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Using supramolecular machinery to engineer directional charge propagation in photoelectrochemical devices

Nature Chemistry volume 15, pages 213–221 (2023)Cite this article

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Abstract

Molecular photoelectrochemical devices are hampered by electron–hole recombination after photoinduced electron transfer, causing losses in power conversion efficiency. Inspired by natural photosynthesis, we demonstrate the use of supramolecular machinery as a strategy to inhibit recombination through an organization of molecular components that enables unbinding of the final electron acceptor upon reduction. We show that preorganization of a macrocyclic electron acceptor to a dye yields a pseudorotaxane that undergoes a fast (completed within ~50 ps) ‘ring-launching’ event upon electron transfer from the dye to the macrocycle, releasing the anionic macrocycle and thus reducing charge recombination. Implementing this system into p-type dye-sensitized solar cells yielded a 16-fold and 5-fold increase in power conversion efficiency compared to devices based on the two control dyes that are unable to facilitate pseudorotaxane formation. The active repulsion of the anionic macrocycle with concomitant reformation of a neutral pseudorotaxane complex circumvents recombination at both the semiconductor–electrolyte and semiconductor–dye interfaces, enabling a threefold enhancement in hole lifetime.

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Fig. 1: Similarities between electron propagation in PSII and pseudorotaxane-based DSSC.
Fig. 2: UV–Vis studies and binding data.
Fig. 3: Photovoltaic performances of the DSSCs based on the P1 dye, PPEG4 dye and PSTATION dye with the 3-NDI-ring.
Fig. 4: TA (λexc. = 500 nm) data of PSTATION on NiO in supporting electrolyte (1.5 ml, 1 M LiTFSI valeronitrile/MeCN,15:85) in the absence and in the presence of the 3-NDI-ring (5.9 mM).

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Data availability

All processed data that support the findings of this study are available within the article and its Supplementary Information (synthesis of compounds and characterization, device fabrication and characterization, and femtosecond TA). All raw data that support the findings of this study have been deposited at the FigShare repository https://doi.org/10.6084/m9.figshare.20508852.v1. Source data are provided with this paper.

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Acknowledgements

This study was supported by the Holland Research School for Molecular Sciences (HRSMC) and the University of Amsterdam. A part of this study was supported Merck GmbH and Dutch Research Council (NWO) for funding. The TA studies were supported by the Advanced Research Center for Chemical Building Blocks (ARC CBBC), which is cofounded and cofinanced by NWO and the Netherlands Ministry of Economic Affairs and Climate Policy. We thank AMOLF (FOM Institute for Atomic and Molecular Physics) for scanning electron microscopy imaging, W. Sikorski for the Brunauer–Emmett–Teller analysis of the NiO, M. Brands for her assistance with the TA measurements, E. von Hauff for her advice on the EIS measurements and S. Woutersen for his valuable contribution during discussions.

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Authors and Affiliations

  1. van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, the Netherlands

    T. Bouwens, T. M. A. Bakker, J. Hasenack, M. Dieperink, A. M. Brouwer, S. Mathew & J. N. H. Reek

  2. PhotoCatalytic Synthesis Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede, the Netherlands

    K. Zhu & A. Huijser

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Contributions

T.B. and J.N.H.R. proposed the research. T.B. synthesized and characterized the dyes, the macrocycle and the pseudorotaxane with assistance from J.N.H.R. and M.D. The DSSC fabrication and characterization was performed by T.B. EIS measurements were performed by T.B. and analysed by T.M.A.B. TA experiments were designed by A.M.B., K.Z. and A.H. together with T.B., S.M. and J.N.H.R. TA measurements were performed by K.Z. and analysed by K.Z. and A.H. The remaining experiments were designed by T.B., S.M., T.M.A.B. and J.N.H.R. The manuscript was prepared by T.B., S.M. and J.N.H.R. with the assistance of T.M.A.B. and revised with the input of all authors.

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Correspondence to J. N. H. Reek.

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Supplementary Information

Supplementary Figs. 1–37, Tables 1–16, Methods and experimental details.

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Source data

Source Data Fig. 2

Unprocessed UV–Vis (binding) data.

Source Data Fig. 3

Unprocessed data on photovoltaic performance and EIS.

Source Data Fig. 4

Unprocessed femtosecond TA data, spectroelectrochemistry data and UV–Vis data.

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Bouwens, T., Bakker, T.M.A., Zhu, K. et al. Using supramolecular machinery to engineer directional charge propagation in photoelectrochemical devices. Nat. Chem. 15, 213–221 (2023). https://doi.org/10.1038/s41557-022-01068-y

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