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org/JACS Communication

Hydroxide Based Integrated CO2 Capture from Air and Conversion

to Methanol
Raktim Sen, Alain Goeppert, Sayan Kar, and G. K. Surya Prakash*
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ABSTRACT: The first example of an alkali hydroxide-based system for CO2 capture and conversion to methanol has been
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established. Bicarbonate and formate salts were hydrogenated to methanol with high yields in a solution of ethylene glycol. In an
integrated one-pot system, CO2 was efficiently captured by an ethylene glycol solution of the base and subsequently hydrogenated to
CH3OH at relatively mild temperatures (100−140 °C) using Ru-PNP catalysts. The produced methanol can be easily separated by
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distillation. Hydroxide base regeneration at low temperatures was observed for the first time. Finally, CO2 capture from ambient air
and hydrogenation to CH3OH was demonstrated. We postulate that the high capture efficiency and stability of hydroxide bases
make them superior to existing amine-based routes for direct air capture and conversion to methanol in a scalable process.

C arbon dioxide, a potent greenhouse gas, is the main

component of industrial effluents and automobile
emissions.1 Over the past two centuries, we witnessed a
major rise of anthropogenic CO2 emissions leading to an
exponential increase in atmospheric CO2 concentration from
about 280 ppm to more than 415 ppm, currently.2 This
phenomenon has already led to a substantial average global
temperature rise of ∼0.8 °C compared to preindustrial levels.
Related problems such as global sea rise, ocean acidification,
and more extreme and unpredictable weather patterns have
also emerged.3 In an united effort to curb global warming, the
Kyoto Protocol followed by the Paris Agreement were signed
by most countries with the aim of curbing greenhouse gas
emissions and transition to renewable energy alternatives.4
Among various proposed solutions, direct air capture of CO2
(DAC) has recently attracted momentous attention. This
process allows the point of capture to be independent from the
emission sources. Hence, it enables capture stations to be free
of geographical constraints and allows the capture of CO2 from
small and dispersed point sources responsible for about half of
total emissions.5 Once CO2 is captured, it can be desorbed,
pressurized, and sequestered under earth’s surface in what is
known as Carbon Capture and Sequestration (CCS).6 An
alternate and value-added route is the utilization of the
captured CO2 (Carbon Capture and Utilization, CCU) as a C1
source by conversion into various products including chemical Figure 1. Reported integrated CO2 capture and conversion systems
feedstocks and polymers.7 CO2 can be hydrogenated with H2 compared to the present study
generated through H2O electrolysis using renewable energy.8
Among possible hydrogenation products, methanol is one of
the most attractive. With a current annual global production of amines as capturing agents. These amine systems can suffer
over 100 billion liters, CH3OH is already a C1 feedstock for a from volatility issues, oxidative degradation, and notable
multitude of chemicals and products and a superior fuel for
internal combustion engines and fuel cells. CH3OH is also an Received: November 25, 2019
attractive liquid hydrogen carrier (12.6 wt % of H2).9
Recently, the integration of CO2 capture from air and
subsequent conversion to methanol was spearheaded by us as
well as others (Figure 1).10 Until now, such systems used

