Highly efficient transformation of alcohol to carbonyl compounds under a hybrid bifunctional catalyst originated from metalloporphyrins and hydrotalcite

• Metalloporphyrins intercalated hydrotalcites were studied as bifunctional catalyst.
• The catalysts exhibited excellent activity, broad scope, and good stability in the oxidation.
• The surficial basicity benefits to improving the catalytic activity and the selectivity.
• Synergistic effect was observed in the MTSPP-Zn2Al-LDH catalytic system.
• A proposed mechanism under for the oxidation under MTSPP-Zn2Al-LDH was postulated.

The development of a highly active and selective catalytic system that is economical, environmentally benign, and easily recoverable is highly desirable. Bifunctional hybrid catalysts originated from metalloporphyrins (MTSPP; M = Co, Fe, and Mn), and hydrotalcite have been synthesized, characterized, and investigated in the aerobic oxidation of alcohols in the presence of isobutyraldehyde. The designed catalysts exhibited excellent activity, broad applicable scope, and good stability in the oxidation. The effect of surface basicity on the catalytic performance has been studied in detail. The research results showed that as well as protecting the metalloporphyrin molecule, the surface basicity of hydrotalcite also contributed to improving the catalytic activity and the selectivity of aldehyde, and a synergistic effect was observed in the catalytic system. A proposed mechanism for the reaction involving the formation of high-valence cobalt–oxo porphyrin intermediate was postulated based on catalytic results and Hammett and H218O experiments.

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