Combining anodic alcohol oxidative coupling for C–C bond formation with cathodic ammonia production  

作　　者：Leitao Xu Wei Chen Cairong Wang Wenjie Wu Yelin Yao Zhifeng Huang Jingcheng Wu Ming Yang Yandong Wu Dianke Xie Yuqin Zou Shuangyin Wang 

机构地区：[1]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Advanced Catalytic Engineering Research Center of the Ministry of Education,Hunan University,Changsha 410082,China

出　　处：《National Science Review》2024年第5期210-219,共10页国家科学评论（英文版）

基　　金：supported by the National Key R&D Program of China(2020YFA0710000);the National Natural Science Foundation of China(21825201,22122901 and 21902047);the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021JJ20024,2021RC3054 and 2022JJ40043);Hunan Provincial Innovation Foundation for Postgraduate(CX20220386).

摘　　要：Electrocatalytic oxidation of alcohols using heterogeneous catalysts is a promising aqueous,energy-efficient and environmentally friendly approach,especially for coupling different alcohols to prolong the carbon chain via co-oxidation.Precisely regulating critical steps to tailor electrode materials and electrolyte composition is key to selectively coupling alcohols for targeted synthesis.However,selectively coupling different alcohols remains challenging due to the lack of effective catalyst and electrolyte design promoting specific pathways.Herein,we demonstrate a paired electrolysis strategy for combining anodic oxidative coupling of ethanol(EtOH)and benzyl alcohol(PhCH2OH)to synthesize cinnamaldehyde(CAL)and cathodic ammonia production.The strategies involve:(i)utilizing the salt-out effect to balance selective oxidation and coupling rates;(ii)developing platinum-loaded nickel hydroxide electrocatalysts to accelerate intermediate coupling kinetics;(iii)introducing thermodynamically favorable nitrate reduction at the cathode to improve coupling selectivity by avoiding hydrogenation of products while generating valuable ammonia instead of hydrogen.We achieved 85%coupling selectivity and 278μmol/h NH3 productive rate at 100 mA/cm^(2) with a low energy input(∼1.63 V).The membrane-free,low energy,scalable approach with a wide substrate scope highlights promising applications of this methodology.This work advances heterogeneous electrocatalytic synthesis through rational design principles that integrate anodic oxidative coupling with cathodic nitrate reduction reactions,having synergistic effects on efficiency and selectivity.

关 键 词：anodic alcohol oxidative coupling C-C bond formation CINNAMALDEHYDE cathodic ammonia production 

分 类 号：O622.6[理学—有机化学]