Citation: ZHAO Pei-Zhu, LI Lin-Yan, XU Sheng-Ming, ZHANG Qin. Synthesis and Structural Transformations of (Gd_1-xCe_x)₂Zr₂O_7+x: An Analogue for Pu Immobilization[J]. Acta Physico-Chimica Sinica, ;2013, 29(06): 1168-1172. doi: 10.3866/PKU.WHXB201304013 shu

Synthesis and Structural Transformations of (Gd_1-xCe_x)₂Zr₂O_7+x: An Analogue for Pu Immobilization

1.
1 College of Mining, Guizhou University, Guiyang 550003, P. R. China;
2 Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 10084, P. R. China

Received Date: 17 December 2012
Available Online: 1 April 2013
Fund Project: 国家自然科学基金委员会和中国工程物理研究院联合基金(11176014)资助项目 (11176014)

Gd₂Zr₂O₇ is a well known host for nuclear waste immobilization because of the high neutron absorption cross section of Gd and low energy transformation between ordered pyrochlore and disordered defect-fluorite structures. Pyrochlore Gd₂Zr₂O₇ was synthesized at relatively low temperature (compared with traditional high temperature solid-state reaction) using Gd(NO₃)₃·nH₂O, Zr(NO₃)₄·nH₂O as a starting material and a small amount of NaF as fluxing agent. Ce⁴⁺ was used as an analogue for Pu⁴⁺ and its immobilization behavior in Gd₂Zr₂O₇ was studied in a series of solidified forms comprising (Gd_1-xCe_x)₂Zr₂O_7+x (0≤x≤0.6). Powder X-ray diffraction (XRD) data showed that the sample structure transformed from pyrochlore to defect-fluorite type with increasing x but maintained constant unit cell volumes. As x was increased to 0.6, the diffraction peaks showed broadening, suggesting considerable lattice distortion. When x=1, i.e., all Gd³⁺ are placed by Ce⁴⁺, the product was not Ce₂Zr₂O₈, but a phase separated mixture of tetra nal (Zr_0.88Ce_0.12)O₂ and an ideal fluorite (Ce_0.75Zr_0.25)O₂. Leach rate measurements indicated that the leach rate of Gd³⁺, Zr⁴⁺, Ce⁴⁺ was low when x≤0.2, but increased significantly when x≥0.4. This suggests that the substitution rate of Pu⁴⁺ for Gd³⁺ should not be more than 40% when Gd₂Zr₂O₇ used as the host matrix for Pu⁴⁺.
- Immobilization of nuclear waste,
- Surrogate of Ce⁴⁺ for Pu⁴⁺,
- Pyrochlore structure,
- Defect fluorite structure,
- Structure transformation
1. [1]
  
