학술논문

Transition Metal B-Site Substitutions in LaAlO3 Perovskites Reorient Bio-Ethanol Conversion Reactions
Document Type
article
Source
Catalysts, Vol 11, Iss 3, p 344 (2021)
Subject
catalysis
oxides
lanthanum
gallium
alcohol reactivity
acetaldehyde
Chemical technology
TP1-1185
Chemistry
QD1-999
Language
English
ISSN
2073-4344
Abstract
LaAlO3 perovskites, as such and with 25% molar Al substitution by Cu, Co, or Ga, have been prepared by sol-gel methods and tested as heterogeneous catalysts in the gas-phase conversion of ethanol. LaAlO3 presented a significant acidic character, with high formation of ethylene by ethanol dehydration. B-site substitutions increased the basicity of the catalysts, favoring the dehydrogenation of ethanol to acetaldehyde. The most reducible Cu- and Co-substituted materials, characterized by easier formation of surface oxygen vacancies, promoted the self-condensation of acetaldehyde by the Tishchenko mechanism, with formation of acetone and odd-carbon number products. Aldol coupling of acetaldehyde, favored on pure and Ga-substituted LaAlO3, led to the formation of butadiene and hexadiene. The role of Ga insertion, favoring both dehydrogenation of ethylene and dehydration of higher alcohols, corresponds to an amphoteric character. The formation of olefins and diolefins on all catalysts suggests that LaAl-based materials present the most acidic character among La-perovskites.