Oligomerization, Isomerization and Carboxylation of Alkanes and Alkenes with Galvanostatically Generated Superoxide in the Al/O
 2
 Electrochemical Cell

Wajdi I. Al Sadat; Lynden A. Archer

doi:10.1002/anie.201810927

Oligomerization, Isomerization and Carboxylation of Alkanes and Alkenes with Galvanostatically Generated Superoxide in the Al/O 2 Electrochemical Cell

Wajdi I. Al Sadat, Lynden A. Archer

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Conversion 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%)

Original language	English (US)
Pages (from-to)	2632-2637
Number of pages	6
Journal	Angewandte Chemie International Edition
Volume	58
Issue number	9
DOIs	https://doi.org/10.1002/anie.201810927
State	Published - Feb 25 2019
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2021-04-13
Acknowledged KAUST grant number(s): KUS-C1-018-02
Acknowledgements: This 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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

General Chemistry
Catalysis

Access to Document

10.1002/anie.201810927

Cite this

@article{b48e2000a0404338901ca94fcbb8efae,

title = "Oligomerization, Isomerization and Carboxylation of Alkanes and Alkenes with Galvanostatically Generated Superoxide in the Al/O 2 Electrochemical Cell",

abstract = "Conversion 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%)",

author = "Al Sadat, {Wajdi I.} and Archer, {Lynden A.}",

note = "KAUST Repository Item: Exported on 2021-04-13 Acknowledged KAUST grant number(s): KUS-C1-018-02 Acknowledgements: This 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2019",

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doi = "10.1002/anie.201810927",

language = "English (US)",

volume = "58",

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AU - Al Sadat, Wajdi I.

AU - Archer, Lynden A.

N1 - KAUST Repository Item: Exported on 2021-04-13 Acknowledged KAUST grant number(s): KUS-C1-018-02 Acknowledgements: This 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2019/2/25

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N2 - Conversion 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%)

AB - Conversion 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%)

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