孔隙结构可调的Cu<sub>2</sub>O球状纳米结构及其NO<sub>2</sub>气体传感性质

引用本文: 张东凤, 张岩, 张华, 齐娟娟, 商旸, 郭林. 孔隙结构可调的Cu₂O球状纳米结构及其NO₂气体传感性质[J]. 物理化学学报, 2015, 31(10): 2005-2010. doi: 10.3866/PKU.WHXB201509071 shu

Citation: ZHANG Dong-Feng, ZHANG Yan, ZHANG Hua, QI Juan-Juan, SHANG Yang, GUO Lin. Cavity-Tunable Cu₂O Spherical Nanostructures and Their NO₂ Gas Sensing Properties[J]. Acta Physico-Chimica Sinica, 2015, 31(10): 2005-2010. doi: 10.3866/PKU.WHXB201509071 shu

孔隙结构可调的Cu₂O球状纳米结构及其NO₂气体传感性质

基金项目:
国家自然科学基金(21173015)资助项目 (21173015)

摘要:

报道在聚乙烯吡咯烷酮(PVP)的协助作用下, 通过简单调节OH^-离子的浓度及Cu²⁺的释放速度, 将Cu₂O调节为具有不同空腔特征(介孔、空心及实心)结构的纳米球. 研究表明, OH^-根离子的扩散动力学是决定产物结构的关键因素. 当[OH^-] > 0.05 mol·L^-1时, 高的化学势使其迅速扩散到PVP胶团内部, 与吸附在PVP链上的Cu²⁺反应形成Cu(OH)₂, 在抗坏血酸(Vc)的还原作用下经过重结晶得到Cu₂O实心球纳米结构; 当[OH^-] <0.025 mol·L^-1时, 其扩散速度下降, 首先与吸附在PVP胶团外部的Cu²⁺反应形成Cu(OH)₂, Cu(OH)₂的形成阻碍了OH^-离子的向内扩散, 形成具有较大空腔(~220 nm)的空心球; 当0.025 mol·L^-1 < [OH^-] < 0.05 mol·L^-1时, 形成较小空腔(30-60 nm)的空心球. 以NH₃水为OH^-缓释源时, 虽然OH^-浓度较低, 但同时Cu²⁺的浓度也低, 胶团外部形成的Cu(OH)₂不足以阻碍OH^-离子的向内扩散, 反应过程中NH₃的释放及较低的OH^-浓度阻碍了重结晶的发生, 从而形成Cu₂O介孔纳米球. 对三种典型结构特征的产物进行了NO₂ 气体传感性质研究, 结果表明,Cu₂O介孔纳米球相比空心结构和实心结构具有更为优异的响应性. 结合比表面积数据, 我们认为介孔纳米球疏散的结构有利于NO₂气体的扩散和O₂的吸附, 从而表现出了更灵敏的气体传感性.

关键词:

English

Cavity-Tunable Cu₂O Spherical Nanostructures and Their NO₂ Gas Sensing Properties

1.
School of Chemistry and Environment, Beihang University, Beijing 100191, P. R. China
Received Date: 22 May 2015
Available Online: 10 October 2015
Fund Project:
国家自然科学基金(21173015)资助项目

Abstract:

