Sains Malaysiana 48(7)(2019): 1447–1457

http://dx.doi.org/10.17576/jsm-2019-4807-14

Chemical Surface Analysis on Post-Thermal Treatment of the K-OMS-2 Catalysts and Catalytic Oxidation Efficiency at Low Temperature

(Analisis Permukaan Kimia Rawatan Pasca Haba pada Mangkin K-OMS-2 dan Kecekapan Pemangkinan Pengoksidaan pada Suhu Rendah)

CHATKAMOL KAEWBUDDEE^1,2, PINIT KIDKHUNTHOD³, NARONG CHANLEK³, RATTABAL KHUNPHONOI^2,4,5 & KITIROTE WANTALA^1,2,5,6*

¹Department of Chemical Engineering, Faculty of Engineering, Khon Kaen University, Khon Kaen 40002, Thailand

²Chemical Kinetics and Applied Catalysis Laboratory (CKCL), Faculty of Engineering, Khon Kaen University, Khon Kaen 40002, Thailand

³Synchrotron Light Research Institute Public Organization, 111 University Avenue, Muang District, Nakhon Ratchasima, 30000, Thailand

⁴Department of Environmental Engineering, Faculty of Engineering, Khon Kaen University, Khon Kaen 40002, Thailand

⁵Research Center for Environmental and Hazardous Substance Management (EHSM), Faculty of Engineering, Khon Kaen University, Khon Kaen 40002, Thailand

⁶Research Program on Development of Appropriate Technologies for Coloring Agent Removal from, Textile Dyeing, Pulp & Paper, Sugar Industries for Sustainable Management, Center of Excellence on Hazardous Substance Management (HSM), Chulalongkorn University, Bangkok 10330, Thailand

Received: 18 December 2018/Accepted: 24 April 2019

ABSTRACT

The effect of calcination temperature on the physical and chemical properties of cryptomelane (K-OMS-2) was investigated. The K-OMS-2 was synthesized via a hydrothermal method and calcined at 200-600ºC. The catalytic activities of the K-OMS-2 samples were tested in packed bed reactor (PBR) on toluene oxidation. The physical and chemical properties were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), specific surface area computed by Brunauer-Emmett-Teller (BET) equation, Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) techniques. The increasing of the calcination temperature from 200-600ºC led to transform the phases from MnO2 to Mn2O3. The morphology of K-OMS-2 which observed in a nest-like type could promote the catalytic activity. With increasing the calcination temperature, the amount of Oads/Olatt molar ratio slightly increased whereas OH vibrations analyzed by FTIR insignificantly increased. The comparison of interaction effect indicated that the Oads/Olatt molar ratio played an important role in the oxidation performance more than the Mn3+/Mn4+ molar ratio.

Keywords: Oxidation state; thermal catalysis; toluene oxidation; VOCs removal; XPS

ABSTRAK

Kesan suhu pengkalsinan pada sifat fizikal dan kimia (K-OMS-2) kriptomelan telah dikaji. K-OMS-2 telah disintesis melalui kaedah hidroterma dan dikalsin pada suhu 200-600ºC. Aktiviti sampel pemangkin K-OMS-2 diuji dalam reaktor lapisan terpadat (PBR) pada pengoksidaan toluena. Sifat fizikal dan kimia telah dicirikan oleh teknik sinar-x difraktometer (XRD), mikroskop elektron imbasan (SEM), kawasan permukaan tertentu yang dihitung melalui persamaan Brunauer-Emmett-Teller (BET), spektroskopi transformasi Fourier inframerah (FTIR), spektroskopi fotoelektron sinar-x (XPS) dan ujian penyerapan sinar- x berhampiran pinggir struktur (XANES). Peningkatan suhu pengkalsinan daripada 200-600ºC membawa kepada perubahan daripada MnO2 kepada Mn2O3. Morfologi K-OMS-2 yang diperhatikan seperti jenis sarang dapat menggalakkan aktiviti pemangkinan. Dengan pertambahan suhu pengkalsinan, jumlah nisbah molar Oads/Olatt sedikit meningkat manakala getaran OH dianalisis FTIR meningkat secara tidak bererti. Perbandingan kesan interaksi menunjukkan bahawa nisbah molar Oads/Olatt memainkan peranan penting dalam prestasi pengoksidaan lebih daripada nisbah molar Mn3 +/Mn4 +.

