Enhanced Performance of Zirconium‐Doped Ceria Catalysts for the Methoxycarbonylation of Anilines
| Autor: | José Luis Núñez-Rico, Anton Vidal-Ferran, Javier Pérez-Ramírez, Begoña Puértolas, Stefan Wershofen, Marcos Rellán-Piñeiro, Núria López |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Zirconium
Fouling 010405 organic chemistry Chemistry Organic Chemistry Inorganic chemistry Doping chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Geometric factor Catalysis 0104 chemical sciences chemistry.chemical_compound Density functional theory Dimethyl carbonate Selectivity |
| Zdroj: | Chemistry – A European Journal. 26:16129-16137 |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | The methoxycarbonylation of anilines stands as an attractive method for the phosgene-free production of carbamates. Despite the high yields obtained for ceria catalysts, the reduction of the amount of side products and the prevention of catalyst deactivation still represent major hurdles in this chemistry. One advantage of ceria is the possibility of tuning its reactivity by doping its lattice with other metals. In the present work, a series of doped ceria-based materials, prepared by substitution with metals, are evaluated in the methoxycarbonylation of 2,4-diaminotoluene with dimethyl carbonate. Among all catalysts, containing Eu, Hf, La, Pr, Sm, Tb, Y or Zr, ceria promoted with 2 mol % Zr exhibited 96 % selectivity towards the desired carbamates, improving the pure CeO2 catalyst. Density functional theory demonstrates that two descriptors are needed: 1) a geometric factor that governs the reduction of energy barriers for carbamate formation through ureas; 2) catalyst basicity as N-H bonds need to be activated. Assessment in subsequent reaction cycles revealed that the CeO2 -ZrO2 catalyst is more stable than bulk CeO2 , along with the reduction of fouling processes. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
| Nepřihlášeným uživatelům se plný text nezobrazuje | K zobrazení výsledku je třeba se přihlásit. |