We report the preparation of cavity-controlled Cu₂O nanospheres, having various mesoporous, hollow, and solid structures, by simply adjusting the OH^- concentration and the release rate of Cu²⁺ with the assistance of polyvinyl pyrrolidone (PVP). It indicates that the OH^- diffusion kinetics is the key factor that determines the morphology of the products. For [OH^-] > 0.05 mol·L^-1, the high chemical potential made them rapidly diffuse into the PVP micelle interiors. Adsorbed Cu²⁺ on the PVP produced Cu(OH)₂, which was subsequently reduced to Cu₂O. After re-crystallization, Cu₂O solid spheres formed. For [OH^-] < 0.025 mol·L^-1, the OH^- diffusion rate was reduced, and the Cu(OH)₂ layer on the PVP micelles blocked diffusion into the interior. After re-crystallization, Cu₂O hollow spheres had large cavities (~220 nm). For 0.025 mol·L^-1 < [OH^-] < 0.05 mol·L^-1, hollow spheres with smaller cavities (30-60 nm) formed. When an aqueous NH₃ solution was the OH^- source, although the concentration of OH^- is low, the small amount of Cu(OH)₂ formed with the limited Cu²⁺ was not enough to block OH^- diffusion into the micelles. The free NH₃ and the low OH^- concentration did not promote re-crystallization; thus, mesoporous Cu₂O spheres were formed. We characterized NO₂ gas sensing of the three structures. The porous structures exhibited more sensitivity than did the hollow or solid structures. Together with the specific surface area data, the improved gas sensitivity suggests that the open structure of the mesoporous spheres facilitates NO₂ diffusion and O₂ adsorption.

Key words:

1. [1]
  
