Article

pubs.acs.org/EF

Second-Generation Aminosilicones as CO2 Capture Solvents

Robert J. Perry*
GE Global Research, 1 Research Circle, Niskayuna, New York 12309, United States

ABSTRACT: Silicones with a variety of linear, branched, star, and cyclic architectures were synthesized that contained electron-
donating ethylaminopropyl groups attached to the silicone core. These solvents were tested for CO2 uptake and their physical
state after reaction. In comparison to analogous materials that only possessed a primary amine, all of the heteroatom-substituted
derivatives displayed excellent CO2 uptake and all maintained a liquid, flowable state after reaction. Optimal CO2 uptake was
achieved at ambient temperatures rather than the typical 40 °C level. This was likely due to the lower heats of reaction for the
secondary amine structure. β-Isomer present in the samples did not adversely affect the reaction with CO2 or the ability to
remain in a liquid state upon complete reaction.

■ INTRODUCTION
Aqueous solutions of organic amines are used as the workhorses
in most carbon capture technologies that have progressed to pilot
scale and beyond. These include the sterically hindered amines
KS-1, KS-2, and KS-3 developed by Mitsubishi Heavy Industries
(MHI),1 Cansolv’s proprietary amine system,2 Fluor’s Econ-
amine FG and Econamine FG Plus solvents,3 and the Linde/
BASF OASE system.4
However, recent developments in non-aqueous-based solvents
for carbon capture have spurred increased interest in this area,
with imidazoles,5 guanidines and amidines,6 CO2 binding organic
liquids (CO2BOLs),7 and even traditional organic amines in
glycol or alcoholic solvents8 being examined. Aminosilicones
have also been investigated as one class of such solvents that
have been calculated to be more economical that conventional
aqueous-based organic amines.9
A mixture of aminosilicone (GAP-1) and triethylene glycol
(TEG) as a CO2 capture solvent (Figure 1) has been examined at
the laboratory and bench scale10 and was recently tested in the
pilot facility at the National Carbon Capture Center (NCCC).
TEG was needed as a co-solvent because the reaction product of
GAP-1 and CO2 formed a soft solid unsuitable for a liquid-based
capture process. While TEG did not absorb any appreciable
amounts of CO2, it did permit the solvent to remain liquid
throughout the process. The pilot testing showed excellent
performance with regard to CO2 capture ability, with 66% CO2
capture efficiency at 0.5 MWe using a continuous stirred-tank
reactor (CSTR) desorption unit. Use of a steam stripper desorp-
tion unit improved the CO2 capture efficiency to 95% at 0.5 MWe.
However, even this promising solvent composition had proper-
ties that might be improved. These included increased capture
capacity, lower heat of reaction with CO2, decreased viscosity,
and elimination of a co-solvent.
The use of secondary amine-functionalized disiloxanes as CO2
capture solvents was reported earlier, and these materials
possessed several features that made them attractive candidates
as improved solvents for CO2 capture.11 Some of these qualities
included lower heats of reaction, higher CO2 uptake capacities,
and, in several cases, the ability to maintain a flowable liquid state
even when fully reacted with CO2 without the need for a
co-solvent. These fully reacted materials only manifested the
liquid state when a very specific arrangement of functional groups
was present on the disiloxane backbone. The functional group
possessed an electron-donating group on the ethylaminopropyl
linking group, as shown in Figure 2, where XR was OEt, OMe, or
NMe2.
This unique property is thought to be derived from the
capacity of the molecule to form intramolecular hydrogen
bonds, as shown in Figure 3. This provided steric bulk around
ammonium nitrogen and diminished the propensity of the
charged carbamate product to self-associate, as occurs with the
unsubstituted primary amine. This contrasts with the preliminary
results from molecular modeling, which indicate that carbamate
molecules cluster together rather than remain dispersed in the
solvent matrix.12 Similar arguments have been made for single-
component switchable ionic liquids.13
This report examines the generality of imparting flowability to
other core structures containing the alkoxyethylaminopropyl and
similar groups and describes the synthesis and CO2 uptake
experiments for an extended class of second-generation materials
as well as a qualitative assessment of their physical state upon
reaction with CO2.
■ EXPERIMENTAL SECTION
All reactions were performed under a nitrogen atmosphere, and all
chemicals purchased from suppliers were used as received.
Bis(3-hydroxylpropyl)siloxane (3). 1,1,3,3,5,5,7,7-Octamethylte-
trasiloxane (5.65 g, 20 mmol) was dissolved in toluene (30 mL), and
then 2 mL of allyl alcohol (2.8 g, 48 mmol) in toluene (10 mL) was
added at ambient temperature, followed by 1 drop of Karstedt’s catalyst
(4.3 wt % Pt in xylenes). The reaction mixture was heated to 40 °C, and
the remainder of the alcohol solution was added over 1 min. Heat was
increased to reflux, and the reaction was allowed to continue for 18 h.
After this time, the solution was concentrated in vacuo, dissolved in
MeOH, filtered through Celite, and concentrated to give 5.6 g (67%) of
product as a viscous brown liquid. 1H NMR (CDCl3): δ 3.83 (m, 1.2H),
3.64 (m, 4H), 2.15 (br, 1.8H), 1.8 (m, 1.6H), 1.62 (m, 4.1H), 0.7
(m, 1.5H), 0.55 (m, 4H), 0.07−0.14 (45H). Literature boiling point:
141−142 °C/0.06 mmHg.14
Received: April 13, 2017
Revised: May 22, 2017
Published: May 25, 2017

© 2017 American Chemical Society 7334 DOI: 10.1021/acs.energyfuels.7b01048

Energy Fuels 2017, 31, 7334−7343
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Figure 1. GAP-1/TEG CO2 capture solvent.
Figure 2. Preliminary second-generation aminosilicone CO2 capture
solvents.
Bis(3-chloropropyl)siloxane (4). Bis(3-hydroxypropyl)siloxane
(3, 5.4 g, 13.5 mmol) was cooled to 3 °C, and then 1 drop of pyridine
was added, followed by thionyl chloride (16.1 g, 135 mmol) dropwise
with ice-bath cooling. After the addition was complete, the bath was
removed and the mixture was stirred at ambient temperature for 4 h,
with reflux for an additional 7 h. Excess thionyl chloride was removed by
distillation, and the residue was dissolved in CH2Cl2, washed with water
and then brine, then dried over MgSO4, concentrated, and allowed to
stand. After 2 days, the solid that had precipitated out was removed by
filtration and the product as a clear orange liquid was obtained (3.2 g,
54%). 1H NMR (CDCl3): δ 3.53 (t, J = 7.1 Hz, 4H), 1.82 (m, 4H), 0.66
(m, 4H), 0.10 (s, 40H). 13C {1H} NMR (CDCl3): 47.84, 27.06, 15.90,
1.15, 0.74, 0.27, 0.11 ppm.
Bis(3-iodopropropyl)siloxane (5). Bis(3-chloropropyl)siloxane
(4, 3.0 g, 4.8 mmol) was dissolved in acetone (20 mL); then NaI
(4.1 g, 27.6 mmol) in acetone (40 mL) was added; and the reaction
mixture was heated to reflux for 3 days. After this time, the reaction was
concentrated and the residue was dissolved in CHCl3, washed with
water (2×), aqueous Na2SO3, and brine, dried over MgSO4, and
concentrated to give 3.26 g (84%) of product as an orange oil. 1H NMR
(CDCl3): δ 3.22 (m, 4H), 1.87 (m, 4H), 0.65 (m, 4H), 0.10 (s, 38H).
13
C {1H} NMR (CDCl3): 28.23, 20.22, 11.12, 1.09, 0.37, 0.19 ppm.
Bis(3-(N-ethoxyethyl)aminopropyl)siloxane (7). Bis(3-
iodopropyl)siloxane (5, 2.7 g, 3.33 mmol) was added to ethoxyamino-
ethane (6, 6.7 g, 75 mmol) at ambient temperature over 15 min and
stirred at ambient temperature for 22 h. Excess amine was removed
in vacuo; the residue was dissolved in heptane and treated with 10%
NaOH (aqueous); and the layers were separated. The organic layer was
washed with water and brine, dried over Na2SO4, filtered, and
concentrated to give 1.9 g (79%) of product as a light orange oil. 1H
NMR (CDCl3): δ 3.58 (m, 8H), 2.79 (t, J = 5.4 Hz, 4H), 2.62 (t, J =
7.4 Hz, 4H), 1.53 (m, 4H), 1.51 (br, 2H), 1.22 (t, J = 7.1 Hz, 6H), 0.53
(m, 4H), 0.09−0.06 (ms, 38.8H). 13C {1H} NMR (CDCl3): 69.99,
66.41, 53.29, 49.53, 23.88, 23.83, 15.88, 15.73, 15.17, 1.17, 1.04, 0.29,
0.10 ppm.
Tris(3-aminopropropyldimethylsiloxy)phenylsilane (11). A
solution of allylamine (2.0 g, 35 mmol) in toluene (5 mL) was added
dropwise to a solution of tris(dimethylsiloxy)phenylsilane (9, 3.0 g,
9.07 mmol) in toluene (5 mL). After 1 mL of amine was added, 1 drop of
Karstedt’s catalyst was added and then the mixture was heated to 80 °C
for a total of 8 h. An additional 1 mL of allylamine and 1 drop of
Karstedt’s catalyst was added at this time, and the reaction was allowed
to proceed for a total of 24 h. The solvent was removed in vacuo (3 h,
80 °C/1 mmHg) to give 4.0 g (88%) of product with 11% β-isomer. 1H
NMR (CDCl3): δ 7.54 (m, 2H), 7.33 (m, 3H), 2.88 (dd, J = 12.5 and
4.7 Hz, 0.4H), 2.60 (t, J = 7.0 Hz, 3.6H), 2.22 (m, 0.2H), 1.40 (m, 3.6H),
1.07 (m, 4H), 0.96 (d, J = 7.4 Hz, 1.8H), 0.75 (m, 0.6H), 0.52 (m. 3.5H),
Figure 3. Intramolecular hydrogen bonding in second-generation aminosilicone CO2 capture solvent.
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0.02−0.20 (m, 18H). 13C {1H} NMR (CDCl3): 133.79, 133.73, 129.63
(m), 45.41, 44.11, 27.56, 26.39, 15.12, 11.50, 0.11, −1.34 ppm.
N-(2-Ethoxyethyl)allylamine (13). Et3N (16 mL, 115 mmol) was
added to a solution of allylamine (32.93 g, 577 mmol) in tetrahydrofuran
(THF, 40 mL) and heated to 60 °C, and then 2-bromoethyl ethyl ether
(12, 17.65 g, 115 mmol) was added over 10 min. After 3 h, excess solvent
and allylamine were removed in vacuo and the residue was dissolved in
CHCl3, washed with water, dried over Na2SO4, filtered, concentrated,
and distilled to give 11.2 g (75%) of product. 1H NMR (CDCl3): δ 5.88
(m, 1H), 5.15 (dm, J = 17.2 Hz, 1H), 5.05 (dm, J = 10.4 Hz, 1H), 3.51
(m, 4H), 3.24 (m, 1H), 3.23 (m, 1H), 2.75 (t, J = 5.1 Hz, 2H), 1.57 (br,
1H), 1.18 (t, J = 7.1 Hz, 3H). 13C {1H} NMR (CDCl3): 136.83, 115.78,
69.85, 66.38, 52.40, 48.81, 15.11 ppm.
