Modeling of an

Enzyme-Based Biofuel Cell Anode

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 Background and Motivation
Enzyme-based biofuel cells (EBFCs) use biomass and
specific enzymes known as biocatalysts in order to convert
chemical energy into electrical energy.
At the anode of an EBFC, the biomass (substrate) is
oxidized to produce protons and electrons. Mediators are
used in the anode to shuttle the electrons from enzymes to
electrodes. At the cathode, the oxidant (oxygen) reacts with
the protons and electrons to produce water.
In this work, transport and reaction of species in an EBFC
anode is simulated.
The reactions occurring in the biofuel cell anode are
modeled using the Chemistry interface.
Mass transport and charge transport in the anode are
modeled using the Transport of Diluted Species and
Secondary Current Distribution interfaces, respectively.
 Model
A 1D isothermal model for an EBFC anode is presented.
The enzymatic reaction for the oxidation or reduction of the
substrate (S) is linked to the electrochemical reduction or oxidation
of the mediator (Mred/Mox) using the electrode as the final electron
acceptor or donor. Enzyme-catalyzed electrochemical oxidation or
reduction of the substrate is referred to as bioelectrocatalysis.
The enzyme
total reaction occurring within the anode is written as follows,
S P + nH+ + ne-
The reaction
k1f mechanism
k2f is given as follows,
S + Eox k1b ES Ered + P + H+
k3f
k3b
Ered + Mox Eox + Mred
iox

Mred ired Mox + e-

 Model
The model consider eight species, substrate (S), oxidized enzyme
(Eox), reduced enzyme (Ered), enzyme-substrate complex (ES),
oxidized mediator (Mox), reduced mediator (Mred), product (P) and
hydrogen ions (H+).
Mass balance equations are written for the above species,
considering that the species S, P and H+ are mobile, and that the
species ES, Eox, Ered, Mox and Mred are immobile. Reactions
source/sinks terms for each species are appropriately accounted
for.
Charge balance equations are written for electronic and ionic
charge transport in the electrode along with the electrochemical
charge transfer reaction.
The model is based on a study presented in Energies, 5, 2524-
2544 2012.
 Model Setup
An EBFC anode of width L filled with enzyme-substrate-mediator complex
is considered (x=0 corresponds to the current collector).

The Chemistry interface is used to specify the chemical reactions occurring

in the EBFC anode.

The Transport of Diluted Species interface is used to model mass balance

of the eight species in the EBFC anode. Note that the reaction source/sink
terms due to the chemical reactions can be directly transferred from the
Chemistry interface. The reaction source/sink terms due to the
electrochemical reaction is modeled using the Porous Electrode Coupling
feature.

The Secondary Current Distribution interface is used to model charge

conservation in the EBFC anode. Concentration dependent kinetics is used
for the electrochemical charge transfer reaction involving the mediator.
 Results: IV curve

The IV curve (current density vs applied voltage) shows the voltage losses in
the bioelectrode. At low applied potential, activation voltage losses are
present. At intermediate applied potentials, ohmic and activation losses occur.
At high applied potentials, ohmic, activation and concentration losses occur.
 Results: Dynamic current density response
Low applied potentials High applied potentials

At low values of the applied potential, the current density increases with time and then
stabilizes at a constant values.
At high values of the applied potential, the current density initially increases and then
decreases slowly with time, finally settling to a constant value.
 Results: Concentration of substrate
V_cell = -0.15V V_cell = 0.1V

At applied potential of -0.15V, it takes a longer time for a steady state substrate distribution to be
established in the bioelectrode. However, the substrate is available at high concentrations all
throughout the domain.
At applied potential of 0.1V, a steady state substrate distribution is established relatively quickly
in the bioelectrode. Also, the substrate concentration drops to zero close to the current collector.
Results: Concentration of oxidized enzyme (Eox)
V_cell = -0.15V V_cell = 0.1V

At applied potential of -0.15V, concentration of E_ox decreases with time, with the
concentration profile shifting to the left, and eventually going to zero.
At applied potential of 0.1V, concentration of E_ox decreases with time, with the concentration
profile shifting to the left, and eventually attaining a stable value of concentration.
 Results: Concentration of enzyme substrate
complex(ES)
V_cell = -0.15V V_cell = 0.1V

The concentration of ES has a peak-type distribution in the bioelectrode.

 Results: Concentration of reduced mediator
(Mred)
V_cell = -0.15V V_cell = 0.1V

At applied potential of -0.15V, concentration of M_red drops from 10mM to 7mM at 10s. At about
50s, concentration of M_red remains close to 10mM because concentration of M_ox is low.
At applied potential of 0.1V, concentration of M_red drops from 10mM to ~6.5mM at 10s. At
about 50s, the concentration of M_red drops further to ~4.4mM.