Citation: Zhang Jianyu, Shao Youxiang, Li Yinwu, Liu Yan, Ke Zhuofeng. Rational design of FLP catalysts for reversible H₂ activation: A DFT study of the geometric and electronic effects[J]. Chinese Chemical Letters, ;2018, 29(8): 1226-1232. doi: 10.1016/j.cclet.2018.02.007 shu

Rational design of FLP catalysts for reversible H₂ activation: A DFT study of the geometric and electronic effects

Zhang Jianyu ^a,1 ,
Shao Youxiang ^a,1 ,
Li Yinwu ^a ,
Liu Yan ^b,, ,
Ke Zhuofeng ^a,,

a.
School of Chemistry, School of Materials Science & Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, China
b.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Higher Education Mega Center, Guangzhou 510006, China

Corresponding author: Liu Yan, yanliu@gdut.edu.cn Ke Zhuofeng, kezhf3@mail.sysu.edu.cn

Received Date: 15 December 2017
Revised Date: 30 January 2018
Accepted Date: 10 February 2018
Available Online: 15 August 2018

Figures(7)

Frustrated Lewis pairs (FLPs) emerge as a new type of bifunctional metal-free catalysts for reversible H₂ activation, which is important for the storage and liberation of H₂ or further controllable utilizing chemical fuels via hydrogenation/dehydrogenation. Herein, a DFT study was conducted to understand the geometric factors and electronic effects of FLPs on reversible H₂ activation. The Lewis base group mainly contributes to the proton attachment, and influences the kinetics of the H₂ activation. The Lewis acid group mainly relates to the hydride attachment, and affects more significantly on the thermodynamics of H₂ activation. The dimer and quenched structure of FLPs also have a degree of influence on the performance of catalyzed H₂ activation. A series of FLPs with para-substituted phenyl derivatives as LA groups were designed and evaluated. The results indicate that the variation of LA groups has significant impact on thermodynamic energy of dihydrogen adducts but insignificant effect on kinetics. Moreover, we found the thermodynamic energy of products has a good linear relationship with Hammett substituent constants. The solvent effect on H₂ activation was also studied, and polar solvent is beneficial for zwitterionic products. These results should provide deeper insight to understand the relation between FLPs structure and reactivity, which is critical for rational design of more efficient FLPs catalysts for reversible H₂ activation.
- Frustrated Lewis pairs,
- Reversible H₂ activation,
- Density functional theory,
- Hammett constants,
- Kinetic,
- Thermodynamic
1. [1]
  S. Satyapal, J. Petrovic, C. Read, G. Thomas, G. Ordaz, Catal. Today 120(2007) 246-256. doi: 10.1016/j.cattod.2006.09.022
2. [2]
  L. Schlapbach, A. Zuttel, Nature 414(2001) 353-358. doi: 10.1038/35104634
3. [3]
  D. Xu, C. Shan, Y. Li, et al., Inorg. Chem. Front. 4(2017) 1813-1820. doi: 10.1039/C7QI00459A
4. [4]
  D. Xu, C. Shan, R. Bai, Y. Lan, Chin. J. Org. Chem. 37(2017) 1231-1236. doi: 10.6023/cjoc201701033
5. [5]
  T. He, N.P. Tsvetkov, J.G. Andino, et al., J. Am. Chem. Soc. 132(2010) 910-911. doi: 10.1021/ja908674x
6. [6]
  T. Kimura, N. Koiso, K. Ishiwata, S. Kuwata, T. Ikariya, J. Am. Chem. Soc. 133(2011) 8880-8883. doi: 10.1021/ja203538b
7. [7]
  D.M. Camaioni, B. Ginovska-Pangovska, G.K. Schenter, S.M. Kathmann, T. Autrey, J. Phys. Chem. A 116(2012) 7228-7237. doi: 10.1021/jp3039829
8. [8]
  G.C. Welch, R.R.S. Juan, J.D. Masuda, D.W. Stephan, Science 314(2006) 1124. doi: 10.1126/science.1134230
9. [9]
  D.W. Stephan, Org. Biomol. Chem. 6(2008) 1535-1539. doi: 10.1039/b802575b
10. [10]
  D.W. Stephan, G. Erker, Angew. Chem. Int. Ed. 49(2010) 46-76. doi: 10.1002/anie.200903708
11. [11]
  D.W. Stephan, Org. Biomol. Chem. 10(2012) 5740-5746. doi: 10.1039/c2ob25339a
12. [12]
  D. W. Stephan, G. Erker, Frustrated Lewis pair mediated hydrogenations, in: G. Erker, D. W. Stephan (Eds. ), Frustrated Lewis Pairs I: Uncovering and Understanding, Springer, Berlin, Heidelberg, 2013, pp. 85-110.
13. [13]
  Y. Wang, W. Chen, Z. Lu, Z.H. Li, H. Wang, Angew. Chem. Int. Ed. 52(2013) 7496-7499. doi: 10.1002/anie.201303500
14. [14]
  M.A. Dureen, A. Lough, T.M. Gilbert, D.W. Stephan, Chem. Commun. (2008) 4303-4305.
15. [15]
  M.H. Holthausen, J.M. Bayne, I. Mallov, R. Dobrovetsky, D.W. Stephan, J. Am. Chem. Soc. 137(2015) 7298-7301. doi: 10.1021/jacs.5b04109
16. [16]
  M.A. Légaré, M.A. Courtemanche, É. Rochette, F.G. Fontaine, Science 349(2015) 513. doi: 10.1126/science.aab3591
17. [17]
  A.E. Ashley, A.L. Thompson, D. O'Hare, Angew. Chem. Int. Ed. 48(2009) 9839-9843. doi: 10.1002/anie.v48:52
18. [18]
  A.J.P. Cardenas, B.J. Culotta, T.H. Warren, et al., Angew. Chem. Int. Ed. 50(2011) 7567-7571. doi: 10.1002/anie.201101622
19. [19]
  R.C. Neu, E. Otten, A. Lough, D.W. Stephan, Chem. Sci. 2(2011) 170-176. doi: 10.1039/C0SC00398K
20. [20]
  Y. Zhang, G.M. Miyake, E.Y.X. Chen, Angew. Chem. Int. Ed. 49(2010) 10158-10162. doi: 10.1002/anie.201005534
21. [21]
  Y. Zhang, G.M. Miyake, M.G. John, et al., Dalton Trans. 41(2012) 9119-9134. doi: 10.1039/c2dt30427a
22. [22]
  E. Piedra-Arroni, C. Ladavière, A. Amgoune, D. Bourissou, J. Am. Chem. Soc. 135(2013) 13306-13309. doi: 10.1021/ja4069968
23. [23]
  T.A. Rokob, A. Hamza, A. Stirling, T. Soós, I. Pápai, Angew. Chem. Int. Ed. 47(2008) 2435-2438. doi: 10.1002/(ISSN)1521-3773
24. [24]
  C. Hou, J. Jiang, S. Zhang, et al., ACS Catal. 4(2014) 2990-2997. doi: 10.1021/cs500688q
25. [25]
  C. Hou, Z. Zhang, C. Zhao, Z. Ke, Inorg. Chem. 55(2016) 6539-6551. doi: 10.1021/acs.inorgchem.6b00723
26. [26]
  C. Hou, J. Jiang, Y. Li, C. Zhao, Z. Ke, ACS Catal. 7(2017) 786-795. doi: 10.1021/acscatal.6b02505
27. [27]
  Z. Zhang, Y. Li, C. Hou, C. Zhao, Z. Ke, Catal. Sci. Technol. 8(2018) 656-666. doi: 10.1039/C7CY02012K
28. [28]
  Y. Li, C. Hou, J. Jiang, et al., ACS Catal. 6(2016) 1655-1662. doi: 10.1021/acscatal.5b02395
29. [29]
  Y. Li, J. Zhang, S. Shu, et al., Chin. J. Org. Chem. 37(2017) 2187-2202. doi: 10.6023/cjoc201703002
30. [30]
  J. Zhang, J. Lin, Y. Li, et al., Catal. Sci. Technol. 7(2017) 4866-4878. doi: 10.1039/C7CY01217A
31. [31]
  R. Roesler, W.E. Piers, M. Parvez, J. Organomet. Chem. 680(2003) 218-222. doi: 10.1016/S0022-328X(03)00384-X
32. [32]
  K. Chernichenko, M. Nieger, M. Leskela, T. Repo, Dalton Trans. 41(2012) 9029-9032. doi: 10.1039/c2dt30926b
33. [33]
  K. Chernichenko, B. Kótai, I. Pápai, et al., Angew. Chem. Int. Ed. 54(2015) 1749-1753. doi: 10.1002/anie.201410141
34. [34]
  K. Kitaura, K. Morokuma, Int. J. Quantum Chem. 10(1976) 325-340. doi: 10.1002/(ISSN)1097-461X
35. [35]
  K.N. Houk, R.W. Gandour, R.W. Strozier, N.G. Rondan, L.A. Paquette, J. Am. Chem. Soc. 101(1979) 6797-6802. doi: 10.1021/ja00517a001
36. [36]
  F.M. Bickelhaupt, J. Comput. Chem. 20(1999) 114-128. doi: 10.1002/(ISSN)1096-987X
37. [37]
  F.M. Bickelhaupt, K.N. Houk, Angew. Chem. Int. Ed. 56(2017) 10070-10086. doi: 10.1002/anie.201701486
38. [38]
  T.A. Rokob, A. Hamza, I. Pápai, J. Am. Chem. Soc. 131(2009) 10701-10710. doi: 10.1021/ja903878z
