Ultra-High SO<sub>2</sub> Capture by Anion-Functionalized Resins through Multiple-Site Adsorption

Citation: HE Xi, L Xiaoyu, FAN Xi, LIN Wenjun, LI Haoran, WANG Congmin. Ultra-High SO₂ Capture by Anion-Functionalized Resins through Multiple-Site Adsorption[J]. Acta Physico-Chimica Sinica, 2018, 34(8): 896-903. doi: 10.3866/PKU.WHXB201711271 shu

阴离子功能化大孔树脂用于二氧化硫的多位点高效捕集

贺熙 ^1, ,
吕逍雨 ^1, ,
樊喜 ^1, ,
林文俊 ^1, ,
李浩然 ^1,2, ,
王从敏 ^{1,
,}

1.
浙江大学化学系，浙大-新和成联合研发中心，杭州 310027
2.
浙江大学化学工程与生物工程学院，杭州 310027

通讯作者: 王从敏, chewcm@zju.edu.cn

基金项目:
国家自然科学基金项目 21322602

国家自然科学基金项目 21176205

国家重点基础研究发展规划项目(973)(2015CB251401), 国家自然科学基金项目(21176205, 21322602), 浙江省自然科学基金项目(LZ17B060001)和中央高校基本科研业务费专项资金资助

国家重点基础研究发展规划项目(973) 2015CB251401

浙江省自然科学基金项目 LZ17B060001

摘要: 提出了一种针对大孔树脂阴离子功能化的新策略并合成了一系列阴离子功能化大孔树脂[IRA-900][An]，在20 ℃和101.3 kPa的吸附条件下实现了对SO₂的超高吸附容量(> 10 mmol·g^-1)。和常规唑基阴离子功能化大孔树脂相比，聚咪唑基硼酸阴离子功能化的大孔树脂[IRA-900][B(Im)₄]在低压条件下仍然展现了卓越的SO₂捕集能力。吸附实验发现，[IRA-900][B(Im)₄]在10.13 kPa和20 ℃的低压环境中能够保持10.62 mmol·g^-1的超高SO₂吸附量。通过红外谱学研究以及密度泛函理论(DFT)计算来进行吸附机理探究，发现聚唑基硼酸阴离子[B(Im)₄]具有独特的正四面体构型，从而打破了阴离子上N负位点之间的电子流动和共轭效应。在[IRA-900][B(Im)₄]捕集SO₂过程中，阴离子连续和SO₂分子发生化学相互作用时，吸附焓变无明显下降。因此，一个[B(Im)₄]阴离子能够提供四个有效的作用位点和SO₂发生化学吸附作用，从而在低压条件下，[IRA-900][B(Im)₄]仍然实现了超高的SO₂捕集能力。此外，我们对阴离子功能化大孔树脂[IRA-900][B(Im)₄]在低压条件下对SO₂吸附的循环稳定性做了探究。结果发现，在20 ℃和10.13 kPa的吸附环境中以及70 ℃的脱附条件下，[IRA-900][B(Im)₄]展现了良好的循环稳定性，具有极大的工业应用价值。最后，这种阴离子功能化的策略以及多位点捕集方法对实现烟气环境中SO₂的高效捕集开拓了新的思路。

关键词:

English

Ultra-High SO₂ Capture by Anion-Functionalized Resins through Multiple-Site Adsorption

HE Xi ^1, ,
L Xiaoyu ^1, ,
FAN Xi ^1, ,
LIN Wenjun ^1, ,
LI Haoran ^1,2, ,
WANG Congmin ^{1,
,}

1.
ZJU-NHU United R & D Center, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
2.
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China

Corresponding author: WANG Congmin, chewcm@zju.edu.cn

Received Date: 27 October 2017
Accepted Date: 23 November 2017
Revised Date: 23 November 2017
Available Online: 15 August 2018
Fund Project:

The project was supported by the National Key Basic Research Program of China (973) (2015CB251401), National Natural Science Foundation of China (21176205, 21322602), Zhejiang Provincial Natural Science Foundation of China (LZ17B060001), and Fundamental Research Funds of the Central Universities

Abstract: The anion-functionalization strategy has been proposed and applied for the synthesis of macro-porous resins [IRA-900][An], thus realizing anultra-high SO₂ adsorption capacity (>10 mmol·g^-1) at 101.3 kPa and 20 ℃. Compared with the normal azole-based anion-functionalized resins, the poly(imidazolyl)borate anion-functionalized resin [IRA-900][B(Im)₄] exhibited an outstanding adsorption capacity at low SO₂ partial pressures (10.62 mmol·g^-1 at 20 ℃ and 10.13 kPa). From the results of the IR spectrum investigation and DFT calculations, the multiple-site adsorption mechanism was verified. On account of the unique tetrahedral configuration of [B(im)₄], the conjugation and electronic communication between the electronegative nitrogen atoms were disrupted, making them behave as local reactive sites. Therefore, at least four electronegative nitrogen atoms could be provided by one [B(im)₄] to react with SO₂ without evident adsorption enthalpy deterioration (from -50.6 kJ·mol^-1 to -37.2 kJ·mol^-1) during the continuous SO₂ capture; this was responsible for the ultra-high SO₂ adsorption capacity achieved by [IRA-900][B(Im)₄] at low partial pressures. Moreover, the thermal stability and reversibility of [IRA-900][B(Im)₄] for SO₂ capture and desorption were investigated. Six cycles where the adsorption was carried out at 20 ℃ and 10.13 kPa and the regeneration was performed at 70 ℃ demonstrated the adequate reversibility of [IRA-900][B(Im)₄] for SO₂ capture, showing the resin's great potential for industrial desulfurization. Thus, the anion-functionalization strategy and multiple-site adsorption behavior provide new perspectives to realize effective SO₂ capture from flue gas.

Key words:

1. [1]
  Ilutiu-Varvara, D. A.; Radulescu, D. Stud. Univ. Babes-Bol. Chem. 2013, 58 (2), 143. http://www.whxb.pku.edu.cn/CN/Y2018/V34/I8/896
2. [2]
  Wang, X. L.; Deng, J. P. Aer. Adv. Eng. Res. 2015, 39, 1207. doi: 10.2991/icadme-15.2015.222
3. [3]
  Lehmann, J.; Solomon, D.; Zhao, F. J.; McGrath, S. P. Environ. Sci. Technol. 2008, 42 (10), 3550. doi: 10.1021/es702315g
4. [4]
  Saastamoinen, J. J. Ind. Eng. Chem. Res. 2007, 46 (22), 7308. doi: 10.1021/ie070567p
5. [5]
  Manovic, V.; Anthony, E. J. Fuel 2008, 87 (8–9), 1564. doi: 10.1016/j.fuel.2007.08.022
6. [6]
  Basinas, P.; Grammelis, P.; Grace, J. R.; Lim, C. J.; Skodras, G.; Sakellaropoulos, G. P. Green Energy Technol. 2010, 329. doi: 10.1007/978-1-4419-1017-2_20
7. [7]
  Wu, Y.; Chen, X. P.; Radosz, M.; Fan, M. H.; Dong, W.; Zhang, Z. L.; Yang, Z. Fuel 2014, 125, 50. doi: 10.1016/j.fuel.2014.02.014
8. [8]
  Dong, R. F.; Lu, H. F.; Yu, Y. S.; Zhang, Z. X. Appl. Energ. 2012, 97, 185. doi: 10.1016/j.apenergy.2011.12.039
9. [9]
  Woodis, T. C.; Cummings, J. M.; Hunter, G. B. Environ. Sci. Technol. 1973, 7 (9), 827. doi: 10.1021/es60081a001
10. [10]
  Srivastava, R. K.; Jozewicz, W.; Singer, C. Environ. Prog. 2001, 20 (4), 219. doi: 10.1002/ep.670200410
11. [11]
  Yang, D. Z.; Hou, M. Q.; Ning, H.; Zhang, J. L.; Ma, J.; Han, B. X. Phys. Chem. Chem. Phys. 2013, 15 (41), 18123. doi: 10.1002/cssc.201300224
12. [12]
  Heldebrant, D. J.; Koech, P. K.; Yonker, C. R. Energ. Environ. Sci. 2010, 3 (1), 111. doi: 10.1039/b916550a
13. [13]
  Deng, R. P.; Jia, L. S.; Song, Q. Q.; Su, S.; Tian, Z. B. J. Hazard. Mater. 2012, 229, 398. doi: 10.1016/j.jhazmat.2012.06.020
14. [14]
  Gurkan, B. E.; de la Fuente, J. C.; Mindrup, E. M.; Ficke, L. E.; Goodrich, B. F.; Price, E. A.; Schneider, W. F.; Brennecke, J. F. J. Am. Chem. Soc. 2010, 132 (7), 2116. doi: 10.1021/ja909305t
15. [15]
  Srivastava, R. K.; Jozewicz, W. J. Air Waste. Manage. 2001, 51 (12), 1676. doi: 10.1080/10473289.2001.10464387
16. [16]
  Slater, A. G.; Cooper, A. I. Science 2015, 348, 6238. doi: 10.1126/science.aaa8075
17. [17]
  Thomas, A. Angew. Chem. Int. Edit. 2010, 49 (45), 8328. doi: 10.1002/anie.201000167
18. [18]
  Drage, T. C.; Snape, C. E.; Stevens, L. A.; Wood, J.; Wang, J. W.; Cooper, A. I.; Dawson, R.; Guo, X.; Satterley, C.; Irons, R. J. Mater. Chem. 2012, 22 (7), 2815. doi: 10.1039/c2jm12592g
19. [19]
  Dawson, R.; Cooper, A. I.; Adams, D. J. Polym. Int. 2013, 62 (3), 345. doi: 10.1002/pi.4407
20. [20]
  Liao, P. Q.; Chen, H. Y.; Zhou, D. D.; Liu, S. Y.; He, C. T.; Rui, Z. B.; Ji, H. B.; Zhang, J. P.; Chen, X. M. Energ. Environ. Sci. 2015, 8 (3), 1011. doi: 10.1039/c4ee02717e
21. [21]
  Cui, X. L.; Yang, Q. W.; Yang, L. F.; Krishna, R.; Zhang, Z. G.; Bao, Z. B.; Wu, H.; Ren, Q. L.; Zhou, W.; Chen, B. L.; et al. Adv. Mater. 2017, 29 (28), 1606929. doi: 10.1002/adma.201606929
22. [22]
  Yang, S. H.; Sun, J. L.; Ramirez-Cuesta, A. J.; Callear, S. K.; David, W. I. F.; Anderson, D. P.; Newby, R.; Blake, A. J.; Parker, J. E.; Tang, C. C.; et al. Nat. Chem. 2012, 4 (11), 887. doi: 10.1038/NCHEM.1457
23. [23]
  Savage, M.; Cheng, Y. G.; Easun, T. L.; Eyley, J. E.; Argent, S. P.; Warren, M. R.; Lewis, W.; Murray, C.; Tang, C. C.; Frogley, M. D.; et al. Adv. Mater. 2016, 28 (39), 8705. doi: 10.1002/adma.201602338
24. [24]
  Wu, W. Z.; Han, B. X.; Gao, H. X.; Liu, Z. M.; Jiang, T.; Huang, J. Angew. Chem. Int. Edit. 2004, 43 (18), 2415. doi: 10.1002/anie.200353437
25. [25]
  Zhang, S. J.; Sun, N.; He, X. Z.; Lu, X. M.; Zhang, X. P. J. Phys. Chem. Ref. Data 2006, 35 (4), 1475. doi: 10.1063/1.2204959
26. [26]
  Lin, H.; Bai, P.; Guo, X. H. Asian J. Chem. 2014, 26 (9), 2501. doi: 10.14233/ajchem.2014.15800
27. [27]
  Yang, D. Z.; Hou, M. Q.; Ning, H.; Ma, J.; Kang, X. C.; Zhang, J. L.; Han, B. X. ChemSusChem 2013, 6 (7), 1191. doi: 10.1002/cssc.201300224
28. [28]
  Mondal, A.; Balasubramanian, S. J. Phys. Chem. B. 2016, 120 (19), 4457. doi: 10.1021/acs.jpcb.6b02553
29. [29]
  Zeng, S. J.; Gao, H. S.; Zhang, X. C.; Dong, H. F.; Zhang, X. P.; Zhang, S. J. Chem. Eng. J. 2014, 251, 248. doi: 10.1016/j.cej.2014.04.040
30. [30]
  Cui, G. K.; Wang, C. M.; Zheng, J. J.; Guo, Y.; Luo, X. Y.; Li, H. R. Chem. Commun. 2012, 48 (20), 2633. doi: 10.1039/c2cc16457d
31. [31]
  Chen, K. H.; Lin, W. J.; Yu, X. N.; Luo, X. Y.; Ding, F.; He, X.; Li, H. R.; Wang, C. M. AIChE J. 2015, 61 (6), 2028. doi: 10.1002/aic.14793
32. [32]
  Wang, C. M.; Cui, G. K.; Luo, X. Y.; Xu, Y. J.; Li, H. R.; Dai, S. J. Am. Chem. Soc. 2011, 133 (31), 11916. doi: 10.1021/ja204808h
33. [33]
  Cui, G. K.; Lin, W. J.; Ding, F.; Luo, X. Y.; He, X.; Li, H. R.; Wang, C. M. Green Chem. 2014, 16 (3), 1211. doi: 10.1039/c3gc41458b
34. [34]
  Tang, H. R.; Lu, D. M. ChemPhysChem 2015, 16 (13), 2854. doi: 10.1002/cphc.201500369
35. [35]
  He, X.; Mei, K.; Dao, R. N.; Cai, J. S.; Lin, W. J.; Kong, X. Q.; Wang, C. M. AIChE J. 2017, 63 (7), 3008. doi: 10.1002/aic.15647
36. [36]
  Srinivasan, A.; Grutzeck, M. W. Environ. Sci. Technol. 1999, 33 (9), 1464. doi: 10.1021/es9802091
37. [37]
  Alesi, W. R.; Kitchin, J. R. Ind. Eng. Chem. Res. 2012, 51 (19), 6907. doi: 10.1021/ie300452c
38. [38]
  Lee, H. J.; Lee, K. I.; Kim, M.; Suh, Y. W.; Kim, H. S.; Lee, H. ACS Sustain. Chem. Eng. 2016, 4 (4), 2012. doi: 10.1021/acssuschemeng.5b01325
39. [39]
  Trofimenko, S. J. Am. Chem. Soc. 1967, 89 (13), 3170. doi: 10.1021/ja00989a017
40. [40]
  Becke, A. D. Phys. Rev. A 1988, 38 (6), 3098. doi: 10.1103/PhysRevA.38.3098
41. [41]
  Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37 (2), 785. doi: 10.1103/PhysRevB.37.785
42. [42]
  Becke, A. D. J. Chem. Phys. 1993, 98 (7), 5648. doi: 10.1063/1.464913
43. [43]
  Firaha, D. S.; Holloczki, O.; Kirchner, B. Angew. Chem. Int. Edit. 2015, 54 (27), 7805. doi: 10.1002/anie.201502296
44. [44]
  Wang, C. M.; Luo, X. Y.; Luo, H. M.; Jiang, D. E.; Li, H. R.; Dai, S. Angew. Chem. Int. Edit. 2011, 50 (21), 4918. doi: 10.1002/anie.201008151
45. [45]
  Goeppert, A.; Meth, S.; Olah, G. A.; Prakash, S. G. K. Energy Environ. Sci. 2010, 3, 1949. doi: 10.1039/C0EE00136H
46. [46]
  Qi, G. G.; Wang, Y. B.; Estevez, L.; Duan, X. N.; Anako, N.; Park, A. H. A.; Li, W.; Jones, C. W.; Giannelis, E. P. Energy Environ. Sci. 2011, 4 (2), 444. doi: 10.1039/c0ee00213e
47. [47]
  Xiang, S. C.; Zhang, Z. J.; Zhao, C. G.; Hong, K. L.; Zhao, X. B.; Ding, D. R.; Xie, M. H.; Wu, C. D.; Das, M. C.; Gill, R.; et al. Nat. Commun. 2011, 2 (1), 1. doi: 10.1038/ncomms1206
48. [48]
  Liao, P. Q.; Zhang, W. X.; Zhang, J. P.; Chen, X. M. Nat. Commun. 2015, 6, 8697. doi: 10.1038/ncomms969

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

阴离子功能化大孔树脂用于二氧化硫的多位点高效捕集

通讯作者: 王从敏, chewcm@zju.edu.cn

English

Ultra-High SO₂ Capture by Anion-Functionalized Resins through Multiple-Site Adsorption

Corresponding author: WANG Congmin, chewcm@zju.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

阴离子功能化大孔树脂用于二氧化硫的多位点高效捕集

通讯作者: 王从敏, chewcm@zju.edu.cn

English

Ultra-High SO2 Capture by Anion-Functionalized Resins through Multiple-Site Adsorption

Corresponding author: WANG Congmin, chewcm@zju.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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