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Enhanced Performance of Zirconium‐Doped Ceria Catalysts for the Methoxycarbonylation of Anilines
Author(s) -
NúñezRico José Luis,
RellánPiñeiro Marcos,
Puértolas Begoña,
VidalFerran Anton,
López Núria,
PérezRamírez Javier,
Wershofen Stefan
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003201
Subject(s) - catalysis , phosgene , zirconium , selectivity , doping , reactivity (psychology) , chemistry , density functional theory , inorganic chemistry , chemical engineering , materials science , organic chemistry , computational chemistry , medicine , alternative medicine , optoelectronics , pathology , engineering
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 CeO 2 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 CeO 2 –ZrO 2 catalyst is more stable than bulk CeO 2 , along with the reduction of fouling processes.