Research Article

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 9360−9368 pubs.acs.org/journal/ascecg

Efficient Hydrogen Production by Direct Electrolysis of Waste

Biomass at Intermediate Temperatures
Takashi Hibino,*,† Kazuyo Kobayashi,† Masaya Ito,† Qiang Ma,† Masahiro Nagao,† Mai Fukui,‡
and Shinya Teranishi‡
†
Graduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, Japan
‡
Soken Inc., Nisshin, Aichi 470-0111, Japan
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Biomass has been considered as an alternative

feedstock for energy and material supply. However, the lack of
high-efficiency and low-cost processes for biomass utilization and
Downloaded via UNIV OF SYDNEY on March 10, 2024 at 11:57:03 (UTC).

conversion hinders its large-scale application. This report

describes electrochemical hydrogen production from waste
biomass that does not require large amounts of energy or high
production costs. Hydrogen was produced by the electrolysis of
bread residue, cypress sawdust, and rice chaff at an onset cell
voltage of ca. 0.3 V, with high current efficiencies of approximately
100% for hydrogen production at the cathode and approximately
90% for carbon dioxide production at the anode. The hydrogen
yields per 1 mg of the raw material were 0.1−0.2 mg for all tested fuels. Electrolysis proceeded continuously at plateau voltages
that were proportional to the current. These characteristics were attributable to the high catalytic activity of the carbonyl-group
functionalized mesoporous carbon for the anode reaction, and that the major components of biomass such as cellulose, starch,
lignin, protein, and lipid were effectively utilized as fuels for hydrogen production.
KEYWORDS: Waste biomass, Electrolysis, Hydrogen production, Mesoporous carbon

■ INTRODUCTION
The Paris Agreement was adopted at COP 21 in 2015, so that
both developed and developing countries aim to reduce
greenhouse gas emissions by tens of percent by 2030.1−3 As
part of this effort, the transition from fossil fuels to biofuels has
been accelerated, due to their much lower carbon footprint.4−6
However, biofuels are not yet competitive with fossil fuels in
terms of cost and performance. To realize the commercializa-
tion of biofuels, various problems must be addressed, such as
the high total cost for biomass utilization, low efficiency of the
conversion process into fuels, and insufficient reactivity of
biomass raw materials.7,8 The use of waste biomass such as
agricultural and food residues, harvested weeds, and wood chips
as feedstock decreases the raw material costs. Furthermore, if
hydrogen is directly produced from such waste biomass, then
processing costs and fuel availability could be significantly
improved.
A major challenge for direct hydrogen production from
biomass is how to gasify carbohydrates, proteins, and fats in the
feedstock with high efficiency and low cost. The gasification of
biomass to hydrogen is generally conducted using water vapor
or air as a gasification agent at temperatures of 800 °C or
higher, followed by the separation and purification of
hydrogen,9,10 which is usually energy expensive. Therefore, it
is necessary to develop an alternative approach that leads to
high-efficiency and cost-effective conversion of biomass into
hydrogen. Furthermore, to obtain a high hydrogen yield, this
approach should be fully applied to all biomass components,
including starch, cellulose, hemicellulose, lignin, protein, and
fat.
Biomass electrolysis enables hydrogen production at onset
cell voltages of less than 1 V, depending on the fuel species.
Although bioethanol is one of the most promising fuels for
electrolysis,11,12 this fuel has the limitations inherent in the
hydrolysis and fermentation of biomass, which requires special
and expensive procedures for processing. Biomass raw
materials, including switchgrass and wood sawdust, can also
be used as fuels for electrolysis; however, polyoxometalates or
ferric chloride are required to function as redox intermedi-
ates.13,14 The raw material previously reacts with the
intermediate to form a reduced intermediate in a tank outside
the electrolysis cell. The reduced intermediate is subsequently
supplied to the anode and releases a proton to the cathode by
the application of a voltage. We have recently reported another
type of biomass electrolysis that does not require pretreatment
of the raw material.15 This method involves the addition (batch
operation) or supply (flow operation) of a mixed solution of
newspaper and phosphoric acid (H3PO4) to the anode,
Received: April 15, 2018
Revised: May 22, 2018
Published: May 24, 2018

© 2018 American Chemical Society 9360 DOI: 10.1021/acssuschemeng.8b01701

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ACS Sustainable Chemistry & Engineering
Figure 1. Characterization of the unheated KB, and KB heated at 600 and 1000 °C: (a) TPD-MS spectra of CO and CO2 for the unheated KB. (b)
BJH pore size distributions. (c) FT-IR spectra. (d) XPS spectra.
