* * ** * 507-0071 10-6-29 ** 755-8510 1985 Evaluation of Physico-Chemical Properties of Magnesium Oxide Masaaki Haneda*, Kiyotaka Kato*, Shouji Sakai** * Advanced Ceramics Research Center, Nagoya Institute of Technology 10-6-29, Asahigaoka, Tajimi, Gifu 507-0071, JAPAN ** Ube Material Industries, Ltd. 1985, Kogushi, Ube, Yamaguchi 755-8510, 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 2 4 7 400 1000

Table1 2 Mg 2+ UD-650 UD-650 550 1000 UGK-x x UGK-800 UCM-200 UGK-1000 UC-95S 40 50 nm 99.98% 500A X MiniFlex II CuK Fig. 1 UD-650 Mg OH 2 500A MgO UD-650 550 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 2 200 Fig. 2 UD- 650 IV 500A II UGK-x 550 800 IV,, II 900 II, Fig. 3 BJH 500A UD-650 550 700 800, 900, Table 1 BET 500A 40 50 nm UD-650 550 700 Fig.1 XRD patterns of magnesium oxide. Fig. 2 N 2 adsorption/desorption isotherms of magnesium oxides.

Table.1 Summary of structural properties of magnesium oxides. 550 700 0 0 1000 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 13 600 CO 1.33 kpa IR FT/IR-4200 Fig. 4 IR UD-650 600 UD-650 1500 1000 cm -1 Carbonate CO 2 3 / Carboxylate CO 2 14 500A 600 UGK-x IR 1250 1100 cm -1 IR Fig. 4 3800 3300 cm -1 OH UD-650 UGK- 550 UGK-700 UGK-800 3600 3300 cm -1 3740 cm -1 O 2 OH H-bonded OH group Mg 2+ OH isolated OH group 15 550 800 500A 900 UGK-900 UGK- 1000 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 -1 1310 cm -1 IR

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 16 1310 cm -1 Mg 2+ O 2 CO 2 2 11 UGK- 900 UGK-1000 CO 2 Temperature-programmed desorption, TPD BP-1 CO 2- TPD 100mg 100% O 2 600 1 Ar 500.5% CO 2 /He 1 CO 2 CO 2 Ar Ar 600 10 min -1 CO 2 M-201QA- TDM Fig. 6 CO 2 -TPD UD-650 CO 2 UGK-550 600 UGK-x CO 2 Table 2 CO 2 CO 2 CO 2 600 IR 500A Fig. 4 100 400 CO 2 Fig. 6 UGK- 700 CO 2 CO 2 500A Mg OH 2 Fig.6 CO 2 -TPD profiles of magnesium oxides.

Table.2 Summary of CO 2 -TPD measurements. 50 700 0 0 1000 CO 2 -TPD Ar 800 10 min -1 H 2 O CO 2 M-201QA-TDM H 2 O Fig. 7 A 100 200 H 2 O UD-650 300 H 2 O UD-650 Mg OH 2 Fig. 1 Mg OH 2 H 2 O UGK-550 Mg OH 2 UD-650 300 H 2 O MgO 500A UGK-700 UGK-800 UGK- 900 200 400 H 2 O H 2 O OH UD-650 Fig. 7 B CO 2 UD-650 150 420 650 3 500A 150 350 2 CO 2 CO 2 UD-650 500A 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.

250 400 550 700 200 CO 2 CO 2 Fig. 7 B UGK-550 100 200 CO 2 UGK-700 UGK-800 900 1000 UGK-900 UGK-1000 UD-650 700 800 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 284.6 ev OH 532.7 ev 530.5 ev 18-20 Fig. 9 UD-650 550 900 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 3600 3300 cm -1 OH ca. 533 ev Fig.9 O 1s XPS spectra of magnesium oxides without pretreatment.

Table.3 Summary of XPS measurements. 550 700 0 0 1000 1000 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 550 800 900 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. 33-41 1978. 2 CREATIVE 9 2008 31-36. 3 H. Hattori, J. Jpn. Petrol. Inst., 47 2 2004 67-81. 4 46 1 2004 36-42. 5 pp. 46-52 1999. 6 pp. 334-336 2008. 7 2013-256488 8 53 6 2011 371-376. 9 J.A. Lercher, C. Gründling, G. Eder-Mirth, Catal. Today, 27 1996 353-376. 10 M. Tamura, K. Shimizu, A. Satsuma, Appl. Catal. A, 433-434 2012 135-145. 11 A. Zecchina, S. Coluccia, G. Spoto, D. Scrano, L. Marchese, J. Chem. Soc., Farady Trans., 86 4 1990 703-709. 12 T. Tashiro, J. Ito, R.-B. Sim, K. Miyazawa, E. Hamada, K.

Toi, H. Kobayashi, T. Ito, J. Phys. Chem., 99 1995 6115-6122. 13CERAMIC DATA BOOK 2016/17 pp. 94-98 2016. 14 A.A. Davydov, Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides Wiley, Chichester, pp. 37-53 1990. 15 C. Chizallet, G. Costentin, M. Che, F. Delbecq, P. Sautet, J. Am. Chem. Soc., 129 2007 6442-6452. 16 J.C. Lavalley, Catal. Today, 27 1996 377-401. 17 G. Pacchioni, J.M. Ricart, F. Illas, J. Am. Chem. Soc., 116 1994 10152-10158. 18 S. Ardizzone, C.L. Bianchi, M. Fadoni, B. Vercelli, Appl. Surf. Sci., 119 1997 253-259. 19 S. Ardizzone, C.L. Bianchi, B. Vercelli, Appl. Surf. Sci., 126 1998 169-175. 20 Y.V. Larichev, B.L. Moroz, V.I. Zaikovskii, S.M. Yunusov, E.S. Kalyuzhnaya, V.B. Shur, V.I Bukhtiyarov, J. Phys. Chem., 111 2007 9427-9436.