Why Choose FE3O4

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“An overview of recent progresses on noble metal modified magnetic Fe3O4 for
Catalysis Science & Technology Accepted Manuscript

photocatalytic pollutant degradation and H2 evolution.
Priti Mishra, Sulagna Patnaik, Kulamani Parida*
Centre for Nano Science and Nano Technology, Institute of Technical Education and
Published on 24 January 2019. Downloaded by University of Winnipeg on 1/24/2019 4:10:18 PM.
Research, Siksha ‘O’ Anusandhan University, Bhubaneswar-751030
*Corresponding author
E-mail: kulamaniparida@soauniversity.ac.in, paridakulamani@yahoo.com,
Tel. No. +91-674-2351777
Fax. +91-674-2350642
Abstract
The search for a low-cost, high-performance and recyclable photo catalysts have became an
important issue in the field of heterogeneous photocatalysis. In this regard, development of
magnetite (Fe3O4) based photocatalyst is found effective as a simple recyclable photo catalytic
material which not only prevent excessive use of the catalyst, but also easy recovery of the
deactivated photocatalyst that makes the process fruit full. Taking into account the cost factor
and efficiency, plasmonic nanostructures of noble metal modified magnetite materials show
significant promise. Here in this review, we focus on the recent progresses on plasmon-enhanced
water splitting and pollutant degradation of magnetite based composite photocatalysts mainly
due to energetic electron driven photocatalysis. We have addressed different green strategies of
designing Fe3O4 based composite photocatalysts and modification with various noble metal nano
particles in strengthening the interface coupling between Fe3O4 and noble metals. This also
highlights a discussion of photo degradation and water reduction reactions on plasmonic-metal/
Fe3O4 nano structured photocatalysts and the SPR effect of noble metal NPs to enhance the
photocatalytic activity of Fe3O4. Through reviewing the recent significant advances on this topic
may provide new opportunities for designing highly efficient, low cost nano-structured materials
for the photo degradation of pollutants and the generation of energy.
Catalysis Science & Technology Page 2 of 55
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1. Introduction

Considering the most alarming problem of energy crisis and environmental pollution,
heterogeneous photocatalysis is emerging as an advanced technology for the direct conversion of
solar to chemical energy.1However, use of sustainable ways of photo catalytic energy generation
has not been realized, partly because of high cost of industrialization, photo corrosion, toxicity of
photocatalysts and separation of photocatalysts after treatment compared to present non-
sustainable alternatives.2-5 To address these challenges, development of magnetite based nano
materials is now hot research topic. Utilization of iron oxide nano composite as a ferromagnetic
material is significant due to its novel properties, biocompatibility, inexpensive and sustainability
nature.6 Again magnetic semiconductor photo catalysts are in demand for easy recycling as a
consequence it checks the generation of secondary pollutant. Also it shows high chemical &
structural stability, well magnetic nature, narrow band gap, visible light active and potential
electric performance.7Although, magnetic nano materials comprising of earth-abundant elements
are reported to show tremendous potential in environmental applications, including catalysis,
pigment, magneto caloric refrigeration, recording materials and drug delivery carrier but in the
pure form these NPs are not stable. However band structure of the material provides
opportunities for designing catalysts with improved efficiency.
Taking into account the limitations of magnetic NPs, considerable efforts have been made to
improve the photo catalytic performance by decreasing the particle size, increasing the surface
area, designing core-shell nano architecture, combining with other semiconducting materials or
by incorporating noble metal NPs. Especially, incorporating noble metal NPs such as silver (Ag),
gold (Au), platinum (Pt) and palladium (Pd) is preferred due to their unique electronic and
catalytic properties.8 The resulting nano-composites by retaining their individual semiconducting,
plasmonic and magnetic properties used to show enhanced optical, catalytic and magnetic
properties compared to their single component.9 In the field of photocatalysis, these noble metal
NPs have substantial effect due to their unique surface plasmonic resonance effect and physio-
chemical properties.10 Also it’s tendency of easy aggregation in solution and small size results in
reduction of their catalytic activities as well as reusability. By incorporating noble metal
nanoparticles, the quantum confinement along with plasmon resonance effects contribute to the
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photocatalytic performance of the composite materials by improving light absorption through

shifts of the VB and CB positions.

In this regard, application of photo catalysis using magnetic nano-material along with noble
metal appears to be the most agreeable solution for the decomposition of hazardous compound to
non-toxic biodegradable products and photo catalytic energy production. Hence the most
important aspect of using magnetic NPs in photo-catalysis is the ease of surface modification,
high surface area-to-volume ratio, extremely small size, absorption of light in the visible region,
great biocompatibility and excellent magnetic properties.11,12 By the way, use of nano-scale
magnetic particles in photo catalysis, in particular, magnetic iron oxides such as maghemite (γ-
Fe2O3) and magnetite (Fe3O4) have been studied intensively.13, 14
2. Theoretical Background
The waste Iron-based recyclable composites are established to be potential absorbant and
photocatalysts used to remove pharmaceuticals, personal care products (PPCPs) and Industrial
pollutants from contaminated water by adsorption, and advanced oxidation process.15 These are
the major cause of antibiotic resistance of pathogenic bacteria, which increases the complexity of
water disinfection and purification. Also it is the cause of chronic toxicity, endocrine disorder to
human beings and aquatic microorganisms.16 Hence, its removal is thus indispensable and a great
challenge to research community. UV-based advanced oxidation processes (AOPs), as well as
selective oxidation involving Ozone, chlorine, chlorine dioxide and adsorption by activated
carbon are effective for removal of PPCPs. However, all these processes involve high treatment
costs and elevated energy consumption. Therefore, more energy-saving and cost-effective
technologies are required for the effective abatement of PPCPs.
A good number of reviews based on Magnetite photocatalysts have been reported so far. The
published literatures include studies such as, recent advances in the use of magnetite-based
adsorbents for removal of radio nuclides,17 the current directions for the synthesis, surface
functionalization and bio application of magnetite.18 A good control of the crystal structure, size
& surface properties of magnetite by nanotechnology have been extensively investigated for
biological and environmental applications.19 The environmental impact of engineered magnetite
nanoparticles20 as recyclable visible light active photocatalyst for degradation of organic
pollutants, promising applications in protein immobilization, biomedical & bioengineering,
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environments treatment, bio separation and food analysis,21 are well discussed in the published
literatures. Also magnetite is a promising platform for electrochemical, magnetic and chemical

biosensors.22 Further magnetite nanoparticles are well known with applications in multi-terabit
magnetic storage devices and iron oxide nano materials for wastewater treatment.23 On the
contrary, not even a single review is yet published on Fe3O4 based nanomaterials as visible light
induced photocatalysts focusing on water reduction reaction for hydrogen production. Hence in
this review, we have tried to focus main attention to the synthesis process of Fe3O4 based
photocatalysts highlighting green methods and their application in water treatment and hydrogen
production.
Keeping in mind the novelty, we have highlighted recent progresses in the photocatalytic trends
of noble metal modified magnetite nanomaterials in heterogeneous photocatalysis for the
effective abatement of PPCPs. Primary attention has been given to the easy, sustainable synthesis
processes using bio-extracts and their superior activity upon loading noble metal NPs. It not only
focuses on the designing strategies, but also gives a clear idea about their photocatalytic activity
towards pollutants degradation and water reduction reaction for the generation of H2.
3. Why magnetite in photocatalysis?
3.1 Magnetite as a photocatalyst
In heterogeneous photocatalysis a semiconducting material plays an important role. A good

visible light semiconductor photo catalyst must have: (a) a suitable band gap, larger than the
energy required for desired reaction, 24 (b) the position of CB and VB (redox potentials of the e−
and h+) suitable for inducing redox processes, (c) rate of e−/h+ recombination should be slower
than the rates of these redox reactions and (d) a visible-light active band gap.
Considering Fe3O4, as a semiconductor photocatalyst, it can be both n- and p-type. Fermi level of
both n- and p-type is in a low-mobility spin-polarised 3d band. However, Fe3O4 possesses a low
band gap energy and presents the lowest resistivity of any metal oxide (ca. 5 x 105Ω m"), a
property attributable due to the rapid exchange of electrons between Fe2+ and Fe3+ in octahedral
sites. The cubic inverse spinel Fe3O4 is ferrimagnetic at temperatures below 858 K. In it’s unit
cell it contains 56 atoms, including 32 oxygen atoms, 16 Fe3+ and 8 Fe2+ and may be denoted as
(Fe3+)tetr8 [Fe3+Fe2+]oct8 O32. Thus in changing the spinel structure to an inverse spinel structure,
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the required changes are: FeII(Td)FeII(Oh); FeIII(Oh) FeII(Td). In FeII (FeIII)2O4 (i.e. Fe3O4),
for the conversion of the spinel form into the inverse spinel form, the CFSE changes are:

FeII[Td, e3t23, CFSE = 6Dq(Td,FeII)] FeII[Oh, t2g4eg2, CFSE = 4Dq(Oh, FeII) ≈ 8Dq(Td, FeII)].
It leads to gain of CFSE = 2Dq(Td, FeII).
FeIII[Oh, t32geg2, CFSE = 0] FeIII(Td, e2t32, CFSE=0)i.e. no gain or loss of CFSF in this change.
Thus, in converting the normal spinel structure to the inverse spinel structure for Fe3O4, there is a
net gain of 2Dq (Td, FeII) CFSE where 10Dq (Td, FeII) gives the crystal field splitting energy of
FeII in the tetrahedral crystal field of O2-. This is why, Fe3O4 adopts the inverse spinel structure
denoted by FeIII (FeIIFeIII)O4. The CF(oct) -+ CF*(oct) electronic transition in magnetite is 0.5-1
eV greater than expected owing to the mixed valence state nature of the octahedrally coordinated
Fe3+/2+ ions in Fe3O4. Thus, the presence of some oxygen 2p character in the CF(oct) levels of
Fe3+/2+ ions not only facilitates a relaxation of the Laporte selection rule, but also lowers the
energy of the CF(oct) levels. Such that the experimentally determined CF (oct)-CF*(oct)
separation is at least 0.5 eV greater than that predicted by SCF (Self-consistent field) calculations
based on the assumption that the crystal field levels are of wholly metal 3d character. The 3d
state of Fe acts as the conduction band minimum and 2p state of oxygen act as the valence band
maximum. Shifting of electrons to the 3d states of Fe, reduce the crystal field sufficiently and
result in the formation of extended 3d gap states. Generation of intermediate gap states in Fe3O4
network enhances light absorption and helps in heterogeneous photocatalysis.25 By synthesizing
Fe3O4 core photocatalytic structure, the magnetic core is useful for the separation of
photocatalysts from treated water whereas the outer semiconductor/metal nanoparticle coating is
beneficial for the photo catalytic reaction.
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a b

