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

Chin.J.Chem.Eng. ›› 2016, Vol. 24 ›› Issue (6): 767-774.DOI: 10.1016/j.cjche.2015.12.016

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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:2016-07-12 Published:2016-06-28
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).

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

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).

Abstract

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

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

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]. Chin.J.Chem.Eng., 2016, 24(6): 767-774.

References

[1] A. Fujishima, X. Zhang, D. Tryk, TiO₂ photocatalysis and related surface phenomena, Surf. Sci. Rep. 63(2008) 515-582.

[2] Changlin Yu, Jimmy C. Yu, A simple way to prepare C-N-codoped TiO₂ photocatalyst with visible-light activity, Catal. Lett. 129(2009) 462-470.

[3] Michael Jean-Claude Nalbandian, Katherine E. Greenstein, Danmeng Shuai, Miluo Zhang, Yong-ho Choa, Gene F. Parkin, Nosang Vincent Myung, David M. Cwiertny, Tailored synthesis of photoactive TiO₂ nanofibers and Au/TiO₂ nanofiber composites:structure and reactivity optimization for water treatment applications, Environ. Sci. Technol. 49(2015) 1654-1663.

[4] Z. Zhang, C.C. Wang, R. Zakaria, J.Y. Ying, Role of particle size in nanocrystalline TiO₂-based photocatalysts, J. Phys. Chem. B 102(1998) 10871-10878.

[5] X. Li, H. Liu, L. Cheng, H. Tong, Photocatalytic oxidation using a newcatalyst TiO₂ microsphere for water and wastewater treatment, Environ. Sci. Technol. 37(2003) 3989-3994.

[6] C. Yu, G. Li, S. Kumar, H. Kawasaki, R. Jin, Stable Au₂₅(SR)₁₈/TiO₂ composite nanostructure with enhanced visible light photocatalytic activity, J. Phys. Chem. Lett. 4(2013) 2847-2852.

[7] Changlin Yu, Qizhe Fan, Yu Xie, Jianchai Chen, shu Qing, Jimmy C. Yu, Sonochemical fabrication of novel square-shaped F doped TiO₂ nanocrystals with enhanced performance in photocatalytic degradation of phenol, J. Hazard. Mater. 237-238(2012) 38-45.

[8] Changlin Yu, Longfu Wei, Xin Li, Jianchai Chen, Qizhe Fan, Jimmy C. Yu, Synthesis and characterization of Ag/TiO₂-B nanosquares with high photocatalytic activity under visible light irradiation, Mater. Sci. Eng. B 178(2013) 344-348.

[9] Changlin Yu, Jimmy C. Yu, Wanqin Zhou, Kai Yang, WO₃ coupled P-TiO₂ photocatalysts with mesoporous structure, Catal. Lett. 140(2010) 172-183.

[10] S. Han, G. Zhang, H. Xi, D. Xu, X. Fu, X. Wang, Sulfated TiO₂ decontaminate 2-CEES and DMMP in vapor phase, Catal. Lett. 122(2007) 106-110.

[11] Pengfei Chen, Du. Mingxing, Lei He, Yan Wang, Guoliang Zhang, Fengbao Zhang, Xiaobin Fan, SO₄^2-/ZrO^2- titania nanotubes as efficient solid superacid catalysts for selective mononitration of toluene, Catal. Commun. 18(2012) 47-50.

[12] H. Yan, Y. Yang, D. Tong, X. Xiang, C. Hu, Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO₄^2-/ZrO₂ and SO₄^2-/ZrO^2-Al₂O₃ solid acid catalysts, Catal. Commun. 10(2009) 1558-1563.

[13] B.M. Reddy, V.R. Reddy, D. Giridhar, Eco-friendly Pt-Mo/ZrO₂ solid acid catalyst for selective protection of carbonyl compounds, Synth. Commun. 31(12) (2006) 1819-1823.

[14] V. Subramanian, E.E.Wolf, P.V. Kamat, Catalysis with TiO₂/gold nanocomposites. Effect of metal particle size on the Fermi level equilibration, J. Am. Chem. Soc. 126(2004) 4943-4950.

[15] W. Zhaobin, X. Qin, G. Xiexian, E. Sham, P. Grange, B. Delmon, Titania-modified hydrodesulphurization catalysts:I. Effect of preparation techniques on morphology and properties of TiO₂-Al₂O₃ carrier, Appl. Catal. 63(1990) 305-317.

[16] Peng Sun, Ding Hua Yu, Yi Hu, Zhen Chen Tang, Jiao Jiao Xia, Heng Li, He Huang, H₃PW₁₂O₄₀/SiO₂ for sorbitol dehydration to isosorbide:High efficient and reusable solid acid catalyst, Korean J. Chem. Eng. 28(2011) 99-105.

[17] J.R. Sohn, J.B. Park, H.W. Kim, Y.I. Pae, Infrared and raman characterization of V₂O₅ on zirconia modified with WO₃ and activity for acid catalysis, Korean J. Chem. Eng. 20(2003) 48-57.

[18] R. Zanella, S. Giorgio, C.R. Henry, C. Louis, Alternative methods for the preparation of gold nanoparticles supported on TiO₂, J. Phys. Chem. B 106(2002) 7634-7642.

[19] J. Zou, J. Gao, Y. Wang, Synthesis of highly active H₂O₂-sensitized sulfated titania nanoparticles with a response to visible light, J. Photochem. Photobiol. A Chem. 202(2009) 128-135.

[20] T. Hirakawa, P.V. Kamat, Charge separation and catalytic activity of Ag@TiO₂ coreshell composite clusters under UV-irradiation, J. Am. Chem. Soc. 127(2005) 3928-3934.

[21] Dan I. Enache, Jennifer K. Edwards, Philip Landon, Benjamin Solsona-Espriu, Albert F. Carley, Andrew A. Herzing, Masashi Watanabe, Christopher J. Kiely, David W. Knight, Graham J. Hutchings, Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO₂ catalysts, Science 311(2006) 362-365.

[22] S. Tsubota, T. Nakamura, K. Tanaka, M. Haruta, Effect of calcination temperature on the catalytic activity of Au colloidsmechanically mixedwith TiO₂ powder for CO oxidation, Catal. Lett. 56(1998) 131-135.

[23] E. Formo, E. Lee, D. Campbell, Y. Xia, Functionalization of electrospun TiO₂ nanofibers with Pt nanoparticles and nanowires for catalytic applications, Nano Lett. 8(2008) 668-672.

[24] J.R. Sohn, D.G. Lee, Characterization of zirconium sulfate supported on TiO₂ and activity for acid catalysis, Korean J. Chem. Eng. 20(2003) 1030-1036.

[25] J.R. Sohn, J.H. Bae, Characterization of tungsten oxide supported on TiO₂ and activity for acid catalysis, Korean J. Chem. Eng. 17(2000) 86-92.

[26] M. Shyamsundar, S.Z.M. Shamshuddin, J.N. Sahu, Catalytic synthesis of biodiesel from pongamia glabra over zirconia and its modified forms, Korean J. Chem. Eng. 30(2013) 2186-2190.

[27] H. Song, P.F. Dong, X. Zhang, Effect of preparation conditions on the catalytic isomerization performance of Pt-S₂O₈^2-/ZrO^2-Al₂O₃, Acta Petrol. Sin. (Petroleum Processing Section) 6(2010) 877-882.

[28] A. Cornia, F. Melo, S. Mendioroz, J. Fierro, State ofmetals in the supported bimetallic Pt-Pd/SO₄^2-/ZrO₂ system, 12th International Congress on Catalysis:Proceedings of the 12th ICC, Granada, Spain, July 9-14, 2000, Elsevier Science Ltd 2000, p. 263.

[29] S. Tauster, S. Fung, R. Garten, Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide, J. Am. Chem. Soc. 100(1978) 170-175.

[30] Z.S. Jin, X.M. Jiang, Y.F. Chen, A new technological development on the synthesis of propylene glycol ethers, Shanghai Chem. Ind. 3(1997) 6-11.

[31] Y.M. Cui, S.H. Fan, A study on the synthesis of amyl butyrate catalyzed by solid superacid, J. Funct. Mater. 37(2006) 452-455.

[32] S. Liu, J.H. Yang, J.H. Choy, Microporous SiO₂-TiO₂ nanosols pillaredmontmorillonite for photocatalytic decomposition of methyl orange, J. Photochem. Photobiol. A Chem. 179(2006) 75-80.

[33] S.K. Kansal, M. Singh, D. Sud, Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts, J. Hazard. Mater. 141(2007) 581-590.

[34] Changlin Yu, Jimmy C. Yu, Mui Chan, Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres, J. Solid State Chem. 182(2009) 1061-1069.

[35] Zhonglai Li, RenataWnetrzak,Witold Kwapinski, James J. Leahy, Synthesis and characterization of sulfated TiO₂ nanorods and ZrO₂/TiO₂ nanocomposites for the esterification of biobased organic acid, ACS Appl. Mater. Interfaces 4(2012) 4499-4505.

[36] Hui Zhao, Pingping Jiang, Yuming Dong,Min Huang, Boliang Liu, Effects of morphology and crystal phase of sulfated nano-titania solid acids on catalytic esterification, React. Kinet. Mech. Catal. 113(2014) 445-458.

[37] Pradeepan Periyat, Suresh C. Pillai, Declan E. McCormack, John Colreavy, Steven J. Hinder, Improved high-temperature stability and sun-light-driven photocatalytic activity of sulfur-doped anatase TiO₂, J. Phys. Chem. C 112(2008) 7644-7652.

[38] Darrin SMuggli, Lefei Ding, Photocatalytic performance of sulfated TiO₂ and Degussa P-25 TiO₂ during oxidation of organics, Appl. Catal. B Environ. 32(3) (2001) 181-194.

[39] S.M. Jung, P. Grange, Characterization and reactivity of pure TiO₂-SO₄^2- SCR catalyst:influence of SO₄^2- content, Catal. Today 59(2000) 305-312.

[40] Hexing Li, Xinyu Zhang, Yuning Huo, Jian Zhu, Supercritical preparation of a highly active S-doped TiO₂ photocatalyst for methylene blue mineralization, Environ. Sci. Technol. 41(2007) 4410-4414.

[41] X.P. Lin, D.M. Song, X.Q. Gu, Y.L. Zhao, Y.H. Qiang, Synthesis of hollow spherical TiO₂ for dye-sensitized solar cells with enhanced performance, Appl. Surf. Sci. (2012) 816-820.

[42] Y.V. Larichev, O.V. Netskina, O.V. Komova, V.I. Simagina, Comparative XPS study of Rh/Al₂O₃ and Rh/TiO₂ as catalysts for NaBH₄ hydrolysis, Int. J. Hydrog. Energy 35(2010) 6501-6507.

[43] Y. Wu, L. Qin, G. Zhang, L. Chen, X. Guo, M. Liu, Porous solid superacid SO₄^2-/Fe_x^2-Zr_xO₃ Fenton catalyst for highly effective oxidation of X-3B under visible light, Ind. Eng. Chem. Res. 52(2013) 16698-16708.

[44] Y.H. Xu, L.Y. Wang, Q. Zhang, S.J. Zheng, X.J. Li, C. Huang, Correlation between photoreactivity and photophysics of sulfated TiO₂ photocatalyst, Mater. Chem. Phys. 92(2005) 470-474.

[45] T. Yamaguchi, Recent progress in solid superacid, Appl. Catal. 6(1990) 11-25.

[46] Y.M. Wang, C.Z. Chen, Z.H. Luo, D.S. Gao, D. Li, M.X.Wu, J.B. Ma, Studies on the acidity, structures and crystalline phases of SO₄^2-/TiO₂, PO₄^3-/TiO₂, BO₃^3-/TiO₂ solid acids, Chin. J. Struct. Chem. 18(1999) 175-181.

[47] Z.S. Jin,W.D. Zhang, L. Zhang, Y.F. Chen, Synthesis of propylene glycol methyl ether acetate, Fine Chem. 18(2001) 376-378.

[48] Pradeepan Periyat, Declan E. McCormack, Steven J. Hinder, Suresh C. Pillai, One-pot synthesis of anionic (Nitrogen) and cationic (Sulfur) codoped high-temperature stable, visible light active, anatase photocatalysts, J. Phys. Chem. C 113(8) (2009) 3246-3253.

[49] B.Neppolian,H. Choi, S. Sakthivel, B. Arabindoo,V.Murugesan, Solar light induced and TiO₂ assisted degradation of textile dye reactive blue 4, Chemosphere 46(2002) 1173-1181.

[50] M.R. Rojas, F. Pérez, D.Whitley, R.G. Arnold, A.E. Sáez, Modeling of advanced oxidation of trace organic contaminants by hydrogen peroxide photolysis and Fenton's reaction, Ind. Eng. Chem. Res. 49(2010) 11331-11343.

[51] G. Zhang, M. Zhang, X. Ye, X. Qiu, S. Lin, X. Wang, Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution, Adv. Mater. 26(2014) 805-809.

[52] N. Zhang, M.-Q. Yang, Z.-R. Tang, Y.-J. Xu, CdS-graphene nanocomposites as visible light photocatalyst for redox reactions inwater:A green route for selective transformation and environmental remediation, J. Catal. 303(2013) 60-69.

[53] G. Zhang, X. Wang, A facile synthesis of covalent carbon nitride photocatalysts by Co-polymerization of urea and phenylurea for hydrogen evolution, J. Catal. 307(2013) 246-253.

[54] W. Wu, L. Wen, L. Shen, R. Liang, R. Yuan, L. Wu, A new insight into the photocatalytic reduction of 4-nitroaniline to p-phenylenediamine in the presence of alcohols, Appl. Catal. B Environ. 130-131(2013) 163-167.

[55] W. Adam, M.A. Arnold, M. Grüne, W.M. Nau, U. Pischel, C.R. Saha-Möller, Spiroiminodihydantoin is a major product in the photooxidation of 2'-deoxyguanosine by the triplet states and oxyl radicals generated from hydroxyacetophenone photolysis and dioxetane thermolysis, Org. Lett. 5(2002) 725-728.

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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