Preparation and characterization of sulfated TiO2 with rhodium modification used in esterification reaction and decomposition of methyl orange

doi:10.1016/j.cjche.2015.12.016

Chinese Journal of Chemical Engineering ›› 2016, Vol. 24 ›› Issue (6): 767-774.DOI: 10.1016/j.cjche.2015.12.016

• 第25届中国过程控制会议专栏 • 上一篇下一篇

Preparation and characterization of sulfated TiO₂ with rhodium modification used in esterification reaction and decomposition of methyl orange

Yu Niu^1,2,3, Fuying Li^2,3,4, Kai Yang⁴, Ting Qiu¹, Renzhang Wang^2,3, Cheng Lin¹

1 School of Chemical Engineering, Fuzhou University, Fuzhou 350002, China;
2 Collaborative Innovation Center of Clean Coal Gasification Technology, Sanming University, Sanming 365004, China;
3 College of Resources and Chemical Engineering, Sanming University, Sanming 365004, China;
4 Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350002, China

收稿日期:2015-08-31 修回日期:2015-11-19 出版日期:2016-06-28 发布日期:2016-07-12
通讯作者: Ting Qiu
基金资助:
Supported by the Youth Fund of Fujian Province (JA14290, JA15475), theNatural Fund of Fujian Province (2015J01601) and the Collaborative Innovation Center of Clean Coal Gasification Technology (XK1403, XK1401).

Preparation and characterization of sulfated TiO₂ with rhodium modification used in esterification reaction and decomposition of methyl orange

Yu Niu^1,2,3, Fuying Li^2,3,4, Kai Yang⁴, Ting Qiu¹, Renzhang Wang^2,3, Cheng Lin¹

1 School of Chemical Engineering, Fuzhou University, Fuzhou 350002, China;
2 Collaborative Innovation Center of Clean Coal Gasification Technology, Sanming University, Sanming 365004, China;
3 College of Resources and Chemical Engineering, Sanming University, Sanming 365004, China;
4 Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350002, China

Received:2015-08-31 Revised:2015-11-19 Online:2016-06-28 Published:2016-07-12
Contact: Ting Qiu
Supported by:
Supported by the Youth Fund of Fujian Province (JA14290, JA15475), theNatural Fund of Fujian Province (2015J01601) and the Collaborative Innovation Center of Clean Coal Gasification Technology (XK1403, XK1401).

摘要/Abstract

摘要： A unique Rh/TiO₂ solid acid catalyst modified with H₂SO₄ was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange (MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium (Rh) nanoparticles were loaded on SO₄^2-/TiO₂ via the photo-deposition method. It was found that SO₄^2-/Rh-TiO₂ exhibited stronger catalytic activity than SO₄^2-/TiO₂. The new catalysts were characterized by X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM) and high-resolution (HRTEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). Results from XRD and BET show that SO₄^2-/Rh-TiO₂ has higher specific surface area and smaller pore size than SO₄^2-/TiO₂. The distribution of loaded Rh was found to be uniform with a particle size of 2-4 nm. Data from XPS reveal that Rh primarily exists as Rh⁰ and Rh³⁺ in Rh-TiO₂ and SO₄^2-/Rh-TiO₂. These valence forms of Rh likely contribute to the enhanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh-TiO₂, and these acidic sites are largely responsible for improving the catalytic performance. This superior SO₄^2-/Rh-TiO₂ catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.

关键词: Rhodium, Esterification reaction, SO₄^2-/TiO₂, Photo-deposition, Methyl orange

Abstract: A unique Rh/TiO₂ solid acid catalyst modified with H₂SO₄ was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange (MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium (Rh) nanoparticles were loaded on SO₄^2-/TiO₂ via the photo-deposition method. It was found that SO₄^2-/Rh-TiO₂ exhibited stronger catalytic activity than SO₄^2-/TiO₂. The new catalysts were characterized by X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM) and high-resolution (HRTEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). Results from XRD and BET show that SO₄^2-/Rh-TiO₂ has higher specific surface area and smaller pore size than SO₄^2-/TiO₂. The distribution of loaded Rh was found to be uniform with a particle size of 2-4 nm. Data from XPS reveal that Rh primarily exists as Rh⁰ and Rh³⁺ in Rh-TiO₂ and SO₄^2-/Rh-TiO₂. These valence forms of Rh likely contribute to the enhanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh-TiO₂, and these acidic sites are largely responsible for improving the catalytic performance. This superior SO₄^2-/Rh-TiO₂ catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.

Key words: Rhodium, Esterification reaction, SO₄^2-/TiO₂, Photo-deposition, Methyl orange

Yu Niu, Fuying Li, Kai Yang, Ting Qiu, Renzhang Wang, Cheng Lin. Preparation and characterization of sulfated TiO₂ with rhodium modification used in esterification reaction and decomposition of methyl orange[J]. Chinese Journal of Chemical Engineering, 2016, 24(6): 767-774.

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Preparation and characterization of sulfated TiO₂ with rhodium modification used in esterification reaction and decomposition of methyl orange

Preparation and characterization of sulfated TiO₂ with rhodium modification used in esterification reaction and decomposition of methyl orange

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