followed by operation of the electrolysis cell at temperatures
between 100 and 150 °C. Cellulose16,17 and lignin18 are
hydrolyzed to mono- and disaccharide derivatives and aliphatic
molecules, respectively, by H3PO4 at the anode. These products
react with water (H2O) to form protons and carbon dioxide
(CO2) at the anode, and hydrogen at the cathode. For example,
cellulose electrolysis is expected to proceed as follows.
Anode: C6H12O6 + 6H 2O → 6CO2 + 24H+ + 24e−
(1)
Cathode: 24H+ + 24e− → 12H 2 (2)
In this study, we present hydrogen production by the direct
electrolysis of waste biomass. First, the anode material is
modified to replace the expensive conventional Pt/C anode
with metal-free mesoporous carbon. The electrolysis character-
istics of the pure biomass components are then evaluated using
the optimized anode. Bread residue, cypress sawdust, and rice
chaff are then examined as biomass feedstock in both batch-
and flow-type electrolysis cells. The hydrogen yield per weight
of biomass is determined in the batch cell. Continuous
hydrogen production is demonstrated in the flow cell.
■
MATERIALS AND METHODS
Materials. A Sn0.9In0.1P2O7-polytetrafluoroethylene (PTFE) mem-
brane was selected as the electrolyte, due to its high proton
conductivity (>0.01 S cm−1) at temperatures between 100 and 150
°C, and a wide voltage range of 0−2 V.19−21 PTFE powder (0.04 g)
was added to 1 g of Sn0.9In0.1P2O7 powder, kneaded using a mortar and
pestle, and then cold-rolled to a thickness of 170 μm using a laboratory
rolling mill. Ketjen black (KB; EC-600JDK) was purchased from Akzo
Nobel and modified as follows. The carbon (1 g) was stirred in 50 mL
of 24% nitric acid (HNO3) at room temperature for 74 h. After
filtering and washing treatment, the residual carbon was dried under
vacuum at 120 °C for 6 h. The oxygenated carbon was subsequently
heated at 600 °C for 4 h in a flow of argon (Ar), unless otherwise
stated. The heat-treated carbon was dispersed with a small amount of
85% H3PO4 (Wako Chemicals) in a mixer (Thinky AR-100) for 30
min. The slurry obtained was deposited on the surface of carbon fiber
paper (Toray TGP-H-090). A commercially available Pt/C (Pt
loading: 2 mg cm−2, Electrochem) anode was used as a control
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anode and as the cathode. Bread, cypress wood, and rice chaff were
milled into powder form using a household mixer (Zojirushi BM-
RT08-GA). Cellulose (Wako Chemicals), starch (Wako Chemicals),
lignin (Tokyo Chemical Industry), protein (Wako Chemicals), and
lipid (Wako Chemicals) were used as model biomass components
without further purification.
