Electrocatalytic synthesis of adipic acid coupled with H2 production enhanced by a ligand modification strategy

Zhenhua Li; Xiaofan Li; Hua Zhou; Yan Xu; Si-Min Xu; Yue Ren; Yifan Yan; Jiangrong Yang; Kaiyue Ji; Li Li; Ming Xu; Mingfei Shao; Xianggui Kong; Xiaoming Sun; Haohong Duan

doi:10.1038/s41467-022-32769-0

Electrocatalytic synthesis of adipic acid coupled with H₂ production enhanced by a ligand modification strategy

Nat Commun. 2022 Aug 25;13(1):5009. doi: 10.1038/s41467-022-32769-0.

Authors

Zhenhua Li^#¹, Xiaofan Li^#¹, Hua Zhou^#^{1

2

3}, Yan Xu^#⁴, Si-Min Xu¹, Yue Ren¹, Yifan Yan¹, Jiangrong Yang¹, Kaiyue Ji², Li Li⁵, Ming Xu¹, Mingfei Shao¹, Xianggui Kong¹, Xiaoming Sun¹, Haohong Duan^{6

7}

Affiliations

¹ State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, China.
² Department of Chemistry, Tsinghua University, Beijing, China.
³ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, China.
⁴ College of energy storage technology, Shandong University of Science and Technology, Qingdao, China.
⁵ College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing, China.
⁶ Department of Chemistry, Tsinghua University, Beijing, China. hhduan@mail.tsinghua.edu.cn.
⁷ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, China. hhduan@mail.tsinghua.edu.cn.

^# Contributed equally.

Abstract

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.

Abstract

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