光催化分解水制备氢气和过氧化氢

引用本文: 王利超, 曹爽, 郭凯, 吴志娇, 马智, 朴玲钰. 光催化分解水制备氢气和过氧化氢[J]. 催化学报, 2019, 40(3): 470-475. doi: S1872-2067(19)63274-2 shu

Citation: Lichao Wang, Shuang Cao, Kai Guo, Zhijiao Wu, Zhi Ma, Lingyu Piao. Simultaneous hydrogen and peroxide production by photocatalytic water splitting[J]. Chinese Journal of Catalysis, 2019, 40(3): 470-475. doi: S1872-2067(19)63274-2 shu

光催化分解水制备氢气和过氧化氢

王利超 ^a,b, ,
曹爽 ^a, ,
郭凯 ^a, ,
吴志娇 ^a, ,
马智 ^b, ,
朴玲钰 ^a,

a 国家纳米科学中心, 中国科学院纳米科学卓越创新中心, 中国科学院纳米标准与检测重点实验室, 北京 100190;
b 天津大学化工学院催化科学与工程系, 天津 300072
基金项目:
国家自然科学基金（21703046）；国家重点研发计划（2016YFF0203803，2016YFA0200902）.

摘要: 过氧化氢不仅是一种广泛应用于化学合成、消毒、废水处理及纸浆漂白等领域的高价值化学品，还是一种具有潜力的能源载体.此外，过氧化氢燃料电池因其结构简单而受到广泛关注.蒽醌法是工业生产过氧化氢的传统方法，但是这种方法不仅能耗高，而且生产过程会造成严重的环境问题.因此，通过环保并且低成本的工艺直接合成过氧化氢具有重要研究意义.以太阳能为动力的光催化法生产过氧化氢被认为是最有前景的方法之一.目前，光催化已在制氢、二氧化碳还原和水处理等诸多领域取得了重要进展.但是，利用光催化分解水制备过氧化氢的研究还非常少.尽管通过光催化还原氧气可以制备过氧化氢，但是通过分解水同时制备高价值过氧化氢和氢气更具有吸引力.
在本项工作中，我们利用Pt/TiO₂（锐钛矿）光催化剂在没有牺牲剂的条件下实现了高效产氢和过氧化氢，氢气和过氧化氢的生成速率分别达到7410和5096μmol g^-1 h^-1（第一小时），远高于市售的Pt/TiO₂（锐钛矿）体系和文献报道数值.本文采用X射线光电子能谱（XPS）、电子自旋共振（ESR）和荧光标记法等表征手段研究了Pt/TiO₂上同时生成氢气和过氧化氢的催化机理.
XPS测试结果表明，Pt/TiO₂在光照射1h后，XPS信号发生明显变化.与其他样品相比，物理吸附水和羟基的峰明显增加.因此，我们推测羟基和物理吸附水对过氧化氢的生成具有重要影响.进一步采用电子自旋共振（ESR）和荧光标记法对羟基进行了测量.ESR结果显示，紫外光照60s即可检测到羟基捕获剂与羟基的结合物5，5-dimethyl-1-pyrroline-N-oxide-OH（DMPO-OH）的特征峰.此外，在体系中加入荧光标记分子对苯二甲酸（TANa）后也可以迅速检测到2-羟基对苯二甲酸（TAOH）在422nm处明显的荧光信号.因此，ESR和荧光结果均表明所产生的羟基自由基在过氧化氢形成中起着重要作用.
上述结果表明，在本体系中氢气和过氧化氢的生成遵循两电子转移过程.与传统全分解水体系生成氢气和氧气相比，两电子转移过程比四电子过程更容易发生.因此，光催化水氧化制过氧化氢是实现大规模生产氢气和过氧化氢的一种很有前景的方法.

关键词:

English

Simultaneous hydrogen and peroxide production by photocatalytic water splitting

a CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, CAS Key Laboratory of Standardization and Measurement for Nanotechnology, Beijing 100190, China;
b School of chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
Received Date: 05 November 2018
Revised Date: 07 December 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (21703046) and the National Key R&D of China (2016YFF0203803 and 2016YFA0200902).

Abstract: Photocatalytic oxidation of water is a promising method to realize large-scale H₂O₂ production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO₂(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H₂ and H₂O₂ production. Both H₂ and H₂O₂ are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^-1 (first 1 h) for H₂ and H₂O₂, respectively, which is much higher than that of a commercial Pt/TiO₂(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H₂O₂, compared with the four-electron oxidation of water to O₂.

Key words:

1. [1] S. Fukuzumi, Y. M. Lee, W. Nam, Chem.-Eur. J., 2018, 24, 5016-5031.
2. [2] B. Puértolas, A. K. Hill, T. García, B. Solsona, L. Tor-rente-Murciano, Catal. Today, 2015, 248, 115-127.
3. [3] M. N. Young, M. J. Links, S. C. Popat, B. E. Rittmann, C. I. Torres, ChemSusChem, 2016, 9, 3345-3352.
4. [4] K. Mase, M. Yoneda, Y. Yamada, S. Fukuzumi, Nat. Commun., 2016, 7, 11470-11476.
5. [5] Y. Yamada, M. Yoneda, S. Fukuzumi, Energy Environ. Sci., 2015, 8, 1698-1701.
6. [6] R. Ciriminna, L. Albanese, F. Meneguzzo, M. Pagliaro, ChemSus-Chem, 2016, 9, 3374-3381.
7. [7] S. Yang, A. Verdaguer-Casadevall, L. Arnarson, L. Silvioli, V. Čolić, R. Frydendal, J. Rossmeisl, I. Chorkendorff, I. E. L. Stephens, ACS Catal., 2018, 8, 4064-4081.
8. [8] M. C. Wu, K. C. Hsiao, Y. H. Chang, S. H. Chan, Appl. Surf. Sci., 2018, 430, 407-414.
9. [9] D. Ni, H. Shen, H. Li, Y. Ma, T. Zhai, Appl. Surf. Sci., 2017, 409, 241-249.
10. [10] F. Li, Q. Gu, Y. Niu, R. Wang, Y. Tong, S. Zhu, H. Zhang, Z. Zhang, X. Wang, Appl. Surf. Sci., 2017, 391, 251-258.
11. [11] Z. Jiang, M. A. Isaacs, Z. W. Huang, W. Shangguan, Y. Deng, A. F. Lee, ChemCatChem, 2017, 9, 4268-4274.
12. [12] P. Devaraji, W. K. Jo, ChemCatChem, 2018, 10, 3813-3823.
13. [13] W. Chen, Y. Wang, S. Liu, L. Gao, L. Mao, Z. Fan, W. Shangguan, Z. Jiang, Appl. Surf. Sci., 2018, 445, 527-534.
14. [14] F. Chen, W. Luo, Y. Mo, H. Yu, B. Cheng, Appl. Surf. Sci., 2018, 430, 448-456.
15. [15] S. Wei, S. Ni, X. Xu, Chin. J. Catal., 2018, 39, 510-516.
16. [16] J. Wen, X. Li, W. Liu, Y. Fang, J. Xie, Y. Xu, Chin. J. Catal., 2015, 36, 2049-2070.
17. [17] L. Pan, J. Zhang, X. Jia, Y. H. Ma, X. Zhang, L. Wang, J. Zou, Chin. J. Catal., 2017, 38, 253-259.
18. [18] K. Qi, B. Cheng, J. Yu, W. Ho, Chin. J. Catal., 2017, 38, 1936-1955.
19. [19] C. Zhang, L. Tian, L. Chen, X. Li, K. Lv, K. Deng, Chin. J. Catal., 2018, 39, 1373-1383.
20. [20] F. Xu, L. Zhang, B. Cheng, J. Yu, ACS Sustainable Chem. Eng., 2018, 6, 12291-12298.
21. [21] A. Meng, J. Zhang, D. Xu, B. Cheng, J. Yu, Appl. Catal. B, 2016, 198, 286-294.
22. [22] J. Chen, T. Ding, J. Cai, Y. Wang, M. Wu, H. Zhang, W. Zhao, Y. Tian, X. Wang, X. Li, Appl. Surf. Sci., 2018, 453, 101-109.
23. [23] L. Kong, X. Zhang, C. Wang, F. Wan, L. Li, Chin. J. Catal., 2017, 38, 2120-2131.
24. [24] Q. F. Liu, Q. Zhang, B. R. Liu, S. Li, I. J. Ma, Chin. J. Catal., 2018, 39, 542-548.
25. [25] Y. Kofuji, S. Ohkita, Y. Shiraishi, H. Sakamoto, S. Ichikawa, S. Tanaka, T. Hirai, ACS Sustainable Chem. Eng., 2017, 5, 6478-6485.
26. [26] Y. Kofuji, Y. Isobe, Y. Shiraishi, H. Sakamoto, S. Tanaka, S. Ichikawa, T. Hirai, J. Am. Chem. Soc., 2016, 138, 10019-10025.
27. [27] A. Naldoni, T. Montini, F. Malara, M. M. Mróz, A. Beltram, T. Virgili, C. L. Boldrini, M. Marelli, I. Romero-Ocaña, J. J. Delgado, V. D. Santo, P. Fornasiero, ACS Catal., 2017, 7, 1270-1278.
28. [28] R. Li, Y. Weng, X. Zhou, X. Wang, Y. Mi, R. Chong, H. Han, C. Li, En-ergy Environ. Sci., 2015, 8, 2377-2382.
29. [29] K. Maeda, Chem. Commun., 2013, 49, 8404-8406.
30. [30] V. M. Daskalaki, P. Panagiotopoulou, D. I. Kondarides, Chem. Eng. J., 2011, 170, 433-439.
31. [31] J. Liu, Y. Zhang, L. Lu, G. Wu, W. Chen, Chem. Commun., 2012, 48, 8826-8828.
32. [32] Z. Wu, S. Cao, C. Zhang, L. Piao, Nanotechnology, 2017, 28, 275706/1-275706/12.
33. [33] Z. Li, B. Tian, W. Zhen, Y. Wu, G. Lu, Appl. Catal. B, 2017, 203, 408-415.
34. [34] M. Liu, L. Piao, W. Lu, S. Ju, C. Zhou, H. Li, W. Wang, Nanoscale, 2010, 2, 1115-1117.
35. [35] M. Liu, M. Zhong, H. Li, L. Piao, W. Wang, ChemPlusChem, 2015, 80, 688-696.
36. [36] M. A. Khalily, H. Eren, S. Akbayrak, H. H. Susapto, N. Biyikli, S. Özkar, M. O. Guler, Angew. Chem. Int. Ed., 2016, 55, 12257-12261.
37. [37] D. Wang, Z. P. Liu, W. M. Yang, ACS Catal., 2017, 7, 2744-2752.
38. [38] J. Cai, M. Wu, Y. Wang, H. Zhang, M. Meng, Y. Tian, X. Li, J. Zhang, L. Zheng, J. Gong, Chem, 2017, 2, 877-892.
39. [39] T. D. Nguyen-Phan, S. Luo, Z. Liu, A. D. Gamalski, J. Tao, W. Xu, E. A. Stach, D. E. Polyansky, S. D. Senanayake, E. Fujita, J. A. Rodriguez, Chem. Mater., 2015, 27, 6281-6296.
40. [40] Z. Wei, D. Liu, W. Wei, X. Chen, Q. Han, W. Yao, X. Ma, Y. Zhu, ACS Appl. Mater. Interfaces, 2017, 9, 15533-15540.
41. [41] J. J. Wang, Z. J. Li, X. B. Li, X. B. Fan, Q. Y. Meng, S. Yu, C. B. Li, J. X. Li, C. H. Tung, L. Z. Wu, ChemSusChem, 2014, 7, 1468-1475.
42. [42] S. Cao, Y. Chen, H. Wang, J. Chen, X. Shi, H. Li, P. Cheng, X. Liu, M. Liu, L. Piao, Joule, 2018, 2, 549-557.
43. [43] T. Tachikawa, M. Fujitsuka, T. Majima, J. Phys. Chem. C, 2007, 111, 5295-5275.
44. [44] X. Li, J. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-2636.
45. [45] K. Sayama, H. Arakawa, J. Chem. Soc., Faraday Trans., 1997, 93, 1647-1654.

扫一扫看文章

计量

PDF下载量: 59
文章访问数: 2433
HTML全文浏览量: 512

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

光催化分解水制备氢气和过氧化氢

English

Simultaneous hydrogen and peroxide production by photocatalytic 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

光催化分解水制备氢气和过氧化氢

English

Simultaneous hydrogen and peroxide production by photocatalytic 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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs