Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction functionalities for energy conversion and storage applications a review

Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

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Journal of Science: Advanced Materials and Devices
journal homepage: www.elsevier.com/locate/jsamd

Review Article

Recent developments in manganese oxide based nanomaterials with
oxygen reduction reaction functionalities for energy conversion and
storage applications: A review
Yilkal Dessie a, *, Sisay Tadesse b, Rajalakshmanan Eswaramoorthy a, Buzuayehu Abebe a
a
b

Department of Applied Chemistry, Adama Science and Technology University, Adama, Ethiopia
Department of Chemistry, Hawassa University, Hawassa, Ethiopia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 22 February 2019
Received in revised form
29 June 2019
Accepted 9 July 2019
Available online xxx

In this article, a brief overview of manganese oxide nanomaterials (NMs) potential towards oxygen

reduction reaction (ORR) for microbial fuel cell (MFC), bioremediations, and battery applications is
discussed. It's known that using non-renewable fossil fuels as a direct energy source causes greenhouse
gas emissions. Safe, sustainable and renewable energy sources for biofuel cell (BFC) and metal-air batteries hold considerable potential for clean electrical energy generators without the need for a thermal
cycle. In an electrochemical reaction system, the four-electron reduction from molecular oxygen at the
air-cathode surface to hydroxide ion or water at a reasonably low overpotential was the ultimate goal of
many investigations and plays a vital role in metal-air batteries and fuel cell device systems. Different
MnxOy nanostructured materials, from Biofunctional structural catalysts up to their electrocatalytic
contributions towards ORR are discussed. Brief descriptions of ORR, principle strategy and mechanism, as
well as recent developments of cationic dopants and electrolytic media, effect on the air-cathode surface
of manganese oxide nanocatalyst are also discussed. Finally, challenges associated with platinum and
carbon support platinum in improving electron and charge transfer between biocatalyst and air-cathode
electrode are summarized.
© 2019 Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an
open access article under the CC BY license ( />
Keywords:
Manganese oxide nanomaterials
Microbial fuel cell
Bioremediations
Batteries
Oxygen reduction reaction

1. Introduction
Recently, the use of fossil fuels (e.g., coal, natural gas, and oil) as a
direct energy source has led to a global energy crisis [1]. This crisis
increased focus on greenhouse gas emissions to the environment,
and the limited and unstable supply of fossil fuel resources for
future forecast makes unsustainability of energy resources [2].
Renewable energy is thus considered as a sustainable way to reduce
the current global warming crisis. However, various efforts have
been devoted to developing an alternative mechanism for renewable energy generation [3].

Safe and sustainable futures can be ensured by making new
innovations and modifications to the existing energy generation
and storage device technologies. The best way to do this is by
utilizing energy from the fuel cell, batteries, supercapacitors, etc.

* Corresponding author.
E-mail address: (Y. Dessie).
Peer review under responsibility of Vietnam National University, Hanoi.

via oxygen reduction reaction (ORR) concerning the best mechanism for a variety of infrastructure applications [4]. Among these,
fuel cells and metal-air batteries are energy generators that hold
considerable potential for future application and relatively clean
electrical energy generators. These electrochemical devices
transform chemical energy from a specific fuel into electricity
without the need for a thermal cycle [5]. During this electrochemical reaction, a four-electron reduction reaction of molecular
oxygen to either hydroxide ion or water at a reasonably low
overpotential is the ultimate goal of many investigations. It also
plays a vital role in electrochemical energy-conversion systems in
metal-air batteries and fuel cells [6]. Therefore, in this review, a
detailed electron transfer and potentials of the ORR mechanisms
are going to be visualized to the reader with a clear and concise
manner.
Currently, fuel cells (either biotic or abiotic) are considered to be
a value add source of energy due to their high gravimetric and
volumetric energy efficiency. Mild operation process, zero emission
and most importantly, unlimited renewable source of reactants
especially biotic fuel cells are commonly known as biological or

/>2468-2179/© 2019 Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

Please cite this article as: Y. Dessie et al., Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction
functionalities for energy conversion and storage applications: A review, Journal of Science: Advanced Materials and Devices, https://
doi.org/10.1016/j.jsamd.2019.07.001


2

Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

MFC. It converts the chemical energy of different fuels into a useful
form of electrical energy similar to that of batteries. However, fuel
cells do not stop working until the fuels and oxidants are continuously fed. The main areas of fuel cell technology are from transportation, stationary to the small-scale portable power source [7].
Goswami et al. reviewed a typical conventional fuel cell in which its
fuel is oxidized at the anode and oxygen as an oxidant is reduced at
the cathode (Fig. 1) [4]. This review aims to investigate the fundamentals and recent progress of manganese oxide-based electrocatalysts towards ORR capability for remediation, electricity
harvesting, and energy conversion at the air-cathode electrode in
the bioelectrochemical device systems. According to the references
cited in each section, a clear and brief summary of the principle,
mechanism, and synthesis strategy for manganese oxide based
NMs (bare, doped or composites, as well as, supported.) involved in
the ORR is presented.

2. Oxygen reduction reaction (ORR) on biocathode
ORR is the most important reaction that occurs in the cathode
surface of fuel cells [4]. Interconnecting living systems or their
parts with simple and low-cost transition metal oxide to speed
up chemical reactions on the surface of an electronic conductor
for energy conversion and waste treatment is known as a biocatalyst [8]. Besides their cost-effectiveness, the durability of the
ORR catalysts in MFC is another major challenge, because the

cathode is constantly exposed to waste effluents containing a
variety of contaminants (either organic or inorganic) and microorganisms. The common assembly of this cell is singlechamber and double chamber system. In single-chamber MFCs
(Fig. 2a) the catalysts directly contact the waste and may be
poisoned by intermediate products such as methanol, chloride,
sulfide, etc. Catalyst poisoning by such intermediates leads to
high potential loss and reduced power production. Furthermore,
organisms can form a biofilm on the cathode surface and
degenerate catalytic performance by blocking the O2 transport.
In some circumstances, the biofilm may serve as a biocatalyst,

however, similar problems may happen in two-chamber system
MFCs (Fig. 2b) [8].
When an appropriate and environmentally safe half potential
electron acceptor (e.g., oxygen) is present in the cathode, the cell is
then thermodynamically favorable, so that the electron flow across
the whole system is spontaneous. The most important reactions
that take place in the cathode of the fuel cell are the ORR. Such a
reaction is a challenge in the field of catalysis and electrochemistry.
Normally, the reaction is a complex four-electron transfer reaction
that involves the breaking of a double bond from oxygen molecule
and the formation of 4 OH-bonds through several elementary steps
and intermediate species. To understand such a complex process in
ORR, Jiang et al. developed manganese oxide catalyst using carbon
as a supported material to understand its intrinsic catalytic
behavior in alkaline electrolytes [9]. A general classical scheme for
this reaction and hydrogen peroxide (H2O2) stability as a reaction
intermediate species was described in Fig. 3 [9]. Therefore, other
approaches due to its broad reaction pathways, a theoretical
calculation are needed to shed light on the microscopic structures
and processes taking place at the surface during the reaction [10].

