Reduction of CuO in H2:: in situ time-resolved XRD studies

被引:228
作者
Rodriguez, JA [1 ]
Kim, JY
Hanson, JC
Pérez, M
Frenkel, AI
机构
[1] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
[2] Cent Univ Venezuela, Fac Ciencias, Caracas 1020A, Venezuela
[3] Yeshiva Univ, Dept Phys, New York, NY 10016 USA
关键词
copper oxide; copper; hydrogen; methanol synthesis; methanol steam reforming; reduction of oxides; X-ray diffraction;
D O I
10.1023/A:1022110200942
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
CuO is used as a catalyst or catalyst precursor in many chemical reactions that involve hydrogen as a reactant or product. A systematic study of the reaction of H-2 with pure powders and films of CuO was carried out using in situ time-resolved X-ray diffraction (XRD) and surface science techniques. Oxide reduction was observed at atmospheric 2 pressures and elevated temperatures (150-300degreesC), but only after an induction period. High temperature or H-2 pressure and a large concentration of defects in the oxide substrate lead to a decrease in the magnitude of the induction time. Under normal process conditions, in situ time-resolved XRD shows that Cu1+ is not a stable intermediate in the reduction of CuO. Instead of a sequential reduction (CuO double right arrow Cu4O3 double right arrow Cu2O double right arrow Cu), a direct CuO double right arrow Cu transformation occurs. To facilitate the generation of Cu1+ in a catalytic process one can limit the supply of H-2 or mix this molecule with molecules that can act as oxidant agents (O-2, H2O). The behavior of CuO-based catalysts in the synthesis of methanol and methanol steam reforming is discussed in the light of these results.
引用
收藏
页码:247 / 254
页数:8
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