  (1) Kuang, Q.; Wang, X.; Jiang, Z. Y.; Xie, Z. X.; Zheng, L. S. Accounts Chem. Res. 2014, 47, 308. doi: 10.1021/ar400092x
  (1) Kuang, Q.; Wang, X.; Jiang, Z. Y.; Xie, Z. X.; Zheng, L. S. Accounts Chem. Res. 2014, 47, 308. doi: 10.1021/ar400092x
2. [2]
  (2) Kim, H. J.; Lee, J. H. Sens. Actuator B-Chem. 2014, 192, 607. doi: 10.1016/j.snb.2013.11.005(2) Kim, H. J.; Lee, J. H. Sens. Actuator B-Chem. 2014, 192, 607. doi: 10.1016/j.snb.2013.11.005
3. [3]
  (3) Meng, H.; Yang, W.; Ding, K.; Feng, L.; Guan, Y. F. J. Mater. Chem. A 2015, 3, 1174. doi: 10.1039/C4TA06024E(3) Meng, H.; Yang, W.; Ding, K.; Feng, L.; Guan, Y. F. J. Mater. Chem. A 2015, 3, 1174. doi: 10.1039/C4TA06024E
4. [4]
  (4) Zhang, S. S.; Zhang, G. L.; He, P.; Lei, W.; Dong, F. Q.; Yang, D. M.; Suo, Z. R. Anal. Methods 2015, 7, 2747. doi: 10.1039/C4AY03001J(4) Zhang, S. S.; Zhang, G. L.; He, P.; Lei, W.; Dong, F. Q.; Yang, D. M.; Suo, Z. R. Anal. Methods 2015, 7, 2747. doi: 10.1039/C4AY03001J
5. [5]
  (5) Zhou, L. S.; Shen, F. P.; Tian, X. K.; Wang, D. H.; Zhang, T.; Chen, W. Nanoscale 2013, 4, 1564.(5) Zhou, L. S.; Shen, F. P.; Tian, X. K.; Wang, D. H.; Zhang, T.; Chen, W. Nanoscale 2013, 4, 1564.
6. [6]
  (6) Deng, S. Z.; Tjoa, V.; Fan, H. M.; Tan, H. R.; Sayle, D. C.; Olivo, M.; Mhaisalkar, S.; Wei, J.; Sow, C. H. J. Am. Chem. Soc. 2012, 134, 4905. doi: 10.1021/ja211683m(6) Deng, S. Z.; Tjoa, V.; Fan, H. M.; Tan, H. R.; Sayle, D. C.; Olivo, M.; Mhaisalkar, S.; Wei, J.; Sow, C. H. J. Am. Chem. Soc. 2012, 134, 4905. doi: 10.1021/ja211683m
7. [7]
  (7) Chen, L. C. Mater. Sci. Semicond. Process. 2013, 16, 1172. doi: 10.1016/j.mssp.2012.12.028(7) Chen, L. C. Mater. Sci. Semicond. Process. 2013, 16, 1172. doi: 10.1016/j.mssp.2012.12.028
8. [8]
  (8) Xiong, L.; Huang, S.; Yang, X.; Qiu, M.; Chen, Z.; Yu, Y. Electrochim. Acta 2011, 56, 2735. doi: 10.1016/j.electacta.2010.12.054(8) Xiong, L.; Huang, S.; Yang, X.; Qiu, M.; Chen, Z.; Yu, Y. Electrochim. Acta 2011, 56, 2735. doi: 10.1016/j.electacta.2010.12.054
9. [9]
  (9) Shang, Y.; Chen, Y.; Shi, Z. B.; Zhang, D. F.; Guo, L. Acta Phys. -Chim. Sin. 2013, 29, 1819. [商旸, 陈阳, 施湛斌, 张东凤, 郭林. 物理化学学报, 2013, 29, 1819.] doi: 10.3866/PKU.WHXB201305281(9) Shang, Y.; Chen, Y.; Shi, Z. B.; Zhang, D. F.; Guo, L. Acta Phys. -Chim. Sin. 2013, 29, 1819. [商旸, 陈阳, 施湛斌, 张东凤, 郭林. 物理化学学报, 2013, 29, 1819.] doi: 10.3866/PKU.WHXB201305281
10. [10]
  (10) Wang, J.; Ma, J.; Li, X. J.; Li, Y.; Zhang, G. L.; Zhang, F. B.; Fan, X. B. Chem. Commun. 2014, 50, 14237. doi: 10.1039/C4CC06869F(10) Wang, J.; Ma, J.; Li, X. J.; Li, Y.; Zhang, G. L.; Zhang, F. B.; Fan, X. B. Chem. Commun. 2014, 50, 14237. doi: 10.1039/C4CC06869F
11. [11]
  (11) White, B.; Yin, M.; Hall, A.; Le, D.; Stolbov, S.; Rahman, T.; Turro, N.; O'Brien, S. Nano Lett. 2006, 6, 2095. doi: 10.1021/nl061457v(11) White, B.; Yin, M.; Hall, A.; Le, D.; Stolbov, S.; Rahman, T.; Turro, N.; O'Brien, S. Nano Lett. 2006, 6, 2095. doi: 10.1021/nl061457v
