Solar-Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions

Article abstract of DOI:10.1002/anie.202006893

Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)-doped BiVO₄ (Mo:BiVO₄) photoanode and an inverse opal ITO (IO-ITO) cathode that gives rise to the coupling of peroxygenase and ene-reductase-mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO₄ are transferred to the IO-ITO and regenerate reduced flavin mononucleotides to drive ene-reductase-catalyzed trans-hydrogenation of ketoisophrone to (R)-levodione. Meanwhile, the photoactivated Mo:BiVO₄ evolves H₂O₂ in situ via a two-electron water-oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)-1-phenyl-1-hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar-powered electrons and water.

Full text of DOI:10.1002/anie.202006893

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Accepted Article
Title: Solar-Assisted eBiorefinery: Photoelectrochemical Pairing of
Oxyfunctionalization and Hydrogenation Reactions
Authors: Da Som Choi, Jinhyun Kim, Frank Hollmann, and Chan Beum
Park
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Angewandte Chemie International Edition
10.1002/anie.202006893
COMMUNICATION
Solar-Assisted eBiorefinery: Photoelectrochemical Pairing of
Oxyfunctionalization and Hydrogenation Reactions
[
a]
[a]
[b]
[a]
Da Som Choi, Jinhyun Kim, Frank Hollmann, and Chan Beum Park*
[
a]
D. S. Choi, J. Kim, Prof. Dr. C. B. Park
Department of Materials Science and Engineering
Korea Advanced Institute of Science and Technology
335 Science Road, Daejeon 34141 (Republic of Korea)
E-mail: parkcb@kaist.ac.kr
[
b]
Prof. Dr. F. Hollmann
Department of Biotechnology
Delft University of Technology
Van der Maasweg 9, 2629HZ Delft (The Netherlands)
Supporting information for this article is given via a link at the end of the document.
Abstract: Inspired by natural photosynthesis, biocatalytic
chose the ene-reductase of the Old Yellow Enzyme family from
Thermus scotoductus (TsOYE). TsOYEs catalyze the
asymmetric trans-hydrogenation of conjugated C=C double
photoelectrochemical (PEC) platforms are gaining prominence for
the conversion of solar energy into useful chemicals by combining
redox biocatalysis and photoelectrocatalysis. Here, we report a dual
biocatalytic PEC platform consisting of a molybdeneum (Mo)-doped
[
5]
bonds. The costly NAD(P)H cofactor can be omitted by
[
6]
regenerating the enzymes directly via reduced FMN. In the
proposed PEC scheme, the hierarchically structured ITO
electrodes reduce FMN redox mediators to promote the TsOYE-
catalyzed asymmetric reduction.
4 4
BiVO (Mo:BiVO ) photoanode and an inverse opal ITO (IO-ITO)
cathode that gives rise to the coupling of peroxygenase and ene-
reductase-mediated catalysis, respectively. In the PEC cell, the
4
photoexcited electrons generated from the Mo:BiVO are transferred
to the IO-ITO and regenerate reduced flavin mononucleotide to drive
ene-reductase-catalyzed trans-hydrogenation of ketoisophrone to
(R)-levodione. Meanwhile, the photoactivated Mo:BiVO
4
evolves
2 2
H O
in situ via a two-electron water oxidation process with the aid of
an applied bias, which simultaneously supplies peroxygenases to
drive selective hydroxylation of ethylbenzene into enantiopure (R)-1-
phenyl-1-hydroxyethane. This study shows that the deliberate
integration of PEC systems with redox biocatalytic reactions can
simultaneously produce valuable chemicals on both electrodes using
solar-powered electrons and water.
Biocatalytic photoelectrochemical (PEC) platforms convert solar
energy into fuels and value-added chemicals by mimicking
[
1]
natural photosynthesis. In the PEC platforms, photoexcited
charge carriers from photoelectrodes are transferred to the
catalytic center of oxidoreductases either directly or indirectly
Scheme 1. Schematic illustration of solar-assisted photoelectrochemical cell
for dual biotransformations. AaeUPO-mediated biotransformation is driven by
[2]
and promote biocatalytic reactions.
Compared with
in situ provision of H
2 2 4
O via two-electron water oxidation at the Mo:BiVO
photoanode under illumination. Simultaneously, the IO-ITO cathode reduces
homogeneous photocatalysis, biocatalytic PEC platforms can
minimize back electron transfer and electron-hole recombination
because of the configuration in which two electrodes are
FMN mediators by delivering the photoexcited electrons from the Mo:BiVO
4
photoanode, and then facilitates the TsOYE-catalyzed asymmetric reduction.
[
3]
connected by an external wire. Furthermore, spatial separation
of anodic and cathodic reactions in a PEC platform avoids
oxidation of reduced redox mediators or products at the anode.
In addition, the Fermi level of electrons can be modulated by the
external bias applied at the working electrode to drive a desired
For the photoelectrochemical oxidation of water, we
employed an n-type BiVO photoanode because it exhibits
promising selectivity toward two-electron water oxidation to
4
[
7]
generate hydrogen peroxide. In addition, the monoclinic BiVO
has intrinsic advantages such as sufficient light absorption
4
[
4]
redox reaction selectively.
To date, most PEC-based
[
8]
biotransformations have been focused on driving cathodic
reactions, whereas the anodic process has rarely been studied.
In this study, we paired enzymatic anodic and cathodic
reactions in a PEC platform to achieve solar-assisted dual
biotransformations. We constructed the PEC platform configured
capacity due to its narrower band gap of 2.4 eV, suitable
[
9]
valence band-edge positions, and superior photostability in
[
10]
aqueous media.
activity in H production, we used hexavalent molybdenum as
a metallic dopant for the BiVO photoanode. In situ production of
on a Mo:BiVO photoanode promotes peroxygenase-
To improve electrical properties and its
2
O
2
4
with a molybdeneum (Mo)-doped bismuth vanadate (Mo:BiVO
4
)
H
2
O
2
4
[
11]
photoanode and an inverse opal ITO (IO-ITO) electrode, as
depicted in Scheme 1. For the biocatalytic reductive reaction, we
catalyzed, selective oxyfunctionalization reactions. As a model
biocatalyst, we used the unspecific peroxygenase from
1
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COMMUNICATION
Agrocybe Aegerita (AaeUPO) to drive enantioselective
hydroxylation of ethylbenzene to (R)-1-phenyl-1-hydroxyethane.
[
12]
We synthesized a high surface area IO-ITO electrode as
a cathode for electron transport to the FMN mediator. IO-ITO
films were fabricated on an F-doped SnO
through a colloidal co-assembly proces using ITO nanoparticles
<50 nm diameter) and polystyrene spheres (800 nm diameter).
After removal of the sacrificial polystyrene template,
mesoporous ITO framework is formed surrounding
2
(FTO) substrate
(
a
interconnected macroporous voids (Figure 1a and S1). By
controlling the amount of polystyrene-ITO dispersion cast on the
FTO substrate, we were able to tune the thickness of the IO-ITO
film approximately from 5 to 21 μm (Figure S2). We estimated
the relative electrochemically active surface area (ECSA) of the
flat ITO and IO-ITO electrodes by analyzing double layer
[
13]
capacitance (Cdl) using cyclic voltammetry (Figure 1b).
The
slope of the linear fit to non-faradaic capacitive currents versus
scan rate corresponded to the capacitance of electrodes. We
found that the Cdl of IO-ITO electrodes increased from 1.77 to
-2
5
.73 mF cm as the IO-ITO thickness increased. In contrast, the
Figure 1. (a) Top-view SEM image of IO-ITO electrode. (b) Cathodic
capacitive current densities of planar ITO and IO-ITO electrodes with varying
thickness plotted against the scan rate. (c) Cyclic voltammetry curves of planar
ITO and IO-ITO electrode before (dashed curve) and after addition of 20 mM
FMN mediator (solid curve) at a scan rate of 50 mV s . (d) Changes in the
UV–vis absorbance spectra of 50 μM FMN in a 50 mM MOPS buffer (pH 7.4)
planar ITO electrode exhibited much lower Cdl value (0.02 mF
-2
cm ). Considering that Cdl is linearly proportional to the ECSA of
[
14]
materials with similar composition,
these results suggest that
-1
the IO structure provides a higher ECSA compared to that of the
planar ITO.
by IO-ITO electrode at an applied bias of -0.5 V (vs. Ag/AgCl) under N
geometrical surface area of all electrodes: 1 cm .
2
. The
2
We investigated charge transfer performance of IO-ITO
electrodes
by
performing
electrochemical
impedance
spectroscopy (EIS) measurements (Figure S3). EIS spectra
were measured at -0.5 V (vs. Ag/AgCl) and plotted in the form of
a Nyquist diagram over the frequency range of 0.1 to 10,000 Hz
for planar ITO and IO-ITO electrodes. We evaluated the charge
transfer resistance of electrodes in terms of the semicircle
diameter of the Nyquist plots at high frequencies. The IO-ITO
electrodes exhibited much smaller arcs than those of the planar
ITO, which indicates that macroporous IO structure promotes
efficient charge transfer at the electrode/electrolyte interface,
as FMN and TsOYE were sequentially added to the electrolyte,
which indicates effective electron transfer from the IO-ITO
electrode to TsOYE via FMN. We further verified asymmetric
reduction of ketoisophorone to (R)-levodione by TsOYE using
the IO-ITO cathode in a three-electrode configuration. The
bioelectrocatalytic system yielded 3.29 mM of (R)-levodione
(
87% ee) after 2h (Figure S6). In the absence of either FMN or
TsOYE, no product formation was detected. Using a flat ITO,
only 0.24 mM of (R)-levodione was produced, which was much
lower than that of the IO-ITO. These data are in line with the
results of electrochemical characterization of planar ITO and IO-
ITO electrodes. In addition, we observed an increase in (R)-
[
15]
hindering the charge recombination.
To compare electrocatalytic characteristics of planar ITO
and IO-ITO electrodes for the reduction of FMN, we carried out
cyclic voltammetric analysis. As shown in Figure 1c, the
reduction peak current density of the IO-ITO electrode was -0.43
-1
levodione production rate from 0.55 to 1.64 mM h as the IO-
ITO thickness increased (Figure S7), which suggests that
increasing the ECSA of electrode enhanced the rate of electron
transport to TsOYE via FMN.
-2
mA cm , which was five times higher than that of the planar ITO,
suggesting that the macroporous architecture facilitates instant
diffusion of reactants to the electrode surface, which should lead
to superior FMN reduction performance. We verified the
reduction of FMN by the IO-ITO electrode using UV-Vis
spectroscopy in a three-electrode configuration. At -0.5 V (vs.
Ag/AgCl), two characteristic absorbance peaks of FMN at 370
and 440 nm decreased simultaneously, indicating the reduction
Next, we prepared a nanoporous BiVO
drive photoelectrochemical in situ H generation from water
oxidation under illumination. The BiOI film was electrodeposited
on the FTO surface, then converted to BiVO by calcination with
During annealing, the nanosheets of
BiOI were transformed to worm-like particles, resulting in the
nanoporous BiVO film with a band gap of 2.51 eV (Figure S8
and S9). To quantitatively evaluate the production of H on
the BiVO photoanode, we conducted a colorimetric assay of
As shown in Figure 2a, H concentration increased
linearly for over 60 min at 0.5 V (vs. Ag/AgCl) under illumination,
4
photoanode to
2
O
2
4
[
16]
vanadium precursor.
[
6c]
2
of FMN to FMNH by the IO-ITO cathode (Figure 1d). On the
other hand, the planar ITO showed a slight change in the
absorption spectra of FMN (Figure S4), indicating that FMN
reduction on the planar ITO cathode is limited due to the low
ECSA. Taken together, these results show that the hierarchical
porosity of the IO-ITO electrode contributes to the enhancement
of the electrode performance for FMN reduction via increased
effective surface area and improved charge transfer kinetics.
