核壳结构Cu@CoCr的合成和对硼氨配合物水解的催化性能

引用本文: 沈晓晨, 戴敏, 高鸣, 王志斌, 赵斌, 丁维平. 核壳结构Cu@CoCr的合成和对硼氨配合物水解的催化性能[J]. 无机化学学报, 2013, 29(5): 999-1006. doi: 10.3969/j.issn.1001-4861.2013.00.145 shu

Citation: SHEN Xiao-Chen, DAI Min, GAO Ming, WANG Zhi-Bin, ZHAO Bin, DING Wei-Ping. Core-Shell Structured Cu@CoCr Catalyst: Synthesis and Catalytic Performance for Hydrolysis of Ammonia Borane Aqueous Solution[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(5): 999-1006. doi: 10.3969/j.issn.1001-4861.2013.00.145 shu

核壳结构Cu@CoCr的合成和对硼氨配合物水解的催化性能

沈晓晨 ^1, ,
戴敏 ^1, ,
高鸣 ^1, ,
王志斌 ^2, ,
赵斌 ^{1,
,} ,
丁维平 ^1,

通讯作者: 赵斌,E-mail:binzhao@nju.edu.cn

基金项目:
江苏省自然科学基金(No.BK2010387) (No.BK2010387)

国家自然科学基金(No.41172239) (No.41172239)

中央高校基础科研业务费专项基金(No.1118020513, 1106020513)资助项目。 (No.1118020513, 1106020513)

摘要: 通过一步法原位合成了核壳结构的Cu@CoCr三元合金催化剂,该合成方法条件温和、步骤简便。25 ℃下,Cu_0.4@Co_0.5Cr_0.1三元合金催化剂对于硼氨配合物水解反应的TOF值达到0.242 0 mol_H₂·moL_cat^-1·s^-1,接近Pt、Pd等贵金属的催化活性,反应的活化能仅为35 kJ·mol^-1,5次重复使用后仍能保持初始活性的35%。与非核壳结构的CuCoCr合金相比,核壳结构的Cu@CoCr三元合金催化剂的催化性能及稳定性均有明显提高。此外材料自身具有磁性,可进行磁分离,适合于实际应用。

关键词:

原位合成;核壳结构;合金;硼氨配合物;多相催化;产氢

English

Core-Shell Structured Cu@CoCr Catalyst: Synthesis and Catalytic Performance for Hydrolysis of Ammonia Borane Aqueous Solution

1.
1. Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry & Chemical Engineering, Nanjing University, Nanjing 210093, China;

Corresponding author: 赵斌,E-mail:binzhao@nju.edu.cn

Received Date: 12 November 2012
Fund Project:
江苏省自然科学基金(No.BK2010387)

国家自然科学基金(No.41172239)

中央高校基础科研业务费专项基金(No.1118020513, 1106020513)资助项目。

Abstract: The core/shell structured ternary alloy of Cu@CoCr was synthesized by a one-step in-situ synthesis method under mild conditions. The catalytic performance of Cu@CoCr was studied for the hydrolysis of NH₃BH₃ (AB) aqueous solution. The TOF (turn over frequency) of 0.242 0 mol_H₂·moL_cat^-1·s^-1 for Cu_0.4@Co_0.5Cr_0.1 catalyst on AB hydrolysis reaction is close to the noble-metal based catalysts, such as Pt, Pd, etc. The activation energy of this catalyst is only 35 kJ·mol^-1. After 5 cycles, this catalyst still keeps 35% of its initial activity. Compared to the non-core/shell structured CuCoCr alloy, the Cu@CoCr catalyst shows great improvements in activity, stability and reusability. Furthermore, the Cu@CoCr catalysts could be recovered by a magnet based on its magnetic properties.

Key words:

in-situ synthesis;core/shell structure;alloy;ammonia borane;heterogeneous catalysis;hydrogen generation

1. [1] Zhou L, Renew. Sust. Energ. Rev., 2005,9(4):395-408[1] Zhou L, Renew. Sust. Energ. Rev., 2005,9(4):395-408
2. [2] http://www1.eere.energy.gov/vehiclesandfuels/pdfs/program/hy- drogen_storage_roadmap.pdf[2] http://www1.eere.energy.gov/vehiclesandfuels/pdfs/program/hy- drogen_storage_roadmap.pdf
3. [3] Peng B, Chen J. Energy Environ. Sci., 2008,1(4):479-483[3] Peng B, Chen J. Energy Environ. Sci., 2008,1(4):479-483
4. [4] Marder T B. Angew. Chem. Int. Ed., 2007,46(43):8116-8118[4] Marder T B. Angew. Chem. Int. Ed., 2007,46(43):8116-8118
5. [5] Rassat S D, Aardahl C L, Smith R S, et al. Energy Fuels, 2010,24(4):2596-2606[5] Rassat S D, Aardahl C L, Smith R S, et al. Energy Fuels, 2010,24(4):2596-2606
6. [6] Baitalow F, Baumann J, Wolf G, et al. Thermochim. Acta, 2002,391(1-2):159-168[6] Baitalow F, Baumann J, Wolf G, et al. Thermochim. Acta, 2002,391(1-2):159-168
7. [7] Carpenter J D, Ault B S, Chem. Phys. Lett., 1992,197(1-2): 171-174[7] Carpenter J D, Ault B S, Chem. Phys. Lett., 1992,197(1-2): 171-174
8. [8] Mohajeri N, T-Raissi A, Ramasamy K K, Thermochim. Acta, 2007,452(1):28-30[8] Mohajeri N, T-Raissi A, Ramasamy K K, Thermochim. Acta, 2007,452(1):28-30
9. [9] Chandra M, Xu Q. J. Power Sources, 2006,156(2):190-194[9] Chandra M, Xu Q. J. Power Sources, 2006,156(2):190-194
10. [10] Xu Q, Chandra M. J. Alloys Compd., 2007,446-447:729- 732[10] Xu Q, Chandra M. J. Alloys Compd., 2007,446-447:729- 732
11. [11] Wang P, Kang X D. Dalton Trans., 2008,40:5400-5413[11] Wang P, Kang X D. Dalton Trans., 2008,40:5400-5413
12. [12] Umegaki T, Yan J M, Zhang X B, et al. Int. J. Hydrogen Energy, 2009,34(5):2303-2311[12] Umegaki T, Yan J M, Zhang X B, et al. Int. J. Hydrogen Energy, 2009,34(5):2303-2311
13. [13] Basu S, Brockman A, Gagare P, et al. J. Power Sources, 2009,188(1):238-243[13] Basu S, Brockman A, Gagare P, et al. J. Power Sources, 2009,188(1):238-243
14. [14] Metin Ö, Sahin S, Özkar S, Int. J. Hydrogen Energy, 2009, 34(15):6304-6313[14] Metin Ö, Sahin S, Özkar S, Int. J. Hydrogen Energy, 2009, 34(15):6304-6313
15. [15] Durap F, Zahmakiran M, Özkar S, Int. J. Hydrogen Energy, 2009,34(17):7223-7230[15] Durap F, Zahmakiran M, Özkar S, Int. J. Hydrogen Energy, 2009,34(17):7223-7230
16. [16] Zahmakiran M, Özkar S. Appl. Catal. B: Environ., 2009,89 (1-2):104-110[16] Zahmakiran M, Özkar S. Appl. Catal. B: Environ., 2009,89 (1-2):104-110
17. [17] Umegaki T, Yan J M, Zhang X B, et al. J. Power Sources, 2010,195(24):8209-8214[17] Umegaki T, Yan J M, Zhang X B, et al. J. Power Sources, 2010,195(24):8209-8214
18. [18] Metin Ö, Özkar S. Energy Fuel, 2009,23(7):3517-3526[18] Metin Ö, Özkar S. Energy Fuel, 2009,23(7):3517-3526
19. [19] Clark T J, Whittell G R, Manners I. Inorg. Chem., 2007,46 (18):7522-7527[19] Clark T J, Whittell G R, Manners I. Inorg. Chem., 2007,46 (18):7522-7527
