Li Zhenhua, Li Xiaofan, Zhou Hua, Xu Yan, Xu Si-Min, Ren Yue, Yan Yifan, Yang Jiangrong, Ji Kaiyue, Li Li, Xu Ming, Shao Mingfei, Kong Xianggui, Sun Xiaoming, Duan Haohong
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, China.
Department of Chemistry, Tsinghua University, Beijing, China.
Nat Commun. 2022 Aug 25;13(1):5009. doi: 10.1038/s41467-022-32769-0.
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 H production over a nickel hydroxide (Ni(OH)) 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) (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 H production, attaining adipic acid productivity of 4.7 mmol coupled with H productivity of 8.0 L at 0.8 A (corresponding to 30 mA cm) in 24 h.
己二酸是聚合物的重要组成部分，其商业生产方法是通过酮醇油（环己醇和环己酮的混合物）的热催化氧化。然而，该过程严重依赖于腐蚀性硝酸的使用，同时会释放一氧化二氮这种强效温室气体。在此，我们报道了一种电催化策略，即在经十二烷基磺酸钠（SDS）改性的氢氧化镍（Ni(OH)）催化剂上，将环己酮氧化为己二酸并同时产氢。插入的SDS有助于在水介质中富集不互溶的环己酮，因此与纯Ni(OH)相比，己二酸的生产率提高了3.6倍，法拉第效率（FE）更高（分别为93%和56%）。该策略对水溶液中多种不互溶的醛和酮均有效。此外，我们设计了一种实际的双电极流动电解槽，用于环己酮电氧化与产氢耦合，在24小时内，在0.8 A（对应于30 mA cm）的电流下，己二酸生产率为4.7 mmol，产氢量为8.0 L。
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