非晶态镍硼酸盐结构的EXAFS研究

引用本文: 刘红艳, 房春晖, 房艳, 周永全, 朱发岩, 戈海文, 杨子祥, 唐玉玲. 非晶态镍硼酸盐结构的EXAFS研究[J]. 物理化学学报, 2014, 30(11): 1979-1986. doi: 10.3866/PKU.WHXB201409251 shu

Citation: LIU Hong-Yan, FANG Chun-Hui, FANG Yan, ZHOU Yong-Quan, ZHU Fa-Yan, GE Hai-Wen, YANG Zi-Xiang, TANG Yu-Ling. EXAFS Study of the Structure of Amorphous Nickel Borate[J]. Acta Physico-Chimica Sinica, 2014, 30(11): 1979-1986. doi: 10.3866/PKU.WHXB201409251 shu

非晶态镍硼酸盐结构的EXAFS研究

基金项目:
国家自然科学基金项目(21373251) (21373251)

中国科学院知识创新工程重要方向项目(KZCX2-EW-307)资助 (KZCX2-EW-307)

摘要:

由摩尔比分别为1:2和1:8的NiCl₂·6H₂O和Na₂B₄O₇·10H₂O作为反应物, 合成两种非晶态镍硼酸盐, 同时通过水热法合成β-Ni(OH)₂. 化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B₂O₃·4.5H₂O和NiO·B₂O₃·3H₂O. 激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B₃O₃(OH)₅^2-和B₂O(OH)₆^2-. 同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析, 通过数据拟合给出样品中Ni 原子周围近邻配位原子种类、配位数以及原子间距离. 用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明, 样品中Ni 原子周围局域结构与Ni₃B₂O₆晶体(ICSD No.31387)中的吻合较好. Ni 原子周围配位原子为O、B和Ni, 对于NiO·0.8B₂O₃·4.5H₂O, 配位数分别为5.7、3.8和3.8, 配位距离分别为0.208、0.263 和0.311 nm; 对于NiO·B₂O₃·3H₂O, 配位数分别为6.0、4.0 和4.0, 配位距离分别为0.207、0.262和0.310 nm.

关键词:

English

EXAFS Study of the Structure of Amorphous Nickel Borate

1.
1. CAS Key Laboratory of Salt Lake Resources and Chemistry, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, P. R. China;
2. University of Chinese Academy of Sciences, Beijing 100049, P. R. China
Received Date: 06 August 2014
Available Online: 30 October 2014
Fund Project:
国家自然科学基金项目(21373251)

中国科学院知识创新工程重要方向项目(KZCX2-EW-307)资助

Abstract:

In this work, two amorphous hydrated nickel borates were synthesized with nickel chloride hexahydrate and borax as reactants at mole ratios of 1:2 and 1:8, respectively. The chemical compositions of these nickel borates were determined to be NiO·0.8B₂O₃·4.5H₂O and NiO·B₂O₃·3H₂O through thermogravimetryderivative thermogravimetry (TG-DTG) and chemical analysis, in which the main anions were determined to be B₃O₃(OH)₅^2- and B₂O(OH)₆^2-, respectively, by Raman spectroscopy. The local structure of these samples was studied by synchrotron radiation extended X-ray absorption fine structure (EXAFS). Based on the processing and fitting of the EXAFS experimental data, the neighboring coordination atoms type, the interatomic distances, and the atom-pair numbers of Ni were determined. The fitting results of the amorphous nickel borate show that the local structure around the Ni atom has a similar structure to that of the Ni₃B₂O₆ crystal. The neighboring coordination atoms of Ni in these amorphous nickel borates are O, B, and Ni. For NiO·0.8B₂O₃·4.5H₂O, the interatomic distances for Ni―O, Ni―B, and Ni―Ni are 0.208, 0.263, and 0.311 nm, and the atom-pair numbers are 5.7, 3.8, and 3.8, respectively. The interatomic distances of NiO·B₂O₃·3H₂O are 0.207, 0.262, and 0.310 nm, and the atom-pair numbers are 6.0, 4.0, and 4.0, respectively. The first shells of Ni²⁺ in NiO·0.8B₂O₃·4.5H₂O and NiO·B₂O₃·3H₂O are octahedral with six oxygen atoms.

