sensors

Review
Carbon-Based Nanomaterials in Biomass-Based
Fuel-Fed Fuel Cells
Le Quynh Hoa 1, * ID
, Mun’delanji C. Vestergaard 2, * and Eiichi Tamiya 3
1 Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87, Berlin 12205, Germany
2 Department of Biochemical Science and Technology, Faculty of Agriculture, Kagoshima University,
Kagoshima 890-0065, Japan
3 Department of Applied Physics, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan;
tamiya@ap.eng.osaka-u.ac.jp
* Correspondence: quynh-hoa.le@bam.de (L.Q.H.); munde@agri.kagoshima-u.ac.jp (M.C.V.);
Tel.: +49-308-104-4667 (L.Q.H.); +81-99-285-3520 (M.C.V.)

Received: 10 October 2017; Accepted: 7 November 2017; Published: 10 November 2017

Abstract: Environmental and sustainable economical concerns are generating a growing interest in
biofuels predominantly produced from biomass. It would be ideal if an energy conversion device
could directly extract energy from a sustainable energy resource such as biomass. Unfortunately, up
to now, such a direct conversion device produces insufficient power to meet the demand of practical
applications. To realize the future of biofuel-fed fuel cells as a green energy conversion device, efforts
have been devoted to the development of carbon-based nanomaterials with tunable electronic and
surface characteristics to act as efficient metal-free electrocatalysts and/or as supporting matrix for
metal-based electrocatalysts. We present here a mini review on the recent advances in carbon-based
catalysts for each type of biofuel-fed/biofuel cells that directly/indirectly extract energy from biomass
resources, and discuss the challenges and perspectives in this developing field.

Keywords: carbon-based nanomaterials; biofuel cells; biomass; carbon nanotubes; graphene;

carbon nanodots

1. Introduction

1.1. From Biomass to Biofuels: Conventional Processes and Challenges

Biomass, a renewable source of fuel made from biological materials such as plants and animal
waste, has been used as the primary energy source since ancient times. In particular wood serves as
the principle energy source till the dawn of the industrial revolution when fossil fuels became the
absolute dominator. Besides a lot of advantages, the reproduction of fossil fuels is impossible making
it a deathly Achilles heel compared to wood crops, the most widely used biomass resource, which
can re-grow every 50–100 years. Moreover, fossil fuel reservoirs are going to emptying and its related
environmental problems are severe. Therefore reducing dependence on fossil fuels becomes a more
and more ultimate request. One of current solutions is to transform a variety of agricultural crops and
their byproducts into a supplementary energy source.
Currently, to extract energy, woody plants and grasses are used in several ways: The first is the
same as our accentors did a hundred years ago which is to burn woody material and grasses to provide
heat and/or steam for households or for generating electric power. This approach is still widely used
in many underdeveloped countries. The second is to thermally decompose biomass under varied
conditions such as pressure, temperature and catalyst to obtain combustible products. Another way is
to ferment carbohydrates and then distil them to obtain ethanol, a highly ranked liquid fuel that can be
blended with gasoline for motor vehicle use. Last but not the least, is the use of an anaerobic digestion

Sensors 2017, 17, 2587; doi:10.3390/s17112587 www.mdpi.com/journal/sensors

Sensors 2017, 17, 2587 2 of 21

processes in which microorganisms breakdown biomass in the absence of oxygen to produce biogas
(mainly CO2 and CH4 ). These gaseous fuels can be further purified in an upgrader system to more
desirable forms that are suitable for engines, gas turbines, fuel cells, boilers, industrial heaters, etc.
albeit at some loss of energy [1–5]. Manufacturing combustible fuels from biomass inevitably involves
intensive energy processes such as drying, pulverizing to minimize heat-transfer resistance and residue
removal which not only results in partial loss of total heating value but also increases the cost of the
conversion process. Consequently, researchers are looking for an optimum breakdown process coupled
with effective energy conversion devices, which can gain a positive net energy and at the same time
have low to acceptable costs. To that end, biomass-based electricity could be an appropriate answer.
As shown in Figure 1, the convention process to generate energy from biomass, especially
electricity, consists of three main processes: (1) scarification (or breakdown process) to convert
biomass to smaller components that are easier to be degraded; (2) fermentation to convert these small
components to bio-fuels; and (3) energy conversion process that generates electricity from bio-fuels
using fuel cells. In order to vastly improve overall efficiency, the scientific portfolio is organized
into three core strategies: (1) improve plants; (2) improve processing; and (3) improve catalysts,
targeting the three main processes, respectively [6–20]. Ideally, crude and abundant fuel sources such
as cellulose or starch could be utilized directly [15]. However, despite the enormous efforts by scientists
worldwide, this goal seems too far from real practical implementation. Thus, researchers aim to increase
energy density and the degradability of plants such as grasses and other non-traditional oil crops by
understanding, and manipulating metabolic flux and genetic modification [6,7]. Another solution
is to improve the breakdown and fermentation processes in which the primitive biomass sources
are degraded into smaller sources such as glucose and/or other monosaccharides, and ultimately to
bio-hydrogen and bio-ethanol [8–14]. This research trend is focusing on the development of genetically
modified microorganisms and efficient low-cost enzymes. Especially, bio-hydrogen and cellulosic
ethanol-producing microbes are at the center of this strategy. After breaking down biomass sources into
biofuels, the last challenge is utilizing as much as possible, the energy stored in the chemical bonds by
energy conversion devices-fuel cells. At this stage, nanotechnology is being employed to improve cell
performance, increase durability, and reduce the cost [16]. For example, precious metal electrocatalysts
used are reduced to the nanoscale, ensuring a high catalytic surface area and minimizing the amount
of precious metal used to maintain high performance. Thus far, many researchers have been studying
inorganic nanostructured catalysts including alloys, bimetallic, and ternary metallics in order to not
only reduce the noble metal loading but also create synergistic effects to enhance catalytic performance
as well as durability [17]. Differing from the inorganic approach, a new strategy is focusing on
organic-based nanomaterials, mostly carbon-based, as supporting matrices to fine-tune the catalytic
activities of low-loading noble or non-noble metals toward desired products [18]. Graphene, for
instance, when coated with cobalt and cobalt-oxide nanoparticles, is reported to be able to catalyze
the oxygen reduction reaction on the cathode side of fuel cells, nearly as well as platinum does and is
substantially more durable [19]. A catalyst made of iron nanoparticles confined inside pea-pod-like
carbon nanotubes exhibits a high activity and remarkable stability as a cathode catalyst in polymer
electrolyte membrane fuel cells [20].
In this mini-review, we discuss the main results from recent studies on fuel cells that directly or
indirectly utilized biomass as fuels and carbon-based nanomaterials as catalytic materials. From the
discussion, the challenges will be made more succinct, exposing the future prospects of this
research trend.
Sensors 2017, 17, 2587 3 of 21
Sensors 2017, 17, 2587 3 of 21

Figure The
1. 1.
Figure conventional
The conventionalprocess and
process andchallenges
challengesinin
converting biomass
converting biomasssources into
sources biofuels
into and
biofuels and
ultimately generate energy in form of electricity.
ultimately generate energy in form of electricity.

