An amino acid based system for CO2capture and catalytic utilization to produce formates

Article abstract of DOI:10.1039/d1sc00467k

Herein, we report a novel amino acid based reaction system for CO2 capture and utilization (CCU) to produce formates in the presence of the naturally occurring amino acid l-lysine. Utilizing a specific ruthenium-based catalyst system, hydrogenation of absorbed carbon dioxide occurs with high activity and excellent productivity. Noteworthy, following the CCU concept, CO2 can be captured from ambient air in the form of carbamates and converted directly to formates in one-pot (TON > 50?000). This protocol opens new potential for transforming captured CO2 from ambient air to C1-related products.

Full text of DOI:10.1039/d1sc00467k

Volume 12
Number 17
7
May 2021
Pages 5967–6212
Chemical
Science
rsc.li/chemical-science
ISSN 2041-6539
EDGE ARTICLE
Henrik Junge, Matthias Beller et al.
An amino acid based system for CO capture
2
and catalytic utilization to produce formates

Chemical
Science
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An amino acid based system for CO capture and
2
catalytic utilization to produce formates†
Cite this: Chem. Sci., 2021, 12, 6020
All publication charges for this article Duo Wei,
have been paid for by the Royal Society
of Chemistry
Henrik Junge * and Matthias Beller
*
2
Herein, we report a novel amino acid based reaction system for CO capture and utilization (CCU) to
produce formates in the presence of the naturally occurring amino acid L-lysine. Utilizing a specific
Received 25th January 2021
Accepted 26th February 2021
ruthenium-based catalyst system, hydrogenation of absorbed carbon dioxide occurs with high activity
and excellent productivity. Noteworthy, following the CCU concept, CO
air in the form of carbamates and converted directly to formates in one-pot (TON > 50 000). This
protocol opens new potential for transforming captured CO from ambient air to C1-related products.
2
can be captured from ambient
DOI: 10.1039/d1sc00467k
rsc.li/chemical-science
2
2
RuBisCO and it stabilizes CO in the form of carbamate for
Introduction
20
subsequent enzyme catalysis.
By contrast, in industry e.g., power plants, the most common
relies on the use of aqueous amine
Carbon dioxide concentration in the atmosphere and global
warming is ever-increasing with the enormous global energy process for capturing CO
2
3,21,22
demand supplied by consuming fossil fuels (mainly coal, oil, solutions (Scheme 1b).
However, the maximum CO
capture and storage (CCS) enable the absorption capacity for an amine system varies based on which
use of fossil fuels with signicantly lower CO
emissions than products are formed. When carbamates are the preferred
usual. CCS is based on the separation of CO
from energy products, this capacity is 50 mol% per amines at most. If
2
1,2
and natural gas). CO
2
2
3
2
conversion or other industrial processes, followed by compres- bicarbonates are mainly formed, this capacity could reach up to
sion, transport, and storage. However, CCS processes are 100 mol% per amines. Alkanolamines have been extensively
23
meanwhile energy intensive as the electricity burden with investigated as chemical absorbents; however, their large-
amine scrubbing (113 kW h per mt CO removed) constitutes scale use also created some environmental concerns.
2
the minimum work to separate and compress CO
Indeed, in two demonstration units, Boundary Dam and boiling and innocuous natural AAs in combining CO
Thompsons, 210–220 kW h per mt were required for this and catalysis is therefore highly relevant. Noteworthy, CO
2
(150 bar). Substituting such conventional amine absorbents with high
capture
2
2
4
24–27
25
purpose. Developing novel CO
methods for converting CO
from air or ue gas not only saves ported, but not its direct valorization. Based on the infusive
energy from CCS (mainly CO2 desorption and compression phenomenon of carbon xation by RuBisCO and our long-term
2
capture and utilization (CCU) capture with aqueous AAs,
including Lys was already re-
2
5
–12
steps) but also provides C1-related products (Scheme 1a).
thus an important opportunity for developing a sustainable enables CO
It's interest in CO
2
reduction, we report herein a CCU process which
capture from ambient air and its conversion to
2
13–15
economy.
formate in the presence of L-lysine. Moreover, to the best of our
In nature, inorganic carbon (particularly CO
2
) is converted to knowledge, there exists no example of catalytic hydrogenation
organic compounds by living organisms, which is known as of CO
assisted by AAs.
2
carbon xation, with photosynthesis as the most prominent
16
example. It is estimated that approximately 258 billion tons of
17
CO are converted into biomass by photosynthesis annually.
2
As the most abundant protein on the Earth, ribulose 1,5-
bisphosphate carboxylase/oxygenase (RuBisCO) is involved in
the rst major step of carbon xation by plants and other
18,19
photosynthetic organisms.
L-Lysine (Lys) is one of the six
crucial amino acids (AAs) that are part of the active site of
Leibniz-Institut f u¨ r Katalyse e.V., Albert-Einstein-Str. 29a, Rostock, 18059, Germany.
E-mail: henrik.junge@catalysis.de; matthias.beller@catalysis.de
Scheme 1 (a) Schematic CCU concept for CO
2
hydrogenation to C1
products. (b) Reaction pathways for CO
aqueous conditions.
2
absorption with amines under
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/d1sc00467k
1
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Fig. 1 Representative catalysts and absorbents for CO
2
hydrogenation to C1 products applied in CCU processes. The highest TON (turnover
number) of formates or methanol are shown in parentheses, respectively.
24–27
Several Rh- and Ru-based homogeneous catalysts have been considered applying AAs for this purpose.
Thus, at the start
previously reported for CO
2
capture and in situ hydrogenation to of our investigations, we evaluated the ability of 12 different
C1 products (Fig. 1). In 2013, pioneering work was performed AAs, including the 6 ones involved in the active site of RuBisCo
by the group of He utilizing RhCl $3H O and phosphine and some analogues to capture CO . For this purpose, CO (2
ligands, for instance CyPPh , DPEphos, and PPh , as catalysts bar) was charged into an aqueous solution of the respective AAs
8,28
3
2
2
2
2
3
29
where gaseous CO was absorbed by polyethyleneimine (PEI),
(5 M) and stirred at r.t. for 2–18 h.
2
30
31
amidines, and potassium phthalimide as well as hydroge-
As shown in Table S1,† most of the tested systems such as L-
proline, L-glutamine, and L-histidine achieved only small to
nated in situ to formates or formic acid.
In addition, ruthenium complexes have also been proven to moderate amounts of CO
be suitable catalysts for the hydrogenation of captured CO to per mol of AA (CO /AA), (Table S1, entries 1–11†). Interestingly,
formate or methanol. In 2014, Heldebrant and co-workers in the presence of L-lysine (Lys), a signicantly improved
captured CO by DBU in methanol to form the methyl performance (3.63 mmol of captured CO , corresponding to
carbonate, which then was hydrogenated to formates catalyzed 0.73 CO /Lys) was obtained in 18 h (Table S1, entry 12†). Such
2 2
capture, around 0.1 mol of CO
2
2
2
2
2
32
by [RuCl (PPh ) ]. One year later, Milstein and co-workers re- high CO capture efficiency could be attributed to the basic side
2
3 3
2
ported a CCU approach, where CO reacted with aminoethanols chain of Lys, as its pK value is 10.7.
2
a
yielding oxazolidinones which were hydrogenated to CH
3
OH in
2
Thus, we investigated the effect of Lys for CO absorption
33
7
8–92% yield with a Ru-PNN pincer catalyst. In the same year, under various conditions (Table 1 and Fig. S2 to S11†). As
the Sanford group reported the CO capture with NHMe to mentioned vide supra, carbon dioxide can be captured in form
form carbamate and subsequent hydrogenation to a mixture of of Lys carbamates or Lys ammonium bicarbonate. Applying
2
2
26
44
34
DMF and CH
3
OH catalyzed by Ru-MACHO-BH complex.
2 2
20 bar of CO , 0.83 CO /Lys were obtained within only 0.5 h
Employing the same catalyst and tetramethylguanidine leading to carbamates and bicarbonate (ratio of 1 : 4, 98% total
3
5
36
(
(
TMG),
metal
hydroxides,
pentaethylenehexamine yield; Table 1, entry 1). A similar result was observed aer 3 h
3
7–39
40
PEHA),
a mixture of metal hydroxides, or a tertiary (Table 1, entry 2). Also, at lower CO pressure (2 bar), signicant
2
41
amine with ethylene glycol as CO
2
absorbent systems, Prakash absorption was achieved with 69–98% total yield of carbamates
capture from air with and bicarbonate within 0.5–18 h (Table 1, entries 3–5). Inter-
and his colleagues combined CO
2
subsequent hydrogenation to produce formates or methanol. estingly, in these cases (0.5 h and 3 h), mainly Lys carbamates
Recently, the group of Heldebrant reported a method where were obtained. This shows that initially the corresponding
epoxides reacted with CO
2
leading to cyclic carbonates. Then, in carbamates are formed, which subsequently form bicarbonate.
situ hydrogenation took place into methanol and glycol, with
Ru-MACHO as catalyst.
