Amine Phase-Transfer Chemistry: A Green and Sustainable Approach

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Amine Phase-transfer Chemistry: A Green and Sustainable Approach to the Non-Biological Mineralization of CO2 Jing Zhao, Jiehui Ye, Ning Zhu, Hailong Hong, Liang Ma, Jinrong Yang, and Jianbin Zhang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b00977 • Publication Date (Web): 20 Apr 2018 Downloaded from http://pubs.acs.org on April 21, 2018

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Amine Phase-transfer Chemistry: A Green and Sustainable Approach to the Non-Biological Mineralization of CO2 Jing Zhao1,2, Jiehui Ye1,2, Ning Zhu1,2, Hailong Hong1,2, Liang Ma1,2, Jinrong Yang1,2, and Jianbin Zhang1,2* 1 College of Chemical Engineering, Inner Mongolia University of Technology, 49 Aimin Street, Hohhot 010051, China 2 Inner Mongolia Engineering Research Center for CO2 Capture and Utilization, 49 Aimin Street, Hohhot 010051, China *To whom correspondence should be addressed. Tel.: +86-471-6575722; Fax: +86-471-6575722. E-mail: [email protected] (J. B. Zhang)

ABSTRACT: An amine phase-transfer approach is nov-

el designed for the facile and recycle fixation and nonbiological mineralization of CO2 into alkaline earth carbonate (MCO3, M = Ca, Sr, and Ba) crystals with uniformed polymorphs at room temperature under atmosphere pressure. The amines’ system based on two phases of water and Zn-tetraphenylporphyrin (ZnTPP) in CH2Cl2 provides a green and sustainable CO2 capture and utilization (CCU) strategy for the mitigation of anthropogenic CO2 emission to atmosphere. Keywords: amine phase-transfer; fixation of CO2; nonbiological mineralization of CO2; Zntetraphenylporphyrin; CO2 capture and utilization; volatility of amine

With the mitigation of global-warming and the sustainable development of inevitable carbon economy, CCU has become a significant topic and aroused considerable interests in green and sustainable chemistry.1-4 The major obstacle of various CCU technologies is the lack of economical processes to convert CO2 into addedvalue chemicals5,6 and ultimately afford environmentally friendly C1 feedstock.7,8 Because carbon in CO2 is at the most thermodynamically stable oxidation state, reactive substances or electro-reductive processes are often required to activate CO2 via chemical reactions under catalysts and/or with high energy need for CCU.9-15 Recently, the non-biological mineralization of CO2 to MCO316-18 crystals can not only directly consume large amounts of CO2, but also produce valuable chemicals, and its thus particularly important. However, the mineralization often requires templates or additives, high temperature, or long reaction times.19 In this work, we designed an amine phase-transfer approach (Fig. 1) to the cyclical non-biological mineralization of CO2 to MCO3 crystals at room temperature under atmosphere pressure. The approach mainly includes a recyclable amine/ammonium ion phase-transfer

process and the controllable conversion between amine and ammonium ion. The amine is first transferred from aqueous phase (water) into CH2Cl2 phase to form a colored coordination complex with ZnTPP (Fig. 2). CO2 is then introduced to compete with ZnTPP and to form carbamate and bicarbonate with the amine in the presence of water, which releases ZnTPP in the CH2Cl2 phase for next cycle. The aqueous carbamate and bicarbonate solution is then briefly mixed with an appropriate amount of M(OH)2 (M = Ca, Sr, and Ba) to precipitate of MCO3 nanocrystals with uniform polymorphs at room temperature, and the filtrate containing free amine is reusable for next circle. The system was tuned and optimized with five amines and three M(OH)2. Our work provides a green and sustainable CCU approach featuring with high efficiency and low cost.