1.2.Biofuel-Fed
1.2. Biofuel-FedFuel
FuelCells
Cellsand
andBiofuel
BiofuelCells
Cells
TheThefirst
first electrochemical
electrochemical cellcell (fuel
(fuel cell)
cell) akin
akin to the
to the VoltaVolta
cell cell (a battery)
(a battery) waswas discovered
discovered in 1839
in 1839 by
SirbyWilliam
Sir William
R. Grove R. Grove
[21]. A[21]. A fuel
fuel cell is ancell is an electrochemical
electrochemical “device”
“device” that that continuously
continuously converts
converts chemical
chemical
energy intoenergy
electricinto electric
energy (and energy
some (and heat)some
for asheat)
longfor as long
as fuel andasoxidants
fuel andare oxidants
supplied. are Asupplied.
fuel cellA
fuel similar
shares cell shares similar electrochemical
electrochemical properties withproperties with a battery.
a battery. However, it does not However, it does operates
need recharging, not need
recharging,
quietly operates A
and efficiently. quietly
fuel cellandalso efficiently. A fuelascell
is considered an also
idealissubstitution
consideredfor as an ideal substitution
combustion engines in for
thecombustion
near future.engines in the near future.
Thermodynamically, the most Thermodynamically,
striking difference isthe thatmostthermalstriking
engines difference
are limited is by
that
thethermal
Carnotengines
efficiencyare while
limited by cells
fuel the Carnot
are not.efficiency
The limitingwhilefactors
fuel cells
are arethe not. The limiting
temperature factorsthe
at which are
theenters
heat temperature at which
the engine, the heat
TH , and enters the engine,
the temperature TH, and the temperature
of the environment into which the of the
engineenvironment
exhausts itsinto
which
waste theTengine
heat, exhausts
C . No device its waste
converting heat,
heat intoTCmechanical
. No deviceenergy, converting heat into
regardless of itsmechanical
construction, energy,
can
regardless
exceed of its construction,
the Carnot cycle efficiency: η ≤ 1 −the
can exceed TCCarnot
/TH . Incycle efficiency:
contrast, since all η ≤the
1-Tcomponents
C/TH. In contrast, since
in fuel cellall
the components
systems work at theinsame fuel temperature
cell systems (T work
= THat= theTC ) same temperature
it is clearly not limited (T =by THthe
= TCarnot’s
C) it is clearly
theorem. not
limited
This by thethe
is because Carnot’s
Carnot’s theorem.
theoremThis is because
applies to enginesthe Carnot’s
converting theorem
thermalappliesenergytointo engines
work,converting
whereas
thermal
fuel energy chemical
cells convert into work, whereas
energy into fuel
work. cells convert the
Therefore, chemical
energyenergy
conversion into efficiency
work. Therefore,can reach the
energy
more than conversion
50% and can efficiency can reach
be enhanced by more
stackingthan 50% fuel
single and cells
can be and enhanced
utilizingbya stacking
vast range single fuel
of fuel
cells and
sources suchutilizing a vast range
as hydrogen, natural of fuel
gas, sources
methanol, such andas ethanol.
hydrogen, natural
Figure gas, methanol,
2 shows the summary and ethanol.
of the
Figureranges
power 2 shows the summaryof of
and applications the power
different typesranges
of fuel and
cells applications
[21–23]. However, of different
the problem types isofthat
fuel
cellswith
even [21–23]. However,
hydrogen fuelthe problem
cells, the most is that even with
successful hydrogen
proton fuel cells,
exchange the most
membrane fuelsuccessful
cell (PEMFC)proton
exchange
system, theremembrane fuel cell (PEMFC)
are huge challenges including system, there are huge
fuel distribution and challenges
safety issues; including
and methanol fuel distribution
of direct
and safety
methanol fuelissues; and methanol
cell (DMFC) is toxic.ofIndirect methanol
addition, the fuelfuelproduction
cell (DMFC) is toxic.
is not In addition,
without concern. the fuel
It has
itsproduction
own print in is greenhouse
not withoutgas concern.
emission It has
andits own change.
climate print in Today
greenhouse96% ofgas emission and
all hydrogen climate
is derived
change.
from fossilToday
fuels,96%with of 48%
all hydrogen
from natural is derived
gas, 30%fromfromfossilhydrocarbons,
fuels, with 48%18% fromfrom
naturalcoal,gas,
and 30% from
about
4% hydrocarbons,
from electrolysis 18%[24].
fromThe coal, and about
situation 4% from
is similar electrolysis
for methanol [24]. Thesince
production situation is similarby
it is produced for
methanol production
steam-methane reforming sincefrom it is produced
natural by steam-methane
gas source. Thus, researchers reforming havefrom been natural
pushed gas source.
to search
forThus,
moreresearchers
practical, saferhaveand been pushed to
“greener” search forbiomass
solution(s): more practical, safer and For
derived-biofuels. “greener”
biofuel solution(s):
cells, it is
notbiomass
necessaryderived-biofuels.
to use biomass Forasbiofuel cells, it is not
fuel. “Bio”-fuel cellsnecessary to use biomass
use biocatalytic systemsassuch fuel.as“Bio”-fuel
enzymes cellsor
use biocatalytic
microorganisms systems In
as catalysts. suchthe asframe enzymes or microorganisms
of green-chemistry, this review asdiscusses
catalysts.theInapplications
the frameofof
green-chemistry,
CBNs for biomass-based this review
fuel-fed discusses
fuel cells, the applications
which of CBNs
include biofuel forand
cells biomass-based
do not exclude fuel-fed fuel
the fuel
cells,
cells thatwhich
utilizeinclude biofuel cellssystems.
non-biocatalytical and do not exclude the fuel cells that utilize non-biocatalytical
systems.
Sensors 2017, 17, 2587 4 of 21
Sensors 2017, 17, 2587 4 of 21

Figure 2. Summary of applications and main advantages of different types fuel cells (CHP stands for
Figure 2. Summary of applications and main advantages of different types fuel cells (CHP stands for
combined heat and power systems. The power unit is Watt).
combined heat and power systems. The power unit is Watt).

1.3. Carbon-Based Nanomaterials

1.3. Carbon-Based Nanomaterials
Carbon-based
Carbon-based nanomaterials(CBNs),
nanomaterials (CBNs), werewerediscovered
discovered about 150 years
about ago, remarkably
150 years in 1991 in
ago, remarkably
1991 byby aaphysicist,
physicist, Sumio
SumioIijima of Nippon
Iijima ElectricElectric
of Nippon Company (NEC) Corporation,
Company Japan, who published
(NEC) Corporation, Japan, who
a ground-breaking
published a ground-breaking paper inpaper
NatureinonNature
multiwalled carbon nanotubes
on multiwalled carbon(CNTs) [25], and
nanotubes in 2004
(CNTs) by and
[25],
Novoselov with the mechanical exfoliation of graphite to produce the first single layer graphene
in 2004 by Novoselov with the mechanical exfoliation of graphite to produce the first single layer
[26]. They have since been thoroughly characterized, and extensively developed for a wide range of
graphene [26]. They have since been thoroughly characterized, and extensively developed for a wide
fields from industrial applications such as high-strength materials, nanoscale electronic, high
rangeefficiency
of fields from industrial
electron emitters,applications
to research such as high-strength
including biosensors, drug materials,
delivery nanoscale
systems,electronic,
and tissuehigh
efficiency electron emitters, to research including biosensors, drug
scaffold reinforcement [27]. CBNs have enjoyed this wide application due to their delivery systems, and tissue scaffold
unique
reinforcement
combinations [27].ofCBNs have enjoyed
mechanical, this wide
optical, thermal, andapplication due to their
electrical properties. unique
Graphene, forcombinations
example, is of
mechanical,
incredibly optical,
strongthermal,
with theand electrical
tensile strength properties.
of ~130 GPa, Graphene, for example,
for a defect free singleislayer,
incredibly
Young’s strong
modulus
with the tensile of strength
1 Tpa, third of order
~130 elastic stiffness
GPa, for a defect≈ 2 Tpa;
free and
singleat the same
layer, time is very
Young’s flexible
modulus ofand lightthird
1 Tpa,
order (0.77
elasticmgstiffness
m−2) with ≈a2very
Tpa;high
andspecific surface
at the same areais(~2630
time m2 g−1) [28].
very flexible andFigure 3 shows
light (0.77 mgthem−CBNs
2 ) withthat
a very
have been significantly used and2can−potentially 1 be used for biofuel-fed fuel cells.
high specific surface area (~2630 m g ) [28]. Figure 3 shows the CBNs that have been significantly
One of the CBNs characteristics, which is important in fuel cell applications, is high electronic
used and can potentially be used for biofuel-fed fuel cells.
conductivity. In the past, this could be achieved by amorphous carbon, which possesses not only
One of the CBNs characteristics, which is important in fuel cell applications, is high electronic
good conductivity but also large surface area and porosity. With CBNs, not only is the conductivity
conductivity.
much more In the past, this
increased, butcould be achieved
also the weight and bysize
amorphous
of electrodecarbon,
couldwhich possesses
be extremely not only
reduced. Forgood
conductivity
instance,but also large
electronic surface
transport in area
carbon and porosity.ballistically
nanotubes With CBNs, not over
occurs only long
is thenanotube
conductivitylengthsmuch
more dueincreased,
to theirbut alsoone-dimensional
nearly the weight andstructure,
size of electrode
thus enablingcouldthembe extremely
to carry high reduced.
currentFor instance,
without
heating
electronic effect. When
transport employed
in carbon as electrode
nanotubes materials
ballistically for fuel
occurs cells,
over a network
long nanotube of CNTs
lengthsas catalytic
due to their
supports not only enhances the active surface area, mass transport
nearly one-dimensional structure, thus enabling them to carry high current without heating of fuels, conductivity, and much effect.
more resistance to corrosion but also is involved in the catalytic mechanism
When employed as electrode materials for fuel cells, a network of CNTs as catalytic supports not only (with or without
precious metals) toward desired products with faster reaction kinetics, leading to higher power
enhances the active surface area, mass transport of fuels, conductivity, and much more resistance to
density and energy conversion efficiency [29–34]. Comparable and higher catalytic effects compared
corrosion but also is involved in the catalytic mechanism (with or without precious metals) toward
to that of traditional Pt/C have been also observed in the case of graphene doped/co-doped with
desired products with faster reaction kinetics, leading to higher power density and energy conversion
various heteroatoms and their composites with metal/metal oxides and/or conducting polymers.
efficiency
Table[29–34].
1 provides Comparable
a summary andof higher
the most catalytic effects compared
recent achievemenst of CBNs,to that of traditional
from 2010 (top) toPt/C 2017have
been (bottom),
also observed in cathodic catalytic systems that deal with oxygen reduction reaction, a main limitingtheir
in the case of graphene doped/co-doped with various heteroatoms and
composites
factor to themetal/metal
with cell performance,oxidesespecially
and/or conducting
in the case polymers.
of microbialTable fuel 1cells
provides
(MFCs). a summary
Further of
applications
the most of carbon-based
recent achievemenst of nanomaterials
CBNs, from 2010 in anodic
(top) catalytic systems, which
to 2017 (bottom), deals with
in cathodic oxidation
catalytic systems
reactions
that deal with of biomass-based
oxygen reduction fuels are discussed
reaction, a maininlimiting
the coming sections.
factor to the cell performance, especially in
the case of microbial fuel cells (MFCs). Further applications of carbon-based nanomaterials in anodic
catalytic systems, which deals with oxidation reactions of biomass-based fuels are discussed in the
coming sections.
Sensors 2017, 17, 2587 5 of 21

Table 1. Summary of carbon-based nanomaterials (CBNs) recent achievements in microbial fuel cells (MFCs) towards enhanced cathode performance.

Reactor Type Anodic Supporting Materials Cathode Materials Power Density (mW m−2 ) Comparision to Pt/C or Bare Materials Ref.
250 mL double chambers Graphite granule Pt/C 1470 ± 10 - [35]
250mL double chambers Graphite granule Co3 O4 /N doped graphene 1340 ± 10 Comparable to Pt/C [35]
6 mL single chamber Carbon paper Co/Fe/N/CNTs 751 1.5 times > Pt/C [36]
80 mL double chamber Carbon fiber N-doped CNTs on C cloth 1600 ± 50 12.8% > Pt/C [37]
Single chamber Carbon felts Fe–N-functionalized graphene 1149.8 2.1 times > Pt/C [38]
Single chamber Carbon cloth Graphene supported Pt–Co 1378 Comparable to Pt/C [39]
Sediment MFCs Graphite felt Polyaniline-Graphene nanosheets 99 116 times > Graphite [40]
Double chamber - N/S co-doped carbon nanosheets 1500 Comparable to Pt/C [41]
15 mL sediment single chamber MWNT coating Graphite MWNT coating Graphite 214.7 ± 9.9 1.6 times higher than that of bare graphite [42]
Single chamber Carbon cloth Graphene/poly(3,4-ethylenedioxythiophene)/Fe3 O4 3525 8.2 times > Carbon cloth [43]
N-doped Graphene/CoNi alloy encased within
Double chamber Carbon brush 2000 Comparable to Pt/C [44]
bamboo-like CNTs
210 mL double chamber Carbon paper CNTs/Polypyrrole 113.5 Comparable to Pt/C [45]
Single chamber Graphite fiber brush Ag/Fe/N/C 1791 1.5 times > Pt/C [46]
20 mL single chamber N-Ni-carbon nanofibers N-doped polymer-Ni–carbon nanofibers 1690 ± 30 - [47]
1.5 L single chamber Carbon fiber Co-doped Carbon nanofibers 92 Stable more than 6000 h [48]
Sensors 2017, 17, 2587 6 of 21
Sensors 2017, 17, 2587 6 of 21

Sensors 2017, 17, 2587 6 of 21

Figure 3.
Figure 3. Carbon-based
Carbon-based nanomaterials
nanomaterialsthat have
that been
have and
been have
and potential
have to be
potential to used for biofuel-fed
be used for biofuel-fed
fuel cells.
fuel cells.

2. Direct EnergyFigure 3.Conversion

Carbon-basedChallenges
nanomaterialsandthatApplications of Carbon-Based
have been and have Nanomaterials
potential to be used for biofuel-fed
2. Direct Energy Conversion
fuel cells.
Challenges and Applications of Carbon-Based Nanomaterials
2.1. Cellulose and Cellulosic Biomass Fuel Cells
2.1. Cellulose
2. Direct and Cellulosic
Energy Biomass
Conversion Fuel Cellsand Applications of Carbon-Based Nanomaterials
Challenges
Since more than 70% of biomass is made of cellulose, the most obvious biomass target for
Since more
biofuel-fed thanis 70%
fuel cells of biomass
cellulose. However, is cellulose,
made of acellulose, the most
straight chain naturalobvious
polymer biomass
(C6H10Otarget
5)n, is
for
2.1. Cellulose and Cellulosic Biomass Fuel Cells
biofuel-fed
insoluble infuel water cells
andisascellulose.
well as mostHowever, cellulose,
other organic a straight
solvents, mustchain natural
first be polymer
hydrolyzed to a(C 6 H10 O5 )n ,
soluble
Since more than 70% of biomass is made of cellulose, the most obvious biomass target for
issubstrate
insoluble that can be oxidized on the surface of anode electrode or to be taken up by the cell. Sugano to
in water and as well as most other organic solvents, must first be hydrolyzed
biofuel-fed fuel cells is cellulose. However, cellulose, a straight chain natural polymer (C6H10O5)n, is
aetsoluble substrate
al. succeeded that can be
in dissolving pureoxidized
celluloseonpowder
the surface of anode
in alkaline solutionelectrode
using aor to be taken up by
freezing/thawing
insoluble in water and as well as most other organic solvents, must first be hydrolyzed to a soluble
the cell.
process Sugano
and oxidizinget al.
it succeeded
on gold in dissolving
electrode as anode, pure cellulose
producing the powder
first directin
substrate that can be oxidized on the surface of anode electrode or to be taken up by the cell. alkaline
cellulose solution
fuel cell with
Sugano using
apower density
freezing/thawing of 44 mW
processm −2 (150 mV and ~450 mA m−2) [15]. Recognizing the high-cost and active
and oxidizing it on gold electrode as anode, producing
et al. succeeded in dissolving pure cellulose powder in alkaline solution using a freezing/thawing the first direct
surfaceprocess
cellulose limitation
fuel cell of the
and with gold-based
power
oxidizing density
it on electrodes,
of 44 mW
gold electrode m−2 (150
further
as anode, research
mV and
producing was
the done
~450
first mAbym
direct −2 )same
the [15].
cellulose group. They the
Recognizing
fuel cell with
utilized
high-cost functionalized
poweranddensity 44 carbon
activeofsurfacemWlimitationnanotubes
m (150
−2 mV theas
ofand ~450catalytic system,
mA m )electrodes,
gold-based −2 which
[15]. Recognizing is research
the
further capable
high-costwasof
andcleaving
active by the
done
same surface They
ß-1,4-glycosyl
group. limitation
bonds ofofthe
utilized thesugar
gold-based electrodes,
substrate
functionalized in the further
carbon same research
way
nanotubes as as was
natural done by
enzyme,
catalytic the cellulase
system, same group.
which isThey
(Figure
capable4) of
[49]. utilized functionalized carbon nanotubes as catalytic system, which is capable of cleaving
cleaving ß-1,4-glycosyl bonds of the sugar substrate in the same way as natural enzyme, cellulase
ß-1,4-glycosyl bonds of the sugar substrate in the same way as natural enzyme, cellulase (Figure 4)
(Figure[49].
4) [49].

