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Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Nature Nanotechnology volume 18, pages 160–167 (2023)Cite this article

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Abstract

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

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Fig. 1: CoPc/CNT catalyst.
Fig. 2: Electrocatalytic properties for DCA dechlorination measured in 0.1 M aqueous KHCO3 saturated with DCA (~87 mM).
Fig. 3: Calculated reaction pathway of electrochemical DCA dechlorination catalysed by CoPc.
Fig. 4: CoPc/CNT-functionalized electrochemical membrane for the treatment of DCA-contaminated water.

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Data availability

The atomic coordinates of the optimized structures (at neutral charge) for DFT calculations are provided in Supplementary Data 1. The measurement data presented within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work (materials synthesis, structural characterization and catalysis work) was primarily supported as part of the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE), an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under award no. DE-SC0021173 (H.W.). Computational work was supported by the Liquid Sunlight Alliance, which is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under award no. DE-SC0021266 (W.A.G.) and an individual fellowship from the Resnick Sustainability Institute at Caltech (S.K.), and used the Extreme Science and Engineering Discovery Environment (XSEDE) for DFT calculations, which is supported by National Science Foundation grant no. ACI-1548562 (W.A.G.). Electrified membrane filtration work was supported by the NSF Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (EEC-1449500; M.E.). STEM and EDX characterizations were supported by the NSF career award no. 1749742 (J.J.C.). We thank J. Lee and J. D. Fortner (Department of Chemical and Environmental Engineering, Yale University) for providing graphene oxide.

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Author notes

  1. These authors contributed equally: Chungseok Choi, Xiaoxiong Wang, Soonho Kwon.

Authors and Affiliations

  1. Department of Chemistry, Yale University, New Haven, CT, USA

    Chungseok Choi, Conor L. Rooney, Nia J. Harmon & Hailiang Wang

  2. Energy Sciences Institute, Yale University, West Haven, CT, USA

    Chungseok Choi, Conor L. Rooney, Nia J. Harmon, Judy J. Cha & Hailiang Wang

  3. Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA

    Xiaoxiong Wang & Menachem Elimelech

  4. Materials and Process Simulation Center (MSC), California Institute of Technology, Pasadena, CA, USA

    Soonho Kwon & William A. Goddard III

  5. Department of Materials Science and Engineering, Cornell University, Ithaca, NY, USA

    James L. Hart, Quynh P. Sam & Judy J. Cha

  6. Department of Mechanical Engineering and Materials Science, Yale University, West Haven, CT, USA

    Judy J. Cha

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Contributions

C.C. and H.W. conceived and designed the project. C.C. and C.L.R. prepared the CoPc/CNT. C.C. conducted the electrocatalytic DCA dechlorination. X.W. conducted the flow-through DCA dechlorination with supervision from M.E. S.K. carried out the DFT calculations with supervision from W.A.G. J.L.H. and Q.P.S. performed the TEM imaging with supervision from J.J.C. N.J.H. performed the ICP-MS measurements. C.C. and H.W. wrote the manuscript with input from X.W. and S.K. H.W. supervised the project. All the authors discussed the results and commented on the manuscript.

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Correspondence to William A. Goddard III, Menachem Elimelech or Hailiang Wang.

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Nature Nanotechnology thanks Guohua Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–25 and Tables 1 and 2.

Supplementary Data 1

Coordinates of the optimized structures (at neutral charge) in this Article.

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Choi, C., Wang, X., Kwon, S. et al. Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene. Nat. Nanotechnol. 18, 160–167 (2023). https://doi.org/10.1038/s41565-022-01277-z

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