Enhanced Performance of Zirconium-Doped Ceria Catalysts for the Methoxycarbonylation of Anilines

Chemistry : a European Journal
José Luis Núñez-RicoStefan Wershofen

Abstract

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.

References

Feb 15, 1995·Physical Review. B, Condensed Matter·G Makov, M C Payne
Oct 15, 1996·Physical Review. B, Condensed Matter·G Kresse, J Furthmüller
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jul 5, 2003·Science·Qi FuMaria Flytzani-Stephanopoulos
Sep 10, 2004·Nature·Zongping Shao, Sossina M Haile
Feb 9, 2007·Angewandte Chemie·Daniel TorresRichard M Lambert
Jan 20, 2010·Angewandte Chemie·Raquel JuárezHermenegildo García
Jul 20, 2012·Angewandte Chemie·Gianvito ViléJavier Pérez-Ramírez
Jan 31, 2013·Physical Chemistry Chemical Physics : PCCP·Ramzi FarraDetre Teschner
Dec 4, 2014·Journal of Chemical Information and Modeling·M Álvarez-MorenoC Bo
Apr 28, 2016·Chemical Reviews·Tiziano MontiniPaolo Fornasiero
May 19, 2017·Nature Communications·Chirranjeevi Balaji GopalWilliam C Chueh
Aug 30, 2017·Nanoscale·Qiang LiNúria López

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.