removal of 4-
chlorophenol [87]. In another similar study, NiFe2O4 NPs/NCs also
have shown strong catalytic property, photo-chemical stability and effi-
cient photodegradation capacity towards different types of dyes, and
their easy of separation from aqueous solution using an external mag-
netic field has also been demonstrated [88–92]. In another study, the
evaluation of photocatalytic properties of core-shell type NiFe2O4@
TiO2, which was synthesised by hydrothermal process exhibited good
photodegradation activity towards RhB in solution [93]. After ten cycles
of photocatalytic experiments, a slight decrease in degradation effi-
ciency from 80 to 69% of RhB was observed. Showing that the stability
and ease of recoverability of the photocatalyst. Similarly, irradiations
of solutions containing RhB dye in the absence of NPs/NCs with visible
light resulted in no removal. While in the presence of NiFe2O4 and mul-
tifunctional Pd-NiFe2O4/rGO resulted in degradation of 18.5 and 89.5%
4 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
RhB, after 4 h irradiation, respectively [91]. The high photodegradation
performance of Pd-NiFe2O4/rGO is mainly related to the manifestation
of complementary behaviour of each nanoparticle.
The efficient performance of the photodegradation capacity of
ZnFe2O4 NPs were observed during the photodegradation of RR198 and
RR120 used as model dyes [94]. The photo-irradiation of solutions con-
taining the aforementioned dye pollutants and H2O2 in the absence of
ZnFe2O4 resulted in 40 and 37% degradation, respectively. While in the
presence of 0.2 g ZnFe2O4 and H2O2, almost complete degradation of
the dyes was reported. Showing that the strong synergetic effect of
ZnFe2O4 and H2O2 and for efficient photodegradation. In another study,
Yang et al. (2015) demonstrated enhanced photocatalytic degradation
of MB over the ZnFe2O4/rGO photocatalyst under visible light irradiation
[95]. Excellent photocatalytic activity of ZnFe2O4/rGO towards the degra-
dation of RhB was also achieved [96]. This is mainly due to the band gap
reduction of ZnFe2O4 as a consequence of GO incorporation. Overall, sim-
ilar to other SFNPs/SFNCs, ZnFe2O4 and its NCs are efficient photocatalyst
in utilisation of visible light portion. Doping of most SFNPs into UV light-
driven photocatalyst effectively assist to convert into visible light-driven
photocatalysts [89,97–100]. In addition, the NCs become highly efficient
in performance, mainly due to the reduction of energy band gap that im-
proves charge transportation and separation.
3. Photocatalytic application of SFNPs and SFNCs for wastewater
remediation
The presence of various contaminants in wastewater discharge from
industries is a global concern. Treatment and removal of toxic organic
contaminants such as dyes, phenols, chlorophenols and nitro-phenols
are extremely a longstanding challenge, particularly under visible light
irradiation. There are several studies that demonstrated the possible re-
moval of these contaminants by a photocatalytic approach using SFNPs,
and it is the main focus areas of recent researches [10,101–103].
In wastewater treatment technology, metal oxides and semiconduc-
tors have gained a considerable attention for their photocatalytic degra-
dation capacity of pollutants. One of the important prerequisites of
these photocatalysts is their stability and durability under photo-
irradiation [104]. It has been reported that SFNPs and their NCs have
both aforementioned properties and suitable to be used as
photocatalysts in wastewater treatment [105]. Application of SFNCs
for wastewater treatment either as an adsorbent or the photocatalyst
is among the current intensive research areas and could be one of the
best cost-effective techniques. Because of their low energy band gaps,
SFNPs utilise visible light energy and easily convert into chemical en-
ergy to support oxidation and reduction. Ideally, wastewater containing
organic pollutants can be treated by photocatalytic materials and the or-
ganic pollutants can be degraded into CO2(g), H2O(l) and other gaseous
chemicals depending upon the elemental composition of the organic pol-
lutants, without the formation of waste [39,106]. Consequently, the pho-
tocatalytic degradation and removal of organic contaminants are
considered environmentally friendly, simple and efficient strategies
[107,108]. The interesting things about SFNPs is that they can be used
as a photocatalyst (without any modification), in composites (surface
coated with semiconductors) and in the presence of oxidants such as
H2O2. Actually, their high photodegradation capacity of pollutants are
well improved when used with other light sensitive strong oxidants
and semiconductors than alone [30,39,49,89,94,109–113]. Under this
section, the mechanism of contaminant degradation due to photocatalyst
effects of SFNPs or their corresponding composites, advantage of SFNPs
incorporation into semiconductors, particularly the reduction of corro-
sion, band gap and electron-hole recombination are briefly reviewed.
3.1. Mechanism of contaminant degradation
In the presence of SFNPs-semiconductors, photodegradation of
organic contaminants could be easily feasible. Because, when
contaminated water is irradiated with light energy, in the presence of
SFNPs-semiconductors, an electron (e−) is excited from the valence
band to conduction band of the photocatalyst leaving behind a photo-
generated hole (h+), provided that the light energy is higher than the
energy band gaps of photocatalytic materials. The produced e- is easily
captured by dissolved oxygen gas available in the water at the conduc-
tion band (reaction 1) [114,115]. The reactive oxygen free radical fur-
ther reacts with hydrogen ion to form an active free hydroxyl radical
and hydroxyl ion (reaction 2). The photo-generated hole (h+) reacts
with water in order to yield active hydroxyl free radicals (reaction 3).
Due to high adsorption capacity of SFNPs, the contaminants are in
close vicinity to the active radicals and then easily attacked by hydroxyl
radicals generated on the surface of the photocatalyst and thereafter,
they are easily degraded (reaction 4) [116]. This is followed by the sub-
sequent desorption of the degraded products from the ferrite active sur-
face sites. In addition to radical attack on organic compounds, direct
reduction by the conduction band electrons (reaction 5) and oxidation
by the valence band holes (reaction 6) could be possible routes of deg-
radation of organic pollutants [117]. The schematic diagram for the for-
mation of reactive oxygen and hydroxyl radicals is shown in Fig. 3. Due
to their low energy band gap, ferrites can utilise visible light and as a re-
sult they are tremendously desired in water and wastewater treatment
in the degradation of pollutants [39,102]. A list of selected ferrites and
semiconductors along with their band gap energies are presented in
Table 1. It is possible to see from Table 1 that ferrites have lower energy
band gap than that of semiconductors, which is suitable for the absorp-
tion of visible light. Thus, NCs prepared by incorporation with SFNPs
have several advantages, such as decreased energy band gap that can
utilise visible light, improved stability, ease of separation from the reac-
tion mixture by an external magnetic field, and several times possible
reusability [118]. Currently, modification of SFNPs properties by incor-
porating semiconductors, graphene based nanomaterials, metals and
non-metals are an active field of research area looking for efficient and
effective photocatalysts.
e− þ O2 →O−
2˙ ð1Þ
O− þ − ˙
2˙ þ 2H þ 2e → OH þ OH
−
ð2Þ
þ
h þ H2 O→ ˙ OH þ Hþ =OH˙ ð3Þ
˙
OH þ Organic contaminant ðOCÞ→CO2 ðgÞ þ H2 O ð1Þ þ other ð4Þ
Fig. 3. Schematic diagram illustrating the formation of reactive oxygen and hydroxyl
radical under visible light irradiation of semiconductor or ferrite-semiconductor
composite, interaction with organic pollutants and possible degradation products
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140 5

Table 1 dye, phenol, phenolic derivatives and antibiotics available in the re-
Energy band gap of some common SFNPS and semiconductors. cently published research work are briefly reviewed.
Ferrite Band gap (eV) Ref. Semiconductor Band gap (eV) Ref.

