Nature Communications ( IF 14.7 ) Pub Date : 2022-08-25 , DOI: 10.1038/s41467-022-32769-0 Zhenhua Li 1 , Xiaofan Li 1 , Hua Zhou 1, 2, 3 , Yan Xu 4 , Si-Min Xu 1 , Yue Ren 1 , Yifan Yan 1 , Jiangrong Yang 1 , Kaiyue Ji 2 , Li Li 5 , Ming Xu 1 , Mingfei Shao 1 , Xianggui Kong 1 , Xiaoming Sun 1 , Haohong Duan 2, 3
Adipic acid is an important building block of polymers, and is commercially produced by thermo-catalytic oxidation of ketone-alcohol oil (a mixture of cyclohexanol and cyclohexanone). However, this process heavily relies on the use of corrosive nitric acid while releases nitrous oxide as a potent greenhouse gas. Herein, we report an electrocatalytic strategy for the oxidation of cyclohexanone to adipic acid coupled with H2 production over a nickel hydroxide (Ni(OH)2) catalyst modified with sodium dodecyl sulfonate (SDS). The intercalated SDS facilitates the enrichment of immiscible cyclohexanone in aqueous medium, thus achieving 3.6-fold greater productivity of adipic acid and higher faradaic efficiency (FE) compared with pure Ni(OH)2 (93% versus 56%). This strategy is demonstrated effective for a variety of immiscible aldehydes and ketones in aqueous solution. Furthermore, we design a realistic two-electrode flow electrolyzer for electrooxidation of cyclohexanone coupling with H2 production, attaining adipic acid productivity of 4.7 mmol coupled with H2 productivity of 8.0 L at 0.8 A (corresponding to 30 mA cm−2) in 24 h.
中文翻译:
配体修饰策略促进己二酸电催化合成与产氢
己二酸是聚合物的重要组成部分,通过酮醇油(环己醇和环己酮的混合物)的热催化氧化在商业上生产。然而,这个过程在很大程度上依赖于腐蚀性硝酸的使用,同时释放出一氧化二氮作为一种强效温室气体。在此,我们报告了一种将环己酮氧化为己二酸并在用十二烷基磺酸钠 (SDS) 改性的氢氧化镍 (Ni(OH) 2 ) 催化剂上产生 H 2的电催化策略。嵌入的 SDS 促进了不混溶的环己酮在水介质中的富集,因此与纯 Ni(OH) 2相比,己二酸的产率和法拉第效率 (FE) 提高了 3.6 倍(93% 对 56%)。该策略被证明对水溶液中的各种不混溶的醛和酮有效。此外,我们设计了一个实际的双电极流式电解槽,用于环己酮的电氧化与 H 2生产耦合,在 24 小时内,在 0.8 A(对应于 30 mA cm -2)下,己二酸产率为 4.7 mmol,H 2产率为 8.0 L。 H。