Characterization. Temperature-programmed desorption (TPD)
analysis for the oxygenated carbon sample was performed using online
mass spectrometry (MS; Pfeiffer Vacuum Thermostar GSD301). 0.5 g
of the sample powder was packed in a glass tube and supplied with Ar
at a flow rate of 60 mL at 100 °C until the signals of carbon monoxide
(CO; m/z = 28) and CO2 (m/z = 44) were stable. The sample was
subsequently heated to the desired temperature in an Ar flow at a rate
of 10 °C min−1. The pore characteristics of the carbon samples were
determined by nitrogen (N2) adsorption at liquid N2 temperature (Bel
Japan BELSORP18PLUS-HT). The specific surface area was
calculated using the Brunauer−Emmett−Teller (BET) method from
adsorption data in the relative pressure range of 0.001 to 0.3. The
mesopore volume distributions were determined using the Barrett−
Joyner−Halenda (BJH) method. Functional group profiles for the
carbon samples were obtained using Fourier-transform infrared
spectroscopy (FT-IR; Agilent Excalibur FTS-4000). The chemical
charge states of C 1s for the carbon samples were analyzed using X-ray
photoelectron spectroscopy (XPS; VG Escallab220i-XL). Morpho-
logical changes before and after heating the biomass raw materials
were observed using scanning electron microscopy (SEM; Keyence
VE-8800). The quantities of hydrogen and CO2 evolved from the
cathode and anode, respectively, were monitored using mass
spectrometry (MS).
Electrochemical Measurements. Electrolysis tests of batch and
flow cells were performed as follows (Figure S1). The anode (area: 1.1
cm2) was used for both cells. The cathode area was adjusted to 0.5 cm2
for the batch cell and 0.2 cm2 for the flow cell, due to the difference in
size between the cells. Details of the procedures have been described
previously.15 The current density was normalized with respect to the
area of the cathode. In the batch cell, fuels (7.5−60.0 mg) were mixed
with appropriate quantities of 85% H3PO4 in a weight ratio of fuel to
85% H3PO4 of 1:15. After deposition of the sample mixtures onto the
surface of the anode, the electrolyte membrane was sandwiched
between the anode and cathode. The anode was attached to a stainless
steel current collector (SUS316, 16 mm diameter; Hohsen) and then
sealed using a PTFE gasket (Nitto Denko) with PTFE tape (Nitto
Denko). In the flow cell, a liquid mixture of fuel and 85% H3PO4 (fuel
concentration: 0.79 wt %) was pumped to the anode chamber with
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Figure 2. Electrolysis characteristics of the batch cells using the unheated KB anode, and the KB anodes heated at 600 and 1000 °C: (a) I−V curves
and (b) impedance spectra of the cells at 150 °C using the unheated KB anode, and the KB anodes heated at 600 and 1,000 °C. (c) I−V curves and
(d) impedance spectra of the cell using the 600 °C-heated KB anode between 100 and 150 °C. Data for the batch cell using the Pt/C anode are also
included.
flow channels at an injection rate of 16 mL h−1 using a syringe feeder
(YMC YPS-301). The anode chamber was sealed using the PTFE
gasket with an elastomeric O-ring. The cathode was supplied with Ar
at a flow rate of 100 mL min−1 in both cells. All electrochemical
measurements were conducted using a potentiostat-galvanostat
(Solartron 1287) and an impedance/gain-phase analyzer (Solartron
1260). Current−voltage (I−V) curves were recorded potentiostatically
at a scan rate of 20 mV s−1. Voltage−time curves were acquired
galvanostatically in the current range of 0.05−0.20 A cm−2. Impedance
spectra were obtained at a bias voltage of 0.4 V in the frequency range
of 0.1−106 Hz.
■ RESULTS AND DISCUSSION
Anode Design. For oxygen-functionalized carbon anodes,
the redox pair between carbonyl (CO) and phenol (C
OH) groups is one of the most important hydrogen carrier
sites.22,23 The origin of this redox reaction is ascribed to the
following equilibrium reaction:
CO + H+ + e− ⇌ COH (3)
In contrast, carboxyl groups (COOH) have little reversible
redox ability and are also one of the least conductive functional
groups.24,25 Accordingly, the overpotential and resistive loss of
the anode would be decreased by enhancement of the density
of carbonyl groups relative to carboxyl groups on the carbon
surface. Figure 1a shows TPD profiles for CO (m/z = 28) and
CO2 (m/z = 44) in a flow of Ar with the HNO3-treated KB.
CO2 attributed to carboxyl group desorption26,27 was observed
in the temperature range of 150 to 550 °C, whereas CO
originating from carbonyl group desorption26,27 became more
intensive at 550 °C or higher, which reflects the difference in
thermal stability between the two functional groups. This also
implies that carboxyl groups are more preferentially eliminated
from the carbon surface than carbonyl groups by heat treatment
of the oxygenated KB at temperatures between 500 and 600 °C
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in an Ar flow. Therefore, the oxygenated KB was heat-treated at
600 and 1000 °C for test and control experiments, respectively.
Figure 1b shows pore size distributions for the unheated KB,
and the KB heated at 600 and 1000 °C. Similar characteristics
were found for the three samples; the average mesopore
diameter and volume were 6.2, 7.1, and 6.8 nm and 2.6, 2.6, and
2.7 cm3 g−1 for the unheated KB, and the KB heated at 600 and
1000 °C, respectively. The BET specific surface areas for the
samples were also almost unchanged among the samples, and
were 1864, 1772, and 1828 m2 g−1, respectively. These results
demonstrate that even heat treatment at 1000 °C does not
cause significant structural deformation of the KB. As shown in
Figure 1c, the FT-IR spectrum for the HNO3-treated KB
indicated the presence of carbonyl groups (absorption at 1720
cm−1) and phenol groups (absorption at 1190 cm−1).28,29 The
intensities of these absorption bands decreased with an increase
of the heating temperature. To obtain additional information
regarding the effect of the heat treatment on the functional
groups, XPS measurements were conducted for the KB before
and after the heat treatment. Figure 1d revealed less intensive
carbonylic CO (287.4 eV) and carboxylic COO (288.5 eV)
peaks30 upon an increase of the heating temperature, the extent
of which was much greater for the COO peak (ca. 44% down)
than for the CO peak (ca. 10% down). It was thus confirmed
that the relatively carbonyl group-rich carbon sample was
successfully obtained by heat treatment at 600 °C, as expected
from the TPD profile.
Electrolysis of pure cellulose (15 mg) was conducted for the
unheated KB anode, and the KB anodes heated at 600 and
1000 °C. Figure 2a shows I−V curves for the electrolysis cells at
a temperature of 150 °C. The onset cell voltage of electrolysis
was ca. 0.3 V for all the tested anodes, whereas the current
density at each cell voltage increased in the order: 600 °C-
heated anode >1000 °C-heated anode > unheated anode.
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Figure 3. Electrolysis characteristics of the batch cell using various model biomass components as fuels at 150 °C: (a) I−V curves and (b) impedance
spectra. (c) Formation rates of hydrogen at the cathode, and CO2 and NO2 at the anode. Theoretical values are included for comparison. (d)
Formation rates of hydrogen, CO2, and NO2 during electrolysis of protein for 600 s at 0.25 A cm−2.
Impedance spectra for the electrolysis cells were measured at a
bias voltage of 0.4 V (Figure 2b), and curve fitting was
performed based on an equivalent circuit model (Figure S2).
The cell with the unheated anode presented a typical Nyquist
plot, the intersection of which with the abscissa at a high
frequency of 40,000 Hz was assigned to the ohmic resistance of
the cell; the semicircular arcs at medium (3−40 000 Hz) and
low (0.1−3 Hz) frequencies correspond to the polarization and
mass-transfer resistances of the electrodes, respectively. This
cell also possessed the largest ohmic and polarization
resistances among the tested cells, which can be explained by
the presence of large amounts of carboxyl groups introduced
onto the surface through the HNO3 treatment. It is most likely
that these functional groups lead to poor electrical contact
between the carbon particles. In contrast, the heat treatment of
such an oxygenated anode, especially at 600 °C, significantly
decreased both the ohmic and polarization resistances due to
the removal of carboxyl groups without significant loss of
carbonyl groups from the carbon surface. Subsequent
experimental trials were assessed using the 600 °C-heated
anode because it was reasonable to conclude that there was no
optimal condition for the carbonyl group at temperatures above
600 °C.
