New and unique electrocatalysis of gold for the carbonylation of methanol to dimethyl oxalate (DMO) and dimethyl carbonate (DMC) was found. The selectivity to DMO and DMC could be controlled over gold anode by electrochemical potential, as you like. Drastic changes of gold electrocatalysis was due to changes of the oxidation state of gold, Au0 or Au3+.

Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO(2). Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au(3+), methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au(0) is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (<+1.2 V (Ag/AgCl)). On the other hand, Au(3+) is the active spices for the selective DMC formation by indirect electrochemical carbonylation through Au(3+)/Au(+) redox at high potentials (>+1.3 V).

Selective and efficient electrochemical carbonylation of MeOH to DMC was performed over PdCl2/VGCF (vapor grown carbon fiber) anode by utilizing the three-phase boundary electrolysis at 1 atm (CO) and 298 K.

The formation rate, the current efficiency, and the selectivity of DMC with LiBr electrolyte were considerably higher than that with other supporting electrolyte, LiClO 4 , NaClO 4 , LiCl, Bu 4 NCl, LiI, and Bu 4 NI. A turnover number of Pd electrocatalyst for DMC formation was over 600 h −1 . Current efficiency of 80% and selectivity based on CH 3 OH and CO of 95% were observed. Data of kinetic experiments and stoichiometric experiments strongly suggested that electrochemically produced Br 2 works as an oxidant for the oxidative carbonylation of methanol to DMC catalyzed by Pd 0 on carbon. A very active and selective carbonylation of methanol to DMC was performed by indirect electrolysis with Br 2 /Br − redox mediator.

The synthesis of an n‐type π‐conjugated hyperbranched polymer, hyperbranched polypyridine, is described. The polymer is obtained by copolymerization of 2,4,6‐tribromopyridine and 2,5‐dibromopyridine via chain‐growth condensation polymerization catalyzed by Ni(dppp)Cl2. The NMR and fourier transform infrared results indicate the successful introduction of the branching unit into polypyridine by this cross coupling approach. The results of UV–vis spectroscopy and cyclic voltammetry suggest that the introduction of the branching unit contributes to a quick response during electrochemical doping due to the diffusion of dopant enhanced by the hyperbranched structure.