Oxygen is an ideal electron acceptor molecule for MFCs due to
its high redox potential, availability, and sustainability. However,
the ORR is kinetically sluggish, resulting in a large proportion of
potential loss known as activation loss next to concentration and
ohmic losses. To reduce such loss, MnO2 as a nanocatalyst has
been successfully used as a cathode material in both aqueous and
non-aqueous fuel cells. However, most of these oxides as ORR
achieved only half of that with platinum/carbon (Pt/C) electrode,
regardless of structure modifications or doping with other transition metals. Therefore, this review also summarizes how this
different nanostructured component of MnXOY (MnO2, Mn2O3,
Mn3O4, Mn5O8, and MnOOH) [8], coexists and their contributions
would be clearly discussed to ORR. Beyond ORR some manganese
oxides such as MnO2, Mn2O3 and Mn3O4, which were synthesized
by a hydrothermally technique, exhibit the best catalytic activity
performance towards NO oxidation with its maximum conversion
efficiency of 91.4% [11]. Thermally decomposed ε-MnO2 from
manganese nitrate using carbon powder as a support mixture was

Fig. 1. A typical fuel cell. Adapted with permission from Elsevier [4].

Please cite this article as: Y. Dessie et al., Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction
functionalities for energy conversion and storage applications: A review, Journal of Science: Advanced Materials and Devices, https://
doi.org/10.1016/j.jsamd.2019.07.001


Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

3

Fig. 2. Schematics of (a) single-chamber MFCs and (b) two-chamber MFCs. Adapted with permission from The Royal Society of Chemistry [8].

mez-Marín et al. is reproduced from Ref. [10] and is licensed under CC BY 2.0 ( />Fig. 3. Reaction pathways proposed for the ORR. This figure by Go
licenses/by/2.0).

tested for ORR in an alkaline electrolyte. The complete 4eÀ
reduction pathway via a 2 plus 2eÀ reduction process were proceeds on MnO2 catalysts through involving H2O2 as an intermediate. The close performance for ε-MnO2/C material in comparison
with 20% (w/w) Pt/C catalyst as a benchmark was observed in the
kinetic control region due to the presence of structural defects in
this oxide. This structurally modified catalyst thus has higher
electrochemical activity for proton insertion kinetics [12]. The art
of these structural defects plus electrical conductivity on a-MnO2
effectively reduce active polarization followed by maximizing
kinetics [13]. Thermal reduction of Mn2O3 to MnO had also
occurred for hydrogen production in solar energy concentration
devices [14]. All this catalytic activity is facilitating due to increase
in activity of the surface amorphous MnOx, especially in a highly
monodisperse amorphous MnXOY nanosphere [15]. NiOx hybrid
could tune the performance for its catalytic superiority towards
reversible oxygen evolution reaction (OER) and ORR, due to the
synergistic effect of NiOx and amorphous MnXOY on the surface of
graphene nanosheets after being synthesized with a selfassembly method [16].
Less ecological impact, low operating temperature and high
energy density proton exchange membrane fuel cells (PEMFCs)

have gained much attention. In such a fuel-cell device, the fuel can
be any of hydrogen, methanol, ethanol, or formic acid, whereas,
highly electronegative oxygen molecule is chosen to receive the
electrons released from the fuel on the cathode electrode. Overall,
between the fuel oxidation reaction and the ORR, electrons flow
outside the cell to power electronic devices and protons migrate

from anode to cathode inside through the Nafion membrane to
complete the charge flow in the circuit [17]. Despite their great
potential, PEMFCs do have their own serious limitations that prevent them from being scaled-up for commercial applications due to
using expensive noble metal [18].
ORR is a multi-electron transfer process that follows an electrocatalytic inner sphere mechanism. The reaction is highly
dependent on the nature of the electrode surface. ORR is, in general,
a suitable mechanism that employed for the formation of different
oxygen-containing intermediates (such as OH, OÀ
2 , O, H2O2 and
HOÀ
2 ) under both acidic and alkaline media [4]. In an aqueous
medium, ORR is highly reversible. The possibility of rapidly
reversible redox transformation in nanophase MnOx at room
temperature triggered by changes in hydration [19] and potential
surface Mn(IV)/Mn(III) redox couple [20,21]. However, the appropriate mechanisms associated with ORR have not been well

Please cite this article as: Y. Dessie et al., Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction
functionalities for energy conversion and storage applications: A review, Journal of Science: Advanced Materials and Devices, https://
doi.org/10.1016/j.jsamd.2019.07.001


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Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

understood in spite of extensive experimentation. From this point
of view, ORR is regarded as the kinetically limiting element of the
electrochemical devices due to slow reaction rate. This inspired the
researchers to fabricate a novel mesoporous MnXOY electrocatalyst
support due to their large specific surface area and unique pore

structure which can permit more active sites for the contact between catalysts and electrolytes. Such contact clearly demonstrated
a good competitive ORR activity at the cathode in fuel cells, which
can be used to reduce the loss of cell energy storage and conversion
efficiency by overcoming the slow kinetics during ORR [22].
Pt based materials have been used as a common ORR owing to
its high electrocatalytic activity, stability and high exchange current
density. However, their high price/or cost, scarcity and low durability limit them from extensive commercialization. In addition, the
stability of Pt is low as it suffers from dissolution, agglomeration,
coalescence, poisoning during fuel cell reaction conditions, and
sintering which finally results in an unusual rise in overpotential
for ORR, thus reducing both the active catalyst surface area and the
catalytic efficiency, which leads to an undesired increase in overpotentials for fuel-cell device system, especially for ORR. Therefore,
exploring highly abundant, low cost and durable electrocatalysts
with comparable or even higher catalytic performance than that of
Pt-based electrocatalysts have become a key interest [23]. Zeng
et al. have proved by hybridizing MnO2 with Ag4Bi2O5 that exhibits
superior long-term durability and stronger methanol tolerance
than commercial Pt/C for ORR in alkaline solution. Based on this
concept one way to make PEMFCs inexpensive and durable is to
incorporate Pt more in the catalyst layers. It can be done by using
effective support materials (e.g., carbon materials) along with Pt
nanoparticles or alloying Pt with other inexpensive metals like Co,
Ni, Fe, etc. [24]. However, this approach didn't work well on a longterm basis due to the ever-growing price of Pt [25]. Therefore, this
review gives attention to non-precious metal or non-noble metal
oxides (e.g., manganese oxide and its nanocomposites) based catalysts in detail as cost-effective alternatives to Pt. For current ORR,
Konev et al. described effective electrocatalytic NMs with good
properties from manganese and cobalt polymorphing films [26].
Other than this mixed metal polymorphing, a highly active and new
microporous based manganese porphyrin-polymer networks
catalyst was successfully fabricated for ORR catalytic activity and its

selectivity [27].

3. Manganese oxide based nanomaterials
Transition metal oxides (TMOs) are attractive noble metal-free
catalysts for oxygen reduction application at the cathode of alkaline based membrane fuel cells or metal-air batteries [28]. Theoretical and experimental studies revealed that TMO based catalysts
having a spinel structure can act as a proficient cathode electrode
material for energy conversion and storage devices. For example,
manganese mixed oxides [29], manganese-iron mixed oxide doped
with TiO2 [30], layered manganese-cobalt-nickel mixed oxides [31],
layered copper-manganese oxide [11], well dispersed spinel cobaltmanganese oxides [32], cubic Mn2O3-carbon [33], and bond
competition control manganese oxide [34] have attracted much
attention for excellent Bifunctional catalytic activity. They also have
higher electrical conductivity than single TMOs. This unique property of TMOs facilitates better ORR performance, due to their variable oxidation states and better mixing ability into one material.
Comparatively, by forming a nanosized bimetallic cluster [35], and
bimetallic oxide, its oxygen reduction and oxidation performance
could be also performed [36]. Furthermore, TMOs are commercially
affordable due to their low price and high abundance, which makes
them to be used often as electrocatalyst [37]. The review extended

