https://doi.org/10.

1038/s41929-022-00828-w

Supplementary information

Enhancing acetate selectivity by coupling

anodic oxidation to carbon monoxide
electroreduction
In the format provided by the
authors and unedited
Supplementary Note 1: Development of durable eCOR MEA:
Before operation in semi-batch, the maximum concentration of acetate capable of being
produced was measured via recirculation of a small amount of 2 M KOH in the cell until failure.
It was found that after recirculation, a maximum concentration of 2.2 M acetate allowed for cell
voltage to not experience a significant increase in potential (Supplementary Figure 29). Long-
term experiments were then completed where the anolyte was replaced every 24 hours in a
semi-batch style recirculation. The cell was operated continuously for 71 hours (Supplementary
Figure 30a), with 3 samples collected containing 1.92, 2.3, and 2.59 M acetate. Acetate purities
of 93.9, 97.1, and 98% (Supplementary Figure 30b) compared to other liquid products was
achieved. The acetate carbon selectivity was also maintained at >60%, achieving a maximum of
77.8% at the 71-hour sample (Supplementary Figure 30c). Acetate Faradaic efficiency (FE)
increases continuously from 35.7% at 24 hours to 48.7% at 71 hours, while ethylene FE decreases
slowly from 39% to 23.2%. This decrease in ethylene, and conversely increase in acetate,
production is attributed to the slow flooding of the Cu surface over the course of the experiment.
The cell performance suffered greatly after 71 hours, and it was determined that the primary
cause was the mechanical failure of FAA-3-50. This mechanical failure could be one of two things,
both related to the low durability of FAA-3-50. One possibility is the exposure of FAA-3-50 to a
mildly acidic environment at 71 hours, where the extreme concentration of acetate neutralized
the buffering capacity of 2 M KOH to a pH of 5.9. Exposure to harsh organics from electrochemical
CO reduction and alcohol partial oxidation could also play a role in the mechanical failure of FAA-
3-50, as seen by the discoloration of the membrane after 71 hours. Additional experiments were
attempted with 3 M KOH to avoid anolyte acidification, but the membrane failed before 50 hours
of durability suggesting that the FAA-3-50 is not stable in harsh alkaline conditions
(Supplementary Figure 31).
To mitigate the impact of the membrane on system durability, a highly alkaline stable
membrane (mTPN1-TMA), was synthesized (Supplementary Note 3). This membrane was used in
place of FAA-3-50 due to its increased durability in the presence of concentrated KOH, removing
one of the possible failure mechanisms seen with FAA-3-50.1 The same Cu nanoparticle cathode
and NiFeOx anode used with FAA-3-50 were implemented. Supplementary Figure 32a shows the
cell performance in the 100-hour continuous CO electrolysis experiment. A stable full cell
potential of 2.25 V (no iR correction applied) was achieved at a constant operating current density
of 200 mA cm-2. A maximum acetate concentration of 3.2 M was obtained at a purity of 97.8 %
(Supplementary Figure 32b). Additionally, a maximum acetate FE of 56.4%, assuming all acetate
was produced at the cathode, was reached simultaneously, representing a carbon selectivity of
80% (Supplementary Figure 32c). The conversion of CO was also maintained at over 40% for the
entirety of the test (Supplementary Figure 33).
Over the course of both initial durability tests, acetate concentration at some point
exceeded the initial KOH concentration. As a result, there are large spikes in cell potential, which
is due to the anolyte dipping below a pH of 10 (Supplementary Figure 8). When the pH of the

1
sample dips below pH 10, there is irreversible losses of Fe from the catalyst surface
(Supplementary Figure 34). This was demonstrated to happen immediately upon the anolyte
dropping below pH 10, as evident when the electrolyzer was run for under 24 hours
(Supplementary Figure 8) and yet the Fe content of the anode was still completely lost
(Supplementary Figure 35). Therefore, it is necessary to maintain the concentration of acetate to
~1:1 with the KOH concentration. For improved anode durability in later experiments, a 0.5-
0.75:1 acetate to KOH ratio was maintained to protect the NiFeOx anode. Additionally, it can be
seen that for both FAA-3-50 and mTPN1-TMA that there is a gradual decay in ethylene FE, with
both cases losing ~50% ethylene production over the durability tests. The most likely cause of
this is flooding of the microporous layer. Previous reports have shown that increasing the wet
proofing in the catalyst layer improves the durability of the system.2 Therefore, an improved gas
diffusion layer was designed to include 20 wt% wet proofing in the catalyst layer. Lastly, both
cases demonstrated a lack of stability in the membrane. FAA-3-50 ruptured after <75 hours in
both 2 and 3 M KOH and suffered significant discoloration. mTPN1-TMA also decay, but to a lower
degree with post reaction 1H NMR indicating a 10% loss in functional groups throughout
operation (Supplementary Figure 36). Lastly, Orion Polymer’s AMX was utilized as the membrane
of choice for the final durability experiment as it has better alkaline resistance and similar alcohol
permeability to FAA-3-50 (Supplementary Figure 22) as well as had the closest CO reduction
performance to acetate (Supplementary Figure 37).1
Additional durability experiments in 5 M KOH were carried out at 100 mA cm-2. Acetate
FE was maintained at >37.5% throughout the experiment, with hydrogen and ethylene changing
modestly by ~5% FE throughout the experiment (Supplementary Figure 38). This shift in FE can
be attributed to accelerated flooding of the cathode due to the higher KOH concentration, as Ni
and Fe were detected on the cathode post reaction (Supplementary Figure 39). The NiFeOx anode
showed minimal degradation even in the harsh 5 M KOH condition, with post reaction XPS
showing minimal change in surface Fe atomic %., with pre and post reaction samples remaining
roughly at ~40-41 atomic % (Supplementary Figure 40). Post reaction inductively coupled plasma
mass spectrometry was performed on the anolytes collected, and only trace Fe (<0.3 ppm) was
detected (Supplementary Figure 41). Very minor surface roughening was observed in the post
reaction SEM, but no significant structural damaging was observed (Supplementary Figure 42).
This roughening could explain why some Fe was found in solution while the surface percentage
remained unchanged, as loose Fe could have dislodged from the anode during reaction.
Additionally, some Fe could have been leached by the stainless steel endplate in the 5 M KOH
environment. The accelerated flooding of the cathode does highlight the need for development
of specialty materials specifically tailored for CO electrolysis for future deployment of this
technology. Additionally, more stable endplates such as Ti based alloys would improve system
durability.