Besides water, the aprotic solvent THF was applied. Aer 3 h
exclusively the carbamate was formed (1.18 mmol correspond-
42
Compared to methanol, no hydrogen is lost in the form of ing to 0.24 CO /Lys, Table 1, entry 6). A much lower CO /Lys
2
2
water when formic acid or formate salts are produced by CO
2
ratio (0.06) was observed under neat conditions (without
hydrogenation. Currently, formic acid is industrially produced by solvent, Table 1, entry 7). Next, to demonstrate the viability of
carbonylation of methanol to methyl formate and subsequent our general CCU methodology, ambient air, containing ca.
43
hydrolysis. It is mainly used as a preservative and antibacterial 415 ppm (parts per million) CO
2
, was bubbled through Lys
agent in livestock feed, e.g. silage and winter feed for cattle. In solution for 1–8 days (Fig. S1†). Indeed, up to 0.49 mol CO
2
addition, formic acid is utilized in the production of leather and per mol Lys were absorbed representing a yield of 98% with
in dyeing and nishing textiles. More recently, it also gained carbamates as sole products. Performing the reaction on multi-
interest as hydrogen storage medium as it contains 4.4 wt% of g scale (20 mmol Lys), 8.20 mmol CO2 were captured corre-
7
hydrogen with 53 g H
2
per L of volumetric storage density.
sponding to 0.41 CO
entry 12).
2
/Lys and 82% carbamate yield (Table 1,
Results and discussion
CO
For the development of a CCU concept to produce formic acid or Next, to identify a suitable reduction system, various metal
formates, suitable CO absorbents must be used. Inspired by pincer complexes were tested for the hydrogenation of gaseous
the carbon xation pattern in nature, specically RuBisCO, we CO
2
capture with amino acids
2
Catalytic hydrogenation of CO to formate
2
2
in the presence of different amino acids (Tables 2 and S2,
©
2021 The Author(s). Published by the Royal Society of Chemistry
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a
Table 1 CO
2
capture with Lys according to Scheme 1b under various conditions
b
b
c
d
Entry
CO
2
source
Time
Carbamates [mmol]
Bicarbonate [mmol]
Yield [%]
2
CO /Lys
1
2
3
4
5
CO
CO
CO
CO
CO
CO
CO
Air
Air
Air
Air
Air
2
2
2
2
2
2
2
(20 bar)
(20 bar)
(2 bar)
(2 bar)
(2 bar)
(2 bar)
(2 bar)
0.5 h
3 h
0.5 h
3 h
18 h
3 h
3 h
1 d
2 d
4 d
8 d
0.75
0.45
1.53
1.83
1.25
1.18
0.30
1.40
1.95
2.42
2.45
8.20
3.40
3.80
0.37
1.22
2.38
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
98%
94%
69%
98%
98%
47%
12%
56%
78%
97%
98%
82%
0.83
0.85
0.38
0.61
0.73
0.24
0.06
0.28
0.39
0.48
0.49
0.41
e
6
7
f
8
9
1
1
1
0
1
2
g
4 d
a
ꢁ1
b
13
Conditions: Lys (5.0 mmol), H O (1.0 mL), stirred at r.t. Air bubbling: 1 L mind . Determined by C NMR-quant with THF (406.2 mL, 5.0 mmol) as
2
c
e
f
internal standard. Total yield of carbamates and bicarbonate based on Lys. Mols of CO
2
captured per mol of Lys. THF (1 mL) as solvent. Neat
condition (without solvent). Lys 20.0 mmol. n.d. ¼ not detectable. Experiments were performed at least twice; average values are used (st. dev. <
0%).
g
1
Fig. S12 and S13†). To our delight, testing the Ru-MACHO-BH S2, entries 2–12†). Taking Lys as a benchmark CO
2
absorbent,
complex (Ru-1, 0.2 mol%) in H O/THF (1 : 1 mixture) revealed the TON of formate can be considerably increased from 2187 to
2
signicant activity in the presence of Lys for the hydrogenation 197 559 when decreasing the loading of Ru-1 from 400 ppm
ꢀ
of gaseous CO to formate (71% yield based on Lys) at 145 C (based on Lys) to 4 ppm (Table 2, entries 1–3). With 4 ppm of Ru-
2
(Table S2, entry 1†).
