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Article
Optimizing utilization of point source and
atmospheric carbon dioxide as a feedstock in
electrochemical CO2 reduction

Alex Badgett,
Alison Feise,
Andrew Star
alex.badgett@nrel.gov

Highlights
Economic optimization of
carbon dioxide (CO2)
reduction in the U.S. is
modeled

Point source CO2 could be

used to create fuels and
chemicals in various
regions

As industrial sectors
decarbonize, supply of
CO2 point sources
diminishes

Direct air capture of CO2

could provide supple-
mental feedstock for
product synthesis

Badgett et al., iScience 25,

104270
May 20, 2022 ª 2022 The
Author(s).
https://doi.org/10.1016/
j.isci.2022.104270
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Article
Optimizing utilization of point source
and atmospheric carbon dioxide as a feedstock
in electrochemical CO2 reduction
Alex Badgett,1,4,* Alison Feise,1,2 and Andrew Star3

SUMMARY
The electrochemical reduction of carbon dioxide is a potential pathway for pro-
duction of fuels and chemicals that uses atmospheric carbon dioxide as a feed-
stock. Here, we present an analysis of the potential for carbon dioxide from point
sources and via direct air capture to be utilized in electrochemical reduction under
different market scenarios. We show that developing a network for production of
these products at scale requires capture and utilization of significant portions of
the carbon dioxide that is currently emitted from large stationary point sources.
Because carbon dioxide point sources are spatially and compositionally variable,
their use for carbon dioxide reduction depends on electricity prices, capture cost,
and location. If the power sector in the United States is decarbonized, carbon di-
oxide supply decreases significantly, increasing the importance of utilizing other
carbon dioxide streams, and increasing the likelihood that direct air capture plays
a role in supplying carbon dioxide feedstocks.

INTRODUCTION
Of the 6.67 billion metric tons (t) of CO2 equivalents emitted annually in the United States, over 1.4 billion t
equivalent (21%) is from the industrial sector (U.S. EPA, 2020). Decarbonizing industry is difficult, as many
industrial processes require natural gas feedstocks, high temperatures, and/or high-grade heat (Davis
et al., 2018). In many cases, natural gas is used as a fuel to generate heat and/or power and as a chemical
reactant for production of higher value chemicals (U.S. EIA, 2014). In the United States, the organic chem-
ical sector (e.g., plastics and rubber products) alone consumes 6.96 EJ of energy annually, which represents
roughly 6.5% of the total energy consumption in the entire country (U.S. EIA, 2018). Renewable energy
technologies such as wind and solar photovoltaics cannot be directly substituted into these processes,
and systems are needed that transform electrons from renewable energy into molecules useful in industrial
processes (Henry et al., 2020).

One opportunity is converting waste CO2 into chemicals and fuels via electrochemical carbon dioxide
reduction (CO2R) (De Luna et al., 2019). CO2R consumes electricity, water, and CO2 as feedstocks into
the reactor, and can produce various carbon-based molecules. Depending on the catalyst and system ar- 1StrategicEnergy Analysis
chitecture, state-of-the-art systems can produce molecules with one to three carbons (C1–C3) at varying se- Center, National Renewable
lectivities, current densities, and efficiencies (Bushuyev et al., 2018). Researchers have identified C1 and C2 Energy Laboratory, 15013
Denver West Parkway,
molecules as key products of interest, as they realize high market prices and can generally be produced at Golden, CO 80401, USA
higher efficiencies than more complex molecules in current systems (Bushuyev et al., 2018; De Luna et al., 2Department of Chemistry,
2019). New and more efficient catalysts (Burdyny and Smith, 2019), membranes (Kaczur et al., 2018), and University of Toronto,
system architectures have been developed in recent years (Weekes et al., 2018), further driving the perfor- Toronto, ON M5S 3J6,
Canada
mance of CO2R to compete with conventional synthesis methods currently used in industry. The need for 3Chemistry and Nanoscience,
scale-up of these systems to industrially relevant levels has also been emphasized (Smith et al., 2019) as National Renewable Energy
existing processes currently operate at significantly larger scales. Laboratory, 15013 Denver
West Parkway, Golden, CO
80401, USA
Recent technoeconomic analyses have considered the current performance of CO2R and market prices for 4Lead contact
various molecules to understand what the economic drivers of this process might be at scale (Bushuyev
*Correspondence:
et al., 2018; Jouny et al., 2018; De Luna et al., 2019; Grim et al., 2019). CO2R requires significant amounts alex.badgett@nrel.gov
of electricity to reduce CO2 into the desired product, thus the cost of electricity is a key driver of production https://doi.org/10.1016/j.isci.
costs. Reducing these production costs usually involves operation of the electrolyzer at high current density 2022.104270

iScience 25, 104270, May 20, 2022 ª 2022 The Author(s). 1

This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
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and faradaic efficiency to reduce capital costs and increase efficiency. In addition, focusing on synthesizing
products that can be sold at high market prices can increase the probability of cost-competitive production
(Jouny et al., 2018). Recent work has also considered the production of fuels and chemicals from a CO2
point source perspective, optimizing the system to utilize highest impact CO2 streams (von der Assen
et al., 2016) and mapped the total production potential from fossil and biogenic CO2 streams (Hansson
et al., 2017). Previous analyses have also discussed the relationships between CO2 point sources and
CO2R product markets, finding that market sizes and prices are key drivers of the economic feasibility of
CO2R products (De Luna et al., 2019). Recent work has also characterized the close connections between
CO2R technologies and existing chemical processes and infrastructure. Since many high-concentration
CO2 streams are produced from chemical processes and CO2R products include multiple organic chemi-
cals, near-term process integration opportunities exist in this space (Barecka et al., 2021a, 2021b).

Finally, life cycle analyses have been conducted on CO2R processes, finding that when powered with
renewable electricity from wind or solar, these processes have the opportunity to reduce greenhouse
gas emissions significantly relative to conventional synthesis pathways (Rosental et al., 2020; Sadok
et al., 2020). The overall environmental impact of CO2R products will vary greatly based on the type of
source stream CO2, the carbon intensity of the energy supply, and the possibility for use of low-carbon
transportation and chemical manufacturing facilities. A system-level life cycle analysis of CO2R product im-
pacts is outside the scope of this work but is an area for future work to investigate.

A concentrated feedstock stream is required for sustained operation of a CO2R system. Research efforts are un-
derway to develop systems capable of utilizing low concentration CO2 streams; however, current systems use
concentrated feedstocks. In this work, we refer to high-concentration CO2 streams as those with concentrations
greater than 90%. Recent progress on CO2R systems utilizing low concentration CO2 streams in addition to
those that are tolerant to specific impurities has demonstrated potential; however, due to the lower maturity
of these technologies, they are not considered in this analysis (Kim et al., 2015; Kumagai et al., 2019; Williams
et al., 2019; Xu et al., 2020). Although the United States emits over 4 billion t of CO2 annually (U.S. EPA, 2020),
only about 2.71 billion t of this CO2 is emitted from large point sources (U.S. EPA, 2019) and could be captured
and purified for use as CO2R feedstock. Of these large point sources, only ethanol plants, ammonia plants, and
natural gas processing facilities emit highly concentrated CO2 streams. The power sector, which comprises most
other point source emissions, usually emits CO2 at concentrations on the order of 10% (IPCC, 2005). If CO2R is to
be deployed at scale, an understanding of the feasibility of capturing, purifying, and allocating CO2 from exist-
ing point sources to CO2R reactors is needed.

Here we present a spatial and economic optimization modeling framework that is used to analyze CO2R
processes and feedstock supply streams. This model allocates CO2 streams from point sources to sink lo-
cations where they can be used in CO2R systems, optimizing the system to utilize CO2 at the lowest
possible cost. This work considers ethylene, formate, and carbon monoxide (C2H4, HCOO
, and CO,
respectively) as possible products from CO2R in the United States. These products are currently consumed
in significant quantities, and they can be produced from a single-step CO2R system with high faradaic ef-
ficiency and current density. Using this framework, we build an understanding of how CO2R could be opti-
mally deployed and integrated into existing and future infrastructure at locations across the United States,
excluding Alaska and Hawaii. We use national data of CO2 sources and organic chemical production along
with the optimization model to understand where and how CO2R might be developed. An analysis of the
spatial challenges related to CO2R infrastructure is presented, including the proximity of CO2R to existing
industrial systems and their potential health and social impacts. Developing a spatially distributed network
of chemical production via CO2R could increase resilience by decentralizing chemical production and
transportation networks while maximizing utilization of CO2 that would be otherwise emitted to the atmo-
sphere. The optimization platform is used to model both the role direct air capture (DAC) could play in
providing supplemental CO2 streams and the impacts of advances in DAC technology. Finally, electricity
demands associated with development of CO2R at scale are considered.

RESULTS
CO2 allocations
Point sources of CO2 and the estimated cost per metric ton ($/t CO2) for capturing and purifying these
streams vary by the composition and source of the stream. A supply curve for CO2 capture and purification
shown in Figure 1 illustrates how costs vary by source of CO2, using CO2 point source data from the United

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Figure 1. National (United States) supply curve for CO2 feedstocks based on estimated cost of CO2 capture
specific to the type of point source
Sections of supply curve with crosshatching indicate fossil fuel point sources from the electric power sector.

States Environmental Protection Agency and carbon capture costs from the National Petroleum Council
(National Petroleum Council, 2019; U.S. EPA, 2019). Costs of capturing CO2 are adopted from the National
Petroleum Council, and they generally decrease as CO2 concentrations in exhaust gases increase (Table S2)
(National Petroleum Council, 2019). Although the total supply of point source CO2 is likely available to meet
demand for all CO2R products including losses from faradaic efficiencies less than 100%, it is not necessarily
available at costs and locations that facilitate its use in CO2R.

The CO2 sources included here could provide 24 times the CO2 needed to produce all the C2H4, HCOO
,
and CO currently produced in the United States via CO2R, albeit this is without consideration of site-spe-
cific sizing and spatial constraints. Electric power sector sources represent about 85% of the total CO2 point
source emissions inventoried, further emphasizing the importance of optimizing the allocation of available
CO2. Ammonia, natural gas processing, and ethanol plants emit significantly less CO2; however, these
streams have higher CO2 concentrations and are therefore less expensive to capture and purify, making
them favorable feedstocks for CO2R. These point sources have conventionally been considered near-
term candidates for supplying CO2 to CO2R. While these high concentration CO2 streams are the lowest
cost feedstocks for CO2R, they are available in significantly lower quantities than other streams. The scope
of these processes is more complex than the simplistic representation in this work, with each plant
leveraging highly integrated and interdependent processes (Bains et al., 2017). In the optimization model,
high concentration CO2 streams are generally utilized first due to their lower carbon capture cost, with
lower concentration streams utilized in whatever extent is necessary to meet remaining product supply.

Several CO2R market scenarios are considered in this work, each with a unique set of assumptions and
model constraints (Table 1) which affect the number, size, and spatial distribution of CO2R systems. In
all scenarios except for the high-concentration feedstock scenario, the model is required to produce
each CO2R product at rates equal to existing supply chains. In the high concentration scenario, the CO2

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Table 1. Summary of model constraints and supply chain design for scenarios modeled

Scenario CO2R Product supply Feedstock CO2R size

name location location source constraint constraint
Base At CO2 Existing manufacturing No DAC 500 MW
source facilities
Distributed At supply Existing petroleum No DAC 500 MW
location terminals
Distributed decarbonized At supply Existing petroleum No coal or natural gas 500 MW
location terminals power plants, no DAC
Distributed decarbonized At supply Existing petroleum No coal or natural gas 500 MW
DAC $300/t location terminals power plants
Distributed decarbonized At supply Existing petroleum No coal or natural gas 500 MW
DAC $100/t location terminals power plants
Distributed decarbonized At supply Existing petroleum No coal or natural gas 500 MW
DAC $50/t location terminals power plants
High-concentration At supply Existing petroleum Only ammonia, No constrainta
feedstock location terminals ethanol, and natural
gas processing plants
a
A constraint on the size of CO2R system was not included for the high-concentration feedstock scenario to enable the opti-
mization model to find a feasible solution subject to other feedstock and distance constraints.

available is less than the amount needed for equal current production rates, and the model is constrained
to utilize all of the available CO2.

Current market sizes for product molecules are based on data gathered from publicly available sources.
Market data indicate that C2H4 has the largest U.S. market size of 27 billion kg supplied per year, compared
to 0.056 and 1.76 billion kg per year for HCOO
and CO, respectively (Table S1) (United States International
Trade Commission, 2020). The maximum CO2R system size is constrained to 500 MW in these scenarios,
which serves as a constraint on the amount of CO2 that can realistically be utilized at a single location.

Development of CO2R in the near-term could depend on the ability to leverage existing infrastructure for
storage and distribution of product molecules. For example, CO2R producing C2H4 would be well suited to
leverage existing downstream infrastructure, including C2H4 pipelines and transportation hubs. In the base
scenario, CO2 is captured and reduced at the point source and the product is transported to existing
manufacturing facilities. In all other scenarios, a more distributed supply chain is depicted, where CO2
from various point sources is aggregated at existing petroleum storage terminals and reduced into a
CO2R product. Petroleum terminals are more numerous and spatially diverse across the United States,
making them possible candidates for a distributed CO2R network.

The total number of CO2R systems needed to meet supply requirements vary drastically by product, with
HCOO
and CO transfers from sources to sinks equal to 17 and 20, respectively, compared to over 1,000 for
C2H4 in the base scenario. This analysis suggests that a spatially and compositionally diverse distribution of
CO2 sources must be used to provide sufficient feedstock for CO2R, with CO2 supply evolving from the
base to distributed scenario (Figures 2A and 2B). Meeting demand for the three molecules requires utili-
zation of CO2 from lower-concentration (and therefore more expensive) CO2 streams once supply from
high-concentration streams is exhausted.

When designating existing infrastructure as sinks for CO2R products, the CO2 supply mix depends heavily
on fossil fuel power plants and natural gas processing systems. C2H4 systems are heavily concentrated on
the Gulf Coast, where most C2H4 manufacturing exists (Figure S1), and similar trends exist for HCOO
and
CO. The sources of CO2 utilized for each product tend to vary depending on the amount of CO2 needed.
C2H4 and CO exhibit large market sizes and must therefore utilize CO2 from a variety of point sources,
which leads to a more diverse supply. Because HCOO
is produced in significantly lower quantities than
other molecules, the model can allocate feedstocks from low-cost, high-concentration emissions.

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Figure 2. Inventories and CO2 supply mixes for C2H4, HCOO
, and CO for base scenario considering product allocation to existing infrastructure
(A and B) and distributed scenario where products are allocated to petroleum terminals.
(C and D). Lines in (B) and (D) connecting points represent flows of product from feedstock source to product sink, with filled points representing sink
locations and hollow points represent sources of CO2.

Co-locating CO2R systems where target molecules are already produced or consumed at scale enables
integration of CO2R technology into existing infrastructure and minimizes ancillary investments but doing
so also limits potential CO2 feedstock streams to those closest to the existing infrastructure. When using
existing chemical manufacturing facilities (Figure S1) as sink locations, flows are concentrated in the East
and Southeast with existing petrochemical infrastructure (Figure 2B). The geographically concentrated
sink locations assumed in the existing infrastructure scenario determine the types of CO2 sources lever-
aged in the model, with nearby sources of CO2 prioritized to minimize transportation costs.

In contrast to the concentrated sink locations in the base scenario, the distributed scenario depicts a flex-
ible implementation of CO2R at scale by imagining the use of petroleum terminals as sink locations
(Figures 2C and 2D). Petroleum terminals are already widely distributed throughout the country, allowing
for greater flexibility in CO2 utilization (Figure S2) (HIFLD Open Data, 2021). Total domestic production for
each product must still equal current market demand but can be allocated to any petroleum terminal rather

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than existing chemical manufacturing facilities as in the base scenario. Spatially distinct industrial electricity
prices by county (NREL, 2018) are assigned for each petroleum terminal sink location, and a CO2R system is
assumed to pay the industrial electricity price at the terminal (Figure S3). Low industrial electricity prices
occur in locations with high variable renewable generation and in the Gulf Coast, where existing petro-
chemical processes exist. Processes are preferentially located in these regions, where low electricity prices
reduce production costs for CO2R.

The entirety of the CO2 supply for HCOO
and large portions of CO2 for C2H4 and CO is sourced from
ammonia plants. Ammonia plants emissions exhibit the lowest carbon capture costs of the point sources
considered (National Petroleum Council, 2019), and the spatial flexibility afforded when products can be allo-
cated to petroleum terminals allows for full utilization of these low-cost feedstocks. C2H4 exhibits a more varied
supply of CO2 in the distributed scenario but becomes less reliant on power sector point sources than in the
base scenario. Across all products, the amount of CO2 captured from power plants decreases from the base to
distributed scenario, and the utilization of smaller scale, lower cost high-concentration streams increases.

The distributed infrastructure scenario demonstrates that CO2R systems for chemical synthesis might not
be deployed in areas already highly concentrated with existing industrial operations. Such a geographic
shift has implications both for existing supply chains and environmental justice and equity. Because indus-
trial manufacturing and other facilities that emit notable amounts of air pollution tend to disproportionately
affect people in poverty and people of color (Elliott et al., 2004; Mikati et al., 2018; Lartey and Laughland,
2019; Carley and Konisky, 2020), a more geographically distributed chemical manufacturing sector with
CO2R could move these processes away from these communities. While a shift of infrastructure away
from marginalized communities might reduce health hazards for these communities, it can also negatively
impact local economies that rely on the jobs that existing infrastructure provides. Understanding the spe-
cific costs and benefits to local communities that would arise from deployment of CO2R infrastructure is an
important consideration for future work in this space.

A spatially distributed network for chemical synthesis also has the potential to create a more resilient sup-
ply chain. Recent research suggests that for multiple sectors, spatially distributed supply chains could be
more economically efficient and resilient to disruptions, in addition to ensuring access to local feedstocks
(Arai et al., 2009; Pettit et al., 2010; Becker et al., 2020). In the United States, hurricanes have significantly
impacted petrochemical operations on the Gulf Coast in recent years, causing plant shutdowns, spills,
and damages (Royal Dutch Shell, 2005; Euan, 2008; Forrester, 2020; Mufson and Fears, 2020). Distributed
CO2R at scale could help create a more resilient supply chain for C2H4, HCOO
, and CO because single
events are unlikely to impact as many producers. In other words, spatially distributed chemical synthesis
suggests that supply chain disruptions from extreme weather and other external stressors could be less
frequent and affect smaller portions of the overall supply chain.

