Abstract
Despite the fact that noncovalent bonding interactions are ubiquitous, it is primarily those interactions, which are amenable to spectroscopic analysis, that have been well investigated and applied in chemical engineering. New principles and techniques for characterizing noncovalent interactions are required to gain insight into their detailed nature and explore their potential applications. Here we introduce the practice of analytical noncovalent electrochemistry for probing such interactions. The strengths of noncovalent interactions can be determined more accurately by electrochemical means than by relying on spectroscopic measurements. Specifically, electrochemical analyses are capable of recording/identifying minor signals, leading to the discovery of an unexpected 2:1 host–guest complex. Moreover, the proposed technique is capable of probing multiple properties and facilitates the design and screening of active complexes as catalysts. We also demonstrate achieving a high energy density of 495 Wh kg−1 in rechargeable batteries. The analytical procedure provides a fresh perspective for supramolecular science and takes noncovalent chemistry closer to practical applications.
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Data availability
The data that support the findings of this study are available within the paper and its Supplementary Information files. Crystallographic data for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2267283. A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.
Code availability
Custom code used in this study is available within the Supplementary Information files.
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Acknowledgements
We would like to thank Northwestern University for their continued support of this research. The authors acknowledge the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University for providing access to equipment for the experiments. We acknowledge the support from the National Natural Science Foundation of China (21825501), Tsinghua-Jiangyin Innovation Special Fund (2022JYTH0101). We thank X. Zhao, G. Wu and W. Zhang for assistance with NMR spectroscopic measurements, S. Yang for assistance with the powder X-ray diffraction characterization and Y.-X. Feng, L. Yu and H. Wu for useful discussions.
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Contributions
J.F.S. and Q.Z. directed the project. C.-X.Z. conceived the idea for the project. C.-X.Z., Y.F. and H.H. designed, synthesized and characterized the compounds. C.T. performed the density functional theory calculations. C.-X.Z., X.-Y.L. and Q.Z. performed the electrochemical evaluations and battery tests. X.L. and L.Z. contributed to the graphical design used in the figures. C.L.S. collected the single-crystal X-ray diffraction data and solved the solid-state structure. H.H., Y.F., X.L. and L.Z. commented on the data. All the authors participated in evaluating the results. C.-X.Z. and C.T. produced numerous drafts of the manuscript and supplementary materials, with input from all authors.
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Nature Chemical Engineering thanks Sang-Young Lee, and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Extended data
Extended Data Fig. 1 Single-crystal superstructure of the 2:1 host–guest complex.
(a) The front view, (b) the top-down view, and (c) the side-on view of the X-ray crystal structure of En⊂2C4+, whose host/guest ratio is determined to be 2:1. MeCN solvent and PF6− counterions are omitted for the sake of clarity.
Extended Data Fig. 2 Sensitivity analyses on UV/Vis titration and electrochemical titrations to compare their accuracy on Ka evaluation.
(a) Normalized absorbance (Abs/Abssat) at different Ka values and different titration equivalent (x), plotting the function image of Abs/Abssat = Abs/Abssat(x, Ka) (a1), the cross profile at Ka = 104, 105, 106 M−1 (a2), and cross profile at x = 1.0 (a3). The cross profile at specific Ka refers to the titration curve. The cross profile at specific x refers to the sensitivity analysis to assess the accuracy of Ka measurements. UV/Vis titrations show little Abs/Abssat gradient when Ka > 103 M−1, implying an unsatisfactory measuring accuracy. (b) Electrochemical signal (Δφ) at different Ka values and different x, exhibited as the function image of Δφ = Δφ(x, Ka) (b1) and the sectional view at Ka = 104, 105, 106 M−1 (b2) and at x = 5.0 (b3). The electrochemical signal varies significantly when Ka > 102 M−1, indicating higher sensitivity against different Ka values.
Extended Data Fig. 3 Inspiration and guidance of analytical noncovalent electrochemistry for battery engineering.
(a) Coenzyme Mechanism: Schematic diagram illustrating the mechanism of coenzymes. Coenzymes play a vital role in enzyme catalysis by engaging in specific chemical reactions as transient carriers of functional groups or electrons, promoting efficient catalytic processes. (b) Noncovalent Regulation Mechanism: Schematic representation of the noncovalent regulation mechanism. In this mechanism, the guest (E6) acts as a cocatalyst, activating C4+ via noncovalent interactions. The resulting complex serves as a synergistic catalyst within operational batteries, akin to the coenzyme mechanism. (c) Schematic representation illustrating the mechanism of noncovalent regulation involving E6 as a cocatalyst for the activation of C4+. E6 displays specific and selective interaction with C4+ via noncovalent binding interactions. This interaction leads to a controlled reduction in the redox potential of C4+, aligning with the fundamental principles of analytical noncovalent electrochemistry. Consequently, this strategic manipulation of C4+ redox potential orchestrates its precise positioning within an optimized range. This optimized redox potential configuration is instrumental in showcasing exceptional catalytic efficacy in polysulfide oxidation process.
Supplementary information
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Supplementary Discussion, Figs. 1–63 and Tables 1–7.
Supplementary Data 1
X-ray structure of the E2⊂2C4+ complex.
Source data
Source Data Fig. 1 (download XLSX )
Experimental data.
Source Data Fig. 2 (download XLSX )
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Numerical simulation and experimental data.
Source Data Fig. 4 (download XLSX )
Numerical simulation and experimental data.
Source Data Fig. 5 (download XLSX )
Experimental data.
Source Data Extended Data Fig. 2 (download XLSX )
Numerical simulation data.
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Zhao, CX., Li, XY., Han, H. et al. Analytical noncovalent electrochemistry for battery engineering. Nat Chem Eng 1, 251–260 (2024). https://doi.org/10.1038/s44286-024-00038-0
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DOI: https://doi.org/10.1038/s44286-024-00038-0
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