2
Supplementary Note 2: Determination of Acetate FE from partial alcohol oxidation
As a non-negligible portion of acetate (~30% at 600 mA cm-2) was produced via the
partial oxidation of ethanol, corrected acetate FE was determined based on Supplementary
Equation 1. This value was solely utilized in Figure 2 and the surrounding discussion, all other
acetate FEs were based on the assumption of a 4e- reduction process.
/(%
FE!"#,%&''(")(* = FE!"&,#+,('-(* − %FE!"#,#+(',-(* − FE!"#,.' & + !"#$
0(%
∗ (FE!"#,#+(',-(* − FE!"#,.' ) (1)
&'#

Where FEAcO,Corrected represents the corrected acetate FE, FEAcO,Oberseved is the measured
acetate FE based on a 4e- reduction, FeAcO,Ir is the FE for acetate measured with the IrOx/Ti Felt
anode, e-EtOH is the electrons required to produce the ethanol that was converted to acetate, and
e-AcO is the number of electrons required to produce acetate. Supplementary Equation 1 is an
estimate of the total amount of charge that was dedicated to producing acetate from eCOR. The
value from this formula was used in Figure 2d for the corrected current density. The ideal route,
however, to measure the percentage of acetate produced via ethanol oxidation is by measuring
the O2 FE from the anode. To confirm these values, the O2 FE was measured via purging argon
gas through the anolyte in a sealed reservoir. The off gas was then passed through a gas
chromatogram where the amount of oxygen produced was collected. The results confirmed that
the missing O2 FE was detected to within ~90% of the expected missing FE (Supplementary Figure
20). This therefore justifies the Supplementary Equation 1 in its prediction of the amount of
alcohols being partially oxidized at the anode.
Supplementary Note 3: Description of mTPN1-TMA synthesis and properties
Materials
All reagents and solvents were purchased from Sigma-Aldrich, Alfa Aesar, and Acros Organics,
and were used as received without further purification.
Instrumentation
1
H nuclear magnetic resonance (NMR) spectra were obtained using a Varian Unity 500 MHz
spectrometer, and chemical shifts were referenced to the residual solvent peaks of CDCl3 (7.26
ppm) or DMSO-d6 (2.50 ppm). The average molecular weight and dispersity of mTPBr were
determined by gel permeation chromatography (GPC) with a Viscotek GPC max model and
TDA302 detector using THF (0.8 mL min-1) as an eluent and polystyrene standards.
Experimental
Synthesis of mTPBr
mTPBr was synthesized following a procedure in our previous report.3 To a 100 mL three-neck
round bottom flask equipped with a magnetic stirring bar under nitrogen atmosphere were
charged with m-terphenyl (2.50 g, 10.9 mmol), 7-bromo-1,1,1-trifluoroheptan-2-one (2.95 g, 11.9
mmol), and methylene chloride (12 mL). The mixture was cooled in an ice-water bath, and

3
trifluoromethanesulfonic acid (5.8 mL, 65.1 mmol) was added dropwise. The reaction mixture
was stirred for 14 hours at room temperature and then diluted with additional methylene
chloride (12 mL) followed by precipitating into methanol (150 mL). The polymer was redissolved
in tetrahydrofuran (25 mL) and reprecipitated into methanol (150 mL) to afford the final product
as a yellow fiber-like solid. Yield: 98%. 1H NMR (CDCl3): δ (ppm) 7.84 (s, 1H), 7.61 (m, 6H), 7.05
(m, 1H), 7.04 (m, 4H), 3.33 (m, 2H), 2.47 (m, 2H), 1.81 (m, 2H), 1.46 (m, 2H), 1.29 (m, 2H). GPC:
Mn = 76 kg mol-1, Ð = 3.1 (Supplementary Figure 43).
Synthesis of mTPN1-TMA
In a 100 mL one-neck round bottom flask mTPBr (2.0 g, 4.4 mmol) was dissolved into N, N-
dimethylacetamide (20 mL), and trimethylamine (1.74 g, 45 wt% aq. solution, 13.2 mmol) was
added. The reaction mixture was stirred at room temperature for 24 h and then precipitated in
tetrahydrofuran (100 mL). The polymer was washed with acetone and dried under reduced
pressure at 60 ˚C. Yield: 96%. 1H NMR (DMSO-d6): δ (ppm) 7.99 (br, 1H), 7.83 (br, 4H), 7.71 (br,
2H), 7.58 (br, 1H), 7.41 (br, 4H), 3.23 (br, 2H), 3.01 (br, 9H), 2.57 (br, 2H), 1.63 (br, 2H), 1.30 (br,
2H), 1.24 (br, 2H) (Supplementary Figure 43).
Membrane casting of mTPN1-TMA
In a glass vial mTPN1-TMA was dissolved into dimethyl sulfoxide (5 wt%) at room temperature.
The solution was filtered through a syringe equipped with a short plug of cotton ball to remove
any insoluble parts. The filtered solution was cast on a leveled glass plate and was dried at 80 ˚C
in an oven under a slight positive air flow for 24 h.
In-plane hydroxide conductivity of mTPN1-TMA
The membrane was cut into rectangular specimen (ca. 3cm × 0.5 cm) and ion-exchanged to
hydroxide form by immersing in 1M NaOH (aq.) for 24 h. The specimen was rinsed and kept in
deionized water overnight inside an argon-filled glovebox. The in-plane hydroxide conductivity
was measured using a four-probe electrode method with BT-512 membrane conductivity test
system. Measurement was carried out under fully hydrated conditions (i.e., the cell was
immersed in deionized water) at 30 and 80 ˚C. The hydroxide conductivity values were
calculated using Supplementary Equation 2 below.
!
𝜎 (𝑚𝑆/𝑐𝑚) = "×$ ×&
(2)

Where L is the distance between two inner electrodes, R, W, T are the resistance, width, and
thickness of membrane specimen, respectively (Supplementary Table 4).

4
Supplementary Note 4: Acetate protonation and electrolyte recovery model
Prior to distillation, the acetate was protonated with an HCl solution to produce acetic acid. The
KOH present in the electroylzer outlet was also converted to KCl in this mixing step. This KCl was
then recovered out of the bottom of the first distillation column and converted back to KOH via
electrolysis. Hydrogen and chlorine gas was also produced in this same electrolyzer and
subsequently converted to HCl via combustion and recycled for acetate protonation. The cost of
this process was estimated using the at-scale process economics of the chloroalkali industry. The
typical electricity demand of NaCl electrolysis (2,500 kWh ton-1) was used to determine the
electricity required to regenerate the KOH electrolyte from KCl.4–6 Assuming an equivalent
number of electron transfers per KOH and Cl-, the energy usage could be adjusted using the molar
mass of NaCl and KCl (Supplementary Table 5). It was also assumed that all K+ ions from KOH
were bound to acetate at the CO electrolyzer outlet. To determine the total cost of the acetate
protonation and electrolyte recovery process, it was assumed that electricity usage captures 50%
of the total cost as reported for a typical industrial chloroalkali process.7

