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org/JPCC Article

Oxidizing Ethanol and 2‑Propanol by Hypochlorous Acid Generated

from Chloride Ions on HxWO3 Photoelectrodes
Andrew G. Breuhaus-Alvarez, Siqi Li, Nathaniel Z. Hardin, and Bart M. Bartlett*
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ABSTRACT: Photoelectrochemically oxidizing aqueous chloride

electrolytes (1 M NaCl, pH 3) to hypochlorous acid proceeds on
Downloaded via UNIV OF WISCONSIN-MADISON on June 23, 2022 at 15:10:35 (UTC).

HxWO3 semiconducting photoelectrodes using 405 nm illumination

at 100 mW/cm2 with 1.0 V versus Ag/AgCl constant potential
chronoamperometry. The hypochlorous acid serves as an oxidation
agent upon adding 100 mM ethanol or 2-propanol into the solution.
1
H NMR spectroscopy shows that 90% of the charge passed results in
oxidized products (acetaldehyde and acetic acid or acetone).
Chemically oxidizing ethanol by calcium hypochlorite shows that
both light and the HxWO3 surface enhance the reaction rate.

■ INTRODUCTION
Solar energy conversion to form fuels and commodity
chemicals remains a pressing, active area of research, with
photoelectrochemical water splitting as the most well-studied
example given the abundance of water on the Earth’s surface.1
During this reaction, hydrogen evolution is coupled with
oxygen evolution, a four-proton/four-electron oxidation
reaction with a large overpotential.2,3 As a result, oxygen
evolution is rate-limiting, the gas has little value, and it poses
vast abundance in terrestrial seawater. Despite its suitability to
carry out mediated reactions for photoelectrochemical syn-
thesis, using chloride is largely scarce.
Here, we report ethanol and 2-propanol oxidation by
photoelectrochemically generated hypochlorous acid from
aqueous chloride solution, mimicking seawater, on an n-type
HxWO3 photoelectrode with ∼90% yield and stable, high
current density. The material also presents excellent stability in
acid, which is beneficial to the coupled target cathodic
hydrogen evolution reaction.

an explosion risk with hydrogen if not properly separated.
As a result, replacing oxygen evolution with faster anodic
reactions that provide valuable products has been inves-
tigated.4 Among them, oxidizing alcohols to aldehydes,
ketones, and carboxylic acids is of high importance in
producing pharmaceuticals and fine chemicals, especially for
the likes of ethanol, which can be derived from biomass
feedstock.5−9 While alcohol oxidation is strategically favored,
direct alcohol oxidation on photoelectrodes usually requires
large applied bias, and the reactant and/or intermediates are
prone to adsorb to the electrode.10 On the other hand, indirect
oxidation by introducing redox mediators circumvents these
problems. The mediator is rapidly oxidized at the anode, which
subsequently oxidizes the alcohol in solution.11 Nitroxyl
radicals12 and metal complexes13 are usually employed as
mediators for alcohol oxidation.
However, these reagents require using organic solvents, and
there are possible detrimental environmental impacts from the
heavy metal cations. From a green chemistry perspective, more
abundant and environmentally friendly mediators are sought.
Inspired by industrial wastewater treatment, where bleach is
used to carry out oxidative destruction of organic waste in
aqueous solution,14,15 we set out to explore chloride as a redox
mediator for the targeted ethanol oxidation reaction due to its
■
METHODS
Chemicals. The water used in all synthesis and experiments
was filtered by a Millipore filtration system (18 MΩ·cm).
Ethanol (200 proof) was purchased from Decon Laboratories.
Ammonium metatungstate (NH4)6H2W12O40·xH2O (AMT)
and poly(ethylene glycol) (Mw = 300 Da, PEG-300) were
purchased from Sigma-Aldrich. Hydrochloric acid (37 w/w %)
and sodium chloride were purchased from Fisher Scientific.
Fluorine tin oxide (FTO, Pilkington Glass TEC-15) substrate
was cut into 1.5 × 2.54 cm2 strips for HxWO3 spin coat
synthesis. The FTO substrate was first coarsely cleaned by
scrubbing with an acetone wetted Kimwipe. This cleaning
procedure was followed by sonicating in the following solvents:
acetone, Sparkleen detergent, water, and acetone again for 10
min each, with each solvent wash, followed by drying under a
Received: July 14, 2021
Revised: November 5, 2021
Published: November 22, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.jpcc.1c06286

26307 J. Phys. Chem. C 2021, 125, 26307−26312
The Journal of Physical Chemistry C
flowing N2 stream. Ag/AgCl reference electrodes were
purchased from CH Instruments and filled with saturated
KCl aqueous solution. Pt disk electrodes (2 mm diameter)
were also purchased from CH Instruments. 99.95% pure Pt
wire (24 gauge, P/N 1981) was purchased from Sure Pure
Chemetals.
Synthesis of HxWO3 Electrodes. HxWO3 electrodes were
synthesized by spin coating AMT sol. The precursor was
prepared by adding 2.51 g (833 μg) of AMT to a 100 mL
round-bottom flask and then 10 mL of water to dissolve
completely with vigorous stirring. In a scintillation vial, 6.6 g
(22 mmol) of PEG-300 was dissolved in 10 mL of ethanol.
Using a syringe pump, the ethanol solution was added at a rate
of 120 mL·h−1. A faint, off-white sol precursor resulted, which
was 0.5 M tungsten. The electrodes were prepared by dropping
70 μL of the precursor sol onto a clean, 1.5 × 1.5 cm2 square
area (2.25 cm2) of FTO, which was masked off on a 1.5 × 2.54
cm2 strip. This was spun at 2500 rpm for 30 s using a Laurell
spin coater. The precursor was constantly and vigorously
stirred and then sealed tightly when not in use. Following spin
coat deposition, the electrodes were transferred to a muffle
furnace at 500 °C for 30 min. These deposition and annealing
cycles were repeated 10 times to achieve films with
approximately 1 μm thickness.
Material Characterization. XRD, SEM images, and
diffuse reflectance UV−vis spectroscopy were collected and
are presented in the Supporting Information. XRD was
performed on a Panalytical Empyrean diffractometer. The
operating power was 1.8 kW (45 kV, 40 mA) using Cu Kα (λ =
1.5418 Å) in θ−θ geometry. The SEM images were collected
with a JEOL JSM-7800FLV field emission scanning electron
microscope. An operating voltage of 15.00 kV and an
Everhart−Thornley secondary electron detector were used.
Diffuse reflectance UV−vis spectroscopy was measured on a
Varian Cary 5000 spectrophotometer with an external diffuse
reflectance accessory and barium sulfate as the 100%
reflectance standard. The spectra were collected in reflectance
mode and converted into absorbance by the Kubelka−Munk
function.
Photoelectrochemistry. The photoelectrochemical
(PEC) experiments were performed using a CH Instruments
Series 760E electrochemical workstation. The light source used
consisted of four 405 nm LEDs (Osram Sylvania, LZ1-
10UB00-01U7) attached to a CPU heat sink and powered by a
700 mA constant current LED driver (ERP Power, ESS015W-
0700-18). The 405 nm light was adjusted to an irradiance of
100 mW·cm−2 with a thermopile detector (Newport 818P-
015-19) and an optical power meter (Newport 1918-R). The
custom-made photoelectrochemical cell was glass with quartz
light windows and featured two compartments with a Nafion
membrane separating the working electrode and counter
electrode compartments. The Nafion membrane was used in
all PEC experiments reported in this work. The HxWO3
electrode was positioned such that it was backlit by the LED
light through the cell’s quartz window. Ag/AgCl reference
electrodes and Pt wire counter electrodes were used in all
experiments. The electrolytes used in this work were 1 M NaCl
set to pH 3 with HCl and 1 M Na2SO4 set to pH 3 with
sulfuric acid, both prepared in a volumetric flask before pH
adjustment. The alcohol substrate, either ethanol or 2-
propanol, was added to the electrolyte to make 100 mM
alcohol solution. Following the 3 h controlled potential
chronoamperometry (CPC) experiments, the light was shut
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off and the cell was allowed to sit under stirring for 1 h before
being placed in a −10 °C fridge for 10 min. The cell was then
removed and shaken to dissolve any alcohol oxidation product
condensed on the cell walls. The 1H NMR sample was then
made from the working compartment electrolyte.
1
H NMR Quantification of Alcohol Oxidation Prod-
ucts. Quantification of products was carried out using
quantitative single pulse 1H NMR performed on 700 MHz
Varian NMR using a relaxation delay of 25 s and a pulse angle
of 90°. A typical NMR sample was composed of 200 μL of 100
mM sodium formate dissolved in D2O as an internal standard
and 300 μL of the electrolyte from the working compartment.