12. [12]
  (12) Morales, J.; Sánchez, L.; Bijani, S.; Martínez, L.; Gabás, M.; Ramos-Barrado, J. R. Electrochem. Solid State 2005, 8, A159.(12) Morales, J.; Sánchez, L.; Bijani, S.; Martínez, L.; Gabás, M.; Ramos-Barrado, J. R. Electrochem. Solid State 2005, 8, A159.
13. [13]
  (13) Xu, Y. T.; Guo, Y; Li, C.; Zhou, X. Y.; Tucker, M. C.; Fu, X. Z.; Sun, R.; Wong, C. P. Nano Energy 2015, 11, 38. doi: 10.1016/j.nanoen.2014.10.011(13) Xu, Y. T.; Guo, Y; Li, C.; Zhou, X. Y.; Tucker, M. C.; Fu, X. Z.; Sun, R.; Wong, C. P. Nano Energy 2015, 11, 38. doi: 10.1016/j.nanoen.2014.10.011
14. [14]
  (14) Zhang, D. F.; Zhang, H.; Guo, L.; Zheng, K.; Han, X. D.; Zhang, Z. J. Mater. Chem. 2009, 19, 5220. doi: 10.1039/b816349a(14) Zhang, D. F.; Zhang, H.; Guo, L.; Zheng, K.; Han, X. D.; Zhang, Z. J. Mater. Chem. 2009, 19, 5220. doi: 10.1039/b816349a
15. [15]
  (15) Susman, M. D.; Feldman, Y.; Vaskevich, A.; Rubinstein, I. ACS Nano 2014, 8, 162. doi: 10.1021/nn405891g(15) Susman, M. D.; Feldman, Y.; Vaskevich, A.; Rubinstein, I. ACS Nano 2014, 8, 162. doi: 10.1021/nn405891g
16. [16]
  (16) Jiao, S. H.; Xu, D. S.; Xu, L. F.; Zhang, X. G. Acta Phys. -Chim. Sin. 2012, 28, 2436. [焦淑红, 徐东升, 许荔芬, 张晓光. 物理化学学报, 2012, 28, 2436.] doi:10.3866/PKU.WHXB201209145(16) Jiao, S. H.; Xu, D. S.; Xu, L. F.; Zhang, X. G. Acta Phys. -Chim. Sin. 2012, 28, 2436. [焦淑红, 徐东升, 许荔芬, 张晓光. 物理化学学报, 2012, 28, 2436.] doi:10.3866/PKU.WHXB201209145
17. [17]
  (17) Lu, C. H.; Qi, L. M.; Yang, J. H.; Wang, X. Y.; Zhang, D. Y.; Xie, J. L. Ma, J. M. Adv. Mater. 2005, 17, 2562.(17) Lu, C. H.; Qi, L. M.; Yang, J. H.; Wang, X. Y.; Zhang, D. Y.; Xie, J. L. Ma, J. M. Adv. Mater. 2005, 17, 2562.
18. [18]
  (18) Kuo, C. H.; Huang, M. H. J. Am. Chem. Soc. 2008, 130, 12815. doi: 10.1021/ja804625s(18) Kuo, C. H.; Huang, M. H. J. Am. Chem. Soc. 2008, 130, 12815. doi: 10.1021/ja804625s
19. [19]
  (19) Wang, W. Z.; Wang, G. H.; Wang, X. S.; Zhan, Y. J.; Liu, Y. K.; Zheng, C. L. Adv. Mater. 2002, 14, 67.(19) Wang, W. Z.; Wang, G. H.; Wang, X. S.; Zhan, Y. J.; Liu, Y. K.; Zheng, C. L. Adv. Mater. 2002, 14, 67.
20. [20]
  (20) Chen, L.; Shet, S.; Tang, H. W.; Wang, H. L.; Deutsch, T.; Yan, Y. F.; Turner, J.; Al-Jassim, M. J. Mater. Chem. 2010, 20, 6962. doi: 10.1039/c0jm01228a(20) Chen, L.; Shet, S.; Tang, H. W.; Wang, H. L.; Deutsch, T.; Yan, Y. F.; Turner, J.; Al-Jassim, M. J. Mater. Chem. 2010, 20, 6962. doi: 10.1039/c0jm01228a
21. [21]
  (21) Siegfried, M. J.; Choi, K. S. Adv. Mater. 2004, 16, 1743.(21) Siegfried, M. J.; Choi, K. S. Adv. Mater. 2004, 16, 1743.
22. [22]
  (22) Siegfried, M. J.; Choi, K. S. J. Am. Chem. Soc. 2006, 128, 10356. doi: 10.1021/ja063574y(22) Siegfried, M. J.; Choi, K. S. J. Am. Chem. Soc. 2006, 128, 10356. doi: 10.1021/ja063574y
23. [23]