Tris(3-(N-ethoxyethyl)aminopropyldimethylsiloxy)-
phenylsilane (14). A solution of N-(2-ethoxyethyl)allylamine (13,
2.6 g, 20 mmol) in toluene (5 mL) was added dropwise to a solution of
tris(dimethylsiloxy)phenylsilane (9, 2.0 g, 6 mmol) in toluene (5 mL)
after 1 mL of olefin had been added to hydride, followed by 1 drop of
Karstedt’s catalyst. The mixture was heated to 50 °C and then to 100 °C
with an additional 1 drop of catalyst added. After 22 h, the reaction
mixture was concentrated, dissolved in CHCl3, washed with water, dried
over Na2SO4, filtered, and concentrated and volatiles were removed at
100 °C/1 mmHg for 1 h to yield 4.3 g (99%) of product as a clear orange
liquid with ∼20% β-isomer. 1H NMR (CDCl3): δ 7.54 (m, 2H), 7.32
(m, 3H), 3.51 (m, 10.1H), 2.75 (m, 5.2H), 2.59 (m, 4.3H), 1.48 (m,
6.1H), 1.21 (m, 8.4H), 1.17 (m, 1.14H), 0.57 (m, 3.7H), 0.12 (m,
19.4H). 13C {1H} NMR (CDCl3): 133.81, 133.76, 129.54, 127.53,
127.49, 69.97, 66.38, 53.22, 51.50, 49.36, 49.24, 23.73, 22.44, 15.66,
15.61, 15.17, 12.02, 1.07, 0.10 ppm.
Tetrakis(3-aminopropropyldimethylsiloxy)silane (16). A sol-
ution of allylamine (4.4 g, 77 mmol) in toluene (5 mL) was added
dropwise to a solution of tetrakis(dimethylsiloxy)silane (15, 5.0 g,
15.2 mmol) with 1 drop of Karstedt’s catalyst and heated to 85 °C. After
24 h, additional allylamine (1 g) and catalyst were added and the
reaction was allowed to continue for another 6 h. The solvent was
removed in vacuo to give 7.0 g (82%) of product with ∼18% β-isomer.
1
H NMR (CDCl3): δ 4.85 (s, 2.6H), 2.90 (dd, J = 12.5 and 4.7 Hz,
0.2H), 2.63 (t, J = 7.0 Hz, 1.8H), 2.56 (m, 0.2H), 1.54 (m, 2H), 1.06 (m,
0.6H), 0.86 (m, 0.2H), 0.61 (s, 2H), 0.15 (s, 10.6H). 13C {1H} NMR
(CDCl3): 44.50 (m), 42.95, 26.34 (m), 25.49, 14.75, 10.44, −1.08,
−2.54 ppm.
Tetrakis(3-(N-ethoxyethyl)aminopropropyldimethylsiloxy)-
silane (17). A solution of N-(2-ethoxyethyl)allylamine (13, 6.0 g,
46.4 mmol) in toluene (5 mL) was added dropwise to a solution of
tetrakis(dimethylsiloxy)silane (15, 3.0 g, 9.3 mmol) with 1 drop of
Karstedt’s catalyst and heated to 85 °C. Two additional aliquots of olefin
and catalyst were added at 5 and 22 h. A small amount of hydride
remained after 24 h; therefore, 1-hexene (0.5 mL) was added to quench
any remaining S−H groups. The solvent was removed in vacuo to give
6.1 g (78%) of product with ∼25% β-isomer. 1H NMR (CDCl3): δ 3.48
(m, 16H), 2.75 (m, 8H), 2.56 (m, 7H), 1.51 (br m, 6H), 1.17 (t, J = 6.8
Hz, 12H), 0.97 (m, 3H), 0.55 (m, 5.85H), 0.07 (s, 32H). 13C {1H} NMR
(CDCl3): 69.91, 66.36, 55.23, 51.42, 23.67, 22.36, 15.53, 15.15, 11.91,
0.95, −0.12 ppm.
DOI: 10.1021/acs.energyfuels.7b01048
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Scheme 1. Preparation of Linear Siloxane with Ethoxyethylaminopropyl End Groups
Tetrakis-1,3,5,7-(3-(N-ethoxyethyl)aminopropropyl)-1,3,5,7-
tetramethycyclotetrasiloxane (19). A solution of N-(2-etho-
xyethyl)allylamine (1, 5.4 g, 41.6 mmol) in toluene (2 mL) was added
dropwise to a solution of 1,3,5,7-tetramethylcyclotetrasiloxane (15,
3.0 g, 9.3 mmol) in toluene (3 mL) with 1 drop of Karstedt’s catalyst and
heated to 90 °C. Two additional aliquots of olefin and catalyst were
added at 5 and 23 h. A small amount of hydride remained after 24 h;
therefore, 1-hexene (0.5 mL) was added to quench any remaining S−H
groups. The solvent was removed in vacuo to give 5.25 g (83%) of
product with ∼50% β-isomer. 1H NMR (CDCl3): δ 3.50 (m, 7.9H), 2.75
(m, 4H), 2.70 (m, 1H), 2.59 (m, 2H), 2.47 (m, 1H), 1.67 (br, 1.8H),
1.52 (m, 2H), 1.19 (m, 6H), 0.97 (m, 3.3H), 0.51 (m, 2H), 0.07 (7.8H).
13
C {1H} NMR (CDCl3): 69.92, 66.36, 53.01, 51.40, 49.36, 23.45, 21.77,
15.15, 14.56, 11.95, 0.75, −2.14 ppm.
