Study on Selective Photocatalytic Oxidation of Ethanol During TiO2 Promoted Water-Splitting Process

doi:10.6023/A16110641

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (5): 508-513.DOI: 10.6023/A16110641 Previous Articles

Article

二氧化钛光解水过程中乙醇选择性光催化氧化反应研究

孟超, 王华, 吴煜斌, 付贤智, 员汝胜

能源与环境光催化国家重点实验室福州大学化学学院福州 350116

投稿日期:2016-11-28 发布日期:2017-04-25
通讯作者: 员汝胜 E-mail:yuanrs@fzu.edu.cn
基金资助:
项目受国家自然科学基金（No.21643009），国家科技支撑计划（No.2014BAC13B03），福建省自然科学基金（No.2015J01046）和能源与环境光催化重点实验室自主课题（No.2014B01）资助.

Study on Selective Photocatalytic Oxidation of Ethanol During TiO₂ Promoted Water-Splitting Process

Meng Chao, Wang Hua, Wu Yubin, Fu Xianzhi, Yuan Rusheng

State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116

Received:2016-11-28 Published:2017-04-25
Contact: 10.6023/A16110641 E-mail:yuanrs@fzu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21643009), the National Key Technologies R & D Program of China (No. 2014BAC13B03), the Natural Science Foundation of Fujian Province of China (No. 2015J01046), and the Independent Research Project of State Key Laboratory of Photocatalysis on Energy and Environment (No. 2014B01).

1. Study on Selective Photocatalytic Oxidation of Ethanol During TiO₂ Promoted Water-Splitting Process.PDF(896KB)

Abstract

In this work, the reaction mechanism of photocatalytic oxidation of sacrificial ethanol during water-splitting process by titanium dioxide (TiO₂) has been studied. The pure rutile TiO₂ or mixed-phase structure titania (P25) was employed as the typical photocatalyst in ethanol oxidation. The as-obtained results showed that the formation of 2,3-butanediol over TiO₂ in heterogeneous systems is mainly due to the photochemical reaction proceeded between acetaldehyde molecule and ethanol molecule instead of the direct coupling of α-hydroxyethyl radicals. This is different from the early work claimed that the fundamental process to produce 2,3-butanediol is based on the direct coupling of α-hydroxyethyl radicals generated by TiO₂ oxidation. The photochemical reaction between acetaldehyde molecule and ethanol molecule to form 2,3-butanediol can also occur when the concentration of the solid catalyst was reduced to certain degree if using P25 as catalyst in heterogeneous model, and the selectivity of 2,3-butanediol would change from ca. 60% to 0% when enlarging the concentration of P25 step by step. However, the selectivity of 2,3-butanediol is relatively invariable when the concentration of catalyst was changed if using rutile as photocatalyst. We thought that the distinct diffusing behaviors for mobile ·OH_f and surface bound ·OH_s generated on different titania can explain the varied selectivity when the solid concentration of TiO₂ changed. The generation and diffusion of ·OH from the surface of P25 (80% anatase) to bulk solution is a key process to inhibit the direct coupling of α-hydroxyethyl radicals to produce acetaldehyde or further overoxidation products, and the reaction zone of ·OH_f depends on the concentration of P25. For the case of rutile TiO₂promoted reaction, the lack of mobile ·OH_f on rutile TiO₂ makes the photochemical reaction between acetaldehyde molecule and ethanol molecule more facile to occur in bulk solution since the surface bound ·OH_s can only have chance to attack the surface adsorbed substrates. This may be an important reason to explain why the selectivity of 2,3-butanediol in ethanol oxidation was not influenced significantly by the variation of rutile TiO₂ concentration. All the results regarding ethanol transformation during photocatalytic process achieved here cast some light on the mechanistic understanding of the reactions proceeded on the surface of solid catalyst in heterogeneous model and in the bulk solution when both catalytic step and photochemical step existed simultaneously.

Key words: photocatalytic, titanium dioxide, ethanol, hydroxyl radicals, 2,3-butanediol

Cite this article

Meng Chao, Wang Hua, Wu Yubin, Fu Xianzhi, Yuan Rusheng. Study on Selective Photocatalytic Oxidation of Ethanol During TiO₂ Promoted Water-Splitting Process[J]. Acta Chim. Sinica, 2017, 75(5): 508-513.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Pan, C.; Gu, Z.-Z.; Dong, L. Acta Chim. Sinica 2009, 67, 1981. (潘超, 顾忠泽, 董丽, 化学学报, 2009, 67, 1981.)
[2] Lv, X.-J.; Xu, Y.-M.; Wang, Z.; Zhao, J.-C.; Wu, Y.-D. Acta Chim. Sinica 2004, 62, 1455. (吕学钧, 许宜铭, 王智, 赵进才, 吴烨铤, 化学学报, 2004, 62, 1455.)
[3] Li, Y.-J.; Cao, T.-P.; Wang, C.-H.; Shao, C.-L. Acta Chim. Sinica 2011, 69, 2597. (李跃军, 曹铁平, 王长华, 邵长路, 化学学报, 2011, 69, 2597.)
[4] Wan, Z.-Q.; Zheng, S.-N.; Jia, C.-Y.; Yan, W. Acta Chim. Sinica 2009, 67, 403. (万中全, 郑树楠, 贾春阳, 延卫, 化学学报, 2009, 67, 403.)
[5] Guo, Q.; Xu, C.-B.; Ren, Z.-F.; Yang, W.-S.; Ma, Z.-B.; Dai, D.-X.; Fan, H.-J.; Minton, T. K.; Yang, X.-M. J. Am. Chem. Soc. 2012, 134, 13366.
[6] Xu, C.-B.; Yang, W.-S.; Ren, Z.-F.; Dai, D.-X.; Guo, Q.; Minton, T. K.; Yang, X.-M. J. Am. Chem. Soc. 2013, 135, 19039.
[7] Bamwenda, G. R.; Tsubota, S.; Nakamura, T.; Haruta, M. J. Photochem. Photobiol. A 1995, 89, 177.
[8] Idriss, H.; Seebauer, E. G. J. Mol. Catal. A: Chem. 2000, 152, 201.
[9] Llorca, J.; Homs, N.; Sales, J.; Piscina, P. R. D. L. J. Catal. 2002, 209, 306.
[10] Murdoch, M.; Waterhouse, G. I. N.; Nadeem, M. A.; Metson, J. B.; Keane, M. A.; Howe, R. F.; Llorca, J.; Idriss, H. Nat. Chem. 2011, 3, 489.
[11] Meng, C.; Yang, K.; Fu, X.-Z.; Yuan, R.-S. ACS Catal. 2015, 5, 3760.
[12] Lu, H.-Q.; Zhao, J.-H.; Li, L.; Gong, L.-M.; Zheng, J.-F.; Zhang, L.-X.; Wang, Z.-J.; Zhang, J.; Zhu, Z.-P. Energy Environ. Sci. 2011, 4, 3384.
[13] Yang, P.-J.; Zhao, J.-H.; Cao, B.-Y.; Li, L.; Wang, J.-Z.; Tian, X.-X.; Jia, S.-P.; Zhu, Z.-P. ChemCatChem 2015, 7, 2384.
[14] Wang, J.; Yang, P.-J.; Cao, B.-Y.; Zhao, J.-H.; Zhu, Z.-P. Appl. Surf. Sci. 2015, 325, 86.
[15] Lu, H.-Q.; Zhao, B.-B.; Zhang, D.; Lv, Y.-L.; Shi, B.-P.; Shi, X. C.; Wen, J.; Yao, J.-F.; Zhu, Z.-P. J. Photochem. Photobiol. A 2013, 272, 1.
