利用非贵金属等离子体Al修饰TiO<sub>2</sub>/Cu<sub>2</sub>O异质结以提高光电催化分解水性能

引用本文: 张劭策, 刘志锋, 闫卫国, 郭振刚, 阮梦楠. 利用非贵金属等离子体Al修饰TiO₂/Cu₂O异质结以提高光电催化分解水性能[J]. 催化学报, 2020, 41(12): 1884-1893. doi: 10.1016/S1872-2067(20)63637-3 shu

Citation: Shaoce Zhang, Zhifeng Liu, Weiguo Yan, Zhengang Guo, Mengnan Ruan. Decorating non-noble metal plasmonic Al on a TiO₂/Cu₂O photoanode to boost performance in photoelectrochemical water splitting[J]. Chinese Journal of Catalysis, 2020, 41(12): 1884-1893. doi: 10.1016/S1872-2067(20)63637-3 shu

利用非贵金属等离子体Al修饰TiO₂/Cu₂O异质结以提高光电催化分解水性能

a 天津城建大学材料科学与工程学院, 天津 300384;
b 天津城建大学建筑绿色功能材料天津重点实验室, 天津 300384
基金项目:
天津市杰出青年基金（17JCJQJC44800）；天津市重点研发计划项目（19YFSLQY00020）.

摘要: 在光电化学（PEC）中，利用半导体纳米材料分解水产生氧气和氢气成为解决能源和环境危机的有效途径，而设计具有较高的光子捕获效率和电荷分离率的低成本光电极是研究的重点.近年来，已有许多半导体材料（例如ZnO，Fe₂O₃，WO₃，Cu₂O，CuInS₂等）被用做光电极参与光电催化分解水.其中，TiO₂作为一种n型半导体，由于其具有适当的导带（CB）和价带（VB）位置、良好的耐光腐蚀性、无毒性和出色的稳定性而引起人们的关注.然而，光响应范围窄，光生载流子复合率高等问题限制了TiO₂光电极在PEC水分解中的应用.因此，选用合适的窄禁带半导体和助催化剂进行复合修饰能够有效地扩大光响应范围，促进载流子的分离和转移，从而提升电极的光电催化性能.
本文利用具有表面等离子体共振（SPR）效应的Al对TiO₂/Cu₂O核/壳异质结进行改性，制备了TiO₂/Cu₂O/Al/Al₂O₃光电阳极.SEM和TEM等结果显示已成功合成核/壳异质结.UV-vis吸收光谱和UPS测试计算表明，Cu₂O不仅可以显著扩展电极的吸光范围，且计算所得TiO₂和Cu₂O导价带位置验证了p-n异质结的合成.结合光电流、EIS等测试，证明了异质结能够有效地促进光生载流子的分离和转移.同时，在光照激发下，UV-vis吸收光谱在550nm出现明显的特征峰，表明Al的SPR效应被成功激发.Al纳米颗粒的SPR效应不仅可以产生热电子，并能够增强与异质结界面处的电场.之后，通过Mott-Schottk测试和Bode图，较为直观地说明了异质结和SPR效应的协同作用能够增加载流子的浓度，抑制电子空穴的复合，使所制备的TiO₂/Cu₂O/Al/Al₂O₃光电阳极表现出良好的光电性能，其光电流达到了4.52mA/cm²（1.23V vs.RHE），是TiO₂/Cu₂O异质结的1.84倍.相比于同样具有SPR效应的Au，Ag等贵金属而言，Al不仅价格低廉，而且在空气中自发形成的超薄Al₂O₃薄膜能够有效地抑制Al的进一步氧化，并作为保护层能够显著提高电极的稳定性.在对样品稳定性的测试中，由于Al₂O₃保护层的存在，电极的稳定性提高了53%.本文对样品的实验测试和原理分析表明了异质结和非贵金属Al的SPR效应的协同作用显著提高了光电极的光电性能，为设计具有良好性能和高实用性的电极提供了新思路.

