Oligomerization, Isomerization and Carboxylation of Alkanes and Alkenes with Galvanostatically Generated Superoxide in the Al/O 2 Electrochemical Cell
KAUST Grant NumberKUS-C1-018-02
Permanent link to this recordhttp://hdl.handle.net/10754/668696
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AbstractConversion of low-value,but thermodynamicallystable chemical byproducts such as alkanes or CO2to morevaluable feedstocksisofbroad-based interest. These so-calledup-conversion processes are expensive because they requireenergy-intensive and catalytic interventions to drive reactionsagainst thermodynamic gradients.Here we show that thenucleophilic characteristics of superoxides,generated galva-nostatically in an Aluminum/O2electrochemical cell, can beused in tandem with the intrinsic catalytic properties of animidazolium/AlCl3electrolyte to facilely upgrade alkanes (n-decane), alkenes (1-decene), and CO2feedstocks.The alumi-num/O2electrochemical cell used to generate the superoxideintermediate is also reported to deliver large amounts ofelectrical energy and therefore offers asystem for high-energydensity storage and for chemical up-conversion of low valuecompounds.Chronopotentiometry,mass spectrometry andnuclear magnetic resonance were used to investigate theelectrochemical features of the system and to analyze thedischarge products.Wefind that even at room temperature,alkanes and alkenes are facilely oligomerized and isomerizedat high conversions (> 97%), mimicking the traditionallyproduced refined products.Incorporating CO2in the alkanefeed leads to formation of esters and formates at moderateyields (21%)
CitationAl Sadat, W. I., & Archer, L. A. (2019). Oligomerization, Isomerization and Carboxylation of Alkanes and Alkenes with Galvanostatically Generated Superoxide in the Al/O 2 Electrochemical Cell. Angewandte Chemie International Edition, 58(9), 2632–2637. doi:10.1002/anie.201810927
SponsorsThis work was made possible by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). It made use of the Cornell Center for Materials Research (CCMR) Shared Facilities which are supported through the NSF MRSEC program (DMR-1719875). This work made use of the Cornell NMR Facility, which is supported in part by the NSF-MRI grant DMR-1719875.