The added sodium formate results in a 40 mM formic acid
standard. Because the acetaldehyde product can react with
water to form hydrate in solution, the total yield of
acetaldehyde reported was the sum of the observed
acetaldehyde and acetaldehyde hydrate yields.16
UV−Vis Spectrophotometry. UV−vis solution absorp-
tion spectra were recorded using a Varian Cary 5000
spectrophotometer. A PEC CPC experiment was performed
using HxWO3 in both 1 M NaCl at pH 3 and 1 M HCl. No
alcohol substrate was added. The HxWO3 electrode was poised
at 1.0 V versus Ag/AgCl for 1 h. Following 1 h of electrolysis,
solution UV−vis absorption was performed on the undiluted
electrolyte. Solution UV−vis absorption spectra were also
obtained for Ca(ClO)2 solutions in order to observe the HClO
absorption feature. 71.5 mg of Ca(ClO)2 was added to a 25
mL volumetric flask. The volumetric flask was then filled to the
line using either 1 M NaCl or 1 M HCl to make 20 mM
solution of Ca(ClO)2. Once all the solid had dissolved, the
solution was quickly diluted by a factor of 10 using the
appropriate 1 M chloride electrolyte. The solution UV−vis
spectrum shown in Figure S10 was recorded immediately after
the solution was made. In the case of 1 M NaCl, the pH was
set to 3 after the dilution and immediately prior to the UV−vis
measurement. When investigating the comproportionation of
hypochlorous acid and chloride shown in Figure S16, 20 mM
Ca(ClO)2 solution was made in 1 M NaCl and the pH was set
to 3. This solution was allowed to react for 45 min. At the end
of the 45 min period, the solution pH had increased and was
set back to 3 before recording the UV−vis spectrum.
Chemical Oxidation of Ethanol by Ca(ClO)2. All
samples were prepared in 5 mL vials. A 20 mM Ca(ClO)2
solution was made by dissolving 286.0 mg of Ca(ClO)2 in 100
mL of 1 M NaCl solution. This concentration of Ca(ClO)2
produces a HClO concentration similar to the amount
generated during the PEC experiments presented in this
paper. The pH was then immediately set to 3, and this was
combined with 460.7 mg of ethanol (100 mM). The
photochemical reactions were performed with the 405 nm
light entering the bottom of the dram vial set to 100 mW·cm−2
irradiance. Experiments with tungsten oxide powder were
performed by adding 5 mg of the tungsten oxide powder to the
4 mL reaction volume. At the end of the reaction, the WO3
powder was filtered out before analyzing the solution with
quantitative 1H NMR spectroscopy. Three trials were averaged
in reporting the results.
Starch−Iodine Titration. Quantification of free chlorine
(HClO and Cl2) was carried out using starch−iodine titration.
The starch−iodine test does not discriminate between HClO
and Cl2, both of which are two-electron oxidation products of
Cl− oxidation. Immediately following a PEC CPC experiment,
the working compartment solution was used to fill a 25.00 mL
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volumetric flask containing KI(s) (415.0 mg, 2.5 mM) to the
line to make a solution with an iodide concentration of 100
mM. Potassium iodide reacts with dissolved chlorine according
to the following equation
2I−(aq) + Cl 2(aq) → I 2(aq) + 2Cl−(aq)
or with hypochlorous acid
HClO(aq) + 2I−(aq) + H+(aq)
→ Cl−(aq) + I 2(aq) + H 2O(l)
Both reactions result in a 1:1 correspondence between the 2-
electron oxidation product of Cl2 or HClO and I2. 5 mL of the
25 mL iodide/iodine solution was then titrated with a stock
Na2S2O3 solution and a starch indicator. The thiosulfate
reduces the generated iodine according to the equation
I 2(aq) + 2S2 O32 −(aq) → 2I−(aq) + S4 O6 2 −(aq)
For the 300 s CPC experiment, a 10 mM sodium thiosulfate
stock solution was used. A 100 mM sodium thiosulfate was
used for the 10,800 s CPC experiment.
■ RESULTS AND DISCUSSION
PEC Chloride Oxidation with the Presence of
Alcohols. Voltammetry. Previous work by our group has
shown that chloride ions can be oxidized in acidic aqueous
solution on HxWO3 photoelectrodes17 to form hypochlorous
acid (pKa = 7.4)18 with near-unity Faradaic efficiency
according to
Cl−(aq) + H 2O(l) → HClO(aq) + H+(aq) + 2e−,
E° = 1.49 − 0.0296 × pH VNHE (1)
In this work, we performed a series of PEC experiments on
HxWO3 photoelectrodes in the chloride electrolyte under 405
nm light at an irradiance of 100 mW·cm−2 to test the
possibility of mediating alcohol oxidation. Characterization of
the HxWO3 photoelectrode and quantification of the oxidized
alcohol products are provided in the Supporting Information:
1 suggesting that the HClO produced at the HxWO3 electrode
H NMR spectra (Figures S1−S5), XRD patterns (Figure S6),
SEM images (Figure S7), and a diffuse reflectance UV−vis
spectrum with the associated Tauc plot (Figures S8 and S9).
Figure 1 shows the linear sweep voltammetry (LSV) of the 1
M NaCl electrolyte with 100 mM ethanol or 2-propanol on
HxWO3. It can be observed that under illumination, the j−E
curves overlap with or without the presence of alcohol,
indicating that the same chemical reaction occurs. From this
data, we surmise that chloride oxidation, and not direct alcohol
oxidation, occurs at the HxWO3 electrode. Moreover, in the
LSV experiments using either 1 M Na2SO4 or 1 M NaClO4
electrolytes, oxoanions with the central atoms in their highest
formal oxidation states show an increase in the j−E response
and an ∼200 mV shift to more negative potential upon adding
the 100 mM ethanol substrate (Figure S15). This shift is the
same for both oxoanions, hinting that the anodic reaction is
likely direct ethanol oxidation because both the persulfate/
sulfate and perchlorate anion/perchlorate radical couples are
>2 V versus NHE. The significant difference between the LSV
with ethanol in the chloride electrolyte and the two oxoanion
electrolytes further indicates that ethanol is not directly
oxidized with the presence of chloride (i.e., chloride acts to
mediate the reaction). Additionally, the Nyquist plots obtained
under irradiation (Figure S16) with and without 100 mM
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Figure 1. LSV traces of the chloride electrolyte with and without
added alcohols. The solid traces are recorded under illumination, and
the dashed traces are the corresponding dark measurements.
ethanol did not show significant changes, indicating that
similar reactions are occurring on the electrode regardless of
the presence of alcohol. The UV−vis spectrum of the solution
recorded immediately after performing the PEC CPC
experiment (vide infra) for 1 h (Figure S10) further supports
chloride oxidation to hypochlorous acid at pH 3. The peak
absorbance at 233 nm corresponds to HClO with no shoulder
centered at 229 nm from dissolved Cl2.19
The Tafel plot (Figure S11) of both 1 M NaCl at pH 3 and
1 M HCl electrolytes recorded on HxWO3 semiconducting
photoelectrodes exhibits a slope of ∼35 mV·dec−1, evidence
that the rate-determining step of chloride oxidation is not
affected by large changes in proton activity and that HClO is
ultimately the favored product of chloride oxidation on
HxWO3 at these pH values. Our solution is unbuffered, and
this result mitigates concern that the chloride oxidation
product is affected by swings in pH during CPC electrolysis.
Controlled Potential Chronoamperometry. Oxidizing
alcohols using hypochlorite anions has been previously
demonstrated using TEMPO or nickel (II) salts as a catalyst,
may also carry out these oxidation reactions.20−24 To test the
efficiency of the chloride oxidation coupled alcohol oxidation
process, we conducted CPC experiments. Figure 2a shows the
reaction progress from quantitative 1H NMR spectroscopy
over the 8 1/2 hour CPC experiment. Despite the large
chloride concentration, we detect no peak splitting indicative
of chlorinated products by 1H NMR spectroscopy. Accord-
ingly, the relevant reactions for generating acetaldehyde and
acetic acid from ethanol and HClO are
CH3CH 2OH + HClO → CH3CHO + H+ + Cl− + H 2O
(2)
CH3CH 2OH + 2HClO
→ CH3CH 2O + 2H+ + 2Cl− + H 2O (3)
The yield of the oxidized ethanol product shown in Figure
2b is calculated according to the equation
F(2 × nacetaldehyde + 4 × nacetic acid)
yield = × 100%
q (4)
where F is Faraday’s constant (96,485 C/mol), n is the number
of moles of the product formed, and q is the charge passed in
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J. Phys. Chem. C 2021, 125, 26307−26312
The Journal of Physical Chemistry C
Figure 2. Ethanol oxidation using a HxWO3 photoelectrode at 1 V
versus Ag/AgCl under illumination. (a) Disappearance of reactants
and appearance of products as a function of time as measured by
quantitative 1H NMR spectroscopy and (b) CPC trace and total
product yield as a function of time.
Coulombs at the HxWO3 electrode at a given time point. At
early time points (low charge passed), a low yield is observed.
It increases until ∼200 C of charge pass at 2.5 h, at which point
the yield begins to stabilize ∼90%. A starch−iodine test shows
that HClO is present throughout the experiment, indicating
that, not surprisingly, the rates of the solution-based chemical
steps are slower than that of PEC chloride oxidation at the
HxWO3 electrode. The HClO concentration increases to 0.2
mM after passing 150 C of charge but increases by only about
50 μM after another 150 C of charge was passed. As the HClO
concentration increases, so does the rate of the subsequent
chemical oxidation steps until the rate is rapid enough to keep
pace with the rate of HClO generation to maintain a consistent
yield of 90%.
