jp300809s_si_001.pdf (246.36 kB)
Phosgene-Free Method for Diphenyl Carbonate Synthesis at the Pd0/Ketjenblack Anode
journal contribution
posted on 2012-05-17, 00:00 authored by Toru Murayama, Tomohiko Hayashi, Ryoichi Kanega, Ichiro YamanakaElectrocarbonylation of phenol (PhOH) with CO to diphenyl
carbonate
(DPC) at a Pd0-supported Ketjenblack electrocatalyst (Pd/KB)
was studied at P(CO) = 1 atm and 25 °C. Electrocarbonylation
was conducted by galvanostatic electrolysis at 1 mA in an electrolyte
containing PhOH, sodium phenoxide (PhONa), LiCl, and CH3CN. The electrocatalytic
activity of DPC formation was strongly affected by the reduction temperature
of a PdCl2/KB electrocatalyst with H2. The Pd/KB
electrocatalyst reduced at 393 K showed the highest electrocatalytic
activity, while that reduced at 673 K showed less activity. Pd/KB
was characterized by X-ray diffraction, transmission electron microscopy–energy-dispersive
X-ray spectroscopy, and X-ray photoelectron spectroscopy. Pd particle
sizes are strongly related to the electrocatalytic activity of DPC
formation. Pd0 particles less than 2 nm were active, whereas
those greater than 6 nm were inactive. To reveal the electrocarbonylation
mechanism, electrocarbonylations using p-cresol, p-chlorophenol, and sodium phenoxides were studied. Cyclic
voltammetry studies were conducted using a palladiumized palladium-wire
electrode. These results strongly indicated that sodium phenoxides
did not incorporate into diaromatic carbonates and also functioned
as proton acceptors during electrocarbonylation.