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demonstrated recently by us and Leitner et al. for integrated Following the capture, the formed aqueous solutions were
CO2 capture and conversion to formate salts.11 hydrogenated at 145 °C in the presence of homogeneous
For the CO2 capture, amines with low vapor pressures are catalysts and 70 bar of H2, after addition of 5 mL 2-MTHF
desirable to avoid atmospheric amine contamination. High (Table 2). When the catalyst Ru-MACHO-BH (C-1) (10
boiling polyamines were therefore selected for capture, along μmol) was used along with PEHA as the capture material, 47%
with two ethanolamines (Table 1). Among various polyamines, CH3OH yield was observed (5.2 mmol) after 72 h (entry 1).
No concomitant CO/CH4 formation was observed through GC
Table 1. CO2 Capture by Aqueous Amine Solutionsa analysis of the reaction gas mixture. 1H and 13C NMR revealed
that 14% of formed CH3OH was present in the upper organic
layer, whereas the remaining CH3OH along with PEHA,
formamide and formate intermediates, was in the bottom
aqueous layer (Figure S6 and S7). The catalyst remained in the
organic layer as observed by 31P NMR (Figure S5), indicating
the possibility of easy catalyst separation from the biphasic
mixture. Increasing the catalyst loading to 20 μmol increased
the methanol yield to 79% (8.7 mmol) (entry 2). Next, various
amine solutions after CO2 capture (from Table 1) were
hydrogenated to identify the most promising amine for an
integrated CO2 capture/hydrogenation system. Switching from
PEHA to BPEI800 or BPEI25k decreased both the amounts of
CH3OH formed (4.5 and 5.2 mmol, respectively) and the
Entry Amine $/kgb CO2 (mmol)/gc CO2/Nd hydrogenation yield (45% and 50%) (entry 3 and 4). For
1 PEHA 105 (S) 11.0 0.43 LPEI2.5k, LPEI100k, and PAA10k, CH3OH yields decreased
2 BPEI800 352 (S) 10.2 0.46 drastically to 0.9, 0.9, and 0.1 mmol, respectively (entry 5−
3 BPEI25k 320 (S) 10.4 0.47 7). Surprisingly, with MEA, no CH3OH was formed (entry 8),
4e PAA10k 7533 (P) 6.2 0.36 but increased amounts of formamide and formate intermediates
5f LPEI2.5k 56,000 (P) 5.5 0.25 were observed. We surmise that in the presence of primary
6f LPEI100k 24,500 (P) 6.1 0.28 amines, such as PAA10k and MEA, the second hydrogenation
7 MEA 35 (S) 11.7 0.71 step of formamide to methanol becomes more challenging.
8 DEEDA 820 (T) 7.2 0.53 Indeed, when DEEDA, a secondary analogue of MEA, was
a
Capture conditions: Amine (1g), water (3 mL), stirring (800 rpm), used, methanol was obtained in 46% yield after 72 h (3.3
rt. Aqueous amine solutions stirred in CO2 atmosphere at a constant mmol; entry 9). Thus, among various amines, PEHA was the
pressure of 1 psi. Captured CO2 amounts calculated through most efficient for the overall CO2 capture and conversion to
gravimetric analysis. Calculations error ± 5%. bPrices from Sigma- CH3OH. The low vapor pressure and easy availability of
Aldrich (S), Polysciences (P) or TCI America (T), as of Nov 14, 2017. inexpensive PEHA (Table 1) make it promising for a large scale
c
CO2 captured per gram of amine. dmols of CO2 captured per mol of
CCU process.
nitrogen. eCommercial 15 wt % PAA10k aqueous solution used directly.
