Citation: Jing Zijun, Khai Chen Tan, He Teng, Yu Yang, Pei Qijun, Wang Jintao, Wu Hui, Chen Ping. Synthesis, Characterization, and Crystal Structure of Lithium Pyrrolide[J]. Acta Physico-Chimica Sinica, ;2021, 37(11): 200903. doi: 10.3866/PKU.WHXB202009039 shu

Synthesis, Characterization, and Crystal Structure of Lithium Pyrrolide

Jing Zijun ^1,2 ,
Khai Chen Tan ^1,2 ,
He Teng ^1,, ,
Yu Yang ^1,2 ,
Pei Qijun ^1,2 ,
Wang Jintao ^1,2 ,
Wu Hui ^3,, ,
Chen Ping ¹

1.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA

Corresponding author: He Teng, heteng@dicp.ac.cn Wu Hui, huiwu@nist.gov
Received Date: 10 September 2020
Revised Date: 19 October 2020
Accepted Date: 19 October 2020
Available Online: 23 October 2020
Fund Project: the K. C. Wong Education Foundation GJTD-2018-06the National Natural Science Foundation of China 51671178The project was supported by the National Key R&D Program of China (2018YFB1502100, 2019YFE0103600), the National Natural Science Foundation of China (51671178, 51472237), the Light Source Fund of Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP DCLS201701), the Liaoning Revitalization Talents Program (XLYC1807157), and the K. C. Wong Education Foundation (GJTD-2018-06)the Liaoning Revitalization Talents Program XLYC1807157the National Natural Science Foundation of China 51472237the National Key R&D Program of China 2018YFB1502100the Light Source Fund of Dalian Institute of Chemical Physics, Chinese Academy of Sciences DICP DCLS201701the National Key R&D Program of China 2019YFE0103600