Supplementary Note 5: Aspen Plus simulation

The distillation costs and energy usage were studied using ASPEN Plus software with the
Economic Analyzer and Energy Analyzer plugins using the NRTL-HOC property method. Operating
costs were determined by linearly scaling the utility costs provided by the simulation with the
desired flow rate. Glacial acetic acid (>99.5 wt%) was produced for outlet acetate concentrations
ranging from 0.5-7 M using a separation scheme previously reported in literature.8,9 Since acetic
acid and water form a pinch point (similar to an azeotrope) that is difficult to overcome via
conventional distillation, azeotropic distillation must be used.10 In the modeled process, ethyl
acetate is used to extract the acetic acid from water in a liquid-liquid extractor modeled in ASPEN
using an Extract column. The amount of solvent was minimized up until a significant amount of
acetic acid was lost to the water dominant phase. The extract was then fed to a dehydration
column where glacial acetic acid was produced out of the bottoms. This column was modeled in
ASPEN using a RadFrac column. The dehydration column distillate was fed to a decanter to
separate the water from the ethyl acetate recycle. Finally, the water stream was then fed to a
water purification column along with the KCl solution from the bottoms of the extractor. The
water purification column was modeled in ASPEN using a RadFrac column. Any remaining ethyl
acetate was separated into the distillate in the water purification column and recycled back to
the decanter. The RadFrac columns were optimized in ASPEN by first modeling the column using
a DSTWU column to determine number of stages, feed stage, and reflux ratio. Information on the
separation columns in the ASPEN simulation can be found in Supplementary Tables 6-8.

5
Supplementary Figures and Tables:

100

80

Carbon Selectivity (%)

60

40

20

0
0 20 40 60 80 100 120
Time (hours)

Acetate Ethylene Propionate Ethanol 1-Propanol

100 Figure 1: Carbon selectivity of eCOR products during 120-hour durability

Supplementary
experiment. Carbon selectivity represents the molar selectivity of the products scaled to the
moles of CO needed to produce said product.
80
(%)

a Ni 2p3/2 Ni 2p
b Fe 2p3/2 Fe 2p
c Fe 3p
Pre Fe 2p1/2
Carbon Selectivity
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

Fe3+ Fe3+
Ni 2p1/2

60
2+
Sat. Sat. Ni

40Binding energy (eV)

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV)

d Ni 2p
e Fe 2p
f Fe 3p
120 h
Ni 2p3/2 Fe 2p3/2
Fe 2p1/2
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

20
Sat.
Ni 2p1/2
Sat. Ni 2+
Fe3+ Fe3+

0
880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50

0
Binding energy (eV)
20 40 60
Binding energy (eV)
80 100 120 Binding energy (eV)

Supplementary Figure 2: Pre and Post reaction X-ray photoelectron spectroscopy of NiFeOx/Ni
Time (hours)
Foam anodes during long term durability testing. (a) Ni 2p, (b) Fe 2p, and (c) Fe 3p spectrum for
pre-reaction sample. (d) Ni 2p, (e) Fe 2p, and (f) Fe 3p spectrum for post-reaction sample for 120-
hour experiment using AMX membrane.

6
 a 100
b 0.25
Fe Fe

Trace metal leach rate (µg/hr)

Anolyte Concentration (ppb) Ni Ni
80 0.20

60 0.15

40 0.10

20 0.05

0 0.00
0 50 100 150 0 50 100 150
Time (hr) Time (hr)

Supplementary Figure 3: Inductively coupled plasma mass spectrometry analysis of trace metals
detected in solution for 3 M KOH durability experiment. (a) Detected concentration of Ni and Fe
ions in anolyte. (b) Rate of trace metal leaching. Ni concentration was below the detection limit
for all data points. Anolytes were recirculated for 24 hours during experiment, and the rate is the
average over the collection period.

a Cu 2p
b Ni 2p
c Fe 3p
Pre Cu 2p3/2

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

Sat. Cu 2p1/2
Cu2+
Sat. F

960 950 940 930 880 875 870 865 860 855 850 845 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

d Cu 2p
e Ni 2p
f Fe 3p
Post Cu 2p3/2
Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

Cu0/1+
Cu 2p1/2 F

960 955 950 945 940 935 930 925 880 875 870 865 860 855 850 845 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplementary Figure 4: Pre and Post reaction X-ray photoelectron spectroscopy for Cu cathode
on gas diffusion electrode. (a) Cu 2p spectra for pre-reaction sample. Cu surface is oxidized, as
sample was exposed to air. Pre-reaction spectra for (b) Ni 2p and (c) Fe 3p, indicating an absence
of these metals. (d) Post-reaction Cu 2p spectra. Samples were stored under Ar gas following
electrolysis causing minimal oxidation of Cu. Post-reaction spectra for (e) Ni 2p and (f) Fe 3p,
indicating no metals were deposited during the durability experiment.

7
 a b

c d

Supplementary Figure 5: Scanning electron microscopy images for durability testing NiFeOx
anodes. (a) Scanning electron microscopy image for pre-reaction NiFeOx on Ni foam at a 500X
magnification. (b) Scanning electron microscopy image for post reaction NiFeOx on Ni foam at a
500X magnification. (c) Scanning electron microscopy image for pre-reaction NiFeOx on Ni foam
at a 10,000X magnification. (b) Scanning electron microscopy image for post reaction NiFeOx on
Ni foam at a 10,000X magnification. All images were taken at a voltage of 3 kV.

8
 50

40

CO Conversion (%)
30

20

10

0
0 20 40 60 80 100 120
Time (hours)

Supplementary Figure 6: Measured conversion of fed CO via eCOR during CO electrolysis during
120 hour long term operation of electrolyzer. Conversion was determined via volumetric flow
rate comparison of inlet and outlet CO. The cell was operated with 3 M KOH at 200 mA cm-2 with
a fixed flow rate of 10 sccm.

a 100
b
2.45
80
CO Conversion (%)

2.40
Cell Voltage (V)

60
2.35

40
2.30

20 2.25

0 2.20
0 5 10 15 20 0 5 10 15 20
CO Flow Rate (mL min-1) CO Flow Rate (mL min-1)

c 50
d 50
Hydrogen Faradaic Efficiency (%)
Ethylene Faradaic Efficiency (%)

40 40

30 30

20 20

10 10

0 0
0 5 10 15 20 0 5 10 15 20
CO Flow Rate (mL min-1) CO Flow Rate (mL min-1)

Supplementary Figure 7: Maximum achievable conversion for CO electrolyzer. Current was held
at 300 mA cm-2 as gas flow rate was stepped down every half hour. A 2 M KOH electrolyte was
used with a NiFeOx/Ni Foam and a Cu nanoparticle cathode. (a) Measured conversion of CO using
volumetric flow rate in and out. (b) Measured cell potential after 30 minutes of stabilization at
each flow rate. (c) Measured ethylene Faradaic Efficiency at each flow rate after 30 minutes of
stabilization. (d) Measured hydrogen Faradaic Efficiency at each flow rate after 30 minutes of
stabilization.