Fig. 1 The proposed amine phase-transfer scheme for the nonbiological mineralization of CO2

Fig. 2 The designed CCU process on the basis of the amine phasetransfer chemistry

In a typical procedure, amines (Table 1) were phasetransferred from the aqueous phase to the CH2Cl2 phase containing ZnTPP as an amine acceptor. The color of CH2Cl2 phase was changed from pink to aquamarine

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Table 1 Association constants for ZnTPP-amine complexes (Kassoc) and equilibrium constants (Keqɵ) of CO2 with amine at 298.15 K Amines

Keqɵ(forward reaction rate constants (L/(mol s)))

K assoc

4 a

Ethylenediamine (EDA)

65.4

(1.2 × 10 )

Diethanolamine (DEA)

65.0

4.52 × 103((1.41 or 5.79) × 103) b, c

Monoethanolamine (MEA)

137

1.75 × 105 (4.89-5.72 × 103)b, c

Diethylamine (DEYA)

681

Triethanolamine (TEA)

8.11

ɵ

ɵ

ɵ

a

— (3.9) d b

c

d

Keq = Keq × C (C = 1 mol/L). ref. 21. ref. 22. ref. 23. ref. 24.

Various CO2 capture systems based on liquid amines including MEA, DEA, TEA, and methyldiethylamine (MDEA)25-30 have been tested to remove CO2. However, these systems usually require solvent regeneration at high energy cost (100 to 120 ºC),31,32 and undergo solvent losses caused by evaporation and thermal degradation during the absorption-desorption cycles, which affects their practical applications. In addition, the released CO2 cannot be fully utilized. Recently, Kang et al.33 used 2-Amino-2-methyl-1-propanol (AMP) as CO2 absorbent to test its regeneration when calcium source were calcium chloride (CaCl2) and calcium hydroxide (Ca(OH)2), found this system could permanently sequester CO2 with high desorption efficiency in precipitated CaCO3 after CO2 desorbing from the amine, and concluded that chemical regeneration deployed a swing in the pH of the amine absorbent rather than the swing in temperature of typical thermal regeneration procedures, and hence reduces the regeneration energy. Simultaneously, Alexander V. Leontiev and Dmitry M. Rudkevich found that ZnTPP could form stable coordination complexes with secondary or tertiary amines,20 which made ZnTPP be an excellent acceptor of amines, but CO2

could not compete with the porphyrin for their experimental amines. However, ZnTPP is only soluble in organic solvents that are often highly volatile. Therefore, we designed the two-phase system of water and CH2Cl2 containing ZnTPP to fix amines for CO2 capture, where water was used as a seal liquid of the CH2Cl2 phase. To evaluate the possibility of such system in CO2 capture and utilization, the spectroscopic features of amine-ZnTPP in the CH2Cl2 phase were investigated using EDA as a representative amine. An aqueous solution of EDA was added stepwise into a ZnTPP CH2Cl2 solution and the absorption of the ZnTPP solution was monitored. The results revealed that the addition of EDA caused ∆λ = 10 nm bathochromic shift of the characteristic peak of Soret band from 418 to 428 nm (Fig. 3 Left), a shift of characteristic peak of Q band from 547 to 563 nm, and the disappearance of the characteristic peak of free ZnTPP at 550 nm. In addition, the clear color of ZnTPP solution changed from pink to aquamarine blue. These results suggested that a ZnTPP-amine complex was formed, where amine nitrogen was coordinated to Zn atom.20, 33-35 3

5 ZnTPP

ZnTPP+EDA

4 2

3

1 0

F0 / F

blue and the Soret band of ZnTPP bathochromically shift of ∆λ = (6-10) nm due to the formation of ZnTPPamine complexes.20 As CO2 gas was bubbled into the CH2Cl2 phase, the pink color was almost restored and the Soret band shifted back to the original position of free ZnTPP. It can be explained that CO2 competed with ZnTPP to react with amines, which dissociated the ZnTPP-amine complexes and formed carbamate and bicarbonate in the presence of water. The aqueous phase was then separated and reacted with an appropriate amount M(OH)2 at room temperature for 30 min to nonbiologically mineralize CO2 to MCO3 crystals with uniform polymorphs. The amines were then recycled for next fixation and conversion cycle. The processes were successfully repeated 6 cycles at room temperature under atmosphere pressure. Other compounds including CH4, CO, NO, O2, H2O, and N2, which typically co-exist with CO2 in industrial exhausts and desulfurized flue gases, was not able to compete with ZnTPP under the reaction conditions, and thus no visible spectral changes were detected.

Abs.

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2

CO2

1 400

420

440

460

Wavelength(nm)

480

0.00

0.02

0.04

0.06

[Q] / (mol/L)

Fig. 3 Absorbance spectra of ZnTPP and complex ZnTPP-EDA (Left) and the binding relation of ZnTPP-EDA (Right).

The emission titration data supported the 1: 1 stoichiometry between the tested amines including EDA (Fig. 3Right), DEA, MEA, DEYA and TEA and ZnTPP with association constants range from 8 to 681 (Table 1), which were much higher than those hydrogen bonding between amines and water. Therefore, the amines can be easily transferred from the aqueous phase into CH2Cl2 phase to form ZnTPP-amine complexes. The equilibrium constants of the tested EDA and MEA with CO2 for the formation of ammonium carbamate (NH2CO2-) were reported as 4.52 × 103 and 1.75 × 105, significantly higher than those association constants between amines and ZnTPP. Meanwhile, the equilibrium constants of the tested EDA, EDYA and TEA with CO2 could not be found. Therefore, CO2 can substitute ZnTPP in the ZnTPP-amine complexes to form carbamates and phase-transfer from the CH2Cl2 phase into the aqueous phase, which restored the Soret band and Q band to their original positions at 418 nm and 547 nm, respectively (Fig. 3 Left). The color of CH2Cl2 phase became pink again (Fig. 2). It has been known for decades that CO2 can react with amines to form stable carbamate.36,37 However, It can form more stable ammonium carbamate and bicarbonate with amines in the presence of water as demonstrated by the FTIR peak of out-of-plane vibration in HCO3- at 822

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cm-1,38-40 and the typical 13C-NMR chemical shift peak of HCO3- at 164.0 ppm.41-43 Meanwhile, the typical 13CNMR chemical shift of RCOO- is determined at 160.0 ppm.44 The solubility of carbamate and bicarbonate in water is stronger than in CH2Cl2, so that they easily phase-transferred into the aqueous phase. The process was tunable and applicable to all tested amines, indicating its broad application. The reaction mechanism and processes were shown in Fig. 4.

Fig. 4 Reaction mechanism and processes of amine fixation and CO2 capture

The aqueous ammonium carbamate and bicarbonate solution and the CH2Cl2 phase containing free ZnTPP were then separated. The CH2Cl2 phase was directly used for next cycle without any treatment needed and exhibited good performances in 25 cycles. The aqueous ammonium carbamate and bicarbonate solution was mixed with 30 mL 0.02 mol/L M(OH)2 and allowed to react for 30 min to form MCO3 crystals with uniform polymorphs (Fig. 5) by a simple static method at room temperature, by which the amines was released and recycled for next cycle (Figs. 1 and 2). Additionally, there is a strong electrostatic interaction between EDA and M2+ (M = Ca, Sr, and Ba) due to lone pair electrons on the nitrogen atoms in EDA, thus EDA could combine with M2+ to easily absorb on the surfaces of MCO3 crystals. That is, the layer formed from adsorbed EDA molecules could be efficient templates to mediate the crystallization behavior of MCO3. Thus, a possible formation process of MCO3 crystals is shown as follows:

M(OH)2 → M2+ + 2OH(1) RNH2 + CO2 + H2O→RNH3+HCO3- (RNH3+CO2-) (2) RNH3+HCO3- (RNH3+CO2-) + OH- →RNH3+OH- + HCO3- (3) HCO3- → H+ + CO32(4) CO32- + M2+ → MCO3 ↓ (5) H+ + OH- → H2O (6) RNH3+OH- → RNH2 + H2O (7)

Fig. 5 SEM images of (A)CaCO3, (B)SrCO3, and (C)BaCO3 acquired by ammonium carbamate and bicarbonate reacted with 30 mL 0.02 mol/L M(OH)2 (Ca(OH)2, Sr(OH)2 or Ba(OH)2) for 30 min