CO2 supply and the role of direct air capture

Annual United States CO2 emissions could provide sufficient feedstock in the near term for production of
the three molecules analyzed here; however, eventual decarbonization of the U.S. power sector (Steinberg
et al., 2017; Lawson, 2018; Victor et al., 2018; Luderer et al., 2019) is likely to reduce the number of point
sources and overall amount of CO2 available, further constraining how and where CO2R might be devel-
oped. For example, if only CO2 point sources from ethanol plants are used in CO2R, this system would
only be able to meet about 23% of annual ethylene production in the United States irrespective of spatial
supply constraints. While certainly not a negligible amount, such a C2H4 supply chain would still be heavily
reliant on fossil fuel feedstocks for the remainder of ethylene production. If CO2R were to be used in the
production of basic chemicals and other industrial products in a future with a decarbonized power sector,
DAC of CO2 might be needed to provide supplemental CO2. A similar need for DAC could emerge as the
chemical industry attempts to reduce emissions. Such is the case with electrolysis-based ammonia produc-
tion, which would reduce the availability of point source CO2 from ammonia plants (Hollevoet et al., 2020).
Given the growing investment and development in DAC technologies, as well as the longevity of excess
atmospheric CO2, this work considers DAC as a possible source of supplemental CO2.

Beyond decarbonization of the power sector, changes in existing industrial operations are likely to impact
non-power sector CO2 streams that are available for use in CO2R systems. In the present work, we consider
how changes in availability of CO2 from the power sector impact CO2R deployment, creating opportunities

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Figure 3. CO2R feedstock supply mix under different scenarios, including existing and distributed sink
infrastructure, with and with varying DAC costs
Scenarios shown from the dashed line to the right have fossil fuel point sources excluded from the model. See Table 1 for
documentation of assumptions specific to the scenarios shown here.

for DAC. Changes in non-power sector CO2 sources are not depicted here because the pathways and time-
lines for decarbonization of these processes are more uncertain than the power sector; however, the impor-
tance of changing industrial processes and the resulting impacts on CO2R deployment should be noted.

To analyze how DAC might support CO2R-based supply chains, a series of model scenarios that vary the
supply of point source CO2 were developed to depict how the dynamics of CO2R might change when
DAC CO2 is available as a feedstock source. These scenarios adopt the same assumptions as the distrib-
uted scenario, and assume DAC takes place on-site at a petroleum terminal. For distributed scenarios with
DAC as a potential source of CO2, it is assumed that fossil fuel power generation is unavailable for capture,
because of either excessive retrofitting costs or plant retirement.

Utilization of CO2 from fossil fuel point sources decreases from the base to distributed scenario as dis-
cussed prior, with capture of smaller and more spatially distributed point sources such as ammonia and
ethanol plants increasing because of the greater spatial flexibility depicted in the distributed scenario (Fig-
ure 3). Natural gas and coal power plants are more expensive for carbon capture than other point sources,
and their use decreases in the distributed scenario.

DAC serves as a source of CO2 only when its cost is competitive with carbon capture of CO2 from existing
point sources. At a cost of $300/t CO2 captured, DAC is not developed because most existing point sources
are more economical to utilize. The amount of DAC utilized evolves depending on how economically
competitive DAC is with carbon capture from existing CO2 point sources. As DAC decreases in cost,
more expensive carbon capture systems are avoided in favor of lower-cost DAC.

At a cost of $50/t CO2 captured, DAC generates about 40% of the CO2 utilized in CO2R. From a purely eco-
nomic perspective, DAC appears to represent a significant opportunity for use in CO2R if cost competitive
with capture and purification of point source streams. Recent research has critically analyzed the potential
for significant scale-up in DAC systems, and it has identified the significant energy and resource demands
inherent in scale-up for these systems (Realmonte et al., 2019, 2020; Chatterjee and Huang, 2020). Although
resource intensity estimates are beyond the scope of this work, they merit consideration as potential con-
straints on the total capacity of DAC deployed.

The high-concentration feedstock scenario was designed to depict the potential impact that utilization of only
high-concentration CO2 sources could have toward meeting total market supplies in the United States. Ethanol
plants, natural gas processing facilities, and ammonia plants are considered high-concentration sources for the
purpose of this scenario, although other smaller scale sources might exist. While using only these sources,

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Figure 4. Optimization model results for high-concentration feedstock scenario

(A) Spatial distribution of sinks (filled points) and sources (empty points).
(B) Product supplied via CO2R by source compared against current market size, illustrating the need for supplemental sources of CO2 when the model is
constrained to only using high-concentration streams from ethanol, ammonia, and natural gas processing facilities.

substantial portions of the total markets for these products can be supplied via CO2R, utilizing a spatially
distributed network of sources (Figure 4). These point sources can be captured and purified to supply CO2R
systems at the lowest cost, making them attractive near-term opportunities for pilot scale system development.
For development of a complete CO2R-based supply chain for the three products considered here, carbon cap-
ture of lower concentration CO2 sources is needed, and/or DAC.

In the high-concentration feedstock scenario, only the market size for formate was met with CO2R, with insuf-
ficient CO2 to meet demand for ethylene and carbon monoxide (Figure 4B). With respect to the entire organic
chemical sector, the three products considered here are an insufficient representation of the total CO2 that
would be required for a complete shift to CO2R-based supply chains. A shift toward a decarbonized power
sector is likely to significantly reduce the amount of CO2 available for these systems, further underscoring
the importance of DAC as a source of CO2. This analysis focuses solely on the potential for CO2R to supply
products in the organic chemicals sector; however, further applications including transportation fuels and in-
dustrial operations could also increase the demand for CO2R products and thus the need for increased DAC.