Figure 2c shows I−V curves for the electrolysis cell using
cellulose as the fuel at temperatures between 100 and 150 °C.
The I−V curve was dependent on the operation temperature,
which resulted in I−V characteristics recorded at 150 °C that
were comparable to the characteristics observed for the Pt/C
anode under the same conditions. This temperature depend-
ency was attributable mainly to the polarization and mass-
transfer resistances of the anode, rather than the ohmic
resistance of the cell (upper panel of Figure 2d); the ohmic
resistance remained almost unchanged and the polarization
resistance decreased from ca. 1.5 to ca. 0.3 Ω cm2 with an
increase in the temperature from 100 to 150 °C. The mass-
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transfer resistance obtained at 100 °C was too large for
quantification. A similar temperature dependency of the
impedance was observed for the Pt/C anode; however, at all
temperatures, the semicircular arcs related to the mass-transfer
resistance were larger than those recorded for the optimized
mesoporous carbon anode (lower of Figure 2d). This is
probably due to the difference in the mesopore volume
between the carbon species used. Vulcan XC-72R used as the
carbon support of the Pt/C anode has a total pore volume of
0.32 cm3 g−1,31 which is approximately one-eighth of that (2.6
cm3 g−1) observed for the KB anode. Therefore, the
decomposition products of cellulose may not diffuse easily in
such a small space.
Electrolysis of Pure Biomass Components. The
electrolysis of expected biomass components other than
cellulose was also investigated at a temperature of 150 °C.
Figure 3a shows I−V curves using various pure components
(15 mg of each) as fuels. The current densities recorded with
the components at each voltage were one and 2 orders of
magnitude greater than those obtained without fuel, which
indicates that these components are viable electrolysis fuels.
The electrolysis onset cell voltage was ca. 0.3 V for cellulose,
starch, and protein and ca. 0.4 V for lignin and lipid. We cannot
calculate the theoretical onset cell voltage for the electrolysis
reactions, because these fuels are partially decomposed to
various products at the anode. However, as shown in Figure 2c,
the onset cell voltage using the 600 °C-heated KB and Pt/C
anodes was independent of the anode species, but dependent
on the temperature. Therefore, it is most likely that the onset
cell voltage is determined by a thermodynamic factor rather
than a kinetic factor. Another important result was the
dependency of the I−V characteristics on the component
species: cellulose = starch > protein > lignin = lipid. The
internal resistances of the cells with the component fuels were
compared using impedance measurements to better understand
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Figure 4. Photographs and SEM micrographs of (a, b, and c) bread, (d, e, and f) cypress, and (g, h, and i) rice chaff impregnated with H3PO4,
followed by heat treatment at 125 °C.
this dependency. As shown in Figure 3b, the impedance spectra
revealed three distinctive features. First, similar polarization and
mass-transfer resistances were observed for cellulose (1.9 Ω
cm2) and starch (1.3 Ω cm2), which suggests a similarity of the
decomposition products (mono- and disaccharides) for these
components. Second, protein showed somewhat larger polar-
ization and mass-transfer resistances (6.2 Ω cm2) than those
acquired for cellulose and starch, which is attributable to the
difference in the reducibility of the functional group in the
molecule between the carbonyl group in glucose and the
carboxyl group in amino acid. Third, the polarization and mass-
transfer resistances obtained for lignin (92.7 Ω cm2) and lipid
(157.6 Ω cm2) were much larger than those recorded for the
other components. These results reflect that the two
components are more acid-insoluble than the other compo-
nents, which leads to a reduction of available small molecule
fuels at the anode. Figure 3b also showed that the ohmic
resistance of the cell was especially large with the use of lignin
as a fuel. Approximately 60 wt % solid residue was observed
with the lignin fuel, which was identified as unreacted lignin, as
previously reported.18 Therefore, the large ohmic resistance
observed for lignin is caused by poor electrical contact at the
interface between the anode and electrolyte, due to the
presence of the solid residue.
Figure 3c shows hydrogen formation rates from the cathode
at a temperature of 150 °C, including the theoretical values
(black dashed line) calculated according to Faraday’s law, based
on the two-electron reaction represented in Reaction 2. The
observed rates agreed approximately with the theoretical values
for all tested components, which demonstrates that the current
efficiency for hydrogen production was 95−106% (see
Supporting Information). Figure 3c also shows CO2 and NO2
formation rates from the anode. The theoretical rates shown by
the red dashed line in Figure 3c were calculated under the
assumption that a carbon or nitrogen atom in the fuel is
oxidized to a CO2 or nitrogen dioxide (NO2) molecule, and
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four protons with two oxygen atoms in the fuel and H2O
molecules through the following four-electron reaction.
C or N in fuel + 2O in fuel and H 2O
→ CO2 or NO2 + 4H+ + 4e− (4)
No products, except CO2 (and only NO2 for protein), were
detected using MS. The current efficiency for CO2 formation
was estimated to be 90% for cellulose, 85% for starch, 74% for
lignin, 70% for lipid, and 67% for protein (see Supporting
Information). It is likely that oxide compounds not detected by
MS are also produced, especially from the lignin and lipid fuels.
However, the current efficiency for NO2 formation from
protein was 29%; therefore, almost all currents were considered
to be consumed for CO2 and NO2 formation at the anode.
(The formation rates of these gases in addition to hydrogen
during a short electrolysis period at 0.25 A cm−2 are shown in
Figure 3d). Based on these observations, it is concluded that
hydrogen is produced by the electrolysis of most of the biomass
components at onset cell voltages less than 0.5 V, which
motivates the development of waste biomass electrolysis
because these feedstock materials are composed mainly of the
biomass components tested.
Electrolysis of Waste Biomass. Bread, cypress, and rice
chaff were tested as fuels in a similar manner to that for
cellulose. The raw materials were used after being milled
without purification; therefore, the species, concentration, and
fragment length of the biomass components varied according to
the biomass source and the manufacturing process. This was
confirmed by room temperature SEM observations, as shown in
Figures 4b,e,h, where the sample powders were impregnated
with H3PO4. The three raw materials presented intrinsic
structures and sizes in the acid solvent. These samples were
gradually liquefied when heated to 125 °C, but not completely
dissolved at this temperature (Figures 4c,f,i). In particular, rice
chaff usually contains ca. 15% silicon dioxide,32 which further
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Figure 5. Electrolysis characteristics of the batch cell using the bread, cypress, and rice chaff fuels at 150 °C: (a) voltage−time curves and (b)
formation rates of H2 at the cathode, and CO2 and NO2 at the anode during continuous electrolysis of the bread, cypress, and rice chaff (15 mg of
each) at 0.1 A cm−2. (c) Voltage−time curves during continuous electrolysis of rice chaff with various weights at 0.1 A cm−2. (d) Weight of produced
hydrogen as a function of the rice chaff fuel weight. Data for the bread and cypress fuels are also included.

Figure 6. Electrolysis characteristics of the flow cell using the bread, cypress, and rice chaff fuels at 150 °C: (a) voltage−time curves, (b) impedance
spectra, and (c) formation rate of hydrogen at the cathode during continuous electrolysis of the bread, cypress, and rice chaff at 0.1 A cm−2. (d)
Voltage−time curves and formation rate of hydrogen during continuous electrolysis of the bread at various current densities.

interferes with dissolution of the fragments into the acid
solvent.