The filtrate containing amines without MCO3 precipitation can be re-fixed by ZnTPP for further CO2 capture. All MCO3 crystals were found with uniform polymorphs and same crystal phase, which could be applied in the fields of catalysis and adsorption after further processing. In conclusion, we develop the amine phase-transfer approach for the capture and utilization of CO2 at room temperature under atmosphere pressure. The method can

overcome the volatility of amine and convert CO2 into MCO3 with added-values. Both amine and organic phase can be recycled for CO2 capture and conversion. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. The reaction mechanism, UV-Vis spectra and photos of ZnTPP coordinated to amines and then displaced by CO2, color changes and UV spectra of five amines with ZnTPP and bubbling through NO, CH4, O2, N2, and CO, FTIR and 13 C-NMR spectra of amine-CO2 storage solutions, FTIR spectrum and SEM images of CaCO3 acquired by the five cycles of the filtrate, and UV spectra of 25 cycling performance of ZnTPP used in immobilizing ethylenediamine and capturing CO2.

AUTHOR INFORMATION Corresponding Author

Tel.: +86-471-6575722; Fax: +86-471-6575722. E-mail: [email protected] Notes The authors declare no competing financial interests.

ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21666027), the Program for Grassland Excellent Talents of Inner Mongolia Autonomous Region, the Natural Science Foundation of Inner Mongolia Autonomous Region (2016JQ02), Key Laboratory of Coalbased CO2 Capture and Geological Storage (Jiangsu Province, China University of Mining and Technology, 2016A06), the Inner Mongolia Science and Technology Key Projects, and training plan of academic backbone in youth of Inner Mongolia University of Technology.

REFERENCES (1) D'Alessandro, D. M.; Smit, B.; Long, J. R. Carbon Dioxide Capture: Prospects for New Materials. Angew. Chem. Int. Edit., 2010, 49, 6058-6082. DOI 10.1002/anie.201000431 (2) Yang, Z.; He, L.; Gao, J.; Liu, A; Yu, B. Carbon Dioxide Utilization with C–N bond Formation: Carbon Dioxide Capture and Subsequent Conversion. Energ. Environ. Sci., 2012, 5, 6602-6639. DOI 10.1039/c2ee02774g (3) Hasib-ur-Rahman, M.; Larachi, F. CO2 Capture in Alkanolamine-RTIL Blends via Carbamate Crystallization: Route to Efficient Regeneration. Environ. Sci. Technol., 2012, 46, 11443-11450 DOI. 10.1021/es302513j (4) Shang, J.; Liu, S.; Ma, X.; Lu L.; Deng, Y. A New Route of CO2 Catalytic Activation: Syntheses of N-substituted Carbamates from Dialkyl Carbonates and Polyureas. Green Chem., 2012, 14, 2899-2906. DOI 10.1039/c2gc36043h (5) MacDowell, N.; Florin, N.; Buchard, A.; Hallett, J.; Galindo, A.; Jackson, G.; Adjiman, C. S.; Williams, C. K.; Shah, N.; Fennell, P. An Overview of CO2 Capture Technologies. Energ. Environ. Sci., 2010, 3, 1645-1669. DOI 10.1039/c004106h (6) Dimitriou, I.; Garcia-Gutierrez, P.; Elder, R. H.; CuellarFranca, R. M.; Azapagicb, A.; Allena, R. W. K. Carbon Dioxide Utilisation for Production of Transport Fuels: Process and Economic Analysis. Energ. Environ. Sci., 2015, 8, 1775-1789. DOI 10.1039/c4ee04117h

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ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(7) Quadrelli, E. A.; Centi, G. Carbon Dioxide Recycling: Emerging Large-Scale Technologies with Industrial Potential. ChemSusChem, 2011, 4, 1194-1215. DOI 10.1002/cssc.201100473 (8) von der Assen, N.; Jung, J.; Bardow, A. Life-cycle Assessment of Carbon Dioxide Capture and Utilization: Avoiding the Pitfalls. Energ. Envion. Sci., 2013, 6, 2721-2734. DOI 10.1039/c3ee41151f (9) Rubin, E. S.; Zhai, H. The Cost of Carbon Capture and Storage for Natural Gas Combined Ccycle Power Plants. Environ. Sci. Technol. 2012, 46, 3076-3084. DOI 10.1021/es204514f (10) Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans, J.; Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.; Sanz, J. F.; Rodriguez, J. A. Catalysis. Highly Active Copper-ceria and Copper-ceria-titania Catalysts for Methanol SynThesis from CO₂ Science 2014, 345, 546-550. DOI 10.1126/science.1253057 (11) Liu, C.; Yang, B.; Tyo, E. C.; Seifert, S.; DeBartolo, J.; von Issendorff, B.; Zapol, P.; Vajda, S.; Curtiss, L. A. Carbon Dioxide Conversion to Methanol over Size-selected Cu4 Clus-ters at Low Pressures. J. Am. Chem. Soc. 2015, 137, 8676-8679. DOI 10.1021/jacs.5b03668 (12) Huang, Z.; Teramura, K.; Asakura, H.; Hosokawa, S.; Tanaka, T. CO2 Capture, Storage, and Conversion Using a PraSeodymium-modified Ga2O3 Photocatalyst. J. Mater. Chem. A, 2017, 5, 19351-19357. DOI 10.1039/c7ta04918h (13) McNamara, N. D.; Hicks, J. C. CO2 Capture and Conversion with a Multifunctional PolyethyleneimineTethered Iminophosphine Iridium Catalyst/Adsorbent. ChemSusChem, 2014, 7, 1114-1124. DOI n10.1002/cssc.201301231 (14) Kothandaraman, J.; Goeppert, A.; Czaun, M.; Olah, G. A.; Prakash, G. K. S. CO2 Capture by Amines in Aqueous Media and Its Subsequent Conversion to Formate with Reusable Ruthenium and Iron Catalysts. Green Chem., 2016, 18, 5831-5838. DOI 10.1039/c6gc01165a (15) Lim, H.; Shin, H.; Goddard, W. A.; Hwang, Y. J.; Min, B. K.; Kim, H. Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO2. J. Am. Chem. Soc. 2014, 136, 11355-11361. DOI 10.1021/ja503782w (16) Vinoba, M.; Bhagiyalakshmi, M.; Song, S. Y.; Park, K. T.; Kim, H. J.; Jeong, S. K. Harvesting CaCO3 Polymorphs from In Situ CO2 Capture Process. J. Phys. Chem. C, 2014, 118, 17556-17566. DOI 10.1021/jp503448y (17) Boyjoo, Y.; Pareek, V. K.; Liu, J. Synthesis of Micro and Nano-sized Calcium Carbonate Particles and Their Applications. J. Mater. Chem. A, 2014, 2, 14270-14288. DOI 10.1039/c4ta02070g (18) Chen, L.; Shen, Y.; Xie, A.; Huang, B.; Jia, R.; Guo, R.; Tang, W. Bacteria-Mediated Synthesis of Metal Carbonate Minerals with Unusual Morphologies and Structures. Cryst. Growth Des., 2009, 9, 743-754. DOI 10.1021/cg800224s (19) Sui, C.; Lu, Y.; Gao, H.; Dong, L.; Zhao, Y.; Ouali, L.; Benczedi, D,; Jerri, H.; Yu, S. Synthesis of Mesoporous Calcium Phosphate Microspheres by Chemical Transformation Process: Their Stability and Encapsulation of Carboxymethyl Chitosan. Cryst. Growth Des., 2013, 13, 3201-3207. DOI 10.1021/cg400595s (20) Leontiev, A. V.; Rudkevich, D. M. Revisiting Noncovalent SO2-Amine Chemistry: An Indicator-Displacement Assay for Colorimetric Detection of SO2. J. Am. Chem. Soc., 2005, 127, 14126-14127. DOI 10.1021/ja053260v (21) Li, J.; Henni, A.; Tontiwachwuthikul, P. Reaction Kinetics of CO2 in Aqueous Ethylenediamine, Ethyl Ethanolamine, and Diethyl Monoethanolamine Solutions in the Temperature Range of 298-313 K, Using the Stopped-Flow Technique. Ind. Eng. Chem. Res. 2007, 46, 4426-4434. DOI 10.1021/ie0614982