Energy demand for a CO2R-based chemical industry

Assuming such a significant deployment of CO2R necessitates consideration of the logistical feasibility and
resource intensity of developing these systems. Conventional synthesis for the products considered here
generally involves using natural gas as a feedstock at large-scale facilities. CO2R does not depend on nat-
ural gas, but it does consume electricity and water in the reduction of CO2, and mature processes are likely
to operate at smaller scales and in more spatially distributed supply chains.

Based on the current required and whole-cell potentials described in literature (Table S1), Figure 5 estimates
the energy required to synthesize the three chemicals at current market sizes. C2H4 comprises most of the total
electricity required because 12 electrons are required per molecule synthesized for C2H4 versus two for
HCOO
and CO, and C2H4 also has a significantly larger market size than HCOO
and CO, and therefore
more current (and in turn energy) is required to meet current market demand (Figure 5).

The total energy required to synthesize the products considered here via CO2R exceeds 1,900 TWh and
would comprise approximately 46% of annual electricity generation in the United States (Figure 5) (U.S.
EIA, 2021). To further contextualize the energy requirements depicted here, total industrial energy
consumed as feedstocks (hydrocarbon gas liquids, natural gas, coal, and coke) in the United States totals

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Figure 5. Energy demands for CO2R compared to feedstock energy consumption in industry and total electricity
generation in the United States

1,550 TWh (U.S. EIA, 2014), or slightly less than the total CO2R energy consumption shown, which is only for
production of C2H4, HCOO
, and CO. The energy intensity for current production pathways of C2H4 is esti-
mated at 26 GJ/t (Worrel et al., 2000). Assuming a domestic market size of 27.12 million t per year, energy
required for today’s C2H4 production pathways is roughly 195 TWh.

The energy consumption for CO2R shown here is solely that used for the CO2R reaction itself and does not
account for energy consumed in point source carbon capture, CO2R reactor outlet separations, and DAC,
and it is therefore an underestimate of total energy required across all systems. For context, commercial
DAC systems require approximately 5 GJ thermal energy/t CO2 in addition to smaller electrical energy re-
quirements (McQueen et al., 2020). If DAC systems are deployed at large scales to support CO2R, the re-
sulting energy demands could be significant.

Of the approximately 2,000 TWh estimated, about 360 TWh are required for the standard reduction poten-
tial (the thermodynamic, reversible energy required) for each reaction (Table S3). The remainder of the en-
ergy represents overpotentials attributable to various components in the CO2R system, reduction of which
has been discussed in recent reviews and experimental work (Li and Kanan, 2012; Jhong et al., 2013; Sun
et al., 2017). Much of this energy is dissipated as heat via ionic Joule heating through the membrane
and imperfect electronic contact of the metal and carbon phases. Some of this energy dissipated as
heat could be reclaimed through thoughtful balance of plant design, increasing the efficiency of the plant.
Thus, we expect that future advances in CO2R system design will reduce the overpotentials of these sys-
tems and reduce the total electricity consumed per kg of product.

Life cycle assessments of electrolysis and other power-to-gas technologies find that the carbon footprint of
power supplied to the process is a key determinant of the carbon intensity of the product (Bhandari et al.,

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2014; Sadok et al., 2020), which underscores the importance of powering CO2R with renewable electricity.
Powering CO2R entirely with renewable electricity implies a significant investment in renewable energy
generation capacity to power these systems. New renewable generation at the scales depicted here is
significantly more than is currently generated in the United States (Figure 5), and the new generation would
represent a significant portion of total energy demand in the United States even without including energy
requirements for carbon capture, product purification, and/or DAC. Although the availability and feasibility
of developing additional renewable generation to meet the demands of CO2R is beyond the scope of the
quantitative evaluation presented, it is an important consideration of the feasibility of developing CO2R
and should be considered in future work.

DISCUSSION
This work analyzed several key questions not yet addressed in existing CO2R research: 1) what CO2 point
sources are best for carbon capture and as sources of feedstock for CO2R, 2) how the dynamics of CO2 sup-
ply shift as CO2 point sources change and across a range of DAC costs, 3) the spatial dynamics of CO2R and
how a network of CO2R facilities can be spatially optimized, and 4) the electricity demands for CO2R at scale
in the context of current energy systems.

From both a cost and a system performance perspective, it is preferable to use high-concentration waste
CO2 streams available from facilities such as ethanol and ammonia plants than low concentration CO2
streams. However, limiting CO2R to only use such sources would severely impact the supply of feedstock
available for use. High-concentration CO2 streams represent just 2.6% of the total CO2 supply. Addressing
this shortage in supply requires either capture and purification of low-concentration CO2 streams or devel-
opment of CO2R reactors that are tolerant to flows with low CO2 concentrations.

The inventory of large stationary CO2 point sources in the United States is not static. Variability is especially
prevalent in the power sector, which comprises the majority of the CO2 feedstock streams considered in
this analysis. When large CO2 sources such as coal power plants are taken offline, the total supply of
CO2 feedstock decreases and thereby reduces total feedstock available for CO2R. DAC could be needed
to supplement CO2 supplied solely from high concentration, non-power sector point sources, depending
on future demand for carbon-based products. Although this analysis only considered three products from
the chemical and petrochemical manufacturing industries, DAC might be needed to provide enough CO2
for production of C2H4, HCOO
, and CO alone via CO2R when fossil fuel point sources and other associ-
ated low-concentration CO2 streams are unavailable. The cost of DAC relative to the cost of carbon capture
from existing point sources determines the favorability of implementing DAC versus carbon capture of
point source CO2.

There are significant spatial considerations when deploying CO2R at scale for both CO2 and electricity sup-
ply. If CO2R is allowed to utilize spatially distributed sources of CO2, CO2R is likely to be sited in places that
provide access to low-cost electricity and CO2. This analysis depicts a system of geographically distributed
CO2R plants, with increased dispersal of infrastructure relative to existing supply chains. A dispersed sys-
tem could prove more resilient to impacts from natural disasters like those that have affected existing
manufacturing infrastructure in recent years. DAC coupled with CO2R further enhances the spatial flexibility
of these systems, thus eliminating constraints associated with fixed CO2 point sources.

