Structure of the active sites on H3PO4/ZrO2 catalysts for dimethyl carbonate synthesis from methanol and carbon dioxide

被引:111
作者
Ikeda, Y [1 ]
Asadullah, M [1 ]
Fujimoto, K [1 ]
Tomishige, K [1 ]
机构
[1] Univ Tokyo, Sch Engn, Dept Appl Chem, Bunkyo Ku, Tokyo 1138656, Japan
关键词
D O I
10.1021/jp0121522
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The catalytic properties of H3PO4/ZrO2 catalysts for dimethyl carbonate (DMC) synthesis from CH3OH and CO2 were investigated. The modification of ZrO2 with H3PO4 promoted the activity for selective DMC formation. The characterization of H3PO4/ZrO2 catalysts was performed by means of BET, XRD, (31)p NIAS NMR, LRS, DRIFT, and NH3-TPD. From the characterization results, it was determined that ZrO2 had Lewis acid sites and did not have Bronsted acid sites. The presence of Bronsted acid sites as well as Lewis acid sites was observed on H3PO4/ZrO2 (P/Zr = 0.05). The acidity of the Bronsted sites is weak, and the site's structure is a bridged OH. Furthermore, this Bronsted site is formed by the interaction between tetragonal Zr and P. In the reaction scheme of DMC formation, the Bronsted acid site can contribute to CH3OH activation and to the enhancement of the catalytic activity.
引用
收藏
页码:10653 / 10658
页数:6
相关论文
共 15 条
[1]   INFRARED STUDY OF ALCOHOLS ADSORPTION ON ZIRCONIUM-OXIDE - REACTIVITY OF ALKOXY SPECIES TOWARDS CO2 [J].
BENSITEL, M ;
MORAVEK, V ;
LAMOTTE, J ;
SAUR, O ;
LAVALLEY, JC .
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1987, 43 (12) :1487-1491
[2]   NMR AND IR STUDIES OF ZEOLITE H-ZSM-5 MODIFIED WITH ORTHOPHOSPHORIC ACID [J].
CARO, J ;
BULOW, M ;
DEREWINSKI, M ;
HABER, J ;
HUNGER, M ;
KARGER, J ;
PFEIFER, H ;
STOREK, W ;
ZIBROWIUS, B .
JOURNAL OF CATALYSIS, 1990, 124 (02) :367-375
[3]   SILICA-SUPPORTED ZIRCONIA .1. CHARACTERIZATION BY INFRARED-SPECTROSCOPY, TEMPERATURE-PROGRAMMED DESORPTION, AND X-RAY-DIFFRACTION [J].
DANG, Z ;
ANDERSON, BG ;
AMENOMIYA, Y ;
MORROW, BA .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (39) :14437-14443
[4]   HIGH-RESOLUTION SOLID-STATE P-31 NMR OF ALKALI PHOSPHATES [J].
HAYASHI, S ;
HAYAMIZU, K .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1989, 62 (10) :3061-3068
[5]   Promoting effect of phosphoric acid on zirconia catalysts in selective synthesis of dimethyl carbonate from methanol and carbon dioxide [J].
Ikeda, Y ;
Sakaihori, T ;
Tomishige, K ;
Fujimoto, K .
CATALYSIS LETTERS, 2000, 66 (1-2) :59-62
[6]   Syntheses of intercalation compounds of tetraamine in α-Zr(HPO4)2•H2O and the structures of guest molecules by solid state NMR [J].
Kaneno, M ;
Yamaguchi, S ;
Nakayama, H ;
Miyakubo, K ;
Ueda, T ;
Eguchi, T ;
Nakamura, N .
INTERNATIONAL JOURNAL OF INORGANIC MATERIALS, 1999, 1 (5-6) :379-384
[7]   PREPARATION OF DIMETHYL CARBONATE FROM METHANOL AND CARBON-DIOXIDE IN THE PRESENCE OF SN(IV) AND TI(IV) ALKOXIDES AND METAL ACETATES [J].
KIZLINK, J ;
PASTUCHA, I .
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1995, 60 (04) :687-692
[8]  
Matsuzaki T., 1997, CATAL SURV JPN, V1, P77, DOI DOI 10.1023/A:1019020812365
[9]   ZIRCONIA AS A SUPPORT FOR CATALYSTS - EVOLUTION OF THE TEXTURE AND STRUCTURE ON CALCINATION IN AIR [J].
MERCERA, PDL ;
VANOMMEN, JG ;
DOESBURG, EBM ;
BURGGRAAF, AJ ;
ROSS, JRH .
APPLIED CATALYSIS, 1990, 57 (01) :127-148
[10]   REACTION OF ORGANOTIN ALKOXIDES WITH CARBON-DISULFIDE, CARBONYL SULFIDE OR CARBON-DIOXIDE [J].
SAKAI, S ;
FUJINAMI, T ;
YAMADA, T ;
FURUSAWA, S .
NIPPON KAGAKU KAISHI, 1975, (10) :1789-1794