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A J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
toxicity, making them less suitable for DAC in a scaled-up
process.11 Alternate CO2 scrubbing agents used on a large scale
are alkali hydroxide solutions. Hydroxides have higher capture
efficiency from dilute CO2 sources than amines.5c However,
recycling of the base through a conventional causticization−
calcination−slaking process leads to a high energy penalty with
required temperatures of 700 °C and above.5c,12 On the other
hand, practical utilization of metal carbonates as C1-building
blocks is not well established.13 In our previous work on alkali
hydroxide-based capture and conversion, we captured CO2
from air and synthesized formate salts. However, further
hydrogenation of the formate to CH3OH was found to be
ineffective.13b,14
Alcohol-assisted CO2 hydrogenation to methanol via
formate ester has been studied in great detail.10h,15 Hence,
we speculated that alcohols should be able to mediate the
hydrogenation pathway from formate salt to methanol through
the key formate ester intermediate. It was also shown that
formamides are essential intermediates for amine assisted
hydrogenation of CO2 to CH3OH (Figure 1).10f Herein, we
report a catalytic system for CO2 capture and conversion to
CH3OH involving alkali-metal hydroxides (capturing agent)
and alcohol (formate ester facilitator). This process has
numerous advantages, including the following: (1) alkali
hydroxides have high efficiency for DAC of CO2; (2)
widespread availability of the hydroxide bases; (3) low toxicity,
volatility, and higher stability over amines; (4) hydrogenation
of ester intermediates is more facile than formamide
intermediates.15d Additionally, for the first time, this system
offers easy integration with already existing hydroxide-based
CO2 scrubbing industries to utilize the captured CO2 to
produce value-added methanol.
To validate our proposed alcohol assisted pathway, we
initially explored the yet unreported hydrogenation of formate
salt to methanol.13a,15g Ethylene glycol was chosen as the
alcohol solvent for its high boiling point and relative
nontoxicity. In accordance with our hypothesis, quantitative
conversion of HCOOK to CH3OH was observed under 70 bar
of H2 at 140 °C in the presence of catalyst Ru-Macho-BH (C-
1). Similarly, KHCO3 under identical conditions formed
CH3OH with a 92% yield as observed by 1H NMR (Scheme
1). The formation of ester could not be detected by NMR after
reaction completion, suggesting that the formate salt is
thermodynamically favored, which is typical under alkaline
conditions.
Scheme 1. Proof of Concept: Hydrogenation of Bicarbonate
and Formate Salts to Methanola
a temperatures.
Reaction conditions: substrate (2.5 mmol), ethylene glycol (5 mL),
70 bar H2, 140 °C, catalyst (0.5 mol %), 48 h. Yields determined by
1
H NMR (tBuOH as internal standard).
B https://dx.doi.org/10.1021/jacs.9b12711
pubs.acs.org/JACS Communication
Analogous to metal hydrogen(bi) carbonates, metal alkyl
carbonates are formed when CO2 reacts with metal alkoxides.
While this concept is well established, its role in the field of
carbon capture has not been well explored.16 In 2016, Wee et
al. demonstrated that CO2 capture in an ethanolic NaOH
solution formed sodium ethyl carbonate having minimal
solubility in ethanol (Table 1, entry 1).17 For the present
Table 1. CO2 Capture by Alcoholic Hydroxide Solutionsa
CO2 captured CO2/ Solubility of
entry Base (mmol)b OHc carbonate
1d NaOH 2.5 ∼1 insoluble
2 NaOH 2.5 ∼1 soluble
3 KOH 2.5 ∼1 soluble
4e Ca(OH)2 1.5 ∼0.6 insoluble
a
Capture conditions: base (2.5 mmol), ethylene glycol (5 mL),
stirring (800 rpm), rt, t = 3 h. bCaptured CO2 amounts determined
gravimetrically. cMoles of CO2 captured per mole of hydroxide.
d
Ethylene glycol replaced by EtOH. e1.25 mmol of Ca(OH)2 was
used. Calculations error ±5%.
study, the alcohol should have the following properties: (1)
high boiling point for easy separation of methanol by
distillation, and (2) high dielectric constant enabling facile
dissolution of the hydroxide base and the formed metal alkyl
carbonate for efficient hydrogenation. Hence, ethylene glycol
(bp = 197.6 °C, ε = 37) was selected for our one-pot CCU
system. Interestingly, a solution of NaOH in ethylene glycol
captured CO2 quantitatively and the obtained carbonates were
completely soluble (entry 2). The capture capacity of a KOH
solution was similar to that of NaOH (entry 3). With
Ca(OH)2, the CO2 capture was significantly lower.
Following the capture, the CO2-loaded solutions were
hydrogenated under 70 bar of H2 in the presence of Ru-
Macho-BH (C-1) (Table 2). This catalyst was already well-
studied by our group and others for CO2 hydrogenation to
methanol. KOH was chosen as the model alkali hydroxide due
to fast dissolution in ethylene glycol. At 140 °C, with 0.5 mol
% catalyst loading, full conversion of the captured CO2 was
achieved with a methanol yield of 80% within 10 h. When the
reaction time was extended to 20 h, quantitative yield of
CH3OH was obtained. Ru-Macho (C-2) displayed an activity
similar to C-1 with 92% CH3OH yield. When the P-
substituents in the pincer catalyst were replaced from R =
Ph to R = iPr, tBu, or Cy (C-3 to C-5), the CH3OH yield
dropped drastically. Similarly, a meager 13% CH3OH yield was
observed when the N−H moiety of C-2 was replaced with N-
Me in C-6 suggesting the involvement of a Ru−N cooperative
mechanism. With NaOH as the base, CH3OH was produced
with 93% yield. CO2-loaded Ca(OH)2 solution was not
hydrogenated efficiently. When the C-1 catalyst loading was
lowered to 0.25 and 0.1 mol %, the CH3OH yield decreased to
90% (TON = 360) and 48% (TON = 480), respectively. Upon
lowering the temperature to 120 °C CH3OH was obtained
with 99% yield after 72 h. Further lowering the temperature to
100 °C resulted in a CH3OH yield of 31% and 60% at 0.5 and
1 mol % catalyst loading, respectively. From these results, it is
clear that the glycol mediated Ru-PNP based catalytic system is
significantly active for CH3OH synthesis even at relatively low
During the hydrogenation reactions, formation of potassium
glycolate (PG) was observed in addition to CH3OH (Table
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
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Table 2. Tandem Hydrogenation of Captured CO2 in Ethylene Glycola

