张宁
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祝贺课题组在《Journal of the American Chemical Society》上发表有关盐析效应提高电催化C-N偶联合成腈类化合物选择性的研究论文!第一作者为博士生刘振中和硕士生刘怡君!
Title: Salting-out effect enables highly selective electrochemical ammoxidation of aldehydes to nitriles.
Abstract: Electrochemical ammoxidation of aldehyde in aqueous electrolyte offers a sustainable and promising way towards nitrile synthesis. Unfortunately, the reaction efficiency, especially for nitrile selectivity, is fundamentally restricted by the competitive reaction of direct aldehyde oxidation, which initializes from the inevitable but uncontrollable hydration of aldehyde itself. Here, we present a salt-out effect, induced by the concentrated potassium cation (K+) in bulk electrolyte, can achieve highly efficient nitrile synthesis. Molecular dynamics simulations and spectroscopic investigations unveil that the high K+ concentration renders the reorientation of H2O structure to govern the stronger K+-H2O ion–dipole interaction. Such solvent-microenvironmental regulation in turn weakens the H2O affinity to aldehyde, thereby suppressing the aldehyde hydration. As a result, the condensation of aldehyde and ammonia is favored to facilitate the nitrile production. Using benzaldehyde as the proof-of-concept substrate, the production of benzonitrile is significantly boosted in concentrated 3.0-M K2CO3 electrolyte, affording a high selectivity up to 97.3% and considerable yield rate of 177.4 µmol cm−2 h−1 when feeding 10- and 100-mM benzaldehyde, respectively. Such salt-out-induced selectivity improvement also exhibits good reaction durability and aldehyde universality, underscoring the great merit for sustainable chemical manufacturing.
