Electrochemically Assisted Cycloaddition of Carbon Dioxide to Styrene Oxide on Copper/Carbon Hybrid Electrodes: Active Species and Reaction Mechanism

Abstract

A novel electrochemically assisted cycloaddition process is proposed, in which highly efficient coupling of CO 2 with styrene oxide (SO) can be achieved to form styrene carbonate (SC) as a high-value-added product. A series of Cu catalysts with different morphologies and chemical states were fabricated on carbon paper (CP) by using in-situ electrodeposition, and the sample with nano-dendrimer structure was found to exhibit a relatively high activity of 74.8 % SC yield with 92.7 % SO conversion under gentle reaction conditions, thus showing its potential for practical applications. The relatively high electrochemically active sur-face area and charge transfer ability of dendrimer-like Cu benefited the electrochemical reaction. In particular, the Cu 2 + species that were formed in situ during the reaction played a vital role in enhancing the activity and selectivity of the proposed Cu/CP hybrid catalyst. Cu 2 + atoms served as active sites that can not only electrochemically activate CO 2 but also facilitate the ring opening of SO. Mechanistic analysis suggested that the reaction followed electrochemical and liquid-phase heterogeneous paths, which provide a new green and sustainable route for efficient utilization of CO 2 resources for fine chemical electrosynthesis.

The highly efficient electrocatalytic oxidation of 5-hydroxymethylfurfural on copper nanocrystalline/carbon hybrid catalysts: structure–function relations

“…4d–f), which indicates that the HMF electrooxidation is accompanied by oxidation of Cu 0 /Cu 1+ species. 26 Furthermore, the content of Cu 2+ in the Cu(NP)/CP-used, Cu(NDD)/CP-used and Cu(NSD)/CP-used catalysts was 53.1%, 59.7% and 63.5%, respectively, showing a trend of gradually increasing (Table S1†). Since Cu 0 and Cu 1+ are not easily distinguished because of their very close binding energies in the Cu 2p3/2 XPS spectrum, 27 Auger electron spectroscopy was used to explore the distribution of Cu 1+ and Cu 0 species in the Cu(NP)/CP, Cu(NDD)/CP and Cu(NSD)/CP catalysts before and after the reaction.…”

Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis

“…In the years following these two reports, only a few articles have been published, most of which deal with the incorporation of CO 2 into organic molecules. The reactions identified include aromatic ketone electrocarboxylation, − electrochemical CO 2 cycloaddition to epoxides, ,, electrocarboxylation of acyl halides, electrosynthesis of dialkyl carbonates from alcohols, CO 2 , and alkyl iodides, − electrosynthesis of carbamates using amines, , electrocarboxylation of alkyl or aryl halides, − and olefin electrocarboxylation . In several cases, the organic electrosynthesis performed with IL electrolytes does not involve the direct reduction of CO 2 to the anion radical.…”