Chen Long, Yin Zhao-Hua, Cui Jun-Yuan, Li Chao-Qun, Song Kepeng, Liu Hong, Wang Jian-Jun
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
J Am Chem Soc. 2024 Oct 2;146(39):27090-27099. doi: 10.1021/jacs.4c09252. Epub 2024 Sep 21.
In pursuit of advancing the electrooxidation of amines, which is typically encumbered by the inertness of C(sp)-H/N(sp)-H bonds, our study introduces a high-performance electrocatalyst that significantly enhances the production efficiency of vital chemicals and fuels. We propose a novel electrocatalytic strategy employing a uniquely designed (NiCo)Se-R electrocatalyst, which is activated through Se-O exchange and electron orbital spin manipulation. This catalyst efficiently generates M species, thus enabling the activation of lattice oxygen and streamlining the electrooxidation of amines. Empirical evidence from isotope labeling, molecular probes, and computational analyses indicates that the electrocatalyst fosters the formation of energetically favorable peroxy radical intermediates, which substantially expedite the reaction kinetics. The refined electrocatalyst achieves an exceptional current density of 20 mA cm at a potential of 1.315 V, with selectivity surpassing 99% for propionitrile, while demonstrating remarkable stability over 560 h. This work emphasizes the criticality of deciphering the fundamental mechanisms of amine electrooxidation and charts a more sustainable pathway for the nitrile and hydrogen production, marking a substantial advancement in the field of electrocatalysis.
为了推动胺的电氧化反应（该反应通常受限于C(sp)-H/N(sp)-H键的惰性），我们的研究引入了一种高性能电催化剂，可显著提高重要化学品和燃料的生产效率。我们提出了一种新颖的电催化策略，采用独特设计的(NiCo)Se-R电催化剂，该催化剂通过Se-O交换和电子轨道自旋操纵实现活化。这种催化剂能有效生成M物种，从而实现晶格氧的活化并简化胺的电氧化过程。同位素标记、分子探针和计算分析的实验证据表明，该电催化剂促进了能量有利的过氧自由基中间体的形成，极大地加快了反应动力学。这种优化后的电催化剂在1.315 V的电位下实现了20 mA cm的优异电流密度，对丙腈的选择性超过99%，同时在560 h内表现出显著的稳定性。这项工作强调了解析胺电氧化基本机制的重要性，并为腈和氢气的生产绘制了一条更具可持续性的途径，标志着电催化领域的重大进展。