entry MOH cat. (mol %) T (°C) time (h) formate (%)b MeOH (%)b TONMeOH
1 KOH C-1 (0.5) 140 10 20 80 160
2 KOH C-1 (0.5) 140 20 0 100 200
3 KOH C-2 (0.5) 140 20 8 92 184
4 KOH C-3 (0.5) 140 20 90 10 20
5 KOH C-4 (0.5) 140 20 100 0 0
6 KOH C-5 (0.5) 140 20 76 6 12
7 KOH C-6 (0.5) 140 20 87 13 26
8 NaOH C-1 (0.5) 140 20 1 93 186
9c Ca(OH)2 C-1 (0.5) 140 20 5 20 24
10 KOH C-1 (0.25) 140 72 10 90 360
11 KOH C-1 (0.1) 140 72 52 48 480
12 KOH C-1 (0.5) 120 72 1 99 198
13 KOH C-1 (0.5) 100 72 69 31 62
14 KOH C-1 (1) 100 72 40 60 60
a
Reaction conditions: solutions from Table 1 (as specified) were directly hydrogenated. Captured CO2 = 2.5 mmol, H2 = 70 bar. bYields
determined by 1H NMR (tBuOH as internal standard). cCaptured CO2 = 1.5 mmol. Yield calculations error ±5%. TON = moles of methanol per
mol of catalyst.