Bis(3-aminopropyl)dimethylsiloxane (25). Allylamine (1.3 g,
22.8 mmol) was added to hydride-capped siloxane (21, 5.02 g,
6.9 mmol) over 2 min with 1 drop of Karstedt’s catalyst and heated to
60 °C for 16 h. Volatiles were removed in vacuo to give 5.39 g (93%) of
product with 25% β-isomer. 1H NMR (CDCl3): δ 2.89 (dd, J = 12.6 and
4.8 Hz, 0.72H), 2.65 (t, J = 6.8 Hz, 3.8H), 2.54 (dd, J = 12.6 Hz, 0.72H),
1.44 (m, 4H), 1.03 (br 4H), 0.97 (d, J = 7.3 Hz, 2H), 0.74 (m, 0.7H),
0.52 (m, 4H), 0.06 (s, 78H). 13C {1H} NMR (CDCl3): 45.41, 44.27,
27.64, 26.37, 15.20, 11.51, 1.12, 0.99, 0.08 ppm.
Bis(3-(N-ethoxyethyl)aminopropyl)siloxane (26). N-(2-
Ethoxyethyl)allylamine (13, 2.0 g, 15.2 mmol) was added to hydride-
capped siloxane (21, 5.0 g, 6.9 mmol) over 2 min with 1 drop of
Karstedt’s catalyst and heated to 80 °C for 18 h. Volatiles were removed
in vacuo to give 5.66 g (83%) of product with 40% β-isomer. 1H NMR
(CDCl3): δ 3.54 (m, 11.5H), 2.76 (m, 6.4H), 2.62 (m, 3.5H), 2.51
(0.9H), 1.59 (m, 3.7H), 1.22 (m, 8.6H), 1.03 (m, 3.7H), 0.59 (m, 4H),
0.09−0.14 (m, 94H). 13C {1H} NMR (CDCl3): 68.74, 66.04, 52.35,
51.03, 48.42, 22.84, 21.75, 15.22, 14.22, 11.07, 0.18, −0.93, −2.56 ppm.
N-(2-Methoxyethyl)allylamine (22). Allylamine (20.5 g,
360 mmol) and NEt3 (13.9 mL, 100 mmol) were added together
followed by slow addition (35 min) of 2-bromoethyl methyl ether
(10.0 g, 72 mmol) while heating to 50 °C. After 2 h, the reaction was two
phases. The upper phase was isolated and concentrated to an orange oil
that was diluted with heptane, washed with 10% NaOH and water, and
then dried over Na2SO4. The aqueous base contained most of the
product, and the base wash was extracted with CHCl3, concentrated, and
distilled (115−120 °C/300 mmHg) to give 1.9 g (23%) of product. 1H
NMR (CDCl3): δ 5.85 (m, 1H), 5.12 (dd, J = 17.2 and 1.5 Hz, 1H), 5.02
(dd, J = 10.4 and 1.5 Hz, 1H), 3.44 (t, J = 5.2 Hz, 2H), 3.30 (s, 3H), 2.72
(t, J = 5.2 Hz, 2H), 3.21 (dt, J = 6.1 and 1.4 Hz, 2H), 1.44 (br, 1H). 13C
{1H} NMR (CDCl3): 136.76, 115.78, 71.99, 58.71, 52.35, 48.62 ppm.
N-(2-Ethylthioethyl)allylamine (23). 2-Hydroxyethyl ethyl thio-
ether (9.0 g, 85 mmol) was dissolved in CH2Cl2 (100 mL) and cooled to
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0 °C, and phosphorus tribromide (8.0 mL, 85 mmol) was added
dropwise over 30 min. The reaction mixture remained at 0 °C for 2 h,
and then the reaction was allowed to come to ambient temperature and
stirred for 18 h. The mixture was again cooled to 0 °C, and water
(10 mL) was added, followed by saturated Na2CO3 (∼60 mL) until pH 7.
The layers were separated, dried over Na2SO4, and concentrated
in vacuo to give 13.1 g (91%) of 2-bromoethyl ethyl thioether as a
colorless liquid. 1H NMR (CDCl3): δ 3.49 (t, J = 7.7 Hz, 2H), 2.95 (t, J =
8.2 Hz, 2H), 2.59 (q, J = 7.3 Hz, 2H), 1.28 (t, J = 7.3 Hz, 3H). 13C {1H}
NMR (CDCl3): 33.71, 30.60, 26.16, 14.91 ppm.15 Allylamine (15 g,
260 mmol), K2CO3 (43 g, 310 mmol), and THF (70 mL) were added
together, followed by dropwise addition (5 min) of 2-bromoethyl ethyl
thioether (7.3 g, 43 mmol) at ambient temperature. After 24 h,
additional allylamine (9.8 g) and THF (40 mL) were added and the
temperature was increased to 40 °C. After 4 days, the mixture was
filtered, concentrated in vacuo, and distilled (160−163 °C/255 mmHg)
to give 4.8 g (77%) of product as a colorless liquid. 1H NMR (CDCl3): δ
5.86 (m, 1H), 5.12 (dm, J = 17.2 Hz, 1H), 5.07 (dm, J = 10.1 Hz, 1H),
3.24 (m, 2H), 2.77 (m, 2H), 2.66 (m, 2H), 2.50 (m, 2H), 1.59 (br, 1H),
1.23 (m, 3H). 13C {1H} NMR (CDCl3): 136.66, 115.95, 52.00, 47.82,
31.84, 25.73, 14.83 ppm.16
N-(2-Dimethylaminoethyl)allylamine (24). Allylamine (3.9 g,
32 mmol) and NEt3 (4.5 mL, 32 mmol) were added together, followed
by dropwise addition (5 min) of allyl bromide (3.9 g, 32 mmol) while
heating to 60 °C. After 18 h, the reaction was diluted with CHCl3,
washed with water, dried over Na2SO4, filtered, and concentrated to give
1.0 g (24%) of product, which was flash-distilled at 80 °C/100 mmHg to
remove color. 1H NMR (CDCl3): δ 5.91 (m, 1H), 5.17 (dd, J = 17.2 and
1.7 Hz, 1H), 5.08 (dd, J = 10.1 and 1.3 Hz, 1H), 3.27 (d, J = 6.1 Hz, 2H),
2.68 (t, J = 6.2 Hz, 2H), 2.41 (t, J = 6.1 Hz, 2H), 2.22 (s, 6H), 1.66 (br,
1H). 13C {1H} NMR (CDCl3): 136.93, 115.81, 59.17, 52.56, 46.68,
45.56 ppm.
Bis(3-(N-2-methoxyethyl)aminopropyl)siloxane (27). N-(2-
Methoxyethyl)allylamine (22, 1.5 g, 13 mmol) was added to hydride-
capped siloxane (21, 4.3 g, 6 mmol) over 1 min with 1 drop of Karstedt’s
catalyst and heated to 50 °C for 1 h. Volatiles were removed in vacuo to
give 5.1 g (89%) of product with 55% β-isomer. 1H NMR (CDCl3): δ
3.48 (t, J = 5.0 Hz, 4H), 3.34 (s, 6H), 2.73 (m, 5.1H), 2.59 (t, J = 6.8 Hz,
1.8H), 2.47 (m, 1.2H), 1.51 (m. 1.9H), 1.35 (br, 1.8H), 0.96 (m, 4.5H),
0.54 (m, 1.8H), 0.06 (m, 60.7H). 13C {1H} NMR (CDCl3): 72.17,
72.14, 58.74, 58.71, 49.28, 49.20, 23.78, 22.38, 15.69, 12.05, 1.12, 0.05,
−1.39 ppm.
Bis(3-(N-2-ethylthioethyl)aminopropyl)siloxane (28). N-(2-
Ethylthioethyl)allylamine (23, 1.9 g, 13 mmol) was added to hydride-
capped siloxane (21, 4.3 g, 6 mmol) with 1 drop of Karstedt’s catalyst.
After 15 min, 4 more drops of catalyst were added and heated to 80 °C
for 18 h. Volatiles were removed in vacuo to give 5.2 g (85%) of product
DOI: 10.1021/acs.energyfuels.7b01048
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Energy & Fuels
Scheme 2. Synthesis of Branched Aminosilicones
with 55% β-isomer. 1H NMR (CDCl3): δ 2.76 (m, 2.4H), 2.69 (m, 2.2H),
2.60 (t, J = 7.4 Hz, 0.9H), 2.53 (m, 2.6H), 1.6 (br, 1H), 1.51 (m, 0.9H),
1.25 (t, J = 7.3 Hz, 3H), 0.97 (m, 2.1H), 0.52 (m, 0.9H), 0.02 (s, 30.8H).
13
C {1H} NMR (CDCl3): 52.80, 51.39, 48.47, 48.44, 31.95, 31.93, 25.75,
23.77, 22.36, 15.67, 14.86, 12.08, 1.15, 1.01, 0.08, −1.34 ppm.
Bis(3-(N-2-dimethylaminoethyl)aminopropyl)siloxane (29).
N-(2-Dimethylaminoethyl)allylamine (23, 0.74 g, 5.8 mmol) was
Scheme 3. Synthesis of Star Aminosilicones
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added to hydride-capped siloxane (21, 1.96 g, 2.7 mmol) at 50 °C
with 1 drop of Karstedt’s catalyst. After 6 h, 2 more drops of catalyst were
added and heated to 75 °C for 24 h. Volatiles were removed in vacuo to
give 1.95 g (74%) of product with 40% β-isomer. 1H NMR (CDCl3): δ
2.70 (m, 1.9H), 2.62 (m, 1.6H), 2.44 (m, 2.5H), 2.23 (s, 6H), 2.02 (br,
1H), 1.54 (m, 1.2H), 0.99 (m, 1.6H), 0.55 (m, 1.2H), 0.09 (s, 73.7H).
13
C {1H} NMR (CDCl3): 59.21, 59.12, 53.40, 51.84, 47.27, 47.19, 45.58,
23.72, 22.21, 15.72, 12.08, 1.17, 1.03, 0.16 ppm. 29Si NMR [CDCl3 +
Cr(acac)3]: 8.11, 7.55, −21.53, −21.95, −22.10 ppm.
Bis(3-chloropropyl)siloxane (32). 1,3-Bis(3-chloroprpyl)-1,1,3,3-
teramethyldisiloxane (25 g, 87 mmol), D4 (64.5 g, 217 mmol), and
Filtrol F-20 (8.3 g, acid-washed clay) were added together and heated at
80 °C for 1 day and then 2 days at 60 °C. The reaction mixture was
filtered and stripped to give 60 g of product. 1H NMR (CDCl3): δ 3.53
(t, J = 7.0 Hz, 4H), 1.82 (m, 4H), 0.67 (m, 4H), 0.10 (s, 69H). 13C {1H}
NMR (CDCl3): 47.69, 27.04, 15.82, 1.10, 0.07 ppm.
Bis(3-iodopropyl)siloxane (33). Bis(3-chloropropyl)siloxane (32,
60 g, 60.6 mmol), NaI (40.8 g, 272 mmol), and acetone (250 mL) were
refluxed together for 5 days. The reaction mixture was concentrated,
filtered, dissolved in CHCl3, washed with water and Na2S2O3, dried over
Na2SO4, filtered, and stripped to give 62 g (87%) of product. 1H NMR
(CDCl3): δ 3.22 (t, J = 7.1 Hz, 4H), 1.88 (m, 4H), 0.67 (m, 4H), 0.09 (s,
72H). 13C {1H} NMR (CDCl3): 28.24, 20.20, 11.22, 1.18, 1.07, 0.18
ppm.