Kata kunci: Keadaan pengoksidaan; pemangkin termal; pengoksidaan toluena; penyingkiran VOC; XPS

REFERENCES

Brock, S.L., Duan, N., Tian, Z.R., Giraldo, O., Hua, Z. & Suib, S.L. 1998. A review of porous manganese oxide materials. Chemistry of Materials 10(10): 2619-2628.

Calvert, C., Joesten, R., Ngala, K., Villegas, J., Morey, A., Shen, X. & Suib S.L. 2008. Synthesis, characterization, and rietveld refinement of tungsten-framework-doped porous manganese oxide (K-OMS-2) material. Chemistry of Materials 20(20): 6382-6388.

Chen, T., Dou, H., Li, X., Tang, X., Li, J. & Hao, J. 2009. Tunnel structure effect of manganese oxides in complete oxidation of formaldehyde. Microporous and Mesoporous Materials 122(1-3): 270-274.

Chen, X., Shen, Y.F., Suib, S.L. & O'Young, C.L. 2002 Characterization of manganese oxide octahedral molecular sieve (M-OMS-2) materials with different metal cation dopants. Chemistry of Materials 14(2): 940-948.

Christel, L., Pierre, A. & Abel, D.A.M.R. 1997. Temperature programmed reduction studies of nickel manganite spinels. Thermochimica Acta 306(1-2): 51-59.

Cockayne, E., Levin, I., Wu, H. & Llobet, A. 2013. Magnetic structure of bixbyite a-Mn2O3: A combined DET+U and neutron diffraction study. Physical Review B 87(18): 184413.

De Luna, M.D., Millanar, J., Yodsa-nga, A. & Wantala, K., 2017. Gas phase catalytic oxidation of VOCS using hydrothermally synthesized nest-like K-OMS 2 catalyst. Sains Malasiana 46(2): 275-283.

Deng, Y.Q., Zhang, T., Au, C.T. & Yin, S.F. 2014. Oxidation of p-chlorotoluene to p-chlorobenzaldehyde over manganese-based octahedral molecular sieves of different morphologies. Catalysis Communications 43: 126-130.

Dong, C., Liu, X., Guan, H., Xiao, X. & Wang, Y. 2017. Combustion synthesized hierarchically porous Mn3O4 for catalytic degradation of methyl orange. The Canadian Journal of Chemical Engineering 95(4): 643-647.

Doucet, N., Bocquillon, F., Zahraa, O. & Bouchy, M. 2006. Kinetics of photocatalytic VOCs abatement in a standardized reactor. Chemosphere 65(7): 1188-1196.

El-Sawy, A.M., King’ondu, C.K., Kuo, C.H., Kriz, D.A., Guild, C.J., Meng, Y., Frueh, S.J., Dharmarathna, S., Ehrlich, S.N. & Suib, S.L. 2014. X-ray absorption spectroscopic study of a highly thermally stable manganese oxide octahedral molecular sieve (OMS-2) with high oxygen reduction reaction activity. Chemistry of Materials 26(19): 5752-5760.

Fang, J., Li, J., Gao, L., Jiang, X., Zhang, J, Xu, A. & Li, X. 2017. Synthesis of OMS-2/graphite nanocomposites with enhanced activity for pollutants degradation in the presence of peroxymonosulfate. Journal of Colloid and Interface Science 494: 185-193.

Feng, Q., Kanoh, H. & Ooi, K. 1999. Manganese oxide porous crystals. Journal of Materials Chemistry 9(2): 319-333.

Fu, Z., Liu, L., Song, Y., Ye, Q., Cheng, S., Kang, T. & Dai, H. 2017. Catalytic oxidation of carbon monoxide, toluene, and ethyl acetate over the xPd/OMS-2 catalysts: Effect of Pd loading. Frontiers of Chemical Science and Engineering 11(2): 185-196.

Gandhe, A.R., Rebello, J.S., Figueiredo, J.L. & Fernandes, J.B. 2007. Manganese oxide OMS-2 as an effective catalyst for total oxidation of ethyl acetate. Applied Catalysis B: Environmental 72(1-2): 129-135.

Genuino, H.C., Meng, Y., Horvath, D.T., Kuo, C.H., Seraji, M.S., Morey, A.M., Joesten, R.L. & Suib, S.L. 2013. Enhancement of catalytic activities of octahedral molecular sieve manganese oxide for total and preferential CO oxidation through vanadium ion framework substitution. ChemCatChem 5(8): 2306-2317.

Ghosh, R., Shen, X., Villegas, J.C., Ding, Y., Malinger, K. & Suib, S.L. 2006. Role of manganese oxide octahedral molecular sieves in styrene epoxidation. The Journal of Physical Chemistry B 110(14): 7592-7599.

Hou, J., Li, Y., Mao, M., Zhao, X. & Yue, Y. 2014. The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation. Nanoscale 6(24): 15048-15058.

Hou, J., Li, Y., Liu, L., Ren, L. & Zhao, X. 2013a. Effect of giant oxygen vacancy defects on the catalytic oxidation of OMS-2 nanorods. Journal of Materials Chemistry A 1(23): 6736-6741.

Hou, J., Liu, L., Li, Y., Mao, M., Lv, H. & Zhao, X. 2013b. Tuning the K+ concentration in the tunnel of OMS-2 nanorods leads to a significant enhancement of the catalytic activity for benzene oxidation. Environmental Science & Technology 47(23): 13730-13736.

Iyer, A., Galindo, H., Sithambaram, S., King'ondu, C., Chen, C.H. & Suib, S.L. 2010. Nanoscale manganese oxide octahedral molecular sieves (OMS-2) as efficient photocatalysts in 2-propanol oxidation. Applied Catalysis A: General 375(2): 295-302.

Jia, J., Zhang, P. & Chen, L. 2016. The effect of morphology of α-MnO2 on catalytic decomposition of gaseous ozone. Catalysis Science & Technology 6(15): 5841-5847.

King'ondu, C.K., Opembe, N., Chen, C.H., Ngala, K., Huang, H., Iyer, A., Garces, H.F. & Suib, S.L. 2011. Manganese oxide octahedral molecular sieves (OMS-2) multiple framework substitutions: A new route to OMS-2 particle size and morphology control. Advanced Functional Materials 21(2): 312-323.

Kowalski, J. & DeBeer, S. 2015 The role of X-ray spectroscopy in understanding the geometric and electronic structure of nitrogenase. Biochimica et Biophysica Acta 1853(6): 1406- 1415.

Kumar, R., Sithambaram, S. & Suib, S.L. 2009. Cyclohexane oxidation catalyzed by manganese oxide octahedral molecular sieves - Effect of acidity of the catalyst. Journal of Catalysis 262(2): 304-313.

Li, D.Y., Liu, H.D. & Chen, Y.F. 2011. Synthesis of manganese oxide octahedral molecular sieve and their application in catalytic oxidation of benzene. Huan Jing Ke Xue= Huanjing Kexue 32(12): 3657-3661.

Liu, L., Song, Y., Fu, Z., Ye, Q., Cheng, S., Kang, T. & Dai, H. 2017. Effect of preparation method on the surface characteristics and activity of the Pd/OMS-2 catalysts for the oxidation of carbon monoxide, toluene, and ethyl acetate. Applied Surface Science 396: 599-608.

Luo, J., Zhang, Q., Huang, A. & Suib, S.L. 2000. Total oxidation of volatile organic compounds with hydrophobic cryptomelane-type octahedral molecular sieves. Microporous and Mesoporous Materials 35-36: 209-217.

Mahdavi, V. & Soleimani, S. 2014. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase. Materials Research Bulletin 51: 153-160.

Millanar, J.M., De Luna, M.D.G., Yodsa-Nga, A. & Wantala, K. 2018. Toluene oxidation using K-OMS-2 synthesized via hydrothermal process by central composite design. Chiang Mai Journal of Science 45(2): 1030-1038.

Mosa, I.M., Biswas, S., El-Sawy, A.M., Botu, V., Guild, C., Song, W., Ramprasad, R., Rusling, J. & Suib, S.L. 2015. Tunable mesoporous manganese oxide for high performance oxygen reduction and evolution reactions. Journal of Materials Chemistry A 4(2): 620-631.

Ousmane, M., Perrussel, G., Yan, Z., Clacens, J.M., De Campo, F. & Pera-Titus, M. 2014. Highly selective direct amination of primary alcohols over a Pd/K-OMS-2 catalyst. Journal of Catalysis 309: 439-452.

Pan, F., Liu, W., Yu, Y., Yin, X., Wang, Q., Zheng, Z., Wu, M., Zhao, D., Zhang, Q., Lei, X. & Xia, D. 2016. The effects of manganese oxide octahedral molecular sieve chitosan microspheres on sludge bacterial community structures during sewage biological treatment. Scientific Reports 6(1): 37518.

Said, S., Maghrabi, H.H.E., Riad, M. & Mikhail, S. 2018. Photo-catalytic selective organic transformations by Fe-doped octahedral molecular sieves (manganese oxide) nano-structure. Journal of Asian Ceramic Societies 6(2): 169-181.

Said, S., Riad, M., Helmy, M., Mikhail, S. & Khalil, L. 2016. Preparation of nano-structured cryptomelane materials for catalytic oxidation reactions. Journal of Nanostructure in Chemistry 6(2): 171-182.

Said, S., Riad, M., Helmy, M., Mikhail, S. & Khalil, L. 2014. Effect of the different preparation methods on the characterization and the catalytic activity of the nano-structured cryptomelane materials. Chemistry and Materials Research 6(12): 27-41.

Santos, V.P., Bastos, S.S.T., Pereira, M.F.R., Orfao, J.J.M. & Figueiredo, J.L. 2010. Stability of a cryptomelane catalyst in the oxidation of toluene. Catalysis Today 154(3-4): 308-311.

Schurz, F., Bauchert, J.M., Merker, T., Schleid, T., Hasse, H. & Glaser, R. 2009. Octahedral molecular sieves of the type K-OMS-2 with different particle sizes and morphologies: Impact on the catalytic properties in the aerobic partial oxidation of benzyl alcohol. Applied Catalysis A: General 355(1-2): 42-49.

Shi, F., Wang, F., Dai, H., Dai, J., Deng, J., Liu, Y., Bai, G., Ji, K. & Au, C.T. 2012. Rod-, flower-, and dumbbell-like MnO2: Highly active catalysts for the combustion of toluene. Applied Catalysis A: General 433-434: 206-213.

Shanthakumar, S., Xu, L., Chen, C.H., Ding, Y., Kumar, R., Calvert, C. & Suib, S.L. 2009. Manganese octahedral molecular sieve catalysts for selective styrene oxide ring opening. Catalysis Today 140(3-4): 162-168.

Soares, O.S.G.P., Rocha, R.P., Orfao, J.J.M., Pereira, M.F.R. & Figueiredo, J.L. 2018. Ethyl and butyl acetate oxidation over manganese oxides. Chinese Journal of Catalysis 39(1): 27-36.

Stobbe, E.R., de Boer, B.A. & Geus, J.W. 1999. The reduction and oxidation behaviour of manganese oxides. Catalysis Today 47(1-4): 161-167.

Suib, S.L. 2008. Structure, porosity, and redox in porous manganese oxide octahedral layer and molecular sieve materials. Journal of Materials Chemistry 18(14): 1623-1631.

Sun, H., Liu, Z., Chen, S. & Quan, X. 2015. The role of lattice oxygen on the activity and selectivity of the OMS-2 catalyst for the total oxidation of toluene. Chemical Engineering Journal 270: 58-65.

Sun, H., Chen, S., Wang, P. & Quan, X. 2011. Catalytic oxidation of toluene over manganese oxide octahedral molecular sieves (OMS-2) synthesized by different methods. Chemical Engineering Journal 178: 191-196.

Sun, L., Cao, Q., Hu, B., Li, J., Hao, J., Jing, G. & Tang, X. 2011. Synthesis, characterization and catalytic activities of vanadium-cryptomelane manganese oxides in low-temperature NO reduction with NH3. Applied Catalysis A: General 393(1-2): 323-330.

Sun, M., Zhang, B., Liu, H., He, B., Ye, F., Yu, L., Sun, C. & Wen, H. 2017. The effect of acid/alkali treatment on the catalytic combustion activity of manganese oxide octahedral molecular sieves. RSC Advances 7(7): 3958-3965.

Tang, X., Li, J. & Hao, J. 2010. Significant enhancement of catalytic activities of manganese oxide octahedral molecular sieve by marginal amount of doping vanadium. Catalysis Communications 11(10): 871-875.

Wang, C., Ma, J., Liu, F., He, H. & Zhang, R. 2015. The effects of Mn2+ precursors on the structure and ozone decomposition activity of cryptomelane-type manganese oxide (OMS-2) catalysts. The Journal of Physical Chemistry C 119(40): 23119-23126.

Wang, R. & Li, J. 2010. Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures. Environmental Science & Technology 44(11): 4282-4287.

Wang, R. & Li, J. 2009. OMS-2 catalysts for formaldehyde oxidation: Effects of Ce and Pt on structure and performance of the catalysts. Catalysis Letters 131(3-4): 500-505.

Xie, Y., Guo, Y., Guo, Y., Wang, L., Zhan, W., Wang, Y., Gong, X. & Lu, G. 2016. A highly effective Ni-modified MnOx catalyst for total oxidation of propane: The promotional role of nickel oxide. RSC Advances 6(55): 50228-50237.

Yang, X., Han, J., Du, Z., Yuan, H., Jin, F. & Wu, Y. 2010. Effect of Pb dopant on structure and activity of Pd/K-OMS-2 catalysts for heterogeneous oxidative carbonylation of phenol. Catalysis Communications 11(7): 643-646.

Yin, H., Dai, X., Zhu, M., Li, F., Feng, X. & Liu, F. 2015. Fe-doped cryptomelane synthesized by refluxing at atmosphere: Structure, properties and photocatalytic degradation of phenol. Journal of Hazardous Materials 296: 221-229.

Yodsa-nga, A., Millanar, J.M., Neramittagapong, A., Khemthong, P. & Wantala, K. 2015. Effect of manganese oxidative species in as-synthesized K-OMS-2 on the oxidation of benzene. Surface and Coatings Technology 271: 217-224.

Yu, L., Diao, G., Ye, F., Sun, M., Zhou, J., Li, Y. & Liu, Y. 2011. Promoting effect of Ce in Ce/OMS-2 catalyst for catalytic combustion of dimethyl ether. Catalysis Letters 141(1): 111-119.

Yu, L., Sun, M., Yu, J., Yu, Q., Hao, Z. & Li, C. 2008. Synthesis and characterization of manganese oxide octahedral molecular sieve and its catalytic performance for DME combustion. Chinese Journal of Catalysis 29(11): 1127-1132.

Zhang, Q., Wang, M., Zhang, T., Wang, Y., Tang, X. & Ning, P. 2015. A stable Ni/SBA-15 catalyst prepared by the ammonia evaporation method for dry reforming of methane. RSC Advances 5(114): 94016-94024.

Zhang, T., Liu, J. & Sun, D.D. 2012. A novel strategy to fabricate inorganic nanofibrous membranes for water treatment: Use of functionalized graphene oxide as a cross linker. RSC Advances 2(12): 5134-5137.

*Corresponding author; email: kitirote@kku.ac.th