c
d
Fig.1 (a) Cubic Fe3O4 nano-hybrid, (b) Inverse spinel of Fe3O4,(c) Electronic configuration for
Fe3+, Fe2+ & (d) Energy diagram for Fe3+ (d5) ,Fe2+ (d6) ions octahedrally coordinated & Fe3+
(d5) ions tetrahedrally coordinated by oxygen.
Optical properties of Fe3O4 nanoparticles like other semiconductor is mainly based on absorption
and photoluminescence (PL) measurements as shown in figure-2(e). A well-defined excitonic
absorption and weak PL is shown by doped and undoped iron oxide nanoparticles in solution. By
drop casting into thin films, the PL disappears and the absorption spectra remains unchanged,
indicating a non-radiative relaxation path ways created by the thin films. Like a hydrogen atom,
the electron-hole pair consists of a single negative charge bound to a single positive charge,
except the positive hole is much lighter than a proton of a hydrogen nucleus. The electron-hole
pair is a bosonic entity, known as exciton, which dominates the optical properties of
semiconducting NPs.12
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Fig. 2 (a) Low & high spin in case ofFe3+ ion, (b) Octahedral crystal field stabilization energy,
(c) The crystal field splitting energy of FeIII in the Octahedral and Tetrahedral field, (d) The
crystal field splitting energy of FeII in the Octahedral & (e) Simple diagram of energy versus
momentum band structure of a semiconductor. The absorption process is shown with the green
arrow, and PL process shown with the red arrow12 Reproduced from ref.12. Copy right (2017)
Wyoming Scholars Repository.
3.2 Benefits of using Fe3O4 as photocatalyst:
Fe3O4 NPs are found beneficial among various iron oxide NPs due to the following properties:
Fe3O4 NPs possess suitable magnetic properties, low toxicity and cost effectiveness.
Based on the particle size, Fe3O4 NPs show high surface area to volume ratios, which in
association with their ability for surface chemical modification, shows enhanced capacity for
heavy metal removal in water treatment procedures.26
Fe3O4 materials not only have a very active surface for the adsorption/immobilization of metals
and ligands but can prevent the aggregation of metal NPs. Also it is easy to prepare and facilitate
the reuse of nanocatalysts through magnetic separation.
3.3 Limitations of using Fe3O4
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Although iron oxide (Fe3O4) NPs possesses a good number of advantages still its photocatalytic
applications are limited owing to:

1. Loading semiconductors directly onto the surface of Fe3O4 particles results in the reduction of
the photo catalytic effectiveness, as Fe3O4 core becomes the recombination centre of photo
generated electron and holes, resulting in the production of less active species.
2. Fe3O4 NPs usually cause aggregation and become unstable.

3. Low band gap energy is prone to easy electron-hole recombination.
3.4 Modifications to overcome the limitations
To eliminate above shortcomings, various modifications were introduced in designing the
magnetic Fe3O4 based photocatalysts as shown in figure-3. Such as:
1. Fe3O4 based photocatalysts were designed by incorporating Fe3O4 as a carrier that can
successfully improve the recycling efficiency, as it can be effortlessly collected with a magnet.
2. Designing core-shell nano-structured composites, by controlling thickness of shell and
introducing several inert substances, like carbon-based materials (AC, CNTs, and graphene) and
ceramics (SiO2 and Al2O3) between the semiconductors can protect the Fe3O4 NPs from
chemical dissolution.
3. By introducing various metal oxides between the shell and the magnetic core material to prevent
the electrons from being trapped by the magnetic core.
4. By incorporating noble metal NPs to improve visible light absorption.
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Fig. 3 Schematic representation of enhancement of photocatalytic activity of Fe3O4 nano-hybrids

by noble metals, metal oxides, non-metals and acids.

4. Role of noble metal NPs in noble metal modified Fe3O4
Recently, nano-materials are becoming important in many technological fields owing to their
small size, high surface area and availability of numerous surface active sites.6 The plasmonic
nature of noble metal NPs such as silver (Ag), gold (Au), palladium (Pd) and platinum (Pt)
remarkably enhances the photo catalytic activity by acting as co-catalysts, photo sensitizers,
good visible light absorbers and also as electron sinks based on Schottky barriers.8 However, the
structural and chemical stability of these noble metal NPs are very poor. The unprotected
plasmonic nanopaticles are very much susceptible to irreversible aggregation in the reaction
medium during synthesis owing to high surface energy and van der Waals forces. Immobilizing
noble metal NPs on magnetic Fe3O4 support has been proved to prevent agglomeration and result
in highly active composites.
In noble metal modified magnetic materials beyond their novel optoelectronic and plasmonic
properties, recycling of the photocatalyst is one of the key advantages for catalysis. The large
surface-area-to-volume ratio makes available most of the atoms on the catalyst surface for
reactions to occur. In most of the reported studies the design of photo catalytic materials often
target to achieve increased number of active sites on the surface. Furthermore, surface plasmon
resonance can be used to generate highly energetic (hot) electrons for photo catalytic reactions.
The increased activity of plasmonic nano materials is due to their SPR effect. The incident
photons and the oscillating surface electrons of noble metal NPs are said to be in resonance when
their frequency matches. The collective oscillation of these conduction band electrons are called
plasmons and this phenomena is known as surface plasmonic resonance (Figure-4). This
resonant photon wavelength is different for different noble metal NPs and depends on the size as
well as shape of the NPs. Due to SPR, the energy of the light photons concentrate in small
volumes surrounding the nanostructure to accelerate photon driven photocatalytic reactions. In
this review, we have focused on the enhancement in the rates of photo catalytic degradation of
pollutants and water splitting reactions of plasmonic-metal/ Fe3O4 composite photocatalysts.27
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Fig.4 SPR effect of noble metal NPs.
5. Design and Construction of Noble–metal loaded Magnetite nanoparticle
In the pure form, Fe3O4 NPs are not suitable semiconductors for the photocatalytic processes as
they go through photo cathodic corrosion, but are inexpensive and possess suitable band gap
energies. Therefore, coupling Fe3O4 with other stable and photoactive materials can enhance its
photocatalytic activity. Noble metals usually act as electron trappers to prevent charge
recombination, thus enhances rate of photocatalytic processes.28 Hybrids of Fe3O4 with various
noble metal NPs not only protect them from corrosion but also retain their magnetic,
semiconducting, and plasmonic properties, to behave as good photocatalyst. 8
Synthesis of Fe3O4 NPs has been associated with some basic challenges in order to make them
suitable for various photo catalytic applications. These NPs are very prone to aggregation due to
high surface energy (>100 dyn/cm), high surface area and high magnetization value. Also they
are easily oxidizable because of the presence of Fe2+ ions and may lose magnetism upon
oxidation. Moreover, it is also difficult to functionalize the surface of magnetite NPs with
various organic materials as the surface contains a few number of hydroxyl groups. To overcome
such difficulties during synthesis, various surfactants and stabilizing agents are used during the
synthesis process to enhance dispersion ability in the reaction media that will prevent
aggregation. These surfactants create electrostatic and steric repulsion between the Fe3O4 NPs
due to long chain hydrocarbons and ionic compounds, to overcome magnetic and surface-related
attractions.29 Synthesise noble metal modified Fe3O4 NPs involves the most common methods
such as; co-precipitation, hydrothermal method, micro-emulsion, sonochemical method, arc
discharge method, microwave, and hydrothermal method.30 In many cases therefore, lots of
synthesized polymers, surfactants, organic and inorganic acids (e.g. polyethylene glycol, poly
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vinyl alcohol, phosphate, polyglycidyl methacrylate, polyamides, poly acrylic acid, chitosan,
dopamine, cystoine, amine, trimethoxy silane, carboxylic acid, phosphoric acid) were also used

to coat the surface of Fe3O4 NPs.31Although this method prevents aggregation of Fe3O4 NPs, but
increase in size of NPS in some cases limit its potential applications. Therefore, to synthesise
Fe3O4 NPs with narrow size distribution smaller molecular compounds like sodium citrate,
polyvinyl alcohol, oleic acid, sodium dodecyl sulfate (SDS) and dextran etc were found
effective. The inter-particle interactions between the particles and van der Waals forces help to
prevent aggregation. Use of polymers (PANI, C-PDA, etc.) to coat the surface of Fe3O4 NPs is
also an effective strategy for designing nano hybrids of Fe3O4. The magnetite microspheres can
easily be coated with polymers shell due to the strong hydrogen bond interaction among the
Fe3O4 and a series of functional monomers. By proper tuning of monomers, various functional
groups such as hydroxyl, carboxyl, ester and amide are provided during the polymerization.
These Fe3O4 NPs can be considered as promising materials for many applications because of
their high saturation magnetization values and easy preparation.
Nowadays environmental friendly bio molecules are in trend. Their polar groups help to form an
absorption layer on the surface of the NPs. This helps to increase the repulsion force between
them, thus prevent aggregation of the particles. Hence act as reducing, capping, and stabilizing
agents. As reported, organic solvents and surfactants can be replaced by Pistachio leaf extract.
The amount of Pistachio leaf extract and the concentration of Fe3+/ Fe2+ both acts as stabilizing
and dispersing agent, which prevents the agglomeration of Fe3O4 NPs during synthesis. The
stabilization of Fe3O4 NPs and coating of noble metal NPs is shown in figure-5(a, b, c).32, 33
Here, in this review, we have highlighted the synthesis procedures of some noble metal modified
Fe3O4 NPs with special reference to Ag, Au, Pt, and Pd and also by using green bio extracts like,
Pistachio leaf extract , Carambola leaf, Blackberry leaf extract etc.34,35
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Fig.5 (a) Polymer coated Magnetite (b) Loading of Noble metal NPs through stabilizing agents,
(c) Stabilization of magnetic materials by surfactants. Reproduced with permission from ref.32,

33 .license no- 4204491421498.
4.1 Synthesis of Ag modified Fe3O4 NPs

In application point of view, Ag is preferred to modify Fe3O4 NPs because it is cheaper and can
be easily incorporated to extend its applications from photovoltaic to biological and chemical
sensors. Attempts were made by different research groups to design Ag modified Fe3O4 nano
hybrids for photo catalytic applications.36-37 Silva group have reported the synthesis of silver
coated Fe3O4 NPs (Fe3O4@Ag) in a two step procedure involving micro emulsion technique.
Using glucose as reducing agent in presence of AgNO3 solution, first a core of 9 ± 2 nm Fe3O4
was obtained and in the next step, a silver shell of 2 ± 1 nm was formed.38 A mono dispersed
Ag/PANI/Fe3O4 ternary nanocomposite was fabricated via a typical in situ copolymerization
method by using a solution of FeCl3, FeCl2 along with aniline and acrylic acid. AgNO3 solution
was used to deposit Ag NPs where acrylate act as the protecting agent and PANI forms the
capping layer. Due to low cost of the raw material, easy preparation and anticorrosion, PANI is
usually selected to compound with noble metals or inorganic particles. The copolymer-capped
Fe3O4 was due to the bonding of N atoms of PANI with carboxyl groups of Acrylic acid.39, 40 In
many cases, methylene bisacrylamide (MBAAm), methacrylic acid (MAA), Fe3O4@P(MBAAm-
co-MAA) microspheres containing carboxyl groups were used, to support loading of metallic
nanoparticles such as Ag, Pt, and Au As shown in scheme-1.36
Scheme.1 Schematic representation on stabilization of Fe3O4 NPs by polymers. Reproduced with

permission from ref.36. Copy right (2011) American Chemical Society.
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Ag/SiO2/ Fe3O4 composite was prepared using a reversed chemical co-precipitation method
involving FeSO4, NH4OH solution as a Fe3O4 precursor and precipitating agent respectively. The

synthesis of the Fe3O4-silica core shell particles was carried out using modified Stober method.
41, 42 Silica, being chemically inert favours the dispersion of magnetic NPs in liquid media
because of its high stability against aggregation and its ability to screen the magnetic dipolar
attraction between the core particles. Due to the presence of silanol groups on the silica layer,
surface modifications are easy which are compatible with various organic and inorganic species.
A silica-coated magnetic nanoparticle with minimal residual magnetism and strong magnetic
susceptibility facilitate easy control of inter particle interactions.38,43
Another Ag/TiO2/ Fe3O4 composite was designed by Chang et al. using hexane as the solvent
CTAB as the surfactant and 1-pentanol as the co-surfactant. CTAB is used as an cationic
surfactant which makes the nanoparticle well stabilized by the formation of a double layered
coating on the surface of Fe3O4 NPS.44 TiO2-capped Fe3O4 NPs were prepared by in situ
hydrolysis and the Ag3PO4 NPs were deposited onto the TiO2/ Fe3O4 surface by the precipitation
method. The enhanced activity of the composite was largely attributed to the basic cytotoxicity
of silver ions, and the eminent bactericidal efficiency of Ag3PO4/TiO2/ Fe3O4.45
4.2 Synthesis of Au modified Fe3O4 NPs

