Dynamic Behavior of CuZn Nanoparticles under Oxidizing and Reducing Conditions

被引:53
作者
Holse, Christian [1 ]
Elkjaer, Christian F. [1 ,2 ]
Nierhoff, Anders [1 ]
Sehested, Jens [2 ]
Chorkendorff, Ib [1 ]
Helveg, Stig [2 ]
Nielsen, Jane H. [1 ]
机构
[1] Tech Univ Denmark, Dept Phys, Ctr Individual Nanoparticle Funct, DK-2800 Lyngby, Denmark
[2] Haldor Topsoe Res Labs, DK-2800 Lyngby, Denmark
基金
新加坡国家研究基金会;
关键词
METHANOL SYNTHESIS CATALYSTS; IN-SITU; STRUCTURAL-CHANGES; SURFACE-AREAS; ACTIVE-SITE; ZINC-OXIDE; CU/ZNO; COPPER; ZNO; ADSORPTION;
D O I
10.1021/jp510015v
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 oxidation and reduction of CuZn nanoparticles was studied using X-ray photoelectron spectroscopy (XPS) and in situ transmission electron microscopy (TEM). CuZn nanoparticles with a narrow size distribution were produced with a gas-aggregation cluster source in conjunction with mass-filtration. A direct comparison between the spatially averaged XPS information and the local TEM observations was thus made possible. Upon oxidation in O-2, the as-deposited metal clusters transform into a polycrystalline cluster consisting of separate CuO and ZnO nanocrystals. Specifically, the CuO is observed to segregate to the cluster surface and partially cover the ZnO nanocrystals. Upon subsequent reduction in H-2 the CuO converts into metallic Cu with ZnO nanocrystal covering their surface. In addition, a small amount of metallic Zn is detected suggesting that ZnO is reduced. It is likely that Zn species can migrate to the Cu surface forming a Cu-Zn surface alloy. The oxidation and reduction dynamics of the CuZn nanoparticles is of great importance to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boosts the catalytic activity. Thus, the present results demonstrate a new model approach that should be generally applicable to address metal-support interactions in coprecipitated catalysts and multicomponent nanomaterials.
引用
收藏
页码:2804 / 2812
页数:9
相关论文
共 49 条
[1]   Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis [J].
An, Kwangjin ;
Somorjai, Gabor A. .
CHEMCATCHEM, 2012, 4 (10) :1512-1524
[2]  
[Anonymous], IN CRYST STRUCT DAT
[3]   Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis [J].
Baltes, C. ;
Vukojevic, S. ;
Schueth, F. .
JOURNAL OF CATALYSIS, 2008, 258 (02) :334-344
[4]  
Behrens M, 2012, SCIENCE, V336, P893, DOI [10.1126/science.1219831, 10.1126/science.12198331]
[5]   Meso- and nano-structuring of industrial Cu/ZnO/(Al2O3) catalysts [J].
Behrens, Malte .
JOURNAL OF CATALYSIS, 2009, 267 (01) :24-29
[6]   The impact of nanoscience on heterogeneous catalysis [J].
Bell, AT .
SCIENCE, 2003, 299 (5613) :1688-1691
[7]   Chemistry and properties of nanocrystals of different shapes [J].
Burda, C ;
Chen, XB ;
Narayanan, R ;
El-Sayed, MA .
CHEMICAL REVIEWS, 2005, 105 (04) :1025-1102
[8]   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
[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]   The influence of ZnO on the differential heat of adsorption of CO on Cu catalysts:: a microcalorimetric study [J].
d'Alnoncourt, RN ;
Kurtz, M ;
Wilmer, H ;
Löffler, E ;
Hagen, V ;
Shen, JY ;
Muhler, M .
JOURNAL OF CATALYSIS, 2003, 220 (01) :249-253