Figure 4. Proposed biomimetic functionalized carbon nanotubes-based catalyst for direct breaking
Figure 4. Proposed biomimetic functionalized carbon nanotubes-based catalyst for direct breaking
Figure
down of Proposed
4.cellulose. biomimetic
Reprinted withfunctionalized
permission from carbon nanotubes-based
ref. [49]. Copyright 2011,catalyst
RSC. for direct breaking
down of cellulose. Reprinted with permission from ref. [49]. Copyright 2011, RSC.
down of cellulose. Reprinted with permission from ref. [49]. Copyright 2011, RSC.
Sensors 2017, 17, 2587 7 of 21

Since cellulose is biodegradable, another approach is using microbial fuel cells (MFCs).
This system uses microorganism(s) to hydrolyze cellulose, then oxidize its metabolites, whichare
at the same time electrochemically active. Thus, they act as electron acceptors. Based on this
principle, Rismani-Yazdi and colleagues succeeded in using rumen microbiota containing both strict
and facultative anaerobes, which effectively hydrolyze cellulose, and conserve energy via anaerobic
respiration or fermentation [50]. This cellulose-fed MFCs, consisting of two chambers separated
by Ultrex proton-exchange membrane and graphite plates as electrodes gained a maximum power
density of 55 mW m−2 (1.5 mA, 313 mV) and the current was sustained for over two months with the
periodically supplementation of cellulose as electron donor. To improve the power density, Rezaei
et al. increased the cathode volume (three times larger), ammonia-treated carbon cloth (type A;
E-Tek, United States) with a total surface area of 1.13 cm2 was used as anode and five two strands of
15-cm-long carbon fiber were used as cathode [51]. Using this modified U-tube MFC and strain ATCC
13047T, a power density of 5.4 ± 0.3 mW m−2 could be achieved with much higher current density
(119 ± 2.2 mA m−2 ). There have been other designs from MFCs, such as air-cathode one chamber
MFCs or three stacked MFCs (achieved 490 mW m−2 (0.5 mA)), which not only simplified the FCs
but also increased the power density up to 1070 ± 15 mW m−2 [52–54]. On the other hand, the use of
carbon-based nanomaterials as supporting matrix for catalytic systems in direct cellulose/cellulosic
biomass-based fuel cells is still under intense research. This is because (i) there are difficulties in
breaking down cellulose, leading to low power density; and (ii) the high-cost of CBNs compared to
the cost of the outcome products. However, with recent developments in preparation processes much
lower cost of CBNs could be expected, opening better and more economically viable opportunities for
further development of direct cellulose fuel cells.

2.2. Starch-Based Fuel Cells

Starch is made of linear/helical amylose and branched amylopectine molecules. It is much
simpler to process than cellulose because it is easier to degrade, thus requires relatively less energy
to process. It changes from a crystalline to an amorphous structure and becomes soluble in water by
simple heating at low temperature. Different from cellulose, starch is one of the main components in
many edible biomass sources, thus, less work has been done to develop a device to extract energy
directly from starch. Focus of the research therefore has been set on the wastewater produced from the
processing of starch-contained biomass.
Spets et al. proposed a direct fuel cell operating with Pt–Pd as an anodic catalyst and the cathode
electrode contained a catalyst loading of 3.15 mg cm−2 of Cobalt-meso-tetraphenylporphyrine (CoTPP)
in concentration of 18% on carbon and of 17.5 mg cm−2 of MnCo2 O4 . This direct fuel cell, operating
with 10 g L−1 of starch in 2 M KOH, although utilized noble metal as catalyst, could not gain more
than 1 mA cm−2 at 51 ◦ C [55]. The reason for the low current density is low degradability of starch
under alkaline conditions, therefore not many active groups that are able to be oxidized on electrode
surface are produced. Still, the current density of starch is much higher than that of cellulose, due
to a relatively higher solubility of the starch in alkaline electrolyte. Another attempt to increase the
performance of direct starch fuel cell was made by Liu et al., utilizing polyoxometalate (POM) solution
without any solid metal or metal oxide as catalyst. This liquid-catalyst fuel cell achieved 34 mW cm−2
(at 150 mA cm−2 ) and 22 mW cm−2 (at 135 mA cm−2 ), respectively, when starch and cellulose were
used directly as fuels at 80 ◦ C [56]. However, since the liquid catalyst is mixed with fuels, it is not yet
clear how the regeneration of the catalyst could be done for the next load of new fuels.
The first MFC based on starch was developed by Niessen and colleagues [57]. They specially
designed an anode made of platinum covered by poly(tetrafluoroaniline) and living cells of the
biocatalysts Clostridium butyricum or C. beijerinckii. This MFC (100 mL in volume) attained maximal
power density of 1.87 mW cm−2 , and a corresponding to a current of 4 mA cm−2 at a potential of
~473 mV from 10 g L−1 of starch. Herrero-Hernandez et al. alternatively used E. coli in a mediatorless
microbial fuel cell to generate electricity from starch extracted from boiled potatoes. A maximum
Sensors 2017, 17, 2587 8 of 21

power density of 502 mW m−2 at a current of 0.90 mA was obtained [58]. The improvement of
power density in this case was attributed to the use of platinized titanium mesh electrode which
was approximately one order of magnitude greater than the maximum output achieved with Pt strip
electrodes (66 mW m−2 ). It is obvious that the catalytic surface area in this case plays a big role in
improved performance. Although active surface area can be increased significantly with the use
of CBNs, such as carbon nanotubes, not much work has been done to utilize CBNs in starch-based
fuel cells.

2.3. Alginate Fuel Cells

The usage of biomass as fuel has to deal with a crucially controversial problem before seeing its
future. This problem is that its growth is able to consume farmland for food production leading to
potential detrimental changesin food supply and therefore increasing food price. To solve this before it
becomes an issue, inedible lignocellulosic biomass materials, marine macroalgae, commonly known
as “seaweed” stands out as a prominent candidate because they require no fresh water, fertilizer, or
land and do not interfere with the human food chain [59]. Energy extraction process from macroalgae
can be divided into two stages: (i) release sugars inside the algae cell walls, which is composed
mainly of alignate; mannitol and glucan and then (ii) use algae-derived sugars as fuels for energy
conversion devices such as fuel cells. Current studies mostly focus on finding an appropriate microbial
platform that converts these sugars into ethanol, which is then used as a fuel in combustion engines
and/or direct fuel cell systems [60]. Despite the successful engineered microbe systems, which can
almost completely degrade glucan and mannitol, the straightforward degradation of alginate remains
a hurdle. The first attempt was carried out with gold sheet as anodic electrode, similar to the above
discussed direct cellulose fuel cells. However, the power density was low (25 mW m−2 at 220 mV
and 110 mA m−2 ) [61]. Gold as anodic catalyst can attain high open circuit voltage (620 mV) but
the potential steeply decreases with increasing current density, due to insufficient alginate active
adsorption on the Au surface and thus results in high internal resistance. To increase the active surface
area and mass transfer of substrate, gold nanoparticles were synthesized and then drop casted on
functionalized multi-walled carbon nanotubes, leading to 2.1 times higher power density and much
lower internal resistance [61]. Although it is still immature, the electrochemical oxidation of alginate in
CBNs-based fuel cells has been shown to result in oxidized alginate that is usable for cell and tissue
engineering, thus opens a chance for simultaneous production of energy and feedstock materials from
inedible biomass.