Key words:

Nickel borate
/ Nickel hydroxide
/ Extended X-ray absorption fine structure
/ Local structure
/ Coordination atom

1. [1]
  
  (1) Dinca, M.; Surendranath, Y.; Nocera, D. G. Proc. Natl. Acad. Sci . U. S. A. 2010, 107, 10337. doi: 10.1073/pnas.1001859107
  (1) Dinca, M.; Surendranath, Y.; Nocera, D. G. Proc. Natl. Acad. Sci . U. S. A. 2010, 107, 10337. doi: 10.1073/pnas.1001859107
2. [2]
  (2) Chen, X.; Xue, H. P.; Chang, X. N.; Zhang, L.; Zhao, Y. H.; Zuo, J. L.; Zang, H. G.; Xiao,W. Q. J. Alloy. Compd. 2006, 425, 96. doi: 10.1016/j.jallcom.2006.01.068(2) Chen, X.; Xue, H. P.; Chang, X. N.; Zhang, L.; Zhao, Y. H.; Zuo, J. L.; Zang, H. G.; Xiao,W. Q. J. Alloy. Compd. 2006, 425, 96. doi: 10.1016/j.jallcom.2006.01.068
3. [3]
  (3) Zhang, Y.; Liang, J. K.; Chen, X. L.; He, M.; Xu, T. J. Alloy. Compd. 2001, 327, 96. doi: 10.1016/S0925-8388(01)01405-0(3) Zhang, Y.; Liang, J. K.; Chen, X. L.; He, M.; Xu, T. J. Alloy. Compd. 2001, 327, 96. doi: 10.1016/S0925-8388(01)01405-0
4. [4]
  (4) Keszler, D. A. Curr. Opin. Solid State Mater. Sci. 1999, 4, 155. doi: 10.1016/S1359-0286(99)00011-X(4) Keszler, D. A. Curr. Opin. Solid State Mater. Sci. 1999, 4, 155. doi: 10.1016/S1359-0286(99)00011-X
5. [5]
  (5) Giese, R. F., Jr. Science 1966, 154, 1453. doi: 10.1126/science.154.3755.1453(5) Giese, R. F., Jr. Science 1966, 154, 1453. doi: 10.1126/science.154.3755.1453
6. [6]
  (6) Ma, R. Z.; Bando, Y.; Sato, T.; lberg, D.; Zhu, H. G.; Xu, C. L.;Wu, D. H. Appl. Phys. Lett. 2002, 81, 3467. doi: 10.1063/1.1517178(6) Ma, R. Z.; Bando, Y.; Sato, T.; lberg, D.; Zhu, H. G.; Xu, C. L.;Wu, D. H. Appl. Phys. Lett. 2002, 81, 3467. doi: 10.1063/1.1517178
7. [7]
  (7) Debart, A.; Revel, B.; Dupont, L.; Montagne, L.; Leriche, J. B.; Touboul, M.; Tarascon, J. M. Chem. Mater. 2003, 15, 3683. doi: 10.1021/cm030057v(7) Debart, A.; Revel, B.; Dupont, L.; Montagne, L.; Leriche, J. B.; Touboul, M.; Tarascon, J. M. Chem. Mater. 2003, 15, 3683. doi: 10.1021/cm030057v
8. [8]
  (8) Bediako, D. K.; Lassalle-Kaiser, B.; Surendranath, Y.; Yano, J. Yachandra, V. K.; Nocera, D. G. J. Am. Chem. Soc. 2012, 134, 6801. doi: 10.1021/ja301018q(8) Bediako, D. K.; Lassalle-Kaiser, B.; Surendranath, Y.; Yano, J. Yachandra, V. K.; Nocera, D. G. J. Am. Chem. Soc. 2012, 134, 6801. doi: 10.1021/ja301018q
9. [9]
  (9) Bediako, D. K.; Surendranath, Y.; Nocera, D. G. J. Am. Chem. Soc. 2013, 135, 3662. doi: 10.1021/ja3126432(9) Bediako, D. K.; Surendranath, Y.; Nocera, D. G. J. Am. Chem. Soc. 2013, 135, 3662. doi: 10.1021/ja3126432
10. [10]
  (10) Nocera, D. G. Inorg. Chem. 2009, 48, 10001. doi: 10.1021/ic901328v(10) Nocera, D. G. Inorg. Chem. 2009, 48, 10001. doi: 10.1021/ic901328v
11. [11]
  (11) Lewis, N. S.; Nocera, D. G. Proc. Natl. Acad. Sci . U. S. A. 2006, 103,15729. doi: 10.1073/pnas.0603395103(11) Lewis, N. S.; Nocera, D. G. Proc. Natl. Acad. Sci . U. S. A. 2006, 103,15729. doi: 10.1073/pnas.0603395103
12. [12]
  (12) Menaka, S. E.; Sharma, S.; Ramanujachary, K. V.; Lofland, S. E.; Ganguli, A. K. J. Colloid Interface Sci. 2011, 360, 393. doi: 10.1016/j.jcis.2011.04.100(12) Menaka, S. E.; Sharma, S.; Ramanujachary, K. V.; Lofland, S. E.; Ganguli, A. K. J. Colloid Interface Sci. 2011, 360, 393. doi: 10.1016/j.jcis.2011.04.100
13. [13]
  (13) Pang, H.; Lu, Q. Y.; Chen, C. Y.; Liu, X. R.; Gao, F. J. Mater. Chem. 2011, 21, 13889. doi: 10.1039/c1jm10923e(13) Pang, H.; Lu, Q. Y.; Chen, C. Y.; Liu, X. R.; Gao, F. J. Mater. Chem. 2011, 21, 13889. doi: 10.1039/c1jm10923e
14. [14]
  (14) Menaka, S. E.; Lofland, S. E.; Ramanujachary, K. V.; Ganguli, A. K. J. Organomet. Chem. 2010, 695, 1002. doi: 10.1016/j.jorganchem.2009.10.023(14) Menaka, S. E.; Lofland, S. E.; Ramanujachary, K. V.; Ganguli, A. K. J. Organomet. Chem. 2010, 695, 1002. doi: 10.1016/j.jorganchem.2009.10.023
15. [15]
  (15) Liu, X. F.; Zhu,W. C.; Cui, X. L.; Liu, T.; Zhang, Q. Powder Technol. 2012, 222, 160. doi: 10.1016/j.powtec.2012.02.026(15) Liu, X. F.; Zhu,W. C.; Cui, X. L.; Liu, T.; Zhang, Q. Powder Technol. 2012, 222, 160. doi: 10.1016/j.powtec.2012.02.026
16. [16]
  (16) Götz,W. Naturwissenschaften 1963, 50, 567.(16) Götz,W. Naturwissenschaften 1963, 50, 567.
17. [17]
  (17) Wu, M. Y.;Wang, J. M.; Zhang, J. Q.; Cao, C. N. Acta Phys. -Chim. Sin. 2005, 21, 523. [吴梅银, 王建明, 张鉴清, 曹楚南. 物理化学学报, 2005, 21, 523.] doi: 10.3866/PKU.WHXB20050513(17) Wu, M. Y.;Wang, J. M.; Zhang, J. Q.; Cao, C. N. Acta Phys. -Chim. Sin. 2005, 21, 523. [吴梅银, 王建明, 张鉴清, 曹楚南. 物理化学学报, 2005, 21, 523.] doi: 10.3866/PKU.WHXB20050513
18. [18]
  (18) Ren, J. X.; Zhou, Z.; Yan, J. Acta phys. -Chim. Sin. 2007, 23, 738. [任俊霞, 周震, 阎杰. 物理化学学报, 2007, 23, 738.] doi: 10.3866/PKU.WHXB20070522(18) Ren, J. X.; Zhou, Z.; Yan, J. Acta phys. -Chim. Sin. 2007, 23, 738. [任俊霞, 周震, 阎杰. 物理化学学报, 2007, 23, 738.] doi: 10.3866/PKU.WHXB20070522
19. [19]
  (19) Qinghai Institute of Salt Lakes, Chinese Academy of Sciences. Analysis of Salt and Brine; Science Press: Beijing, 1988; pp 47-55. [中国科学院青海盐湖研究所. 卤水和盐的分析方法. 北京: 科学出版社, 1988: 47-55.](19) Qinghai Institute of Salt Lakes, Chinese Academy of Sciences. Analysis of Salt and Brine; Science Press: Beijing, 1988; pp 47-55. [中国科学院青海盐湖研究所. 卤水和盐的分析方法. 北京: 科学出版社, 1988: 47-55.]
20. [20]
  (20) Teo, B. K. EXAFS: Basic Principles and Data Analysis; Springer-Verlag: New York, 1986; pp 34-78.(20) Teo, B. K. EXAFS: Basic Principles and Data Analysis; Springer-Verlag: New York, 1986; pp 34-78.
21. [21]
  (21) Koningsberger, D. C.; Prins, R. X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES ; Wiley-Interscience: New York, 1988; pp 42-88.(21) Koningsberger, D. C.; Prins, R. X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES ; Wiley-Interscience: New York, 1988; pp 42-88.
22. [22]
  (22) Newville, M.; Ravel, R.; Haskel, D.; Rehr, J. J.; Stern, E. A.; Yacoby, Y. Phys. B: Condensed Matter 1995, 208&209, 154.(22) Newville, M.; Ravel, R.; Haskel, D.; Rehr, J. J.; Stern, E. A.; Yacoby, Y. Phys. B: Condensed Matter 1995, 208&209, 154.
23. [23]
  (23) Newville, M.; Livins, P.; Yacoby, Y.; Rehr, J. J.; Stern, E. A. Phys. Rev. B 1993, 47, 14126. doi: 10.1103/PhysRevB.47.14126(23) Newville, M.; Livins, P.; Yacoby, Y.; Rehr, J. J.; Stern, E. A. Phys. Rev. B 1993, 47, 14126. doi: 10.1103/PhysRevB.47.14126
24. [24]
  (24) Wang, Q.W.; Liu,W. H. X-ray Absorption Fine Structure and Application; Science Press: Beijing, 1994; pp 14-52. [王其武, 刘文汉. X 射线吸收精细结构及其应用. 北京: 科学出版社, 1994: 14-52.](24) Wang, Q.W.; Liu,W. H. X-ray Absorption Fine Structure and Application; Science Press: Beijing, 1994; pp 14-52. [王其武, 刘文汉. X 射线吸收精细结构及其应用. 北京: 科学出版社, 1994: 14-52.]
25. [25]
  (25) Stern, E. A. Phys. Rev. B 1993, 48, 9825. doi: 10.1103/PhysRevB.48.9825(25) Stern, E. A. Phys. Rev. B 1993, 48, 9825. doi: 10.1103/PhysRevB.48.9825
26. [26]
  (26) Xing,W.; Li, F.; Yan, Z. F.; Lu, G. Q. J. Power Sources 2004, 134, 324. doi: 10.1016/j.jpowsour.2004.03.038(26) Xing,W.; Li, F.; Yan, Z. F.; Lu, G. Q. J. Power Sources 2004, 134, 324. doi: 10.1016/j.jpowsour.2004.03.038
27. [27]
  (27) Wang, C. C.; Li, J. H.; Sun, Y. F.; Zhu, X. Q.; Huang, C. J.; Weng,W. Z.;Wan, H. L. Acta Phys. -Chim. Sin. 2011, 27, 2421. [汪彩彩, 李建辉, 孙毅飞, 朱晓权, 黄传敬, 翁维正, 万惠霖. 物理化学学报, 2011, 27, 2421.] doi: 10.3866/PKU.WHXB20110932(27) Wang, C. C.; Li, J. H.; Sun, Y. F.; Zhu, X. Q.; Huang, C. J.; Weng,W. Z.;Wan, H. L. Acta Phys. -Chim. Sin. 2011, 27, 2421. [汪彩彩, 李建辉, 孙毅飞, 朱晓权, 黄传敬, 翁维正, 万惠霖. 物理化学学报, 2011, 27, 2421.] doi: 10.3866/PKU.WHXB20110932
28. [28]
  (28) Yan, J.; Sun,W.; Zhang, Q.; Fan, Z. J.;Wei, F. J. Mater. Chem. 2012, 22, 11494. doi: 10.1039/c2jm30221g(28) Yan, J.; Sun,W.; Zhang, Q.; Fan, Z. J.;Wei, F. J. Mater. Chem. 2012, 22, 11494. doi: 10.1039/c2jm30221g
29. [29]
  (29) Fu, G. R.; Hu, Z. A.; Xie, L. J.; Jin, X. Q.; Xie, Y. L.;Wang, Y. X.; Zhang, Z. Y.; Yang, Y. Y.;Wu, H. Y. Int. J. Electrochem. Sci. 2009, 4, 1052.(29) Fu, G. R.; Hu, Z. A.; Xie, L. J.; Jin, X. Q.; Xie, Y. L.;Wang, Y. X.; Zhang, Z. Y.; Yang, Y. Y.;Wu, H. Y. Int. J. Electrochem. Sci. 2009, 4, 1052.
30. [30]
  (30) Ni, X. M.; Zhao, Q. B.; Li, B. B.; Cheng, J.; Zheng, H. G. Solid State Commun. 2006, 137, 585. doi: 10.1016/j.ssc.2006.01.033(30) Ni, X. M.; Zhao, Q. B.; Li, B. B.; Cheng, J.; Zheng, H. G. Solid State Commun. 2006, 137, 585. doi: 10.1016/j.ssc.2006.01.033
31. [31]
  (31) Liu, Z. H.; Gao, B.; Li, S. N.; Hu, M. C.; Xia, S. P. Spectrochim. Acta A 2004, 60, 3125. doi: 10.1016/j.saa.2004.02.027(31) Liu, Z. H.; Gao, B.; Li, S. N.; Hu, M. C.; Xia, S. P. Spectrochim. Acta A 2004, 60, 3125. doi: 10.1016/j.saa.2004.02.027
32. [32]
  (32) Jia, Y. Z.; Gao, S. Y.; Xia, S. P.; Li, J. Spectrochim. Acta A 2000, 56, 1291. doi: 10.1016/S1386-1425(99)00227-9(32) Jia, Y. Z.; Gao, S. Y.; Xia, S. P.; Li, J. Spectrochim. Acta A 2000, 56, 1291. doi: 10.1016/S1386-1425(99)00227-9
33. [33]
  (33) Yamauchi, S.; Doi, S. J. Wood Sci. 2003, 49, 227. doi: 10.1007/s10086-002-0466-x(33) Yamauchi, S.; Doi, S. J. Wood Sci. 2003, 49, 227. doi: 10.1007/s10086-002-0466-x
34. [34]
  (34) Zhou, Y. Q.; Fang, C. H.; Fang, Y.; Zhu, F. Y. Spectrochim. Acta A 2011, 83, 82. doi: 10.1016/j.saa.2011.07.081(34) Zhou, Y. Q.; Fang, C. H.; Fang, Y.; Zhu, F. Y. Spectrochim. Acta A 2011, 83, 82. doi: 10.1016/j.saa.2011.07.081
35. [35]
  (35) Zhu, F. Y.; Fang, C. H.; Fang, Y.; Zhou, Y. Q.; Xu, S.; Tao, S.; Cao, L. D. Acta Chim. Sin. 2012, 70, 445. [朱发岩, 房春晖, 房艳, 周永全, 许沙, 陶松, 曹领帝. 化学学报, 2012, 70, 445.] doi: 10.6023/A1105313(35) Zhu, F. Y.; Fang, C. H.; Fang, Y.; Zhou, Y. Q.; Xu, S.; Tao, S.; Cao, L. D. Acta Chim. Sin. 2012, 70, 445. [朱发岩, 房春晖, 房艳, 周永全, 许沙, 陶松, 曹领帝. 化学学报, 2012, 70, 445.] doi: 10.6023/A1105313
36. [36]
  (36) Frost, R. L.; Xi, Y. F. Spectrochim. Acta A 2012, 96, 89. doi: 10.1016/j.saa.2012.04.087(36) Frost, R. L.; Xi, Y. F. Spectrochim. Acta A 2012, 96, 89. doi: 10.1016/j.saa.2012.04.087
37. [37]
  (37) Rajamathi, M.; Kamath, P. V.; Seshadri, R. J. Mater. Chem. 2000, 10, 503. doi: 10.1039/a905651c(37) Rajamathi, M.; Kamath, P. V.; Seshadri, R. J. Mater. Chem. 2000, 10, 503. doi: 10.1039/a905651c
38. [38]
  (38) Kostecki, R.; Mclarnon, F. J. Electrochem. Soc. 1997, 144, 485. doi: 10.1149/1.1837437(38) Kostecki, R.; Mclarnon, F. J. Electrochem. Soc. 1997, 144, 485. doi: 10.1149/1.1837437
39. [39]
  (39) McEwen, R. S. J. Phys. Chem. 1971, 75, 1782. doi: 10.1021/j100681a004(39) McEwen, R. S. J. Phys. Chem. 1971, 75, 1782. doi: 10.1021/j100681a004
40. [40]
  (40) Wells, A. F. Srrucrural Inorganic Chemistry; Oxford University Press: London, 1975; pp 257-259.
  (40) Wells, A. F. Srrucrural Inorganic Chemistry; Oxford University Press: London, 1975; pp 257-259.

扫一扫看文章

计量

PDF下载量: 581
文章访问数: 816
HTML全文浏览量: 33

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

非晶态镍硼酸盐结构的EXAFS研究

English

EXAFS Study of the Structure of Amorphous Nickel Borate

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

非晶态镍硼酸盐结构的EXAFS研究

English

EXAFS Study of the Structure of Amorphous Nickel Borate

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

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs