AgII -Mediated Electrocatalytic Ambient CH4 Functionalization Inspired by HSAB Theory
Danlei Xiang1, Jesus A Iñiguez1, Jiao Deng1
1Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA, 90095, USA.
Divalent silver (AgII) readily functionalizes methane (CH4) into methyl bisulfate under ambient conditions. This breakthrough offers efficient methane conversion with high selectivity, paving the way for natural gas utilization.
Area of Science:
- Inorganic Chemistry
- Electrochemistry
- Catalysis
Background:
- Methane (CH4) activation is crucial for utilizing natural gas.
- Class (b) transition metals are widely studied for CH4 activation.
- Divalent silver (AgII) was previously uninvestigated for CH4 activation due to its reactivity.
Purpose of the Study:
- To investigate the potential of electrochemically generated AgII for CH4 activation.
- To characterize the mechanism and efficiency of AgII-mediated CH4 functionalization.
- To explore the feasibility of using this system for practical methane conversion.
Main Methods:
- Electrochemical generation of AgII metalloradical.
- Methane functionalization in 98% sulfuric acid.
- Mechanistic studies involving activation energy and rate constant determination.
- Kinetic analysis to determine Faradaic efficiency.
Main Results:
- AgII readily functionalizes CH4 into methyl bisulfate at ambient conditions.
- Low activation energy (13.1 kcal/mol) and high rate constant (2.8×10^3 h^-1) for CH4 activation.
- Two competing reaction pathways identified, favoring CH4 activation over solvent oxidation.
- High Faradaic efficiency (>99%) at elevated CH4 pressures suggests industrial applicability.
Conclusions:
- Electrochemical AgII is an effective catalyst for CH4 activation and functionalization.
- The process demonstrates high efficiency and selectivity under mild conditions.
- This method presents a promising route for sustainable methane valorization from natural gas.
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