3. Indirect Energy Conversion Challenges and Applications of CBNs

As discussed above, the energy conversion and therefore power density from lignocellulosic
biomass is extremely small for practical applications, although it requires less treatment steps and
energy loss during degradation process. Researchers therefore focus on the potentially higher power
density generating fuel cells from biomass-derived and smaller molecules such as monosaccharides,
ethanol and hydrogen. From these studies, CBNs have been successfully utilized as supporting
materials for catalysts, contributing to the improvements of power density and low cost of expected
fuel cells as commercial products.

3.1. Monosaccharide Fuel Cells

Glucose, the most well known monosaccharide, is attractive as a fuel for fuel cells, not for energy
production applications but for medical applications such as cardiac pacemakers, artificial hearts and
glucose sensors [62]. This research trend is still growing, and most of the work has been devoted to the
development of catalytic systems that can work in physiological conditions. The power density in this
type of fuel cell is not a target for the research, but the stability of the catalysts in implants environment,
either noble metal-based or enzymatic types [63]. To date, even pure noble metals suffer from absorbed
poisons and intermediates, resulting in performance degradation [64]. The same problem appears
Sensors 2017, 17, 2587 9 of 21
Sensors 2017, 17, 2587 9 of 21

problems, CBNs, mainly functionalized carbon nanotubes and graphene-based materials were used
in the case of monosaccharide-fed fuel cells as energy conversion devices in addition to the high
as the catalytic backbone for noble nanoparticles to (i) increase the active surface area; (ii) decrease
cost of catalytic materials versus energy proficiency. In order to solve these problems, CBNs, mainly
noble metal loading; leading to lower cost and (iii) increase stability of catalyst by fine-tuning
functionalized carbon nanotubes and graphene-based materials were used as the catalytic backbone
catalytic mechanism [65].
for noble nanoparticles to (i) increase the active surface area; (ii) decrease noble metal loading; leading
It has been shown that the functionalized multi-walled carbon nanotubes (fMWCNTs), which
to lower cost and (iii) increase stability of catalyst by fine-tuning catalytic mechanism [65].
contain a lot of –COOH and –OH groups, are hydrophilic and prevent the aggregation of
It has been shown that the functionalized multi-walled carbon nanotubes (fMWCNTs), which
nanoparticles during activation and thermal treatment processes, thus maintain high total active
contain a lot of –COOH and –OH groups, are hydrophilic and prevent the aggregation of nanoparticles
surface area [66,67]. The use of fMWCNTs as supporting matrix resulted in higher catalytic
during activation and thermal treatment processes, thus maintain high total active surface area [66,67].
performance, indicated by ~150–200 mV negative shifts of oxidation peaks compared to that from
The use of fMWCNTs as supporting matrix resulted in higher catalytic performance, indicated by
bare gold electrodes, meaning that relatively less activation energy is needed to overcome.
~150–200 mV negative shifts of oxidation peaks compared to that from bare gold electrodes, meaning
Furthermore, different monosaccharides exhibit different oxidation peaks in terms of position,
that relatively less activation energy is needed to overcome. Furthermore, different monosaccharides
shape, and current intensity [66]. Since the structures of these monosaccharides differ only at the
exhibit different oxidation peaks in terms of position, shape, and current intensity [66]. Since the
orientation of –OH groups on C2 and C3, the different oxidation potentials suggest that the specific
structures of these monosaccharides differ only at the orientation of –OH groups on C2 and C3,
structural attachments of intermediate complexes on gold nanoparticles decorated on fMWCNTs
the different oxidation potentials suggest that the specific structural attachments of intermediate
(AuNPs/f-MWCNTs) induce different activated energies for further oxidization. By dispersing
complexes on gold nanoparticles decorated on fMWCNTs (AuNPs/f-MWCNTs) induce different
AuNPs on fMWCNTs, the gold surface is much more active and respond more sensitively to the
activated energies for further oxidization. By dispersing AuNPs on fMWCNTs, the gold surface is
change in –OH orientation, leading to higher oxidation current density than that of bare gold
much more active and respond more sensitively to the change in –OH orientation, leading to higher
electrode. Consequently, the power density generated from AuNPs/fMWCNTs-based FCs is more
oxidation current density than that of bare gold electrode. Consequently, the power density generated
than twice of that from Au-based FCs (Figure 5). With this approach, two homemade small (2 mL in
from AuNPs/fMWCNTs-based FCs is more than twice of that from Au-based FCs (Figure 5). With this
volume, Figure 6) glucose or fructose fuel cells could run a led lamp that requires a working voltage
approach, two homemade small (2 mL in volume, Figure 6) glucose or fructose fuel cells could run
of 2 V [66,68].
a led lamp that requires a working voltage of 2 V [66,68].

Figure 5. Power density of monosaccharide-based fuel cells using AuNPs/fMWCNTs as anodic

Figure 5. Power density of monosaccharide-based fuel cells using AuNPs/fMWCNTs as anodic
catalyst in comparison with bare Au electrode. Reprinted with permission from ref. [66]. Copyright
catalyst in comparison with bare Au electrode. Reprinted with permission from ref. [66].
2011, Elservier.
Copyright 2011, Elservier.
Sensors 2017, 17, 2587 10 of 21
Sensors 2017, 17, 2587 10 of 21

Figure 6. (A) Air-glucose fuel cell prototype and (B) its performance in terms of polarization and
Figure 6. (A)power
Air-glucose fuel cell prototype and (B) its performance in terms of polarization and
density. Glucose concentration was 0.4 M in 0.3 M NaOH and 0.1 M PBS; temperature was
power density.
25 ° Glucose concentration
C. The working voltage of thewas
LED 0.4
lampM in20.3
was M NaOH
V. Reprinted withand 0.1 Mfrom
permission PBS;ref.temperature
[66]. was
25 ◦ C. The working
Copyright 2011, Elsevier.
voltage of the LED lamp was 2 V. Reprinted with permission from ref. [66].
Copyright 2011, Elsevier.nanomaterials are not only excellent supports for noble catalytic metals, but also
Carbon-based
for enzymatic systems in enzymatic-based FCs (EFCs). Different from the direct oxidation of fuels on
Carbon-based nanomaterials
catalytic metal arecenters
surface, the active not only excellent
in enzymes are buriedsupports for by
and insulated noble catalytic
the protein shell, metals, but
leading tosystems
also for enzymatic detrimentalineffect of electron transferFCs
enzymatic-based between
(EFCs).the enzyme and thefrom
Different currentthe collector.
direct oxidation
Based on electron transfer mechanism, EFCs can be divided into two types: Direct electron transfer
of fuels on catalytic metal surface,
(DET) and mediator the active
electron transfer (MET). DETcentersrequiresin both
enzymes are buried
proper orientation of anandenzyme,insulated
as by the
protein shell,well
leading
as the to detrimental
distance between the effect
activeofcenter
electron transfer
as electron donorbetween the enzyme
and the electrode and the current
as electron
acceptor.
collector. Based This distance
on electron has to bemechanism,
transfer within ~2 nm. SinceEFCs the can
electronbe transfer
divided rateinto
depends
twoexponentially
types: Direct electron
on this distance, it is commonly believed that MET which uses mediator cofactor to shuttle electrons
transfer (DET)fromandenzyme mediator
to electrode,electron transfer
might be the (MET).
better choice of theDET requires
two. However, CBNsbothhaveproper orientation of
altered this
an enzyme, mindset.
as wellCNTs, as the distance between
graphene-based materials andthemostactive center
recently asnanodots
carbon electron donor
(CNDs) have and
beenthe electrode
used to create
as electron acceptor. Thisdirect “wiring”has
distance systems
to besince their size
within ~2is nm.
quite close
Since to the
that of enzymes transfer
electron [69–74]. Forrate depends
instance, Ivnitski et al. demonstrated direct glucose oxidation on glucose oxidase (GOx) immobilized
exponentially on on this distance,
CNT-modified porousitbioanode
is commonlyas well as believed
the direct that METof which
reduction useslaccase
oxygen with mediator[70]. cofactor to
shuttle electrons
Althoughfrom enzyme
direct enzymatic tooxidation
electrode, might
of glucose behighly
is still the betterdebatedchoice of the two.
and the mechanism However,
is not yet CBNs
clearly proven, the fact that glucose oxidase is able to simultaneously
have altered this mindset. CNTs, graphene-based materials and most recently carbon nanodots undergo DET with the
electrode and to retain its catalytic activity has been confirmed by the cyclic voltammetry study of
(CNDs) havethebeen used to create
GOx immobilized directof“wiring”
on the surface CNTs modified systems
electrodes since
in thetheir
absence size
and is quite
in the close to that of
presence
enzymes [69–74]. For This
of glucose. instance, Ivnitski et
GOx–CNTs-based al. demonstrated
membraneless FC achieved direct glucose
an open oxidation
circuit potential on glucose
of ~400 mV oxidase
vs Ag/AgCl. Graphene was used in the same way as CNTs to
(GOx) immobilized on CNT-modified porous bioanode as well as the direct reduction of oxygen co-immobilize with GOx on anode and
bilirubin oxidase (BOD) for cathodic catalyst, resulting in a maximum power density of about 24.3 ±
with laccase 4[70].
μW cmAlthough direct
−2. This is nearly enzymatic
three times greater thanoxidation
that of the of glucose isbiofuel
SWCNT-based still cell
highly
[71], anddebated
the and the
mechanism is not yet clearly
performance proven,
of the graphene the cell
biofuel factlasted
thatfor glucose
a week. oxidase
Instead of is able to
graphene simultaneously
sheets, Zheng and undergo
DET with thecolleagues
electrode made
and usetoofretain
nanographene plateletsactivity
its catalytic (NGPs) tohas immobilize GOx and BOD,
been confirmed byand the achieved
cyclicavoltammetry
maximum power density of 57.8 μW cm−2 [73]. A higher open circuit potential (0.93 V) and a
study of the maximum
GOx immobilized
power densityon theμW
of 40.8 surface
cm−2 (atof CNTs
0.41V) weremodified electrodes
achieved recently by Zhaoinand thecolleagues
absence and in the
presence of glucose.
with DET of This
GOxGOx–CNTs-based
and BOD at Carbon Nanodots membraneless
(CNDs) electrodesFC achieved an open circuit
[72]. This CND-based glucose potential of
FCs surpassedGraphene
~400 mV vs Ag/AgCl. the power density
was used couldin bethe
achieved
samefrom wayMET-type
as CNTs BFCs
to in which an oxygenwith GOx on
co-immobilize
independent Pyrroloquinoline Quinone (PQQ)–GDH–MWCNT-electrode coupled with a
anode and bilirubin oxidase (BOD) for cathodic catalyst, resulting in a maximum power density of
about 24.3 ± 4 µW cm−2 . This is nearly three times greater than that of the SWCNT-based biofuel
cell [71], and the performance of the graphene biofuel cell lasted for a week. Instead of graphene sheets,
Zheng and colleagues made use of nanographene platelets (NGPs) to immobilize GOx and BOD, and
achieved a maximum power density of 57.8 µW cm−2 [73]. A higher open circuit potential (0.93 V) and
a maximum power density of 40.8 µW cm−2 (at 0.41V) were achieved recently by Zhao and colleagues
with DET of GOx and BOD at Carbon Nanodots (CNDs) electrodes [72]. This CND-based glucose FCs
surpassed the power density could be achieved from MET-type BFCs in which an oxygen independent
Pyrroloquinoline Quinone (PQQ)–GDH–MWCNT-electrode coupled with a BOD–MWCNT-electrode
were used (23 µW cm−2 ). The success of CBNs and enzymatic systems has meant that the use of noble
metals could be avoided, thus reducing significantly the cost of the final product. However, when the
Sensors 2017, 17, 2587 11 of 21

power density is the target, the composite of CBN with noble metals increases power density even
more. By anchoring AuNPs on reduced graphene oxide, followed by electrochemical polymerization
of neutral red (RGO/AuNPs/PNR) before drop-casting GOx, the power density gained from this
electrode was increased up to 176 µW cm−2 [74]. Zebda and colleagues, thus far, have reported the
highest power density. In their work, glucose oxidase and laccase were mechanically compressed
into CNT disks [75]. This led to homogenous dispersion of biomolecules within the CNT supporting
matrix. However, in the presence of oxygen within the non-wired GOx matrix, a possible formation of
hydrogen peroxide may degrade GOx performance. To overcome this problem, catalase was added to
the GOx–NT mixture before compression to decompose H2 O2 . This improved mediatorless glucose
biofuel cell generated a high power density up to 1.3 mW cm−2 and achieved an open circuit voltage
of 0.95 V. Moreover, the fuel cell performance remained stable for a month and delivered 1 mW cm−2
power density under physiological conditions (5 × 10−3 M glucose, pH 7).
When using for MET-based glucose fuel cell, CNTs-based FCs achieved up to 740 µW cm−2 in
the presence of 0.015 M glucose, which is tenfold higher than that of the same catalytic system using
traditional carbon fiber supporting matrix [76]. Kim et al. recently reported a simple method for
simultaneous CNT dispersion and sequential enzyme adsorption, precipitation, and crosslinking that
resulted in 7.5 times higher power output than that from the covalently-attached GOx on acid-treated
CNTs and GOx activity remained stable for 270 days [77].

3.2. Bio-Ethanol Fuel Cell

Bioethanol is now practically being used as a blend or fossil petrol substitute. For example, in
the USA the use of ethanol as a blended component has increased dramatically from about 1.7 billion
gallons in 2001 to about 14.4 billion in 2016 [78]. However, the “food-versus-fuel” issue is still
problematic because ethanol is mostly produced from edible feedstock such as corn. Researchers are
therefore, targeting non-edible feedstock including waste from agriculture and forestry and brown
macroalgae to produce second generation of bioethanol [79,80]. This is done by fermentation followed
by distillation and drying process. Burning ethanol in the way it has been done with fossil fuel,
however, is not the best and “green” way to utilize energy from ethanol. Direct ethanol fuel cells
(DEFCs) have been reviewed in detail by Kamarudin et al. and Badwal et al., revealing the current
challenges, developments and applications of DEFCs [81,82]. However, there is lack of information
about CBNs’ studies. An effective yet durable catalytic system for ethanol oxidation reaction in PEMFC
has been the target of research and could be divided into two different categories. First, the focus
was on understanding the catalytic mechanisms; increasing the durability and decreasing the cost of
noble-based materials by making alloys such as Sn/SnO2 /Pt. One of the main advantages of using
these non-noble metal/metal oxide is to create –OH absorption, thus enhancing the removal of COad
and other poisonous species out of Pt surface (Figure 7). In some special cases, such as Pt–S—Rh/C
catalysts, it has been reported that C–C cleavage could be achieved, producing CO2 as final product
instead of acetic
Sensorsacid [83].
2017, 17, 2587 12 of 21

Figure 7. Ethanol oxidation reaction pathway.