f
10 mL water, capture at 70 °C Next, known hydrogenation catalysts were screened to
investigate their efficacy. Ru-MACHO (C-2), expectedly, was
almost equally effective to Ru-MACHO-BH, in the presence of
an additional base K3PO4 (entry 10). The P-substituent in the
pentaethylenehexamine (PEHA), and branched polyethyleni- PNP ligand heavily influenced the CH3OH yield. With
mines (BPEI) were found efficient for CO2 capture. The RuHClPNPiPr(CO) (C-3), a meager 5% methanol yield was
aqueous PEHA solution captured 11.0 mmol of CO2 per g of observed (entry 11). Complex MnBrPNPiPr(CO)2 (C-4),
PEHA after 4 h, corresponding to 0.43 mol of CO2 captured recently reported by us to catalyze sequential CO2 hydro-
per mol of amino group (CO2/N), (Table 1, entry 1). The 13C genation to methanol, was only capable of producing CH3OH
NMR of the CO2 loaded aqueous PEHA solution revealed the in 5% yield (0.5 mmol; entry 12). No methanol formed with
presence of carbamate and carbonate/bicarbonate (Figure S2). FeHBrPNPiPr(CO) (C-5) (entry 13). Accumulation of
Similarly, BPEI800 and BPEI25k captured 0.46 and 0.47 CO2/N, formamide and formate intermediates in the case of C-3 to
respectively (10.2 and 10.4 mmol of CO2/g, respectively) C-5 suggests lower activities of these catalysts for the effective
(entry 2−3). CO2 capture by aqueous PAA10k solution was hydrogenation of formamides and formates to CH3OH under
slower, as after 4 h only 6.2 mmol/g of CO2 was captured, the present conditions.
corresponding to 0.36 CO2/N (entry 4). Linear polyethyleni- The most suitable organic solvent for the biphasic hydro-
mines (LPEI2.5k, LPEI100k) displayed limited solubility in water genation system was subsequently explored. A slight decrease in
at room temperature, making them less convenient for aqueous methanol formation was observed when switching from 2-
CO2 capture. With more water (10 mL), and a higher MTHF to cyclopentyl methyl ether (CPME) or p-xylene (52%
temperature (70 °C), LPEI2.5k and LPEI100k captured 5.5 and and 57%, respectively) (entry 14 and 15). The reason behind
6.1 mmol of CO2/g, respectively. Monoethanolamine (MEA), the decrease in methanol yield with more hydrophobic solvents
which has long been used industrially for scrubbing CO2 and is not entirely clear, but is most probably a combination of
H2S from flue gases, was the most effective for CO2 capture different catalyst/H2/CO2/CH3OH solubility in different
both by mass and efficiency of amine utilization (11.7 mmol/g; organic solvents (see SI). Also, the higher hydrophobicity of
0.71 CO2/N) (entry 7). Similarly, 7.2 mmol/g CO2 (0.53 these solvents compared to 2-MTHF resulted in an
CO2/N) was captured by diethanolethylenediamine (DEEDA) accumulation of the produced methanol exclusively in the
(entry 8). aqueous layer (Figure S13). However, the lower solubility of C-
B DOI: 10.1021/jacs.7b12183
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society Communication
Entry Amine Captured CO2 (mmol) Catalyst (μmol) Formate (%)b Formamide (%)b MeOH (mmol)b Yield (%)b PMeOHc TON
1 PEHA 11.0 C-1(10) 11 10 5.2 47 0.16 520
2 PEHA 11.0 C-1(20) 5 2 8.7 79 0.17 435
3 BPEI800 10.2 C-1(20) 16 13 4.5 45 0.18 225
4 BPEI25k 10.4 C-1(20) 10 7 5.2 50 0.13 260
5 LPEI2.5k 5.5 C-1(20) 30 15 0.9 16 0.11 45
6 LPEI100k 6.1 C-1(20) 21 44 0.9 15 0.11 45
7 PAA10k 6.2 C-1(20) 32 38 0.1 2 0 5
8 MEA 11.7 C-1(20) 26 17 0 0 nd 0
9 DEEDA 7.2 C-1(20) 15 6 3.3 46 0.14 165
10d PEHA 11.0 C-2(20) 6 13 7.4 67 0.15 370
11d PEHA 11.0 C-3(20) 15 20 0.5 5 0 25
12d PEHA 11.0 C-4(20) 18 19 0.5 5 0 25
13d PEHA 11.0 C-5(20) 20 18 0.0 0 nd 0
14e PEHA 11.0 C-1(20) 12 11 5.7 52 0 285
15f PEHA 11.0 C-1(20) 9 6 6.3 57 0 315
16g PEHA 11.0 C-1(50) 3 0 10.4 95 0.17 208
17h PEHA 5.4 C-1(50) 5 0 4.8 89 0.11 96
a
Reaction conditions: Solutions from Table 1 (as specified) were hydrogenated after adding organic solvent and catalyst. 2-MTHF (5 mL), H2 (70
bar), 145 °C, 72 h. bYields based on 1H NMR with 1,3,5-trimethoxybenzene (TMB) and imidazole (Im) as internal standards for organic and
aqueous layer, respectively. cPMeOH = methanol in organic layer/methanol in aqueous layer. dK3PO4 (1 mmol) added. eCPME used as organic
solvent. fP-xylene used as organic solvent. gH2 (80 bar). hCO2 captured from simulated air (CO2 concentration: 408 ppm) with 0.79 g PEHA. Yield
calculations error ± 5%. TON = mols of methanol formed per mol of catalyst. nd = nondefinable
Among the catalysts tested, a well-defined and commercially Klankermayer, J.; Leitner, W. Chem. Sci. 2015, 6, 693−704.