9
 a 3.5 100
b 2.5
Ethylene 16 pH
Hydrogen Acetate Concentration

Acetate Concentration (M)

3.0

Faradaic Efficiency (%)

80 2.0
14
Cell Voltage (V)

2.5
60 12 1.5

pH
2.0
40 10 1.0
1.5
8
20 0.5
1.0
6
0.5 0 0.0
0 120 240 360 480 600 720 840 960 0 120 240 360 480 600 720 840 960
Time (min) Time (min)

Supplementary Figure 8: Impact of acetate concentration on performance of CO electrolyzer. (a)

Measured cell voltage and gaseous Faradaic efficiencies for CO electrolyzer. (b) Measured pH of
anolyte during concentrating and acetate concentration. 20 mL of 2 M KOH was recirculated
through the anolyte, cell was held at 200 mA cm-2 and 15 sccm CO using AMX membrane. Acetate
concentration is based on the final concentration measured of 2.489 M acetate and assumed
constant production. Vertical dashed light orange line indicates where the acetate to KOH ratio
reaches 1:1 and the vertical dashed purple line indicates where the ratio reaches 1.2:1.

a 50
b
100
Acetate Faradaic Efficiency (%)

Acetate Carbon Selectivity (%)

40 90

30 80

70
20

60
10
50
0
0 1 2 3 4 5 6 7 8 9 10 0 2 4 6 8 10
KOH Concentration (M) KOH Concentration (M)

Supplementary Figure 9: Maximum concentration of acetate before degradation is observed for

CO electroreduction in an MEA system using AMX membrane. (a) Measured acetate Faradaic
efficiency post concentration. (b) Acetate carbon selectivity at varying initial KOH concentrations.
Cell was operated at 300 mA cm-2 and 15 sccm CO flow rate. Complete cell degradation was
assumed when the cell voltage reached 2.8 V, representing a voltage increase of ~20%.

10
 a Ni 2p
b Ni 2p
c Co 2p
Ni 2p3/2 Ni 2p3/2 Co 2p3/2

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)
Sat. Ni 2p1/2
Ni2+ Ni2+ Co2+
Ni 2p1/2 Co 2p1/2
Sat. Ni0
Sat. Sat. Sat. Sat.

Ni0

880 875 870 865 860 855 850 845 880 875 870 865 860 855 850 845 810 800 790 780 770
Binding energy (eV) Binding energy (eV) Binding energy (eV)

d Ni 2p
e Fe 2p3/2 Fe 2p
f Fe 3p
Ni 2p3/2
Fe 2p1/2

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2 Fe3+ Fe3+

Sat. Sat. Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplementary Figure 10: X-ray photoelectron spectroscopy imaging of Ni based anodes. (a)
Spectra for bare Ni foam anode in Ni 2p. (b,c) Spectra for CoOx/Ni foam anode in the (b) Ni 2p
and (c) Co 2p energies. (d-f) Spectra for NiFeOx/Ni foam in (d) Ni 2p, (e) Fe 2p, and (f) Fe 3p
energies.

a Ir 4f
b Ti 2p
Ir 4f5/2 Ir 4f7/2
Intensity (a.u.)

Intensity (a.u.)

Ir3+/4+

Sat.
Sat.

72 70 68 66 64 62 60 58 475 470 465 460 455 450

Binding energy (eV) Binding energy (eV)

Supplementary Figure 11: X-ray photoelectron spectroscopy for IrOx deposited on Ti felt. (a) Ir 4f
and (b) Ti 2p spectrum. Absence of Ti signal indicates full coverage of Ti felt, exposing only IrOx
for activity.

11
 a b

c d

Supplementary Figure 12: Scanning electron microscopy, energy dispersive X-ray analysis for
anodes. (a) Scanning electron microscopy image for bare Ni foam. Inlay is the energy dispersive
X-ray measurement of the bare Ni Foam. (b) Scanning electron microscopy image of NiFeOx
electrodeposited on Ni foam. Inlay is the energy dispersive x-ray measurement of deposited Fe
(c) Scanning electron microscopy image for electrodeposited CoOx on Ni foam. Inlay is the energy
dispersive x-ray measurement of deposited Co. (d) Scanning electron microscopy image for
calcinated IrOx on titanium felt. Inlay is the energy dispersive X-ray measurement of the
deposited species, Ir. Images for energy dispersive x-ray measurements were taken at a
magnification of 800X and a voltage of 15 kV.

12
Supplementary Figure 13: Scanning electron microscopy images for anodes. (a) Scanning
electron microscopy image for bare Ni foam. (b) Scanning electron microscopy image for
electrodeposited NiFeOx on Ni foam. (c) Scanning electron microscopy image for
electrodeposited CoOx on Ni foam. (d) Scanning electron microscopy image of IrOx on Ti felt. All
images were taken at 800X magnification at a voltage of 3 kV.

13
 a b

c d

Supplementary Figure 14: Scanning electron microscopy images for anodes. (a) Scanning
electron microscopy image for bare Ni foam. (b) Scanning electron microscopy image for
electrodeposited NiFeOx on Ni foam. (c) Scanning electron microscopy image for
electrodeposited CoOx on Ni foam. (d) Scanning electron microscopy image of IrOx on Ti felt. All
images were taken at 10,000X magnification at a voltage of 3 kV.

14
 400
0 M EtOH

Current Density (mA cm-2)

0.01 M EtOH
0.05 M EtOH
300
0.1 M EtOH
0.5 M EtOH
1 M EtOH
200

100

0
100 150 200 250 300
Overpotential (VRHE - 1.23 V)

Supplementary Figure 15: Impact of ethanol concentration on the activity of a NiFeOx/Ni Foam
anode. Experiments were run in H-type cell at a scan rate of 25 mV s-1 from 1 to 1.6 V vs. RHE.
Supporting electrolyte was 2 M KOH and listed ethanol concentration.

Supplementary Figure 16: Schematic for flow alcohol oxidation experiments. Anolyte (2 M KOH
or 2 M KOH + 0.5 M ethanol + 0.5 M n-propanol) is fed through a reference electrode holder prior
to the electrolyzer. Using a Luggin Capillary, the potential of the anode is measured in reference
to a Hg/HgO electrode.

15
 a 120
Acetaldehyde Propionate Acetate
b 120
Acetaldehyde Propionate Acetate

Current Density NiFeOx/Ni Foam Current Density CoOx/Ni Foam

600 600

Current Density (mA cm-2)

Current Density (mA cm-2)

100 100
Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 80
400 400
60 60

40 40
200 200
20 20

0 0 0 0
1.36 1.37 1.38 1.39 1.40 1.375 1.400 1.425 1.450 1.475 1.500
Potential (V vs. RHE) Potential (V vs. RHE)

c 120
Acetaldehyde Propionate Acetate
d Acetaldehyde Propionate Acetate

Current Density Bare Ni Foam Current Density IrOx/Ti Felt

100
600 Current Density (mA cm-2) 600

Current Density (mA cm-2)

100
Faradaic Efficiency (%)

Faradaic Efficiency (%)

80
80
400 60 400
60

40 40
200 200
20 20

0 0 0 0
1.40 1.42 1.44 1.46 1.485 1.490 1.495 1.500 1.505 1.510
Potential (V vs. RHE) Potential (V vs. RHE)

Supplementary Figure 17: Carboxylate Faradaic efficiencies, measured via 1H-NMR for (a)
NiFeOx/Ni Foam, (b) CoOx/Ni Foam, (c) Bare Ni foam, and (d) IrOx/Ti Felt. Experiments were
performed in 2 M KOH + 1 M ethanol using a Hg/HgO reference electrode and a Pt/C counter
electrode. Cathodic reaction was hydrogen evolution under an argon flow at a rate of 20 sccm.
Cell was divided by an FAA-3-50 membrane. Potential was 85% iR corrected.