Initially, we note that the rate of acetaldehyde formation is
greater than the rate of acetic acid formation. However, as the
acetaldehyde concentration increases, the rate of its subsequent
oxidation to acetic acid also increases. Under these
experimental conditions, the plateau occurs when acetaldehyde
reaches 20 mM concentration. To test that acetaldehyde is at
steady state under these conditions, a linear fit (zero-order
kinetics) was performed on the concentration of both ethanol
and acetic acid versus time kinetic profile after 400 C of charge
was passed (Figure S12). The slopes d[EtOH]/dt and
d[CH3COOH]/dt are (−1.77 ± 0.04) × 10−6 M/s and
(1.53 ± 0.02) × 10−6 M/s, respectively. These rates are in
excellent agreement, and we note any discrepancy is likely due
to the volatility of acetaldehyde lost in the headspace. From the
two fits, the rate at which both ethanol and acetaldehyde are
oxidized is (3.30 ± 0.04) × 10−6 M/s. The current density
corresponding to this rate from Faraday’s law given the 2.25
cm2 geometric area of our HxWO3 electrodes is 9.9 ± 0.3 mA/
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cm2, which is the average current density observed during the
PEC CPC experiment (Figure 2b).
Furthermore, the data in Figure 2 show that acetaldehyde
essentially behaves as an extremely long-lived intermediate
during ethanol oxidation to acetic acid. When we used the
same experimental conditions in a 16 h PEC CPC experiment
(j−t curve shown in Figure S13), 1H NMR spectroscopy
revealed a final solution composition of 3 mM acetaldehyde
(2% yield) and 75 mM acetic acid (86% yield).
Secondary alcohols can also be oxidized to ketones, and
Table 1 shows the product yields following a 3 h CPC
Table 1. Oxidation of 100 mM Ethanol and 2-Propanol in 1
M NaCl and Na2SO4 Electrolytes at pH 3
i
EtOH PrOH
electrolyte % MeCHO % MeCOOH % Me2CO
NaCl 50 ± 3 39 ± 2 92 ± 4
Na2SO4 16 ± 2 7±4 16 ± 2
experiment described previously with either 100 mM ethanol
or 2-propanol in 1 M NaCl and 1 M Na2SO4 electrolytes as a
control experiment. Unsurprisingly, a single product, acetone,
results from 2-propanol oxidation. Plots of the photocurrent
response during these PEC CPC experiments are shown in
Figure S14. In 1 M NaCl, both ethanol and 2-propanol
oxidation by HClO generated on HxWO3 proceeds with 90%
of the charge passed contributing to an oxidized product.
Previous work by our group has shown that the oxygen
evolution reaction is the dominant reaction on HxWO3 in the
sulfate electrolyte,25 which should result in a lower yield for
alcohol oxidation in the sulfate electrolyte. Indeed, in a control
experiment containing 1 M Na2SO4, we observe significantly
lower conversion. This result further indicates the superiority
of our chloride-oxidation-based indirect ethanol oxidation
mechanism.
Decoupling Dark, Homogeneous Chemical Oxidation
Steps from Light−Driven Reactions. The irradiation used
in the PEC CPC experiments is an intense energy input into
the reaction. Furthermore, metal oxide surfaces are well known
to serve as heterogeneous oxidation catalysts.26,27 Therefore,
we carried out a series of experiments to decouple the PEC
chloride oxidation from the chemical steps of alcohol
oxidation, as shown in Figure 3. First, as a control experiment,
we combined the 100 mM ethanol solution in 1 M NaCl and
Figure 3. Product yield of 100 mM ethanol oxidation after 3 h under
varying conditions to distinguish the activity of WO3, HClO (at pH
3), and illumination on the yield and selectivity.
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The Journal of Physical Chemistry C
adjusted the pH to 3 with commercial WO3 powder (5 mg in 4
mL reaction volume) and observed no conversion after
reacting for 3 h in the dark. We conclude that ethanol
oxidation by dissolved O2 on WO3 does not occur. Next, we
carried out chemical oxidation of 100 mM ethanol by 20 mM
Ca(ClO)2 in 1 M NaCl solution at pH 3, still in the dark, to
measure the propensity for HClO to serve as the oxidant. The
pH was set after all the salts were dissolved, and the 4 mL
solution reacted for 3 h in a sealed vial. The yields of
acetaldehyde and acetic acid are 11.3 ± 0.6 and 6.8 ± 0.7%,
respectively.