Fe3O4 1.92 [126] ZnO 3.2 [109]

3.2.1. Dye degradation
γ-Fe2O3 2.03 [127] TiO2 3.2 [128] Dyes are organic compounds used in industries for colouring pur-
CoFe2O4 2.31 [129] WO3 2.5 [130] poses such as textiles and clothing. They are usually classified based
NiFe2O4 2.2 [131] ZnS 3.7 [132] on their particle charge generated on dissolution when dissolved in an
CuFe2O4 1.89 [133] CdS 2.62 [134]
aqueous medium. They categorised mainly into natural and synthetic
ZnFe2O4 1.91 [135] NiO 4.0 [131]
dyes, which still further grouped with respect to their charges during
ionisation such as anionic, cationic and non-ionic dyes [136]. The unique
thing about dyes is that they have complex structures, consequently,
e− þ OC→OC− →→degradation products ð5Þ most dyes are stable and not easily degradable. If dyes enter into
water resources, they can easily pollute the whole water system and
þ cause extreme health impacts on all beneficiaries [136,137]. Researches
h þ OC→OCþ →→degradation products ð6Þ
on the toxicity of dyes have shown even at low concentration, dyes can
induce serious toxicity on aquatic life mainly due to the release of toxic
There are many photocatalysts that have been successfully used for chemicals through slow degradation by oxidation, hydrolysis, physical
water treatment, particularly for organic removal such as Ce/TiO2 interaction and chemical reactions. In addition, dyes inhibiting light
[119], ZnO/GO [120], Bi2O3/TiO2 [121], TiO2/ZnO [122] and Eu, C, N, S- penetration into the water system and reducing the photosynthetic re-
ZrO2 [123], among others. These photocatalysts are important for the re- action and severely affect life in the aquatic environment. Besides this,
moval of dye via the degradation route from aqueous wastewater. De- dyes are toxic to humans, animals and aquatic life due to their
spite their efficiency and stability, the separation problems of the cancerogenic and mutagenic effects [41,138–140]. Thus, from health
aforementioned photocatalysts from aqueous solutions are among one and environmental perspective, for adequate protection of human
of the awfully limits for their practical application in wastewater treat- health and other organisms dependent on the water, removal of dyes
ment [120,124]. Incorporating SFNPs into the photocatalytic semicon- from water and wastewater is one of an environmental priority. On
ductors solve the aforementioned problems due to their ease of the other hand, treatment of water contaminated with dyes is a chal-
recovery and reuse, and also improve the efficiency of organic pollut- lenge due to their resistant to chemical and biological degradation
ants removal from water and wastewater through adsorption and pho- [141,142]. Recently, SFNPs and their NCs have been recognised having
tocatalytic effect. For example, two duplicate aqueous solutions strong photocatalytic properties towards dye degradation in the visible
containing tetracycline was irradiated for 8 min, in the presence of dif- light [143]. For example, Fe3O4@SiO2 NCs acted as Fenton-like catalyst
ferent photocatalysts such as Ag/Ag3VO4 and 5% CoFe2O4/Ag/Ag3VO4 for the decomposition of H2O2 and resulted in high rate of decolouration
composite. The result has shown that 49.75 and 61.48% tetracycline of MB under neutral pH, which showed much higher activity of this
was photo-degraded, respectively [125], which confirmed enhance- composite than bare Fe3O4 [144]. In another study, high stability of
ment of Ag/Ag3VO4 photocatalytic activity due to incorporation of 5% Fe3O4@TiO2 with 99% degradation of MB was observed after addition
CoFe2O4. In addition, the latter is easily recovered by an external mag- of H2O2 within 5 min in the absence of UV-irradiation [145]. UV irradi-
netic field and could be reused several times, and adds value to cost- ation (8 W UV lamp) of a solution containing 1.28 mg L−1 of MB in
effectiveness. A schematic representation of pollutant adsorption on the presence of 1.0 g L−1 Fe3O4/chitosan/TiO2 NCs, 93% of MB were
the surface of SFNPs/SFNCs, photodegradation and adsorbent recovery completely removed within 40 min [146]. Similarly, super photocata-
and reuse are shown in Fig. 4. lytic activity of Fe3O4/ZnO/CuWO4 NCs was observed for photodegr-
adation of RhB under visible light irradiation compared to the binary
3.2. Organic pollutant degradation Fe3O4/ZnO or Fe3O4/CuWO4 [147]. In addition, the experimental results
have shown significant impacts of weight percentage of CuWO4 incor-
Studies have witnessed the efficient and strong photocatalytic ca- porated to the NCs, detailed comparison is presented in Fig. 5a and b.
pacity of SFNPs and SFNCs for organic pollutant degradation. In the fol- In a recent study, the efficient removal of Congo red (CR) through ad-
lowing section, SFNPs and their NCs photodegradation capacity towards sorption on Fe3O4@SiO2 NCs has also been reported [52]. However,

Fig. 4. Schematic diagram for wastewater treatment using SFNPs/SFNCs and possible recovery and reuse.
6 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140

Fig. 5. a) Magnetisation curves for the Fe3O4 NPs and Fe3O4/ZnO/CuWO4 (40%) NCs, the inserted figure shows the photograph of a separation process by using a magnet, b) degradation of
RhB over different NPs and NCs (Reproduced by permission from Ref. [147], Copyright 2016, Elsevier), c) photodegradation capacity of different catalysts towards RhB under visible light
irradiation at room temperature d) Photodegradation of different dyes on CoFe2O4/g-C3N4 (2:1 ratio) NCs (Reproduced by permission from Ref [158], Copyright 2016, Springer Nature)