Nation-scale CO2R deployment was analyzed with national datasets and an optimization framework. The
amount of energy consumed is determined by the throughput of the reactor and the electrical potential
of the reactor. At current system potentials, this work estimates that producing the three molecules consid-
ered here at their current market sizes would consume about 50% of the electricity that is generated
annually in the United States, although we expect advances in reactor design and materials to reduce over-
potentials and increase the energy efficiency of the process. CO2R coupled with renewable energy repre-
sents a significant opportunity for implementation of flexible loads that can utilize excess renewable power.

Limitations of the study

This work uses numerical optimization to model possible pathways toward integrating electrolysis of point
source and direct air capture (DAC) CO2 into existing organic chemical supply chains. The demand side
(organic chemicals) and feedstock side (point source and DAC CO2) are subject to evolve because of policy
drivers and concurrent changes in other sectors that are not considered in this work. Additionally, project

10 iScience 25, 104270, May 20, 2022

iScience ll
Article OPEN ACCESS

resources only permitted modeling of three possible products from CO2 reduction; however, many other
possible products exist. These other products could be produced directly in a single-step CO2R system or
could be produced from multi-stage processes. Depending on the size of the market and selling prices for
these products, they could create competition and further increase demand for point source and atmo-
spheric CO2. Finally, advances in the performance and design of CO2R systems might create near-term op-
portunities for deployment that are not obvious given today’s state of this technology.

STAR+METHODS
Detailed methods are provided in the online version of this paper and include the following:

d KEY RESOURCES TABLE

d RESOURCE AVAILABILITY
B Lead contact
B Materials availability
B Data and code availability
d METHOD DETAILS

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.isci.2022.104270.

ACKNOWLEDGMENTS
The authors would like to thank Doug Arent, Mark Ruth, Mike Meshek, Wilson Smith, Allison Crow, Randy
Cortright, Ling Tao, Gary Grim, David Garfield, Colin McMillan, and Dan Bilello for their insights and con-
tributions to this work.

This work was authored by the National Renewable Energy Laboratory (NREL), operated by Alliance for
Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-
08GO28308. This work was supported by Planning and Assessment funds at NREL. The views expressed
in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Govern-
ment retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Gov-
ernment retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the pub-
lished form of this work, or allow others to do so, for U.S. Government purposes. This work was supported in
part by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers
and Scientists (WDTS) under the Science Undergraduate Laboratory Internship (SULI) program.

AUTHOR CONTRIBUTIONS
Conceptualization, A.B. and A.S.; Methodology, A.B., A.F., and A.S; Software, A.B., A.F., and A.S; Re-
sources, A.B. and A.F.; Writing – Original Draft, A.B., A.F., and A.S; Writing – Review & Editing, A.B.,
A.F., and A.S; Visualization, A.B. and A.F.; Supervision, A.B.; Funding Acquisition, A.B.

DECLARATION OF INTERESTS
The authors declare no competing interests.

Received: December 22, 2021

Revised: March 14, 2022
Accepted: April 12, 2022
Published: May 20, 2022

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STAR+METHODS

KEY RESOURCES TABLE

REAGENT or RESOURCE SOURCE IDENTIFIER

Deposited data
Point source CO2 emission data EPA FLIGHT https://ghgdata.epa.gov/ghgp/main.do
CO2 flue gas capture and purification National Petroleum Council: Meeting th https://dualchallenge.npc.org/
cost estimates e Dual Challenge A Roadmap to At-Scale downloads.php
Deployment of Carbon Capture, Use,
and Storage

Software and algorithms

Spatial CO2R optimization model Original work https://github.com/NREL/CO2ROpt
https://doi.org/10.5281/zenodo.6385504

RESOURCE AVAILABILITY
Lead contact
Further information and requests for resources should be directed to and can be fulfilled by the lead con-
tact, Alex Badgett: alex.badgett@nrel.gov.

Materials availability
This study did not generate unique reagents.

Data and code availability

d Optimization model code and input data have been deposited at a GitHub repository and are publicly
available as of the date of publication. Accession links are listed in the key resources table.
d All original code has been deposited at Zenodo and is publicly available as of the date of publication.
DOIs are listed in the key resources table.
d Any additional information required to reanalyze the data reported in this paper is available from the
lead contact upon request.

METHOD DETAILS
Most CO2R reactors have a cathode where CO2 is reduced and an anode where oxygen is generated (evolved).
The oxygen evolution reaction (OER) can be written to reflect the pH of the media it takes place in.

Acidic 2H2 O / O2 + 4H + + 4e
(Equation 1)

Alkaline 4OH
/ O2 + H2 O + 4e
(Equation 2)
This work considers CO2R to three specific products: ethylene (C2H4), formate (HCOO
), and carbon
monoxide (CO). Anode, cathode, and overall reactions to form these products are shown in Equations
3, 4, 5, 6, 7, 8, 9, 10, and 11. All reactions are assumed to take place in alkaline media. The optimization
model developed in this work incorporates current performance metrics for CO2R systems, assuming
constant performance for these systems. The performance of a CO2R determines the amount of
product per kWh of electricity supplied to the system, and advances in performance are expected to
increase the rate of product synthesis from these systems. Scenario and sensitivity analysis, while
beyond the scope of the present analysis, is an important opportunity for future work to address.

C2 H4 CO2 R 2CO2 + 8H2 O + 12e
/ C2 H4 + 12OH
(Equation 3)

C2 H4 OER 12OH
/ 3O2 + 6H2 O + 12e
(Equation 4)
Net reaction 2CO2 + 8H2 O/C2 H4 + 3O2 + 6H2 O (Equation 5)

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HCOO
CO2 R CO2 + H2 O + 2e
/ HCOO
+ OH
(Equation 6)

1
HCOO
OER 2OH
/ O2 + H2 O + 2e
(Equation 7)
2
1
Net reaction CO2 + 2H2 O/HCOOH + O2 + H2 O (Equation 8)
2
COCO2 R CO2 + H2 O + 2e
/ CO + 2OH
(Equation 9)
1
CO OER 2OH
/ O2 + H2 O + 2e
(Equation 10)
2
1
Net reaction CO2 + H2 O/CO + O2 + H2 O (Equation 11)
2
Recent studies have focused on advances in the electrochemical CO2R system itself under the assumption
that CO2 feedstock streams are without impurities. Although notable amounts of high-concentration CO2
streams exist across the United States, lower-concentration CO2 sources must be utilized to provide suffi-
cient carbon for operating CO2R at scale. In this work, we assume CO2 point source emissions are captured
and purified and used as the carbon source for CO2R.

Point-by-point annual CO2 emissions equaling 2.13 billion metric tons annually (Ely and Rock, 2014; U.S.
EIA, 2020b) and the cost of capturing and purifying various CO2 streams (Bains et al., 2017; National Petro-
leum Council, 2019) as a function of facility type are used to model feedstock allocation for CO2R (Table S2).
According to the United States Environmental Protection Agency (EPA) Inventory of U.S. Greenhouse Gas
Emissions and Sinks, large facilities emit approximately 2.71 billion metric tons of CO2 annually, indicating
our model considers approximately 79% of CO2 emitted from large point sources. This 21% discrepancy
results from our model not considering smaller point sources in the EPA dataset (U.S. EPA, 2019), such
as universities, food processing, other manufacturing, and point sources without sufficient CO2 capture
cost information to be included in our model. CO2 point sources vary by concentration and composition,
and how the carbon emitted from them is accounted for in greenhouse gas inventories. The optimization
model used in this work only considers economic and not environmental factors for utilizing different CO2
sources, and solely optimizes CO2 supply at the lowest cost.

We define a net present value (NPV) function (Equation 12), which estimates the NPV of a CO2R system as a
function of cost and revenue streams for a CO2 point source i, product sink j, and CO2R product k in units of
dollars per year. xi;j;k represents the flow of a given CO2R product k from a CO2 point source i to product
consumer j in kilograms per year (kg/year). In the following text, we discuss each term of this equation in
detail.

NPV = vk xi;j;k
ei;k xi;k
Di;j ti;j;k xi;j;k
si;k xi;k
ci xi;j;k (Equation 12)
The first term in Equation 12 represents the value of the product from the CO2R system, where vk is the
product value in $=kg. The value of this term is influenced by the amount of product and the product market
price. High market prices, such as those for HCOO
increase the revenue stream and overall NPV.

In the second term of Equation 12, ei;k represents the cost of electrons required to reduce CO2 to product k
in dollars per kg. ei;k is estimated using Faradays Law of electrolysis (Equation 13) (Jouny et al., 2018). Ek is
the applied cell potential in volts, qk is the number of electrons required per molecule of species k (Jouny
et al., 2018), Pi is the regional industrial electricity price in dollars per kWh (NREL, 2018), F is Faraday’s con-
stant (96,485C/mol), mwk is the molar mass of species k, and FEk is the faradaic efficiency of CO2R for spe-
cies k (Grim et al., 2019).

E k qk P i F
ei;k = (Equation 13)
mwk FEk
The third term of Equation 12 estimates the transportation cost of moving CO2 from CO2 point source i to a
product consumer j. In this term, Di;j represents the city block distance between a CO2 point source i and prod-
uct consumer j in meters. The city block distance formula is used to approximate the distance between sink and
source points (Equation 14). In reality, the distance between two points is a function of the transportation mode
used, and city-block distance is used as an approximate distance relationship in this case. The cost per kg per
kilometer to transport each ton CO2 is represented by the variable ti;j;k (Doctor et al., 2018).






Di;j = jix
jx j +
iy
jy
(Equation 14)

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In the fourth term, the variable si;k represents the capital and operating costs (excluding electricity costs,
which are accounted for in the second term of Equation 12) of the electrochemical reactor. To estimate
the balance-of-plant cost of these systems, we adopt and modify a technoeconomic model by Jouny
et al. (2018) to approximate separation system costs at different scales (Jouny et al., 2018). Jouny et al. as-
sume a simplified outlet separations process and are likely an underestimate of costs of outlet separation
for CO2R systems, which are likely to produce multiple products that need to be separated from unreacted
CO2 in the outlet stream. Also included in these estimates are costs for the electrolyzer stack and down-
stream separations train. Capital costs for CO2R electrolyzers are assumed to be equal to $10,000/m2.
Active area of electrolyzer required is determined based on the amps required to produce product xi;j;k ,
the current density, and faradaic efficiency of the system (Table S1) (Ma et al., 2016; Grim et al., 2019;
Chen et al., 2020; Garcı́a de Arquer et al., 2020).

In the last term, ci represents the cost of CO2 feedstock, normalized to dollars per kg of product k based on
the carbon content of the product. Operation of a CO2R system requires a high-concentration flow of CO2.
Because many of the CO2 point sources considered in this work generate low-concentration streams (10%
CO2), we include the cost of purifying these streams (National Petroleum Council, 2019). Carbon capture
costs are differentiated between CO2 point sources and generally depend on the initial concentration of
CO2 in the outlet stream.

Optimization of the NPV function (Equation 12) is subject to four constraints. These assumptions constrain
CO2R systems to realistic scales and ensure nearby sources of CO2 are allocated by the model. Our model
seeks to maximize the objective function, Equation 12, subject to the constraints (Equation 15).
X
xi;k % ai
8 i;k
>
>
>
> X
>
> xi;j % dj
<
max NPV s:t: i;j
(Equation 15)
>
> X
>
>
>
> ei;k % 500
:
i;k

Di;j < 1; 000

The first constraint represents the mass balance at each CO2 point source. Total flows from a point source i
for all CO2R products k must be less than or equal to the total feedstock available at that point (ai ). Because
the products modeled have different molecular compositions, flows and CO2 feedstocks are normalized to
a kilograms-carbon basis.

The second constraint ensures total inflows to a product consumer point j that consumes a product species
k do not exceed the total demand at that point across all point sources i. In the base, distributed, and DAC
P P
scenarios a > d, indicating that the system is not feedstock constrained. In the limited feedstock sce-
P P
nario, the system is constrained by the amount of CO2, and a< d.

The third constraint requires that power consumed in a CO2R reactor not exceed 500 MW. This constraint
ensures the size of a CO2R plant is kept within a realistic range. For reference, the largest proton exchange
membrane water electrolysis system planned for construction in Germany has a power consumption of 100
MW (Freist, 2019; FuelCellsWorks, 2019).

The final constraint in Equation 15 represents a limitation on distance in kilometers (1,000) between CO2
point source and product sink. This constraint is chosen to confirm the model prioritizes nearby sources
of CO2 while ensuring sufficient CO2 is available to meet the demand at all sink points. This distance
constraint minimizes the development of transportation infrastructure for moving CO2R products from
source to sink locations.

To estimate a maximized solution to Equation 12, this work uses the JuMP optimization framework within
the Julia programming language to develop solutions to the linear optimization problem presented (Be-
zanson et al., 2017; Dunning et al., 2017). JuMP uses the GNU linear programming kit, which implements
a revised simplex method to minimize the relevant variables.

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Several different product allocation scenarios are considered. Most of the molecules considered here are
produced by a handful of industrial sites in the United States. A literature search was conducted to identify
the location and capacity of these sites.

For C2H4, products are allocated to ethane crackers, which use heat to crack ethane into C2H4. Most ethane
crackers exist along the Gulf Coast, close to the petrochemical infrastructure they rely on for ethane feed-
stocks (DOE, 2018).

It is assumed HCOO
is produced via CO2R, with a subsequent acid titration step to produce formic acid
(HCOOH). We assume the added cost of the acid titration step is negligible with respect to overall costs.
We were only able to identify one plant producing formic acid in the United States, located in the Gulf
Coast. About 6 million kg per year of formic acid is imported through various ports, which are also desig-
nated as sinks for formic acid (United States International Trade Commission, 2020).

It is assumed the carbon monoxide produced from CO2R would be used in acetic acid production. Equa-
tion 16 shows the methanol carbonylation reaction to form acetic acid, using carbon monoxide as an input
to the process (Kalck et al., 2020). Using stoichiometric ratios of the reaction, we estimate consumption of
CO to be 0.46 kg CO per kg acetic acid. Acetic acid facility production rates are used to back-calculate the
amount of CO required.

CH3 OH + CO/CH3 COOH (Equation 16)

We assume a 50% single pass conversion efficiency of CO2 in CO2R reactors. Low single pass conversion
significantly increases downstream outlet separations costs by increasing the magnitude of outlet flows
and diluting product streams (Jeng and Jiao, 2020). Based on current performance of these systems at
benchtop scales, 50% is an optimistic estimate of single pass conversion. Reported values can range
from 0.3% to 68%, and this topic has only recently been examined (Ripatti et al., 2019; Ross et al., 2019).

As renewable power sources are temporally variable sources of electricity, we account for the purchase of
battery energy storage to deliver consistent power to a CO2R facility. Battery costs per unit capacity of
$1,500/kW are used to represent an average cost rate from short-duration (<0.5 h) to medium-duration
(2-4 h) energy storage (U.S. EIA, 2020a). We assume the total battery power purchased is equal to the total
power rating of the CO2R system.

The inventory of large CO2 point sources in the United States is not static, and the eventual decarbonization
of the U.S. power sector (Steinberg et al., 2017; Lawson, 2018; Victor et al., 2018; Luderer et al., 2019) will
impact the availability of CO2 streams and make it more difficult to source CO2 for production of organic
chemicals via CO2R. Although the exact timeline and degree of power sector decarbonization is unknown,
we assume 1) not all fossil fuel generation CO2 sources are feasible for carbon capture, because either ret-
rofitting costs are excessively high or the generator has been closed and 2) electricity prices remain equal to
current 2018 rates.

Though recent work has reviewed the technical side of CO2R and the application of large-scale DAC systems
for geological storage, it remains unclear how DAC would realistically respond to the large demand for CO2
from CO2R process at a nationwide scale (Jouny et al., 2018; Fasihi et al., 2019; McQueen et al., 2020). Unlike
the CO2 source streams from emissions point sources, there are no fixed DAC locations in the United States. A
DAC plant that is co-located at a chemical sink would ideally minimize transportation costs and allow for inte-
gration into a closed-loop system, such as the pairing of DAC with CO2R (Keith et al., 2018). For DAC locations,
it is assumed each plant can supply up to 100,000 t of CO2 per year for downstream use in the electrochemical
system. This estimate is based on DAC production from private companies with an operational DAC plant. A
DAC plant proposed by Carbon Engineering would produce a stream of 1 million t of CO2/year (Carbon En-
gineering, 2020), placing our assumption on the size of DAC facilities well within realistic limits. Also for this
study, 100,000 t/year is chosen because it is the minimum size for a DAC plant to qualify for Section 45Q of
the U.S. tax code (U.S. House of Representatives, 2018).

Cost estimates for DAC are highly variable and have ranged from over $1,000 to less than $50/t CO2
captured (Ishimoto et al., 2017; Keith et al., 2018; Fasihi et al., 2019). For this work, we analyze DAC costs
ranging from $300 to $50/t CO2 captured.

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The molar and mass rate of water consumed for all three products is estimated with Equations 17 and 18,
where sh is the stoichiometric coefficient equaling 2, 3/2, 1/2 for C2H4, and CO, respectively, from Equations
3, 4, 5, 6, 7, 8, 9, 10, and 11.

n_water;consumed =
sh n_product;generated (Equation 17)

MMwater
m_ water;consumed = sh m_ product (Equation 18)
MMproduct
For calculations of standard reduction potentials, the following is assumed:

 Boiling points for C2H4/HCOO
/CO z -100 C/+100 C/-191 C.

 Products generated are gas/liquid/gas for C2H4/HCOO
/CO respectively.

 The reactor is operated at 25 C.
 The anode is fed aqueous electrolyte and is therefore always liquid-saturated.
 Because of the reactor temperature and water balance in a reactor fed with water vapor-saturated
CO2, the high heating value (HHV) for water should be used in thermodynamic calculations. This as-
sumes water generated in the cathode is not vaporized, and thus, the latent heat energy is not sub-
tracted from the thermodynamic potential.

The standard reduction potentials for the HHV are determined from Equations 19 and 20. q denotes a stan-
dard state property (Table S3).

DGqf = DHqf
Tstd DSfq (Equation 19)

P
DGq
Eq =
(Equation 20)
nF
Standard reduction potentials for the three reactions are 1.15 V, 1.39 V and 1.33 V for C2H4, HCOO-, CO
respectively.

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