available complex, Ru-MACHO-BH (C-1) was found most (f) Schneidewind, J.; Adam, R.; Baumann, W.; Jackstell, R.; Beller,
effective, whereas, among various amines, high boiling poly- M. Angew. Chem., Int. Ed. 2017, 56, 1890−1893. (g) Li, Y.-N.; Ma, R.;
amine, PEHA, provided the best CH3OH yields. Our next focus He, L.-N.; Diao, Z.-F. Catal. Sci. Technol. 2014, 4, 1498−1512.
(h) Alberico, E.; Nielsen, M. Chem. Commun. 2015, 51, 6714−6725.
in the context of integrated CO2 capture and hydrogenation (i) Sordakis, K.; Tsurusaki, A.; Iguchi, M.; Kawanami, H.; Himeda, Y.;
will be toward developing a continuous CO2 to CH3OH flow Laurenczy, G. Chem. - Eur. J. 2016, 22, 15605−15608.
system.
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(7) Rezayee, N. M.; Huff, C. A.; Sanford, M. S. J. Am. Chem. Soc.
2015, 137, 1028−1031.
ASSOCIATED CONTENT (8) Kothandaraman, J.; Goeppert, A.; Czaun, M.; Olah, G. A.;
*
S Supporting Information Prakash, G. K. S. J. Am. Chem. Soc. 2016, 138, 778−781.
The Supporting Information is available free of charge on the (9) (a) Zhang, L.; Han, Z.; Zhao, X.; Wang, Z.; Ding, K. Angew.
ACS Publications website at DOI: 10.1021/jacs.7b12183. Chem., Int. Ed. 2015, 54, 6186−6189. (b) Khusnutdinova, J. R.; Garg,
J. A.; Milstein, D. ACS Catal. 2015, 5, 2416−2422. (c) Kar, S.;
General information and experimental details (PDF) Goeppert, A.; Kothandaraman, J.; Prakash, G. K. S. ACS Catal. 2017,
■ AUTHOR INFORMATION
Corresponding Author
7, 6347−6351. (d) Ribeiro, A. P. C.; Martins, L. M. D. R. S.;
Pombeiro, A. J. L. Green Chem. 2017, 19, 4811−4815. (e) Everett, M.;
Wass, D. F. Chem. Commun. 2017, 53, 9502−9504. (f) Sordakis, K.;
Tang, C.; Vogt, L. K.; Junge, H.; Dyson, P. J.; Beller, M.; Laurenczy, G.
*gprakash@usc.edu Chem. Rev. 2017, DOI: 10.1021/acs.chemrev.7b00182. (g) Kar, S.;
ORCID Kothandaraman, J.; Goeppert, A.; Prakash, G. K. S. J. CO2 Util. 2018,
G. K. Surya Prakash: 0000-0002-6350-8325 23, 212−218.
(10) (a) Rochelle, G. T. Science 2009, 325, 1652−1654.
Notes
(b) Oyenekan, B. A.; Rochelle, G. T. Ind. Eng. Chem. Res. 2006, 45,
The authors declare no competing financial interest.
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Chem. Res. 2003, 42, 3179−3184. (d) Yang, H.; Xu, Z.; Fan, M.;
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Support of our work by the Loker Hydrocarbon Research 20, 14−27. (e) Aaron, D.; Tsouris, C. Sep. Sci. Technol. 2005, 40, 321−
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