39. [39]
  D.J. Scott, M.J. Fuchter, A.E. Ashley, Chem. Soc. Rev. 46(2017) 5689-5700. doi: 10.1039/C7CS00154A
40. [40]
  C. Hansch, A. Leo, R.W. Taft, Chem. Rev. 91(1991) 165-195. doi: 10.1021/cr00002a004
41. [41]
  D. Xu, X. Qi, M. Duan, et al., Org. Chem. Front. 4(2017) 943-950. doi: 10.1039/C6QO00841K
1. [1]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
2. [2]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
3. [3]
  Xu Huang , Kai-Yin Wu , Chao Su , Lei Yang , Bei-Bei Xiao . Metal-organic framework Cu-BTC for overall water splitting: A density functional theory study. Chinese Chemical Letters, 2025, 36(4): 109720-. doi: 10.1016/j.cclet.2024.109720
4. [4]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
5. [5]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
6. [6]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
7. [7]
  Yu-Hang Li , Shuai Gao , Lu Zhang , Hanchun Chen , Chong-Chen Wang , Haodong Ji . Insights on selective Pb adsorption via O 2p orbit in UiO-66 containing rich-zirconium vacancies. Chinese Chemical Letters, 2024, 35(8): 109894-. doi: 10.1016/j.cclet.2024.109894
8. [8]
  Tao Ban , Xi-Yang Yu , Hai-Kuo Tian , Zheng-Qing Huang , Chun-Ran Chang . One-step conversion of methane and formaldehyde to ethanol over SA-FLP dual-active-site catalysts: A DFT study. Chinese Chemical Letters, 2024, 35(4): 108549-. doi: 10.1016/j.cclet.2023.108549
9. [9]
  Lingling Su , Qunyan Wu , Congzhi Wang , Jianhui Lan , Weiqun Shi . Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ). Chinese Chemical Letters, 2024, 35(8): 109402-. doi: 10.1016/j.cclet.2023.109402
10. [10]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
11. [11]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
12. [12]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
13. [13]
  Ze Zhang , Lei Yang , Jin-Ru Liu , Hao Hu , Jian-Li Mi , Chao Su , Bei-Bei Xiao , Zhi-Min Ao . Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination. Chinese Chemical Letters, 2025, 36(2): 110013-. doi: 10.1016/j.cclet.2024.110013
14. [14]
  Teng Wang , Jiachun Cao , Juan Li , Didi Li , Zhimin Ao . A novel photocatalytic mechanism of volatile organic compounds degradation on BaTiO₃ under visible light: Photo-electrons transfer from photocatalyst to pollutant. Chinese Chemical Letters, 2025, 36(3): 110078-. doi: 10.1016/j.cclet.2024.110078
15. [15]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
16. [16]
  Yongheng Ren , Yang Chen , Hongwei Chen , Lu Zhang , Jiangfeng Yang , Qi Shi , Lin-Bing Sun , Jinping Li , Libo Li . Electrostatically driven kinetic Inverse CO2/C2H2 separation in LTA-type zeolites. Chinese Journal of Structural Chemistry, 2024, 43(10): 100394-100394. doi: 10.1016/j.cjsc.2024.100394
17. [17]
  Ruixue Liu , Xiaobing Ding , Qiwei Lang , Gen-Qiang Chen , Xumu Zhang . Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation. Chinese Chemical Letters, 2025, 36(3): 110037-. doi: 10.1016/j.cclet.2024.110037
18. [18]
  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
19. [19]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
20. [20]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(647)
HTML views(3)

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

Rational design of FLP catalysts for reversible H2 activation: A DFT study of the geometric and electronic effects

Metrics

通讯作者: 陈斌, bchen63@163.com

Rational design of FLP catalysts for reversible H₂ activation: A DFT study of the geometric and electronic effects