Identification and quantification of redox-active centers at relevant conditions for catalysis is pivotal to understand reaction mechanisms and requires development of advanced operando methods. Herein, we demonstrate operando EPR spectroscopy as an important technique to quantify the oxidation state of representative CrPO and EuOCl catalysts during propane oxychlorination, an attractive route for propylene production. In particular, we show that the space-time-yield of C H correlates with the amount of Cr and Eu ions generated over the catalysts during reaction. These results provide a powerful strategy to gather quantitative understanding of selective alkane oxidation, which could potentially be extrapolated to other functionalization approaches and operating conditions.
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Quantification of Redox Sites during Catalytic Propane Oxychlorination by Operando EPR Spectroscopy.
Angew Chem Int Ed Engl
February 2021
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland.
Identification and quantification of redox-active centers at relevant conditions for catalysis is pivotal to understand reaction mechanisms and requires development of advanced operando methods. Herein, we demonstrate operando EPR spectroscopy as an important technique to quantify the oxidation state of representative CrPO and EuOCl catalysts during propane oxychlorination, an attractive route for propylene production. In particular, we show that the space-time-yield of C H correlates with the amount of Cr and Eu ions generated over the catalysts during reaction.
View Article and Find Full Text PDFOperando Photoelectron Photoion Coincidence Spectroscopy Unravels Mechanistic Fingerprints of Propane Activation by Catalytic Oxyhalogenation.
J Phys Chem Lett
February 2020
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland.
Herein, we demonstrate photoelectron photoion coincidence (PEPICO) spectroscopy as a pivotal technique for evidencing unprecedented mechanistic insights by isomer-selective radical detection within complex hydrocarbon-functionalization reaction networks, such as those of catalyzed propane oxychlorination and oxybromination. In particular, while the oxychlorination is surface-confined, we show that in oxybromination alkane activation follows a gas-phase reaction mechanism with evolved bromine and bromine radicals, favoring 2-propyl over 1-propyl radical formation, as evidenced by isomer-selective threshold photoelectron analysis. Furthermore, we provide new mechanistic insights into the cracking and coking pathways that are observed in oxybromination.
View Article and Find Full Text PDFOlefins from Natural Gas by Oxychlorination.
Angew Chem Int Ed Engl
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Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland.
Ethylene and propylene are the key building blocks of the chemical industry, but current processes are unable to close the growing gap between demand and manufacture. Reported herein is an exceptional europium oxychloride (EuOCl) catalyst for the selective (≥95 %) production of light olefins from ethane and propane by oxychlorination chemistry, thus achieving yields of ethylene (90 %) and propylene (40 %) unparalleled by any existing olefin production technology. Moreover, EuOCl is able to process mixtures of methane, ethane, and propane to produce the olefins, thereby reducing separation costs of the alkanes in natural gas.
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