Citation: CHEN Qiang, JIANG Li-Xue, LI Hai-Fang, CHEN Jiao-Jiao, ZHAO Yan-Xia, HE Sheng-Gui. Thermal Activation of Methane by Diatomic Vanadium Boride Cations[J]. Acta Physico-Chimica Sinica, ;2019, 35(9): 1014-1020. doi: 10.3866/PKU.WHXB201811039 shu

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

CHEN Qiang ^1,2 ,
JIANG Li-Xue ^1,2,3 ,
LI Hai-Fang ^1,2,3 ,
CHEN Jiao-Jiao ^1,2,3 ,
ZHAO Yan-Xia ^1,2,, ,
HE Sheng-Gui ^1,2,3,,

1.
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
2.
Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences, Beijing 100190, P. R. China
3.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: ZHAO Yan-Xia, chemzyx@iccas.ac.cn HE Sheng-Gui, shengguihe@iccas.ac.cn
Received Date: 28 November 2018
Revised Date: 19 December 2018
Accepted Date: 27 December 2018
Available Online: 3 September 2019
Fund Project: The project was supported by the National Natural Science Foundation of China 21773253Youth Innovation Promotion Association, Chinese Academy of Sciences 2018041China Postdoctoral Science Foundation 2017M611002The project was supported by the National Natural Science Foundation of China (91645203, 21773253), China Postdoctoral Science Foundation(2017M611002), Beijing Natural Science Foundation, China (2182092), and Youth Innovation Promotion Association, Chinese Academy of Sciences(2018041)Beijing Natural Science Foundation, China 2182092The project was supported by the National Natural Science Foundation of China 91645203

Methane activation by transition metal species has been extensively investigated over the past few decades. It is observed that ground-state monocations of bare 3d transition metals are inert toward CH₄ at room temperature because of unfavorable thermodynamics. In contrast, many mono-ligated 3d transition metal cations, such as MO⁺ (M = Mn, Fe, Co, Cu, Zn), MH⁺ (M = Fe, Co), and NiX⁺ (X = H, CH₃, F), as well as several bis-ligated 3d transition metal cations including OCrO⁺, Ni(H)(OH)⁺, and Fe(O)(OH)⁺ activate the C―H bond of methane under thermal collision conditions because of the pronounced ligand effects. In most of the above-mentioned examples, the 3d metal atoms are observed to cooperate with the attached ligands to activate the C―H bond. Compared to the extensive studies on active species comprising of middle and late 3d transition metals, the knowledge about the reactivity of early 3d transition metal species toward methane and the related C―H activation mechanisms are still very limited. Only two early 3d transition metal species HMO⁺ (M = Ti and V) are discovered so far to activate the C―H bond of methane via participation of their metal atoms. In this study, by performing mass spectrometric experiments and density functional theory calculations, we have identified that the diatomic vanadium boride cation (VB⁺) can activate methane to produce a dihydrogen molecule and carbon-boron species under thermal collision conditions. The strong electrostatic interaction makes the reaction preferentially proceed the V side. To generate experimentally observed product ions, a two-state reactivity scenario involving spin conversion from high-spin sextet to low-spin quartet is necessary at the entrance of the reaction. This result is consistent with the reported reactions of 3d transition metal species with CH₄, in which the C―H bond cleavage generally occurs in the low-spin states, even if the ground states of the related active species are in the high-spin states. For VB⁺ + CH₄, the insertion of the synergetic V―B unit (rather than a single V or B atom) into the H₃C―H bond causes the initial C―H bond activation driven by the strong bond strengths of V―CH₃ and B―H. The mechanisms of methane activation by VB⁺ discussed in this study may provide useful guidance to the future studies on methane activation by early transition metal systems.
- Methane activation,
- Early transition metal,
- Boron,
- Mass spectrometry,
- Density functional theory
1. [1]
  Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879. doi: 10.1021/cr9411886 doi: 10.1021/cr9411886
2. [2]
  Wang, V. C.; Maji, S.; Chen, P. P.; Lee, H. K.; Yu, S. S.; Chan, S. I. Chem. Rev. 2017, 117, 8574. doi: 10.1021/acs.chemrev.6b00624 doi: 10.1021/acs.chemrev.6b00624
3. [3]
  Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. doi: 10.1038/417507a doi: 10.1038/417507a
4. [4]
  Olivos-Suarez, A. I.; Szécsényi, À.; Hensen, E. J. M.; Ruiz-Martinez, J.; Pidko, E. A.; Gascon, J. ACS Catal. 2016, 6, 2965. doi: 10.1021/acscatal.6b00428 doi: 10.1021/acscatal.6b00428
5. [5]
  Böhme, D. K.; Schwarz, H. Angew. Chem. Int. Ed. 2005, 44, 2336. doi: 10.1002/anie.200461698 doi: 10.1002/anie.200461698
6. [6]
  Johnson, G. E.; Mitrić, R.; Bonačić-Koutecký, V.; Castleman, A. W., Jr. Chem. Phys. Lett. 2009, 475, 1. doi: 10.1016/j.cplett.2009.04.003 doi: 10.1016/j.cplett.2009.04.003
7. [7]
  Zhai, H. -J.; Wang, L. -S. Chem. Phys. Lett. 2010, 500, 185. doi: 10.1016/j.cplett.2010.10.001 doi: 10.1016/j.cplett.2010.10.001
8. [8]
  Yin, S.; Bernstein, E. R. Int. J. Mass Spectrom. 2012, 321-322, 49. doi: 10.1016/j.ijms.2012.06.001 doi: 10.1016/j.ijms.2012.06.001
9. [9]
  O'Hair, R. A. J. Int. J. Mass Spectrom. 2015, 377, 121. doi: 10.1016/j.ijms.2014.05.003 doi: 10.1016/j.ijms.2014.05.003
10. [10]
  Lang, S. M.; Bernhardt, T. M.; Chernyy, V.; Bakker, J. M.; Barnett, R. N.; Landman, U. Angew. Chem. Int. Ed. 2017, 56, 13406. doi: 10.1002/anie.201706009 doi: 10.1002/anie.201706009
11. [11]
  Asmis, K. R.; Fielicke, A. Top. Catal. 2018, 61, 1. doi: 10.1007/s11244-018-0906-5 doi: 10.1007/s11244-018-0906-5
12. [12]
  Roithová, J.; Schrӧder, D. Chem. Rev. 2010, 110, 1170. doi: 10.1021/cr900183p doi: 10.1021/cr900183p
13. [13]
  Schwarz, H. Angew. Chem. Int. Ed. 2011, 50, 10096. doi: 10.1002/anie.201006424 doi: 10.1002/anie.201006424
14. [14]
  Schwarz, H.; González-Navarrete, P.; Li, J.; Schlangen, M.; Sun, X.; Weiske, T.; Zhou, S. Organometallics 2017, 36, 8. doi: 10.1021/acs.organomet.6b00372 doi: 10.1021/acs.organomet.6b00372
15. [15]
  Wang, D.; Ding, X. -L.; Liao, H.; Dai, J. Acta Phys. -Chim. Sin. 2019, in press. doi: 10.3866/PKU.WHXB201809006
16. [16]
  Buckner, S. W.; MacMahon, T. J.; Byrd, G. D.; Freiser, B. S. Inorg. Chem. 1989, 28, 3511. doi: 10.1021/ic00317a024 doi: 10.1021/ic00317a024
17. [17]
  Irikura, K. K.; Beauchamp, J. L. J. Am. Chem. Soc. 1991, 113, 2769. doi: 10.1021/ja00007a070 doi: 10.1021/ja00007a070
18. [18]
  Irikura, K. K.; Beauchamp, J. L. J. Phys. Chem. 1991, 95, 8344. doi: 10.1021/j100174a057 doi: 10.1021/j100174a057
19. [19]
  Shayesteh, A.; Lavrov, V. V.; Koyanagi, G. K.; Bohme, D. K. J. Phys. Chem. A 2009, 113, 5602. doi: 10.1021/jp900671c doi: 10.1021/jp900671c
20. [20]
  Schröder, D.; Schwarz, H. Angew. Chem. Int. Ed. Engl. 1990, 29, 1433. doi: 10.1002/anie.199014331 doi: 10.1002/anie.199014331
21. [21]
  Schröeder, D.; Fiedler, A.; Hrusak, J.; Schwarz, H. J. Am. Chem. Soc. 1992, 114, 1215. doi: 10.1021/ja00030a014 doi: 10.1021/ja00030a014
22. [22]
  Chen, Y. -M.; Clemmer, D. E.; Armentrout, P. B. J. Am. Chem. Soc. 1994, 116, 7815. doi: 10.1021/ja00096a044 doi: 10.1021/ja00096a044
23. [23]
  Ryan, M. F.; Fiedler, A.; Schröeder, D.; Schwarz, H. Organometallics 1994, 13, 4072. doi: 10.1021/om00022a051 doi: 10.1021/om00022a051
24. [24]
  Ryan, M. F.; Fiedler, A.; Schroeder, D.; Schwarz, H. J. Am. Chem. Soc. 1995, 117, 2033. doi: 10.1021/ja00112a017 doi: 10.1021/ja00112a017
25. [25]
  Schröder, D.; Schwarz, H.; Clemmer, D. E.; Chen, Y.; Armentrout, P. B.; Baranov, V. I.; Böhme, D. K. Int. J. Mass Spectrom. Ion Processes 1997, 161, 175. doi: 10.1016/S0168-1176(96)04428-X doi: 10.1016/S0168-1176(96)04428-X
26. [26]
  Aguirre, F.; Husband, J.; Thompson, C. J.; Stringer, K. L.; Metz, R. B. J. Chem. Phys. 2002, 116, 4071. doi: 10.1063/1.1448489 doi: 10.1063/1.1448489
27. [27]
  Dietl, N.; van der Linde, C.; Schlangen, M.; Beyer, M. K.; Schwarz, H. Angew. Chem. Int. Ed. 2011, 50, 4966. doi: 10.1002/anie.201100606 doi: 10.1002/anie.201100606
28. [28]
  Ard, S. G.; Melko, J. J.; Ushakov, V. G.; Johnson, R.; Fournier, J. A.; Shuman, N. S.; Guo, H.; Troe, J.; Viggiano, A. A. J. Phys. Chem. A 2014, 118, 2029. doi: 10.1021/jp5000705 doi: 10.1021/jp5000705
29. [29]
  Yue, L.; Li, J.; Zhou, S.; Sun, X.; Schlangen, M.; Shaik, S.; Schwarz, H. Angew. Chem. Int. Ed. 2017, 56, 10219. doi: 10.1002/anie.201703485 doi: 10.1002/anie.201703485
30. [30]
  Carlin, T. J.; Sallans, L.; Cassady, C. J.; Jacobson, D. B.; Freiser, B. S. J. Am. Chem. Soc. 1983, 105, 6320. doi: 10.1021/ja00358a027 doi: 10.1021/ja00358a027
31. [31]
  Zhang, Q.; Bowers, M. T. J. Phys. Chem. A 2004, 108, 9755. doi: 10.1021/jp047943t doi: 10.1021/jp047943t
32. [32]