(22) Teramoto, M.; Huang, Q.; Matsuyama, H. Facilitated Transport of Carbon Dioxide Through Supported Liquid Membranes of Aqueous Amine Solutions. ACS Symposium Series, 1996, Chapter 17, 239-251. DOI 10.1021/ie950112c (23) Versteeg, G. F.; van Swaaij, W. P. M. On the Kinetics between CO2 and Alkanolamines both in Aqueous and Non-aqueous Solutions-II. Tertiary Amines. Chem. Eng. Sci. 1988, 43(3), 573-591. DOI 10.1016/0009-2509(88)87018-0 (24) Littel, R. J.; van Swaaij, W. P. M.; Versteeg, G. F. Kinetics of Carbon Dioxide with Tertiary Amines in Aqueous Solution. AIChE J. 1990, 36(11), 1633-1640. DOI 10.1002/aic.690361103 (25) Aroonwilas, A.; Veawab, A.; Tontiwachwuthikul, P. Behavior of the Mass-transfer Coefficient of Structured Packing in CO2 Absorbers with Chemical Reactions. Ind. Eng. Chem. Res. 1999, 38, 2044-2050. DOI 10.1021/ie980728c (26) Mandal, B.; Bandyopadhyay, S. S. Simultaneous Absorption of CO2 and H2S into Aqueous Blends of Nmethyldiethanolamine and Diethanolamine. Environ. Sci. Technol., 2006, 40 (19), 6076-6084. DOI 10.1021/es0606475 (27) Lawal, O.; Bello, A.; Idem, R. The Role of Methyl Diethanolamine (MDEA) in Preventing the Oxidative Degradation of CO2 Loaded and Concentrated Aqueous Monoethanolamine (MEA)-MDEA Blends during CO2 Absorption from Flue Gases. Ind. Eng. Chem. Res., 2005, 44 (6), 1874-1896. DOI 10.1021/ie049261y (28) Lastoskie, C. Caging Carbon Dioxide. Science, 2010, 330, 595-596. DOI 10.1126/science.1198066 (29) Kemper, J.; Ewert, G.; Grunewald, M. Absorption and Regeneration Performance of Novel Reactive Amine Solvents for Post-combustion CO2 Capture. Energy Procedia, 2011, 4, 232-239. DOI 10.1016/j.egypro.2011.01.046 (30) Zhang, J. F.; Nwani, O.; Tan, Y.; Agar, D. W. Carbon Dioxide Absorption into Biphasic Amine Solvent with Solvent Loss Reduction. Chem. Eng. Res. Design. 2011, 89, 1190-1196. DOI 10.1016/j.cherd.2011.02.005 (31) Rochelle, G. T. Amine Scrubbing for CO2 Capture. Science, 2009, 325, 1652-1654. DOI 10.1126/science.1176731 (32) Barzagli, F.; Lai. S.; Mani, F. A New Class of Single-Component Absorbents for Reversible Carbon Dioxide Capture under Mild Conditions. ChemSusChem, 2015, 8, 184191. DOI 10.1002/cssc.201402421 (33) Kang, J. M.; Murnandari, A.; Youn, M. H.; Lee, W.; Park, K. T.; Kim, Y. E.; Kim, H. J.; Kang, S. P.; Lee, J. H.; Jeong, S. K. Energy-efficient chemical regeneration of AMP using calcium hydroxide for operating carbon dioxide capture process. Chem. Eng. J. 2018, 335, 338-344. DOI 10.1016/j.cej.2017.10.136 (34) El-Halim, H. F. A.; Mohamed, G. G. Synthesis, Spectroscopic Studies, Thermal Analyses, Biological Activity of Tridentate Coordinated Transition Metal Complexes of Bi(pyridyl-2-ylmethyl)amine]ligand. J. Mol. Struct., 2016, 1104, 91-95. DOI 10.1016/j.molstruc.2015.09.030 (35) Angiolini, L.; Benelli, T.; Giorgini, L. React. Polymethacrylic Zinc Porphyrin: A New Approach to Chiral Recognition. Funct. Polym., 2011, 71, 204-209. DOI 10.1016/j.reactfunctpolym.2010.12.005 (36) Angiolini, L.; Benelli, T.; Giorgini, L. Novel Optically Active Methacrylic Polymers Containing Side-chain Porphyrin Moieties for Chiral Recognition. Polymer, 2011, 52, 2747-2756. DOI 10.1016/j. polymer.2011.04.055 (37) Sayari, A.; Heydarigorji, A.; Yang, Y. CO2-induced Degradation of Amine-containing Adsorbents: Reaction Products and Pathways. J. Am. Chem. Soc., 2012, 134, 1383413842. DOI 10.1021/ja304888a (38) Gunathilake, C.; Jaroniec, M. Mesoporous Organosilica with Amidoxime Groups for CO2 Sorption ACS Appl. Mat. Inter., 2014, 6, 13069-13078. DOI 10.1021/am5028742

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ACS Sustainable Chemistry & Engineering (39) Xu, W. U.; Xia, A. N.; Xie, X. M. Preparation of Ni(HCO3)2 and Its Catalytic Performance in Synthesis of Benzoin Ethyl Ether. T. Nonferr. Metal. Soc., 2014, 24, 1440-1445. DOI 10.1016/s1003-6326(14)63210-6 (40) Heldebrant, D. J.; Jessop, P. G.; Thomas, C. A.; Eckert, C. A.; Liotta, C. L. The Reaction of 1,8Diazabicyclo[5.4.0]undec-7-ene (DBU) with Carbon Dioxide. J. Org. Chem., 2005, 70, 5335-5338. DOI 10.1021/jo0503759 (41) Scott, L. M.; Robert, T.; Harjani, J. R.; Jessop, P. G. Designing the Head Group of CO2-triggered Switchable Surfactants. RSC Adv., 2012, 2, 4925-4931. DOI 10.1039/c2ra01242a (42) Choi, J. H.; Oh, S. G.; Yoon, Y. I.; Jeong, S. K.; Jang, K. R.; Nam, S. C. A Study of Species Formation of Aqueous tertiary and Hindered Amines Using Quantitative 13C-NMR

spectroscopy. J. Ind. Eng. Chem., 2012, 18, 568-573. DOI 10.1016/j.jiec (43) Garcia, A. A.; Gomez, D. D.; Navaza, J. M.; Rumbo, A. NMR Studies in Carbon Dioxide - Amine Chemical Absorption. Energy Procedia, 2012, 42, 1242-1249. DOI 10.1016/j. proeng.2012.07.516 (44) Phan, L.; Andreatta, J. R.; Horvey, L. K.; Edie, C. F.; Luco, A.; Mirchandani, A.; Darensbourg, D. J.; Jessop, P. G. Switchable-Polarity Solvents Prepared with a Single Liquid Component. J. Org. Chem., 2008, 73, 127-132. DOI 10.1021/jo7017697 (45) Mani, F.; Peruzzini, M.; Stoppioni, P. CO2 Absorption by Aqueous NH3 Solutions: Speciation of Ammonium Carbamate, Bicarbonate and Carbonate by a 13C NMR Study. Green Chem. 2006, 8, 995-1000. DOI 10.1039/b602051h

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The designed CCU process on the basis of the amine phase-transfer chemistry An novel designed amine phase-transfer chemistry could overcome the volatility of amine, fix speedily and non-biologically mineralize recyclable CO2 into MCO3 crystals, which provides a green and sustainable CCU strategy.

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ACS Sustainable Chemistry & Engineering

The TOC of work is shown as follows:

The designed CCU process on the basis of the amine phase-transfer chemistry An novel designed amine phase-transfer chemistry could overcome the volatility of amine, fix speedily and non-biologically mineralize recyclable CO 2 into MCO 3 crystals, which provides a green and sustainable CCU strategy.

ACS Paragon Plus Environment