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Enhanced activity for the oxygen reduction reaction in microporous water


Electrocatalysis of small gas molecules driven by renewable energy sources offers a promising route to carbon-neutral fuels and chemicals. Such small-molecule conversion reactions rely on water as a source of protons and electrons, however, thus limiting energy and power densities owing to the low solubility of gas molecules in water. The oxygen reduction reaction (ORR) is an exemplar of such limitations. Here we demonstrate that the high O2-carrying capacity of aqueous solutions endowed with porosity arising from microporous nanocrystals with hydrophobic internal surfaces and hydrophilic external surfaces—termed microporous water—enhances ORR electrocatalysis in water. Use of silicalite-1 nanocrystals to form an O2-concentrating microporous electrolyte solution increases the ORR current so much that the activity of Pt, typically thought to be an ideal ORR catalyst, is partially limiting, thus allowing the intrinsic catalytic ORR activity of Pt to be measured directly.

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Fig. 1: Characterization of A-silicalite-1-NCs in solid state and aqueous solution.
Fig. 2: ORR catalysis.
Fig. 3: Electrokinetics modelling of ORR catalysis.

Data availability

Details of BET surface area analysis of zeolite-NCs, O2 solubility in electrolyte solutions, O2 capacity in zeolite-NC solutions, density of zeolite-NC solutions and electrokinetics modelling along with additional physical and electrochemical characterization data are included in Supplementary Information. Other data are available from the corresponding authors upon reasonable request.


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This work was supported by a Multidisciplinary University Research Initiative, sponsored by the US Department of the Navy, Office of Naval Research, under grant no. N00014-20-1-2418 (D.G.N. and J.A.M.), Star-Friedman Challenge grant from Harvard University (D.G.N. and J.A.M.), and Labex ARCANE, CBµH-EUR-GS and ANR-17-EURE-0003 from the Agence Nationale de la Recherche (C.C.). J.A.M. acknowledges support from the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator Grant. Part of this work was performed at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network (NNCI), which is supported by the National Science Foundation under NSF award no. 1541959. A.E.T. acknowledges the Harvard University Center for the Environment for a postdoctoral fellowship, and D.P.E. acknowledges support from a DoD National Defense Science and Engineering (NDSEG) fellowship. We thank B. Johnston, J. Cho and J. Shen for experimental assistance and M. J. Nava, J. Ryu, M. I. Gonzalez and Z. Yan for helpful discussions. We also thank G. M. Whitesides and M. S. Kodaimati for lending us a mass flow controller for the electrochemical experiments.

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Authors and Affiliations



A.E.T., D.P.E., D.G.N. and J.A.M. conceived the project. D.P.E. and J.A.M. designed the zeolite materials, and D.P.E. carried out the synthesis. A.E.T., D.G.N., C.C. and J.A.M. designed electrochemical experiments, and A.E.T. performed the electrochemical experiments. A.E.T. and D.P.E. performed testing and characterizations. C.C. performed electrokinetics modelling. All authors contributed to the manuscript preparation.

Corresponding authors

Correspondence to Cyrille Costentin, Jarad A. Mason or Daniel G. Nocera.

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Competing interests

D.P.E. and J.A.M. are inventors on a patent application related to O2 concentration in microporous aqueous solutions held and submitted by Harvard University (application number PCT/US21/54267). The other authors declare no competing interests.

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Nature Catalysis thanks Christopher Batchelor-McAuley, Serhiy Cherevko and the other, anonymous, reviewer for their contribution to the peer review of this work.

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Supplementary Notes 1–5, Figs. 1–33, Tables 1–23 and references.

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Thorarinsdottir, A.E., Erdosy, D.P., Costentin, C. et al. Enhanced activity for the oxygen reduction reaction in microporous water. Nat Catal 6, 425–434 (2023).

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