  (1) Moriga, T.; Yoshiasa, A.; Kanamaru, F.; Koto, K.; Yoshimura,M.; Somiya, S. Solid State Ionics 1989, 31 (4), 319.doi: 10.1016/0167-2738(89)90472-4
2. [2]
  (2) Nyman, H.; Andersson, S.; Hyde, B. G.; O'Keeffe, M. J. SolidState Chem. 1978, 26, 123." target=_blank>10.1016/0167-2738(89)90472-4
3. [3]
  (2) Nyman, H.; Andersson, S.; Hyde, B. G.; O'Keeffe, M. J. SolidState Chem. 1978, 26, 123.
4. [4]
  (3) Raison, P. E.; Haire, R. G.; Sato, T.; Ogawa, T. Mater. Res. Symp.Proc. 1999, 556, 3. doi: 10.1557/PROC-556-3
5. [5]
  (4) Kulkarni, N. K.; Sampath, S.; Venu pal, V. J. Nucl. Mater.2000, 281, 248. doi: 10.1016/S0022-3115(00)00336-6
6. [6]
  (5) Li, H. J.; Chen, G.; Li, Z. H.; Zhou, C. Acta Phys. -Chim. Sin.2007, 23 (5), 761. [李鸿建, 陈刚, 李中华, 周超. 物理化学学报, 2007, 23 (5), 761.] doi: 10.3866/PKU.WHXB20070527
7. [7]
  (6) Qu, Z. X.;Wan, C. L.; Pan,W. Chem. Mater. 2007, 19 (20),4913. doi: 10.1021/cm071615z
8. [8]
  (7) Wu, D. C. Chinese Journal of Nuclear Science and Engineering1992, 12 (3), 280. [吴德昌. 核科学与工程, 1992, 12 (3), 280.]" target=_blank>10.1557/PROC-556-3
9. [9]
  (4) Kulkarni, N. K.; Sampath, S.; Venu pal, V. J. Nucl. Mater.2000, 281, 248. doi: 10.1016/S0022-3115(00)00336-6
10. [10]
  (5) Li, H. J.; Chen, G.; Li, Z. H.; Zhou, C. Acta Phys. -Chim. Sin.2007, 23 (5), 761. [李鸿建, 陈刚, 李中华, 周超. 物理化学学报, 2007, 23 (5), 761.] doi: 10.3866/PKU.WHXB20070527
11. [11]
  (6) Qu, Z. X.;Wan, C. L.; Pan,W. Chem. Mater. 2007, 19 (20),4913. doi: 10.1021/cm071615z
12. [12]
  (7) Wu, D. C. Chinese Journal of Nuclear Science and Engineering1992, 12 (3), 280. [吴德昌. 核科学与工程, 1992, 12 (3), 280.]
13. [13]
  (8) Wang, S. X.;Wang, L. M.; Ewing, R. C.; Kutty, K. V. G. Nucl.Instrum. Methods Phys. Res. Sec. B 2000, 169 (1-4), 135.doi: 10.1016/S0168-583X(00)00030-6
14. [14]
  (9) Wang, S. X.; Begg, B. D.;Wang, L. M.; Ewing, R. C.;Weber,W. J.; Kutty, K. V. G. J. Mater. Res. 1999, 14 (12), 4470.doi: 10.1557/JMR.1999.0606
15. [15]
  (10) Weber,W. J.; Ewing, R. C. Science 2000, 289, 2051. doi: 10.1126/science.289.5487.2051
16. [16]
  (11) Stefanovsky, S. V.; Yudintsev, S. V.; Livshits, T. S. Mater. Sci.Eng. 2010, 9, 012001." target=_blank>10.1016/S0168-583X(00)00030-6
17. [17]
  (9) Wang, S. X.; Begg, B. D.;Wang, L. M.; Ewing, R. C.;Weber,W. J.; Kutty, K. V. G. J. Mater. Res. 1999, 14 (12), 4470.doi: 10.1557/JMR.1999.0606
18. [18]
  (10) Weber,W. J.; Ewing, R. C. Science 2000, 289, 2051. doi: 10.1126/science.289.5487.2051
19. [19]
  (11) Stefanovsky, S. V.; Yudintsev, S. V.; Livshits, T. S. Mater. Sci.Eng. 2010, 9, 012001.
20. [20]
  (12) Cleave, A.; Grimes, R.; Sickafus, K. Philos. Mag. 2005, 85 (9),967. doi: 10.1080/14786430412331314672
21. [21]
  (13) Ewing, R. C.;Weber,W. J.; Lian, J. J. Appl. Phys. 2004, 95,5949. doi: 10.1063/1.1707213
22. [22]
  (14) Lu, X. R.; Dong, F. Q.; Hu, S.;Wang, X. L.;Wu, Y. L. ActaPhys. Sin. 2012, 61 (15), 152401-1. [卢喜瑞, 董发琴, 胡淞,王晓丽, 吴彦霖. 物理学报, 2012, 61 (15), 152401-1.]doi: 10.7498/aps.61.152401
23. [23]
  (15) Zhong, Y. H.; Tang, J. Y.; Mao, X. L.; Lu, X. R.; Yang, Y. S.Journal of Southwest University of Science and Tchnology 2011,26 (2), 10. [钟宇宏, 唐敬友, 毛雪丽, 卢喜瑞, 杨玉山. 西南科技大学学报, 2011, 26 (2), 10.]" target=_blank>10.1080/14786430412331314672
24. [24]
  (13) Ewing, R. C.;Weber,W. J.; Lian, J. J. Appl. Phys. 2004, 95,5949. doi: 10.1063/1.1707213
25. [25]
  (14) Lu, X. R.; Dong, F. Q.; Hu, S.;Wang, X. L.;Wu, Y. L. ActaPhys. Sin. 2012, 61 (15), 152401-1. [卢喜瑞, 董发琴, 胡淞,王晓丽, 吴彦霖. 物理学报, 2012, 61 (15), 152401-1.]doi: 10.7498/aps.61.152401
26. [26]
  (15) Zhong, Y. H.; Tang, J. Y.; Mao, X. L.; Lu, X. R.; Yang, Y. S.Journal of Southwest University of Science and Tchnology 2011,26 (2), 10. [钟宇宏, 唐敬友, 毛雪丽, 卢喜瑞, 杨玉山. 西南科技大学学报, 2011, 26 (2), 10.]
27. [27]
  (16) Reid, D. P.; Stennett, M. C.; Hyatt, N. C. J. Solid State Chem.2012, 191, 2. doi: 10.1016/j.jssc.2011.12.039
28. [28]
  (17) Patwe, S. J.; Ambekar, B. R.; Tyagi, A. K. J. Alloy. Compd.2005, 389 (1-2), 243. doi: 10.1016/j.jallcom.2004.06.094
29. [29]
  (18) Jantzen, C. M.; Bibler, N. E.; Beam, D. C.; Ramsey,W. G.;Waters, B. J. Standard Test Method Relative to Durability ofNuclear Waste Glasses: the Product Consistency Test (PCT),Version 5.0, 1991." target=_blank>10.1016/j.jssc.2011.12.039
30. [30]
  (17) Patwe, S. J.; Ambekar, B. R.; Tyagi, A. K. J. Alloy. Compd.2005, 389 (1-2), 243. doi: 10.1016/j.jallcom.2004.06.094
31. [31]
  (18) Jantzen, C. M.; Bibler, N. E.; Beam, D. C.; Ramsey,W. G.;Waters, B. J. Standard Test Method Relative to Durability ofNuclear Waste Glasses: the Product Consistency Test (PCT),Version 5.0, 1991.
32. [32]
  (19) Wang, G. B.;Wang, Y. J.; Zhao, X. Q.; Song, B. J. ActaPhys. -Chim. Sin. 2005, 21 (5), 84. [王桂斌, 王延吉, 赵新强,宋宝俊. 物理化学学报, 2005, 21 (5), 84.] doi: 10.3866/PKU.WHXB20050117
33. [33]
  (20) Chen, R.; ng, Y. J.; Li, Q.; Dou, T.; Zhao, Z.; Xu, Q. H. ActaPhys. -Chim. Sin. 2009, 25 (3), 539. [陈然, 巩雁军, 李强,窦涛, 赵震, 徐庆虎. 物理化学学报, 2009, 25 (3), 539.]doi: 10.3866/PKU.WHXB20090323
34. [34]
  (21) Subramanian, M. A.; Sleight, A.W. Handbook on the Physicsand Chemistry of Rare Earths; Elsevier Science Publishers:Oxford, UK, 1993; Vol. 16, pp 225-240." target=_blank>10.3866/PKU.WHXB20050117
35. [35]
  (20) Chen, R.; ng, Y. J.; Li, Q.; Dou, T.; Zhao, Z.; Xu, Q. H. ActaPhys. -Chim. Sin. 2009, 25 (3), 539. [陈然, 巩雁军, 李强,窦涛, 赵震, 徐庆虎. 物理化学学报, 2009, 25 (3), 539.]doi: 10.3866/PKU.WHXB20090323
36. [36]
  (21) Subramanian, M. A.; Sleight, A.W. Handbook on the Physicsand Chemistry of Rare Earths; Elsevier Science Publishers:Oxford, UK, 1993; Vol. 16, pp 225-240.
37. [37]
  (22) Perez-Y-Jorba, M. Ann. Chim. 1962, 7, 479. (23) Subramanian, M. A.; Aravamudan, G.; Rao, G. V. S. Prog.Solid State Chem. 1983, 15, 55. doi: 10.1016/0079-6786(83)90001-8
38. [38]
  (24) Mandal, B. P.; Shukla, R.; Achary, S. N.; Tyagi, A. K. Inorg.Chem. 2010, 49, 10415. doi: 10.1021/ic1018482
39. [39]
  (25) McCullough, J. D.; Britton, J. D. J. Am. Chem. Soc. 1952, 74,5225." target=_blank>10.1016/0079-6786(83)90001-8
40. [40]
  (24) Mandal, B. P.; Shukla, R.; Achary, S. N.; Tyagi, A. K. Inorg.Chem. 2010, 49, 10415. doi: 10.1021/ic1018482
41. [41]
  (25) McCullough, J. D.; Britton, J. D. J. Am. Chem. Soc. 1952, 74,5225.
42. [42]
  (26) Ringwood, A. E.; Kesson, S. E.; Reeve, K. D.; Levins, D. M.;Ramm, E. J. Radioactive Waste Forms for the Future; ElsevierScience: Amersterdam, 1988; pp 233-234. (27) Icenhower, J. P.;Weber,W. J.; Hess, N. J.; Thevuthasen, S.;Begg, B.; McGrail, P.; Rodriguez, E. A.; Steele, J. L.; Geiszler,K. N. Scientific Basis for Nuclear Waste Management XXVI;Material Research Society: Pittsburgh, 2003; pp 23-30.
1. [1]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
2. [2]
  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
3. [3]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
4. [4]
  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
5. [5]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
6. [6]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
7. [7]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
8. [8]
  Dongju Zhang . Exploring the Descriptions and Connotations of Basic Concepts of Teaching Crystal Structures. University Chemistry, 2024, 39(3): 18-22. doi: 10.3866/PKU.DXHX202304003
9. [9]
  Weina Wang , Fengyi Liu , Wenliang Wang . “Extracting Commonality, Delving into Typicals, Deriving Individuality”: Constructing a Knowledge Graph of Crystal Structures. University Chemistry, 2024, 39(3): 36-42. doi: 10.3866/PKU.DXHX202308029
10. [10]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050
11. [11]
  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
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]
  Hongwei Ma , Hui Li . Three Methods for Structure Determination from Powder Diffraction Data. University Chemistry, 2024, 39(3): 94-102. doi: 10.3866/PKU.DXHX202310035
14. [14]
  Yanxin Wang , Hongjuan Wang , Yuren Shi , Yunxia Yang . Application of Python for Visualizing in Structural Chemistry Teaching. University Chemistry, 2024, 39(3): 108-117. doi: 10.3866/PKU.DXHX202306005
15. [15]
  Guoxian Zhu , Jing Chen , Rongkai Pan . Enhancing the Teaching Quality of Atomic Structure: Insights and Strategies. University Chemistry, 2024, 39(3): 376-383. doi: 10.3866/PKU.DXHX202305027
16. [16]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
17. [17]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
18. [18]
  Zhiguang Xu , Xuan Xu , Qiong Luo , Ganquan Wang , Bin Peng . Reform and Practice of Online and Offline Blended Teaching in Structural Chemistry Course. University Chemistry, 2024, 39(6): 195-200. doi: 10.3866/PKU.DXHX202310112
19. [19]
  Jin Jia , Shangda Jiang . Is the z Axis Special in Atomic Structure?. University Chemistry, 2024, 39(6): 400-404. doi: 10.12461/PKU.DXHX202403091
20. [20]
  Wen Shi , Zhangwen Wei , Mei Pan , Chengyong Su . Explorations on the Course Construction of Structural Chemistry Practice and Application Targeting the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 96-100. doi: 10.12461/PKU.DXHX202409036

Get Citation

PDF

XML

Metrics

PDF Downloads(659)
Abstract views(658)
HTML views(14)

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

Synthesis and Structural Transformations of (Gd1-xCex)2Zr2O7+x: An Analogue for Pu Immobilization

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis and Structural Transformations of (Gd_1-xCe_x)₂Zr₂O_7+x: An Analogue for Pu Immobilization