To probe the capability of the IO-ITO electrode to transfer
electrons to TsOYE via the electron mediator FMN, we observed
chronoamperometric response of the IO-ITO electrode. As
displayed in Figure S5, the cathodic current was enhanced
4
2
O
2
4
[17]
H
2
O
2
.
2 2
O
whereas a negligible amount of H
absence of light, reflecting that H
2
O
2
was detected in the
2
O was generated via a
2
photoelectrocatalytic water oxidation process. We further
observed that the formation of H on the BiVO photoanode
2
O
2
4
under illumination enhanced continuously as the applied
potential increased from 0.2 to 0.8 V (vs. Ag/AgCl) (Figure 2b).
2
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COMMUNICATION
4
Finally, we wired the 1.0% Mo:BiVO photoanode to the
IO-ITO cathode in a two‐compartment setup connected by a salt
bridge and investigated its photocurrent response using linear
sweep voltammetry. Under illumination, a significantly enhanced
photocurrent was obtained over the entire potential range
(
Figure S13a). From the J-V curve of the PEC system, we
estimated the applied bias photon-to-current efficiency
ABPE, %) for the evolution of H and FMNH . ABPE values
can be calculated using: ABPE
(
2
O
2
2
=
J(Vth−Vbias−Vchem)/Ptotal,
-2
where J is the photocurrent density (mA cm ) under the applied
bias voltage (Vbias), Vth (1.54 V) is the thermodynamic voltage
determined by the difference between the redox potentials of
H
2
2 2 2
O/H O (1.35 V vs. NHE) and FMN/FMNH (-0.19 V vs. NHE),
V
chem is the chemical bias between the two compartments (0.02
-
V), and Ptotal is the illumination power density (100 mW cm
2
)
. The ABPE of whole PEC system reached 0.13% at an
applied voltage of 0.86 V (Figure S13b).
4
To evaluate the performance of the 1.0% Mo:BiVO /IO-ITO
system for paired bioelectrosynthesis, we measured the amount
of products from each biocatalytic redox reaction by varying the
applied bias from 0.5 to 1.0 V. Because the photovoltage (≈1.0
Figure 2. (a) Time profiles of the generated
2 2 4
H O from pristine BiVO
photoanode at 0.5 V (vs. Ag/AgCl) in dark and under visible light illumination.
b) H generation rates of BiVO photoanodes as a function of applied
potential under illumination. (c) Nyquist plots of BiVO and Mo:BiVO
(
O
2 2
4
[
20]
4
4
4
V) generated from the Mo:BiVO is smaller than the Vth for the
electrodes (0.05% , 0.1%, 0.5%, 1%, and 5% concentration of Mo) measured
at 0.3 V (vs. Ag/AgCl) in a 0.1 M KPi buffer (pH 7) under 1 sun illumination. (d)
overall reaction, at least 0.5 V of applied bias was required to
drive biocatalytic reactions. As shown in Figure 3a, we observed
a highly enantioselective conversion of ethylbenzene to (R)-1-
phenyl-1-hydroxyethane (ee > 99%) regardless of the scale of
applied bias. (R)-1-phenyl-1-hydroxyethane formation increased
with the increasing applied voltage, and it reached the highest
conversion rate of 0.51 mM h at 0.8 V. At more positive
voltages, however, a decrease in product yield was observed.
This decrease is attributed partly to the competition with one-
Effects of Mo doping on formation rates of H
2 2
O and corresponding FEs for
2
BiVO photoanode. The geometrical surface areas of all electrodes: 1.5 cm .
4
2 2
To enhance the efficacy of the photoelectrocatalytic H O
6
+
-1
generation on BiVO
4
, we introduced a metallic dopant (Mo ) into
film. Comparing the X-ray diffraction (XRD) patterns of
and pure BiVO revealed that the scheelite-monoclinic
was not changed by the Mo doping (Figure S10).
