Electrocatalytic Oxyesterification of Hydrocarbons by Tetravalent Lead

Khenkin, Alexander M.; Herman, Adi; Haviv, Eynat; Neumann, Ronny

doi:10.1021/acscatal.1c01674

“…While versatile for various gaseous alkanes, its Faradic Efficiency (FE) for CH4 was just about 2%. 39 Furthermore, cathodic aerobic activation employing in-situ generated H2O2 from a two-electron oxygen reduction reaction was introduced. Due to the low solubility of CH4 in water and the low selectivity of reactive oxygen species (ROS, as detailed in Eq.…”

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confidence: 99%

Electrothermal Conversion of Methane to Methanol at Room-Temperature with Phosphotungstic Acid

Yan,

Chang,

Wang

et al. 2023

Preprint

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Traditional methods for anerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2-O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 μmol gPTA-1 h-1 with approximately 10% overall Faradic efficiency. Under continuous operation, we achieved 19.90 μmol gPTA-1 h-1 catalytic activity, over 88.6% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in-situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the selective methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo- and electrochemical methane oxidation at ambient conditions.

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Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic Acid

Chang,

Wang,

Hülsey

et al. 2024

Angewandte Chemie

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Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2‐O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 [[EQUATION]] with approximately 20.3% overall electron yield. Under continuous operation, we achieved 19.90 [[EQUATION]] catalytic activity, over 74.3% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in‐situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo‐ and electrochemical methane oxidation at ambient conditions.

show abstract

Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic Acid

Chang,

Wang,

Hülsey

et al. 2024

Angew Chem Int Ed

0

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Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2‐O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 [[EQUATION]] with approximately 20.3% overall electron yield. Under continuous operation, we achieved 19.90 [[EQUATION]] catalytic activity, over 74.3% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in‐situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo‐ and electrochemical methane oxidation at ambient conditions.

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Electrocatalytic Oxyesterification of Hydrocarbons by Tetravalent Lead

Cited by 3 publications

References 37 publications

Electrothermal Conversion of Methane to Methanol at Room-Temperature with Phosphotungstic Acid

Electrothermal Conversion of Methane to Methanol at Room-Temperature with Phosphotungstic Acid

Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic Acid

Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic Acid

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