Scheme 2. Insights into the Reaction Sequences and Base Regeneration

S3). To investigate this unforeseen observation, a set of control under the hydrogenation conditions, a solution of KOH in
experiments were performed (Scheme 2B). It was revealed that ethylene glycol was converted to PG. This phenomenon was
C https://dx.doi.org/10.1021/jacs.9b12711
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Journal of the American Chemical Society
not observed in the absence of catalyst. Dehydrogenation of
alcohols using such catalytic systems have been well
documented.18 Yet, our observation of dehydrogenation at
such high H2 pressure is entirely unprecedented. The
formation of PG during the hydrogenation reactions indicates
that only a fraction of the base remained available for
subsequent CO2 capture (Scheme 2A). To confirm the partial
regeneration of the base, a scaled-up reaction was performed
with 20 mmol of captured CO2 and a catalyst loading of 0.1%
(Scheme 2C). 9.6 mmol of CH3OH, 10.4 mmol of HCOOK,
and 3.3 mmol of PG were produced after 72 h. When this
reaction solution was directly subjected to subsequent CO2
capture, only about 5 mmol of CO2 was captured by the
regenerated base.
Finally, the efficacy of the system was tested for DAC of
CO2 and conversion to CH3OH. Following our reported
protocol,13b indoor air was bubbled through a solution of 5
mmol of KOH in 10 mL of ethylene glycol. After 48 h, 3.3
mmol of CO2 was captured in the form of carbonate and alkyl
carbonate salts (Table 3). Additionally, there was an
Table 3. CO2 Capture from Ambient Air and Conversion to
CH3OHa
entry captured CO2 (mmol) time (h) formate (%)b MeOH (%)b
1 3.3 20 75 25
2 3.3 72 0 100
a
Reaction conditions: 140 °C. bYields determined by 1H NMR
(tBuOH as internal standard). Yield calculations error ±5%.
accumulation of around 3 mL of H2O from moisture in air.
When the resulting solution was hydrogenated, CH3OH was
obtained with a 25% yield after 20 h. When the reaction was
extended to 72 h, the captured CO2 was completely converted
to CH3OH.
In conclusion, we have developed a novel amine-free system
for integrated CO2 capture and conversion to methanol. The
alkali hydroxide captured CO2 quantitatively in ethylene glycol,
forming alkyl carbonate salts, which were efficiently hydro-
genated using Ru-PNP catalysts. With Ru-Macho-BH,
quantitative conversion to CH3OH was achieved within 20 h
at 140 °C. The catalyst showed significant activity for CH3OH
synthesis at temperatures as low as 100 °C (yield = 60%).
Additionally, to the best of our knowledge, the present report
is the first example demonstrating hydrogenation of bicar-
bonate and formate salts to CH3OH; as well as low
temperature regeneration of the hydroxide base. Insights into
the reaction pathways revealed that a fraction of the base
produced was rendered inactive by the formation of
carboxylates through in situ dehydrogenation of ethylene
glycol. The current system offers various advantages: (1) high
efficiency with minimal stability issues for CO2 capture; (2)
facile hydrogenation to CH3OH via an ethylene glycol
mediated pathway; (3) highly promising for direct air capture.
For large-scale deployment of the CCU process revealed in this
study, recycling of the active elements will play a key role. Our
ongoing efforts are therefore geared toward retaining complete
D https://dx.doi.org/10.1021/jacs.9b12711
pubs.acs.org/JACS Communication
efficiency of the capturing species and developing a flow
system to achieve continuous CO2 capture and methanol
production. This report is essentially the first key step toward
employing hydroxide-based CO2 scrubbing and economical
regeneration of the base in addition to the production of value-
added methanol with the goal of achieving a sustainable and
carbon neutral cycle.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.9b12711.
General information and experimental details, including
Figures S1−S12 and Tables S1−S3 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
G. K. Surya Prakash − Loker Hydrocarbon Research Institute
and Department of Chemistry, University of Southern
California, Los Angeles, California 90089-1661, United States;
orcid.org/0000-0002-6350-8325; Email: gprakash@
usc.edu
Authors
Raktim Sen − Loker Hydrocarbon Research Institute and
Department of Chemistry, University of Southern California,
Los Angeles, California 90089-1661, United States;
orcid.org/0000-0001-7992-3956
Alain Goeppert − Loker Hydrocarbon Research Institute and
Department of Chemistry, University of Southern California,
Los Angeles, California 90089-1661, United States;
orcid.org/0000-0001-8667-8530
Sayan Kar − Loker Hydrocarbon Research Institute and
Department of Chemistry, University of Southern California,
Los Angeles, California 90089-1661, United States;
orcid.org/0000-0002-6986-5796
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.9b12711
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Support of our work by the Loker Hydrocarbon Research
Institute, USC is gratefully acknowledged.
■
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