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
[11]   ON THE DETERMINATION OF COPPER SURFACE-AREA BY REACTION WITH NITROUS-OXIDE [J].
EVANS, JW ;
WAINWRIGHT, MS ;
BRIDGEWATER, AJ ;
YOUNG, DJ .
APPLIED CATALYSIS, 1983, 7 (01) :75-83
[12]   In situ investigations of structural changes in Cu/ZnO catalysts [J].
Grunwaldt, JD ;
Molenbroek, AM ;
Topsoe, NY ;
Topsoe, H ;
Clausen, BS .
JOURNAL OF CATALYSIS, 2000, 194 (02) :452-460
[13]   Characterization of Cu/SiO2 catalysts prepared by ion exchange for methanol dehydrogenation [J].
Guerreiro, ED ;
Gorriz, OF ;
Rivarola, JB ;
Arrua, LA .
APPLIED CATALYSIS A-GENERAL, 1997, 165 (1-2) :259-271
[14]  
HABRAKEN FHPM, 1980, SURF SCI, V97, P264, DOI 10.1016/0039-6028(80)90118-1
[15]   Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals [J].
Hansen, PL ;
Wagner, JB ;
Helveg, S ;
Rostrup-Nielsen, JR ;
Clausen, BS ;
Topsoe, H .
SCIENCE, 2002, 295 (5562) :2053-2055
[16]   Dynamic behavior of the surface structure of Cu/ZnO/SiO2 catalysis [J].
Jansen, WPA ;
Beckers, J ;
Van der Heuvel, JC ;
Van der Gon, AWD ;
Bliek, A ;
Brongersma, HH .
JOURNAL OF CATALYSIS, 2002, 210 (01) :229-236
[17]   Structural change of Cu/ZnO by reduction of ZnO in Cu/ZnO with methanol [J].
Jung, KD ;
Joo, OS ;
Han, SH .
CATALYSIS LETTERS, 2000, 68 (1-2) :49-54
[18]   METHANOL SYNTHESIS [J].
KLIER, K .
ADVANCES IN CATALYSIS, 1982, 31 :243-313
[19]   Partial reduction of Si(IV) in SiO2 thin film by deposited metal particles:: an XPS study [J].
Komiyama, M ;
Shimaguchi, T .
SURFACE AND INTERFACE ANALYSIS, 2001, 32 (01) :189-192
[20]   SURFACE AND SUB-SURFACE OXIDATION OF COPPER AND SUPPORTED COPPER-CATALYSTS BY NITROUS-OXIDE [J].
LUYS, MJ ;
VANOEFFELT, PH ;
BROUWER, WGJ ;
PIJPERS, AP ;
SCHOLTEN, JJF .
APPLIED CATALYSIS, 1989, 46 (01) :161-173