Unravelling the key factors in the chlorine-promoted epoxidation of ethylene over a silver-copper oxide nanocatalyst
Type
ArticleAuthors
Urbiztondo, MiguelRamirez, Adrian
Hueso, Jose L

Santamaria, Jesus
Ruiz-Salvador, A Rabdel

Hamad, Said

KAUST Department
Catalysis Center Department King Abdullah University of Science and Technology, KAUST, 4700 Thuwal 23955-6900, Kingdom of Saudi ArabiaKAUST Catalysis Center (KCC)
Date
2022-04-19Embargo End Date
2023-04-19Permanent link to this record
http://hdl.handle.net/10754/676734
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Show full item recordAbstract
Ethylene oxide is one of the most important raw materials in the chemical industry, with an annual production close to 35 million metric tons. Despite its importance, to date, no metal has been found that can compete with the original silver bulk material catalyst discovered in 1931. Recently, a few copper and copper–silver based nanostructures have demonstrated remarkable selectivity and activity, especially when coupled with an industrial chlorine promoter. The present work evaluates the mechanistic role of chlorine as an active promoter of the selective oxidation of ethylene to ethylene oxide in the presence of a silver–copper oxide hybrid nanocatalyst (AgCuO). Experimental kinetic studies combined with density functional theory (DFT) calculations provide insight into the influence that Ag/CuO-supported chlorine atoms have over the ethylene epoxidation reaction. Remarkably, the typically described indirect route via the formation of an oxametallacycle (OMC) is also accompanied by a direct route. Furthermore, the presence of chlorine seems to facilitate a more favorable adsorption energy for ethylene oxide (EO) than for acetaldehyde (AA), the main reaction by-product. As a result, complete oxidation of EO can be further prevented in the presence of this AgCuO hybrid heteronanostructure.Citation
Urbiztondo, M., Ramirez, A., Hueso, J. L., Santamaria, J., Ruiz-Salvador, A. R., & Hamad, S. (2022). Unravelling the key factors in the chlorine-promoted epoxidation of ethylene over a silver–copper oxide nanocatalyst. Nanoscale. https://doi.org/10.1039/d2nr00702aSponsors
We acknowledge financial support from the European Research Council ERC-Advanced Grant HECTOR (project number 267626) is gratefully acknowledged. The computations were performed on resources provided by the supercomputer “Caesaraugusta” (node of the Spanish Supercomputer Network) provided by BIFI (Universidad de Zaragoza). The TEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. S.H. acknowledges funding from the Agencia Estatal de Investigación and the Ministerio de Ciencia, Innovación y Universidades, of Spain (PID2019-110430G B-C22), and from the EU FEDER Framework 2014-2020 and Consejería de Conocimiento, Investigación y Universidad of the Andalusian Government (FEDER-UPO-1265695). The synthesis of materials has been performed by the Platform of Production of Biomaterials and Nanoparticles of the NANBIOSIS ICTS, more specifically by the Nanoparticle Synthesis Unit of the CIBER in BioEngineering, Biomaterials & Nanomedicine (CIBER-BBN).Publisher
Royal Society of Chemistry (RSC)Journal
NanoscalePubMed ID
35535713Additional Links
http://xlink.rsc.org/?DOI=D2NR00702Aae974a485f413a2113503eed53cd6c53
10.1039/d2nr00702a
Scopus Count
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