关键词:

English

Decorating non-noble metal plasmonic Al on a TiO₂/Cu₂O photoanode to boost performance in photoelectrochemical water splitting

a School of Materials Science and Engineering, Tianjin Chengjian University, Tianjin 300384, China;
b Tianjin Key Laboratory of Building Green Functional Materials, Tianjin Chengjian University, Tianjin 300384, China
Received Date: 13 March 2020
Revised Date: 21 April 2020
Fund Project:
This work was supported by the Science Funds of Tianjin for Distinguished Young Scholar (17JCJQJC44800) and Key Research and Development Plan of Tianjin (19YFSLQY00020).

Abstract: Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting. Here, a novel TiO₂/Cu₂O/Al/Al₂O₃ photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO₂/Cu₂O core/shell heterojunction for the first time. The Al nanoparticles, which exhibit a surface plasmon resonance (SPR) effect and are substantially less expensive than noble metals such as Au and Ag, generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination. The as-prepared TiO₂/Cu₂O/Al/Al₂O₃ photoelectrodes have an extended absorption range and enhanced carrier separation and transfer. Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs. RHE represents an 1.84-fold improvement over that of TiO₂/Cu₂O. Specifically, the ultrathin Al₂O₃ passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability. In this work, the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance, providing a novel concept for the design of electrodes with good properties and high practicability.

Key words:

1. [1] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
2. [2] R. B. Wei, P. Y. Kuang, H. Cheng, Y. Chen, J. Y. Long, M. Zhang, Z. Q. Liu, ACS Sustain. Chem. Eng., 2017, 5, 4249-4257.
3. [3] D. Chen, Z. Liu, S. Zhang, Appl. Catal. B, 2020, 265, 118580.
4. [4] Y. Li, Z. Liu, Z. Guo, M. Ruan, X. Li, Y. Liu, ACS Sustain. Chem. Eng., 2019, 7, 12582-12590.
5. [5] M. N. I. Salehmin, L. J. Minggu, W. F. Mark-Lee, M. A. Mohamed, K. Arifin, M H. H. Jumali, M. B. Kassim, Sol. Energy Mater. Sol. Cells, 2018, 182, 237-245.
6. [6] Z. Liu, X. Lu, D. Chen, ACS Sustain. Chem. Eng., 2018, 6, 10289-10294.
7. [7] S. Zhou, K. Chen, J. Huang, L. Wang, M. Zhang, B. Bai, H. Liu, Q. Wang, Appl. Catal. B, 2020, 118513.
8. [8] K. Guo, Z. Liu, C. Zhou, J. Han, Y. Zhao, Z. Liu, Y. Li, T. Cui, B. Wang, J. Zhang, Appl. Catal. B, 2014, 154, 27-35.
9. [9] M. H. Elbakkay, W. M. A. El Rouby, S. I. El-Dek, A. A. Farghali, Appl. Surf. Sci., 2018, 439, 1088-1102.
10. [10] P. P. Liu, X. Liu, X. H. Huo, Y. Tang, J. Xu, H. Ju, ACS Appl. Mater. Interfaces, 2017, 9, 27185-27192.
11. [11] Y. C. Pu, G. Wang, K. D. Chang, Y. Ling, Y. K. Lin, B. C. Fitzmorris, C. M. Liu, X. Lu, Y. Tong, J. Z. Zhang, Y. J. Hsu, Y. Li, Nano Lett., 2013, 13, 3817-3823.
12. [12] Q. Liu, H. Lu, Z. Shi, F. Wu, J. Guo, K. Deng, L. Li, ACS Appl. Mater. Interfaces, 2014, 6, 17200-17207.
13. [13] G. Ai, H. Li, S. Liu, R. Mo, J. Zhong, Adv. Funct. Mater., 2015, 25, 5706-5713.
14. [14] J. A. Seabold, K. Shankar, R. H. T. Wilke, A. Jason, M. Paulose, O. K. Varghese, C. A. Grimes, K. S. Choi, Chem. Mater., 2008, 20, 5266-5273.
15. [15] M. Chandra, K. Bhunia, D. Pradhan, Inorg. Chem., 2018, 57, 4524-4533.
16. [16] L. Yang, W. Wang, H. Zhang, S. Wang, M. Zhang, G. He, J. Lv, K. Zhu, Z. Sun, Sol. Energy Mater. Sol. Cells, 2017, 165, 27-35.
17. [17] Y. Tolstova, S. T. Omelchenko, R. E. Blackwell, A. M. Shing, H. A. Atwater, Sol. Energy Mater. Sol. Cells, 2017, 160, 340-345.
18. [18] M. Wang, L. Sun, Z. Lin, J. Cai, K. Xie, C. Lin, Energy Environ. Sci., 2013, 6, 1211-1220.
19. [19] T. Zhou, Z. Zang, J. Wei, J. Zheng, J. Hao, F. Ling, X. Tang, L. Fang, M. Zhou, Nano Energy, 2018, 50, 118-125.
20. [20] C. H. Ma, Z. F. Liu, J. Q. Cai, C. C. Han, Z. F. Tong, Inorg. Chem. Front., 2018, 5, 2571-2578.
21. [21] S. K. Saraswat, D. D. Rodene, R. B. Gupta, Renew. Sust. Energy Rev., 2018, 89, 228-248.
22. [22] C. Clavero, Nature Photon., 2014, 8, 95-103.
23. [23] Y. Tian, T. Tatsuma, J. Am. Chem. Soc., 2005, 127, 7632-7637.
24. [24] D. Chaudhary, S. Singh, V. D. Vankar, N. Khare, Int. J. Hydrogen Energy, 2017, 42, 7826-7835.
25. [25] M. W. Knight, N. S. King, L. Liu, H. O. Everitt, P. Nordlander, N. J. Halas, ACS Nano, 2013, 8, 834-840.
26. [26] D. Chen, Z. Liu, Z. Guo, W. Yan, M. Ruan, Chem. Eng. J., 2020, 381, 122655.
27. [27] Z. Li, L. Shi, D. Franklin, S. Koul, A. Kushima, Y. Yang, Nano Energy, 2018, 51, 400-407.
28. [28] Z. F. Liu, K. Y. Guo, J. H. Han, Y. J. Li, T. Cui, B. Wang, J. Ya, C. L. Zhou, Small, 2014, 10, 3153-3161.
29. [29] D. Chen, Z. Liu, Z. Guo, W. Yan, Y. Xin, J. Mater. Chem. A, 2018, 6, 20393-20401.
30. [30] H. She, P. Yue, J. Huang, L. Wang, Q. Wang, Chem. Eng. J., 2019, 123703.
31. [31] Y. Wei, Y. Zhang, W. Geng, H. Su, M. Long, Appl. Catal. B, 2019, 259, 118084.
32. [32] L. Zheng, H. Su, J. Zhang, L. S. Walekar, H. V. Molamahmood, B. Zhou, M. Long, Y. H. Hu, Appl. Catal. B, 2018, 239, 475-484.
33. [33] M. P. Suryawanshi, S. W. Shin, U. V. Ghorpade, J. Kim, H. W. Jeong, S. H. Kang, J. H. Kim, J. Mater. Chem. A, 2018, 6, 20678-20685.
34. [34] G. Zhu, S. Li, J. Gao, F. Zhang, C. Liu, Q. Wang, M. Hojamberdiev, Appl. Surf. Sci., 2019, 493, 913-925.
35. [35] S. Ma, Y. Deng, J. Xie, K. He, W. Liu, X. Chen, X. Li, Appl. Catal. B, 2018, 227, 218-228.
36. [36] B. F. Zheng, T. Ouyang, Z. Wang, J. Long, Y. Chen, Z. Q. Liu, Chem. Commun., 2018, 54, 9583-9586.
37. [37] L. Yu, G. Li, X. Zhang, X. Ba, G. Shi, Y. Li, P. K. Wong, J. C. Yu, Y. Yu, ACS Catal, 2016, 6, 6444-6454.
38. [38] S. Zhang, Z. Liu, M. Ruan, Z. Guo, L. E, W. Zhao, D. Zhao, X. Wu, D. Chen, Appl. Catal. B, 2020, 262, 118279.
39. [39] L. Pan, S. Wang, J. Xie, L. Wang, X. Zhang, J. J. Zou, Nano Energy, 2016, 28, 296-303.
40. [40] W. Yuan, J. Yuan, J. Xie, C. M. Li, ACS Appl. Mater. Interfaces, 2016, 8, 6082-6092.
41. [41] B. Parkinson, Acc. Chem. Res., 1984, 17, 431-437.
42. [42] P. Wang, S. Xu, F. Chen, H. Yu, Chin. J. Catal., 2019, 40, 343-351.
43. [43] Z. Liu, X. Wang, Int. J. Hydrogen Energy, 2018, 43, 13276-13283.
44. [44] Y. Zhu, Z. Zhang, N. Lu, R. Hua, B. Dong, Chin. J. Catal., 2019, 40, 413-423.
45. [45] M. Long, J. Brame, F. Qin, J. Bao, Q. Li, P. J. J. Alvarez, Environ. Sci. Technol., 2017, 51, 514-521.
46. [46] D. Chen, Z. Liu, ChemSusChem, 2018, 11, 3438-3448.
47. [47] K. He, J. Xie, Z. Liu, N. Li, X. Chen, J. Hu, X. Li, J. Mater. Chem. A, 2018, 6, 13110-13122.
48. [48] S. He, K. Xiao, X. Z. Chen, T. Li, T. Ouyang, Z. Wang, M. L. Guo, Z. Q. Liu, J. Colloid Interface Sci., 2019, 557, 644-654.
49. [49] L. Zheng, J. Zhang, Y. H. Hu, M. Long, J. Phys. Chem., C, 2019, 123, 13693-13701.
50. [50] Y. Q. Ye, G. H. Gu, X. T. Wang, T. Ouyang, Y. Chen, Z. Q. Liu, Int. J. Hydrogen Energy, 2019, 44, 21865-21872.
51. [51] X. Li, J. Xiong, Y. Xu, Z. Feng, J. Huang, Chin. J. Catal., 2019, 40, 424-433.
52. [52] Z. Liu, J. Zhang, W. Yan, ACS Sustain. Chem. Eng., 2018, 6, 3565-3574.
53. [53] J. Shen, R. Wang, Q. Liu, X. Yang, H. Tang, J. Yang, Chin. J. Catal., 2019, 40, 380-389.
54. [54] F. Rao, G. Zhu, M. Hojamberdiev, W. Zhang, S. Li, J. Gao, F. Zhang, Y. Huang, Y Huang, J. Phys. Chem. C, 2019, 123, 16268-16280.
55. [55] X. Lu, J. Xie, S. Liu, A. Adamski, X. Chen, X. Li, ACS Sustain. Chem. Eng., 2018, 6, 13140-13150.
56. [56] A. Paracchino, V. Laporte, K. Sivula, M. Grätzel, E. Thimsen, Nat. Mater., 2011, 10, 456-461.

扫一扫看文章

计量

PDF下载量: 52
文章访问数: 2750
HTML全文浏览量: 302

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

利用非贵金属等离子体Al修饰TiO₂/Cu₂O异质结以提高光电催化分解水性能

English

Decorating non-noble metal plasmonic Al on a TiO₂/Cu₂O photoanode to boost performance in photoelectrochemical water splitting

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

利用非贵金属等离子体Al修饰TiO2/Cu2O异质结以提高光电催化分解水性能

English

Decorating non-noble metal plasmonic Al on a TiO2/Cu2O photoanode to boost performance in photoelectrochemical water splitting

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

利用非贵金属等离子体Al修饰TiO₂/Cu₂O异质结以提高光电催化分解水性能

Decorating non-noble metal plasmonic Al on a TiO₂/Cu₂O photoanode to boost performance in photoelectrochemical water splitting

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs