Enhancing Ether Hydrogenolysis via Support Surface Proton Adsorption and Transfer Using Off-Field Electrocatalysis

Area of Science:

• Catalysis
• Materials Science
• Electrochemistry

Background:

• Efficient electrocatalytic hydrogenolysis of C-O bonds is crucial for biomass valorization.
• The role of catalyst supports in proton transfer during C-O activation is not well understood.

Purpose of the Study:

• To investigate the effect of catalyst supports on proton transfer in electrocatalytic hydrogenolysis.
• To enhance the efficiency and selectivity of C-O bond cleavage for biomass conversion.

Main Methods:

• Utilized a europium (Eu2+/Eu3+) redox mediator with a Palladium on Titanium Dioxide (Pd/TiO2) catalyst.
• Performed hydrogenolysis of benzyl phenyl ether under a dilute acidic environment.
• Compared the performance of Pd/TiO2 with Palladium on Carbon (Pd/C).

Main Results:

• Achieved >99% conversion and selectivity in benzyl phenyl ether hydrogenolysis using Pd/TiO2.
• Demonstrated 7-fold higher activity compared to Pd/C.
• Showed that TiO2 facilitates proton transfer, creating localized high proton concentrations at Pd active sites.
• Found that protonation of the ether linkage lowers the energy barrier for hydrogenolysis, increasing Faradaic efficiency.

Conclusions:

• TiO2 supports significantly enhance electrocatalytic C-O bond cleavage by improving proton transfer kinetics.
• Localized high proton concentration and ether linkage protonation are key to improved hydrogenolysis efficiency.
• The findings provide insights for designing advanced electrocatalysts for biomass valorization and C-O bond cleavage.