Asymmetrical electrohydrogenation of CO2 to ethanol with copper-gold heterojunctions.

Copper is distinctive in electrocatalyzing reduction of CO2 into various energy-dense forms, but it often suffers from limited product selectivity including ethanol in competition with ethylene. Here, we describe systematically designed, bimetallic electrocatalysts based on copper/gold heterojunctions with a faradaic efficiency toward ethanol of 60% at currents in excess of 500 mA cm-2. In the modified catalyst, the ratio of ethanol to ethylene is enhanced by a factor of 200 compared to copper catalysts. Analysis by ATR-IR measurements under operating conditions, and by computational simulations, suggests that reduction of CO2 at the copper/gold heterojunction is dominated by generation of the intermediate OCCOH*. The latter is a key contributor in the overall, asymmetrical electrohydrogenation of CO2 giving ethanol rather than ethylene.

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.

Fast-Charging Zn-Air Batteries with Long Lifetime Enabled by Reconstructed Amorphous Multi-Metallic Sulfide.

Developing fast-charging Zn-air batteries is crucial for widening their application but remains challenging owing to the limitation of sluggish oxygen evolution reaction (OER) kinetics and insufficient active sites of electrocatalysts. To solve this issue, a reconstructed amorphous FeCoNiSx electrocatalyst with high density of efficient active sites, yielding low OER overpotentials of 202, 255, and 323 mV at 10, 100, and 500 mA cm-2 , respectively, is developed for fast-charging Zn-air batteries with low charging voltages at 100-400 mA cm-2 . Furthermore, the fabricated 3241.8 mAh (20 mA cm-2 , 25 °C) quasi-solid Zn-air battery shows long lifetime of 500 h at -10 and 25 °C as well as 150 h at 40 °C under charging 100 mA cm-2 . The detailed characterizations combine with density functional theory calculations indicate that the defect-rich crystalline/amorphous ternary metal (oxy)hydroxide forms by the reconstruction of amorphous multi-metallic sulfide, where the electron coupling effect among multi-active sites and migration of intermediate O* from Ni site to the Fe site breaks the scaling relationship to lead to a low theoretical OER overpotential of 170 mV, accounting for the outstanding fast-charging property. This work not only provides insights into designing advanced OER catalysts by the self-reconstruction of the pre-catalyst but also pioneers a pathway for practical fast-charging Zn-air batteries.