Development of clean energy is an urgent requirement because of the depletion of fossil energy sources and increasingly severe environmental pollution. However, the lack of safe and efficient hydrogen storage materials is one of the bottlenecks in the implementation of hydrogen energy. Liquid organic hydrogen carriers (LOHCs) have been recognized as potential materials for the storage and transportation of hydrogen owing to their high gravimetric and volumetric hydrogen densities, reversible hydrogen absorption and desorption ability, and ease of widespread implementation with minimal modification on the existing fueling infrastructure. While some LOHCs such as cycloalkanes and N-heterocycles have been developed for hydrogen storage, they require a high hydrogen release temperature due to the large enthalpy change of dehydrogenation. In our previous work, a metallation strategy was proposed to improve the thermodynamic properties of liquid organic hydrogen carriers for hydrogen storage, and a series of metalorganic hydrides were synthesized and investigated. Among them, sodium phenoxide-cyclohexanolate pair, lithium carbazolide-perhydrocarbazolide, and sodium anilinide-cyclohexylamide pair showed promising dehydrogenation thermodynamics and improved hydrogen storage properties. Sodium pyrrolide and sodium imidazolide were also synthesized. However, pyrrolides were not well characterized, and the structure of lithium pyrrolide was not resolved. In the present study, we synthesized sodium and lithium pyrrolides by ball milling and wet chemical methods. One equivalent of hydrogen could be released from the reaction of pyrrole and metal hydrides, indicating the replacement of H by metal. The formation of pyrrolides was confirmed by nuclear magnetic resonance (NMR), X-ray diffraction (XRD) and ultraviolet-visible spectroscopy analyses. The ¹H signals attributed to C－H in the NMR spectra of the alkali metal pyrrolides shifted upfield due to the replacement of the H of N－H with a stronger electron-donating species (Li or Na), resulting in a greater shielding environment upon metallation. The absorption peaks of lithium and sodium pyrrolides showed red shifts, and the intensities became obviously stronger in the UV-Vis spectra, suggesting an enhancement of the conjugation effect, in accordance with theoretical calculations. The structure of lithium pyrrolide was determined by the combined direct space method and first-principles calculations on XRD data and Rietveld refinement. This molecule crystallizes in the monoclinic P2₁/c (14) space group, with lattice parameters of a = 4.4364(7) Å, b = 11.969(2) Å, c = 8.192(2) Å, β = 108.789(8)°, and V = 411.8(2) Å³ (1 Å = 0.1 nm). Each Li⁺ cation is surrounded by three pyrrolides via cation－N σ bonding with two pyrrolides and a cation–π interaction with the third pyrrolide, where the Li⁺ is on the top of the π face. Our experimental findings are different from the theoretical prediction in the literature.
- Lithium pyrrolide,
- Crystal structure,
- Metal replacement,
- Liquid organic hydrogen carrier,
- Metallo-N-heterocycle,
- Hydrogen storage
1. [1]
  He, T.; Pachfule, P.; Wu, H.; Xu, Q.; Chen, P. Nat. Rev. Mater. 2016, 1(12), 16059. doi: 10.1038/natrevmats.2016.59 doi: 10.1038/natrevmats.2016.59
2. [2]
  Zhu, Q. L.; Xu, Q. Energy Environ. Sci. 2015, 8(2), 478. doi: 10.1039/C4EE03690E doi: 10.1039/C4EE03690E
3. [3]
  Sakintuna, B.; Lamari-Darkrim, F.; Hirscher, M. Int. J. Hydrogen Energy 2007, 32(9), 1121. doi: 10.1016/j.ijhydene.2006.11.022 doi: 10.1016/j.ijhydene.2006.11.022
4. [4]
  Gutowska, A.; Li, L.; Shin, Y.; Wang, C. M.; Li, X. S.; Linehan, J. C.; Smith, R. S.; Kay, B. D.; Schmid, B.; Shaw, W.; et al. Angew. Chem. 2005, 117(23), 3644. doi: 10.1002/ange.200462602 doi: 10.1002/ange.200462602
5. [5]
  Xiong, Z.; Yong, C. K.; Wu, G.; Chen, P.; Shaw, W.; Karkamkar, A.; Autrey, T.; Jones, M. O.; Johnson, S. R.; Edwards, P. P.; David, W. I. F. Nat. Mater. 2008, 7(2), 138. doi: 10.1038/nmat2081 doi: 10.1038/nmat2081
6. [6]
  Bogdanović, B.; Schwickardi, M. J. Alloys Compd. 1997, 253–254, 1. doi: 10.1016/S0925-8388(96)03049-6 doi: 10.1016/S0925-8388(96)03049-6
7. [7]
  Chen, P.; Xiong, Z.; Luo, J.; Lin, J.; Tan, K. L. Nature 2002, 420(6913), 302. doi: 10.1038/nature01210 doi: 10.1038/nature01210
8. [8]
  Züttel, A.; Wenger, P.; Rentsch, S.; Sudan, P.; Mauron, P.; Emmenegger, C. J. Power Sources 2003, 118(1), 1. doi: 10.1016/S0378-7753(03)00054-5 doi: 10.1016/S0378-7753(03)00054-5
9. [9]
  Xiao, X.; Chen, L.; Wang, X.; Li, S.; Chen, C. Acta Phys. -Chim. Sin. 2006, 22(12), 1511. doi: 10.3866/PKU.WHXB20061215
10. [10]
  Modisha, P. M.; Ouma, C. N. M.; Garidzirai, R.; Wasserscheid, P.; Bessarabov, D. Energy Fuels 2019, 33(4), 2778. doi: 10.1021/acs.energyfuels.9b00296 doi: 10.1021/acs.energyfuels.9b00296
11. [11]
  Müller, K.; Thiele, S.; Wasserscheid, P. Energy Fuels 2019, 33(10), 10324. doi: 10.1021/acs.energyfuels.9b01939 doi: 10.1021/acs.energyfuels.9b01939
12. [12]
  Preuster, P.; Papp, C.; Wasserscheid, P. Acc. Chem. Res. 2017, 50(1), 74. doi: 10.1021/acs.accounts.6b00474 doi: 10.1021/acs.accounts.6b00474
13. [13]
  Yang, J.; Sudik, A.; Wolverton, C.; Siegel, D. J. Chem. Soc. Rev. 2010, 39(2), 656. doi: 10.1039/B802882F doi: 10.1039/B802882F
14. [14]
  Clot, E.; Eisenstein, O.; Crabtree, R. H. Chem. Commun. 2007, No. 22, 2231. doi: 10.1039/B705037B doi: 10.1039/B705037B
15. [15]
  Pez, G. P.; Scott, A. R.; Cooper, A. C.; Cheng, H. Hydrogen storage by reversible hydrogenation of pi-conjugated substrates. US Patent US07101530, 2006.
16. [16]
  Cui, Y.; Kwok, S.; Bucholtz, A.; Davis, B.; Whitney, R. A.; Jessop, P. G. New J. Chem. 2008, 32(6), 1027. doi: 10.1039/B718209K doi: 10.1039/B718209K
17. [17]
  Jing, Z.; Yu, Y.; Chen, R.; Tan, K. C.; He, T.; Wu, A.; Pei, Q.; Chua, Y. S.; Zheng, D.; Zhang, X.; et al. Chem. Commun. 2020, 56(13), 1944. doi: 10.1039/C9CC08593A doi: 10.1039/C9CC08593A
18. [18]
  Tan, K. C.; Yu, Y.; Chen, R.; He, T.; Jing, Z.; Pei, Q.; Wang, J.; Chua, Y. S.; Wu, A.; Zhou, W.; et al. Energy Storage Mater. 2020, 26, 198. doi: 10.1016/j.ensm.2019.12.035 doi: 10.1016/j.ensm.2019.12.035
19. [19]
  Yu, Y.; He, T.; Wu, A.; Pei, Q.; Karkamkar, A.; Autrey, T.; Chen, P. Angew. Chem. Int. Ed. 2019, 58(10), 3102. doi: 10.1002/anie.201810945 doi: 10.1002/anie.201810945
20. [20]
  Blanco, F.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2008, 112(33), 7682. doi: 10.1021/jp801936v doi: 10.1021/jp801936v
21. [21]
  Ruan, C.; Yang, Z.; Rodgers, M. T. Int. J. Mass Spectrom. 2007, 267(1), 233. doi: 10.1016/j.ijms.2007.02.041 doi: 10.1016/j.ijms.2007.02.041
22. [22]
  Scott, M. S.; Lucas, A. C.; Luckhurst, C. A.; Prodger, J. C.; Dixon, D. J. Org. Biomol. Chem. 2006, 4(7), 1313. doi: 10.1039/B515356E doi: 10.1039/B515356E
23. [23]
  Baltazzi, E.; Krimen, L. I. Chem. Rev. 1963, 63(5), 511. doi: 10.1021/cr60225a004 doi: 10.1021/cr60225a004
24. [24]
  Yu, G.; Huang, X. R.; Chen, W.; Sun, C. C. J. Comput. Chem. 2011, 32(9), 2005. doi: 10.1002/jcc.21789 doi: 10.1002/jcc.21789
25. [25]
  Goddard, R.; Heinemann, O.; Krüger, C. Acta Cryst. 1997, 53(12), 1846. doi: 10.1107/S0108270197009682 doi: 10.1107/S0108270197009682
1. [1]
  Ke-Ai Zhou , Lian Huang , Xing-Ping Fu , Li-Ling Zhang , Yu-Ling Wang , Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172
2. [2]
  Tiantian Li , Ruochen Jin , Bin Wu , Dongming Lan , Yunjian Ma , Yonghua Wang . A novel insight of enhancing the hydrogen peroxide tolerance of unspecific peroxygenase from Daldinia caldariorum based on structure. Chinese Chemical Letters, 2024, 35(4): 108701-. doi: 10.1016/j.cclet.2023.108701
3. [3]
  Xinyi Cao , Yucheng Jin , Hailong Wang , Xu Ding , Xiaolin Liu , Baoqiu Yu , Xiaoning Zhan , Jianzhuang Jiang . A tetraaldehyde-derived porous organic cage and covalent organic frameworks: Syntheses, structures, and iodine vapor capture. Chinese Chemical Letters, 2024, 35(9): 109201-. doi: 10.1016/j.cclet.2023.109201
4. [4]
  Fei Jin , Bolin Yang , Xuanpu Wang , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne (CnH2n-2) electron transport layer. Chinese Journal of Structural Chemistry, 2023, 42(12): 100198-100198. doi: 10.1016/j.cjsc.2023.100198
5. [5]
  Hui Gu , Mingyue Gao , Kuan Shen , Tianli Zhang , Junhao Zhang , Xiangjun Zheng , Xingmei Guo , Yuanjun Liu , Fu Cao , Hongxing Gu , Qinghong Kong , Shenglin Xiong . F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage. Chinese Chemical Letters, 2024, 35(9): 109273-. doi: 10.1016/j.cclet.2023.109273
6. [6]