  Liu, S.; Geng, Z.; Wang, Y.; Yan, Y. J. Phys. Chem. A 2012, 116, 4560. doi: 10.1021/jp210924a doi: 10.1021/jp210924a
33. [33]
  Schlangen, M.; Schroder, D.; Schwarz, H. Chem. Eur. J. 2007, 13, 6810. doi: 10.1002/chem.200700506 doi: 10.1002/chem.200700506
34. [34]
  Armélin, M.; Schlangen, M.; Schwarz, H. Chem. Eur. J. 2008, 14, 5229. doi: 10.1002/chem.200800029 doi: 10.1002/chem.200800029
35. [35]
  Schlangen, M.; Schwarz, H. Helv. Chim. Acta 2008, 91, 2203. doi: 10.1002/hlca.200890238 doi: 10.1002/hlca.200890238
36. [36]
  Fiedler, A.; Kretzschmar, I.; Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 9941. doi: 10.1021/ja960157k doi: 10.1021/ja960157k
37. [37]
  Schlangen, M.; Schroder, D.; Schwarz, H. Angew. Chem. Int. Ed. 2007, 46, 1641. doi: 10.1002/anie.200603266 doi: 10.1002/anie.200603266
38. [38]
  Dede, Y.; Zhang, X.; Schlangen, M.; Schwarz, H.; Baik, M. H. J. Am. Chem. Soc. 2009, 131, 12634. doi: 10.1021/ja902093f doi: 10.1021/ja902093f
39. [39]
  Lakuntza, O.; Matxain, J. M.; Ruiperez, F.; Besora, M.; Maseras, F.; Ugalde, J. M.; Schlangen, M.; Schwarz, H. Phys. Chem. Chem. Phys. 2012, 14, 9306. doi: 10.1039/C2CP23502A doi: 10.1039/C2CP23502A
40. [40]
  Schröder, D.; Schwarz, H. Angew. Chem. Int. Ed. Engl. 1991, 30, 991. doi: 10.1002/anie.199109911 doi: 10.1002/anie.199109911
41. [41]
  Kretschmer, R.; Schlangen, M.; Schwarz, H. Angew. Chem. Int. Ed. 2013, 52, 6097. doi: 10.1002/anie.201300900 doi: 10.1002/anie.201300900
42. [42]
  Chen, Q.; Zhao, Y. -X.; Jiang, L. -X.; Li, H. -F.; Chen, J. -J.; Zhang, T.; Liu, Q. -Y.; He, S. -G. Phys. Chem. Chem. Phys. 2018, 20, 4641. doi: 10.1039/C8CP00071A doi: 10.1039/C8CP00071A
43. [43]
  Chen, Q.; Zhao, Y. -X.; Jiang, L. -X.; Chen, J. -J.; He, S. -G. Angew. Chem. Int. Ed. 2018, 57, 14134. doi: 10.1002/anie.201808780 doi: 10.1002/anie.201808780
44. [44]
  Shaik, S.; Danovich, D.; Fiedler, A.; Schröder, D.; Schwarz, H. Helv. Chim. Acta 1995, 78, 1393. doi: 10.1002/hlca.19950780602 doi: 10.1002/hlca.19950780602
45. [45]
  Wu, X. -N.; Xu, B.; Meng, J. -H.; He, S. -G. Int. J. Mass Spectrom. 2012, 310, 57. doi: 10.1016/j.ijms.2011.11.011 doi: 10.1016/j.ijms.2011.11.011
46. [46]
  Yuan, Z.; Zhao, Y. -X.; Li, X. -N.; He, S. -G. Int. J. Mass Spectrom. 2013, 354-355, 105. doi: 10.1016/j.ijms.2013.06.004 doi: 10.1016/j.ijms.2013.06.004
47. [47]
  Yuan, Z.; Liu, Q. -Y.; Li, X. -N.; He, S. -G. Int. J. Mass Spectrom. 2016, 407, 62. doi: 10.1016/j.ijms.2016.07.004 doi: 10.1016/j.ijms.2016.07.004
48. [48]
  Gioumousis, G.; Stevenson, D. P. J. Chem. Phys. 1958, 29, 294. doi: 10.1063/1.1744477 doi: 10.1063/1.1744477
49. [49]
  Kummerlowe, G.; Beyer, M. K. Int. J. Mass Spectrom. 2005, 244, 84. doi: 10.1016/j.ijms.2005.03.012 doi: 10.1016/j.ijms.2005.03.012
50. [50]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 09, Revision D.01; Gaussian Inc.: Wallingford CT, USA, 2009.
51. [51]
  Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2006, 125, 194101. doi: 10.1063/1.2370993 doi: 10.1063/1.2370993
52. [52]
  Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829. doi: 10.1063/1.467146 doi: 10.1063/1.467146
53. [53]
  Schlegel, H. B. J. Comput. Chem. 1982, 3, 214. doi: 10.1002/jcc.540030212 doi: 10.1002/jcc.540030212
54. [54]
  Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154. doi: 10.1063/1.456010 doi: 10.1063/1.456010
55. [55]
  Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO 3.1; Theoretical Chemistry Institute, University of Wisconsin: Madison, WI, USA, 1996.
56. [56]
  Lide, D. R. Handbook of Chemistry and Physics, 84th Ed.; CRC Press: Boca Raton, USA, 2003; Sect. 9, p. 52.
1. [1]