  (23) Shang, Y.; Shao, Y. M.; Zhang, D. F.; Guo, L. Angew. Chem. Int. Edit. 2014, 53, 11514. doi: 10.1002/anie.201406331(23) Shang, Y.; Shao, Y. M.; Zhang, D. F.; Guo, L. Angew. Chem. Int. Edit. 2014, 53, 11514. doi: 10.1002/anie.201406331
24. [24]
  (24) Luo, X. L.; Han, Y. F.; Yang, D. S.; Chen, Y. S. Acta Phys. -Chim. Sin. 2012, 28, 297. [罗小林, 韩银凤, 杨德锁, 陈亚芍. 物理化学学报, 2012, 28, 297.] doi: 10.3866/PKU. WHXB201112012(24) Luo, X. L.; Han, Y. F.; Yang, D. S.; Chen, Y. S. Acta Phys. -Chim. Sin. 2012, 28, 297. [罗小林, 韩银凤, 杨德锁, 陈亚芍. 物理化学学报, 2012, 28, 297.] doi: 10.3866/PKU. WHXB201112012
25. [25]
  (25) Sun, D.; Yin, P. G.; Guo, L. Acta Phys. -Chim. Sin. 2011, 27, 1543. [孙都, 殷鹏刚, 郭林. 物理化学学报, 2011, 27, 1543.] doi: 10.3866/PKU.WHXB20110619(25) Sun, D.; Yin, P. G.; Guo, L. Acta Phys. -Chim. Sin. 2011, 27, 1543. [孙都, 殷鹏刚, 郭林. 物理化学学报, 2011, 27, 1543.] doi: 10.3866/PKU.WHXB20110619
26. [26]
  (26) Yang, S. Y.; Zhang, S. S.; Wang, H. J.; Yu, H.; Fang, Y. P.; Peng, F. RSC Adv. 2014, 4, 43024. doi: 10.1039/C4RA07593E(26) Yang, S. Y.; Zhang, S. S.; Wang, H. J.; Yu, H.; Fang, Y. P.; Peng, F. RSC Adv. 2014, 4, 43024. doi: 10.1039/C4RA07593E
27. [27]
  (27) Xu, Z.; Xie, Y.; Xu, F.; Xu, D.; Liu, X. H. Inorg. Chem. Commun. 2004, 7, 417. doi: 10.1016/j.inoche.2003.12.031(27) Xu, Z.; Xie, Y.; Xu, F.; Xu, D.; Liu, X. H. Inorg. Chem. Commun. 2004, 7, 417. doi: 10.1016/j.inoche.2003.12.031
28. [28]
  (28) Teng, X. W.; Han, W. Q.; Ku, W.; Hucker, M. Angew. Chem. Int. Edit. 2008, 47, 2055.(28) Teng, X. W.; Han, W. Q.; Ku, W.; Hucker, M. Angew. Chem. Int. Edit. 2008, 47, 2055.
29. [29]
  (29) Zhang, D. F.; Sun, L. D.; Yin, J. L.; Yan, C. H.; Wang, R. M. J. Phys. Chem. B 2005, 109, 8786. doi: 10.1021/jp050631l(29) Zhang, D. F.; Sun, L. D.; Yin, J. L.; Yan, C. H.; Wang, R. M. J. Phys. Chem. B 2005, 109, 8786. doi: 10.1021/jp050631l
30. [30]
  (30) Banfield, J. F.; Welch, S. A.; Zhang, H.; Ebert, T. T.; Penn, R. L. Science 2000, 289, 751. doi: 10.1126/science.289.5480.751(30) Banfield, J. F.; Welch, S. A.; Zhang, H.; Ebert, T. T.; Penn, R. L. Science 2000, 289, 751. doi: 10.1126/science.289.5480.751
31. [31]
  (31) Penn, R. L.; Banfield, J. F. Science 1998, 281, 969. doi: 10.1126/science.281.5379.969(31) Penn, R. L.; Banfield, J. F. Science 1998, 281, 969. doi: 10.1126/science.281.5379.969
32. [32]
  (32) Shishiyanu, S. T.; Shishiyanu, T. S.; Lupan, O. I. Sens. Actuators B 2006, 113, 468. doi: 10.1016/j.snb.2005.03.061
  (32) Shishiyanu, S. T.; Shishiyanu, T. S.; Lupan, O. I. Sens. Actuators B 2006, 113, 468. doi: 10.1016/j.snb.2005.03.061

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

孔隙结构可调的Cu₂O球状纳米结构及其NO₂气体传感性质

English

Cavity-Tunable Cu₂O Spherical Nanostructures and Their NO₂ Gas Sensing Properties

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

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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

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