EIS measurements on pure BiVO and Mo:BiVO showed that
the BiVO
Mo:BiVO
4
4
4
•
[21]
phase of BiVO
4
electron water oxidation for OH generation and/or inactivation
•
[22]
4
4
of the biocatalyst by OH radicals, limiting the overall efficiency.
In particular, OH radicals can oxidize the heme iron in the active
site of peroxygenases, leading to their inactivation. We expect
that these issues associated with OH radicals could be
•
the charge transfer resistance at the electrode interface was
reduced significantly with the increasing concentration of Mo
dopant from 0 to 1.0% (Figure 2c and S11). The result suggests
that Mo facilitates charge transport at the electrode interface,
eventually enhancing the activity of water oxidation. Furthermore,
[23]
•
addressed by further optimization of BiVO
dopants or forming a heterojunction
4
using different
for two-electron water
oxidation reaction and by physical separation of AaeUPO from
[
7c]
[24]
the photocurrent densities of the Mo:BiVO
improved considerably across the entire potential range
compared to the pure BiVO photoanode (Figure S12). The
4
photoanodes
[
25]
the photoelectrode.
In contrast, the generation of (R)-
4
levodione by TsOYE enhanced with the increasing applied bias
-
enhanced photocurrent is ascribed to the improved electronic
conductivity, which arises from the intrinsically enhanced charge
carrier mobility and concentration resulting from the Mo
(
Figure 3b). At 1.0 V, the maximum conversion rate of 0.5 mM h
1
was observed with 82% ee. The relatively low optical purity of
the product is attributed to non-enzymatic racemization of (R)-
[
18]
doping.
A further increase in the dopant concentration (i.e.,
5.0%), however, resulted in much higher interface resistance
and lower photocurrent density, which is ascribed to unfavorable
surface recombination due to the aggregation of excessive
[
19]
Mo.
photoelectrocatalytic H
the improvements in the PEC performance, H
increased with the increase of Mo concentration from 0 to 1.0%.
The 1.0% Mo:BiVO photoanode exhibited the highest H
formation rate of 38 μM cm min , which was 4.2 times higher
than that of the pure BiVO photoanode, whereas much slower
oxidation of H O to H was observed for the 5.0% Mo:BiVO
photoanode. The faradaic efficiency (FE) of H generation
reached a peak value of 52% in the 1.0% Mo:BiVO photoanode,
suggesting that the selectivity toward H is improved by the
introduction of Mo. Taken together, the moderate Mo doping of
BiVO enhanced the activity of BiVO toward H production
due to the improved PEC properties.
We examined the effect of Mo doping on the
production (Figure 2d). In line with
production rate
2
O
2
2
O
2
4
2 2
O
-2
-1
4
2
2
O
2
4
Figure 3. (a) Comparison of (R)-1-phenyl-1-hydroxyethane formation at the
2
O
2
4
1.0% Mo:BiVO photoanode as a function of applied bias for 2 h. (b)
4
Comparison of (R)‐levodione formation and optical purity at the IO-ITO
2
O
2
cathode as a function of applied bias for 2 h. The geometrical surface areas of
2
the Mo:BiVO
4
and IO-ITO: 1.5 and 1 cm , respectively.
4
4
2 2
O
3
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Angewandte Chemie International Edition
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COMMUNICATION
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least 0.8 V to drive the complete reaction with an optimized
conversion rate. Future research will address limitations
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2
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Angewandte Chemie International Edition
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A biocatalytic photoelectrochemical platform for solar-assisted dual biotransformations is constructed by wiring a Mo-doped BiVO
photocathode and a hierarchical porous ITO electrode. The deliberate integration of enzymatic redox processes into the
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photoelectrochemical cell simultaneously facilitates peroxygenase- and ene-reductase-mediated enantioselective synthesis of high-
value chemicals using solar-powered electrons and water.
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This article is protected by copyright. All rights reserved.