MACHO (Ru-2) as catalyst, the highest TON 212 139 was ach-
On the other hand, L-cysteine, L-histidine, L-serine, and L- ieved (Table 2, entry 4). Interestingly, in these reactions, CO2
threonine led to formates in much lower yields (up to 13%), was selectively converted to formate in up to 87% yield with less
while other AAs, such as glycine, L-proline, and L-glutamine than 1% of formamide. Next, several ruthenium pincer
showed no activity at all in the presence of catalyst Ru-1, (Table complexes were tested at 4 ppm loading for the hydrogenation
of gaseous CO
2
in the presence of Lys within 3 h (Table 2, entries
6
–10). Ru-1 and Ru-2 gave formate in 55% and 58% yields,
iPr
Table 2 Ru-catalyzed hydrogenation of gaseous CO
of Lys
2
in the presence
respectively, whereas Ru-MACHO
(Ru-3) was less active
a
leading to formate in only 6% yield. With Milstein's Ru-PNP
complex (Ru-4) as catalyst, formate was obtained in 47% yield.
However, no formate can be detected in the reaction catalyzed
iPr
by Fe-MACHO -BH complex (Fe-1).
Several blank reactions were also carried out (Table S3†): in
the absence of either Lys, Ru-1, or CO , no formate was
2
detectable. These results clearly demonstrate that Lys and Ru-1
are both crucial to promote the hydrogenation of CO from air
2
to formate. Reactions with other solvents, for example, triglyme,
methanol, ethylene glycol or their 1 : 1 mixture with water could
not improve the reaction efficiency (Table S4†). When replacing
THF with the more eco-friendly green solvent 2-methyltetrahy-
b
c
d
Entry
Cat. [mmol, ppm]
Formate [mmol]
% Yield (TON)
1
2
3
4
5
Ru-1 [2.0, 400]
Ru-1 [0.2, 40]
Ru-1 [0.02, 4]
Ru-2 [0.02, 4]
Ru-2 [0.01, 2]
Ru-1 [0.02, 4]
Ru-2 [0.02, 4]
Ru-3 [0.02, 4]
Ru-4 [0.02, 4]
Fe-1 [0.02, 4]
4.37
3.89
3.95
4.24
1.48
2.77
2.90
0.29
2.35
n.d.
87 (2187)
45
drofuran (2-MTHF), a comparable yield of formate (86%) was
78 (19 440)
79 (197 559)
85 (212 139)
30 (147 906)
55 (138 510)
58 (144 990)
6 (14 580)
47 (117 450)
—
ꢀ
observed. Lowering the temperature from 145 to 105 C, the
yield of formate decreased only slightly from 79% to 64% (Table
S5†).
e
6
e
7
8
e
Development of a general CCU concept
e
9
e
Aer having studied the individual processes of (a) CO
absorption and (b) CO reduction in the presence of Lys, the
overall CCU concept was demonstrated by combining CO
2
2
1
0
a
2
Conditions: catalyst, Lys (5.0 mmol), H
2
O (5.0 mL), THF (5.0 mL), CO
2
ꢀ
b
1
(20 bar), H
2
(60 bar), 145 C, 12 h. Determined by H NMR with DMF
c
(
250 mL, 3.24 mmol) as internal standard. Calculated by formate capture and in situ hydrogenation to formate (Table 3 and
d
[
mmol]/Lys [mmol]. Calculated by formate [mmol]/catalyst [mmol].
Fig. S14–S16†).
e
3
h. n.d. ¼ not detectable. Experiments were performed at least
2
Using captured CO (2.42 mmol) as substrate in the presence
twice; average values are used (st. dev. < 10%).
of Ru-1 (2.0 mmol) as catalyst, 46% formate yield (based on
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a
2
Table 3 Combining CO capture from ambient air and in situ conversion to formate
b
c
d
Entry
Captured CO
2
[mmol]
Cat. [mmol]
Formate [mmol]
% Yield (TON)
1
2
3
4
5
2.42
2.42
2.42
2.42
2.42
8.20
8.20
8.20
Ru-1 [2.0]
1.10
1.15
1.02
1.10
1.04
2.40
3.31
1.00
46 (551)
48 (1353)
42 (6004)
45 (54 998)
43 (52 245)
29 (29 993)
40 (41 330)
12 (25 110)
Ru-1 [0.85]
Ru-1 [0.17]
Ru-1 [0.02]
Ru-2 [0.02]
Ru-1 [0.08]
Ru-2 [0.08]
Ru-2 [0.04]
e
6
e
7
e
8
a
Conditions: CO
2 2
captured from air within 4 d applying 5 mmol Lys, given amount of catalyst dosed from stock solution, H O (5.0 mL), THF (5.0
b 1 c
ꢀ
mL), H
captured CO
twice; average values are used (st. dev. < 10%).