I−V curves using the biomass fuels were measured for batch
operation at a temperature of 150 °C (Figure S3a). Electrolysis
of the three fuels commonly began at cell voltages greater than
ca. 0.3 V and provided current densities of ca. 0.3 A cm−2 at a
cell voltage of 1 V, which are characteristics similar to those
recorded for cellulose and starch. This is supported by the high
content of starch or cellulose contained in these feedstock
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materials: 70% starch in bread32 and 35% and 38% cellulose in
cypress33 and rice chaff,34 respectively. Furthermore, the
magnitudes of the total impedance measured for the three
fuels (Figure S3b) were closer to those obtained for cellulose
and starch than those observed for protein, lignin, and lipid
(Figure 3b). Nevertheless, there were some differences in the
ohmic, polarization and mass-transfer resistances among the
cells with the three fuels, which is related to the differences in
the component species and their proportions in the fuels.32−34
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The amount of available fuel at the anode decreased with
time for galvanostatic batch-mode electrolysis, which leads to
the depletion of fuel at the anode at some point in time.
Therefore, the quantity of produced hydrogen per unit weight
of fuel can be estimated from the depletion time according to
Faraday’s law. Figure 5a,b shows voltage−time curves for the
cells and formation rates for hydrogen, CO2, and NO2,
respectively, during continuous electrolysis of the bread,
cypress, and rice chaff (15 mg of each) fuels with a current
density of 0.1 A cm−2 at 150 °C. The voltage−time curves were
characterized by plateau-like behavior in voltage and by a
subsequent rapid increase in voltage. These characteristics were
associated with the consumption and depletion of the fuel
because hydrogen and CO2 were constantly produced until the
plateau-like behavior of the voltage was terminated. (The
current efficiencies for hydrogen, CO2, and NO2 were 98−
101%, 83−99%, and 0−4%, respectively, during this period.)
The depletion time varied from 4000 to 6000 s, depending on
the fuel. Voltage−time curves obtained for rice chaff fuel with
various weights are displayed in Figure 5c. The cell voltage
recorded at each time before depletion of the fuel became
gradually decreased as the fuel weight increased, which is
reflected by an increase in the amount of the available fuel
captured by the anode, as will be discussed later. More
importantly, the depletion time lengthened as the fuel weight
increased. As a result, the weight of the hydrogen estimated
from the depletion time increased with the weight of the fuel
used, as shown in Figure 5d. Similar results were also obtained
for the bread and cypress fuels. Based on these results, 0.12−
0.22 mg, 0.14−0.24 mg, and 0.13−0.27 mg of hydrogen can be
produced from 1 mg of rice chaff, cypress, and bread,
respectively. It is also noted that the hydrogen yield per unit
weight of fuel tends to decrease with the weight of the fuel, due
to the deterioration of the utilization efficiency of the fuel at the
anode. This issue would be avoided by stirring the fuel in a
batch cell.
For batch-mode electrolysis, the voltage−time characteristics
could be improved by an increase in the weight of the fuel;
however, this effect decreased with time (Figure 5c), due to an
increase in the internal resistance of the cell. Accordingly,
continuous electrolysis characteristics of the present approach
were reassessed in flow mode. Figure 6a shows voltage−time
curves for the flow cells with the bread, cypress, and rice chaff
fuels with a current density of 0.1 A cm−2 at 150 °C. Data
recorded for the batch cell with the rice chaff fuel (60 mg) is
also included for comparison. The flow cells exhibited more
plateau-like voltages and lower cell voltages compared with the
results obtained for the batch cells. The sudden small increase
in voltage observed for the cypress fuel at ca. 2000 s is probably
due to unknown disturbance of the flow in the fuel nozzle. The
voltage plateau value at 3000 s was decreased in the order: rice
chaff > bread > cypress. Figure 6b shows impedance spectra for
the flow cells at a bias voltage of 0.4 V, including data obtained
for the batch cell with the rice chaff fuel. The difference in
impedance among the flow cells was too small to explain the
difference in the plateau voltage among them. However, note
that the impedances of the flow cells were much smaller than
that of the batch cell, which is ascribable to the constant supply
of fresh fuel to the anode in the flow process.