Figure 7. Ethanol oxidation reaction pathway.
The second and recently explored type of research is the use of CBNs as supporting matrix
which can act much less the same as the alloyed systems in terms of detoxification; or be combined
with alloyed catalyst to further increase the electrocatalytic activities toward complete ethanol
oxidation [84–94]. Goel and Basu reported a comparative study of CBNs-supported Pt–Ru and
revealed that the maximum power density to be in the order Pt–Ru/MCN (mesoporous carbon
nitride) > Pt–Ru/t-MWCNTs > Pt–Ru/MWCNTs > Pt–Ru/Vulcan-XC [84]. The highest power density
of 61.1 mW cm−2 at 100 °C, 1 bar pressure with catalyst loading of 2 mg cm−2 using 2 M ethanol feed
Sensors 2017, 17, 2587 12 of 21

The second and recently explored type of research is the use of CBNs as supporting matrix
which can act much less the same as the alloyed systems in terms of detoxification; or be combined
with alloyed catalyst to further increase the electrocatalytic activities toward complete ethanol
oxidation [84–94]. Goel and Basu reported a comparative study of CBNs-supported Pt–Ru and
revealed that the maximum power density to be in the order Pt–Ru/MCN (mesoporous carbon nitride)
> Pt–Ru/t-MWCNTs > Pt–Ru/MWCNTs > Pt–Ru/Vulcan-XC [84]. The highest power density of
61.1 mW cm−2 at 100 ◦ C, 1 bar pressure with catalyst loading of 2 mg cm−2 using 2 M ethanol
feed could be achieved. Our group alternatively fabricated conducting polymers composited with
low-loading Pt nanoparticles decorated on functionalized carbon nanotubes (Pt/MWCNTs) and
examined catalytic activities toward ethanol oxidation reaction [88]. In native form, polyaniline
(PANI) and polypyrrole (PPY) individually deposited on Pt/MWCNTs exhibited lower catalytic
activities over ethanol oxidation than the bare Pt/MWCNTs. However, the co-assembled PANI–PPY
deposited on Pt/MWCNTs significantly enhanced both the reaction kinetics and stability of catalysts
compared to the one without conducting polymers as revealed by electrochemical measurements.
These enhancements were attributed first to the active interface between Pt nanoparticles and
conducting polymers, and second to the interaction between PANI and PPY and their contribution
to the reaction on Pt surface. Based on the understanding from co-assembled PANI–PPY, it was
suggested that the functional groups on polymer backbone may have a crucial effect during the
ethanol oxidation reaction. To explore their roles, MWCNTs were used as a highly conductive and
chemically inert backbone to attach the desired functional groups. –COOH and –NH2 groups were
chosen since both of them could create the dissociative adsorption with water molecules via H-bonding
and simultaneously induce charged non-covalent interactions [89,90]. The results showed that the
COOH–MWCNTs supported Pt/MWCNTs enhanced the ethanol oxidation reaction kinetics by about
three times more than NH2 —-MWCNTs and the bare Pt/MWCNTs, in terms of oxidation current
density and stability. The results indicated that functional groups functionalized on supporting matrix
for catalytic enhancement on Pt active sites play a very important role. In addition, they clearly
showed the differences in the effect from specific functional groups depending on their chemical
species. We also studied the various structural assemblies between f–MWCNTs and Pt/MWCNTs and
how they affected kinetic reactions (Figure 8).
Sensors 2017, 17, 2587 13 of 21

Figure 8.
Figure 8. Development
Development of anodic catalytic
of anodic catalytic materials
materials for
for enhanced
enhanced direct
direct ethanol
ethanol fuel
fuel cells
cells using
using
co-assembled PANI–PPY and functionalized carbon nanotubes matrices.
co-assembled PANI–PPY and functionalized carbon nanotubes matrices.

Instead of CNTs, graphene oxide was exploited and successfully applied as matrix to attach
noble metals such as Pt and Pd [85]. Kumar et al. reported a simple procedure to synthesize
large-scale perforated graphene oxide nanosheets-Pd hybrids (Pd–FP–rGONSs) using microwave
irradiation. The prepared Pd–FP–rGONSs were composed of a large amount of structural surface
defects which created porosity inside the nanosheets, leading to lower charge transfer resistance and
Sensors 2017, 17, 2587 13 of 21

Instead of CNTs, graphene oxide was exploited and successfully applied as matrix to attach noble
metals such as Pt and Pd [85]. Kumar et al. reported a simple procedure to synthesize large-scale
perforated graphene oxide nanosheets-Pd hybrids (Pd–FP–rGONSs) using microwave irradiation.
The prepared Pd–FP–rGONSs were composed of a large amount of structural surface defects which
created porosity inside the nanosheets, leading to lower charge transfer resistance and negative
oxidation peak shifts. As a result, Pd–FP–rGONSs performed much better in terms of current density
(10.2 mA cm−2 ) than Pd/MWCNTs (0.4 mA cm−2 ) at the same initial ethanol concentration. To date,
however, there is no published work yet on the final prototype and its power density of DEFCs, which
use graphene oxide-based catalyst.
Similar to other types of biofuel cells, ethanol biofuel cells can be divided into two main
types: Enzyme-based and microbial-based FCs. The former one uses alcohol dehydrogenase to
catalyze the oxidation of ethanol, and faces similar electron transfer problems as the above-discussed
enzyme-based glucose BFCs. Additionally, the use of NAD-dependent enzymes such as ADH
needs to regenerate NAD+ species and restore the enzyme cycle. Last but not least is the
high over potential of NADH (more than 1 V) and the passivation of the electrode surface
such as noble metals. To overcome this problem, the electrode surface was modified with
MWCNTs to mediate the electrocatalytic oxidation of NAD-dependent enzymes [91], decreasing
the high overvoltage for NADH oxidation of 0.16 V [92]. Besides decreasing the over voltage of
NAD+ /NADH system, modification of electrode by CNTs has been proved to enhance the efficiency
of enzyme in power density and electron transfer kinetics [93]. Gouranlou et al. recently reported
an ethanol–oxygen biofuel cell design in which PDDA/ADH/PDDA/HOOC–MWCNTs/PMG/GC
and PDDA/Lac/PDDA/HOOC-MWCNTs/PMG/Gr operated as bioanode and biocathode,
respectively (PDDA and PMG stand for polydiallyldimethylammonium chloride and polymethylene
green, respectively). HOOC–MWCNTs beside PDDA has been proved to provide a suitable
microenvironment to preserve the activity of ADH and laccase [80]. In the optimized condition,
this BFC produced a power density of 3.98 mW cm−2 with the OCP of 0.504V. With the use of
COOH–MWCNTs as cathodic catalyst, the power density was increased much more than that of
traditional Pt/C electrode, which could achieve only 1.713 mW cm−2 and OCP of 0.281 V [94].

3.3. Bio-Hydrogen Fuel Cell

Among all types of fuel cells, the hydrogen fuel cell is the most successful one in terms of power
density, hence high possibilities for wide application. Although a hydrogen fuel cell is a zero emission
energy device, it is still not a true “green” option since the hydrogen production is mostly from
large-scale natural gas reforming processes. Furthermore, storage and transportation issues still
present problems for the commercialization of hydrogen as a fuel [95]. To solve the production
problem, much works have been devoted to developing bio-H2 production technologies based
on either “classical” metabolically engineered microorganism or mixed bacterial consortia under
controlled nutrient condition to modify gene expression towards increased H2 production [96–100].
These approaches enable H2 production from not only pure biomass-based fuel such as glucose but
also raw and complex materials such as starch or wastewater. On the other hand, direct connection of
biohydrogen reactors and onsite energy conversion devices could be an answer to storage and transport
problems. Most recently, Wenzel and colleagues reported a MFC coupled to biohydrogen reactor as
a feasible technology to increase energy yield from cheese whey. Effluent from dark fermentation of
cheese whey was successfully used to produce a maximal power density of 439 mW m−2 [100].
Unfortunately, hydrogen production processes from biomass often involve the use of
microorganisms, which require voluminous bioreactors to ensure a sufficient production rate; and
a filter to remove unwanted gases. Researchers so far have tried to integrate the whole fermentation
system and a proton-exchange-membrane fuel cell (PEMFC) for electricity generation [101–104].
Still much extra energy is needed to maintain the bioreactor, filter, and the pumping system. In our
group, we demonstrated a compact single chamber-based fuel cell that changes the anode chamber of
 439 mW m−2 [100].
Unfortunately, hydrogen production processes from biomass often involve the use of
microorganisms, which require voluminous bioreactors to ensure a sufficient production rate; and a
filter to remove unwanted gases. Researchers so far have tried to integrate the whole fermentation
system and a proton-exchange-membrane fuel cell (PEMFC) for electricity generation [101–104].
Sensors 2017, 17, 2587
Still
14 of 21
much extra energy is needed to maintain the bioreactor, filter, and the pumping system. In our
group, we demonstrated a compact single chamber-based fuel cell that changes the anode chamber
the hydrogen
of the hydrogen PEMFC
PEMFCto an anaerobic
to an anaerobic fermentation
fermentationbioreactor (Figure
bioreactor (Figure9).9).This
Thiscombination
combinationgreatly
greatly
reduced the external energy needed for maintaining the bioreactor, condenser and/or
reduced the external energy needed for maintaining the bioreactor, condenser and/or filter, for filter, for storing
gases
storingunder
gases high pressure
under (optional)(optional)
high pressure and for the
andhumidifier before pumping
for the humidifier the hydrogen
before pumping into the
the hydrogen
PEMFC.
into the Consequently, the total useful
PEMFC. Consequently, energy
the total from
useful the whole
energy system
from the increased
whole [105,106]. [105,106].
system increased

Figure9.9.Fuel
Figure Fuelcell
cellcomponents
componentsand
andthe
theassembly
assemblyof
ofhydrogen
hydrogenfuel
fuelcell
cellwith
withbioreactor.
bioreactor.

However,
However,due duetotodirect
directattachment
attachmentofofbioreactor
bioreactortotoanode,
anode,unwanted
unwantedgases
gasesand
andmicroorganisms
microorganisms
ininthe
theanode
anodechamber
chamber could enterenter
could the pores of the of
the pores electrodes via watervia
the electrodes vapor,
waterresulting
vapor, inresulting
a significant
in a
reduction
significantofreduction
gas dispersion
of gasinside the catalyst
dispersion inside layers and lower
the catalyst catalytic
layers activity.
and lower To address
catalytic activity.this
To
problem, doped
address this polyaniline
problem, doped(PANI) nanofibre-based
polyaniline composites withcomposites
(PANI) nanofibre-based Pt/fMWNTs were
with used instead
Pt/fMWNTs of
were
traditional
used instead PtNPs
of on carbon black
traditional PtNPsto achieve
on carbonmuch higher
black to conductivity,
achieve muchhigher
highercatalytic activity under
conductivity, higher
humid condition,
catalytic activitymore access
under to the gases
humid resulting
condition, morefrom a three-dimensional
access to the gasesstructure
resultingwith morea
from
active sites, and morestructure
three-dimensional resistancewith
to corrosion. The hybrid
more active structure
sites, and more was made intotwo
resistance ways: multilayered
corrosion. The hybrid
and core-shell. The maximum power density from the former (733 mW m−2 of PANI/Pt/fMWNTs)
was more than twice compared to that of the later one (352.75 mW m−2 of Pt/fMWNTs@PANI).
The enhanced performance in case of multilayer structure was made possible by the active contact
between the PANI nanofiber layer and Pt/fMWNTs that facilitates selective hydrogen absorption
and increases conductivity at high humidity [106]. The power density of this biohydrogen fuel cell
was much higher than the MFCs using CNTs/PANI composite as anode material (42 mW m−2 ) in
Qiao et al. [107], and comparable with other single chambered, glucose-fed mediatorless MFCs using
E. coli or mixed anaerobic consortia [108–112].
Another approach is using H2 /O2 biofuel cells, in which hydrogenase is used as anodic catalyst
and multicopper oxidase as cathodic catalyst. It is estimated that the maximum current density
would be 1 mA cm−2 , when the enzyme forms an electrocatalytically active monolayer on a planar
electrode. Thus, three-dimensionally structured CBNs have been explored to increase enzyme loading
and efficient orientation of enzyme towards enhanced electron transfer rate. The power density of
FCs has reached 8 mW cm−2 and the current density is up to 10 mA cm−2 [113–117]. The fuel in
these cases was mostly pure H2 or mixture of pure H2 and O2 or air, which is different from biogas
generated directly from biohydrogen reactors, and therefore out of our scope in this mini review.
Nevertheless the development of H2 /O2 biofuel cells towards the use of biomass-generated hydrogen
Sensors 2017, 17, 2587 15 of 21

could be a promising future study. Details about recent studies on CBNs in H2 /O2 biofuel cells were
thoroughly reported in a review article by Mazurenko et al [118].

4. Concluding Remarks
It is obvious that the future of biofuels as alternative to fossil fuel requires technological
development of efficient but low-cost biofuel-based energy conversion devices. Biofuel-fed fuel
cell, which can work at low temperature, are non-toxic, have low carbon emissions, and utilize
a wide range of biofuel sources in both pure and non-pure forms (e.g., from wastewater), is therefore
a promising technology. However, there are still many challenges that need to be overcome before
reaching practical and commercial states. As presented above, although the direct biofuel-fed fuel cells
generate electricity directly from main biomass components such as cellulose, starch, and alginate,
the power density is too low, thus the only possible application is coupling with the wastewater
treatment process to extract energy simultaneously with the degradation of biomass as organic wastes.
Along with the development of breakdown technology, many more efforts have been devoted to
develop fuel cells that indirectly extract energy from biomass i.e., from secondary fuels such as
monosaccharides, bioethanol, and biohydrogen. So far, the power density of such biofuel-fed fuel
cells could reach the demand of portable devices but fuel cell fabrication cost and its durability
are still the main hurdles. For both direct and indirect biofuel-fed fuel cells, the main challenges
are high cost yet low durability of catalytic systems, resulting in limited fuel cell performance.
To replace expensive noble metal-based catalysts, carbon-based nanomaterials have been explored
and contributed significantly to the improvement of fuel cell performance. When used as supporting
matrix, carbon-based nanomaterials such as graphene, CNTs, and their functionalized materials create
a 3-D architecture for anchoring metal nanoparticles/microorganism/enzyme with much higher
surface area to volume ratio, enhanced electrolyte diffusion and simultaneously act as electron transfer
network. Furthermore, functionalized carbon-based nanomaterials have been proven to be involved
in removing toxic intermediates on the embedded nanoparticles in case of metallic catalysts and
enhanced immobilization and stabilization of enzymatic systems, resulting in improvement of catalytic
durability. As a result of using CBNs, the power density of biofuel-fed FCs increased from nW to mW
cm−2 , open circuit potential increased to more than 1 V (fucose and glucose FCs) and life-time of fuel
cell performance was significantly extended. Based on these achievements, future research trends
could be seen targeting (i) deeper understanding and optimizing current successful CBNs for each type
of biofuel-fed FCs; and (ii) discovery of new materials such as composites of well-established and/or
entirely new metal-free CBNs towards low-cost but long-term large scale practical applications.

Author Contributions: The paper is a review articles drawn from our group and other groups, as shown by the
citations. H.Q.L., M.C.V. and E.T. discussed the subject matter, H.Q.L drafted the paper, M.C.V. revised the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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