Influence of Al2O3 on the performance of CeO2 used as catalyst in the direct carboxylation of methanol to dimethylcarbonate and the elucidation of the reaction mechanism

Michele Aresta, Angela Dibenedetto, Carlo Pastore, Antonella Angelini, Brunella Aresta, I. Pápai

Research output: Contribution to journalArticle

78 Citations (Scopus)

Abstract

In this paper we show that modification of ceria by loading alumina strongly reduces the oxidation of methanol and the consequent reduction of Ce(IV) to Ce(III) with increase of both the life of the catalysts and their selectivity. The combination of surface techniques (XPS and BET) with structural techniques (XRD) has allowed a good characterisation of the working catalysts. Spectroscopic analyses (DRIFT and multinuclear solid state and solution NMR) have permitted the monitoring of the species formed on the surface of the catalyst and released from it. The formation of DMC takes place in successive steps such as (i) interaction of methanol with the catalyst surface with the formation of the surface-bound {single bond}OCH3; (ii) building on the catalyst surface of the hemicarbonate moiety [-OCH3 → -OC(O)OCH3]; and (iii) reaction of the latter with the gas-phase methanol to afford the organic carbonate.

Original languageEnglish
Pages (from-to)44-52
Number of pages9
JournalJournal of Catalysis
Volume269
Issue number1
DOIs
Publication statusPublished - Jan 1 2010

Fingerprint

carboxylation
Carboxylation
Methanol
methyl alcohol
catalysts
Catalysts
Catalyst selectivity
Aluminum Oxide
Carbonates
Cerium compounds
carbonates
solid solutions
Alumina
X ray photoelectron spectroscopy
aluminum oxides
Gases
selectivity
Nuclear magnetic resonance
vapor phases
solid state

Keywords

  • Dimethyl carbonate
  • DRIFT studies
  • Effect of AlO on CeO catalysts
  • Methanol carboxylation
  • NMR solid state and solution
  • Reaction mechanism
  • Surface modification
  • Surface techniques

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Influence of Al2O3 on the performance of CeO2 used as catalyst in the direct carboxylation of methanol to dimethylcarbonate and the elucidation of the reaction mechanism. / Aresta, Michele; Dibenedetto, Angela; Pastore, Carlo; Angelini, Antonella; Aresta, Brunella; Pápai, I.

In: Journal of Catalysis, Vol. 269, No. 1, 01.01.2010, p. 44-52.

Research output: Contribution to journalArticle

Aresta, Michele ; Dibenedetto, Angela ; Pastore, Carlo ; Angelini, Antonella ; Aresta, Brunella ; Pápai, I. / Influence of Al2O3 on the performance of CeO2 used as catalyst in the direct carboxylation of methanol to dimethylcarbonate and the elucidation of the reaction mechanism. In: Journal of Catalysis. 2010 ; Vol. 269, No. 1. pp. 44-52.
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