Figure 6c shows the rates of hydrogen formation during
continuous flow electrolysis under the same conditions as those
shown in Figure 6a. The formation rate for hydrogen was
almost the same in the three cells, which is in agreement with
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the theoretical rates calculated using Faraday’s law. The
electrical energy (kWh) consumed for electrolysis of each
fuel was calculated by integrating the area under the voltage−
time curve shown in Figure 6a and multiplying by the current.
These energies were then normalized according to the volumes
of experimentally produced hydrogen that were computed by
integration of the data shown in Figure 6c. The estimated
energies were 0.75, 0.50, and 0.83 kWh (Nm3)−1 for bread,
cypress, and rice chaff, respectively, which are much less than
those reported for water electrolysis [ca. 5 kWh (Nm3)−1] and
ethanol electrolysis [ca. 2 kWh (Nm3)−1].35 It is evident that
these significant energy savings could be achieved by
suppression of the cell voltage to ca. 0.4 V at 0.1 A cm−2. To
confirm such energy savings over a wide range of current
densities, electrolysis tests were performed using bread as the
fuel at various current densities. Figure 6d shows that the flow
cell provided voltages of 0.19, 0.35, and 0.53 V at 0.05, 0.10,
and 0.15 A cm−2, respectively. There is a proportional
relationship between the voltage and current density, where
the voltage increases by ca. 0.18 V per increment of 0.05 A
cm−2. However, at a current density of 0.20 A cm−2, the cell
voltage increased gradually from 0.64 to 0.72 V with time. The
initial voltage of 0.64 V is likely counted lower, compared with
the other data sets, while the terminal voltage of 0.72 V is in the
proportional region. One possible explanation for this behavior
is the temperature increase of the cell due to the heat generated
by the internal resistance of the cell, and subsequent recovery of
the temperature by an external heater. This also suggests the
possibility of the thermal sustainability of the cell that would
allow maintenance of the operation temperature in practical
applications.36 Figure 6d also shows that hydrogen was
produced in proportion to the current density and that the
rate recorded at each current density was approximately 100%
of that calculated using Faraday’s law. These results, together
with the results obtained for the batch cell, demonstrate that
the biomass feedstocks examined could be electrolyzed
efficiently and continuously in one step to hydrogen. It is
also concluded that any of these feedstock materials could be
utilized as fuels without significant differences in performance.
These characteristics are attributed to the effective production
of hydrogen from most of the raw material components.
In conclusion, hydrogen could be successfully produced
directly from biomass waste such as bread residue, cypress
sawdust, and rice chaff by electrolysis of a mixture of the raw
material and an 85% H3PO4 solvent at a temperature of 150 °C.
A carbonyl-group functionalized mesoporous carbon exhibited
electrochemically catalytic activity for the anode reaction that
was comparable to the activity observed for a Pt/C anode. The
current efficiency for hydrogen production reached approx-
imately 100% for all the tested fuels in both the batch and flow
operations. Note that the present approach provided more
significant savings in terms of the energy required for hydrogen
production compared to that reported for the electrolysis of
water and bioethanol.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b01701.
Illustrations of electrolysis cells, impedance spectra for
the cells at 150°C, and electrolysis characteristics of the
DOI: 10.1021/acssuschemeng.8b01701
ACS Sustainable Chem. Eng. 2018, 6, 9360−9368
ACS Sustainable Chemistry & Engineering
batch cell using the bread, cypress, and rice chaff fuels at
150 °C (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*T. Hibino. E-mail: hibino@urban.env.nagoya-u.ac.jp.
ORCID
Qiang Ma: 0000-0001-5993-819X
Author Contributions
All authors contributed to the paper and approved the final
version.
Funding
Nagoya University received grants from the Japan Society for
the Promotion of Science (JSPS): Nos. 26000008, 17H01895,
and 17K19087.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank Dr. Miki Niwa (Professor Emeritus, Tottori
University) for numerous useful discussions. This work was
supported by Kakenhi Grants-in-Aid (Nos. 26000008,
17H01895, and 17K19087) from JSPS.
■
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9368 DOI: 10.1021/acssuschemeng.8b01701

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