more focuses on manganese oxide; one part of TMO based catalyst
synthesis, principle, and mechanism activities towards ORR.
In the last few years, the study of nanoparticles has acquired
enormous interest due to their variation in physicochemical, electronic, and morphological properties. As a functional material, they
can be synthesized in the nanometric scale ranges. Due to changes
in their structure and bonds, they have also displayed interesting
electronic and catalytic properties. Controlling the structure of
catalysts at the atomic level provides an opportunity to establish a
detailed understanding of the catalytic form-to-function and
realize new non-equilibrium catalytic structures [38]. Molecularlevel by itself is a factor that determines reaction mechanisms
and electrocatalytic activity [39]. Due to these properties, manganese oxides can be considered to be the most complex of the

metallic oxide compound. Afterward, manganese oxides as NMs
have been studied due to their efficient uses in rechargeable
lithium-ion batteries [40e42], a simple energy conversion [43],
catalysts [44,45], capacitors [46], sensors [47,48], remediation [49],
flame retardants [50], fire safety [51], alkaline fuel cells [52], radical
scavenging and cytoprotection [53], pharmaceutically active compounds removal [54,55], biofilters [56], oxidative transformation
[57], and water splitting [58].
For an effective application, the synthesis of nanocrystalline
manganese oxides has been used more widely within the context of
solution chemistry. For example, synthesis using thermolysis from
organometallic precursors [59], directly mixing of potassium permanganate [60] and polyelectrolyte aqueous solutions [61], coprecipitation [62e64], room-temperature synthesis [65], hydrothermal [66,67], solvothermal [22], plant [68], biological [69e71],
wet chemical method [72,73], electrospinning [74], solegel [75,76],
sonochemical [77e79], microwave-assisted [80e82], complex
decomposition [83], chemical reduction [84], electrochemical
method [85,86], direct electrodeposition [87], sulfur-based reduction followed by acid leaching [88], are the most common and
simple types of techniques to fabricate MnXOY nanocatalyst. Obviously by simple thermal treatment method different forms of
manganese oxides (MnO, Mn3O4, Mn2O3, MnO2, as well as the
metastable Mn5O8) could be fabricated at different conditions [89].
These oxides as shown from Table 1 could coexist and progressively
change one into the other during the oxidation process, which is
usually controlled by the diffusion of oxygen. There are also several
relations between these manganese oxides [59,90].
Manganese monoxide, MnO, occurs as the mineral manganosite.
Nanocrystals of this oxide are capped with organic ligands and
highly dispersible in nonpolar solvents. It can generate particle
sizes between 7 and 20 nm by controlling the reaction conditions
and from 5 to 40 nm particle sizes were controlled by changing the
surfactant. Structural characterization showed that the nanoparticles had core/shell structures with a thin Mn3O4 shell [90].
The manganese oxide hausmannite, Mn3O4, is a black mineral
that forms the spinel structure with tetragonal distortion due to a

JahneTeller effect on Mn3ỵ. In the Mn2ỵ(Mn3ỵ)2O4 structure, the
Mn2ỵ and Mn3ỵ ions occupy the tetrahedral and octahedral sites,
respectively, and Mn3O4 is ferrimagnetic below 43 K. Nanocrystalline Mn3O4 has been synthesized by a number of methods

Table 1
Different manganese oxide nanostructural products obtained at different calcination
temperature ranges.
In air, N2 or O2
In H2
In pure O2 gas

550o CÀ600o C

850o CÀ1050o C

950o CÀ1050o C

MnO2 ƒƒƒƒƒƒƒƒƒƒƒ!Mn5 O8 ƒƒƒƒƒƒƒƒƒƒƒƒ!Mn2 O3 ƒƒƒƒƒƒƒƒƒƒƒƒ!Mn3 O4
o

o

400 CÀ500 C

MnO2 ƒƒƒƒƒƒƒƒƒƒƒ!MnO
$190o C

$430o CÀ470o C

$390 C

$450 C

$510o C

MnOƒƒƒƒƒ!Mn3 O4 ƒƒƒƒƒƒƒƒƒƒƒƒ!Mn5 O8 ƒƒƒƒƒ!Mn2 O3
o

o

MnOƒƒƒƒƒ!Mn3 O4 ƒƒƒƒƒ!Mn2 O3

Please cite this article as: Y. Dessie et al., Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction
functionalities for energy conversion and storage applications: A review, Journal of Science: Advanced Materials and Devices, https://
doi.org/10.1016/j.jsamd.2019.07.001


Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

that produce relatively monodisperse particles. 6e15 nm nanoparticles were obtained by thermal decomposition of manganese
(II) acetylacetonate in oleylamine under an inert atmosphere. They
manipulate the particle size changing the employed reaction
temperature. Pure MnO with size in between 11 and 22 nm can also
be obtained when a small amount of water was added to the reaction slurry; therefore, the metal-oxide phase is controlled by the
presence or absence of water. Mn2O3 exists in two forms, a-Mn2O3
and g-Mn2O3. Almost pure a-Mn2O3 occurs as the mineral bixbyite
with black and crystallizes form in a cubic structure [90].
The manganite, g-MnOOH is the most stable and abundant
mineral of the three polymorphs of manganese oxyhydroxide. The
other two are feitknechtite and groutite. Both of them have the

same chemical formula, Mn3ỵO(OH) but differ with their crystal
system. The crystal system of feitknechtite is a hexagonal while
groutite is orthorhombic. The manganite crystal structure is similar
to that of pyrolusite, but, in all the Mn is trivalent and one-half of
the oxygen atoms are replaced by hydroxyl anions. The Mn(III)
octahedral are quite distorted because of JahneTeller effects. In air
manganite alters at 300  C to pyrolusite. The metastable oxide,
Mn5O8 is not a well-known compound of manganese. It may be
formed together with pyrolusite during the diagenetic decomposition of manganite. Mn5O8 is established as an intermediate phase
too, forming between MnO2 and Mn2O3 at or above 300  C. The unit
cells of pyrolusite, manganite, and Mn5O8 are closely related, their
crystallographic axes remain in nearly the same relative orientations. Mn5O8 crystallizes in a monoclinic structure containing
4ỵ
mixed valences of Mn2ỵ and Mn4ỵ as Mn2ỵ
2 Mn3 O8 [90]. Doping
manganese with latest transition metals such as cobalt encased
within bamboo-like N-doped carbon nanotubes [91] and
lanthanum at a time can increase the stability and improving the
catalytic activity for ORR [92,93].
One of the challenges in the synthesis of oxide nanoparticles is
obtaining monodisperse nanoparticles. Furthermore, it is also
necessary to control the overall sizes of nanoparticles, as well as to
know its exact composition. In particular for manganese oxides,
one of the most important challenges is to obtain a single phase,
because in almost all procedures the obtained result is significant
for coreeshell structures. All these challenges are not easy to solve
since nanoparticles are unstable during long periods of time.
Furthermore, since nanoparticles are highly reactive, they oxidize
easily in air, losing catalytic activity and dispersibility. Because of
this, protection strategies are used, like capping with surfactants,

organic products or inorganic membranes [90].
4. Principle and mechanism of ORR on MnxOy surface
Based on the principle of physical adsorption of oxygen molecule (O2) on manganese oxides surface due to high contact between
electrolyte and active catalyst, O2 is converted to either OHÀ or H2O.
During this conversion, manganese oxides are known active catalysts in a given media [94]. Practically, in alkaline solution, the
mechanism of oxygen reduction at MnO2 catalyzed air cathode was
investigated by measurements of polarization curves in a wide
range hydroxide ion (OHÀ) concentration, oxygen pressures, and
using different crystalline MnO2 catalysts [95]. ORR at the cathode
surface precedes either partially or two electron reduction pathways results in the formation of adsorbed H2O2 species and direct
four-electron reduction pathways. Direct four electron pathways
are more desirable for ORR than the partial reduction pathway
since the reactivity of H2O2 is comparatively higher than that of the
stability of H2O [96]. The direct conversion of O2 into H2O involves a
dissociative mechanism, where the first step is the adsorption of O2
on the metal/catalyst surface followed by breaking off the
oxygeneoxygen bond to give adsorbed oxygen atoms.

5

Subsequently, transfer of electrons to the adsorbed oxygen atoms in
the form of hydrogen addition, yields surface-bound hydroxyl
groups. Further reduction and protonation of the hydroxyl group
produce the H2O molecule leaving behind the metal/catalyst surface. On the other hand, partial reduction of O2 follows an associative mechanism in which the adsorption of O2 on the metal
surface doesn't lead to the cleavage of oxygeneoxygen. This alternative two-electron reduction pathway finally generates H2O2 [17].
For more clarifications, Table 2 shows the pathways of ORR in
alkaline and acidic medium [97]. It is interesting that grapheneoxide-intercalated layered manganese oxide enhanced four electron transfer activity towards ORR in alkaline media at 0.8 V vs. RHE
[98]. Because, electrodeposition of manganese oxide into a graphene hydrogel not only improves the carbon material's capacitive
performance, but also affects the surface chemical environment of
the graphene-oxide framework [99]. Controllable growth from

uniform nanoparticles with specific morphology to obtain a high
active electrocatalyst is a key common problem in developing
efficient energy conversion and storage devices [91,100]. Even
though to reduce such challenge, Sun and his coworker Liu have
fabricated a nanoflake oxygen reduction ternary composite catalyst
from manganese oxide and CNTs-graphene support for an elevated
power performance in pilot scale manufacturing technology [101].
A typical ORR polarization curve (Fig. 4) is generally divided into
three regions, these are kinetically controlled region, diffusion
controlled region and mixed kinetic and diffusion controlled regions. On the kinetically controlled region the rate of O2 reduction
is slow with a small increase in the current density as decreasing
potential. A substantial rise in the current density is observed in the
mixed kinetic and diffusion controlled area. In this region, acceleration of the reaction takes place with a marked drop in the potential value. In the diffusion controlled region, the current density
is determined by the rate at which diffusion of the reactants occurs.
Quantitative analysis of the catalyst in terms of its activity can be
done from the two parameters i.e., the onset potential (Eonset) and
the half-wave potential (E1/2). The more positive is the potential,
the more active will be the catalyst towards ORR. JL denotes the
diffusion limited current density [102].
Achieving efficient catalysis for ORR plays an important role in
energy conversion, even if manganese oxides have attracted enormous interest due to their unique catalytic properties, manganese
as an element in a higher extent may cause a potential limitation to
plant growth on acidic and poorly drained soils [103]. Due to the
high theoretical capacitance of manganese oxide nanomaterials,
1370 F gÀ1, a huge number of works is devoted to these materials
[46]. Due to its variable oxidation state of manganese
(ỵ2, ỵ3, ỵ4, þ6 and þ7), it contains various morphologies and
crystallographic forms. The structural flexibility in its oxides form
(e.g., available in binary oxide type or capable of incorporating)
with another metal can also form a composite structures perovskite

[104], three-dimensionally ordered macroporous perovskite
LaMnO3 with increased specific surface area and pore volume [105],
and spinels [106]. Moreover, the Mn2O3 nanoparticles catalyst
with ỵ3 oxidation state exhibits higher ORR activity compared to

Table 2
ORR pathways in alkaline and acidic medium [97].
Electrolyte

Pathway

ORR

Alkaline aqueous solution

4 e
2 e

Acidic aqueous solution

4 e
2 e

O2 ỵ H2O ỵ 4 e / 4OH

O2 ỵ H2O ỵ 2 e / HO
2 ỵ OH


HO

2 ỵ H2O ỵ 2 e / 3OH
O2 ỵ 4Hỵ ỵ 4 e / H2O
O2 ỵ 2Hỵ ỵ 2 e / H2O2
H2O2 ỵ 2Hỵ ỵ 2 eÀ / 2H2O

Please cite this article as: Y. Dessie et al., Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction
functionalities for energy conversion and storage applications: A review, Journal of Science: Advanced Materials and Devices, https://
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Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

Fig. 4. A characteristic ORR curve of an individual catalyst. Adapted with permission from the Wiley publishing group [102].

the Mn3O4 nanoparticles catalyst with mixed (ỵ2, ỵ3) oxidation
state [107]. Tang et al. have reported a nanobelt bundles manganese
oxide with its specific surface area of 160 m2 gÀ1. The nanobelt
bundle exhibits good capacitive behavior and cycling stability in a
neutral electrolyte system, and its initial capacitance value is
268 F gÀ1 [108]. A nanostructured manganese oxide which is synthesized by a simple hydrothermal route at a very low temperature
of 60  C using potassium permanganate as oxidant and ethanol as
reductant succeeded with a maximum specific capacitance of
198 F gÀ1 [109]. A flexible and binder-free cathodic electrode for
electrochemical capacitors was prepared from electrodeposition of
manganese oxide onto reduced graphene oxide paper. From (Fig. 5)
hausmannite phase manganese oxide coated electrodes exhibit a
promising performance at a specific capacitance of 546 F gÀ1 with
current density 0.5 A gÀ1 and 308 F gÀ1 with a scan rate of 1 mV sÀ1

in chargeedischarge and cyclic voltammetry measurements,
respectively. During potential cycling, phase transformation of
Mn3O4 to mixed-valent MnOx was observed. Consequently, MnOx
nanostructures on self-standing reduced graphene oxide electrodes
have succeeded with 154% capacitance retention at 10,000 cycles
from cyclic voltammetric data [110].
In order to fully leverage their potential application, a precise
control over particle size, surface area, and Mnxỵ oxidation state
properties is required. Here, the inverse micelle solegel method
which is categorized by the heat treatment can control such
properties followed by keeping tenability and crystallinity [111]
and calcination of Mn(II) glycolate nanoparticles using polyol
technique was used to synthesize a mesoporous a-Mn2O3, Mn3O4,
and Mn5O8 nanoparticles. The authors conclude that these
different oxidation states of manganese oxide nanoparticles using
such route can facilitate their actual structuraleproperty relationship. In situ X-ray diffractometer measurements suggested
that different MnOx phases were observed. From the analysis, it is
conclude that a complete time and temperature dependent phase
transformations were occurred successfully from Mn(II) glycolate
precursor oxidation to a-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. From sweep voltammetry measurements, mesoporous

a-Mn2O3 showed a good kinetic enhancement potentials for ORR
in aprotic media [59].
In the electrochemical ORR, H2O2 has been detected as a reaction intermediate on TMO and other electrode materials. Hence, the
electrocatalytic and catalytic reactions of H2O2 on a set of manganese oxides such as Mn2O3, MnOOH, LaMnO3, MnO2, and Mn3O4,
were studied. All of these different crystal structures were adopted
to shed light on ORR mechanisms. Among MnO2 has attracted great
attention due to its high catalytic activity, thermal stability, facile
synthesis with low-cost materials and availability in various crystal
morphologies [112]. Kinetic modeling and experiment objective

correlates the differences in the ORR activity to the kinetics of the
elementary reaction steps displayed that the catalytic activity of
Mn2O3 was better in the ORR due to its high catalytic activity both
in the reduction of oxygen to H2O2 detection with its unique crystal
structure and reactivity shown from the tentative mechanisms
(Fig. 6) [47]. Previously, aggregates of gold nanoparticles (AuNPs)
on manganese dioxide nanoparticles (nano-MnO2) was developed
for better H2O2 amperometric sensing [113]. Electrodeposited
manganese oxide in the average size range of 21e40 nm was
identified with different phases (MnO, MnO2, and Mn3O4) for H2O2
detection [114].
Till now, a represented divalent alkaline-earth metal ion or
trivalent rare-earth metal ion (such as perovskite (AMnO3) or spinel
(AMn2O4) structure) adopted by Mn-based oxides displays an
efficient ORR activity [115]. To improve the activity of Mn-based
oxides oxygen defects have been introduced by thermal reduction
which reduces Mn4ỵ to more active Mn3ỵ, and improves the electrical conductivity. However, the overall ORR activity of Mn-based
oxides has been still higher than that of Pt/C. To design an active
ORR catalyst the oxidation state of manganese centers is critical.
The intermediate species for this reaction is Mn3ỵ, which plays a
signicant role in the success of catalytic activity in ORR. To boost
the catalytic activity, numerous approaches have been made to
generate the active Mn3ỵ species. The high catalytic activity of
Mn3ỵ species is attributed to the presence of one electron resulting
in JahneTeller (JeT) distortion [116]. Therefore, to achieve high

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7

Fig. 5. (a) Cyclic voltammograms of Mn3O4/rGO with different mass loads at 20 mV sÀ1; (b) Cyclic voltammograms of Mn3O4/rGO deposited at À1.1 V with a fixed charge of
500 mC at different scan rates; (c) Capacitance retention of the film as a function of cycle number; (d) Nyquist diagram of Mn3O4/rGO along with the equivalent circuit to fit the
experimental data (solid line represents the fitted curve). Adapted with permission from Elsevier [110].

Fig. 6. A tentative mechanism for the oxygen reduction/H2O2 reactions. Adapted with permission from the Wiley publishing group [47].

specic ORR activities, the presence of Mn3ỵ with some Mn4ỵ is the
key in perovskites.
Cao et al. also showed the dependence of electrochemical activity on the crystalline structure of manganese oxides. The obtained result shows that, the ORR current of different MnO2
catalysts increase in the following order: b-MnO2 < l-MnO2 < gMnO2 < a-MnO2 < d-MnO2 [95]. The specific morphology and

crystalline structure effect on a-MnO2 nanowires, a-MnO2 nanorods, b-MnO2 nanowires, and b-MnO2 nanorods have been successfully synthesized via a hydrothermal process, and their
microstructures and electrocatalytic activities were investigated for
ORR. Among the four different types of one-dimension MnO2, the
a-MnO2 nanowires exhibited significantly larger electrocatalytic
property than the others. This is due to the highest electron transfer

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8

Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

number, which may contribute to the special crystalline structure
and larger specific surface area. As a result, more active sites could
be exposed in the three-phase (electrolyte, oxygen, and catalyst)
interfaces during the whole reaction process and thus enhance the
ORR catalytic performance [117]. Lower valence state manganese
oxides are also targeted for ORR; Mn3O4 is rich in electrochemical
properties due to the mixed valence of Mn. However, because of its
poor electrochemical structural stability and low electrical conductivity, its use as ORR catalyst is diminished. Goswami et al. have
reviewed carbon-coated tubular monolayer superlattices (TMSLs)
of hollow Mn3O4 NCs (h-Mn3O4-TMSLs) by exploiting the structural
evolution of MnO nanocomposites. They have characterized the
catalyst by various techniques. From transmission electron microscopy and x-ray diffractometer characterization result (Fig. 7a), it
can be seen that the average diameter of the particles is 18 nm.
Fig. 7b and c shows the effectiveness of this in achieving highquality nanocrystal monolayers within anodized aluminum-oxide
channels. The XRD pattern of MnO@Mn3O4@AAO mainly ascribed
to the cubic MnO phase shown in Fig. 7d. The presence of Mn2ỵ and
Mn3ỵ can be clearly showed from x-ray photoemission spectroscopy result (Fig. 7e) [4]. Due to lack of accepted protocols for its
precise catalytic activity measurement, Mn/polypyrrole (PPy)
nanocomposite has a unique quantitative assessment for the ORR
electrocatalytic activity in alkaline aqueous solutions based on the
rotating risk electrode method [118].
Hazarika et al. have synthesized mesoporous cubic Mn2O3
nanoparticles supported on carbon (Vulcan XC 72-R) for both ORR
and OER. They have shown that the ORR activity of Mn2O3/C

material is much better compared to the commercially available Pt/
C and Pd/C in alkaline media. However, Mn2O3 without the carbon
support shows less ORR activity compared to Mn2O3/C, Pt/C and Pd/
C. From the parallel fitting lines of the KeL plots the average electron transfer number was found to be z1.2 and z4.1 for Mn2O3

and Mn2O3/C, respectively. The high catalytic activity is due to the
synergistic influence of Mn2O3 and carbon interface. They have also
proved that Mn2O3/C is quite stable up to 1000 cycles and the reaction follows a 4-electron pathway for ORR [33].
The combination of Mn oxide with other TMOs (such as Co, Fe,
Cu oxides, etc.) provides excellent ORR activity useful for a range
of applications. The high catalytic activity is due to the synergistic
effect of the mixed TMOs. Li et al. have prepared ultra-small cobalt
manganese spinels using simple solution-based oxidation precipitation and insertion-crystallization process at the mild condition. They have studied the catalyzation of nanocrystalline
spinels for ORR. Furthermore, strongly coupled carbon support
spinel nanocomposites exhibit similar activity except superior
durability to carbon support platinum catalyst [42]. Even structural and surface changes can happen on manganese oxide after
modification using cobalt during activation within ethanol steam
reforming reaction [119].
5. Effect of cationic dopants and media on MnOx structure
A series of calcium-manganese oxides (CaMnO3, Ca2Mn3O8,
CaMn2O4, and CaMn3O6) and the detailed investigation of their
electrocatalytic properties were reported through a simple

Fig. 7. (a) TEM image of octahedral MnO NCs used for constructing h-Mn3O4-TMSLs; Cross section SEM images of MnO NC monolayers self-assembled within the AAO template
having (b) circular and (c) hexagonal channels, respectively; (d) XRD patterns of MnO@Mn3O4@AAO and h-Mn3O4-TMSLs, respectively. The blue asterisks denote the reflections of
Mn3O4; (e) High-resolution Mn 2p XPS spectra of MnO@Mn3O4 NCs and h-Mn3O4-TMSLs, respectively. Adapted with permission from Elsevier [4].

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calcination route using Ca1ÀxMnxCO3 solid-solution precursors. The

parallel formation of highly crystalline CaeMneO porous microspheres with similar textures and its ORR catalytic activities of the
synthesized CaeMneO compounds were compared with MnOx in
alkaline conditions and Pt/C was used as a benchmark. The experimental and theoretical study demonstrated that the surface Mn
oxidation state and crystal structure are influential factors to
determine CaeMneO electrocatalysts activity. In recent years,
CaeMneO has captured strong scientific interest due to exceptional catalytic activities, inexpensive method of synthesis, abundant, and environmentally benign nature of elements. In particular,
the catalytic properties of CaeMneO systems have been reviewed
as a potentially useful new tool in addressing energy and environmental problems [120].
Structurally, cation dopants on a-MnO2 have a vital role for ORR.
Hydrothermally synthesized nickel-doped a-MnO2 nanowires (Nia-MnO2) at different weight ratio in general, had higher n values
(n ¼ 3.6), faster kinetics (k ¼ 0.015 cm sÀ1), and lower in charge
transfer resistance (RCT ¼ 2264 U at the half-wave) values than
MnO2 or Cu-a-MnO2. This was happened due to the effective surface defect functionality between nickel and manganese. Therefore,
the overall catalytic activity for Ni-a-MnO2 trended with increasing
Ni content, i.e., Ni-4.9% > Ni-3.4% was increasing [121]. Off course
other than cation doping, surface topography or shape of a catalyst
have had different catalytic activity towards ORR. For example,
Affandi and Setyawan reported that nanocatalysts were prepared
electrochemically from KMnO4 precursor in different media conditions at a temperature of 60  C. The result surface morphology
was nanorod at pH ¼ 0.2 and nanoflake at pH ¼ 9, respectively. The
acidity of the solution systematically influenced the particle
morphology. As shown in Fig. 8, the particles had nano-rod
morphology at a very acid solution whereas they had a nanoflake shape at the base condition. XRD revealed that the particle
generated at very acid condition was a-MnO2 while at basic condition MnO2 was amorphous. So, the electrocatalytic activity for
nanorod and nanoflake MnO2 towards ORR of the materials was

9

studied in oxygen saturated 0.6 M KOH solution. Thus, the number
of electrons transferred during ORR was 2.23 and 1.75, respectively.

This result suggested that nanorod MnO2 particles was exhibited
better ORR activity than nanoflake MnO2 [86]. Surface manganese
valence of manganese oxides exhibits better catalytic activity toward the ORR than those with lower Mn valences on the activity of
ORR in alkaline media [122].
A porous spinel-type of magnetic iron-manganese oxide nanocubes with a hollow structure deposited on the reduced graphene
oxide nanoflakes nanocomposite [123] and (CoMn2O4 and
MnCo2O4) spinel microspheres reflect a high efficient catalyst for
OER, as well as for the ORR. The as-prepared cubic MnCo2O4 displays better OER activity compared to the tetragonal CoMn2O4
material in an alkaline medium. However, the tetragonal CoMn2O4
material display better ORR activity and stability compared to cubic
MnCo2O4 and also Pt catalysts. Spinels structural features such as
microspherical morphology and their unique porous results in the
higher catalytic activity and stability of the material [106]. Its spinel
arrangements are continued because manganese oxides structure
flexibility under working conditions remains a great challenge for
identifying their active structures [124]. Liang et al. reported a
manganese-cobalt spinel MnCo2O4/graphene hybrid is highly efficient in electrocatalyst for ORR in alkaline conditions. They have
suggested from the X-ray absorption near edge structure of Co Ledge and Mn L-edge that substitution of Co3ỵ sites by Mn3ỵ
resulting in higher catalytic sites that enhance the ORR activity
compared to the pure cobalt oxide hybrid. Mechanically, such
hybrid material possesses greater activity and durability than the
physical mixture of nanoparticles and N-rmGO and the MnCo2O4/
N-graphene hybrid displays higher ORR current density and stability compared to Pt/C in alkaline solutions at the same mass
loading [109]. In addition, the use of manganese ore as an oxygen
carrier has recently gained interest, primarily due to the combination of low cost and moderate to high reactivity. The possibility of
an oxygen uncoupling reaction enhancing reactivity may be an
additional advantage [125].

Fig. 8. Tafel plots of electrodes for KMnO4 solution at pH 0.2 and pH 9 electrolysis. Adapted with permission from the Ceramic Society of Japan [86].

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6. Applications of manganese oxide nanomaterial
6.1. Microbial fuel cells (MFCs)
The need to reduce the costs of renewable energy conversion
sources such as bioelectrochemical systems (BES) has pushed the
research towards alternative cathodes performing ORR to maintain
a catalytic efficiency close to that of platinum or platinum-based
catalysts [126]. Conventional MFCs set up consist of biological anodes and abiotic cathodes. Abiotic cathode usually requires a
catalyst or an electron mediator to achieve high electron transfer,
increasing the cost and lowering operational sustainability. Such
disadvantages can be overcome by low cost biocathodes, which use
microorganisms to assist cathodic reactions. The classification of
biocathodes is based on which terminal electron acceptor is available. For aerobic biocathodes with oxygen as the terminal electron
acceptor, electron mediators, such as iron and manganese are first
reduced by the cathode (abiotically) and then reoxidized by bacteria. Anaerobic biocathodes directly reduce terminal electron acceptors, such as nitrate and sulfate, by accepting electrons from a
cathode electrode through microbial metabolism [127]. Manganese
by itself as a manganese peroxidase enzymes as catalyst could
apply as an enzymatic electrode in the cathode chamber of an MFC.
Its output power density was 100% higher than that for the conventional graphite electrode. As a biocathode, its activation overpotential loss was diminished during H2O2 reduction (Fig. 9) [128].
Air cathode (open air at the cathode) in a single chambered MFC
is the one which uses oxygen (O2) as a direct electron acceptor
species and is reduced by the electrons coming from the anode and

the protons via the membrane into water. However, ORR on the
surface of air-cathode is one of the main drawbacks in MFCs. The
reaction kinetics is limited by an activation energy barrier (activation polarization loss) which impedes the conversion of oxygen into
the reduced form at the cathode surface; hence, it requires an
efficient and effective catalyst for ORR. Even at the laboratory scale
platinum (Pt) is the most practically used catalyst for the ORR in
MFC. But due to its special case, Pt-based catalyst in large scale air
cathode MFCs is limited due to high-cost and dissolution at a short
lifetime in a given media. In addition, other external factors also
directly affect MFC performance. Therefore, to reduce cost followed

by increasing ORR rate, synthesizing a non-precious a-MnO2 catalyst using a hydrothermal method is being a unique strategy for aircathode application [67]. Results from Table 3 found that
28.57 mg cmÀ2 a-MnO2 was going to be an optimum catalyst load
with 13.40 mW power output. Later, nanostructured Mn2O3/Pt/CNTs
was also used as a selective electrode for ORR and membrane less
micro-direct methanol fuel cells (DMFC) in alkaline media. Interestingly, during the cell reaction, there is no activity for methanol
oxidation reaction, in contrast with Pt. Even the bilayer cathode
was tested in this membrane less micro fuel cell under mixedreactant conditions, producing an open circuit voltage (OCV) with
0.54 V and a maximum power density of 2.16 mW cmÀ2 [129].
Tan et al. have manufactured MnO containing mesoporous
nitrogen-doped carbon (m-N-C) nanocomposite which was lowcost non-precious metal catalysts that perform high ORR in alkaline solution with four-electron transferred per molecule. This
nanocomposite involves the one-pot hydrothermal synthesis of
Mn3O4@polyaniline core/shell nanoparticles from a mixture containing aniline, Mn(NO3)2, and KMnO4, conducting polymer with
metal precursors; and followed by heat treatment to produce Ndoped ultrathin graphitic carbon coated MnO hybrids partial acid
leaching of MnO. The composite exhibits superior stability and
methanol tolerance to commercial Pt/C catalyst, making it a
promising cathode catalyst for alkaline containing methanol fuel
cell applications. The synergetic effect between MnO and N-doped
carbon described, provides a new route to design advanced catalysts for such energy conversion device [130]. Later, a 4ỵ oxidation
states of MnO2 nanostructured material was fabricated by hydrothermal technique; it was potentially applicable as cathode catalyst

in MFC due to their unique properties. Hydrothermally synthesized
MnO2 (HSM) was one-dimensional nanorod structured that
accomplish a noticeable oxygen reduction peak current due to high
Table 3
Maximum current and power produced by the MFCs with different catalyst loadings.
Catalyst loadings (mg cmÀ2)

Maximum current (mA)

Maximum power (mW)

14.28
21.43
28.57

68.58
98.91
130.14

4.14
7.26
13.40

Fig. 9. Open circuit voltageetime curve of MFC after H2O2 addition to the cathode in the presence of MnP. Adapted with permission from the World Renewable Energy Congress
[128].

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Y. Dessie et al. / Journal of Science: Advanced Materials and Devices xxx (xxxx) xxx

aspect ratio, multivalve surface topography, and positivity nature
than naturally synthesized method (NSM) of MnO2. When the HSM
was employed as the cathode catalyst in MFC with leachate fed, it
produced 119.07 mW mÀ2 power densities and delivered 64.68%
efficiency than that of NSM at the same environmental conditions.
Furthermore, HSM proceeds its catalytic activity via a four-electron
pathway while NSM was via a two-electron pathway towards ORR
in alkaline solution; the HSM was more positive onset potential
than NSM [131]. The same year publicized research reported that
maximum power density of the MFC equipped with electrodeposited MnO2 on activated carbon (AC) air cathode was
1554 mW mÀ2, which was 1.5 times higher than the control cathode [132].
Continually, hydrothermally synthesized nanoflowers, nanorods, and nanotubes catalysts at different run times were effectively
demonstrated for ORR at air cathode. Cyclic voltammetry and linear
sweep voltammetry investigations indicated that all of the MnO2
nanostructures can catalyze the ORR at different catalytic activities.
However, only nanotubes are appeared to possess the highest
catalytic activity, with a more positive peak potential shift, as well
as, a larger ORR peak current. In MFC a maximum power density of
11.6 W/m3 was recorded using nanotube as a cathode electrode.
The results of this study demonstrated that nanotubes are ideal
crystal structures for MnO2 and that they offer a good alternative to
Pt/C for practical MFC applications [43]. The other catalytic performance of nanostructured MnO2 is also existed in the form of
nanoflowers, which has high beneficial structural features for
fabricating stable and cost-effective electrocatalytic activity when
hybridized with sulfonated graphene sheets (denoted as d-MnO2/
SGS) using simple hydrothermal method [133]. Although a novel
nanocomposite from manganeseepolypyrroleecarbon nanotube

(MnePPyeCNT) was synthesized and demonstrated as an efficient
and stable cathode catalyst for ORR in air-cathode MFCs (Fig. 10). Its
electrocatalytic capability of this novel material in neutral electrolyte media has been investigated by cyclic voltammetry and the
data showing that MnePPyeCNT can catalyze ORR with quite good
activity; this is possibly due to manganese-nitrogen active sites. It
has been found that an efficient and stable performance with
maximum power density of 169 mW mÀ2 and 213 mW mÀ2 were
recorded at the loading of 1 mg cmÀ2 and 2 mg cmÀ2, respectively,
with comparable to platinum/carbon black (Pt/C) catalyst as a
benchmark in MFCs devices [18].

11

In addition to the protic and aprotic solution, functionalized
manganese oxide/carbon nanotubes (MnO2/f-CNT) nanocomposite
is a good catalyst for ORR in neutral solution. From this study, the
unique interaction between MnO2 and f-CNT was enhanced for fast
electron transfer process during ORR. Raman spectra result proved
that more surface defect was formed after functionalization with
manganese dioxide. The XRD spectra showed crystallinity existence
in MnO2/f-CNT catalyst. During the test from the power curve, as
shown in Fig. 11, the higher maximum power density was achieved
at 520 mW mÀ2 for MnO2/f-CNT compared to CNT (275 mW mÀ2)
and f-CNT (440 mW mÀ2) alone in a MFC. Moreover, for better
performance clarification a 28.65% coulombic efficiency and 86.6%
chemical oxygen demand (COD) removal efficiency was recorded
throughout the analysis [134].
Finally, a low cost iron phthalocyanine (FePc)-MnOx composite
catalyst was prepared for ORR in the cathode of membranelles
single chamber MFC and more power using composite FePcMnOx/

carbon monarch 1000 air cathodes (143 mW mÀ2) on the setup was
generated than commercial platinum catalyst (140 mW mÀ2) and
unmodified FePc/carbon monarch 1000 (90 mW mÀ2) [135]. Sindhuja et al. have reported the possibility of synthesizing phase
specific a-MnO2 by MFC for energy storage with simultaneous
power conversion applications [136].
6.2. Bioremediation
The demand for new technologies to accelerate the decontamination of contaminated sites and reduce the costs of these
technologies is increasingly growing. Recently, the use of NMs as
an innovative method to contaminated site remediation has
received greater attention [49]. The many techniques used in the
remediation of wastes fall under the major categories of physical,
biological, photolytic, chemical, and bioelectrochemical. Of these,
BES is regarded as a promising alternative biological wastewater
treatment technology, as the energy recovered could offset partial
energy consumption during the process. MFC is a typical BES
which can remove organic pollutants through oxidation and
reduction at anode and cathode electrode system [55], respectively. To replace carbon supported platinum catalysts, manganese oxide is a promising alternative electrocatalyst for ORR to
reduce cost and minimize sluggish ORR rate at air cathode during
wastewater treatment and power generation in MFC. The MnO2

Fig. 10. Schematic representation of the preparation procedure for manganeseepolypyrroleecarbon nanotube composite. Adapted with permission from the Elsevier [18].

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Fig. 11. (a) Polarisation and power curves of MFC equipped with CNT, f-CNT, and MnO2/f-CNT as a cathode catalyst in dual chambers MFC test and; (b) coulombic efficiency and COD
removal of MFC with different cathode catalysts. Adapted with permission from Elsevier [134].

catalyst prepared by hydrothermal, solegel, and a wet impregnation method was used to catalyze palm oil mill effluent in the
anode chamber with active anaerobic sludge. Cyclic voltammogram results showed that platinum support MnO2 could effectively catalyze ORR at air cathode electrode and generates a
maximum power density of 165 mW mÀ3, which was higher than
MnO2 catalyst alone (95 mW mÀ3) [76].
Decomposition of organic compounds via oxidative reactions
using microorganism as a catalyst is increasingly examined as an
alternative approach to wastewater treatment and soil remediation for decomposing organic pollutants but are limited by an
external constraints, such as denaturation and cost. Recently,
manganese oxide NMs has been found to exhibit a pollution
control application with reactivity similar to laccase and phenol
oxidase containing enzymes. The substrates of many organic
contaminants can decompose and change color during treatment.
Oxidation of sulfonated aromatic compound, such as 2, 20 -azinobis-(3-et hylbenzthiazoline-6-sulfonate) has been employed in
the presence of laccase microorganism to assess its activity. In
comparison to such microorganism, certain manganese oxides
(MnOx) can utilize substrate oxidation via single electron transfer
mechanism, while the resultant reduced MnOx red can be reoxidized to MnOx by the dissolved oxygen molecules. The dissolved molecular species under optimum conditions could be
reduced to water, this clearly leading to the net electron shuttling
formation from substrates to oxygen [137].
Wang et al. have reported the laccase-like reactivity of nanostructured manganese oxides with diverse crystallinity, including
a-, b-, g-, d-, and 3-MnO2, and Mn3O4 [137]. From the reaction rate
behaviors, researchers have examined g-MnO2 exhibits the best
performance. Simultaneous approaches for generating electricity
and remediation from waste and biomass using MFCs have been
devoted to clean and renewable energy sources. Some significant
research has been dealing with the cathode reaction and catalysts

for ORR; which remains a major factor in the design of low-cost
MFCs. Indeed, poor kinetics of ORR at neutral pH and low temperatures have hindered the improvement of MFC performances.
Platinum is known to be the best catalyst for the ORR in acidic and
alkaline media and is the most commonly used catalyst in the MFC
[7]. However, Pt cost is prohibitive to economic MFCs and
platinum-free electrocatalysts represent a necessary alternative.
Roche et al. have thus investigated the performance of operating
MFC using (MnO2/C) catalysts formed chemically on AC as cathode
materials. The test was performed at neutral and alkaline pH [44].

Later, the electrocatalytic activity of MnOx modied with Cr3ỵ,
Fe2ỵ, Co2ỵ [138], Zr4ỵ [139], and metal (e.g., Ni, Mg) ion [44] have
been performed for better efficiency through doping. The result
shows that, and all the catalysts improve O2 adsorption for superior
catalytic activity towards the ORR. Beyond hybridization with
metals, electrodeposition of MnO2 on polymers like polypyrrolecoated stainless steel (SS) greatly improved MFC efficiency (better
in power generation and best for remediation) with almost 100%
COD removal and maximum power density of 440 mW mÀ2. This
indicates that MnO2/PPy-coated SS316 is one of the most promising
electrode materials applicable for remediation and power generation in MFCs device system [140].
6.3. Batteries
High activity with low cost Bifunctional electrocatalysts for ORR
is a current strategy research priority in the improvement of energy
conversion and storage devices [91]. Unique structural spinel-type
oxides electrocatalysts are technologically important in electrochemical energy conversion and storage fields. Ultra-small
CoeMneO spinels were synthesized at moderate condition for
such applications. Its phase and composition co-dependence
showed better catalytic activity towards ORR and OER. Furthermore, its synthesis strategy at optimum condition allowed for homogeneous and strongly coupled nanocomposite formation, which
exhibit a comparable and superior activity in comparison to Pt/C,
and it served as an effective and capable catalysts to construct and

rebuild a rechargeable Zn [141] and Li [42] air batteries.
Today in comparison to common rechargeable batteries like
lead-acid and Li-ion batteries [142], metal-air batteries [143]
represent a low cost, low pollution, lightweight, relatively high
specific capacity/energy density, and considered as a safe technology. However, among metal-air batteries secondary zinc-air, batteries are based on an aqueous alkaline electrolyte are still under
development due to the short life cycle of their electrodes.
Regarding the Bifunctional air electrode, the large overpotential
(DV) between OER and ORR reduces the cycle life limits secondary
zinc-air batteries performance. The search for low-cost catalysts
with sufficient manganese oxides NMs exhibits a promising electrocatalytic for OER and ORR under alkaline conditions and possess
many advantages such as abundance in natural ores, low toxicity,
low-cost, and environmental friendliness. Due to the presence of
more active centers, e.g., edges and kinks and an increase of reoxidation efficiencies on carbon powder-based electrodes, as well

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13

Table 4
Summary of parameters compared with the reviewed data on manganese oxide based materials.
Precursors

Synthesis method

Electrode

Electrolyte

Cell
voltage

Number of
cycles

Energy
density

Discharge
capacity

Mn(NO3)2, Co(NO3)2

CoeMn

KCl

0.800 V

12,000

650 Wh kgÀ1

e

KMnO4, SnCl2

Two step oxidation precipitation
and crystallization
Wet method

SnO2/Mn2O3

e

0.750 V

400

e

1365 mA h gÀ1

EMD

Thermal method

a-MnO2

KOH

1.420 V

200

e

10 mAh cmÀ2

KMnO4

Hydrothermal method

Mn2O3/Mn3O4

KOH

0.830 V

e

e

**1.75

Mn(CO3)2, AgNO3

Pyrolysis

AgeMnO2

KOH

0.859 V

e

*204

**199

KMnO4, Ce(NO3)3$6H2O

Modified redox synthesis

CeeMnO2

KOH

0.900 V

10

*348.8

**100

Note: EMD ¼ Electrolytic manganese dioxide, * ¼ Power Density (mW cm

À2

), ** ¼ Current Density (mA cm

À2

Reference

[42]
[142]
[144]
[146]
[147]
[148]

).

as an overall decrease of potential gaps between OER and ORR
enhance the activity of a-Mn2O3/C compared to pure carbon
powder alone, Mn3O4/C and Mn5O8/C electrodes [59]. Mainar et al.
produced an efficient durable and low-cost air cathode for a secondary zinc-air battery with low polarization between the ORR and
OER [144].
We would like to emphasize that change in surface behavior of
air-cathode NMs electrode for its novel and superior electrocatalytic activity during ORR activity. This ORR activity are systematically investigated by KouteckýeLevich plots in the diagnoses
of charge-transfer mechanisms at rotating disk electrodes [145].
From morphological studies, due to its anisotropic structures
manganese oxide exhibits better significance in ORR kinetics with
an improved onset potential of þ0.83 V versus reversible hydrogen
electrode in alkaline media [146]. When the smaller diameter of
silver nanoparticles is anchored on the surface of a-MnO2 would
result for strong interaction between Ag and MnO2 components.
The electrochemical tests show that the activity and stability from
50% AgeMnO2 composite catalyst toward ORR are greatly
enhanced. Moreover, the peak power density in the aluminum-air
battery with 50% AgeMnO2 can reach up to 204 mW cmÀ2 [147].
Cerium ion intercalated birnessite-type manganese oxide (d-MnO2)
dispersed on CeeMnO2/C has high-efficient ORR electrocatalytic

ability and exhibits excellent in long-term stability with current
retention of 96.4% after aging for 40,000 s in aluminum-air battery
[148]. Therefore, Table 4 represents the general summary and
performance of manganese oxide based nanomaterials modifications with oxygen reduction reaction functionalities for battery
application.

nanorods, nanoflower, nanotube, nanoflake, etc. as an alternative
ORR catalyst have been reviewed. A wide range of MnxOy based
catalysts using the hydrothermal synthesis methods followed by
calcination is found to exhibit higher ORR activities but their
designing as a catalyst with superior ORR activity still remains a
difficult task. Due to this problem, various researches from their
scientific reports are trying to analyze the mechanism of these
oxides by modifying manganese oxides with other materials in the
form of composites. This can lower the challenges found in Pt
catalyst and may also provide some extra stability. Manganese
oxides with spinel and perovskite structures as advanced catalysts
would be a recommended strategy to increase an energy conversion and storage devices with facilitating reaction kinetics, reaction
mechanisms, and reaction pathways of ORR in aqueous alkaline
media. Therefore, for the future, a complete and noticeable manganese oxide based catalyst will be likely the key to unlock superior
ORR activity. This future direction may help the researchers to
address all the challenges that effectively facilitate the electron
transfer between the active sites and adsorbed oxygen molecules.
This intention illustrates that how a facile pathway could improve a
catalytic activity of mixed valence metal oxides.

7. Conclusion and future outlook

The authors gratefully acknowledge Adama Science and Technology University for financial support to this review article.

The ORR potential system continues to play an important role in
energy conversion and storage applications, such as BFC and metalair batteries. Pt is the most common type of catalyst for ORR within
various energy conversion and storage systems, however, due to its
high cost, an alternative manganese oxide nanocatalyst is going on
to reduce the use of Pt in ORR potentials. To reduce the cost and
enhance the ORR performance, much work has been focused on
manganese oxides as catalysts due to their varied valence state,
crystallite structure, exceptional electrical and redox properties,
studies of which are helpful to understand their behavior and
mechanism. So far, to increase the ORR performance, various strategies are employed, such as mixing with other metals as a support,
doping, etc. The performance of ORR can also be improved within a
better electrocatalytic performance towards the fuel cell, batteries
and bioremediation technologies due to its synergy effect.
In this review, some of the most important trends using manganese oxides based nanostructured crystalline materials, like

Conflict of interest
The authors declared no potential conflicts of interest with
respect to this review article.

Acknowledgments

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