The nano contact among Au and Fe3O4 produces a red-shift of the surface plasmon of the Au
NPs and slow increase in magnetization of the Fe3O4 NPs (8 nm or smaller).46 Mono dispersed
Au– Fe3O4 nano composites with various morphologies,47-49 including core/shell, core/satellite,
multilayer, flower-like and dumbbell-like architectures as shown in scheme-2.50 Dumbbell-like
Au- Fe3O4 NPs was fabricated by Yu et al. in oxidation method by mixing Au NPs with Fe
(CO)5 in 1-octadecene solvent along with oleic acid and oleylamine. The size and thickness of
both the Au and Fe3O4 components can be controlled to optimize their properties.51 The
dumbbell structure is obtained by epitaxial growth of Fe3O4 on the Au seeds and the growth can
be monitored by the polarity of the solvent, as the use of more polar solvent leads to flower-like
Au- Fe3O4 composite particles.52
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Scheme. 2 Schematic representation of the formation process of Au-Fe3O4 nanocomposite.

Reprinted from ref.50. license no. 4203510755914.
Mono dispersed core−shell Fe3O4@Au or Fe3O4@Ag NPs were prepared by Chin and co-
workers at room temperature in a simple wet chemical impregnation method. In this method, a
pre-formed 2−3 nm Au NPs were attached to −NH2 functionalized Fe3O4 NPs, in a “seed-
mediated growth” method and then glucose was used to reduce Au3+ or Ag+ on the surface of the
composite NPs thus achieve complete encapsulation in ultrathin shells was achieved.53
Magnetically separable Fe3O4@TiO2-Au composites, having a core-shell structure, were
synthesized by Ma et al. in a liquid-phase deposition method.TiO2NPs were uniformly deposited
on Fe3O4 to form core–shell Fe3O4@TiO2 spheres and Au NPs were evenly distributed on the
core-shell Fe3O4@TiO2 spheres through a seed-mediated growth procedure.54 Bagga et al.
designed another Fe3O4 core prepared by co-precipitation or by thermal decomposition method,
in which Fe3O4 surface is usually passivated by using triethoxy silane (TEOS) to produce a thick
silica layer on the surface prior to reduction of Au in water as in figure-6.55
Fig.6 Schematic representation of the formation process of bilayered core-shell Au-Fe3O4

nanocomposite with non-conductive SiO2. Reproduced from ref.55. License no. 4203540181379.
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Sun et al. prepared a stable aqueous stabilising CTAB bilayer on the surface of Fe3O4 with
oleylamine as the reducing agent to form 2.5-3 nm thickness Au shell.56

4.3 Synthesis of Pd modified Fe3O4 NPs
Among the four noble metals (Ag, Au, Pt, and Pd) incorporation of Pd was reported to be
effective because of the fact that Pd is comparatively stable towards surface oxidation (unlike
Ag) and inexpensive (unlike Au and Pt). Further Pd has a high work function value, which is
very much suitable to receive the conduction band electrons from other semiconducting
materials. To easily synthesise Pd based nano hybrids, scientists have reported the deposition of
the Pd NPs on the surface of the magnetic NPs.57-59 By applying an external magnet magnetic
catalyst carriers can be easily separated from the reaction medium. Palladium-based catalysts, in
particular Pd NPs, have attracted much attention due to their versatile role in many
photocatalytic reactions, organic conversions, oxidation reactions etc.60 Loading Pd on Fe3O4
NPs simultaneously catalyse the photo catalytic reaction and provides a possible approach to
recycling the catalyst after treatment.61 Tuo et al. reported Pd/ Fe3O4 by adding Pd (II) salt
solutions to the water-washed biogenic Fe3O4 suspension and incubated for 48 hrs under an
anoxic conditions. The bio extract containing surface-bound cellular components and
exopolysaccharides act as shape-directing agent to convert some Fe3O4 NPs to nano rods, also
participate in the formation of PdAu alloy NPs on magnetite.
4.4 Synthesis of Pt modified Fe3O4 NPs
Although costlier, Pt NPs have attracted much interest owing to superior catalytic response
especially for hydrogen oxidation and oxygen reduction reactions. When loaded on Fe3O4 NPs,
Pt links epitaxially to Fe3O4 NPs and becomes rich in electrons to endow the system with
superiority. It is highly desirable to prepare narrow-sized distribution of Pt NPs to get maximum
interaction with metal oxide NPs to increase efficiency.62 Most of the synthesise procedures of Pt
NPs mainly involves organic stabilizers in the preparation of colloidal Pt solution. Designing
magnetically responsive Pt based substances makes the recovery process easy and extends the
potential application of magnetite NPs.63-65 He et al. reported a facile and versatile approach for
the preparation of CNT-supported Fe3O4 catalysts and loaded Pt NPs on it without using a
stabilizing agent. Initially Fe3O4 NPs decorate the carboxyl-functionalized CNTs in a controlled
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manner followed by subsequent deposition of Pt NPs on the unoccupied carboxyl groups on

CNTs. The resulting Fe3O4/Pt NPs decorated CNTs were found to maintain strong magnetism.66

Using oleic acid as a surfactant and toluene as a carrier liquid, Pt/Fe3O4 composites were
prepared by the wet chemical method and increasing the Pt content large metal crystallites (up to
60 nm) were formed. The concentration of noble metal controls the magnetization in the resulted
composite.
It can be concluded that designing of noble metal decorated core-shell nanostructure is preferred
for constructing a suitable magnetite based photocatalyst. Core-shell nanostructure helps in
protecting the Fe3O4 NPs from corrosion and favours recovery process. If the shell consists of a
non-conductive porous metal oxide, free access of the adsorbents from outside is possible to
speed up the photo catalytic reactions. Furthermore, use of environment friendly bio extract is
beneficial as it acts both as stabilizing and dispersing agent, which prevents the agglomeration of
Fe3O4 NPs during synthesis. Because the natural surfactants get absorbed on the surface of the
composite through polar groups, it influences the morphology.34 It can be said that bio
surfactants not only plays an important role in controlling the shape and size of the NPs, but also
enhances the surface area.
5. Physicochemical characterization of noble metal modified Fe3O4 NPs

5.1 Structural characterization
Furthermore an insight into the structure of noble metal modified Fe3O4 NPs composites is
discussed by different types of structural analysis like XRD, SEM, and TEM etc. The structural
parameters, crystalinity, phase purity, crystallite size of Fe3O4 based photo catalytic materials
can be known from X-ray diffraction technique. XRD patterns of pure Fe3O4 gives seven
characteristic peaks marked by the indices (220), (311), (400), (422), (440), (511) and (622) at 2θ
value 30.810, 36.480, 54.590, 56.830, 62.340 respectively representing well crystalline fcc
structure in a single phase in good agreement with JCPDS file no.19-0629.67 Modifying the
surface with sodium citrate and the oleic acid, the crystalline structure of Fe3O4 MNPs found
remain intact. The average crystallite size reported are about 12.6 nm (a), 13.4 nm (b) in sodium
citrate and 14.2 nm (c) 13.8 nm (d) with oleic acid respectively as shown in figure-7a.68 After
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modifying pure Fe3O4 with noble metal NPs, there was no considerable change in the crystal
structure of the Fe3O4. Therefore, the modification with various noble metal NPs do not disturb

the lattice structure, although a substantial broadening of the main peak confirms the formation
of the nano composites.
It was found that upon non-conductive metal oxide modification, there is a decrease in
diffraction peak intensity and small contraction in lattice constants. Stefan et al. found that when
modified by TiO2, XRD patterns indicate formation of ilmenite (FeTiO3) with decrease in
crystallite size. This decrease of the crystallite size from ∼20 nm to ∼13 nm along with anatase
TiO2 phase can be recognized to the presence of Fe-O-Ti interactions in the doped samples
which prevent the growth of crystal grains.69 Hence it can be predicted that after hybridization
with various metal oxides the crystal phase of Fe3O4 did not change, but the positions of
diffraction peak of Fe3O4 were slightly shifted to lower angle than those for pure Fe3O4,
suggesting a strong interaction between Fe3O4 and the metal oxides. In noble metal loaded
composites, the crystalline structure of magnetite NPs corresponded well with the pure magnetite
NPs structure along with the characteristic diffraction peaks of respective noble metals. The
XRD patterns for cubic spinel structure of Fe3O4 nanoparticle, cubic close packed structure of
Ag NPs and hetero structure of Ag coated Fe3O4 NPs are shown in figure-7(b). The absence of
diffraction peaks of Fe3O4 in the XRD of Fe3O4@Ag is a strong evidence for a absolute coverage
of the oxide by Ag, confirming the formation of Fe3O4@Ag core-shell NPs.38
Fig.7 (a) XRD patterns of as-prepared Fe3O4 NPs with various surfactants (sodium citrate and
the oleic acid), (Reproduced from reference (Weia et al., 2012),license no 4184670094453).
(b)-XRD patterns for the NPs: (a) Uncoated (b) AgNPs and (c) Ag- Fe3O4 hetero structures.
Reprinted from ref.38. license no 4184660610484).
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In m-MWNTs@Pt (Pt decorated multriwalled carbon nanotubes) with increasing the ratios of
FeCl3 and NaOH/ diethylene glycol from 0.2/1 to 1/1 and then to 5/1, Fe3O4 nanoparticles with

average size of 4-5 nm shows, an increase in its deposition on the nano tubes. The enlargement
of feed ratios results intense diffraction peaks of the Fe3O4 in comparison those of CNTs as
shown in figure- 8.66
Fig.8 XRD pattern of (Magnetic Multiwalled Carbon Nanotubes) m-MWNTs@Pt Reproduced

with permission from ref.66. Copy right Hindawi Publishing Corporation.
As explained by Lin et al. in the XRD pattern of Au-Fe3O4 hetero structures, the weak diffraction
peaks of Fe3O4 may be due to the intense atom effect of Au coating on the Fe3O4 supports.2 For
PdAu/ Fe3O4 nanocomposite, in addition to the characteristic peaks of Fe3O4, the peaks of Pd and
Au (2θ = 38.24° and 44.48°) situate between those of monometallic fcc Pd and Au were obtained
by the formation of bimetallic alloy.61 XRD patterns of the noble metal–Fe3O4 hetero structures
are shown in figure-9.36
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Fig.9 XRD patterns of the noble metal–Fe3O4 hetero structures. Reprinted from ref.36 with
permission. Copy right (2011) Springer.
The Scanning electron microscopic study of the noble metal modified Fe3O4 nano composites
further provides information relating to morphology, topographical features, crystal structure,
crystal orientation, phase distribution, compositional differences and the existence of electrical
defects.70SEM images of Fe3O4 NPs with average diameter size less than 100 nm prepared by
using ammonia and NaOH show the effect of solvent on morphology as in figure-10.71 The
change of temperature and concentration of the solvents effects the morphology and particle size
of Fe3O4 NPs. SEM images of Fe3O4 NPs prepared from pistachio leaf extract were almost
sphere-shaped with an average diameter ranges from 5-18 nm. The concentration of Fe3+/ Fe2+
and the amount of pistachio leaf extract control the size and shape of magnetite nanoparticle.
Also pistachio leaf extract function as a stabilizing agent for Fe3O4 NPs and prevents
agglomeration of particle.36 SEM image of the Ag-Fe3O4 nano composite in figure-11, shows
the presence of two different types of spherical NPs in the nano hybrid.36By investigating the
SEM images of Au-Fe3O4 prepared by biogenic method (G-Fe3O4) and by chemogenic method
(C-Fe3O4), the particle size of C-Fe3O4 was found to be coarser compared to G-Fe3O4 as shown
in figure-12. Because, the natural surfactant get absorbed on the surface of the composite through
polar groups and influences the morphology. It can be concluded that bio surfactants not only
enhances the surface area, but also plays an important role in controlling the shape and size of
the NPs.72
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Fig.10 SEM images of Fe3O4 NPs in presence of NH3 (a) and NaOH (b) Reproduced with
permission from ref.71. Copy right (2016) Springer.
Fig.11 SEM images of Ag3PO4 and Ag- Fe3O4 nanocomposite. Reproduced from ref.36. License
no. 4184700410334.
(a) (b)
Fig.12 SEM images of Fe3O4 prepared by chemical method (C-Fe3O4) and by biogenic method
(G-Fe3O4). Reproduced from ref.72. License no 4184710478942.
Further high resolution transmission electron microscopy (TEM) of the magnetite nanomaterials
was used to obtain information about the particle size, nature of distribution and morphological
parameters.73Neat Fe3O4 NPs, when synthesised in deionised water, undergo aggregation. But in
presence of surfactants like sodium citrate and oleic acid Fe3O4 NPs show good dispersion
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capability as found in the TEM image (Figure-13). It is due the decrease in high surface energy
and dipolar attraction of the NPs by the surfactants.68,74,75

When mild reducing agent like glucose was used to control shell growth of silver onto Fe3O4,
spherical mono disperse Fe3O4@Ag NPs can be changed to poly disperse nanoparticle.76 It has
been reported that Ag NPs were uniformly deposited on the hetero silica–silver interface and
possesed good stability by using Sn2+ ions as reducing agent. The Sn2+ ions helps in the reduction
of Ag+ to Ag0 and Ag get easily adsorbed on the negatively charged surface of SiO2 due to the
presence of hydroxyl groups.77 In the preparation of Fe3O4@TiO2@Ag nano composite by
hydrothermal method, the porosity was found to be enhanced by increasing the hydrothermal
time.21 The Au-Fe3O4 nanostructure is derived from the epitaxial growth of Fe3O4 on the Au
seeds where Au has a fcc structure while Fe3O4 has a cubic structure. During the process of
nucleation, the free electrons of Au compensate the charge induced at the interface. As the Au
particle has only a narrow resource of electrons, makes the other facet of Au electron deficient
and undergo multi nucleation to form dumbbell shaped structure. In presence of polar solvent,
the formation of multiple facet was favoured due to compensation of electron density to form a
flower like Au-Fe3O4 NPs with Au core of ~ 8 nm and shell of ~ 4 nm. The TEM image indicates
clearly the multi-nucleation of iron oxide on the faceted Au seeds.51 The TEM images (Figure-
14) of chemogenic and biogenic Fe3O4 shows spherical and tetragonal shapes, owing to the
interaction of bio-molecules with some specific plane of Fe3O4 NPs. Upon Au loading, a good
interaction in the composite is confirmed.
(a) (b) (c)
Fig.13 (a) Represents the TEM images of Fe3O4 NPs (a) in DI water (b) in presence of sodium
citrate (c) in presence of Oleic acid. Reproduced from ref.68. License no. 4184720634102.
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Fig.14 TEM images of chemogenic, biogenic Fe3O4 and Au-biogenic Fe3O4. Reproduced from
ref.72. License no 4184720634102.
As reported by Lopes et al. dithiocarbamate-functionalized magnetic sorbents in contact with

noble metal hydrosols gives rise to stable colloidal noble metal (Ag,Au,Pt,Pd) nanoparticles
having narrow particle size distributions as in figure.15.8
Fig.15TEM images of surface-functionalized magnetite particles

that have contacted with distinct metal colloids. The type of noble
metal nanoparticles adsorbed at the surface of the functionalized
Fe3O4 particles are indicated by arrows in the right panel images.
Reproduced with permission from ref.8.Copy right (2016 ) Elsevier
Inc.
The type of noble metal nanoparticles adsorbed at the surface of the functionalized Fe3O4
particles are indicated by arrows in the right panel images In Fe3O4/Au/Ag NPs the overall
diameter of the particles increases as compared to the neat Fe3O4 NPs, by controlling the coating
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during synthesis. By controlling the coating of either Ag or Au on the Fe3O4/Au NPs the
plasmonic properties of these core/shell NPs can be tuned to facilitate charge transfer.78

In Fe3O4@TiO2-Au composites, the Fe3O4@TiO2 nano-sphere tied to small Au seeds acts as the
core along with nucleation site for the growth of the Au nano shell that deposited through the
reduction of Au3+ by formaldehyde to yield Au0. Also it was indicated that the surface
modification of the Fe3O4 spheres with PDADMAC (poly diallyldimethylammonium chloride) is
essential for the formation of a uniform TiO2 shell on the Fe3O4 surface providing a negatively
charged Au seed colloid particles and positively charged exterior surface, which were electro
statically adsorbed on the surface.54
In case of Pt/ Fe3O4, by increasing the platinum content from 1.1 wt % to 7.4 wt %, without
change in carrier phase composition Pt NPs shows good dispersion on the surface of larger
magnetite NPs.79But in Fe3O4@SiO2@TiO2@Pt composites, presence of silica core helps to
distribute Pt NPs at the edge and junction sites of the interlaced TiO2 nano platelets, thus
improves its potential.62 By the reaction of Pt- Fe3O4 hetero dimers with Ag (C2H3O2) in toluene
at 60 °C, Ag NPs nucleate completely on the Pt domain to form Ag-Pt- Fe3O4 hetero trimers
(Figure-16). Proper arrangement of constituent domains leads to cooperative processes within the
particles that facilitate functionalities like applications in solar energy conversion, heterogeneous
catalysis, magnetism, electronics, and biomedical imaging.75
Fig.16 TEM image of (a) Pt-Fe3O4 heterodimer and (b)Ag-Pt- Fe3O4 hetero trimmers
Reproduced with permission from ref.75. Copy right (2013) American Chemical Society.
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5.2 Study of optical and electronic properties of Noble metal modified Fe3O4 materials

UV-Visible diffuse reflectance spectroscopy (DRS) is used to study the optical properties of
noble metal modified Fe3O4 nanostructures. Pure Fe3O4 is not a suitable semiconductor for the
photocatalytic process as its band gap energy is not proper and they go through photo cathodic
corrosion. As a result pure Fe3O4 NPs do not harvest light energy efficiently.80Upon light
irradiation, d–d transitions shows absorption due to the availability of Fe3+/ Fe 2+ ions. Generally,
in optical-magnetic based photocatalysts the interactions between the surface coating materials
(such as Au, Ag, QDs and fluorescent molecules), having excellent localized surface plasmon
resonance (LSPR) and light waves gives rise to superior optical performance. When loaded with
noble metals, Fe3O4 NPs show a red shift of the absorption edge, indicating good interaction
between Fe3O4 and noble metals. The exact shift in the absorption band position is dependent on
the morphology and size of the particles. Presence of excess electrons on the noble metal NPs
shifts the plasmonic absorption to shorter wavelength region, whereas electron deficiency shifts
the plasmonic band towards longer wavelength region.51 UV-Vis absorption spectra of Fe3O4/Ag
nano composites show intermediate absorption in comparison to neat Ag and neat Fe3O4 NPs.
Although the SPR band of Ag NPs is observed at 355 nm, in Fe3O4/Ag nano composites the SPR
band is slightly shifted to higher wave length region, confirming the presence of Ag NPs in the
composite.81 In Ag/TiO2/Fe3O4 when Ag was loaded on Fe3O4 in presence of a non-conducting
metal oxide (TiO2), there is an increase in optical absorption and the corresponding band gap
energies were found to be 1.12 eV, 2.88 eV and 3.12 eV, for Ag/TiO2/ Fe3O4, Ag/TiO2 and
Degussa P25 TiO2, respectively as shown in figure-17.82 This red shift in absorption edge may be
due to the charge transfer between Ag NPs and Fe3O4 NPs in the nano-composite. With increase
in size, the band shows a red shift and broadens. When the particle size is more than 80 nm, a
secondary peak is also visible at a shorter wave length region.83 The co-existence of Ag in the
nanocomposite is confirmed by a broad absorption in the UV-Vis wavelength.
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Fig.17 (a) Optical absorption and (b) corresponding band gap energies of Degussa P25 TiO2,
Ag/TiO2, and Ag/TiO2/ Fe3O4 samples. Reproduced with permission from ref.82. Copy right
(2014) Langmuir.
The UV-Vis absorption spectra of Fe3O4 NPs show different absorption properties when capped
with CTAB and citrate, due to change in optical property by the change of surface charge. When
the surface of the Au NPs is charged, the surface plasmon show strong absorption. However,
loading with both Au and Ag, the absorption shifts towards lower wavelength because of
increase in the thickness of the core as shown in figure 18. By controlling the shell thickness the
plasmonic properties of the noble metal changes, to show red shift. When CTAB is used as
cationic surfactant, it makes the nano particle well stabilised due to formation of a double layered
coating on the surface of Fe3O4 NPs. The synthesis of composite nanoparticle system with
controlled plasmonic and magnetic properties not only shows good photocatalytic property; but
also it stabilizes the Fe3O4 NPs by surface functionalization.56
Fig.18 (a) Effect of shell thickness of the noble metal changes in shifting absorption edge, (b)
Size dependent UV-vis absorption spectra of the core/shell Fe3O4/Au and Fe3O4/Ag NPs with
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various Au and Ag coating. Reproduced with permission from ref.65. copy right (2007)
American chemical society.

7. Magnetic Properties of noble metal modified Fe3O4.
Although Fe3O4 is not a suitable semiconductor for photocatalytic process, but the advantage of
magnetic property is highly beneficial for the recovery of the phtocatalyst after being used. Due
to high magnetic moment, Fe3O4 NPs are prone to aggregation and leads to decrease in surface
area as well as the photo catalytic applications. However, on noble metal incorporation the
magnetization or magnetic saturation value decreases to an optimum value required for recycling
the photo catalytic material. The magnetic saturation (Ms) value of Fe3O4 based composites is
mainly dependent on surface anisotropy, porosity in a core-shell, surface defects and
temperature. With noble metal loading, the surface anisotropy effects the magnetic moments of
Fe3O4 NPs through the exchange interaction with surface active groups, thus Ms of the noble
metal loaded nanohybrids decreases. Whereas core-shell nano-architecture allows oxidation of
Fe3O4, resulting defective nanohybrids and shows low saturation magnetisation. The variation of
the magnetization with temperature for Fe3O4 and Fe3O4@Ag NPs are studied by Silva et al.
(Figure 19). In case of coated Fe3O4 NPs, the value of magnetization was found decrease (at least
20 times). Thus improves recyclability. The biogenic nano composites were reported to possess
nearly zero magnetic coercivity or remanence values, indicating their super paramagnetic
behaviour. With the addition of non-magnetic noble metal NPs, the value of saturation
magnetization in case of biogenic Fe3O4 (44.34 emu g−1) decreases. However, even the lowest
saturation magnetization, obtained in Pd/Au-Fe3O4 nano composite (23.63 emu g−1) was found
sufficient for effective separation of the nanocomposite. By measuring magnetization and
coercivity of Fe3O4, Fe3O4@TiO2 and Fe3O4@TiO2-Au, at 300 K using a magnetometer, Ma et
al. reported super paramagnetic character in all the three samples. The saturation magnetization
(Ms) was measured to be 73.1 emu g−1 in case of the Fe3O4 spheres, which after being coated
with TiO2, shows decreased Ms (56.8 emu g−1). Upon Au loading, the Ms was further reduced to
44.6 emu g−1. This decrease in the Ms was due to the presence of non-magnetic coating layers of
TiO2 and presence of Au NPs, which reduced the Fe3O4 content in the photocatalyst. Although
the value of Ms was decreased, but it was still sufficiently high to make the photocatalyst
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magnetically separable, and was beneficial for the separation of the photocatalyst after treatment.
The magnetic hysteresis curves of Fe3O4, Fe3O4@TiO2 and Fe3O4@TiO2-Au are shown in

figure-20.84
Fig.19 Effect of Temperature on magnetization for Fe3O4 and Fe3O4@Ag NPs Reproduced from
ref.38. license no 4184670094453.
Fig.20 Magnetic hysteresis loops of (a) Fe3O4, (b)Fe3O4/TiO2,and(c)Fe3O4/TiO2@Au.

Reproduced from ref.84. License no.4203600029570.
8. Photo catalytic Applications of noble metal modified Fe3O4 NPs
In the field of photo catalysis, Fe3O4 NPs are considered superior to the bulk counterpart owing
to quantum size effect, mesoscopic effect, surface effect and most importantly because of their
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super paramagnetism. Though neat Fe3O4 is not a suitable semiconductor, but suitable band gap
energies can be developed by coupling Fe3O4 with other stable photoactive materials and by

morphological variation. 85
The noble metal NPs have been widely used to improve the photo catalytic performance of
Fe3O4 due to their strongly enhanced surface plasmonic resonance in presence of visible light as
excellent scatterers or absorbers. The increased photocatalytic activity of noble metal NPs
modified Fe3O4 plasmonic nano hybrids is due to their SPR effect. Enhanced photo catalytic
activity due to SPR effect of noble metal may occur in the following two different ways
depending on the Fermi level of the noble metal NPs.86
a) When the Fermi level of the noble metal NPs lies just below the CB of the semiconductor,
visible light irradiation results shifting of Fermi level to attain equilibrium and helps in charge
delocalization (Scheme-3a).
b) Noble metal NPs absorb light radiation in UV-Vis region, generate photoelectrons and easily
transfer the same to the surface of the semiconductor, when the CB of the semiconductor lies
below the Fermi level of the noble metal NPs (Scheme-3b).87
Scheme.3 Schematic representation of Transfer of photo generated electron-hole pair in noble

metal loaded Fe3O4 with, (a) noble metal having Fermi level at lower potential than the CB of the
semiconductor (b) noble metal having Fermi level at higher potential than the CB of the
semiconductor.
When light radiation of greater energy than the band gap is incident on the Fe3O4 based nano-
composites, an electron/hole pair is produced on the surface. The photo generated electrons and
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holes undergo redox reactions. For instance in water splitting, H2O is reduced by the electrons to
evolve H2 and oxidized by the holes to form O2. In case of dye degradation holes may react with

water to form hydroxyl radicals and electrons are utilised to produce superoxide radicals which
can subsequently degrade the pollutant into H2O and CO2. However, suitable potential of the
conduction and valence band of semiconductor is the thermo dynamical requirement. Other
factors such as mobility, charge separation, and lifetime of photo generated electrons and holes
also have an intensive role on the photo catalytic activity of semiconductors.88 Here in this
review we have discussed the photo catalytic activity of Fe3O4 towards various inorganic &
organic pollutant degradation and water splitting reaction for the generation of H2.
8.1 Mechanism of Pollutant degradation by noble metal modified Fe3O4 nano composites
Pollutant degradation by noble metal modified Fe3O4 based nano composites involve advanced
oxidation mechanism by electron/hole pairs in presence of sun light (eqn-1). The photocatalytic
oxidation of pollutant often proceeds via its adsorption on the surface of the catalyst.
Degradation may proceed by using e– at the CB to form •O2− (superoxide radical) (3) or by using
h+ at the VB to form •OH (hydroxyl radical) (4). First, the oxidation process is induced by the
formation of •OH which is formed from the holes of photocatalyst (2). The pollutants can be
easily undergo oxidation process in presence of •OH. Both reactions may proceed
simultaneously and the type of mechanism dominates depending on the chemical nature and
adsorption properties of the pollutant.
Meanwhile, some electrons can reduce the molecular oxygen adsorbed on the surface of
photocatalyst forming superoxide anion (•O2−). This superoxide anion can further produce •OH
radicals via the formation of HOO• radicals and H2O2 (eqn 1−6). These formed highly reactive
radicals or intermediate substances, such as h+, •OH, •O2−, HOO•, and H2O2, would act
concomitantly to oxidize various organic/inorganic compounds. It is accepted that the •OH attack
mechanism is applicable in the most photocatalytic processes to degrade organic/inorganic
pollutants.89, 90
UV-Vis + Noble metal NPs/ Fe3O4 Noble metal NPs/ Fe3O4 (h+ + e-) ------- (1)
2h+ + 2H2O H+ + H+ + ( OH + OH) ------------( 2 )
e- + O2 O2- (Super Oxide) ----------- (3)
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O2-⸰ + H+ HO2⸰ ----------- (4)

HO2⸰ + HO2⸰ H2O2 + O2 ------------ (5)

H2O2 2OH⸰ ------------ (6)
A large number of studies have been reported on the photo catalytic activity of Fe3O4 based nano
composites towards degradation of MB, MO, RhB, CR, Phenol, hexavalent chromium etc under
solar light irradiation. Depending on the nature of the pollutants the photo degradation process
can be further classified into the following two types.
8.1.1 Degradation of Colouring Substances
Under visible-light irradiation, both Fe3O4 based semiconductor photocatalysts and the adsorbed
dye molecules get excited; result in the formation of electron–hole pairs. The electrons then get
transferred from the excited states of the dye molecules into the CB of the semiconductor and
initiate the photo degradation reactions, represented by the following equations:91
Dye + hv (visible) → Dye* --------------------------------- (7 )
Dye* + Fe3O4 -→ Dye+ + Fe3O4 (ecb) --------------------------------- (8 )
This, synergism effect among the dye and the semiconductor during the process of
photosensitization is an important factor which affects the conversion efficiency. At the same
time, SPR effect of noble metal NPs can also absorb the visible light and generate photo-
electrons. This increases the photo excited electron shift from solar light-sensitized dye molecule
to the CB of the Fe3O4 composites and subsequently the efficiency of the catalyst.A careful
control of Fe3O4 loading in the nanocomposite gives access for improvement in photocatalytic
activity in hetero junction nano composites.92 Also as reported, ‘Green synthesis’ methods and
influence of different conditions of synthesis on morphology and size of neat Fe3O4 NPs enhance
its photocatalytic activity.93 Rahimi and co-workers synthesized Fe3O4 NPs from urea which has
the highest photo degradation activity for MB under visible light among Fe3O4-DDA (dodecyl
amine), Fe3O4-NH4Ac (ammonium acetate) and Fe3O4-Urea.94As reported, Fe3O4/TiO2 NPs
prepared hydrothermally remove 50% of MB in 90 min. Further addition of H2O2 the
degradation of MB increases rapidly and reaches 99% in 5 minute. But excess loading of Fe3O4
causes detrimental effect and consequently lowers catalytic activity.95 However, by incorporating
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noble metal NPs (Ag, Au, Pt, Pd) the light absorption range of the photocatalyst increases. The
noble metal NPs trap the excited electrons, increases the electron−hole separation and

subsequently act as electron donor to O2 (Harifi et al., 2014). In Fe3O4/TiO2/Ag treated polyester
fabric prepared at optimum Fe2+/TiO2 and Ag/TiO2 molar ratios shows maximum self-cleaning
ability and MB degradation in comparison to that of TiO2, TiO2/Ag and Fe3O4/TiO2 treated
fabrics.96 A direct coating of TiO2 on Fe3O4 experiences photo dissolution. A silica layer was
usually inserted to overcome such limitations. Fe3O4@SiO2@Ag nanorods prepared by Li et al.
showed a better MB degradation due to improved dispersibility, smaller size, large surface area,
and synergistic effect between Fe3O4@SiO2 nanorods and Ag NPs. The dye molecules upon
interaction result intimate contact with Ag NPs and lower their interfacial potential barrier. 97,98
Here, the Ag NPs supported on Fe3O4@SiO2 nanorods show a fast electron transfer rate through
the interface. It shows a noticeable MB removal within 12 min in comparison to Fe3O4@
hierarchical hollow silica showing a removal of MB up to 97.6% within120 min at high pH. It is
because silanol group of silica interacts with pH dependant MB.99 In another study Li and group
fabricated lysine modified Fe3O4 magnetic core coated with SiO2 prior to the deposition of TiO2
as an adsorbent and photocatalyst, which can be recycled for 10 times.100Similarly
TiO2/SiO2@Fe3O4 nano composite, having outer layer of porous TiO2 and interlayer of
amorphous SiO2, shows complete degradation of MB in 60 min under visible light. The rattle
particles (hollow structure) where thin SiO2 layer is left on the outer and inner surfaces of the
Fe3O4 and TiO2 reported showing superiority by 90% degradation of MB in 30 minute.101
However, Ag@Fe3O4@SiO2@TiO2 exhibits excellent total removal performance (including
adsorption and photocatalytic degradation). The order of photo degradation of MB was;
Ag@Fe3O4@SiO2@TiO2 (unannealed)> Fe3O4@SiO2@TiO2 > Ag@Fe3O4@SiO2@TiO2
(annealed) P25> TiO2. 23
Similarly, as reported by Mahmood et al. Au doping on Fe3O4 under visible light irradiation
exhibits the effectiveness of catalyst for MB degradation due to red shift in absorption edge. This
increased Au contents in pure Fe3O4 can instigate the reduction of band gap and enhance the
light absorption, improving the activity. But excess Au covers the Fe3O4 surface, which lowers
the surface area of the catalysts and decreases the photocatalytic activity.102 By introducing
nonconductive oxide coating and TiO2 the degradation of MB further increases to 87.4 % in
Fe3O4@SiO2@mTiO2–Au (FSTA) (mTiO2: mesoporous TiO2) core–shell nano-architecture
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(Figure 21a). Unlike Ag, Au NPs/TiO2 microsphere on the surface of Fe3O4@SiO2, results in the
development of a schottky barrier at the metal–semiconductor hetero junction and acts as

