Abstract
The selective oxidation of light hydrocarbons and their valorization with only dioxygen (O2) are important transformations toward development of efficient chemical processes. Monooxygenase enzymes can catalyze selective aerobic reactions under reducing and protic conditions. The translation of such enzymatic pathways to the practical electrocatalytic oxidation of light, gaseous hydrocarbons, using O2 as sole oxidant is now reported. An iron-tungsten oxide inorganic molecular catalyst with a capsular structure {Fe30W72} stabilized inside by sulfate/bisulfate anions provides a protic environment where three iron atoms are located at each of the pores of the capsule leading to a unique and potent active site for the oxidation reactions. Under mild electrochemical conditions, 1.8 V, in water at room temperature, using O2 from air, we demonstrate the low-pressure (1-2 bar) hydroxylation of alkanes, notably ethane to acetic acid, and the ozone like cleavage of the carbon-carbon double bonds of alkenes. Typical turnover frequencies were 300-400 min-1. Initial mechanistic studies support a reaction through a very active iron-oxo species.
| Original language | English |
|---|---|
| Pages (from-to) | 3232-3236 |
| Number of pages | 5 |
| Journal | ACS Catalysis |
| Volume | 8 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - Apr 6 2018 |
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Keywords
- C-H bond activation
- cathodic oxidation
- electrocatalysis
- hydroxylation
- Polyoxometalate
ASJC Scopus subject areas
- Catalysis
Cite this
Aerobic Electrochemical Oxygenation of Light Hydrocarbons Catalyzed by an Iron-Tungsten Oxide Molecular Capsule. / Bugnola, Marco; Carmieli, Raanan; Neumann, Ronny.
In: ACS Catalysis, Vol. 8, No. 4, 06.04.2018, p. 3232-3236.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Aerobic Electrochemical Oxygenation of Light Hydrocarbons Catalyzed by an Iron-Tungsten Oxide Molecular Capsule
AU - Bugnola, Marco
AU - Carmieli, Raanan
AU - Neumann, Ronny
PY - 2018/4/6
Y1 - 2018/4/6
N2 - The selective oxidation of light hydrocarbons and their valorization with only dioxygen (O2) are important transformations toward development of efficient chemical processes. Monooxygenase enzymes can catalyze selective aerobic reactions under reducing and protic conditions. The translation of such enzymatic pathways to the practical electrocatalytic oxidation of light, gaseous hydrocarbons, using O2 as sole oxidant is now reported. An iron-tungsten oxide inorganic molecular catalyst with a capsular structure {Fe30W72} stabilized inside by sulfate/bisulfate anions provides a protic environment where three iron atoms are located at each of the pores of the capsule leading to a unique and potent active site for the oxidation reactions. Under mild electrochemical conditions, 1.8 V, in water at room temperature, using O2 from air, we demonstrate the low-pressure (1-2 bar) hydroxylation of alkanes, notably ethane to acetic acid, and the ozone like cleavage of the carbon-carbon double bonds of alkenes. Typical turnover frequencies were 300-400 min-1. Initial mechanistic studies support a reaction through a very active iron-oxo species.
AB - The selective oxidation of light hydrocarbons and their valorization with only dioxygen (O2) are important transformations toward development of efficient chemical processes. Monooxygenase enzymes can catalyze selective aerobic reactions under reducing and protic conditions. The translation of such enzymatic pathways to the practical electrocatalytic oxidation of light, gaseous hydrocarbons, using O2 as sole oxidant is now reported. An iron-tungsten oxide inorganic molecular catalyst with a capsular structure {Fe30W72} stabilized inside by sulfate/bisulfate anions provides a protic environment where three iron atoms are located at each of the pores of the capsule leading to a unique and potent active site for the oxidation reactions. Under mild electrochemical conditions, 1.8 V, in water at room temperature, using O2 from air, we demonstrate the low-pressure (1-2 bar) hydroxylation of alkanes, notably ethane to acetic acid, and the ozone like cleavage of the carbon-carbon double bonds of alkenes. Typical turnover frequencies were 300-400 min-1. Initial mechanistic studies support a reaction through a very active iron-oxo species.
KW - C-H bond activation
KW - cathodic oxidation
KW - electrocatalysis
KW - hydroxylation
KW - Polyoxometalate
UR - http://www.scopus.com/inward/record.url?scp=85045092329&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85045092329&partnerID=8YFLogxK
U2 - 10.1021/acscatal.8b00477
DO - 10.1021/acscatal.8b00477
M3 - Article
AN - SCOPUS:85045092329
VL - 8
SP - 3232
EP - 3236
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 4
ER -