Bis(3-(N-ethoxyethyl)aminopropyl)siloxane (37). 2-(Etho-
xyethyl)aminoethane (6.1 g, 68.5 mmol) was heated to 60 °C, and
then bis(3-iodopropyl)siloxane (33, 7.5 g, 6.2 mmol) was added over
15 min. The reaction mixture was heated for 20 h; then excess amine was
removed in vacuo; and the residue was diluted in CHCl3, washed with
10% NaOH, water, and brine, dried over Na2SO4, filtered, and
concentrated to give 4.3 g (61%) of product as a light yellow liquid.
1
H NMR (CDCl3): δ 3.54 (m, 8H), 2.80 (m, 4H), 2.64 (m, 4H), 1.57
(m, 6H), 1.25 (m, 6H), 0.57 (m, 4H), 0.13 (m, 77H). 13C {1H} NMR
(CDCl3): 69.96, 66.39, 53.21, 49.43, 23.85, 15.78, 15.09, 1.113, 0.99,
DOI: 10.1021/acs.energyfuels.7b01048
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Energy & Fuels Article

Scheme 4. Synthesis of Cyclic Aminosilicone (19)

Scheme 5. Synthesis of Linear Silicones

Scheme 6. Preparation of Olefins Bis(3-(N-2-methoxyethyl)aminopropyl)siloxane (38).

0.05 ppm. 29Si NMR [CDCl3 + Cr(acac)3]: 87.54, −21.50, −21.98,
−22.13 ppm.
2-(Methoxyethyl)aminoethane (7.5 g, 100 mmol) was heated to 60 °C,
and then bis(3-iodopropyl)siloxane (33, 7.5 g, 6.2 mmol) was added
over 15 min. The reaction mixture was heated for 16 h; then excess
amine was removed in vacuo; and the residue was diluted in heptane,
washed with 10% NaOH, water, and brine, dried over Na2SO4, filtered,
and concentrated to give 5.6 g (82%) of product as a light yellow liquid.
1
H NMR (CDCl3): δ 3.50 (t, J = 5.2 Hz, 4H), 3.36 (s, 6H), 2.78 (t, J =
5.2 Hz, 4H), 2.62 (t, J = 7.2 Hz, 4H), 1.63 (br, 2H), 1.53 (m, 4H), 0.56
(m, 4H), 0.08 (m, 75H). 13C {1H} NMR (CDCl3): 72.14, 58.67, 53.15,
49.22, 23.77, 15.71, 1.07, 0.95, 0.04 ppm.
Bis(3-(N-2-methylthioethyl)aminopropyl)siloxane (39).
2-(Methylthioethyl)aminoethane (4.85 g, 53 mmol) was heated to
60 °C, and then bis(3-iodopropyl)siloxane (33, 6.08 g, 5.0 mmol) was
added over 15 min. The reaction mixture was heated for 16 h; then
excess amine was removed in vacuo; and the residue was diluted in
heptane, washed with 10% NaOH, water, and brine, dried over Na2SO4,
filtered, and concentrated to give 4.3 g (69%) of product as a light yellow
liquid. 1H NMR (CDCl3): δ 2.81 (t, J = 6.3 Hz, 4H), 2.65 (t, J = 6.3 Hz,
4H), 2.61 (t, J = 7.4 Hz, 4H), 2.09 (s, 6H), 1.52 (m, 4H), 0.54 (m, 4H),
0.07 (m, 86H). 13C {1H} NMR (CDCl3): 52.73, 447.92, 34.57, 23.86,
15.69, 1.07, 0.93, 0.05 ppm.

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Energy & Fuels
Scheme 7. Synthesis of the Linear Siloxane Precursor
Scheme 8. Synthesis of All γ-Isomer Linear Siloxanes
Bis(3-(N-2-dimethylaminoethyl)aminopropyl)siloxane (40).
2-(Dimethylaminoethyl)aminoethane (6.1 g, 69.2 mmol) was heated
to 60 °C, and then bis(3-iodopropyl)siloxane (33, 6.08 g, 5.0 mmol) was
added over 15 min. The reaction mixture was heated for 16 h; then
excess amine was removed in vacuo; and the residue was diluted in
heptane, washed with 10% NaOH, water, and brine, dried over Na2SO4,
filtered, and concentrated to give 5.9 g (84%) of product as a light yellow
liquid. 1H NMR (CDCl3): δ 2.69 (m, 4H), 2.62 (m, 4H), 2.42 (m, 4H),
2.21 (s, 6H), 1.54 (m, 4H), 0.54 (m, 4H), 0.09 (m, 75H). 13C {1H}
NMR (CDCl3): 59.37, 53.39, 47.36, 45.53, 23.79, 15.77, 1.11, 0.98, 0.08
ppm.
N-(2-Ethoxyethyl)aminopent-5-ene (42). 2-(Ethoxyethyl)-
aminoethane (6, 38.2 g, 429 mmol), K2CO3 (10.1 g, 73.2 mmol), and
THF (50 mL) were heated to 60 °C; then 5-bromo-1-pentene (10.02 g,
67.2 mmol) was added over 25 min; and the reaction was allowed to
continue for 22 h. The reaction mixture was filtered, concentrated, and
distilled (130 °C/130 mmHg) to give 7.2 g (68%) of product as a
colorless liquid. 1H NMR (CDCl3): δ 5.81 (m, 1H), 5.01 (d, J = 16.9 Hz,
1H), 4.93 (d, J = 10.1 Hz, 1H), 3.52 (t, J = 5.5 Hz, 2H), 3.49 (q, J =
7.1 Hz, 2H), 2.76 (t, J = 5.2 Hz, 2H), 2.62 (t, J = 7.3 Hz, 2H), 2.08 (q, J =
6.8 Hz, 2H), 1.60 (m, 2H), 1.46 (br, 1H), 1.19 (t, J = 7.1 Hz, 3H). 13C
{1H} NMR (CDCl3): 138.49, 114.53, 69.88, 66.39, 49.48, 49.45, 31.54,
29.27, 15.14 ppm.