Then, adding WO3 powder to a solution containing 20 mM
Ca(ClO)2, still in the dark, results in the doubling of the
acetaldehyde yield to 26.0 ± 0.2% and an increase in the yield
of acetic acid to 10.2 ± 0.2%. The WO3 powder enhances the
rate of oxidation by HClO, hinting that the surface of our
HxWO3 semiconductor photoelectrodes may assist in the PEC
CPC conversion of ethanol to acetaldehyde and acetic acid.
Finally, we illuminated the reaction mixture, now without WO3
powder, with 405 nm light at 100 mW/cm2 entering the base of
the vial reaction. In this experiment, the yields of acetaldehyde
and acetic acid increased to 29.3 ± 0.4 and 10.7 ± 0.2%,
respectively. The solution temperature was 23.3 °C in the dark
and was measured at 24.2 °C during the irradiated experiments
(nearly constant). We therefore attribute the increase in yield
to the light rather than the <1 °C increase in temperature.
Moreover, hypochlorous acid undergoes homolytic bond
cleavage with near-UV light to generate the highly reactive
Cl• and OH• radicals, both strong oxidants.28−30 While the
major absorption maximum of the aqueous chlorine-containing
species (i.e., - Cl2, HClO, and ClO−) exists at λ < 300 nm,
using longer wavelength light to generate radicals has been
previously demonstrated.28,29,31−34 The UV−vis spectrum of
20 mM solution of Ca(ClO)2 is shown in Figure S17. The 405
nm light output by the LED overlaps with the tail in the
absorption band at λmax ≈ 325 nm.
■ CONCLUSIONS
We demonstrate that chloride can be oxidized photo-
electrochemically to form hypochlorous acid in acidic aqueous
solution on HxWO3 semiconductor photoelectrodes with 98%
Faradaic efficiency. The hypochlorous acid performs ethanol
and 2-propanol oxidation in high yield; 90% of the charge
passed results in alcohol oxidation. In the ethanol case, the
yield for acetaldehyde is 50 ± 3% and the yield for acetic acid
is 39 ± 2% after 3 h. Then, 86% acetic acid results after 16 h. 2-
Propanol oxidation produces acetone with 92 ± 4% yield.
Using a sulfate electrolyte dramatically suppresses the alcohol
oxidation yield, showing that chloride oxidation must precede
alcohol oxidation. Furthermore, we used Ca(ClO)2 to
demonstrate that the tungsten oxide surface catalyzes the
conversion of alcohol to acetaldehyde and acetic acid. The 405
nm, 100 mW/cm2 light used in the CPC PEC experiments was
also shown to increase the rate of ethanol conversion, likely by
increasing the •OH and •Cl radical concentrations through
photoinduced homolytic cleavage of hypochlorous acid. Our
work reveals the capability to perform more attractive alcohol
oxidation reactions coupled with the PEC chloride oxidation,
which is an overall more valuable anodic reaction to couple
with the hydrogen evolution reaction in fuel-forming systems.
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■
pubs.acs.org/JPCC Article
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c06286.
1
H NMR spectra, XRD patterns, SEM images, UV−vis
spectra, Tafel plots, GC data, and CPC and LSV traces
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Bart M. Bartlett − Department of Chemistry, University of
Michigan, Ann Arbor, Michigan 48109-1055, United States;
orcid.org/0000-0001-8298-5963; Email: bartmb@
umich.edu
Authors
Andrew G. Breuhaus-Alvarez − Department of Chemistry,
University of Michigan, Ann Arbor, Michigan 48109-1055,
United States
Siqi Li − Department of Chemistry, University of Michigan,
Ann Arbor, Michigan 48109-1055, United States
Nathaniel Z. Hardin − Department of Chemistry, University
of Michigan, Ann Arbor, Michigan 48109-1055, United
States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c06286
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the U.S. Department of Energy,
Office of Science, Basic Energy Sciences, under Award DE-
SC0006587 (Catalysis Science). A.G.B.-A. thanks the Horace
H. Rackham Graduate School at the University of Michigan for
a Rackham Merit Fellowship. The authors acknowledge the
financial support from the University of Michigan College of
Engineering and NSF grant #DMR-9871177 and #DMR-
0723032 and technical support from the Michigan Center for
material characterization.
■
REFERENCES
(1) Nielander, A. C.; Shaner, M. R.; Papadantonakis, K. M.; Francis,
S. A.; Lewis, N. S. A taxonomy for solar fuels generators. Energy
Environ. Sci. 2015, 8, 16−25.