16
 a Acetate Propionate
b Acetate Propionate

NiFeOx/Ni Foam Current Density CoOx/Ni Foam Current Density

100
100 600 600

Current Density (mA cm-2)

Current Density (mA cm-2)

Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 80

400 60 400
60

40 40
200 200
20 20

0 0 0 0
1.395 1.400 1.405 1.410 1.415 1.420 1.375 1.400 1.425 1.450 1.475
Potential (V vs. RHE) Potential (V vs. RHE)

c Acetate Propionate
d 100
Acetate Propionate

Bare Ni Foam Current Density IrOx/Ti Felt Current Density

100
600 Current Density (mA cm-2) 600

Current Density (mA cm-2)

80
Faradaic Efficiency (%)

Faradaic Efficiency (%)

80

400 60 400
60

40
40
200 200
20 20

0 0 0 0
1.40 1.42 1.44 1.46 1.48 1.44 1.45 1.46 1.47 1.48 1.49
Potential (V vs. RHE) Potential (V vs. RHE)

Supplementary Figure 18: Carboxylate Faradaic efficiencies, measured via 1H-NMR for (a)
NiFeOx/Ni Foam, (b) CoOx/Ni Foam, (c) Bare Ni Foam, and (d) IrOx/Ti Felt. Experiments were
performed in 2 M KOH + 0.5 M ethanol + 0.5 M n-propanol using a Hg/HgO reference electrode
and a Pt/C counter electrode. Cathodic reaction was hydrogen evolution under argon
atmosphere. Cell was divided by an FAA-3-50 membrane. Potential was 85% iR corrected. Data
presented is the average of three independent experiments with the error bars representing the
standard deviation of the three independent measurements.

17
 Propionate Acetate 1-Propanol Propionate Acetate 1-Propanol
a Ethanol Ethylene Hydrogen
700
b Ethanol Ethylene Hydrogen
700
NiFeOx/Ni Foam Current Density CoOx/Ni Foam Current Density
100 100
600 600

Current Density (mA cm-2)

Current Density (mA cm-2)

Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 500 80 500

400 400
60 60

300 300
40 40
200 200
20 20
100 100

0 0 0 0
1.95 2.00 2.05 2.10 2.15 2.20 2.25 2.30 2.00 2.05 2.10 2.15 2.20 2.25 2.30 2.35
Cell Voltage (V) Cell Voltage (V)

c
Propionate Acetate 1-Propanol
d
Propionate Acetate 1-Propanol
Ethanol Ethylene Hydrogen Ethanol Ethylene Hydrogen
700 700
Bare Ni Foam Current Density IrOx/Ti Felt Current Density
100 100
600 Current Density (mA cm-2) 600

Current Density (mA cm-2)

Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 500 80 500

400 400
60 60

300 300
40 40
200 200
20 20
100 100

0 0 0 0
2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.0 2.1 2.2 2.3 2.4 2.5
Cell Voltage (V) Cell Voltage (V)

Supplementary Figure 19: Faradaic efficiency and measured current density for different anode
catalysts using an FAA-3-50 membrane. All tests used the same design Cu nanoparticle catalyst
and anodes were changed after each experiment to either (a) NiFeOx/Ni Foam, (b) CoOx/Ni Foam,
(c) Bare Ni Foam, or (d) IrOx/Ti Felt. All tests were performed using 20 sccm CO flow rate at
ambient temperature with a set pressure of 15.5 psia. Anolyte was kept constant as 2 M KOH and
fed at a rate of 0.5 mL min-1, catholyte was collected in the DI water trap. Data presented is the
average of three independent experiments with the error bars representing the standard
deviation of the three independent measurements.

18
 100

Oxygen Faradaic Efficiency (%)

80

60

40

20
Predicted
Measured
0
0 200 400 600
Applied Current Density (mA cm-2)

Supplementary Figure 20: Measurement of O2 Faradaic Efficiency from anode compared with
predicted O2 Faradaic efficiency from comparison of NiFeOx/Ni foam and IrOx/Ti Felt anodes.
Measured oxygen Faradaic efficiency is within error bar of the predicted value based on the shift
in carboxylate production. The test was performed using a CO flow rate of 20 sccm at ambient
temperature. Anolyte was kept constant as 2 M KOH and 100 sccm Ar was bubbled through the
anolyte to carry produced O2 to the gas chromatogram. Data presented is the average of three
independent experiments with the error bars representing the standard deviation of the three
independent measurements.

a b
Ethylene + Acetate Carbon Selectivity (%)

100 100
NiFeOx/Ni Foam NiFeOx/Ni Foam
CoOx/Ni Foam
CoOx/Ni Foam
Anolyte Acetate Purity (%)

90 Bare Ni Foam
Bare Ni Foam IrOx/Ti Felt
80
IrOx/Ti Felt
80

60 70

60
40

50
0 200 400 600 0 200 400 600
Total Current Density (mA cm-2) Total Current Density (mA cm-2)

Supplementary Figure 21: (a) Single pass acetate purity in anolyte measured on a mol basis
relative to other multicarbon products in the anolyte. (b) Combined carbon selectivity towards
acetate and ethylene for all anodes. All experiments were performed with a Cu nanoparticle
cathode, a FAA-3-50 membrane, a 2 M KOH anolyte, and a CO flow rate of 20 sccm. Data
presented is the average of three independent experiments with the error bars representing the
standard deviation of the three independent measurements.

19
 a 5
b 5
FAA-3-50 FAA-3-50

n-Propanol Concentration (mM)

Ethanol Concentration (mM)
FAAM-40 FAAM-40
4 mTPN1-TMA 4 mTPN1-TMA
AMX AMX
3 3

2 2

1 1

0 0
0 50 100 150 0 50 100 150
Time (min) Time (min)

Supplementary Figure 22: Diffusion results for alcohols through varied anion exchange
membranes. (a) Measured concentration of ethanol at different times. (b) Measured
concentration of n-propanol at different times. The two chambers were separated with the
corresponding anion exchange membrane, one containing 2 M KOH and the other 2 M KOH + 0.5
M ethanol + 0.5 M n-propanol. Alcohols were allowed to diffuse exclusively via conduction
through the membrane and the concentration was measured every 30 minutes.

a b
Propionate Acetate 1-Propanol Propionate Acetate 1-Propanol
Ethanol Ethylene Hydrogen Ethanol Ethylene Hydrogen
700 700
NiFeOx/Ni Foam IrOx/Ti Felt
100 100
600 600
Current Density (mA cm-2)

Current Density (mA cm-2)

Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 500 80 500

400 400
60 60

300 300
40 40
200 200
20 20
100 100

0 0 0 0
2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9
Cell Voltage (V) Cell Voltage (V)

Supplementary Figure 23: Faradaic efficiency and measured current density for different anode
catalysts using FAAM-40 membrane. All tests used the same design Cu nanoparticle catalyst and
anodes were changed after each experiment to either (a) NiFeOx/Ni Foam or (b) IrOx/Ti Felt. All
tests were performed using a CO flow rate of 20 sccm at ambient temperature at a fixed pressure
of 15.5 psia. Anolyte was kept constant as 2 M KOH and fed at a rate of 0.5 mL min-1, catholyte
was collected in the DI water trap.

20
 a b
Propionate Acetate 1-Propanol Propionate Acetate 1-Propanol
Ethanol Ethylene Hydrogen Ethanol Ethylene Hydrogen
700 700
NiFeOx/Ni Foam IrOx/Ti Felt
100 100
600 600

Current Density (mA cm-2)

Current Density (mA cm-2)

Faradaic Efficiency (%)

Faradaic Efficiency (%)

80 500 80 500

400 400
60 60

300 300
40 40
200 200
20 20
100 100

0 0 0 0
2.0 2.1 2.2 2.3 2.4 2.0 2.1 2.2 2.3 2.4 2.5 2.6
Cell Voltage (V) Cell Voltage (V)

Supplementary Figure 24: Faradaic efficiency and measured current density for different anode
catalysts with an mTPN1-TMA membrane. All tests used the same design Cu nanoparticle catalyst
and anodes were changed after each experiment to either (a) NiFeOx/Ni foam or (b) IrOx/Ti felt.
All tests were performed using a CO flow rate of 20 sccm at ambient temperature at a set
pressure of 15.5 psia. Anolyte was kept constant as 2 M KOH and fed at a rate of 0.5 mL min-1,
catholyte was collected in the DI water trap.

21
Supplementary Figure 25: Process flow diagram for 0.5-7 M acetate at electrolyzer outlet.

22
 a b

Supplementary Figure 26: Scanning electron microscopy, energy dispersive X-ray analysis for
cathode. (a) Scanning electron microscopy image for commercial 40-60 nm Cu nanoparticles.
Inlay is the energy dispersive X-ray measurement for Cu. (b) Scanning electron microscopy image
for commercial 40-60 nm Cu nanoparticles deposited on carbon gas diffusion layer (GDL). Inlay is
the energy dispersive X-ray measurement for Cu.

23
 a 1500 b 1000
NiFeOx/Ni Foam CoOx/Ni Foam
Current Density (mA cm-2)

Current Density (mA cm-2)

1200 800

900 600

600 400

300 200
KOH KOH
KOH + EtOH KOH + EtOH
0 0
0.5 1.0 1.5 2.0 0.5 1.0 1.5 2.0
Potential (V vs. RHE) Potential (V vs. RHE)

c 750
d
Bare Ni Foam IrOx/Ti Felt
1000
Current Density (mA cm-2)

Current Density (mA/cm2)

600
800
450
600

300
400

150 200
KOH KOH
KOH + EtOH KOH + EtOH
0 0
0.5 1.0 1.5 2.0 0.5 1.0 1.5 2.0
Potential (V vs. RHE) Potential (V vs. RHE)

Supplementary Figure 27: Linear sweep voltammograms for anodes. Linear sweep
voltammograms for (a) NiFeOx/Ni Foam, (b) CoOx/Ni Foam, (c) Bare Ni Foam, (d) IrOx/Ti Felt. All
voltammograms were recorded in either 1 M KOH or 1 M KOH + 1 M ethanol at a sweep rate of
25 mV s-1. An FAA-3-50 membrane was used to divide the H-cell along with a Pt wire counter
electrode and a Hg/HgO reference electrode. All potentials were 85 % iR corrected based on
resistance measured via i-interrupt.

24
 25
Ti Felt

Current Density (mA cm-2)

20

15

10

5 1 M KOH
1 M KOH + 1 M Ethanol
0
0.5 1.0 1.5 2.0
Potential (V vs. RHE)

Supplementary Figure 28: Linear sweep voltammograms for anodes. Linear sweep
voltammograms for bare Ti felt. Voltammogram was recorded in either 1 M KOH or 1 M KOH + 1
M ethanol at a sweep rate of 25 mV s-1. An FAA-3-50 membrane was used to divide the H-cell
along with a Pt wire counter electrode and a Hg/HgO reference electrode. Applied potential was
85 % iR corrected based on resistance measured via i-interrupt.

a 70 3.0
b 3
c 100
Cell Voltage
60 2.5
80
Anolyte Concentration (M)
Faradaic Efficiency (%)

Carbon Selectivity (%)

50
2.0 2
Cell Voltage (V)

60
40
1.5
30
Ethylene 40
Hydrogen 1.0 1
20
20
10 0.5

0 0.0 0 0
0 30 60 90 120 150 180 210 240 270 300 Acetate Propionate Ethanol 1-Propanol Acetate Propionate Ethanol 1-Propanol Ethylene
Time (min) Product Species Product Species

Supplementary Figure 29: Maximum concentration of acetate before degradation is observed

for CO electroreduction in an MEA system. (a) Faradaic efficiency for gaseous products and
operating cell voltage for CO reduction electrolyzer using 2 M KOH and FAA-3-50 membrane with
10 sccm CO flow rate. (b) Carbon selectivity of all multi-carbon products from electrochemical
CO reduction. (c) Maximum achieved anolyte concentration of dissolved liquid products before
accelerated degradation was observed.

25
 a 100
Hydrogen Ethylene Acetate b 4
c 100
Cell Potential 3 Acetate Purity
100

80 80

Anolyte Concentration (M)

3
Faradaic Efficiency (%)

80

Carbon Selectivity (%)

Acetate Purity (%)
Cell Potential (V)
60 2 60
60
2
40 40
40
1
1
20 20 20

0 0 0 0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (hours) Time (hours) Time (hours)

Acetate Ethylene Propionate Ethanol 1-Propanol

100
Supplementary Figure 30: Production of concentrated acetate streams via eCOR using FAA-3-50
membrane. (a) Faradaic efficiency of acetate, 80 hydrogen, and ethylene and total cell voltage
measured for eCOR system in 2 M KOH. (b) Measure of anolyte concentrations and purity of all

Carbon Selectivity (%)

liquid products detected. (c) Carbon selectivity60 of all multi-carbon products, ethylene is the
average over the period in which the anolyte was collected. Experiments were performed using
2 M KOH, 10 sccm CO feed, and 50 mL recirculated40 electrolyte. Cell current was held constant at
-2
200 mA cm and anolyte was replaced every 24 hours. Membrane was ruptured after 71 hours
allowing oxygen to cross over, causing cell failure.
20

2.5
0
0 10 20 30 40 50 60 70
Time (hours)
2.4
Cell Voltage (V)

2.3

2.2

2.1

2.0
0 10 20 30 40
Time (hr)

Supplementary Figure 31: Durability of CO electroreduction in an MEA using FAA-3-50

membrane and 3 M KOH. Experiment was done using a 50 mL electrolyte replaced every 24
hours, NiFeOx/Ni Foam anode, Cu nanoparticle cathode, and a CO flow rate of 10 sccm. Current
density was fixed at 200 mA cm-2. Pink arrow indicated where membrane rupture occurred,
leading to instability in cell voltage and crossover of oxygen, indicated by a loss of cathode
detected Faradaic efficiency and sudden drop in cell potential.

26
 a 100
Hydrogen Ethylene Acetate
3
b 4
c 100
Cell Potential Acetate Purity
100

80 80

Anolyte Concentration (M)

3
Faradaic Efficiency (%)

80

Carbon Selectivity (%)

Acetate Purity (%)
2

Cell Potential (V)

60 60
60
2
40 40
40
1
1
20 20 20

0 0 0 0 0
0 20 40 60 80 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Time (hours) Time (hours) Time (hours)

Acetate Ethylene Propionate Ethanol 1-Propanol

100
Supplementary Figure 32: Production of concentrated acetate streams via eCOR using mTPN1-
TMA membrane. (a) Faradaic efficiency of acetate,
80 hydrogen, and ethylene and total cell voltage
measured for eCOR system in 3 M KOH. (b) Measure of anolyte concentrations and purity of all

Carbon Selectivity (%)

liquid products detected. (c) Carbon selectivity
60 of all multi-carbon products, ethylene is the
average over the period in which the anolyte was collected. Experiments were performed using
3 M KOH, 10 sccm CO feed, and 50 mL recirculated
40 electrolyte. Cell current was held constant at
-2
200 mA cm and anolyte was replaced every 24 hours.
20

100
0
0 10 20 30 40 50 60 70
80 Time (hours)
CO Conversion (%)

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100
Time (hours)

Supplementary Figure 33: Measured conversion of fed CO via eCOR during CO electrolysis in long
term operation of electrolyzer. Conversion was determined via volumetric flow rate comparison
of inlet and outlet CO. The cell was operated with 3 M KOH at 200 mA cm-2 with a fixed flow rate
of 10 sccm using mTPN1-TMA membrane in 100 hour durability experiment.

27
 a b c
Pre Ni 2p3/2 Ni 2p
Fe 2p1/2
Fe 2p3/2 Fe 2p Fe 3p

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2 Fe3+ Fe3+

Sat. Sat. Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

d e f
72 h Ni 2p3/2 Ni 2p Fe 2p Fe 3p
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2
Sat. Sat. Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

g h i
100 h Ni 2p3/2 Ni 2p Fe 2p Fe 3p
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2
Sat. Sat.
Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplementary Figure 34: Pre and Post reaction X-ray photoelectron spectroscopy of NiFeOx/Ni
Foam anodes during long term durability testing. (a) Ni 2p, (b) Fe 2p, and (c) Fe 3p spectrum for
pre-reaction sample. (d) Ni 2p, (e) Fe 2p, and (f) Fe 3p spectrum for post-reaction sample for 72-
hour experiment using FAA-3-50 membrane. (g) Ni 2p, (h) Fe 2p, and (i) Fe 3p spectrum for post-
reaction sample for 100-hour durability test using mTPN1-TMA membrane.

a Ni 2p
b Fe 2p
c Fe 3p
Ni 2p3/2
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

Ni2+
Ni 2p1/2
Sat. Sat.

Ni0

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplementary Figure 35: Post reaction X-ray photoelectron spectroscopy of NiFeOx/Ni Foam
anodes during acidification experiment. (a) Ni 2p, (b) Fe 2p, and (c) Fe 3p spectrum for acidified
sample using AMX membrane. It is evident that all Fe content is lost.

28
Supplementary Figure 36: Pre and Post reaction 1H NMR of mTPN1-TMA membrane. (a) Pre
reaction, i.e. fresh, mTPN1-TMA, (b) post-reaction 1H NMR. Change in functional group peak
height shows a 10% loss in functionality of the membrane.

a b
Propionate Acetate 1-Propanol
Ethanol Ethylene Hydrogen
200
100 Current Density FAA-3-50
AMX
Acetate Current Density (mA cm-2)

600
mTPN1-TMA
Current Density (mA cm-2)

80 150 FAAM-40
Faradaic Efficiency (%)

60 400
100

40
200
50
20

0 0 0
2.00 2.05 2.10 2.15 2.20 2.25 2.30 2.0 2.1 2.2 2.3 2.4 2.5 2.6
Cell Potential (V) Cell Potential (V)

Supplementary Figure 37: (a) Performance curve for Faradaic efficiency and measured current
density for CO reduction with a NiFeOx/Ni Foam anode with an AMX membrane. (b) Comparison
of FAA-3-50, AMX, and mTPN1-TMA membranes for CO reduction towards acetate. Acetate
current density is not adjusted. All tests were performed using a CO flow rate of 20 sccm at
ambient temperature at a set pressure of 15.5 psia. Anolyte was kept constant as 2 M KOH and
fed at a rate of 0.5 mL min-1, catholyte was collected in the DI water trap.

29
 100 3
Hydrogen Cell Potential
Ethylene
80
Faradaic Efficiency (%)
Acetate

Cell Potential (V)

2
60

40
1

20

0 0
0 10 20 30 40 50
Time (hours)

Supplemental Figure 38: Stability testing for CO reduction in 5 M KOH. Faradaic efficiency
towards primary products and cell potential for 5 M KOH durability experiment. Experiment was
performed using 5 M KOH, 30 sccm CO feed, AMX membrane, and 40 mL recirculated electrolyte.
Current density was fixed at 100 mA cm-2 and anolyte was replaced every 24 hours.

a Cu 2p
b Ni 2p
c Fe 3p
Cu 2p3/2
Intensity (a.u.)

Intensity (a.u.)
Intensity (a.u.)

Cu0/1+
Cu 2p1/2 F

960 950 940 930 880 875 870 865 860 855 850 845 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplemental Figure 39: Post reaction X-ray photoelectron spectroscopy for Cu cathode on gas
diffusion electrode after 5 M KOH durability experiments (a) Cu 2p, (b) Ni 2p and (c) Fe 3p
spectra for post-reaction Cu sample operated at 100 mA cm-2 for 48 hours in 5 M KOH. Sample
shows no indication of Ni or Fe deposited on Cu surface.