Bis(3-(N-ethoxyethyl)aminopropyl)siloxane (43). A solution of
N-(2-ethoxyethyl)aminopent-5-ene (42, 5.0 g, 31.8 mmol) in toluene
(10 mL) was added dropwise to 1,1,3,3,5,5-hexamethyltrisiloxane (41,
3.32 g, 15.9 mmol) heated at 55 °C with 1 drop of Karstedt’s catalyst.
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The temperature was raised to 65 °C after the addition was complete,
and after 8 h, the reaction mixture was concentrated in vacuo to give
7.95 g (91%) of product (95% pure with ∼10% β-isomer) with ∼5% of
unreacted olefinic amine isomers. 1H NMR (CDCl3): δ 3.52 (t, J =
5.3 Hz, 4.5H), 3.48 (q, J = 7.1 Hz, 4.5H), 2.76 (m, 4.4H), 2.59 (m,
4.4H), 2.08 (q, J = 6.8 Hz, 2H), 1.58 (m, 0.3H), 1.48 (m, 4.4H), 1.33 (m,
11.1H), 1.18 (t, J = 7.0 Hz, 6.7H), 0.91 (m, 0.7H), 0.52 (m, 4H), 0.05−
0.01 (m, 21.7H). 13C {1H} NMR (CDCl3): 69.94, 66.37, 50.05, 49.55,
31.12, 29.91, 23.17, 18.22, 15.13, 1.25, 1.16, 0.16 ppm.
CO2 Uptake Experiments. A known amount of solvent (typically
2−4 g) was added to a pre-tared, 25 mL, three-neck round-bottom flask
equipped with a gas inlet tube, a mechanical stirrer with a Teflon blade,
and a gas outlet adapter connected to a bubbler. The flask was either
immersed in a constant temperature bath at 30 or 40 °C or left at
ambient temperature. CO2 was introduced via the sublimation of dry ice
that was passed through a CaCl2 drying tube prior to introduction into
the reaction flask. The solvent was stirred at 200 rpm from 30 min to 2 h
depending upon the experiment. The reaction was considered complete
when either the preset time was reached or a constant weight was
achieved. The percentage of theory uptake calculation was based on the
weight of CO2 absorbed divided by the theoretical amount, which was
predicted from the weight of the initial sample and the molecular weight
of the candidate solvent.
■
RESULTS AND DISCUSSION
Synthesis. It was clear from the preliminary studies reported
above12 that the tetramethyldisiloxane core did not inhibit the
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Energy & Fuels
Table 1. Comparison between Primary Amines and Substituted Secondary Amines at 40 °C
beneficial effects of the electron-donating ethylaminopropyl
linking group. However, it was not clear if a longer siloxane chain
or a more congested cyclic, branched, or star core would show
the same effects. To probe these various architectures, a number
of derivatives were made.
A short-chain linear siloxane with ethoxyethylaminopropyl
termini was made via the route shown in Scheme 1. Hydro-
silylation of the starting hydride (1) with allyl alcohol (2) gave
the chain-lengthened 3-hydroxypropyl intermediate (3), which
was converted to the corresponding chloride (4) by refluxing in
neat thionyl chloride. Chloride was converted to more reactive
iodide (5) via the Finklestein reaction. The reaction of iodide
with 2-ethoxyethylamine gave the final material (7), with an
average chain length of 4.5, as determined by 1H NMR. The
parent aminopropyl compound (8) was purchased, used as
received, and tested as a comparative example.
Branched compounds were made via hydrosilylation of the
corresponding tris hydride (9) with allylamine or (2-ethoxy-
ethyl)allylamine (13), as shown in Scheme 2. In both cases, some
of the Markovnikov addition product giving the β-isomer was
observed. For compound 11, 11% β-isomer was made, and for
compound 14, 20% was produced.
The candidates with a star core were produced in a manner
similar to that above, with tetrahydride (15) serving as the com-
mon starting material (Scheme 3). The aminopropyl derivative
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(16) contained 18% β-isomer, and the ethoxyethylaminopropyl
material (17) had 25% β-isomer.
The final core variation examined was derived from the cyclic
siloxane, DH4 (18). 1,3,5,7-Tetrakis(3-aminopropyl)tetrameth-
ylcyclotetrasiloxane (20) was obtained from an independent
source. Derivative 19 was synthesized from compound 18 via
hydrosilylation, as seen in Scheme 4. Compound 19 contained
25% β-isomer.
In addition to expanding the silicone portion of the core,
extending the functionality at the termini of the solvents was also
explored. Previously, it was found that dimethylamino, methoxy,
and ethoxy end groups all provided materials that readily
absorbed CO2 and remained flowable liquids.12 However, it was
not clear if that was only a manifestation of having a small
disiloxane core or if these groups could lower viscosity while
maintaining high CO2 uptake with longer silicone chains.
A series of linear silicones were prepared via the hydro-
silylation of a hydride end-capped siloxane with either allyl amine
or a variety of electron-donating allyl amine derivatives shown in
Scheme 5. The addition reaction was not very selective, and a
large proportion of both β- and γ-isomers were produced as
noted.
Olefins used to make linear solvents (25−29) were made as
shown in Scheme 6. Three of the four olefins were obtained by a
simple displacement reaction of allyl amine with the correspond-
ing bromoethane derivative. The dimethylamino compound
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Energy & Fuels
Table 2. Comparison of Branched versus Linear Functional Groups
Scheme 9. Long-Chain Spacer
Figure 4. Inverted aminosilicone structure.
(24) was also made via displacement, but the nucleophile was
N,N-dimethylethylenediamine.
As shown in Scheme 5, the solvent candidates possessed a
significant amount of branching. To determine if this factor
played a role in CO2 uptake or viscosity attributes, a similar series
of linear materials were made that had only γ-isomer modes of
attachment to the silicone core. The initial step was to make the
backbone a required length. This was performed as shown in
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Scheme 7 with the equilibration of D4 (31) and 1,3-bis(3-
chloropropyl)-1,1,3,3-tetramethyldisolaxane (30), followed by
conversion of chloride (32) to more reactive iodide (33).