[16] Cao, B.-Y.; Zhang, J.; Zhao, J.-H.; Wang, Z.-J.; Yang, P.-J.; Zhang, H.-X.; Li, L.; Zhu, Z.-P. ChemCatChem 2014, 6, 1673.
[17] Li, N.; Yan, W. J.; Yang, P.-J.; Zhang, H.-X.; Wang, Z.-J.; Zheng, J.-F.; Jia, S.-P.; Zhu, Z.-P. Green Chem. 2016, 18, 6029.
[18] Ohno, T.; Izumi, S.; Fujihara, K.; Masaki, Y.; Matsumura, M. J. Phys. Chem. B 2000, 104, 6801.
[19] Chai, Z.-G.; Zeng, T.-T.; Li, Q.; Lu, L.-Q.; Xiao, W.-J.; Xu, D.-S. J. Am. Chem. Soc. 2016, 138, 10128.
[20] Shimizu, Y.; Sugimoto, S.; Kawanishi, S.; Suzuki, N. Bull. Chem. Soc. Jpn. 1991, 64, 3607.
[21] Asmus, K. D.; Mockel, H.; Henglein, A. J. Phys. Chem. 1973, 77, 1218.
[22] Sun, L. Z.; Bolton, J. R. J. Phys. Chem. 1996, 100, 4127.
[23] Wu, W.-M.; Wen, L.-R.; Shen, L.-J.; Liang, R.-W.; Yuan, R.-S.; Wu, L. Appl. Catal. B 2013, 130~131, 163.
[24] Wu, W.-M.; Liu, G.; Liang, S.-J.; Chen, Y.; Shen, L.-J.; Zheng, H.-R.; Yuan, R.-S.; Hou, Y.-D.; Wu, L. J. Catal. 2012, 290, 13.
[25] Xu, Y.; Schoonen, M. A. A. Am. Mineral. 2000, 85, 543.
[26] Fujishima, A.; Zhang, X.; Tryk, D. A. Surf. Sci. Rep. 2008, 63, 515.
[27] Li, R.-G.; Weng, Y.-X.; Zhou, X.; Wang, X.-L.; Mi, Y.; Chong, R.-F.; Han, H.-X.; Li, C. Energy Environ. Sci. 2015, 8, 2377.
[28] Kavan, L.; Gratzel, M.; Gilbert, S. E.; Klemenz, C.; Scheel, J. J. Am. Chem. Soc. 1996, 118, 6716.
[29] Yamakata, A.; Ishibashi, T. A.; Onishi, H. Chem. Phys. 2007, 339, 133.
[30] Xu, M.; Gao, Y.; Moreno, E. M.; Kunst, M.; Muhler, M.; Wang, Y.; Idriss, H.; Wçll, C. Phys. Rev. Lett. 2011, 106, 138302.
[31] Tang, H.; Prasad, K.; Sanjines, R.; Schmid, P. E.; Levy, F. J. Appl. Phys. 1994, 75, 2042.
[32] Luttrell, T.; Halpegamage, S.; Tao, J.; Kramer, A.; Sutter, E.; Batzill, M. Sci. Rep. 2014, 4, 4043.
[33] Goto, H.; Hanada, Y.; Ohno, T.; Matsumura, M. J. Catal. 2004, 225, 223.
[34] Bui, T. D.; Kimura, A.; Ikeda, S.; Matsumura, M. J. Am. Chem. Soc. 2010, 132, 8453.
[35] Kim, W.; Tachikawa, T.; Moon, G. H.; Majima, T.; Choi, W. Angew. Chem., Int. Ed. 2014, 53, 14036.

二氧化钛光解水过程中乙醇选择性光催化氧化反应研究

Study on Selective Photocatalytic Oxidation of Ethanol During TiO₂ Promoted Water-Splitting Process

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Guoqiang Zhang, Jinghao Huo, Xin Wang, Shouwu Guo. P-doped TiO₂/C Nanotubes as Anodes for High-performance Li-ion Capacitors [J]. Acta Chimica Sinica, 2023, 81(1): 6-13.
[2]	Pengfei Zhu, Chensi Lou, Yuhan Shi, Chuanyi Wang. Study on Preparation of Ag/AgCl/ZIF-8 Composite and Photocatalytic NO Oxidation Performance [J]. Acta Chimica Sinica, 2022, 80(10): 1385-1393.
[3]	Tong Jiao, Xue-lian Xu, Lei Zhang, You-yun Weng, Yu-bing Weng, Zhi-xian Gao. Research on CuO/CeO₂-ZrO₂/SiC Monolithic Catalysts for Hydrogen Production by Methanol Steam Reforming [J]. Acta Chimica Sinica, 2021, 79(4): 513-519.
[4]	Huan Liu, Li Li, Ping Li, Guangzhi Zhang, Xun Xu, Hao Zhang, Lingfang Qiu, Hui Qi, Shuwang Duo. In-situ Construction of 2D/3D ZnIn₂S₄/TiO₂ with Enhanced Photocatalytic Performance [J]. Acta Chimica Sinica, 2021, 79(10): 1293-1301.
[5]	Guopeng Xiao, Weijun Qiao, Lei Zhang, Shaojun Qing, Caishun Zhang, Zhixian Gao. Study on Hydrogen Production Catalytic Materials for Perovskite Methanol Steam Reforming [J]. Acta Chimica Sinica, 2021, 79(1): 100-107.
[6]	Yang, Junhang, Fu, Xiaobo, Lu, Zenghui, Zhu, Gangguo. Visible-Light Photocatalytic Remote Thiolation of Aldehydes Triggered by Sulfonylation of Alkenes With Thiosulfonates [J]. Acta Chimica Sinica, 2019, 77(9): 901-905.
[7]	Wang Yongsheng, Zhao Yunlu, Zhao Zhenzhen, Lan Xiaolin, Xu Jinxia Xu Weixiang, Duan Zhengkang. Study on Preparation of Cu-ZrO₂ Catalyst Coated by Nitrogen-Doped Carbon and Catalytic Dehydrogenation Performance [J]. Acta Chim. Sinica, 2019, 77(7): 661-668.
[8]	Fu Wenwen, Li Yan, Liang Changhai. Dehydrogenation Mechanism of Ethanol on Co(111) Surface: A First-principles Study [J]. Acta Chim. Sinica, 2019, 77(6): 559-568.
[9]	Ren Xiang, Zhang Xiaoping, Wang Yufen, Cao Jingyu, Cheng Yuanyuan, Feng Shouhua, Chen Huanwen. Intramolecular and Intermolecular Methyl Migration of Fenthion Studied by Electrospray Ionization Mass Spectrometry [J]. Acta Chimica Sinica, 2019, 77(4): 358-364.
[10]	Liu Jiao, Sun Hailong, Yin Lu, Yuan Yaxian, Xu Minmin, Yao Jianlin. On-line Monitoring on the Micro-synthesis of α-Phenylethanol by Microfluidic Chip Combined with Surface Enhanced Raman Spectroscopy [J]. Acta Chim. Sinica, 2019, 77(3): 257-262.
[11]	Li Xin, Zhang Taiyang, Wang Tian, Zhao Yixin. Recent Progress of Photocatalysis Based on Metal Halide Perovskites [J]. Acta Chimica Sinica, 2019, 77(11): 1075-1088.
[12]	Liu Yucan, Su Miaomiao, Zhang Yan, Duan Jinming, Li Wei. Influence Rule of Organic Solvents Methanol from Sample Preparation on Degradation Rate and Mechanism of Atrazine in UV-based Oxidation Processes [J]. Acta Chim. Sinica, 2019, 77(1): 72-83.
[13]	Jia Zhenlong, Tu Yunbao, Wang Jianqiang, Frenkel Anatoly I., Yang Weimin, Liu Zhongneng, Xu Zhongqianga. In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO₂ Catalyst [J]. Acta Chim. Sinica, 2018, 76(8): 639-643.
[14]	Chu Wanyi, Tang Xiao, Li Zhen, Lin Jingcheng, Qian Jueshi. Influence Factors on the Microstructure of Ultrathin TiO₂ Nanosheets Synthesized by Liquid Phase Method [J]. Acta Chim. Sinica, 2018, 76(7): 549-555.
[15]	Wu Kuangheng, Zhou Yawei, Ma Xianyin, Ding Chen, Cai Wenbin. Controlled Synthesis of Gold-Platinum Catalysts for Ethanol Electro-oxidation Reaction [J]. Acta Chim. Sinica, 2018, 76(4): 292-297.