Citation: WU Xuanjun, LI Lei, PENG Liang, WANG Yetong, CAI Weiquan. Effect of Coordinatively Unsaturated Metal Sites in Porous Aromatic Frameworks on Hydrogen Storage Capacity[J]. Acta Physico-Chimica Sinica, ;2018, 34(3): 286-295. doi: 10.3866/PKU.WHXB201708172 shu

Effect of Coordinatively Unsaturated Metal Sites in Porous Aromatic Frameworks on Hydrogen Storage Capacity

WU Xuanjun ^1,2,, ,
LI Lei ¹ ,
PENG Liang ¹ ,
WANG Yetong ¹ ,
CAI Weiquan ^1,3,,

1.
School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, P. R. China
2.
Department of Chemical and Biomolecular Engineering, National University of Singapore 117576, Singapore
3.
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, P. R. China

Corresponding author: WU Xuanjun, wuxuanjun@whut.edu.cn CAI Weiquan, caiwq@whut.edu.cn
Received Date: 4 July 2017
Revised Date: 4 August 2017
Accepted Date: 8 August 2017
Available Online: 17 March 2017
Fund Project: the National Natural Science Foundation of China 51272201the China Scholarship Council for the Scholarship Support [2016]3099the Fundamental Research Funds for the Central Universities 175220002the National Natural Science Foundation of China 21476179The project was supported by the National Natural Science Foundation of China (51272201, 21476179), the China Scholarship Council for the Scholarship Support ([2016]3099), the Fundamental Research Funds for the Central Universities (175220002), and 2016 Wuhan Yellow Crane Talents (Science) Program

The effect of inserting coordinatively unsaturated metal sites (CUS) into porous aromatic frameworks (PAFs) on their hydrogen storage capacity was investigated systematically by density functional theory and grand canonical Monte Carlo simulations. The results indicate that the maximum excess gravimetric uptake of hydrogen possible with PAF-302MgO₂_PBE100 is 7.97% (w) at 77 K. The total uptakes of hydrogen by PAF-302 and PAF-303 functionalized with 100% magnesium alkoxide at 77 K and 10 MPa were determined to be 9.9% (w) (65.9 g∙L^-1) and 15.0% (w) (50.5 g∙L^-1), respectively. These uptake values are 80% (64.8%) and 173% (26.3%), respectively, more than the gravimetric and volumetric targets set by the Department of Energy (DOE) of USA. They also exceed the targets set by NU-1101, presenting the highest measured performance of 9.9% (w) (46.6 g∙L^-1) under the same conditions. Even at 243 K and 10 MPa, the total gravimetric and volumetric uptakes of hydrogen in the former are up to 5.13% (w) and 34.19 g∙L^-1, which are about 93.3% and 85.5% of the targets set by DOE, respectively. By analyzing the isosteric heat of adsorption (Q_st), radial distribution function, and mass center probability density, it is found that increasing the length of the organic linkers of PAFs incorporated with CUS will result in decreasing volumetric surface areas in spite of the increase in void fractions, which is the root of trade-offs between the total gravimetric and volumetric H₂ uptake in porous materials. Additionally, CUS incorporation improves the affinity of PAF materials to H₂ molecules, resulting in an enhancement of the volumetric hydrogen storage capacity.
- Porous aromatic framework,
- CUS,
- Hydrogen storage,
- Molecular adsorption,
- GCMC simulation
1. [1]
  Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M. Science 2013, 341, 1230444. doi: 10.1126/science.1230444 doi: 10.1126/science.1230444
2. [2]
  Durbin, D. J.; Malardier-Jugroot, C. Int. J. Hydrog. Energy 2013, 38, 14595. doi: 10.1016/j.ijhydene.2013.07.058 doi: 10.1016/j.ijhydene.2013.07.058
3. [3]
  Cipriani, G.; Dio, V. D.; Genduso, F.; Cascia, D. L.; Liga, R.; Miceli, R.; Galluzzo, G. R. Int. J. Hydrog. Energy 2014, 39, 8482. doi: 10.1016/j.ijhydene.2014.03.174 doi: 10.1016/j.ijhydene.2014.03.174
4. [4]
  https://energy.gov/eere/fuelcells/physical-hydrogen-storage(accessed 12 June 2017).
5. [5]
  Mulder, F. M.; Dingemans, T. J.; Wagemaker, M.; Kearley, G. J. Chem. Phys. 2005, 317, 113. doi: 10.1016/j.chemphys.2005.06.003 doi: 10.1016/j.chemphys.2005.06.003
6. [6]
  Tranchemontagne, D. J.; Park, K. S.; Furukawa, H.; Eckert, J.; Knobler, C. B.; Yaghi, O. M. J. Phys. Chem. C 2012, 116, 13143. doi: 10.1021/jp302356q doi: 10.1021/jp302356q
7. [7]
  Mendoza-Cortes, J. L.; Goddard, W. A., III; Furukawa, H.; Yaghi, O. M. J. Phys. Chem. Lett. 2012, 3, 2671. doi: 10.1021/jz301000m doi: 10.1021/jz301000m
8. [8]
  Ding, S. Y.; Wang, W. Chem. Soc. Rev. 2013, 42, 548. doi: 10.1039/C2CS35072F doi: 10.1039/C2CS35072F
9. [9]
  Huang, L.; Yang, X.; Cao, D. J. Phys. Chem. C 2015, 119, 3260. doi: 10.1021/jp5128404 doi: 10.1021/jp5128404
10. [10]
  Huang, L.; Xiang, Z.; Cao, D. J. Mater. Chem. A 2013, 1, 3851. doi: 10.1039/C3TA10292K doi: 10.1039/C3TA10292K
11. [11]
  Tozzini, V.; Pellegrini, V. Phys. Chem. Chem. Phys. 2013, 15, 80. doi: 10.1039/C2CP42538F doi: 10.1039/C2CP42538F
12. [12]
  Ben, T.; Ren, H.; Ma, S.; Cao, D.; Lan, J.; Jing, X.; Wang, W.; Xu, J.; Deng, F.; Simmons, J. M.; Qiu, S.; Zhu, G. Angew. Chem. 2009, 121, 9621. doi: 10.1002/ange.200904637 doi: 10.1002/ange.200904637
13. [13]
  Lan, J.; Cao, D.; Wang, W.; Ben, T.; Zhu, G.J. Phys. Chem. Lett. 2010, 1, 978. doi: 10.1021/jz900475b doi: 10.1021/jz900475b
14. [14]
  Lan, J.; Cao, D.; Wang, W. J. Phys. Chem. C 2010, 114, 3108. doi: 10.1021/jp9106525 doi: 10.1021/jp9106525
15. [15]
  Xiang, Z.; Cao, D.; Wang, W.; Yang, W.; Han, B.; Lu, J. J. Phys. Chem. C 2012, 116, 5974. doi: 10.1021/jp300137e doi: 10.1021/jp300137e
16. [16]
  Gómez-Gualdrón, D. A.; Simon, C. M.; Lassman, W.; Chen, D.; Martin, R. L.; Haranczyk, M.; Farha, O. K.; Smit, B.; Snurr, R. Q. Chem. Eng. Sci 2017, 159, 18. doi: 10.1016/j.ces.2016.02.030 doi: 10.1016/j.ces.2016.02.030
17. [17]
  Gygi, D.; Bloch, E. D.; Mason, J. A.; Hudson, M. R.; Gonzalez, M. I.; Siegelman, R. L.; Darwish, T. A.; Queen, W. L.; Brown, C. M.; Long, J. R. Chem. Mater. 2016, 28, 1128. doi: 10.1021/acs.chemmater.5b04538 doi: 10.1021/acs.chemmater.5b04538
18. [18]
  Getman, R. B.; Miller, J. H.; Wang, K.; Snurr, R. Q. J. Phys. Chem. C 2011, 115, 2066. doi: 10.1021/jp1094068 doi: 10.1021/jp1094068
19. [19]
  Colón, Y. J.; Fairenjimenez, D.; Wilmer, C. E.; Snurr, R. Q. J. Phys. Chem. C 2014, 118, 5383. doi: 10.1021/jp4122326 doi: 10.1021/jp4122326
20. [20]
  Wu, X.; Wang, R.; Yang, H.; Wang, W.; Cai, W.; Li, Q. J. Mater. Chem. A 2015, 3, 10724. doi: 10.1039/c5ta01290b doi: 10.1039/c5ta01290b
21. [21]
  Wu, X. J.; Zhao, P.; Fang, J. M.; Wang, J.; Liu, B. S.; Cai, W. Q. Acta Phys. -Chim. Sin. 2014, 30, 2043. doi: 10.3866/PKU.WHXB201409222
22. [22]
  Kresse, G.; Furthmüller, J. Comp. Mater. Sci. 1996, 6, 15. doi: 10.1016/0927-0256(96)00008-0 doi: 10.1016/0927-0256(96)00008-0
23. [23]
  Düren, T.; Millange, F.; Ferey, G.; Walton, K. S.; Snurr, R. Q. J. Phys. Chem. C 2007, 111, 15350. doi: 10.1021/jp074723h doi: 10.1021/jp074723h
24. [24]
  Willems, T. F.; Rycroft, C. H.; Kazi, M.; Meza, J. C.; Haranczyk, M. Microporous Mesoporous Mater. 2012, 149, 134. doi: 10.1016/j.micromeso.2011.08.020 doi: 10.1016/j.micromeso.2011.08.020
25. [25]
  Blöchl, P. E. Phys. Rev. B 1994, 50, 17953. doi: 10.1103/PhysRevB.50.17953 doi: 10.1103/PhysRevB.50.17953
26. [26]
  Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758 doi: 10.1103/PhysRevB.59.1758
27. [27]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865 doi: 10.1103/PhysRevLett.77.3865
28. [28]
  Kiefer, J. Proc. Am. Math. Soc.1953, 4, 502. doi: 10.2307/2032161 doi: 10.2307/2032161
29. [29]
  Chempath, S.; Clark, L. A.; Snurr, R. Q. J. Chem. Phys. 2003, 118, 7635. doi: 10.1063/1.1562607 doi: 10.1063/1.1562607
30. [30]
  Peng, D. Y.; Robinson, D. B. Ind. Eng. Chem. Fund. 1976, 15, 59. doi: 10.1021/i160057a011 doi: 10.1021/i160057a011
31. [31]
  Wu, X.; Li, L.; Fang, T.; Wang, Y.; Cai, W.; Xiang, Z. Phys. Chem. Chem. Phys. 2017, 19, 9261. doi: 10.1039/C7CP01230F doi: 10.1039/C7CP01230F
32. [32]
  Gómez-Gualdrón, D. A.; Wang, T. C.; García-Holley, P.; Sawelewa, R. M.; Argueta, E.; Snurr, R. Q.; Hupp, J. T.; Yildirim, T.; Farha, O. K. ACS Appl. Mater. Interfaces 2017, doi: 10.1021/acsami.7b01190 doi: 10.1021/acsami.7b01190
33. [33]
  Farha, O. K.; Yazaydın, A. Ö.; Eryazici, I.; Malliakas, C. D.; Hauser, B. G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. Nat. Chem. 2010 2, 944. doi: 10.1038/nchem.834 doi: 10.1038/nchem.834
34. [34]
  Gómez-Gualdrón, D. A.; Colón, Y. J.; Zhang, X.; Wang, T. C.; Chen, Y.-S.; Hupp, J. T.; Yildirim, T.; Farha, O. K.; Zhang, J.; Snurr, R. Q. Energy Environ. Sci. 2016, 9, 3279. doi: 10.1039/C6EE02104B doi: 10.1039/C6EE02104B
35. [35]
  Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. Ö.; Snurr, R. Q.; O'Keeffe, M.; Kim, J. Science 2010, 329, 424. doi: 10.1126/science.1192160 doi: 10.1126/science.1192160
36. [36]
  Kaye, S. S.; Dailly, A.; Yaghi, O. M.; Long, J. R. J. Am. Chem. Soc. 2007, 129, 14176. doi: 0.1021/ja076877g
37. [37]
  Furukawa, H.; Miller, M. A.; Yaghi, O. M. J. Mater. Chem. 2007, 17, 3197. doi: 10.1021/ja9015765 doi: 10.1021/ja9015765
38. [38]
  Yuan, D.; Zhao, D.; Sun, D.; Zhou, H. C. Angew. Chem. Int. Ed. 2010, 49, 5357. doi: 10.1002/anie.201001009 doi: 10.1002/anie.201001009
39. [39]
  Lim, W. X.; Thornton, A. W.; Hill, A. J.; Cox, B. J.; Hill, J. M.; Hill, M. R. Langmuir 2013, 29, 8524. doi: 10.1021/la401446s doi: 10.1021/la401446s
40. [40]
  Frost, H.; Snurr, R. Q. J. Phys. Chem. C 2007, 111, 18794. doi: 10.1021/jp076657p doi: 10.1021/jp076657p
1. [1]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
2. [2]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
3. [3]
  Zhifang SU , Zongjie GUAN , Yu FANG . Process of electrocatalytic synthesis of small molecule substances by porous framework materials. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2373-2395. doi: 10.11862/CJIC.20240290
4. [4]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
5. [5]
  Pingping Zhu , Yongjun Xie , Yuanping Yi , Yu Huang , Qiang Zhou , Shiyan Xiao , Haiyang Yang , Pingsheng He . Excavation and Extraction of Ideological and Political Elements for the Virtual Simulation Experiments at Molecular Level: Taking the Project “the Simulation and Computation of Conformation, Morphology and Dimensions of Polymer Chains” as an Example. University Chemistry, 2024, 39(2): 83-88. doi: 10.3866/PKU.DXHX202309063
6. [6]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢. Acta Physico-Chimica Sinica, 2025, 41(1): 2308032-. doi: 10.3866/PKU.WHXB202308032
7. [7]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
8. [8]
  Zhuo WANG , Xiaotong LI , Zhipeng HU , Junqiao PAN . Three-dimensional porous carbon decorated with nano bismuth particles: Preparation and sodium storage properties. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 267-274. doi: 10.11862/CJIC.20240223
9. [9]
  Ming Li , Zhaoyin Li , Mengzhu Liu , Shaoxiang Luo . Unveiling the Artistry of Mordant Dyeing: The Coordination Chemistry Beneath. University Chemistry, 2024, 39(5): 258-265. doi: 10.3866/PKU.DXHX202311085
10. [10]
  Quanguo Zhai , Peng Zhang , Wenyu Yuan , Ying Wang , Shu'ni Li , Mancheng Hu , Shengli Gao . Reconstructing the “Fundamentals of Coordination Chemistry” in Inorganic Chemistry Course. University Chemistry, 2024, 39(11): 117-130. doi: 10.12461/PKU.DXHX202403065
11. [11]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
12. [12]
  Junli Liu . Practice and Exploration of Research-Oriented Classroom Teaching in the Integration of Science and Education: a Case Study on the Synthesis of Sub-Nanometer Metal Oxide Materials and Their Application in Battery Energy Storage. University Chemistry, 2024, 39(10): 249-254. doi: 10.12461/PKU.DXHX202404023
13. [13]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
14. [14]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
15. [15]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . 高性能双金属氧化物负极的理性设计及储锂特性. Acta Physico-Chimica Sinica, 2025, 41(3): 2311005-. doi: 10.3866/PKU.WHXB202311005
16. [16]
  Mengzhen JIANG , Qian WANG , Junfeng BAI . Research progress on low-cost ligand-based metal-organic frameworks for carbon dioxide capture from industrial flue gas. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 1-13. doi: 10.11862/CJIC.20240355
17. [17]
  Limei CHEN , Mengfei ZHAO , Lin CHEN , Ding LI , Wei LI , Weiye HAN , Hongbin WANG . Preparation and performance of paraffin/alkali modified diatomite/expanded graphite composite phase change thermal storage material. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 533-543. doi: 10.11862/CJIC.20230312
18. [18]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
19. [19]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
20. [20]
  Congying Lu , Fei Zhong , Zhenyu Yuan , Shuaibing Li , Jiayao Li , Jiewen Liu , Xianyang Hu , Liqun Sun , Rui Li , Meijuan Hu . Experimental Improvement of Surfactant Interface Chemistry: An Integrated Design for the Fusion of Experiment and Simulation. University Chemistry, 2024, 39(3): 283-293. doi: 10.3866/PKU.DXHX202308097

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(450)
HTML views(43)

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