(2) Lhermitte, C. R.; Sivula, K. Alternative Oxidation Reactions for
Solar-Driven Fuel Production. ACS Catal. 2019, 9, 2007−2017.
(3) McCrory, C. C. L.; Jung, S.; Ferrer, I. M.; Chatman, S. M.;
Peters, J. C.; Jaramillo, T. F. Benchmarking Hydrogen Evolving
Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar
Water Splitting Devices. J. Am. Chem. Soc. 2015, 137, 4347−4357.
(4) Bender, M. T.; Yuan, X.; Choi, K. S. Alcohol oxidation as
alternative anode reactions paired with (photo)electrochemical fuel
production reactions. Nat. Commun. 2020, 11, 4594.
(5) Ley, S. V.; Norman, J.; Griffith, W. P.; Marsden, S. P.
Tetrapropylammonium Perruthenate, Pr4N+RuO4−, TPAP : A
Catalytic Oxidant for Organic Synthesis. Synthesis 1994, 1994,
639−666.
(6) Arends, I. W. C. E.; Sheldon, R. A. Modern Oxidation of
Alcohols Using Environmentally Benign Oxidants. Modern Oxidation
Methods; John Wiley & Sons, Ltd, 2005; Chapter 4; pp 83−118.
(7) Hudlicky, M. Oxidations in Organic Chemistry; American
Chemical Society; Washington DC, 1990.
https://doi.org/10.1021/acs.jpcc.1c06286
J. Phys. Chem. C 2021, 125, 26307−26312
The Journal of Physical Chemistry C pubs.acs.org/JPCC Article

(8) Davis, S. E.; Ide, M. S.; Davis, R. J. Selective Oxidation of Selective Oxidation of Primary Alcohols. Nat. Commun. 2017, 8,
Alcohols and Aldehydes over Supported Metal Nanoparticles. Green 14039.
Chem. 2013, 15, 17−45. (28) Remucal, C. K.; Manley, D. Emerging investigators series: the
(9) Zerk, T. J.; Moore, P. W.; Harbort, J. S.; Chow, S.; Byrne, L.; efficacy of chlorine photolysis as an advanced oxidation process for
Koutsantonis, G. A.; Harmer, J. R.; Martínez, M.; Williams, C. M.; drinking water treatment. Environ. Sci.: Water Res. Technol. 2016, 2,
Bernhardt, P. V. Elucidating the Mechanism of the Ley-Griffith 565−579.
(TPAP) Alcohol Oxidation. Chem. Sci. 2017, 8, 8435−8442. (29) Bulman, D. M.; Mezyk, S. P.; Remucal, C. K. The Impact of pH
(10) DiMeglio, J. L.; Terry, B. D.; Breuhaus-Alvarez, A. G.; Whalen, and Irradiation Wavelength on the Production of Reactive Oxidants
M. J.; Bartlett, B. M. Base-Assisted Nitrate Mediation as the during Chlorine Photolysis. Environ. Sci. Technol. 2019, 53, 4450−
Mechanism of Electrochemical Benzyl Alcohol Oxidation. J. Phys. 4459.
Chem. C 2021, 125, 8148−8154. (30) Yan, X.; Cheng, H.; Zare, R. N. Two-Phase Reactions in
(11) Badalyan, A.; Stahl, S. S. Cooperative electrocatalytic alcohol Microdroplets without the Use of Phase-Transfer Catalysts. Angew.
oxidation with electron-proton-transfer mediators. Nature 2016, 535, Chem., Int. Ed. 2017, 56, 3562−3565.
406−410. (31) Izadifard, M.; Langford, C.; Achari, G. Alternative View of
(12) de Nooy, A. E. J.; Besemer, A. C.; van Bekkum, H. Selective Chlorine Oxidation Stimulated by Longer Wavelength Light. J.
oxidation of primary alcohols mediated by nitroxyl radical in aqueous Environ. Eng. 2016, 142, 04016048.
solution. Kinetics and mechanism. Tetrahedron 1995, 51, 8023−8032. (32) Forsyth, J. E.; Zhou, P.; Mao, Q.; Asato, S. S.; Meschke, J. S.;
(13) Shapley, P. A.; Zhang, N.; Allen, J. L.; Pool, D. H.; Liang, H.-C. Dodd, M. C. Enhanced Inactivation of Bacillus Subtilis Spores During
Selective alcohol oxidation with molecular oxygen catalyzed by Os− Solar Photolysis of Free Available Chlorine. Environ. Sci. 2013, 47,
Cr and Ru− Cr complexes. J. Am. Chem. Soc. 2000, 122, 1079−1091. 12976−12984.
(14) Chung, M.; Jin, K.; Zeng, J. S.; Manthiram, K. Mechanism of (33) Shu, Z.; Li, C.; Belosevic, M.; Bolton, J. R.; El-Din, M. G.
Chlorine-Mediated Electrochemical Ethylene Oxidation in Saline Application of a Solar UV/Chlorine Advanced Oxidation Process to
Water. ACS Catal. 2020, 10, 14015−14023. Oil Sands Process-Affected Water Remediation. Environ. Sci. 2014, 48,
(15) Behin, J.; Akbari, A.; Mahmoudi, M.; Khajeh, M. Sodium 9692−9701.
hypochlorite as an alternative to hydrogen peroxide in Fenton process (34) Horton, J. A.; Laura, M. A.; Kalbag, S. M.; Petterson, R. C.
for industrial scale. Water Res. 2017, 121, 120−128. Reaction of Hypochlorous Acid with Ketones. Novel Baeyer-Villiger
(16) Scheithauer, A.; Brächer, A.; Grützner, T.; Zollinger, D.; Thiel, Oxidation of Cyclobutanone with Hypochlorous Acid. J. Org. Chem.
W. R.; Von Harbou, E.; Hasse, H. Online 1H NMR Spectroscopic 1969, 34, 3366−3368.
Study of the Reaction Kinetics in Mixtures of Acetaldehyde and Water
using a New Microreactor Probe Head. Ind. Eng. Chem. Res. 2014, 53,
17589−17596.
(17) Breuhaus-Alvarez, A. G.; Cheek, Q.; Cooper, J. J.; Maldonado,
S.; Bartlett, B. M. Chloride Oxidation as an Alternative to the Oxygen
Evolution Reaction on HxWO3 Photoelectrodes. J. Phys. Chem. C
2021, 125, 8543−8550.
(18) Perrin, D. D. Ionisation Constants of Inorganic Acids and Bases in
Aqueous Solution; Elsevier Science: Burlington, 2013.
(19) Belz, M.; Boyle, W. J. O.; Klein, K.-F.; Grattan, K. T. V. Smart-
sensor approach for a fibre-optic-based residual chlorine monitor.
Sens. Actuators, B 1997, 39, 380−385.
(20) Lucio Anelli, P.; Biffi, C.; Montanari, F.; Quici, S. Fast and
selective oxidation of primary alcohols to aldehydes or to carboxylic
acids and of secondary alcohols to ketones mediated by
oxoammonium salts under two-phase conditions. J. Org. Chem.
1987, 52, 2559−2562.
(21) Grill, J. M.; Ogle, J. W.; Miller, S. A. An Efficient and Practical
System for the Catalytic Oxidation of Alcohols, Aldehydes, and α,β-
Unsaturated Carboxylic Acids. J. Org. Chem. 2006, 71, 9291−9296.
(22) Cheng, L.; Wang, J.; Wang, M.; Wu, Z. Mechanistic Insight into
the Alcohol Oxidation Mediated by an Efficient Green [CuBr2(2,2′-
bipy)]-TEMPO Catalyst by Density Functional Method. Inorg. Chem.
2010, 49, 9392−9399.
(23) Liu, A. T.; Kunai, Y.; Cottrill, A. L.; Kaplan, A.; Zhang, G.; Kim,
H.; Mollah, R. S.; Eatmon, Y. L.; Strano, M. S. Solvent-Induced
Electrochemistry at an Electrically Asymmetric Carbon Janus Particle.
Nat. Commun. 2021, 12, 3415.
(24) Das, A.; Stahl, S. S. Noncovalent Immobilization of Molecular
Electrocatalysts for Chemical Synthesis: Efficient Electrochemical
Alcohol Oxidation with a Pyrene-TEMPO Conjugate. Angew. Chem.,
Int. Ed. 2017, 56, 8892−8897.
(25) Breuhaus-Alvarez, A. G.; DiMeglio, J. L.; Cooper, J. J.;
Lhermitte, C. R.; Bartlett, B. M. Kinetics and Faradaic Efficiency of
Oxygen Evolution on Reduced HxWO3 Photoelectrodes. J. Phys.
Chem. C 2019, 123, 1142−1150.
(26) Védrine, J. C. Metal Oxides in Heterogeneous Oxidation
Catalysis: State of the Art and Challenges for a More Sustainable
World. ChemSusChem 2019, 12, 577−588.
(27) Zhao, G.; Yang, F.; Chen, Z.; Liu, Q.; Ji, Y.; Zhang, Y.; Niu, Z.;
Mao, J.; Bao, X.; Hu, P.; et al. Metal/Oxide Interfacial Effects on the

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