neither the mechanism for decolourisation nor desorption was made for
confirmation of the organic dye removal via adsorption. The wastewater
containing dyes could be decolourised when the chromophore groups
of dye, the bonds responsible for the colouring, are breaking down. In
most studies, only the decolourisation is reported but the complete con-
version into the water, carbon dioxide and other non-toxic chemicals
are lacking. In order to protect the health of the treated water user,
proper evaluation of the complete removal of the contaminant and in-
termediate product is mandatory.
Ye et al. [148] synthesised core shell structured Fe3O4/SiO2/TiO2 NCs
by using the sol-gel process with calcination. The photocatalytic activity
of the SFNCs was enhanced compared to the commercial photocatalyst
TiO2 (Degussa P25). The effectiveness of the synthesised SFNCs over
SiO2 or TiO2 was confirmed by efficient degradation of RhB. In addition,
the SFNCs have shown additional advantages such as high chemical sta-
bility, fast magnetic separation and maintenance of the photocatalytic
activity for at least eighteen cycles. Similarly, Wang et al. [149] synthe-
sised Fe3O4/SiO2/TiO2 NCs using the sol-gel method and investigated its
photocatalytic activity on MB that was present in an aqueous solution at
room temperature and pH = 10. Under UV irradiation, the NCs showed
higher photodegradation of MB (78%) within 5 min. In another study
[150], application of SrFe12O19/Zn0.65Ni0.25Cu 0.1Fe2O4 (1:1 ratio), a
core-shell type nanocomposites showed complete degradation of
methyl violet (MV) in aqueous solution within 3 minutes. While in
the absence of nanocomposites and presence of reducing agent
(NaBH4) over 24 h reaction time, a small reduction in UV-Vis absorption
spectra were observed.
SFNCs such as SFNPs-graphite carbon nitride (g-C3N4) hybrids are
currently becoming one of the most studied and important NCs. For ex-
ample, the photocatalytic effect and stability of Fe3O4 is highly improved
when 8 nm Fe3O4 NPs were deposited on g-C3N4 sheets. The
photodegradation of RhB under visible light irradiation is significantly
improved over NCs compared to when used individually. Furthermore,
the authors reported good recyclability without loss of apparent photo-
catalytic activity even after six cycles [151]. Such synergic effects are
commonly observed when different nanomaterials are incorporated
into SFNPs. Similarly, 1.8 times increase in photocatalytic activity of
Fe2O3@g-C3N4 was observed, compared to the conventional pure g-
C3N4, when water contaminated with RhB irradiated under visible
light [152]. In another study, under visible light irradiation, CuFe2O4@
g-C3N4 core-shells were synthesised through a self-assembly method,
and this composite exhibited excellent performance in the degradation
of Orange II dye in the presence of H2O2 as an oxidant [153]. The com-
posite showed superior activity compared with CuFe2O4 or g-C3N4. At
a temperature of 65oC, complete degradation of Orange II dye (0.28
mM) within 90 min, with catalyst dose of 0.1 g L−1 and 0.01 M of
H2O2 were observed. In addition, this study demonstrated the impor-
tance of increasing temperature in order to overcome the activation en-
ergy barrier for the decomposition of H2O2, thereby enhancing
generation of more hydroxide radicals. Generally, these findings clearly
showed the synergic effects of each component in the SFNCs, thus the
application of SFNCs are a feasible and efficient approach for industrial
wastewater treatment. The summaries of recently used SFNPs/SFNCs
as photocatalysts in wastewater treatment are presented in Table 2.
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140 7

Table 2
Summary of recently used SFNPs/SFNCs in wastewater treatment and their corresponding pollutant removal capacity

Type of SFNPs/FNCs Size (nm) Pollutant/s pH Contact time Catalyst dose Pollutant Light Removal Cycle Ref.
(min) (g L−1) (mg L−1) source capacity (mg g−1)

ZnFe2O4 9 AO II - 360 0.5 20 UV 38.8 - [182]

Fe3O4/Cr2O3 - 4-CPc - 150 2.0 12.9 UV 100% 4 [183]
Co0.6Zn0.4CuFeO4 40−60 MO - 60 1.0 30 Vis 25.8 - [184]
Ag/TiO2/NiFe2O4 - MO 7 120 1.0 10 Vis 100% - [185]
Cu2O/Fe3O4 - MO - 90 1.0 30 Vis 90% 5 [186]
MnFe2O4/g−C3N4/TiO2 - MO - 180 0.05 10 Solar light 93.% 4 [85]
Co0.5Zn0.25N0.25Fe2O4−TiO2 - MO 360 1.0 13.09 UV-vis 12.44 - [187]
Co0.5Zn0.25N0.25Fe2O4−TiO2 MB 80 1.0 12.79 UV-vis 12.66 - [187]
Ni-Cu-Zn - MB 360 1.0 20 Vis 83.9% 7 [188]
ferrite@SiO2@TiO2
Fe3O4/TiO2 35 MB - 240 0.2 10 UV 50 3 [189]
RGO/Fe3O4 10 MB - 60 0.167 10 Sun-light 100% 8 [190]
CoFe2O4−GR - MB - 120 0.25 20 Vis 100% - [72]
CuFe2O4@TiO2 64 MB 180 0.5 20 Vis 40 3 [191]
FeWO4/Fe3O4 - MB - 60 0.4 20 UV-Vis 97.1% - [192]
Ni0.65Zn035Fe2O4 MB - 56 1.0 5 UV-Vis 55% - [193]
Ni0.65Zn035Fe2O4.rGO MB - 56 1.0 5 UV-Vis 95% - [193]
Ag/NiFe2O4 - MB - 120 0.25 20 Vis 80% 6 [194]
Cu0.25Fe1.75 O4 11.1 MGb oxalate - 150 1.0 33.4 UV 33.4 - [195]
ZnFe2O4 + persulfate 20−40 Orange II 6.0 300 0.5 + 1.0 100 Vis 191.8 5 [196]
Fe3O4/TiO2 17 ± 1.5 Quinoline 6.1 120 1.5 71.04 UV 40.1 3 [197]
Fe3O4/TiO2 - RhB 75 0.45 4.8 UV 6.22 6 [198]
Fe3O4@SiO2@meso−TiO2 325 RhB - 30 0.40 9.6 UV 8.6 10 [199]
ZnFe2O4@TiO2 20 RhB - 150 1.0 9.6 UV 9.55 2 [200]
Fe3O4@SiO2@TiO2 140−160 RhB 5 5.7 60 0.10 50 UV 455 4 [201]
MoS2/CoFe2O4 (1:3) - RhB - 90 1.0 20 Vis 18.8 7 [202]
- CR - 50 1.0 30 Vis 28.3 7 [202]
CuFe2O4+H2O2 21 RR120 3 45 0.02 50 Vis 2500 6 [203]
Ni0.4Cu0.6Fe2O4 50−100 Tetracycline - 360 1.0 10 Vis 7.81 5 [204]