  Zeyu XU , Tongzhou LU , Haibo SHAO , Jianming WANG . Preparation and electrochemical lithium storage performance of porous silicon microsphere composite with metal modification and carbon coating. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1995-2008. doi: 10.11862/CJIC.20240164
7. [7]
  Wengao Zeng , Yuchen Dong , Xiaoyuan Ye , Ziying Zhang , Tuo Zhang , Xiangjiu Guan , Liejin Guo . Crystalline carbon nitride with in-plane built-in electric field accelerates carrier separation for excellent photocatalytic hydrogen evolution. Chinese Chemical Letters, 2024, 35(4): 109252-. doi: 10.1016/j.cclet.2023.109252
8. [8]
  Luyan Shi , Ke Zhu , Yuting Yang , Qinrui Liang , Qimin Peng , Shuqing Zhou , Tayirjan Taylor Isimjan , Xiulin Yang . Phytic acid-derivative Co₂B-CoPO_x coralloidal structure with delicate boron vacancy for enhanced hydrogen generation from sodium borohydride. Chinese Chemical Letters, 2024, 35(4): 109222-. doi: 10.1016/j.cclet.2023.109222
9. [9]
  Ying Li , Yanjun Xu , Xingqi Han , Di Han , Xuesong Wu , Xinlong Wang , Zhongmin Su . A new metal–organic rotaxane framework for enhanced ion conductivity of solid-state electrolyte in lithium-metal batteries. Chinese Chemical Letters, 2024, 35(9): 109189-. doi: 10.1016/j.cclet.2023.109189
10. [10]
  Jinfeng Chu , Lan Jin , Yu-Fei Song . Exploration and Practice of Flipped Classroom in Inorganic Chemistry Experiment: a Case Study on the Preparation of Inorganic Crystalline Compounds. University Chemistry, 2024, 39(2): 248-254. doi: 10.3866/PKU.DXHX202308016
11. [11]
  Yan Liu , Yuexiang Zhu , Luhua Lai . Introduction to Blended and Small-Class Teaching in Structural Chemistry: Exploring the Structure and Properties of Crystals. University Chemistry, 2024, 39(3): 1-4. doi: 10.3866/PKU.DXHX202306084
12. [12]
  Junqiao Zhuo , Xinchen Huang , Qi Wang . Symbol Representation of the Packing-Filling Model of the Crystal Structure and Its Application. University Chemistry, 2024, 39(3): 70-77. doi: 10.3866/PKU.DXHX202311100
13. [13]
  Jiangping Chen , Hongju Ren , Kai Wu , Huihuang Fang , Chongqi Chen , Li Lin , Yu Luo , Lilong Jiang . Boosting hydrogen production of ammonia decomposition via the construction of metal-oxide interfaces. Chinese Journal of Structural Chemistry, 2024, 43(2): 100236-100236. doi: 10.1016/j.cjsc.2024.100236
14. [14]
  Liangji Chen , Zhen Yuan , Fudong Feng , Xin Zhou , Zhile Xiong , Wuji Wei , Hao Zhang , Banglin Chen , Shengchang Xiang , Zhangjing Zhang . A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids. Chinese Chemical Letters, 2024, 35(9): 109344-. doi: 10.1016/j.cclet.2023.109344
15. [15]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
16. [16]
  Minying Wu , Xueliang Fan , Wenbiao Zhang , Bin Chen , Tong Ye , Qian Zhang , Yuanyuan Fang , Yajun Wang , Yi Tang . Highly dispersed Ru nanospecies on N-doped carbon/MXene composite for highly efficient alkaline hydrogen evolution. Chinese Chemical Letters, 2024, 35(4): 109258-. doi: 10.1016/j.cclet.2023.109258
17. [17]
  Xiao Li , Wanqiang Yu , Yujie Wang , Ruiying Liu , Qingquan Yu , Riming Hu , Xuchuan Jiang , Qingsheng Gao , Hong Liu , Jiayuan Yu , Weijia Zhou . Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption. Chinese Chemical Letters, 2024, 35(8): 109166-. doi: 10.1016/j.cclet.2023.109166
18. [18]
  Ping Wang , Ting Wang , Ming Xu , Ze Gao , Hongyu Li , Bowen Li , Yuqi Wang , Chaoqun Qu , Ming Feng . Keplerate polyoxomolybdate nanoball mediated controllable preparation of metal-doped molybdenum disulfide for electrocatalytic hydrogen evolution in acidic and alkaline media. Chinese Chemical Letters, 2024, 35(7): 108930-. doi: 10.1016/j.cclet.2023.108930
19. [19]
  Zhijia Zhang , Shihao Sun , Yuefang Chen , Yanhao Wei , Mengmeng Zhang , Chunsheng Li , Yan Sun , Shaofei Zhang , Yong Jiang . Epitaxial growth of Cu_2-xSe on Cu (220) crystal plane as high property anode for sodium storage. Chinese Chemical Letters, 2024, 35(7): 108922-. doi: 10.1016/j.cclet.2023.108922
20. [20]
  Jiao Li , Chenyang Zhang , Chuhan Wu , Yan Liu , Xuejian Zhang , Xiao Li , Yongtao Li , Jing Sun , Zhongmin Su . Defined organic-octamolybdate crystalline superstructures derived Mo₂C@C as efficient hydrogen evolution electrocatalysts. Chinese Chemical Letters, 2024, 35(6): 108782-. doi: 10.1016/j.cclet.2023.108782

Get Citation

PDF

XML

Metrics

PDF Downloads(21)
Abstract views(949)
HTML views(122)

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