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2 * * ** * ** Evaluation of Physico-Chemical Properties of Magnesium Oxide Masaaki Haneda*, Kiyotaka Kato*, Shouji Sakai** * Advanced Ceramics Research Center, Nagoya Institute of Technology , Asahigaoka, Tajimi, Gifu , JAPAN ** Ube Material Industries, Ltd. 1985, Kogushi, Ube, Yamaguchi , JAPAN This article describs physico-chemical properties of magnesium oxides supplied from Ube Material Industries, Ltd. as a catalyst material for controlling plant diseases. Not only structural characterizations such as X-ray diffraction XRD and N 2 adsorption/desorption isotherms but also surface characterization techniques such as temperature-programmed desorption TPD, in situ Fourier transform infrared FT-IR spectroscopy and X-ray photoelectron spectroscopy XPS are introduced. The knowledges reported in this article are expected to be utilized for research and development of various functional materials. Keywords: Magnesium oxide, Surface characterizations MgO Mg 2+ Mg OH 2 1,2 3-6 Mg 2+ O 2 Mg 2+ O 2 O

3 Table1 2 Mg 2+ UD-650 UD UGK-x x UGK-800 UCM-200 UGK-1000 UC-95S nm 99.98% 500A X MiniFlex II CuK Fig. 1 UD-650 Mg OH 2 500A MgO UD UGK-550 Mg OH 2 MgO 700 MgO X MgO 200 Table 1 BELSORP-mini-II BET BJH 300 UD-650 TG/ DTA 300 Mg OH Fig. 2 UD- 650 IV 500A II UGK-x IV,, II 900 II, Fig. 3 BJH 500A UD , 900, Table 1 BET 500A nm UD Fig.1 XRD patterns of magnesium oxide. Fig. 2 N 2 adsorption/desorption isotherms of magnesium oxides.

4 Table.1 Summary of structural properties of magnesium oxides Fig.3 Pore size distribution of magnesium oxides in mesopore region determined by BJH method. CO 2 FT-IR 8-10 CO 2 Mg 2+ O 2 CO 11,12 in situ FT-IR 20mm 25 mg cm -2 CaF 2 IR CO 1.33 kpa IR FT/IR-4200 Fig. 4 IR UD UD cm -1 Carbonate CO 2 3 / Carboxylate CO A 600 UGK-x IR cm -1 IR Fig cm -1 OH UD-650 UGK- 550 UGK-700 UGK cm cm -1 O 2 OH H-bonded OH group Mg 2+ OH isolated OH group A 900 UGK-900 UGK isolated OH group CO CO C 2n O 2 2n+1 11,12 Fig. 5 CO IR 500A IR CO UD-650 UGK-550 UGK-700 UGK-800 CO 1670 cm cm -1 IR

5 Fig. 4 FT-IR spectra of magnesium oxides pretreated with O 2 at 600. Fig.5 FT-IR difference spectra of adsorbed CO species remaining on magnesium oxides after the evacuation at room temperature. IR 1670 cm -1 OH hydrogen carbonate cm -1 Mg 2+ O 2 CO UGK- 900 UGK-1000 CO 2 Temperature-programmed desorption, TPD BP-1 CO 2- TPD 100mg 100% O Ar 500.5% CO 2 /He 1 CO 2 CO 2 Ar Ar min -1 CO 2 M-201QA- TDM Fig. 6 CO 2 -TPD UD-650 CO 2 UGK UGK-x CO 2 Table 2 CO 2 CO 2 CO IR 500A Fig CO 2 Fig. 6 UGK- 700 CO 2 CO 2 500A Mg OH 2 Fig.6 CO 2 -TPD profiles of magnesium oxides.

6 Table.2 Summary of CO 2 -TPD measurements CO 2 -TPD Ar min -1 H 2 O CO 2 M-201QA-TDM H 2 O Fig. 7 A H 2 O UD H 2 O UD-650 Mg OH 2 Fig. 1 Mg OH 2 H 2 O UGK-550 Mg OH 2 UD H 2 O MgO 500A UGK-700 UGK-800 UGK H 2 O H 2 O OH UD-650 Fig. 7 B CO 2 UD A CO 2 CO 2 UD A UD-650 Mg OH 2 CO 2 hydrogencarbonate 500A UGK-x UD-650 CO 2 Fig.7 Desorption profiles of A H 2 O and B CO 2 from magnesium oxides without pretreatment.

7 CO 2 CO 2 Fig. 7 B UGK CO 2 UGK-700 UGK UGK-900 UGK-1000 UD CO 2 17 ESR XPS O 2 IR XPS Fig. 8 Surface Science Instruments M-Probe Al Kα 10 kv 20mA UGK-800 XPS Mg 2s Mg 2p O 1s C 1s XPS Fig.8 XPS spectrum of UGK-800. Fig. 9 O 1s XPS C 1s ev OH ev ev Fig. 9 UD UGK-x 533 ev 530 ev IR OH Fig. 4 XPS OH ca. 533 ev ca. 530 ev isolated OH group 3740 cm -1 H-bonded OH group cm -1 OH ca. 533 ev Fig.9 O 1s XPS spectra of magnesium oxides without pretreatment.

8 Table.3 Summary of XPS measurements IR H-bonded OH group OH XPS H-bonded OH group IR 500A XPS Table 3 OH O s O b O b /O s OH OH O negative charge O b /O s 19 CO 2 -TPD UGK-x Table 2 Table 3 UGK-x O b /O s CO 2 -TPD OH O b /O s Table 1 Table 3 O b /O s 50m 2 g -1 O b /O s 50m 2 g -1 O b /O s 1 pp CREATIVE H. Hattori, J. Jpn. Petrol. Inst., pp pp J.A. Lercher, C. Gründling, G. Eder-Mirth, Catal. Today, M. Tamura, K. Shimizu, A. Satsuma, Appl. Catal. A, A. Zecchina, S. Coluccia, G. Spoto, D. Scrano, L. Marchese, J. Chem. Soc., Farady Trans., T. Tashiro, J. Ito, R.-B. Sim, K. Miyazawa, E. Hamada, K.

9 Toi, H. Kobayashi, T. Ito, J. Phys. Chem., CERAMIC DATA BOOK 2016/17 pp A.A. Davydov, Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides Wiley, Chichester, pp C. Chizallet, G. Costentin, M. Che, F. Delbecq, P. Sautet, J. Am. Chem. Soc., J.C. Lavalley, Catal. Today, G. Pacchioni, J.M. Ricart, F. Illas, J. Am. Chem. Soc., S. Ardizzone, C.L. Bianchi, M. Fadoni, B. Vercelli, Appl. Surf. Sci., S. Ardizzone, C.L. Bianchi, B. Vercelli, Appl. Surf. Sci., Y.V. Larichev, B.L. Moroz, V.I. Zaikovskii, S.M. Yunusov, E.S. Kalyuzhnaya, V.B. Shur, V.I Bukhtiyarov, J. Phys. Chem.,

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