20. [20] Yan J M, Zhang X B, Han S, et al. Angew. Chem. Int. Ed., 2008,47(12):2287-2289[20] Yan J M, Zhang X B, Han S, et al. Angew. Chem. Int. Ed., 2008,47(12):2287-2289
21. [21] Fernandes R, Patel N, Miotello A. Appl. Catal. B: Environ., 2009,92(1-2):68-74[21] Fernandes R, Patel N, Miotello A. Appl. Catal. B: Environ., 2009,92(1-2):68-74
22. [22] Fernandes R, Patel N, Miotello A, et al. J. Mol. Catal. A: Chem., 2009,298(1-2):1-6[22] Fernandes R, Patel N, Miotello A, et al. J. Mol. Catal. A: Chem., 2009,298(1-2):1-6
23. [23] Patel N, Fernandes R, Miotello A. J. Power Sources, 2009, 188(2):411-420[23] Patel N, Fernandes R, Miotello A. J. Power Sources, 2009, 188(2):411-420
24. [24] Fernandes R, Patel N, Miotello A. Int. J. Hydrogen Energy, 2009,34(7):2893-2900[24] Fernandes R, Patel N, Miotello A. Int. J. Hydrogen Energy, 2009,34(7):2893-2900
25. [25] Chen G Z, Desinan S, Nechache R, et al. Chem. Commun., 2011,47(22):6308-6310[25] Chen G Z, Desinan S, Nechache R, et al. Chem. Commun., 2011,47(22):6308-6310
26. [26] Jiang H L, Akita T, Xu Q. Chem. Commun., 2011,47(39): 10999-11001[26] Jiang H L, Akita T, Xu Q. Chem. Commun., 2011,47(39): 10999-11001
27. [27] Jeong S U, Cho E A, Nam S W, et al. Int. J. Hydrogen Energy, 2007,32(12):1749-1754[27] Jeong S U, Cho E A, Nam S W, et al. Int. J. Hydrogen Energy, 2007,32(12):1749-1754
28. [28] Retnamma R, Novais A Q, Rangel C M. Int. J. Hydrogen Energy, 2011,36(16):9772-9790[28] Retnamma R, Novais A Q, Rangel C M. Int. J. Hydrogen Energy, 2011,36(16):9772-9790
29. [29] Wang Y, Toshima N. J. Phys. Chem. B, 1997,101(27):5301- 5306[29] Wang Y, Toshima N. J. Phys. Chem. B, 1997,101(27):5301- 5306
30. [30] Chen G Z, Desinan S, Rosei R, et al. Chem. Eur. J., 2012, 18(25):7925-7930[30] Chen G Z, Desinan S, Rosei R, et al. Chem. Eur. J., 2012, 18(25):7925-7930
31. [31] Rakap M, Özkar S. Int. J. Hydrogen Energy, 2010,35(3): 1305-1312[31] Rakap M, Özkar S. Int. J. Hydrogen Energy, 2010,35(3): 1305-1312
32. [32] Yan J M, Zhang X B, Akita T, et al. J. Am. Chem. Soc., 2010,132(15):5326-5327[32] Yan J M, Zhang X B, Akita T, et al. J. Am. Chem. Soc., 2010,132(15):5326-5327

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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

核壳结构Cu@CoCr的合成和对硼氨配合物水解的催化性能

通讯作者: 赵斌,E-mail:binzhao@nju.edu.cn

English

Core-Shell Structured Cu@CoCr Catalyst: Synthesis and Catalytic Performance for Hydrolysis of Ammonia Borane Aqueous Solution

Corresponding author: 赵斌,E-mail:binzhao@nju.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

核壳结构Cu@CoCr的合成和对硼氨配合物水解的催化性能

通讯作者: 赵斌,E-mail:binzhao@nju.edu.cn

English

Core-Shell Structured Cu@CoCr Catalyst: Synthesis and Catalytic Performance for Hydrolysis of Ammonia Borane Aqueous Solution

Corresponding author: 赵斌,E-mail:binzhao@nju.edu.cn

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？

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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