30
 a Ni 2p3/2 Ni 2p
b Fe 2p
c Fe 3p
Fe 2p3/2
Fe 2p1/2
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2 Fe3+ Fe3+
Sat. Sat. Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

d Ni 2p
e Fe 2p
f Fe 3p
Ni 2p3/2 Fe 2p3/2
Fe 2p1/2
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Ni 2p1/2 Fe3+
Fe3+
Sat. Sat. Ni2+

880 875 870 865 860 855 850 845 735 730 725 720 715 710 705 700 62 60 58 56 54 52 50
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Supplemental Figure 40: Pre and Post reaction X-ray photoelectron spectroscopy of NiFeOx/Ni
Foam anodes during 5 M KOH durability testing. (a) Ni 2p, (b) Fe 2p, and (c) Fe 3p spectrum for
pre-reaction NiFeOx sample. (d) Ni 2p, (e) Fe 2p, and (f) Fe 3p spectrum for post-reaction sample
for sample operated at 100 mA cm-2.

a 0.5
b 0.5
Fe Fe
Trace metal leach rate (µg/hr)
Anolyte Concentration (ppm)

Ni Ni
0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
20 30 40 50 20 30 40 50
Time (hr) Time (hr)

Supplemental Figure 41: Inductively coupled plasma mass spectrometry analysis of trace metals
detected in solution for 5 M KOH durability experiment. (a) Detected concentration of Ni and Fe
ions in anolyte. (b) Rate of trace metal leaching. Ni concentration was below the detection limit
for all data points. Anolytes were recirculated for 24 hours during experiment, and the rate is the
average over the collection period.

31
Supplemental Figure 42: Scanning electron microscopy images for durability testing NiFeOx
anodes in 5 M KOH. (a) Scanning electron microscopy image for pre-reaction NiFeOx on Ni foam
at a 500X magnification. (b) Scanning electron microscopy image for post reaction NiFeOx on Ni
foam at a 500X magnification. (c) Scanning electron microscopy image for pre-reaction NiFeOx on
Ni foam at a 10,000X magnification. (b) Scanning electron microscopy image for post reaction
NiFeOx on Ni foam at a 10,000X magnification. All images were taken at a voltage of 3 kV.

32
Supplementary Figure 43: 1H NMR spectra of mTPN1-TMA (top) and mTPBr (bottom).

33
Supplementary Table 1: Summary of recent CO reduction systems performance (value listed for
This Work is the adjusted acetate current density)
System Membrane Used Maximum Acetate Maximum Acetate Purity Stability @ Reference
Current Density @ Concentration (mol %) Applied Current
Cell Voltage of Acetate (M) Density

Anode Collected mTPN1-TMA & 260 mA cm-2 @ 7.57 99.3 120 hours @ 200 This Work
MEA Orion AMX 2.24 V mA cm-2

Cathode Nafion 1110 34 mA cm-2 @ 2.32 1.1 92.7 24 hours @ 144 [11]
Collected MEA V mA cm-2

Cathode Sustainion X37- 29.8 mA cm-2 @ 0.0011 80 110 hours @ 150 [12]
Collected MEA 50 grade 60 2.7 V mA cm-2

3-Compartment Sustainion X37- 210 mA cm-2 @ 4.5 0.33 95 10 hours @ 700 [13]
Design 50 grade 60 V* mA cm-2

3-Compartment Fumasep FAA-3- 131 mA cm-2 @ 3.4 0.04 96.2 3 hours @ 100 [14]
Design 50 V** mA cm-2

3-Compartment Fumasep FAA-3- 98 mA cm-2 @ 3.3 0.03 45.1 1 hour @ 500 [15]
Design 50 V** mA cm-2

* iR-compensated full cell voltage

** Estimated full cell voltage based off comparison of half-cell and full cell potential using
electrolyzer design

Supplementary Table 2: Key membrane properties for those used in experiments (information
provided by manufacturer).
Membrane Manufacturer Functional Thickness (μm) Ion Exchange Water Uptake
Group Capacity at 25 oC
(meq./g)

FAA-3-50 Fumasep Tetramethyl 45–55 1.6–2.1 10–25 wt%

ammonia (R-
N(CH3)3+)

FAAM-40 Fumasep N/A 35–45 N/A (Equal to N/A

help electrolyte,
9 M KOH)

mTPN1-TMA Experimental Tetramethyl 33–43 2.18 45 wt%

ammonia (R-
N(CH3)3+)

AMX Orion Polymer N/A 35 2.2 unknown

34
Supplementary Table 3: Adjusted parameters from previously published electrochemical
production model.16

Parameter Value
Plant Operating Time 330 days yr-1
Electricity Price 0.05 USD kWh-1
CO Cost 0.06 USD kg-1
Base Electrolyzer Cost 587 USD kW-1
IrOx Anode Loading 4 mg cm-2
Outlet Acetate Purity 100%
Current Density 600 mA cm-2
Cell Voltage 2.2 V
Faradaic Efficiency 60%

Supplementary Table 4: In-plane hydroxide conductivity of mTPN1-TMA in water

Temperature (oC) OH- Conductivity (mS cm-2)

30 54
80 124

Supplementary Table 5: Estimation of KOH regeneration/acetate protonation costs with an

electricity cost of $0.05/kWh. Calculation is detailed in Supplementary Note 4.

Parameter Value

Electricity Usage 1.58 kWh kg-1 KOH

Electricity Usage Cost 7.90E-2 USD kg-1 KOH
Total Cost 0.15 USD kg-1 Acetic Acid

35
Supplementary Table 6. ASPEN Plus dehydration column parameters
Acetic Acid Reflux Ratio Stages Feed Stage Reboiler Duty (MJ hr-1) Condenser Duty (MJ hr-1)
Concentration (M)

0.5 0.24 30 15 1.60E+05 1.39E+05

1 0.24 22 10 1.09E+05 9.16E+04

2 0.24 18 5 7.33E+04 6.35E+04

3 0.24 16 5 2.74E+04 2.27E+04

5 0.22 14 5 1.30E+04 1.09E+04

7 0.19 14 5 7.42E+03 6.11E+03

Supplementary Table 7. ASPEN Plus water purification column parameters

Acetic Acid Reflux Ratio Stages Feed Stage Reboiler Duty (MJ hr-1) Condenser Duty (MJ hr-1)
Concentration (M)

0.5 0.1 12 2 9.82E+03 1.08E+03

1 0.1 12 2 9.77E+03 9.94E+02

2 0.1 10 2 4.63E+03 5.95E+02

3 0.1 7 2 2.83E+03 2.88E+02

5 0.1 7 2 6.63E+03 5.00E+03

7 0.1 7 2 2.65E+03 1.64E+03

Supplementary Table 8. ASPEN Plus extractor and decanter parameters

Acetic Acid Stages Solvent Feed (kg hr-1) Decanter Heat Exchanger
Concentration (M) Duty (MJ hr-1)

0.5 15 3.00E+05 2.13E+04

1 12 1.70E+05 1.81E+04

2 12 9.00E+04 9.72E+03

3 12 4.00E+04 4.46E+03

5 12 1.50E+04 2.06E+03

7 12 7.00E+03 1.15E+03

36
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