A supporting-electrolyte-free four-compartment electrochemical reactor for aqueous and organic phase electrosynthesis

H Huan Wu (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) B Baoquan Liu (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) C Chenliang Su (Institute of Microscale Optoelectronics) D Deyin Chen (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) L Longhao Jiao (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) H Huajun Zheng (Department of Applied Chemistry, Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion) L Lianbang Wang (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) Z Zhenyuan Teng (Department of Materials Science and Engineering) L Lianchong Shao (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) Y Yinghua Xu B Bin Liu

Abstract

Electrosynthesis offers a promising method to make valuable chemicals under mild conditions; however, its application has been greatly hampered by issues including the requirement of a supporting electrolyte, the limited solubility of reactant(s) in electrochemical compartments, the complex product(s) separation processes, etc. Herein, we innovatively present a four-compartment electrochemical reactor equipped with delicately designed active species diffusion membrane electrodes. Four compartments include two chemical (reduction and oxidation) compartments and two electrochemical (cathode and anode) compartments. The unique membrane electrodes physically separate the chemical compartments (containing organic reactants in pure solvent) from the electrochemical compartments (containing supporting electrolytes), while allowing electrosynthesis of high-value-added chemicals in both nonconducting aqueous and organic environments without the need of a supporting electrolyte. The reactor is able to drive both the anodic electrosynthesis (e.g., oxidation with a halogenation yield > 93%) and the cathodic electrosynthesis (e.g., reduction with a hydrogenation yield > 95% and a deuteration incorporation > 85%). The batch four-compartment electrochemical reactor can be engineered into a continuous type, where substrates in pure solvent can be converted into products with a conversion > 90% as they travel from the inlet to the outlet of the continuous reactor.

Article Details

Volume / Issue Vol. 122, Issue 39
Published September 30, 2025
ISSN 0027-8424
Publisher National Academy of Sciences

Authors (11)

H

Huan Wu

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

B

Baoquan Liu

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

C

Chenliang Su

Institute of Microscale Optoelectronics

D

Deyin Chen

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

L

Longhao Jiao

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

H

Huajun Zheng

Department of Applied Chemistry, Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion

L

Lianbang Wang

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

Z

Zhenyuan Teng

Department of Materials Science and Engineering

L

Lianchong Shao

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

Y

Yinghua Xu

B

Bin Liu