Iodide was then allowed to react with the corresponding sub-
stituted ethylamine derivative, as seen in Scheme 8. To avoid any
significant amount of overalkylation, slow inverse addition of
iodide to a large excess of amine was performed to give products
37−40, as shown in Scheme 8.
CO2 Uptake Testing. Preliminary uptake measurements on
the silicone solvents were performed by contacting dry CO2 gas,
generated from dry ice and passed through a Drierite drying tube,
with 2−4 g of solvent being mechanically stirred at 200 rpm for
30 min at 40 °C. The difference in weight gain was the amount of
CO2 reacted, and this was compared to the theoretical amount
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Energy & Fuels
calculated assuming 1 mol of CO2 required 2 mol of primary
or secondary amine for complete reaction. Additionally, the
physical state of the reaction product after 30 min was observed
and reported. The physical state was determined by manually
turning the Teflon paddle on a stir shaft that was used during the
CO2 absorption reaction. This qualitative assessment of the
reaction product viscosity increased in the order: low-viscosity
liquid (10−2 Pa s) < moderate-viscosity liquid (10−1 Pa s) < flow-
able liquid (100 Pa s) < very viscous, flowable liquid (101 Pa s) <
very viscous, non-flowable liquid (102 Pa s). The values in
parentheses are order of magnitude estimates of the viscosity
associated with these descriptors. Table 1 shows the comparison
between the various core architectures with primary amines and
substituted secondary amines.
It is clear looking at the pairs of solvents that, upon reaction
with CO2, the primary amine-containing compounds form very
viscous materials, while the corresponding ethoxyethylamine
derivatives remained as flowable liquids. Although the linear
primary amines (8 and 24) showed good CO2 reactivity with
90% or greater absorption, they would not be useful in a liquid-
based process given their very high viscosities. In contrast, the
ethoxyethylamine compounds gave very low viscosity liquids.
It was odd that compound 26 only reached 78% of theoretical
CO2 uptake, but this will be discussed below.
In a similar fashion, the branched (11 and 15), star (16 and
17) and cyclic (18 and 19) series displayed the same trends. All
of the primary amines gave solids and very low conversions, while
the substituted analogues showed higher CO2 uptake and were
all flowable liquids.
Further comparisons were also made between the baseline
primary amine (25) and a series of substituted silicones (26−29)
(Table 2). These solvents all had a significant amount of
branching, in the form of the β-isomer, and all showed modest
CO2 uptake levels in the range of 48−78% at 40 °C. One
explanation theorized to account for this observation was that
CO2 could not access the slightly more hindered substituted
amine groups in solvents 26−29. This along with the longer
silicone chain in the core that could potentially shield reacting
CO2 might account for the modest theoretical uptake values.
To probe this possibility, a series of similarly substituted
materials were made via a route that did not permit any β-isomer
to form. Compounds 37−40 were tested under similar condi-
tions, and modest yields of carbamates were obtained again.
Obviously, the β-isomer had little impact on the CO2 uptake
reaction.
An alternate explanation was that the reaction temperature was
too high to permit effective CO2 absorption. Isotherms gen-
erated for the structure shown in Figure 1, where XR = OEt,
showed that, with 16.4% CO2 in N2, only 58% of the theoretical
CO2 uptake was achieved at 40 °C. This was due to the much
lower heat of reaction (∼1860 versus 2560 kJ/kg of CO2)
compared to GAP-1. When the temperature was lowered to
23 °C, in all but one case, theoretical uptake was achieved.
In several cases, slightly greater than theoretical absorption was
observed. Some of this may be attributed to experimental error
because most of the uptake experiments were run only once.
However, replicates of some reactions provided reproducibility
in the range of ±4%. There may have also been a small con-
tribution of physical solubility of CO2 in the solvent.
A final example of this new class of CO2 capture solvents that
employ a longer alkyl chain spacer and a short siloxane core is
shown in Scheme 9. A five-carbon spacer with an ethoxyethy-
lamino group was introduced via hydrosilylation of compound
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42 on hexamethyltrisiloxane (41). Approximately 10% β-isomer
was formed in compound 43, and CO2 uptake experiments
showed ∼106% theoretical uptake, with the solvent maintaining
a low-viscosity profile upon full reaction with CO2.
If intramolecular hydrogen bonding is responsible for the
decreased viscosity observed in these solvents upon reaction with
CO2, the same principle should apply to an inverted structure
shown in Figure 4, wherein reactive nitrogen is on the terminus
and the hydrogen-bonding heteroatom is located internally.
Several examples of these solvents are in preparation, and the
results of their testing will be reported later.
■ CONCLUSION
Silicones with a variety of linear, branched, star, and cyclic
architectures were synthesized that contained electron-donating
ethylaminopropyl groups attached to the silicone core. These
solvents were tested for CO2 uptake and their physical state
after reaction. In comparison to analogous materials that only
possessed a primary amine, all heteroatom-substituted deriva-
tives displayed excellent CO2 uptake and all maintained a liquid,
flowable state after reaction. Optimal CO2 uptake was achieved at
ambient temperatures rather than the typical 40 °C level. This
was likely due to the lower heats of reaction for the secondary
amine structure. β-Isomers present in the samples did not
adversely affect the reaction with CO2 or the ability to remain in a
liquid state upon complete reaction. Further examination of this
class of materials is warranted to optimize performance under
conditions of interest. Measurement of additional physical prop-
erties of the down-selected solvents is in progress.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: perryr@research.ge.com.
ORCID
Robert J. Perry: 0000-0003-2027-4829
Notes
The author declares no competing financial interest.
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