Among dyes, Azo dyes are hardly biodegradable organic compounds
due to their high stability to light and resistance to microbial attack
[138]. However, a recent study demonstrated that application of
SFNCs such as MnFe2O4@PANI@Ag [154] and Co0.53Mn0.31Fe2.16O4@
TiO2 [155], have a high degradation capacity with high efficiency for
azo dyes, relative to the corresponding SFNPs.
The study which compared the degradation capacity of Ni2+ doped
into MnFe2O4 (M1-xNixFe2O4, where x = 0.0, 0.1. 0.2, 0.3, 0.4 and 0.5)
observed that Mn0·5Ni0.5Fe2O4 NPs exhibit superior photocatalytic ac-
tivity when applied for the degradation of indigo carmine synthetic
dye among all the synthesised NPs [156]. The optimum catalyst dose
and concentration of indigo carmine dye under acidic pH was 500 mg
L−1 and 150 mg L−1, optimum degradation of 96% within 3 h was
achieved. In another study, sulphur modified CoFe2O4 (S-CoFe2O4) cat-
alyst was used for the effective and efficient degradation of acid orange
II (AO II) in the presence of bicarbonate activated hydrogen peroxide
[157]. With dosage of 0.1 g L−1 of S-CoFe2O4, 0.3 mM H2O2 and 0.1 g
L−1 NaHCO3 almost 99% degradation of 50 mg L−1 of AO II was achieved
within 15 min. Generally, these results confirm that the significance of
SFNPs and SFNCs for photocatalytic degradation of organic contami-
nants from wastewater. The CoFe2O4/g-C3N4 (2:1 ratio) NCs enabled
the degradation of multiple dyes also its stability, recoverability, reus-
ability has been confirmed.
3.2.2. Phenol and phenol derivatives degradation
Phenol and phenol derivatives are among the serious largest groups
of environmental pollutants. This is mainly due to their wide industrial
application as antibacterial and antifungal agents. Usually, they avail-
able in industrial effluents [159]. These compounds are particularly con-
sidered priority organic pollutants by the US Environmental Protection
Agency (USEPA) due to their toxicity, carcinogenicity and mutagenic
nature [8]. They can cause severe harm to human and animal liver,
lung and red blood cells even at very low concentrations [160]. In addi-
tion, the degradation of these pollutants is difficult due to their stability.
Consequently, they remain in the environment for longer periods [161].
In the subsequent sections, possible photodegradation of phenol and its
most commonly used derivatives such as chloro- and nitro-phenol are
briefly reviewed.
3.2.2.1. Phenol. Phenol is one of the pollutants with high toxicity and
poor biodegradability chemicals and the most commonly available in
wastewater. It could cause serious damage to human health even at
low concentrations [162]. Recently, photocatalytic application of
SFNPs for complete degradation and removal of phenol from wastewa-
ter is becoming a common practice. For example, application of Fe3O4
mixed with H2O2 in wastewater containing phenol removed 85% of phe-
nol in 3 h at a temperature of 16oC, without any secondary pollutant for-
mation [163]. Incorporating semiconductors into ferrite also improves
the rate of phenol degradation, for example, the degradation of phenol
through photocatalytic process using Fe3O4−ZnO hybrid NPs has re-
cently been investigated [109]. During the study, the stability and the
recoverability of the hybrid NPs were also evaluated. The result has
shown 89% of the photocatalyst used was recovered after three cycles,
with phenol removal of 82.8, 72.4 and 65.1% in cycle one, two and
three, respectively. These values are much greater than that of freshly
prepared ZnO, in which only 52% degradation of phenol was observed,
indicating enhanced photo-catalytic activities, stability and ease of re-
coverability of synthesised hybrid photocatalysts. The enhanced photo-
catalytic performance could be attributed to the synergic effects
between the SFNPs and semiconductors that reduced fast recombina-
tion of photo-generated electrons and holes, thereby increasing the ef-
ficiency of charge separation and allowing more of electrons and holes
to be available for reduction and oxidation of contaminants
[39,109,164,165].
3.2.2.2. Chlorophenols. There are several types of chlorophenols which
differs by the position of chlorine attachment and number of chlorine
such as 2-chlorophenol, 2, 4-dichlorophenol, pentachlorophenol and
para-chlorophenol. They are widely used in many industries in the pro-
duction of dyes, pesticides, fungicides, pharmaceuticals, explosives,
8 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
disinfectants and antiseptics. Its wide utilisation and importance re-
sulted in its environmental contamination via the industries discharge.
They are among the group of highly toxic environmental pollutants as
per the USEPA [166]. They are suspected as one of carcinogenic and mu-
tagenic chemicals [167]. SFNPs based NCs are also very effective in the
degradation of chlorophenols. Recently, effective degradation of 4-
chlorophenol by Cu0.5Mn0.5Fe2O4−TiO2 composite than bare CuFe2O4
has been reported [168]. The enhanced photocatalytic performance
of the composite is attributed to the interconnected spinel
Cu0.5Mn0.5Fe2O4 to TiO2 semiconductor. In another study, 88.6% of 4-
chlorophenol degradation was achieved in the presence of ZrO2/
Fe3O4/chitosan NCs in 3 h under natural sunlight photo irradiation
[169]. The semiconductor metal oxide hetero-junction reduced
electron-hole recombination and enhanced charge separation and elec-
tron transfer. While the chitosan increased the surface area for adsorp-
tion and improved the stability and prevented the particle
agglomerations. Similarly, the effective, efficient and recyclable photo-
catalytic activity of chitosan/CoFe2O4 composites for complete degrada-
tion of 2-chlorophenol from wastewater when irradiated with sun light
has been demonstrated by Taleb [167]. Such an outstanding perfor-
mance of SFNPs and SFNCs in the degradation of stable and toxic envi-
ronmental pollutants could be an indication of their future importance
in solving the problems of wastewater treatment.
3.2.2.3. Nitrophenol. Organic nitro compounds are one of the hazardous
pollutants due to their carcinogenic character and they are among the
non-biodegradable organic pollutants, and commonly found in waste-
water discharged from industries and agricultural wastes [170]. Thus,
the removal of nitrophenol from wastewater either through degrada-
tion or conversion into their corresponding useful amino-aromatic com-
ponents is extremely necessary. Actually, conversion into amino-
aromatics has more advantages because amino-aromatics are among
the most essential organic compound for the synthesis of several indus-
trial dyes, pharmaceuticals, photographic developers, corrosion inhibi-
tors and some biologically active compounds [171,172]. There are
several techniques that could be used to convert nitro-phenol into use-
ful amino-aromatic such as photo-reduction [68,173], heterogeneous
catalytic hydrogenation [174], and so on. However, these techniques
are associated with one or more limitations such as difficulty in catalyst
recovery, energy and time-consuming [172]. In fact, all these limitations
could be reduced by the application of pure or substituted SFNPs for the
reduction of nitro-phenol [172,175]. For example, among three different
spinel ferrites (MnFe2O4 10.6 nm, CoFe2O4 8.72 nm and ZnFe2O4 6.27
nm) synthesised by using sol-gel hydrothermal technology, MnFe2O4
NPs have shown high catalytic performances in the reduction of 4-
nitrophenol, 2, 4, 6 tri-nitro-phenol and 4-nitroaniline with 100% con-
version into their corresponding amino derivatives in 4.5 min reaction
time. The superiority of the MnFe2O4 was reported in terms of the in-
crease of pore radius and volume [172]. In another study, the Fe3O4-3-
aminopropyl-triethoxysilane (APTES)-Pd(0) [176], NiFe2O4-APTES-Pd
(0) [177], and NiFe2O4-Pd [178], offered high catalytic activity in hydro-
genation of 4-nitroaniline and 1,3-dinitrobenzene in a liquid phase.
Similarly, the synthesised CoFe2O4-APTES-Pd(0) was found a highly ef-
ficient photocatalyst for hydrogenation of 4-nitroaniline and 1,3-dini-
tro-cyclohexanone [179]. In all these studies, the importance of
incorporating SFNPs in achieving a high degree of stability, ease of re-
coverability by an external magnetic field, reusability without a signifi-
cant decrease in catalytic activities of the synthesised nanocomposites
have been demonstrated.
The catalytic applications of Fe3O4 composites are also common for
possible conversion of nitro-phenol into useful amino-aromatic. Re-
cently, Au-Fe3O4 organic coated NCs (Au-Fe3O4@metal–organic frame-
work (MOF)) catalyst has been synthesised and shown outsmart
performance in the reduction of 4-nitrophenol in the presence of
NaBH4. The magnetic recycling and reuse is supported by the presence
of Fe3O4 while the Au NPs act as an active site for catalytic reduction
of 4-nitrophenol. Similarly, in another study, the Fe3O4@SiO2–Ag NCs
have shown a good catalytic reduction of p-nitrophenol to p-
aminophenol with conversion corresponding to 95% within 14 min in
the presence of an excess amount of NaBH4, and it is one of the promis-
ing photocatalytic materials for various catalytic reactions in the future
[180]. Despite its lower performance at second and third cycle recovers
and reuse, 1 mole% Pd loaded titania nanotubes in the presence of
NaBH4 has shown effective and efficient reduction of p-nitrophenol to
p-aminophenol [181]. It is believed that incorporation of SFNPs ex-
pected to enhance its recovery and reuse, and requires future research.
3.2.3. Antibiotics
The overuse or misuse of antibiotic by human potentially contribute
to the emergence and widespread of various types of antibiotics into
aquatic ecosystem, thereby increases the development of antibiotic re-
sistant bacteria. Even, under normal usage of infection treatments, anti-
biotics are not easily metabolised and their residues are expelled
through faeces and urine to the environment [205]. The discharge of an-
tibiotics into the environment may cause developments of bacterial re-
sistance, which could extremely affect the effectiveness of antibiotics. In
addition, these antibiotics are hardly removed by conventional water
treatment techniques [206]. In recent years, degradation of antibiotic
from water and wastewater through photocatalytic treatment has
gained more attention. For example, graphitic carbon sand composite
(GSC) and bentonite (BT) supported superparamagnetic MnFe2O4 NPs
were used for the synthesis of MnFe2O4/GSC and MnFe2O4/BT NCs, re-
spectively [207]. These NCs have been used for photodegradation of am-
picillin (AMP) and oxytetracycline (OTC) antibiotics under solar light.
The reported results have shown 96 and 83% of AMP and 99 and 90%
OTC degradation in 60 and 120 min by using MnFe2O4/GSC and
MnFe2O4/BT under solar light irradiation, respectively. Both
Photocatalysts were magnetically separated from the reaction mixture
within 10 s under solar light irradiation and also displayed significant
recycle efficiency for at least 10 consecutive catalytic cycles without
loss of photocatalytic activity. Similarly, Fe3O4-GO-Ce-TiO2 hybridised
composite exhibited good adsorption capacity and effective degrada-
tion of tetracycline [208]. It is considered as one of the promising
photocatalyst for antibiotic degradation. In another study, pyrrole
imprinted CoFe2O4/MWCNTs NCs photocatalytic performance for the
degradation of 2-mercaptobenzothiazole was evaluated [209]. The re-
sult has shown the double activities of the photocatalyst such as high
photocatalytic efficiency and strong ability of selective recognition and
photodegradation of 2-mercaptobenzothiazole. Overall, these findings
demonstrate that SFNC photocatalysts are promising for effective degra-
dation of antibiotics.
3.3. Photo-corrosion reduction
Several researches have shown that all semiconductors with appro-
priate energy band gaps are not suitable for photocatalytic purposes in
wastewater treatment. This is due to the photo-instability of some semi-
conductors which result in dominance of photo-corrosion of semicon-
ductors rather than the oxidation of water [130]. For example, in
aqueous solution, CdS and ZnO show photo-instability when irradiated
with UV light and undergo photo-corrosion (see reaction 7 and 8). In
addition, poor utilisation of visible light and high recombination rates
of charge carriers are the main problems with pure ZnO [117]. It should
be noted that 90% of photo-generated electron-hole pairs recombine in
less than 10 nano-seconds and consequently photo-generated charge
carriers available for surface reactions will be limited [210]. In order to
improve the photo-stability of these semiconductors, incorporating a
small amount of SFNPs resolves the problem. For example, Xiong et al.
[211] synthesised CdS−ZnFe2O4(0.10) (CdS- with 10% ZnFe2O4) and
CdS−CoFe2O4(0.05) NCs and compared their photocatalytic effect on
the degradation of RhB with pure CdS. Under the employed condition,
80% of RhB was degraded during the first cycle of pure CdS application;
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
however, during the third cycle, only 30% of RhB was degraded, indicat-
ing a significant photocatalytic activity reduction. On the other hand,
the recycled use of CdS−ZnFe2O4(0.10) and CdS−CoFe2O4(0.05) NCs
did not result in a noticeable effect on photocatalytic activities after
three cycles (Fig. 6a). The schematic diagram for both NCs under visible
light irradiation is shown in Fig. 6b. The result has clearly shown the im-
portance of SFNPs incorporation into CdS, which reduced its photo-
corrosion by minimising the rate of electron-hole pair recombination
probability and enhanced the charge separation efficiency, leading to
high stability and photocatalytic performance. Similar results have
been reported for Fe3O4−ZnO hybrid [109]. It should be noted that 4
and 43% of the total energy of the sunlight on the earth account for UV
light and visible light contribution, respectively. Therefore, modification
of semiconductors with large band gap such as TiO2, ZnO, NiO and ZnS
are very important in order to make them utilise high percentage of
free visible light energy for photocatalytic activation. For example, as
the result of doping CoFe2O4 on the surface of ZnO, the energy band
gap of ZnO is reduced to 2.19 eV and its photocatalytic activities have
been improved with increased harvesting capacity of visible light
[113]. Similarly, the multi-porous nanotubes synthesised by the combi-
nation of ZnFe2O4 and ZnO (1:1, ratio) using facile electrospinning and
then followed by calcination processes has shown high photocatalytic
stability. Its application for water polluted by MB dye has shown 99%
photodegradation within 150 min [212]. In addition to high photo-
corrosion resistance, the synthesised ZnFe2O4@ZnO easily separated
by an external magnetic field and has been utilised for four times with-
out loss of its photocatalytic efficiency.
þ
CdS þ 2h →CdðIIÞ þ S
þ
ZnO þ 2h →ZnðIIÞ þ 1=2O2
4. Improving catalytic efficiency and selectivity of SFNPs
For efficient photocatalytic performance, preliminary, the NPs or NCs
material must have good stability and adsorption capacity of aqueous
phase pollutants [213]. There are several techniques for improving the
catalytic efficiency and selectivity of SFNPs, when they are used either
for catalytic photodegradation purposes or selective removal of contam-
inants through adsorption. For example, surface immobilisation with
metals/semiconductors, elemental doping, construction of binary or ter-
tiary hetero-junction with various photo active materials such as g-
C3N4, TiO2, ZnO, ZnS, MoS2 improve the catalytic efficiency. While
Fig. 6. a) Photodegradation of RhB over CdS, CdS−ZnFe2O4(0.10), and CdS−CoFe2O4(0.05) for three cycles. b)schematic diagram of electron-hole generation during visible light irradiation
of CdS−ZnFe2O4(0.10) and CdS−CoFe2O4(0.05) NCs, and degradation of dye mechanism.(Reproduced by permission from ref. [211], Copyright 2013, American Chemical Society)
9
functionalisation of photocatalytic materials using specific organic moi-
eties of high adsorption capacity of targeted contaminants aid for the se-
lective contaminant removal. In most cases, the modified SFNPs are
expected to withstand the oxidative and reductive process of chemicals
during exposure to light and with boosted photocatalytic activity. In ad-
dition, the surface modification could help for stabilisation of SFNPs, im-
proving in water dispersibility through end-grafting, encapsulation,
hyper-branching, or enhancing hydrophobic interactions [214]. Simi-
larly, doping small sized representative, transition or rare earth metal
ions into ferrite can improve the photocatalytic activity of SFNPs either
by decreasing the energy band gap [215] or improving the crystalline
characteristics. For example, stable and crystalline Ru-doped SFNPs
such as NiRu0.4Fe1.6O4 and CuRu0.1Fe1.9O4 were synthesised by sol-gel
method and used for complete photodegradation of remazol deep red
dye and antibiotic ciprofloxacin within 5 and 90 min, respectively
[216]. Compared with un-doped one, R-doped SFNPs photocatalytic ac-
tivities were boosted. Similarly, doping trace amount of aluminium (5
mmol) into six different SFNPs improved the photodegradation of mal-
achite green (MG) relative to the non-doped NPs [217]. Each Al doped
SFNPs exhibited extremely high photodegradation capacity towards
MG, in the order of Zn N Co NCu N Ni N Cd N Cr SFNPs. The improved pho-
tocatalytic with a small amount of Al doping may be related to the in-
creased crystallinity and ease of ion mobility. As the dopant and
parent metal ions are different in ionic size, the substituted dopant
will cause crystal defects in the crystal lattice. Consequently, the varia-
tion in crystal defects in the structure will rise to the difference in elec-
tron concentration and active site on the doped surface, and attributes
to the difference in photodegradation activity of SFNPs. In the subse-
ð7Þ quent sections, the impact of surface immobilisation, functionalisation
of photocatalysts and doping of rare earth metals are briefly discussed.
ð8Þ
4.1. Surface immobilisation with metal or semiconductors
The modifications of photocatalytic materials by incorporation of
SFNPs improve their efficiency and recoverability. In fact, it is believed
that surface immobilisation of photocatalysts result in a reduction of
surface area, and has got direct implication on their photocatalytic activ-
ity reduction [10]. However, combination or doping of high energy band
gap semiconductor with SFNPs aid in decreasing the energy band gap
from UV to visible light ranges and improve their photocatalytic activity
and recoverability through external magnetic field [218,219]. In addi-
tion, surface immobilisation of SFNPs with metals, semiconductors or
organometallic improve the stability of the NPs in basic and acidic con-
ditions, improve the photocatalytic activities and reduce possible e- and
10 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
h+ recombination [3,27,220,221]. For example, a photocatalyst synthe-
sised using the phosphor-tungstic acid supported on imidazole
functionalised silica and coated with cobalt ferrite nanoparticles (PTA/
Si-imid@ Si-CoFe2O4 NCs) was effectively employed for aerobic oxida-
tion and conversion of several primary and secondary benzyl alcohols
into carbonyl compounds [222]. Similarly, the TiO2−SiO2 coated with
CoFe2O4 NPs synthesised by Sol-gel technique have shown high
photodegradation capacity towards MB dye available in contaminated
water when irradiated with UV light [223]. This study demonstrated
the possibility of 98.3% removal of organic dyes within only 40 min. Fur-
thermore, similar to other studies, the degradation efficiency of the or-
ganic dyes was found dependent on the initial dye concentration, pH
of the wastewater, and on the amount of photocatalytic loading.
4.2. Surface functionalisation with organic compounds
Surface functionalisation of SFNPs improves their selectivity of con-
taminant removal as well as their overall properties and it’s among the
major subject areas of recent study [224]. Particularly, photocatalytic
properties of surface functionalised SFNPs using organic components
are dependent on the type of organic compounds used to modify the
surface. Direct surface functionalisations of SFNPs with organic moieties
are relatively difficult due to limited interactions of organic compounds.
However, the surface of SFNPs could be improved by forming SiO2 layer
onto the surface of SFNPs. Thereafter, the silica-shell surface can be eas-
ily modified via covalent bonding [225,226]. For example, the catalytic
effect of Fe3O4 has been improved by anchoring glutathione and dopa-
mine, and then followed by immobilising Cu NPs on the surface of the
composite. The synthesised catalyst showed better activity for C-S cou-
pling and active for cyclo-addition reactions, respectively [227]. Gluta-
thione coated Fe3O4 NPs also have been used as organic catalysts for
synthesis of several valuable compounds. The improved recovery and
reuse of ruthenium complex catalysts for selective synthesis of 1,5-di-
substituted 1,2,3-triazoles have also been observed when bound to
Fe3O4 NPs [228].
The deposition of magnetic ferrite over the layer of graphitic carbon
nitride (g-C3N4), improved the catalytic effect of g-C3N4 showing excel-
lent reactivity for efficient C-H activation and cyanation of amines [42].
Similarly, iron NPs supported on graphene oxide (GO) enhanced mag-
netic recoverability and improved catalytic efficiency for the oxidative
cyanation of tertiary amines into valuable compounds of α-
aminonitriles with high yields [229]. Generally, observed surface
functionalised SFNPs by organic compounds are not commonly used
for photocatalytic degradation of contaminants in wastewater but
could be used for selective adsorption of contaminants from wastewater
and synthesis of valuable organic compounds [225]. For example, the
selective removal of Hg2+ was achieved by surface functionalisation of
ferrite NPs using Mercaptopropyl [230,231]. Because sulphur has high
sensitivity towards adsorption of Hg2+ and then its ease of removal
from wastewater. Overall, surface functionalisation is inhibiting ag-
glomeration, improves photocatalytic activity, stability and reduce
leachability, which is among the main cause of concern for the toxicity
of SFNPs.
4.3. Doping rare earth metals into SFNPs
Substitution of transition metal by rare earth metals in SFNPs are
also emerged as a new class of photocatalytic activity enhancement.
Rare earth metal doped SFNPs improve their photodegradation effi-
ciency toward different type of organic pollutants, improve their visible
light absorption by decreasing energy band gap, and increase their sat-
uration magnetisation (Ms) and separation [232,233]. For example, dop-
ing Y3+ into pure CoFe2O4 (CoYxFe2-xO4, x = 0.0, 0.1, 0.2, 0.3), resulted
in enhancement of photocatalytic activity as well as improved the sta-
bility of the composite compared with pure CoFe2O4 NPs [233]. The
highest photocatalytic activity was achieved when x = 0.2, and the
doped NPs is with reduced energy band gap (1.26 to 1.14 eV) and im-
proved surface area (53 to 79 m2 g−1). In addition, the doping also im-
proved the stability and efficiency of CoFe2O4 NPs when irradiated using
visible light. Furthermore, no photodegradation reduction in activity
was observed after four consecutive reuse of the same photocatalyst,
showing long term stability of Y3+ doped CoFe2O4 under visible light
for wastewater treatment. However, higher metal ion concentration
greater than x = 0.2, might be result in loss of crystallite and increased
internal defects of the photocatalyst. Consequently, acted as electron re-
combination centre and thereby reduced the photocatalytic perfor-
mance. In another work, doping rare earth metals (Eu3+, Gd3+, Dy3+
and Nd3+) also improved the photocatalytic efficiency [234]. This
mainly due to the octahedral site preference of the rare elements cations
and lattice distortion, which in turn resulted in small size and high sur-
face area. The best photocatalytic performance was observed when the
substitution is x = 0.08, in CoRxFe2−xO4 for all four rare earth metal
ions. Similarly, doping Sm+3 into pure ZnFe2O4 (ZnSmxFe2−XO4, x =
0.0, 0.5, 1.0, 1.5 and 2.0) improved the photocatalytic efficiency with de-
creasing the energy band gap (1.95 to 1.42) when x = 1.5. This study
has shown high photocatalytic degradation of a model pollutant MO
in the presence of ZnSm1.5Fe0.5O4 NPs. The degradation of MO was
reached 92.3% after 80 min of the first run [235]. Furthermore, no loss
in photocatalytic degradation activity of ZnSm1.5Fe0.5O4 NPs was de-
tected after four runs, while the loss of activity was reported after the
second use for the pure ZnFe2O4 under UV- irradiation during the deg-
radation of MO [236]. The Improved magnetic properties and inter gran-
ular pores have also been reported when rare earth metal ions doped
into NiFe2O4 [237], Mn-Zn ferrite [238,239], and CoFe2O4 [240]. Overall,
these work demonstrate that the photocatalytic activity of ferrites
under visible light could be improved by doping small amount of rare
earth metal ions into SFNPs.
4.4. Increasing surface area and crystallinity
Photocatalytic materials with high surface area and crystalline mor-
phologies have high adsorption capacity of contaminants [234,241]. A
good photocatalysis NPs or NCs have high adsorption capacity of pollut-
ants, and it is among the important precondition for efficient pollutant
degradation in wastewater treatment. Because when the pollutants
are in close vicinity with photocatalytic materials, they can be easily
attacked by active radicals generated by photocatalytic materials during
the reaction and easily degraded. Similarly, crystalline NPs facilitates the
charge transport and improve the photocatalytic activity [241]. NPs
with a good crystallinity can be obtained by treating under high-
temperature, however, this may increase the particle size. Therefore,
one has to design all possible means of optimising the surface area of
the particles without affecting the crystallinity.
5. Comparison of photocatalytic efficiency of SFNPs with their NCs
Surface modifications of SFNPs improve the selectivity as well as the
stability of NCs toward various contaminants available in the wastewa-
ter. Several research works confirmed the high performance of modified
SFNPs relative to the bare once. For example, under the same conditions,
the comparison Fe3O4 NPs, Fe3O4@TiO2, TiO2 and Fe3O4@TiO2/SiO2 NCs
adsorption capacity and photodegradation of RhB dye under visible
light have shown high performance of the Fe3O4@TiO2/SiO2 NCs com-
pared to others [9]. Similarly, the comparison of Zn0.7Co0.3Fe2O4 versus
Zn0.7Co0.3Fe2O4-rGO for MB dye degradation under visible light demon-
strated that high degradation capacity of MB by the NCs than NPs
(Fig. 7a) [242]. In another study, doping of 10% europium into Fe3O4@
TiO2 NPs (with average particle size of 23−25 nm) improved the
photodegradation capacity of RhB from 65.8 to 85.3%, under visible
light irradiation of 3 h [243]. The enhanced photocatalytic effects may
be attributed to the electron trapping properties of europium.
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140 11

Fig. 7. Photodegradation rate curves of a) MB under visible light irradiation in the presence of Co0.3Zn0.7Fe2O4 NPs and rGO-Co0.3Zn0.7Fe2O4 NCs (Reproduced from reference [242],
Copyright 2016, Elsevier) b) RhB over different NPs and NCs with different mass percentage of CoWO4 incorporated as given in the legend (Reproduced from reference [10], Copyright
2017, Elsevier). C) MO under the visible light over ZnS, ZnFe2O4 and ZnFe2O4/ZnS, Reproduced from reference [245], Copyright 2017, Elsevier)

High photodegradation capacity of Fe3O4/ZnO/CoWO4(30%) NCs
compared to Fe3O4/ZnO and Fe3O4/CoWO4 NCs towards RhB with
nearly 24 and 5 times higher degradation rate constant of RhB were
also reported, respectively (Fig. 7b). From this and other results, it is
possible to come up with the conclusion that the photocatalytic activity
of tertiary NCs is significantly higher than their corresponding binary
counterparts. This is possible provided that individual components are
photocatalytic materials and synthesised under optimum condition in
order to manifest their synergic effects. Similarly, modification of
Fe2O3−Fe3O4 NCs supported by montmorillonite and modified by
graphene improved the photocatalytic activity in visible region [244].
The experimental results have shown, the degradation rate of MO
reached 2.77 and 1.61 times faster than Fe2O3−Fe3O4 and Fe2O3
−Fe3O4-montmorillonite within the irradiation time of 30 min, respec-
tively. Similarly, the comparison study conducted on the
photodegradation of MO dye using visible light in the presence of ZnS,
ZnFe2O4 and ZnFe2O4/ZnS confirmed higher degradation rates by com-
posite than ZnS and ZnFe2O4 (Fig. 6C) [245]. In another study, ZnFe2O4/
CdS photocatalytic composite has shown higher photocatalytic activity
for the reduction of Cr(VI) compared to ZnFe2O4 or CdS [246]. The sub-
stantial improvements of photodegradation as well as photo-reduction
capacity of the SFNPs based NCs is mainly related to the synergic contri-
bution in energy band gap reduction, which in turn increase the effi-
ciency of visible light absorption and effective charge separation and
transfer. Table 3, presents the comparison summary of some selected
SFNPs, SFNCs and other photocatalysts materials. As shown in Table 3,
SFNCs have higher photodegradation capacity compared to individual
semiconductors and SFNPs.
6. Gaps and research needs
This review has shown the existing challenges as well as available
opportunities of SFNPs/SFNCs possible practical application in future
at variable industries. All published articles which deal with
photocatalysis application of SFNCs conducted at the lab scale report
that the superiority of SFNCs, however, their practical applicability in in-
dustrial scale is not yet reported. Therefore, this area requires the inter-
vention of engineers to develop the appropriate reactor design that will
serve for practical application at an industrial scale. The published
works in spinel ferrite based photocatalytic applications reveal, less em-
phasis has been given on the theoretical study such as on the appropri-
ate type of dopant, surface functionalising groups and the amount
needed to be incorporated. Information on the assessment of complete
degradation are among commonly research gaps observed in the litera-
ture, particularly for dyes which shows colour, the disappearance of col-
our does not mean that the organic compounds are completely
removed, incomplete degradation may introduce secondary pollutants
that might be more toxic than the parent pollutants.
12 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140

Table 3
Comparison of SFNPs, SFNCs and other photocatalysts.

NO Adsorbents Part. size Pollutant Temp. Light source Initial conc. Catalyst dose Irradiation time Removal Ref.
(nm) (oC) (mg L−1) (g L−1) (min) efficiency (%)

1 NiFe2O4 103 CR 25 ± 0.2 Simulated Solar light 20 1.0 10 7.84 [89]

20 1.0 10 64.69
ZnO - 20 1.0 10 94.55
NiFe2O4/ZnO -
2 Fe3O4 41 Phenol Sunlight 0.4 mM 0.5 120 57.00 [8]
- - 120 83.45
- - 120 61.08
0.4 mM 0.5 120 92.43
TiO2 - - - 120 92.43
ZnO -
AG/Fe3Oa4 -
ZnO/rGO -
3 Fe3O4 21 ± 5 phenol 25 ± 1 Metal halide lamp - - 150 0 [109]
- - 150 52
ZnO 49 ± 7 - 0.325 150 65.5
Fe3O4−ZnO(1:2 ratio) 43 ± 8 - - 150 82.8
Fe3O4−ZnO (1:4 ratio) 45 ± 8
4 ZnFe2O4@TiO2 - MB 25-30 Sunlight 10 0.4 60 100 [247]
5 Peroxydisulphate(PDS) - MB - Halogen lamp - - 75 12 [248]
75 16
CuFe2O4 22 75 95
CuFe2O4/PDS -
6 NiFe2O4 11.2 MB - Vis light, Hg light source 10 1.0 90 99.5 [249]
10 1.0 90 99.2
- 10 1.0 90 98.5
MnFe2O4 12.03 - 10 1.0 90 98
SrFe2O4 12.01 -
CuFe2O4 12.07
7 Fe3O4@TiO2 23-25 RhB - Halogen lamp - - 180 61.8 [243]
Fe3O4@TiO2:Eu 10% 85.3
8 TiO2 13.06 Rh 6G - Vis light 50 0.83 10 52.52 [250]
50 0.83 10 71.73
ZnFe2O4@TiOb2 12.47 50 0.83 10 97.87
ZnFe2O4@TiOc2 11.69 50 0.83 10 1.38
ZnFe2O4 9.25
9 Blank - MO - UV 18.3 - 240 2 [100]
ZnO 34 UV 0.66 240 77
0.66 240 99
240 5
240 16
UV 240 63
Visible
ZnFe2O4@ZnO 17 Visible
Blank - Visible
ZnFe2O4 8
ZnFe2O4@ZnO 17

The presence of higher pollutant concentration in the wastewater,
irrespective of the one targeted to be removed, always need to be con-
sidered when evaluating the degradation capacity of photocatalytic ma-
terials. This is because the pollutant can cover the active surface of the
photocatalyst and inhabit its proper function. Therefore, pre-
determination of the concentration of the pollutant and optimising
the catalyst dosage need to be considered, in fact, such tests are rarely
available in the literature.
From this review, SFNCs are better performing in their photocata-
lytic than bare SFNPs, however, there is no best dopants or surface func-
tionalisation materials reported, which provides high photocatalytic
activity, and further work is required. Theoretical software can help in
predicting and guiding the selection of the appropriate type of dopant
or surface functionalisation materials, amounts of photocatalytic load-
ing. Consequently, it helps in reducing the numbers of tedious experi-
mental trials in order to determine the optimum amount of dopant
required or functionalisation materials. However, no effort has been
made in developing powerful software. In order to have the best
SFNCs, in the first case, one has to give more emphasis on selection of
the SFNPs based on less toxicity, stability, Ms value and photocatalyst
performance. Thereafter, among the available dopants and surface
modifies best should be selected. The later may be selected, in their en-
vironmental familiarities, their surface stabilisation and visible light
harvesting capacity, band position and their high pollutant adsorption
capacity. The best combination could be determined experimentally.
In this case, the leachability, stability, Ms value, recoverability and reus-
ability need to be addressed. Such methodology is not quiet observed in
the literature.
Application of visible light sensitive photocatalyst for wastewater
treatment and degradation of organic contaminants such as dyes, phe-
nols, pharmaceuticals, brominated flame retardants and other persis-
tent organic pollutants (POPs) are the major concerns and among the
most current intensive research areas. The area requires proper atten-
tion because application of SFNPs and their NCs are easily recovered
through an external magnetic field and reused over and over, which
makes the process cost-effective and environmentally sustainable.
However, in most of these researches, the application on the real envi-
ronmental samples are less emphasised and simulated experimental
tests are more common. For SFNCs future application on a large scale,
extensive research work on the real wastewater treatment is required.
In addition, the reason why the composite of two or more photocatalytic
NPs manifest synergic effect on pollutant degradation is not only due to
 K.K. Kefeni, B.B. Mamba / Sustainable Materials and Technologies 23 (2020) e00140
the decrease in energy band gap but also due to the availability of differ-
ent degradation routes and deformation of the SFNPs, and the area still
requires in-depth investigation.
Despite several studies on the improvement of synthesis methods of
photocatalytic materials to be used in the visible light range, there is no
standard reference photocatalytic material which could be used for
comparison purpose for new SFNCs based photocatalyst. As previously
discussed, doping trace rare earth metals into different types of SFNPs
improve the photocatalytic capacity. However, optimisation of the stoi-
chiometric ratio of metal ions to be incorporated into SFNPs usually re-
quire tedious experimental work. In order to reduce cost, time and
wastage of chemicals, the optimum amount of dopant required to be in-
corporated should be predetermined via theoretical means. Therefore,
there is a need for powerful software which assists to do the same.
No systematic comparison of different SFNCs are available or lacking
in the literature, and requires further research. Furthermore, coating
SFNPs is important in order to increase their lifetime and stability but
there is no standard technique yet available in literature in order to uni-
formly functionalise or coating the surface of SFNPs. The thickness of
coating extremely affects the Ms values of the SFNCs, thereby decreasing
possible separation and reuse of SFNCs. Therefore, proper optimisation
of coating techniques require detailed future study. Furthermore, the
higher the surface coating may mask the photo-sensitive part and re-
duce the photocatalytic effect.
In addition to the type of photocatalyst materials, the size of NPs,
crystallinity, accessibility of the active surface to pollutant and diffusion
resistance of organic pollutants are very important characteristics for
enhancing photocatalytic properties. With this respect, small particle
sizes with high crystallinity are important due to their higher specific
surface area and several active sites that favour higher photocatalytic
activity. In order to synthesis particles with high crystallinity, high-
temperature synthesis is required but high-temperature increase the
particle size. Thus, one has to think about the optimisation of crystallin-
ity without compromising the particle size.
7. Conclusions
Utilisation of SFNPs/SFNCs for the purpose of wastewater treatment
is very important due to their high adsorption capacity of pollutants and
ease of separation by an external magnetic field. Beyond their magnetic
properties contribution for separation and reuse, they also easily har-
vest the free sunlight energy due to their low energy band gap. This
highly contributes to the cost-effectiveness of wastewater treatment.
Because once SFNPs/SFNCS are recovered after being used for wastewa-
ter treatment, they can be reused several times compared with those
catalysts which lack magnetic characteristics and photoactivity at ambi-
ent temperature. Consequently, they are eco-sustainable and economi-
cally advantageous. Thus, it is possible to conclude that the application
of SFNPs and their NCs as a photocatalyst for an effective organic com-
pound degradation is eco-friendly and convenient, provided that proper
precaution is taken. For example, the risk and toxicity of some SFNPs
should be considered and evaluated well at the laboratory scale before
further application at the industrial scale. This may reduce unantici-
pated consequences and also attribute to their sustainable application.
Their incorporation into semiconductors and other nanomaterials also
hinders electron recombination and facilitate the rate of contaminant
degradation and removal by photodegradation.
Generally, the attractive physical and chemical properties of SFNPs
such as stability, ease of modification of their surface with suitable
semiconductors and organic moieties makes them a promising
nanomaterials for solving many problems that are currently challenging
the generation. Furthermore, despite several studies on SFNPs, the im-
pact of the incorporation of different types of dopants are not yet clearly
understood, thus, there is a need for powerful software which could
help for theoretical prediction of possible combinations and their
impacts.
13
Declaration of Competing Interest
None.
Acknowledgements
The authors are grateful to the University of South Africa for making
all the necessary resources available for this work and support.
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