The effect of the reduction temperature on the structure of Cu/ZnO/SiO2 catalysts for methanol synthesis

被引:56
作者
Batyrev, EB
van den Heuvel, JC
Beckers, J
Jansen, WPA
Castricum, HL
机构
[1] Univ Amsterdam, Dept Chem, NL-1018 WV Amsterdam, Netherlands
[2] Clin Phys, Dept Radiotherapy, NL-3075 EA Rotterdam, Netherlands
关键词
methanol synthesis; Cu/ZnO catalysts; Cu/ZnO/SiO2; catalysts; N2O chemisorption; surface characterisation; surface oxidation state; surface structure;
D O I
10.1016/j.jcat.2004.10.012
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 structure of Cu/SiO2 and Cu/ZnO/SiO2 catalysts was studied after reduction at 450-1300 K. The influence of the ZnO promoter on the exposed Cu surface area and metal cluster size was determined by N2O chemisorption and X-ray diffraction. After reduction at 450 K, the metal surface area amounted to 9 m(2)/g(cat) for both catalysts. Oxygen uptake during N2O chemisorption increased significantly up to reduction temperatures of 800-900 K. This increase was most prominent for the ZnO-promoted catalyst, although no oxygen uptake was observed for a similarly treated ZnO/SiO2 sample. The behaviour of the promoted catalyst can be explained by formation of Zn-0, surface alloying, and segregation of ZnOx species on top of Cu clusters. The high thermostability of the catalysts was confirmed by in situ XRD measurements. The Cu crystallite size in both catalysts was about 4 nm, and did not increase when the reduction temperature was raised to 1100 K for 1 h. (C) 2004 Elsevier Inc. All rights reserved.
引用
收藏
页码:136 / 143
页数:8
相关论文
共 31 条
[1]   SPECTROSCOPIC EVIDENCE FOR ADSORPTION SITES LOCATED AT CU/ZNO INTERFACES [J].
BAILIE, JE ;
ROCHESTER, CH ;
MILLAR, GJ .
CATALYSIS LETTERS, 1995, 31 (04) :333-340
[2]   RELIABILITY OF PULSE-CHROMATOGRAPHIC NITROUS-OXIDE TITRATIONS OF THE COPPER SURFACE-AREA ON CU-ZNO-MEOX CATALYSTS IN CONNECTION WITH THE CHARACTERIZATION OF THEIR THERMOSTABILITY [J].
BERNDT, H ;
BRIEHN, V ;
EVERT, S .
APPLIED CATALYSIS A-GENERAL, 1992, 86 (02) :65-69
[3]   PULSE-CHROMATOGRAPHIC N2O TITRATION OF THE COPPER SURFACE-AREA ON CU-ZNO-MEOX CATALYSTS IN CONNECTION WITH THEIR HYDROGEN ADSORPTION [J].
BERNDT, H ;
BRIEHN, V ;
EVERT, S .
JOURNAL OF MOLECULAR CATALYSIS, 1992, 73 (02) :203-214
[4]  
Brands D.S., 1998, THESIS U AMSTERDAM A
[5]   The relation between reduction temperature and activity in copper catalysed ester hydrogenolysis and methanol synthesis [J].
Brands, DS ;
Poels, EK ;
Krieger, TA ;
Makarova, OV ;
Weber, C ;
Veer, S ;
Bliek, A .
CATALYSIS LETTERS, 1996, 36 (3-4) :175-181
[6]   Mechanochemical reactions in Cu/ZnO catalysts induced by mechanical milling [J].
Castricum, HL ;
Bakker, H ;
van der Linden, B ;
Poels, EK .
JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (33) :7928-7937
[7]   THE MEASUREMENT OF COPPER SURFACE-AREAS BY REACTIVE FRONTAL CHROMATOGRAPHY [J].
CHINCHEN, GC ;
HAY, CM ;
VANDERVELL, HD ;
WAUGH, KC .
JOURNAL OF CATALYSIS, 1987, 103 (01) :79-86
[8]   THE ACTIVITY AND STATE OF THE COPPER SURFACE IN METHANOL SYNTHESIS CATALYSTS [J].
CHINCHEN, GC ;
WAUGH, KC ;
WHAN, DA .
APPLIED CATALYSIS, 1986, 25 (1-2) :101-107
[9]   Wetting/non-wetting phenomena during catalysis: evidence from in situ on-line EXAFS studies of Cu-based catalysts [J].
Clausen, Bjerne S. ;
Schiotz, Jakob ;
Grabaek, Lars ;
Ovesen, Charlotte V. ;
Jacobsen, Karsten W. ;
Norskov, Jens K. ;
Topsoe, Henrik .
TOPICS IN CATALYSIS, 1994, 1 (3-4) :367-376
[10]  
de Boer FR., 1988, COHESION METALS TRAN