  Tian Feng , Yun-Ling Gao , Di Hu , Ke-Yu Yuan , Shu-Yi Gu , Yao-Hua Gu , Si-Yu Yu , Jun Xiong , Yu-Qi Feng , Jie Wang , Bi-Feng Yuan . Chronic sleep deprivation induces alterations in DNA and RNA modifications by liquid chromatography-mass spectrometry analysis. Chinese Chemical Letters, 2024, 35(8): 109259-. doi: 10.1016/j.cclet.2023.109259
2. [2]
  Cheng Guo , Xiaoxiao Zhang , Xiujuan Hong , Yiqiu Hu , Lingna Mao , Kezhi Jiang . Graphene as adsorbent for highly efficient extraction of modified nucleosides in urine prior to liquid chromatography-tandem mass spectrometry analysis. Chinese Chemical Letters, 2024, 35(4): 108867-. doi: 10.1016/j.cclet.2023.108867
3. [3]
  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
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]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
6. [6]
  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
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]
  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
9. [9]
  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
10. [10]
  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
11. [11]
  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
12. [12]
  Wei Shao , Wanqun Zhang , Pingping Zhu , Wanqun Hu , Qiang Zhou , Weiwei Li , Kaiping Yang , Xisheng Wang . Design and Practice of Ideological and Political Cases in the Course of Instrument Analysis Experiment: Taking the GC-MS Experiment as an Example. University Chemistry, 2024, 39(2): 147-154. doi: 10.3866/PKU.DXHX202309048
13. [13]
  Boqiang Wang , Yongzhuo Xu , Jiajia Wang , Muyang Yang , Guo-Jun Deng , Wen Shao . Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines. Chinese Chemical Letters, 2024, 35(9): 109502-. doi: 10.1016/j.cclet.2024.109502
14. [14]
  Qianqian Song , Yunting Zhang , Jianli Liang , Si Liu , Jian Zhu , Xingbin Yan . Boron nitride nanofibers enhanced composite PEO-based solid-state polymer electrolytes for lithium metal batteries. Chinese Chemical Letters, 2024, 35(6): 108797-. doi: 10.1016/j.cclet.2023.108797
15. [15]
  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
16. [16]
  Qiang Fu , Shouhong Sun , Kangzhi Lu , Ning Li , Zhanhua Dong . Boron-doped carbon dots: Doping strategies, performance effects, and applications. Chinese Chemical Letters, 2024, 35(7): 109136-. doi: 10.1016/j.cclet.2023.109136
17. [17]
  Tinghui Yang , Min Kuang , Jianping Yang . Mesoporous CuCe dual-metal catalysts for efficient electrochemical reduction of CO2 to methane. Chinese Journal of Structural Chemistry, 2024, 43(8): 100350-100350. doi: 10.1016/j.cjsc.2024.100350
18. [18]
  Chunxiu Yu , Zelin Wu , Hongle Shi , Lingyun Gu , Kexin Chen , Chuan-Shu He , Yang Liu , Heng Zhang , Peng Zhou , Zhaokun Xiong , Bo Lai . Insights into the electron transfer mechanisms of peroxydisulfate activation by modified metal-free acetylene black for degradation of sulfisoxazole. Chinese Chemical Letters, 2024, 35(8): 109334-. doi: 10.1016/j.cclet.2023.109334
19. [19]
  Yinyin Xu , Yuanyuan Li , Jingbo Feng , Chen Wang , Yan Zhang , Yukun Wang , Xiuwen Cheng . Covalent organic frameworks doped with manganese-metal organic framework for peroxymonosulfate activation. Chinese Chemical Letters, 2024, 35(4): 108838-. doi: 10.1016/j.cclet.2023.108838
20. [20]
  Yunfei Shen , Long Chen . Gradient imprinted Zn metal anodes assist dendrites-free at high current density/capacity. Chinese Journal of Structural Chemistry, 2024, 43(10): 100321-100321. doi: 10.1016/j.cjsc.2024.100321

Get Citation

PDF

XML

Metrics

PDF Downloads(14)
Abstract views(1073)
HTML views(110)

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