2
(80 bar), 145 C, 12 h. Determined by H NMR with DMF (250 mL, 3.24 mmol) as internal standard. Calculated by formate [mmol]/
d
e
2
2
[mmol]. Calculated by formate [mmol]/catalyst [mmol]. CO captured with 20 mmol Lys. Experiments were performed at least
2
captured CO ) was obtained (TON 551; Table 3, entry 1). The superiority of using Lys for carbon dioxide capture and direct
highest TON reached 54 998 with 0.02 mmol Ru-1, while the valorizations. It also indicates the crucial presence of an a-
yield was maintained at 45% (Table 3, entries 2–4). Ru-2 showed amino acid moiety and an additional amine function in the side
comparable activity for the hydrogenation of captured CO2 chain of AA.
yielding 43% of formate (Table 3, entry 5). With 8.20 mmol
captured CO , 29% of formate were obtained with Ru-1 at 0.08 current study, we conducted further experiments by heating up
mmol loading (Table 3, entry 6). 3.31 mmol formate (40% yield) the mixture of formic acid and Lys or PEHA in H
To rationalize the perfect selectivity towards formates in the
2
ꢀ
O at 145 C
2
were obtained with the same amount of Ru-2 (Table 3, entry 7). (Table S6†). Indeed, Lys led to formate in quantitative yield
Finally, some Lys analogues and derivatives as well as without any formamide detectable aer 12 h, whereas PEHA
35,37,39
selected benchmark amines
were applied according to our gave 28% yield of formamide along with 71% formate. Obvi-
overall protocol (Fig. 2). In the presence of 6-aminohexanoic ously, the less basic conditions applying Lys (pH 10.2 for a 5 M
acid and 1,5-diaminopentane, 0.12 and 0.82 CO /amine were aqueous solution) prevented the formation of formamides
2
achieved and formates were obtained in yields of 25% and 34%, taking place in the presence of PEHA (pH 13.4).
respectively. Noticeably, 2,3-diaminopropanoic acid and the
simplest amino acid glycine did not show any activity in both
Conclusions
CO
2
absorption and hydrogenation processes. In the case of
was captured with 0.86 and 0.83 CO /TMG
TMG and PEHA, CO
2
2
In conclusion, we described an amino acid based catalyst
system for the highly relevant CO capture and utilization (CCU)
process to produce formates in one-pot. The naturally occurring
amino acid L-lysine affords formate generation with a high
efficiency. Among the investigated catalysts, the most active
ones are identied with Ru-MACHO complexes (Ru-1 and Ru-2)
or PEHA, respectively. However, the presence of TMG inhibited
2
the hydrogenation of CO , whereas PEHA led to formate and
2
formamides in 38% and 8% yield, respectively. Applying the
36
inorganic base NaOH resulted in a CO
2
/base ratio of 1.08 and
23% formate yield. All these experiments demonstrate the
for the hydrogenation of gaseous CO
in situ hydrogenation of captured CO
2
(TON > 210 000) and the
(TON > 50 000). Note-
2
worthy, in the present CCU concept, CO can be captured from
2
ambient air in the form of carbamates and hydrogenated to
formate directly.
Author contributions
D. W. conducted all the experimental work, collected and analyzed
the data. D. W., H. J. and M. B. wrote the paper. H. J. and M. B.
proposed and supervised the project. All the authors discussed the
results and commented on the manuscript. All authors have given
approval to the nal version of the manuscript.
Fig. 2 Various Lys analogues and benchmark amines applied in the
CO absorption and hydrogenation processes performed under
conditions in Table 1, entry 4 and Table 2 entry 6, respectively. CO
amine (mols of CO captured per mol of amine) are shown with yield
and TON of formates in parentheses; n.d. ¼ not detectable.
2
2
/
2
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2021 The Author(s). Published by the Royal Society of Chemistry
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2
2
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