Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides

New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX₂). Use of a different halide on ZnX₂ dictates the selectivity, wherein the NaH‐ZnI₂ system delivers alcohols and NaH‐ZnCl₂ gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH₂)_∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)₂ is the key species for the production of amines.     

Photoelectroreduction of Building‐Block Chemicals

Conventional photoelectrochemical cells utilize solar energy to drive the chemical conversion of water or CO₂ into useful chemical fuels. Such processes are confronted with general challenges, including the low intrinsic activities and inconvenient storage and transportation of their gaseous products. A photoelectrochemical approach is proposed to drive the reductive production of industrial building‐block chemicals and demonstrate that succinic acid and glyoxylic acid can be readily synthesized on Si nanowire array photocathodes free of any cocatalyst and at room temperature. These photocathodes exhibit a positive onset potential, large saturation photocurrent density, high reaction selectivity, and excellent operation durability. They capitalize on the large photovoltage generated from the semiconductor/electrolyte junction to partially offset the required external bias, and thereby make this photoelectrosynthetic approach significantly more sustainable compared to traditional electrosynthesis.