electron trapper.103 The enhanced photocurrent data (Figure 21b) of the composite further
supports its efficiency. Further Fe3O4@Ag3PO4/AgCl shows 100% degradation of MB within
60 min.83 Presence of both Au & Ag in Au(Ag)/AgCl/Fe3O4@PDA@Au, show complete
degradation of MB under visible light in 20 min, compared to Fe3O4@PDA-Ag microspheres

showing an adsorption of 90% MB. Here Au NPs onto the PDA shell enhances the adsorption
due to the presence of hollow Au (Ag)/AgCl structure, where the reactants are in contact with
both inner and the outer surfaces of the catalyst and shows improved visible light-harvesting
efficiency.103 Due to SPR effect of Ag under visible light illumination, complete MB degradation
was observed by plasmonic, magnetic Fe3O4/ZnO/Ag nanocomposite in 6 h but during the same
irradiation time only 20% MB removal was realised over Fe3O4/ZnO.104 Gohari et al. reported
ZnO/Ag3VO4/Fe3O4 nano composites showing much higher activity for MB degradation than
ZnO/Ag3VO46. On further study by using calcined ZnO/AgBr/Fe3O4/Ag3VO4 nanocomposite
the degradations of MB is about 4 fold higher than that of the ZnO/AgBr/ Fe3O4 nanocomposite
105 As ZnO remains inactive under visible light, co-catalysts like AgBr, Ag3VO4, AgCl, along
with Fe3O4 are responsible for improved visible light absorption. Hence noble metal loaded
magnetite based multi component photocatalyst with low recombination of charge carrier, wide
visible-light absorption range are suitable for degradation of pollutants. 103,106
Fig. 21- (a) Photo degradation efficiency activity of P25, FT, FST, and FSTA microspheres. (b)
Time-based photocurrent response of FT, FST, and FSTA microspheres under UV light
illumination. Reproduced from ref.103. License no 4185910154.
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According to Jianqi Ma and co workers Fe3O4@TiO2-Au system shows an enhanced photo

degradation of RhB of about 95% in 120 min than Fe3O4@TiO2 system under UV irradiation.79
Using Fe3O4@C@TiO2 yolk–shell nano composites there was a 100% degradation of RhB in 80
min under UV light.107 But incorporating noble metals, Ag@Fe3O4@C-Au@TiO2 microspheres,
the degradation rates of RhB is about 97.0%>92.6% for Ag@Fe3O4@TiO2> 43.8% for pure
porous TiO2, and> 36.9% for P25, after 6h of visible-light illumination. It may be due to the
increase in the surface area of the samples.108 Again using SiO2 to prevent photo dissolution of
Fe3O4, composites like Fe3O4@SiO2@TiO2@Pt and Fe3O4@SiO2@TiO2 microspheres in
identical condition shows a 100% degradation of RhB within 20 min and 25 min respectively
under UV, proving the effect of Pt NPs in improving the activity of Fe3O4@SiO2@TiO2
microspheres.62 The Pt NPs, when comes in contact with n-type semiconductor TiO2 a band
bending occurs at the surface of the TiO2 due to electron transfer from TiO2 to Pt inducing arrest
of more transferred electrons. The excited electrons in the conduction band of TiO2 (−4.3 eV vs
vacuum) could overcome the schottky barrier and then transfer to Pt with a lower Fermi level
(−5.1 eV vs vacuum), inducing to spatial charge separation. Also the Fe3O4 core and SiO2 outer
layer hinders the transfer of excited electrons from TiO2 into the lower-lying conduction band of
the Fe3O4 core. Further using Ag, Fe3O4@SiO2@TiO2-Ag shows 100% photo degradation of
RhB in 10 min under visible light irradiation.109 The stability and photo catalytic activity were
shown in figure-22. The presence of noble metal Pd in Pd@CdS@Fe3O4 composite of dose 0.8
g/L, shows the catalytic degradation of RhB about 95% in 45 min.110
Fig.22 (a) Photo catalytic activity of various nano composites, (b) Reusability tests to show the
stability of various nano composites. Reproduced with permission from ref.62. Copy right (2013)
Elsevier .
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Fe3O4/N-TiO2/Ag photocatalyst showed large improvement in the degradation MO compared to

undoped TiO2. Under visible light irradiation highest degradation of 100% within 3h was

obtained with a Ag content of 1.0 wt% and 90.5% within 80 min with a Ag content of 1.5 wt%
under solar-light irradiation. Photo catalytic activity of Fe3O4/N-TiO2@Ag in the presence of
visible-light is a composite effect of both Fe3O4/N-dopped TiO2 and SPR of Ag NPs. Under UV–
Vis light irradiation, the photo-generated electrons excited from the VB of TiO2 or N impurity
energy level to the CB of TiO2, were trapped by the Ag. Thus decreases the recombination
possibility with photo induced holes. On the other hand, the SPR of metallic Ag dramatically
amplifies the visible-light absorption. A strong coulombic restoring force is established, due to
the redistribution of the charge density which further resulted in oscillation of charge density
resembling a harmonic oscillator in phase with the incident light. The photo catalytic efficiency
increases with the increase in the Ag loading amount below the optimum value, but further
increase in Ag loading shows a decrease in efficiency. The degradation efficiency (89.6%) was
found unchanged even after fifth cycle indicating stability of the catalyst.103Further, loading
Fe3O4 on AgBr particles, there is a significant increase in visible light absorption. This may be
due to strong absorption both in UV and Visible regions by Fe3O4, due to its small band gap and
good visible light sensitizer AgBr, having bandgap of 2.64 eV. As reported by CaO et al. the
degradation of MO by Fe3O4/AgBr was 85 % within 12 min, loading very low amount of AgBr.
It may be due to, CB of AgBr (−1.1 V vs. NHE) is much higher than the CB level of Fe3O4 (1 V
vs. NHE). The electrons on the conduction band (CB) of AgBr can transfer to the CB of Fe3O4
and react with the surface pollutants indicating high conductivity of Fe3O4. Simultaneously, the
electrons captured and trapped by Ag nano particles on the surface of AgBr, and by improving
charge separation enhanced the photocatalytic efficiency.87 Using 0.5 mg/ml
Ag3PO4/TiO2/Fe3O4 there was100% decomposition of AO7 in 2 min 45
Noble metal modified Fe3O4 hybrid nano composites also show good photocatalytic efficiency
towards the degradation of most toxic, carcinogenic heavy metal ion Cr (VI). In our group, Au
doped Fe3O4 NPs prepared by green method (G-Fe3O4) was reported to show superior activity
towards photocatalytic reduction of Cr (VI) than prepared by chemical method (C-Fe3O4. It was
reported that the activity towards photocatalytic reduction of Cr (VI) is in the order Au/G-Fe3O4
> G-Fe3O4 > C-Fe3O4. Au/G-Fe3O4 and G-Fe3O4 showed complete reduction of Cr (VI) in 45
min and 60 min respectively, where as C-Fe3O4 showed only 67% reduction of Cr (VI) in 60
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min.72 Ag@ Fe3O4@SiO2@TiO2 photocatalyst shows almost 90% Cr(III) and Cr(VI) removal in
4 h under natural sunlight which is a better result than Xe lamp as shown in figure-23 23

Fig.23 Time-dependent concentration of CrVI ions at pH 3.3 with different photocatalysts under
different light source illuminations: I. Ag@ Fe3O4@SiO2@TiO2 under visible light; II.
Ag@Fe3O4@TiO2 under visible light; III. Ag@ Fe3O4@SiO2@TiO2 under sunlight; IV.Ag@
Fe3O4@TiO2 under sunlight; V. Fe3O4@SiO2@TiO2 under visible light. Reproduced from ref.23.
License no-4203601483120.
8.1.2 Degradation of Non-colouring Substances:
When the degradation process proceeds without dye sensitization, it involves absorption of light
only by the semiconductor, results in the formation of electron–hole pairs. At the same time, due
to SPR effect noble metal NPs can also absorb light and generate photo-electrons. The photo
generated electrons get transferred from the CB of Fe3O4 to the noble metal NPs or vice-versa
depending on the Fermi level of the noble metal NPs. Whereas photo generated holes remain in
the VB of Fe3O4 to undergo photocatalytic degradation process. Photo degradation of non-
colouring substances gives actual efficiency of a photocatalyst. Most commonly various phenolic
compounds undergo degradation by following a non-sensitized path. Phenolic compounds are
among the most common pollutants in the industrial and agricultural wastewater. The photo
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catalytic removal of these pollutants by Au NPs in presence of NaBH4 was an effective strategy,
which results amino phenols and can be investigated easily by UV-Vis spectroscopy. Due to

LSPR, the electron density on one side of the photo catalytic system decreases under light
irradiation resulting adsorption of BH4- onto the Au NPs. This facilitates the transfer of electrons
to the acceptor 4-NP (4-nitrophenol) through BH4- as shown in scheme-4. When the photo
degradation of 4-NP was carried out using neat Fe3O4 microspheres as catalysts, very small
reduction of 4-NP was observed under visible light irradiation even more than 180 min.
However, by introducing TiO2@Au, Fe3O4@TiO2@Au micro-spheres showed complete
reduction of 4-NP to 4-AP in 10 min by adding NaBH4 through LSPR effect of noble metal
NPs.84 Chang et al. studied the photocatalytic degradation of 4-CP (4-Chlorophenol) under UV
irradiation of Ag/TiO2/Fe3O4 nanocomposite and reported 82% degradation which was much
higher than the neat counterparts.82
Scheme.4 SPR Effect of noble metal NPs.
Pd/Fe3O4 catalyst shows improved Pd-based electro-Fenton process, with 98% of phenol
degradation (Figure 24). Most of the phenol was mineralized into CO2 and the removal of TOC
(Total organic carbon) attained 67%.111 By using Au/ Fe3O4, Pd/ Fe3O4 and Pd/ Fe3O4 +
Au/Fe3O4 (physical mixture) as photocatalyst the degradation rates for 4-aminophenol are found
to be 24.5 + 2.6%, 76.4 + 1.6% and 76.1 + 0.4% respectively, whereas by loading bimetallic Pd,
Au/ Fe3O4 as catalyst the rate increases to 94.0 + 1.0% in 8 min.61(Tuo) There is a decrease in
absoption peak intensity at 400 nm and enhancement at 300 nm with increase of contaminant
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was observed within 10 min after addition of Au-Fe3O4 instead of NaBH4 alone for reduction of
4-NP as shown in figure-25a. Also for 2,4-dinitrophenol a similar pattern was observed

showing a decrease in peak at 357 nm and increase in absorption at 450 nm as shown in figure-
25b.
Fig.24 Water splitting and Dye degradation by Pd loaded Magnetite based nano composite
Reproduced from ref.111. Copy right ( 2013) Elsevier Ltd.
Fig.25 Time-dependent UV-Vis spectral changes in (a) p-nitrophenol (4-NP) and (b) 2,4
dinitrophenol (2,4-DNP) catalyzed by Au-Fe3O4 hetero structures. Reproduced with permission
from ref. 52. Copy right (2011) American Chemical Society.
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Table-1 A detailed comparative study of synthesis methods and pollutant degradation over
noble metal loaded Fe3O4

Catalys
Synthesis Incident %
t Precursors used Ref

Method light Degraded
Fresh ABL leaf , Sunlight
Green Co-precipitation MB>>CR> 35
1, 1-diphenyl-2- (850-1050
Fe3O4 method MO
picrylhydrazyl cd/m2)
MB
FeCl2.4H2O, FeCl3.6H2O, For Fe3O4-
i) Urea, Hydrothermal 7 W LED Urea >Fe3O4-
Fe3O4 94
ii) NH4Ac, C2H5OH, method lamps DDA
iii) DDA(Dodecylamine) >Fe3O4-
NH4Ac
FeCl3·6H2O, FeCl2·4H2O
MB
FeSO4·7H2O, KNO3,
Fe3O4/ seed-mediated Hg lamp Degradation 95
Glutamic acid, Tetrabutyl
TiO2 method.method 365 nm 50% in 90
titanate, CTAB
min
Ag/ In situ followed
FeCl3,FeSO4.7H2O,TiO2,A Sunlight 116
Fe3O4/ alkaline MB
gNO3, NaOH
TiO2 hydrolysis
MB
Fe3O4/ TEOS, NH4OH, Oleic Visible light
Degradation 99
Hollow acid, CTAB, FeCl3·6H2O Co-Precipitation ,
97.6% in 120
SiO2 FeSO4·7H2O λ > 420nm
min
FeCl3·6H2O, TEOS, MB
Fe3O4/
Titanium(IV) butoxide , Hydrothermal UV light , Degradation 101
TiO2/Si
Sodium citrate, Dihydrate method λ = 254 nm 90% in 30
O2
polyacrylamide, NH4OH min
anh FeCl3 , AgNO3,FeCl2
⋅4H2O, NaOH Xe lamp MB
Ag/Fe3
Titanium (IV) Hydrothermal (XBO 500 Degradation 23
O4/TiO
isopropoxide, method W/H almost 100%
2/SiO2
Isopropyl alcohol, OFR VS1) in 4h
Acetylacetone
MB
(Fe(NO3)3·9H2O), degradation
Au/Fe3 Visible light 102
Glycine , 98% NaOH, Sol-gel method 60%
O4 λ > 420 nm
AuCl4 degradation.
Au- FeCl3.6H2O, Hydrothermal UV Light, MB 103

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Fe3O4/S Ethyleneglycol,NH4OH Hg lamp of Degradation

iO2/m- Tetrabutyl titanate, NaBH4 250 W, λ= 87.4% in 60

TiO2 365 nm) min
MB
Fe3O4/
Solvothermal Degradation
Ag3PO4 Solar lamp, 83
NaH2PO4, AgNO3, NaCl method 100% in 60
/ AgCl λ > 530 nm.
min
Au(Ag)
/AgCl/ MB
AgNWs, iron(III)
Fe3O4 Galvanic Visible Degradation 103
Acetylacetonate, HAuCl4
@ replacement λ > 420 nm 100% in 20
PDA/A min
u
MB
Ag/
Degradation
Fe3O4/S FeCl3, (NH4)HPO4, Hydrothermal Visible 98
96% in 12
iO2 [Ag(NH3)2], NaBH4 method λ > 420 nm
min
RhB
Au- FeCl3.6H2O, (NH4)2TiF6, UV light
Solvothermal Degradation 54
Fe3O4 NaAc, NaBH4 ,
Method 95%in 120
@ TiO2 HAuCL4.4H2O
min
FeCl3,tetrabutyl titanate , RhB
Fe3O4
C2H5OH, NH4OH, Solvothermal Degradation 107
@C@ UV light
isopropyl alcohol Method 100%in
TiO2
Poly(acrylic acid) 80min
Ethylene glycol,
Ag@Fe
(Fe(NO3)3·9H2O), RhB
3O4@C Hydrothermal Visible light 108
isopropyl alcohol, AgNO3, Degradation
-Au@ Method λ > 420 nm
HAuCl4·4H2O,Titanium 97%in 6hr
TiO2
isopropoxide
Hydroxypropyl cellulose
Fe3O4 (HPC) RhB
@SiO2 Polyvinyl pyrrolidone Hydrothermal Degradation 109
UV light
@TiO2 (PVP) Degussa P25, Method 100%in
@Ag anatase rutile 10min
RhB
Mohr Salt, NaBH4,PVP, Modified
Fe3O4/P Visible light Degradation 110
CdSO4.8H2O Hydrothermal
d/CdS W Lamp 95% in 45
PdCl2
min.
Fe3O4 RhB
FeCl3, (CH2OH)2, Hydrothermal 62
@SiO2 UV light Degradation
Na3C6H5O7, C2H3NaO2 Method
@TiO2 100% in
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@Pt 20min

AgBr@ MO
Ag3PO Fe3O4, AgNO3, precipitation Visible light Degradation 120
4/Fe3O Na2HPO4, NaBr method >400 nm (94% in
4 15min
Acid
FeCl3.6H2O, FeCl2.3H2O,
Fe3O4/ Orange7
AgNO3, urea, Na2HPO4, Visible light
Ag3PO4 (AO7) 45
Ti(SO4) Insitu-Hydrolysis laser at 405
/ TiO2 Degradation
nm
86% in 30
min
Titanium (IV) Cr (VI)
Ag@Fe
Isopropoxide, IPA, Acetyl reduction
3O4@Si Co-Precipitation 23
acetone, AgNO3, Sunlight for nearly 100%.
O2 and sol-gel
FeCl3.6H2O, FeCl2.4H2O, in 4h
@TiO2
NaOH
Cr (VI)
FeCl3, FeSO4.7H2O, Co-precipitation
Au/G- reduction 72
Carambola leaf extract, method Sun light
Fe3O4 100% in 45
NH4OH, K2Cr2O7
min
Degradation
Fe3O4/ TiO2, AgNO3, D-Glucose, of
82
Ag/ FeCl3, FeSO4.7H2O, Micro-emulsion Visible light 4-
TiO2 C2H5OH, HNO3 chlorophenol
70% in 5hr.
FeCl3.6H2O, FeCl2.4H2O, Degradation
Fe3O4 AgNO3,NH3, of
80
@Nico/ NaBH4 Reflux Method UV light 4-nitrophenol
Ag 100% in
7min.
Degradation
of-
Fe3O4/ 4-
Fe (acac), NH4OAc, GO, UV/Vis 63
G/ Pt/ Sonication nitrophenol
PVP, K2PtCl2 light
Pd 100% in
40sec.
Degradation
Pd(II), NaOH,
Pd/Au/ of 61
FeCl3.6H2O, Na2PdCl4 Insitu Reduction UV light
Fe3O4 4-nitrophenol
HAuCl4
94% in 8min.
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8.2 Mechanism of water splitting to generate H2 fuel by noble metal modified Fe3O4

nanocomposites
Now a days Heterogeneous semiconductor photo catalysis for water splitting and generation of
H2 is found effective.112, 113 When visible light with energy greater than or equivalent to the band
gap of Fe3O4 was irradiated, electrons and holes are generated. The photo generated electrons
carry out reduction reaction in the conduction band, while the holes in the valence band are
responsible for oxidation of adsorbed species on the surface of the semiconducting material. As
the reduction potential of H+ to H2 is 0 V at pH=0, the CB of Fe3O4 must be at a negative
potential than 0V for water reduction and the VB must be more positive than the oxidation
potential of H2O to O2 i.e. 1.23 V at pH=0. The Fe3O4 based semiconductor system are supposed
to be efficient solar energy converter, when they possess a suitable band gap energy so as to
make maximum utilization of solar radiation, and must be sufficiently stable against photo
corrosion.114,115,116 Presence of various sacrificial agents (electron donor or proton acceptor)
increases the efficiency of H2/O2 production by suppressing the electrons and holes
recombination process.
Fe3O4 is one of the semiconductors which has a low band gap, enables it to absorb nearly 40% of
the solar radiation. In spite of its potential advantage of abundance and non-toxicity, it was not
used as a good catalyst for water splitting reaction owing to high rate of recombination of photo
generated electron hole pair. Moreover, its conduction band edge potential is not suitable for
hydrogen evolution. Till date very few research groups have reported on photo catalytic H2
evolution over Fe3O4. However, nano-Fe3O4 was reported as a catalyst for H2 evolution through
water reduction in the presence of a suitable sacrificial donor and also shown good stability in
hydrogen production up to 30 h.117 Loading noble metal on the surface of Fe3O4 results in the
formation of a schottky barrior at the metal-semiconductor interface and increases the separation
efficiency of photo generated electron-hole pairs. Usually, loading noble metals, such as Pt, Pd,
Au and Ag as co-catalysts enhance the H2 evolution as these metals have a low over potential for
H2 evolution and can make the process easier.
Mangrulkar et al. studied photo catalytic water reduction reaction of Fe3O4 NPs to evaluate H2
evolution in presence of a sacrificial donor and Pt as co-catalyst under visible light irradiation.
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The rate of H2 evolution was found to be 8.275 µmol h-1 for Pt/Fe3O4 as compared to H2
evolution rate of 0.0046 µmol h-1 in case of neat Fe3O4 under similar experimental conditions.

The results showed that the H2 evolution was dramatically increased in presence of Pt as co-
catalyst. The optimum amount of Pt as co-catalyst was observed to be 0.095 mg. In the photo
catalytic water reduction reaction Pt acts as an electron trap to retard the recombination tendency
and thus enhances the activity. Further increase in co-catalyst loading may lead to decrease
photon absorption and may also act as recombination centre for photo generated electrons and
holes thereby decreasing the photo catalytic activity. When the effect of scavenger was studied, it
was observed that addition of suitable hole scavenger prevent the recombination process and
increases the efficiency of the photo catalytic reaction. By using three different sacrificial agents
the order of H2 evolution was ethanol > methanol > mono ethanol amine (Figure- 26). In
presence of water and ethanol, holes generate H+ ions during the course of the reaction, which
then get reduced by the photo electrons to H2 as shown in the following reactions.
2h+ + H2O = 2H+ + ½O2 or H+ + •OH ------------------- (9)
2h+ + C2H5OH = 2H+ + CH3CHO ------------------- (10)
It was also reported that temperature plays a vital role in the enhancement of photo catalytic
activity of Pt loaded Fe3O4 nano composites in water reduction reaction in the presence of
alcohol as sacrificial agent. At an elevated temperature 85–100 ˚C, oxidation of alcohol by holes
results decrease in recombination rate of exitrons with consequent increase in H2 evolution rate
of 59.55 µmol h-1.118 Zhang et al. reported a ternary Fe3O4@PPy@Pt core-shell nano-
architectural photocatalyst, to explain the role of magnetic property of a photocatalyst on H2
evolution reaction under visible light irradiation. The rate of H2 evolution and electron transfer
process was remarkably enhanced by changing the interaction of the electromagnetic radiation
with the magnetic photocatalysts. Super-paramagnetic properties of Fe3O4 hollow sphere acting
as the core provide a good number of hydrophilic groups and conductive poly-pyrrole shell
favour channelization of photo-generated charge, as well as compensates the surface defects of
Fe3O4 spheres.
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(a) (b)

Fig. 26 (a). Effect of irradiation time on hydrogen generation by Fe3O4 nanoparticle. (b).Effect of
sacrificial donors on hydrogen generation by Fe3O4 nanoparticles. Reprinted with permission
from ref.115. Copy right (2012 ) The Royal Society of Chemistry.
It was interesting to find that the rate of H2 evolution was remarkably affected by tuning the
magnetic character of the photocatalyst. With different saturation magnetization (Ms) the charge
transfer process is greatly affected. The photo-catalysts with different saturation magnetization
(Ms) are marked as Fe3O4@PPy@Pt-A (Ms = 44.8 emu g-1), Fe3O4@PPy@Pt-B (Ms = 47.2
emu g-1), and Fe3O4@PPy@Pt-C (Ms = 47.2 emu g-1) and H2 evolution were studied under
visible light irradiation in the presence of a sensitizer (Eosin Y Dye) and tri-ethanolamine as the
sacrificial agent. After 3h of reaction, H2 evolutions are 3.6, 2.8 and 2.0 times greater than
Fe3O4@Pt catalyst (Figure.27a). It was interesting to find that the rate of H2 evolution was
remarkably affected by tuning the magnetic nature of the photocatalyst (Figure.27b). As the
Lorentz force acting on the electrons gives rise to Hall resistance, Photo-generated electrons in
Fe3O4@PPy@Pt-C experience a lower Lorentz force in comparison to Fe3O4@PPy@Pt-A
(Figure-27c). The photo generated charge transfer process for H2 evolution over Fe3O4@PPy@Pt
was associated with different extent of magneto-electronic coupling effect originated by the
intrinsic magnetic nature of the Fe3O4 photocatalyst. The electrons in Fe3O4@PPy@Pt-C were
less likely to be deflected from their original motion path, whereas the electrons endured more
resistance when they transmitted in the Fe3O4@PPy@Pt-A (Figure-27d). Furthermore, the space-
charge density of electrons in the material is controlled by the magnetic field and the maximum
current could only be given at a suitable magnetic field. The sensitization effect of the dye
influences the migration of photo-electrons to the surface of Pt and shows higher H2 evolution.
119
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Fig.27 (a) H2 evolution, λ > 420 nm, EY as the sensitizer and TEOA as the sacrifice reagent, (b)
magnetic hysteresis curves (c) Hall-effect and (d) transient photocurrent-time profiles of the
Fe3O4@PPy@Pt-A(FPP-A), Fe3O4@PPy@Pt-B(FPP-B),and Fe3O4@PPy@Pt-C (FPP-C) photo-
catalyst at room temperature. Reproduced from ref.116. license number-4203580948450.
Mishra et al. have reported Au/Fe3O4 nano-composite prepared from natural surfactant to study
photo catalytic H2 evolution. In this work, Fe3O4 was synthesised by two methods i) By
chemical method (C-Fe3O4) and ii) By green method using a bio extract (G-Fe3O4) and compared
their activity towards H2 evolution.73. The rate of H2 evolution were 167 µmolh-1 for C-Fe3O4,
whereas 212 µmolh-1 for G-Fe3O4 under visible light irradiation. This enhancement was due to
the high surface area and nano-rod morphology of G-Fe3O4, which retards the rate of
recombination to favour photo catalytic activity. However, upon Au loading the rate of H2
evolution further increases to 267 µmolh-1 under the same condition, which may be attributed to
the SPR effect of Au NPs. Due to SPR the electrons from the CB of magnetite migrate to the
surface of Au NPs and get reduced to generate H2 (Figure-28a). The activities of the catalysts
were also in good agreement with PL studies (Figure-28b).
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Fig.28 PL spectra of C-Fe3O4, G-Fe3O4 and Au/G-Fe3O4. Reproduced from ref.72.
Table-2 A detailed comparative study of synthesis methods and H2 evolution over noble
metal loaded Fe3O4
H2
Synthesis Incident Sacrificial evolutio
Catalyst Precursors used Ref
Method light agent n in
µmol h-1
Visible
FeSO4.7H2O, co-
light Ethanol 118
Pt/ Fe3O4 Fe2(SO4)3 precipitatio 8.275
λ > 420
NH4OH (25%) n method
nm
FeCl3,
Co-
FeSO4.7H2O, Visible
Au/G- precipitatio 72
Carambola leaf light Methanol 267
Fe3O4 n method
extract, NH4OH, irradiation
K2Cr2O7
Visible-
polypyrrole (PPy)
light Tri
Fe3O4@P Fe3O4 hollow microwave 119
λ > 420 ethanolamin 1.0 x103
Py@Pt sphere method
nm e (TEOA)
Pt quantum dots.
9. Conclusion
This review covers a screened portion of a vast and ever increasing body of recent literature on
successful utilization of noble metal modified Fe3O4 based semiconducting nanomaterials for
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environmental remediation and energy conversion. This paper reviews various synthesis methods
employed for loading different types of noble metal NPs and the characterization techniques

used to investigate their physicochemical properties. Furthermore, their application as
photocatalysts for energy and environment under visible range of the solar spectrum were
reviewed. The incorporation of noble metal NPs (Au, Ag, Pd and Pt) in the magnetite framework
has been proven to be effective method to alter the physicochemical properties of Fe3O4 based
materials and make them efficient in heterogeneous photocatalysis. Some important conclusions
are summarized below:
1. Primary attention is given to summarise different methods to construct noble metal modified
Fe3O4 based photocatalysts to find superior ways for improving the performance of Fe3O4.
2. The various synthesis strategies not only focus on designing of catalysts, but also highlight easy,
sustainable processes using bio-extracts. Use of these bioextract as natural surfactant is
beneficial both as stabilizing and dispersing agent, which prevents the agglomeration of Fe3O4
NPs during synthesis. Moreover, the bio surfactants, when get absorbed on the surface of the
composite through polar groups, influence the morphology and play an important role in
controlling the shape and size of the nanoparticles, and enhances the surface area.
3. Core-shell nanostructure was found to be an important method, which helps in protecting the
Fe3O4 nanoparticles from corrosion and favours recovery process. Moreover, the shell consisting
of a non-conductive porous metal oxide, allows free access of the adsorbents from outside to
speed up the photo catalytic reactions.
4. Noble metal modified Fe3O4 core–shell nanomaterials provide a great opportunity for enhancing
the interaction between the different components to improve structural stability or photocatalytic
activity of the hybrid materials through SPR.
5. To overcome the limitation of high magnetic moment, which results aggregation of Fe3O4
nanomaterials and decreases the surface area as well as the photo catalytic applications, noble
metal incorporation was a suitable way out. On noble metal incorporation the magnetization or
magnetic saturation value decreases to an optimum value required for recycling the photo
catalytic material. Moreover with noble metal loading, the surface anisotropy effects the
magnetic moments of Fe3O4 NPs through the exchange interaction with surface active groups,
thus magnetic saturation value of the noble metal loaded nanohybrids decreases and was found
sufficient for effective separation of the nanocomposite.
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6. The synthesis of plasmonic-metal/Fe3O4 nanostructured with controlled plasmonic and magnetic

properties not only shows good photocatalytic property; but also it stabilizes the Fe3O4 NPs from

photo corrosion by surface functionalization.
7. In addition, the designed semiconductor should have superior solar light utilization efficiency
with suitable energy levels to carry out specific photo catalytic redox processes.
The ultimate goal in heterogeneous photocatalysis is to solve the ever-growing environmental

and energy issues. As proper surface modifications help plasmonic-metal/Fe3O4 nanostructured
photocatalysts to be biocompatible, the research should be focused on the process design and
explore ways to cost effectively synthesize magnetite NPs for energy and environment.
Moreover, some more characterizations and theoretical simulations may also provide profound
insight into the relationship between photo catalytic performance and semiconductor properties.
In this regard, it is anticipated that this review will provide valuable directions to develop
practical methods for designing plasmonic-metal/ Fe3O4 nanostructures and can stimulate the
research on Fe3O4 nanostructured photocatalysts in future, that can make heterogeneous
photocatalysis more practicable for energy conversion and environmental remediation. Although
a good number of photocatalysts have been explored and investigated in the past few decards, the
obtained photo catalytic efficiency is still far from practical applications. For which tremendous
research activities are needed to achieve the real goal in artificial photocatalysis towards cleaner
environment.
Conflicts of interest
There are no conflicts to declare.
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Pollutant

Water Degradation
splitting
Fe3O4 Visible
Energy light
evolution Pt utilisation
Noble metal modified magnetic Fe3O4 for photocatalytic pollutant degradation and H2
evolution.

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Research, Siksha ‘O’ Anusandhan University, Bhubaneswar-751030

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photocatalytic performance of the composite materials by improving light absorption through

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3. Why magnetite in photocatalysis?

3.1 Magnetite as a photocatalyst

In heterogeneous photocatalysis a semiconducting material plays an important role. A good

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3.2 Benefits of using Fe3O4 as photocatalyst:

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2. Fe3O4 NPs usually cause aggregation and become unstable.

Fig. 3 Schematic representation of enhancement of photocatalytic activity of Fe3O4 nano-hybrids

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Fig.4 SPR effect of noble metal NPs.

5. Design and Construction of Noble–metal loaded Magnetite nanoparticle

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4.1 Synthesis of Ag modified Fe3O4 NPs

Scheme.1 Schematic representation on stabilization of Fe3O4 NPs by polymers. Reproduced with

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4.2 Synthesis of Au modified Fe3O4 NPs

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Scheme. 2 Schematic representation of the formation process of Au-Fe3O4 nanocomposite.

Fig.6 Schematic representation of the formation process of bilayered core-shell Au-Fe3O4

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4.4 Synthesis of Pt modified Fe3O4 NPs

manner followed by subsequent deposition of Pt NPs on the unoccupied carboxyl groups on

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5. Physicochemical characterization of noble metal modified Fe3O4 NPs

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Fig.8 XRD pattern of (Magnetic Multiwalled Carbon Nanotubes) m-MWNTs@Pt Reproduced

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(a) (b) (c)

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As reported by Lopes et al. dithiocarbamate-functionalized magnetic sorbents in contact with

Fig.15TEM images of surface-functionalized magnetite particles

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Fig.20 Magnetic hysteresis loops of (a) Fe3O4, (b)Fe3O4/TiO2,and(c)Fe3O4/TiO2@Au.

8. Photo catalytic Applications of noble metal modified Fe3O4 NPs

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Scheme.3 Schematic representation of Transfer of photo generated electron-hole pair in noble

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O2-⸰ + H+ HO2⸰ ----------- (4)

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8.1.1 Degradation of Colouring Substances

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