Acetamide Electrosynthesis from CO2 and Nitrite in Water.

Renewable electricity driven electrocatalytic CO2 reduction reaction (CO2 RR) is a promising solution to carbon neutralization, which mainly generate simple carbon products. It is of great importance to produce more valuable C-N chemicals from CO2 and nitrogen species. However, it is challenging to co-reduce CO2 and NO3 - /NO2 - to generate aldoxime an important intermediate in the electrocatalytic C-N coupling process. Herein, we report the successful electrochemical conversion of CO2 and NO2 - to acetamide for the first time over copper catalysts under alkaline condition through a gas diffusion electrode. Operando spectroelectrochemical characterizations and DFT calculations, suggest acetaldehyde and hydroxylamine identified as key intermediates undergo a nucleophilic addition reaction to produce acetaldoxime, which is then dehydrated to acetonitrile and followed by hydrolysis to give acetamide under highly local alkaline environment and electric field. Moreover, the above mechanism was successfully extended to the formation of phenylacetamide. This study provides a new strategy to synthesize highly valued amides from CO2 and wastewater.

Multiscale CO2 Electrocatalysis to C2+ Products: Reaction Mechanisms, Catalyst Design, and Device Fabrication.

Electrosynthesis of value-added chemicals, directly from CO2, could foster achievement of carbon neutral through an alternative electrical approach to the energy-intensive thermochemical industry for carbon utilization. Progress in this area, based on electrogeneration of multicarbon products through CO2 electroreduction, however, lags far behind that for C1 products. Reaction routes are complicated and kinetics are slow with scale up to the high levels required for commercialization, posing significant problems. In this review, we identify and summarize state-of-art progress in multicarbon synthesis with a multiscale perspective and discuss current hurdles to be resolved for multicarbon generation from CO2 reduction including atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes, and macroscale electrolyzers with guidelines for future research. The review ends with a cross-scale perspective that links discrepancies between different approaches with extensions to performance and stability issues that arise from extensions to an industrial environment.