High catalytic efficiency of nanostructured molybdenum trioxide in the benzylation of arenes and an investigation of the reaction mechanism.
摘要:
The synthesis and characterization of nanostructured MoO3 with a thickness of about 30nm and a width of about 450nm are reported. The composition formula of the MP (precipitation method) precursor was estimated to be [(NH4)2O]0.169MoO3 (H2O)0.239. The calcination of the precursor in air afforded nanostructured pellets of the -MoO3 phase. The nanostructured MoO3 catalyst exhibited high efficiency in catalyzing the benzylation of various arenes with substituted benzyl alcohols, which were strikingly different to common bulk MoO3. Most reactions offered >99% conversion and >99% selectivity to monoalkylated compounds. MoO3 is a typical acid catalyst. However, the benzylation reaction over nanostructured MoO3 does not belong to the acid-catalyzed type or defect site-catalyzed type, since the catalyst has no acidity and defect site on surface. Characterization with thermal, spectroscopic, and electronic techniques reveal that the catalyst contains fully oxygen-coordinated MoO6 octahedrons on the surface but partially reduced species (Mo5+) within the bulk phase. The terminal oxygen atoms of MoO bonds on the (010) basal plane resemble oxygen anion radicals and act as active sites for the adsorption and activation of benzyl alcohols by electrophilic attack. Such sites are indispensable for catalytic reactions since the blocking of these sites by electron acceptors, such as tetracyanoethylene (TCNE), can greatly decrease catalytic activity. This work represents a successful example of combining a heterogeneous catalysis study with nanomaterial synthesis.
展开
关键词:
benzylation heterogeneous catalysis molybdenum trioxide molybdenum nanostructures surface chemistry TEMPERATURE-PROGRAMMED DESORPTION ELECTRON-SPIN RESONANCE OXIDATIVE DEHYDROGENATION SELECTIVE OXIDATION SINGLE-CRYSTAL ALPHA-MOO3 NANOSTRUCTURES NANOCRYSTALLINE MGO SURFACE-CHEMISTRY AQUEOUS-SOLUTION REDOX PROPERTIES
DOI:
10.1002/chem.200801153
被引量:
年份:
2009
相似文献
参考文献
引证文献
辅助模式
引用
文献可以批量引用啦~
欢迎点我试用!