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A photosensitizer–polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production

Nature Chemistry volume 14, pages 321–327 (2022)Cite this article

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Abstract

Decoupling the production of solar hydrogen from the diurnal cycle is a key challenge in solar energy conversion, the success of which could lead to sustainable energy schemes capable of delivering H2 independent of the time of day. Here, we report a fully integrated photochemical molecular dyad composed of a ruthenium-complex photosensitizer covalently linked to a Dawson polyoxometalate that acts as an electron-storage site and hydrogen-evolving catalyst. Visible-light irradiation of the system in solution leads to charge separation and electron storage on the polyoxometalate, effectively resulting in a liquid fuel. In contrast to related, earlier dyads, this system enables the harvesting, storage and delayed release of solar energy. On-demand hydrogen release is possible by adding a proton donor to the dyad solution. The system is a minimal molecular model for artificial photosynthesis and enables the spatial and temporal separation of light absorption, fuel storage and hydrogen release.

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Fig. 1: Schematic illustration of the coupled light and dark reaction.
Fig. 2: Synthesis and spectroscopic properties of PS-POM.
Fig. 3: Irradiation stability assays for PS-POM and the POM-free PS reference system.
Fig. 4: Photophysical properties of PS-POM.
Fig. 5: Spectral evolution of PS-POM upon photoreduction and acid addition.
Fig. 6: Delayed on-demand hydrogen production.

Data availability

All the data supporting the findings of this study are available within the main text of the paper and the Supplementary Information and have been deposited on Zenodo.org under https://doi.org/10.5281/zenodo.5533869.

Crystallographic data for the structure reported in this Article has been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC no. 2045447. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

References

  1. Roger, I., Shipman, M. A. & Symes, M. D. Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting. Nat. Rev. Chem. 1, 0003 (2017).

    Article  CAS  Google Scholar 

  2. Chen, S., Takata, T. & Domen, K. Particulate photocatalysts for overall water splitting. Nat. Rev. Mater. 2, 17050 (2017).

    Article  CAS  Google Scholar 

  3. Listorti, A., Durrant, J. & Barber, J. Artificial photosynthesis: solar to fuel. Nat. Mater. 8, 929–930 (2009).

    Article  CAS  PubMed  Google Scholar 

  4. Cook, T. R. et al. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 110, 6474–6502 (2010).

    Article  CAS  Google Scholar 

  5. Rausch, B., Symes, M. D., Chisholm, G. & Cronin, L. Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting. Science 345, 1326–1330 (2014).

    Article  CAS  PubMed  Google Scholar 

  6. Symes, M. D. & Cronin, L. Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer. Nat. Chem. 5, 403–409 (2013).

    Article  CAS  PubMed  Google Scholar 

  7. Borgschulte, A. The hydrogen grand challenge. Front. Energy Res. 4, 11 (2016).

    Article  Google Scholar 

  8. McHugh, P. J., Stergiou, A. D. & Symes, M. D. Decoupled electrochemical water splitting: from fundamentals to applications. Adv. Energy Mater. 10, 2002453 (2020).

    Article  CAS  Google Scholar 

  9. Huang, J. & Wang, Y. Efficient renewable-to-hydrogen conversion via decoupled electrochemical water splitting. Cell Rep. Phys. Sci. 1, 100138 (2020).

    Article  CAS  Google Scholar 

  10. Ifkovits, Z. P., Evans, J. M., Meier, M. C., Papadantonakis, K. M. & Lewis, N. S. Decoupled electrochemical water-splitting systems: a review and perspective. Energy Environ. Sci. https://doi.org/10.1039/D1EE01226F (2021).

  11. Yan, Z., Hitt, J. L., Turner, J. A. & Mallouk, T. E. Renewable electricity storage using electrolysis. Proc. Natl Acad. Sci. USA 117, 12558–12563 (2020).

    Article  CAS  PubMed  Google Scholar 

  12. Pellow, M. A., Emmott, C. J. M., Barnhart, C. J. & Benson, S. M. Hydrogen or batteries for grid storage? A net energy analysis. Energy Environ. Sci. 8, 1938–1952 (2015).

    Article  CAS  Google Scholar 

  13. Rothschild, A. & Dotan, H. Beating the efficiency of photovoltaics-powered electrolysis with tandem cell photoelectrolysis. ACS Energy Lett. 2, 45–51 (2017).

    Article  CAS  Google Scholar 

  14. Sakar, M., Nguyen, C.-C., Vu, M.-H. & Do, T.-O. Materials and mechanisms of photo-assisted chemical reactions under light and dark conditions: can day–night photocatalysis be achieved? ChemSusChem 11, 809–820 (2018).

    Article  CAS  PubMed  Google Scholar 

  15. Bloor, L. G. et al. Solar-driven water oxidation and decoupled hydrogen production mediated by an electron-coupled-proton buffer. J. Am. Chem. Soc. 138, 6707–6710 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Lau, V. W. et al. Dark photocatalysis: storage of solar energy in carbon nitride for time-delayed hydrogen generation. Angew. Chem. Int. Ed. 129, 525–529 (2017).

    Article  Google Scholar 

  17. Konduri, R. et al. Ruthenium photocatalysis capable of reversibility storing up to four electrons in a single acceptor ligand: a step closer to artificial photosynthesis. Angew. Chem. Int. Ed. 41, 3185–3187 (2002).

    Article  CAS  Google Scholar 

  18. Schulz, M. et al. Photoinduced charge accumulation and prolonged multielectron storage for the separation of light and dark reaction. J. Am. Chem. Soc. 142, 15722–15728 (2020).

    Article  CAS  PubMed  Google Scholar 

  19. Proust, A. et al. Functionalization and post-functionalization: a step towards polyoxometalate-based materials. Chem. Soc. Rev. 41, 7605–7622 (2012).

    Article  CAS  PubMed  Google Scholar 

  20. Anyushin, A. V., Kondinski, A. & Parac-Vogt, T. N. Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications. Chem. Soc. Rev. 49, 382–432 (2020).

    Article  CAS  PubMed  Google Scholar 

  21. Matt, B. et al. Elegant approach to the synthesis of a unique heteroleptic cyclometalated iridium(III)-polyoxometalate conjugate. Organometallics 31, 35–38 (2012).

    Article  CAS  Google Scholar 

  22. Matt, B. et al. Long lived charge separation in iridium(iii)-photosensitized polyoxometalates: synthesis, photophysical and computational studies of organometallic–redox tunable oxide assemblies. Chem. Sci. 4, 1737–1745 (2013).

    Article  CAS  Google Scholar 

  23. Parrot, A. et al. Photochromism and dual-color fluorescence in a polyoxometalate-benzospiropyran molecular switch. Angew. Chem. Int. Ed. 56, 4872–4876 (2017).

    Article  CAS  Google Scholar 

  24. Matt, B. et al. Charge photo-accumulation and photocatalytic hydrogen evolution under visible light at an iridium(iii)-photosensitized polyoxotungstate. Energy Environ. Sci. 6, 1504–1508 (2013).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Schönweiz, S. et al. Experimental and theoretical investigation of the light-driven hydrogen evolution by polyoxometalate–photosensitizer dyads. Chem. Eur. J. 23, 15370–15376 (2017).

    Article  PubMed  Google Scholar 

  26. Luo, Y. et al. Yield—not only lifetime—of the photoinduced charge‐separated state in iridium complex–polyoxometalate dyads impact their hydrogen evolution reactivity. Chem. Eur. J. 26, 8045–8052 (2020).

    Article  CAS  PubMed  Google Scholar 

  27. Luo, Y. et al. Is electron ping-pong limiting the catalytic hydrogen evolution activity in covalent photosensitizer–polyoxometalate dyads? Chem. Commun. 56, 10485–10488 (2020).

    Article  CAS  Google Scholar 

  28. Schaming, D. et al. Synthesis and photocatalytic properties of mixed polyoxometalate–porphyrin copolymers obtained from Anderson-type polyoxomolybdates. Langmuir 26, 5101–5109 (2010).

    Article  CAS  PubMed  Google Scholar 

  29. Schönweiz, S. et al. Covalent photosensitizer-–polyoxometalate-catalyst dyads for visible-light-driven hydrogen evolution. Chem. Eur. J. 22, 12002–12005 (2016).

    Article  PubMed  Google Scholar 

  30. Azcarate, I. et al. Generation of photocurrent by visible-light irradiation of conjugated Dawson polyoxophosphovanadotungstate–porphyrin copolymers. Chem. Eur. J. 21, 8271–8280 (2015).

    Article  CAS  PubMed  Google Scholar 

  31. Black, F. A. et al. Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates. Chem. Sci. 9, 5578–5584 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  32. Odobel, F. et al. Coupled sensitizer–catalyst dyads: electron-transfer reactions in a perylene–polyoxometalate conjugate. Chem. Eur. J. 15, 3130–3138 (2009).

    Article  CAS  PubMed  Google Scholar 

  33. Toupalas, G. et al. Tuning photoinduced electron transfer in POM-bodipy hybrids by controlling the environment: experiment and theory. Angew. Chem. Int. Ed. 60, 6518–6525 (2021).

    Article  CAS  Google Scholar 

  34. Kirchhoff, B., Rau, S. & Streb, C. Detecting and preventing the formation of photosensitizer-catalyst colloids in homogeneous light-driven water oxidation. Eur. J. Inorg. Chem. 2016, 1425–1429 (2016).

    Article  CAS  Google Scholar 

  35. Heussner, K., Peuntinger, K., Rockstroh, N., Rau, S. & Streb, C. Cluster-controlled dimerisation in supramolecular ruthenium photosensitizer–polyoxometalate systems. Dalton Trans. 44, 330–337 (2015).

    Article  CAS  PubMed  Google Scholar 

  36. Heussner, K. et al. Solution and solid-state interactions in a supramolecular ruthenium photosensitizer–polyoxometalate aggregate. Chem. Commun. 47, 6852–6854 (2011).

  37. Amthor, S. et al. Tailored protective groups for surface immobilization of ruthenium dyes. Dalton Trans. 49, 3735–3742 (2020).

    Article  CAS  PubMed  Google Scholar 

  38. Streb, C. New trends in polyoxometalate photoredox chemistry: from photosensitisation to water oxidation catalysis. Dalton Trans. 41, 1651–1659 (2012).

    Article  CAS  PubMed  Google Scholar 

  39. Prenzler, P. D., Boskovic, C., Bond, A. M. & Wedd, A. G. Coupled electron- and proton-transfer processes in the reduction of α-[P2W18O62]6– and α-[H2W12O40]6– as revealed by simulation of cyclic voltammograms. Anal. Chem. 71, 3650–3656 (1999).

    Article  CAS  PubMed  Google Scholar 

  40. Pegis, M. L. et al. Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N,N-dimethylformamide. Inorg. Chem. 54, 11883–11888 (2015).

    Article  CAS  PubMed  Google Scholar 

  41. Soupart, A., Alary, F., Heully, J. L., Elliott, P. I. P. & Dixon, I. M. Recent progress in ligand photorelease reaction mechanisms: theoretical insights focusing on Ru(II) 3MC states. Coord. Chem. Rev. 408, 213184 (2020).

    Article  CAS  Google Scholar 

  42. Siebert, R. et al. Spectroscopic investigation of the ultrafast photoinduced dynamics in π-conjugated terpyridines. ChemPhysChem 10, 910–919 (2009).

    Article  CAS  PubMed  Google Scholar 

  43. Damrauer, N. H. Femtosecond dynamics of excited-state evolution in [Ru(bpy)3]2+. Science 275, 54–57 (1997).

    Article  CAS  PubMed  Google Scholar 

  44. Tarnovsky, A. N., Gawelda, W., Johnson, M., Bressler, C. & Chergui, M. Photexcitation of aqueous ruthenium(II)-tris-(2,2′-bipyridine) with high-intensity femtosecond laser pulses. J. Phys. Chem. B 110, 26497–26505 (2006).

    Article  CAS  PubMed  Google Scholar 

  45. Müller, P. & Brettel, K. [Ru(bpy)3]2+ as a reference in transient absorption spectroscopy: differential absorption coefficients for formation of the long-lived 3MLCT excited state. Photochem. Photobiol. Sci. 11, 632–636 (2012).

    Article  PubMed  Google Scholar 

  46. Kemmegne-Mbouguen, J. C. et al. Electrochemical properties of the [SiW10O36(M2O2E2)]6− polyoxometalate series (M = Mo(V) or W(V); E = S or O). New J. Chem. 43, 1146–1155 (2019).

    Article  CAS  Google Scholar 

  47. Dobryakov, A. L., Kovalenko, S. A. & Ernsting, N. P. Coherent and sequential contributions to femtosecond transient absorption spectra of a rhodamine dye in solution. J. Chem. Phys. 123, 044502 (2005).

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

We gratefully acknowledge the Deutsche Forschungsgemeinschaft DFG for financial support through the TRR234 ‘CataLight’ (project no. 364549901, projects A1, A4, B2, B6 and Z2; U.S.S., S.R., B.D. and C.S.). Funding by the Federal State of Baden-Württemberg and Ulm University for a PhD fellowship (LGFG; S.K.) and a Margarete von Wrangell fellowship (M.A.) is gratefully acknowledged. We thank T. Meyer-Zedler for assistance with the time-resolved emission measurements.

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Authors and Affiliations

  1. Institute of Inorganic Chemistry I, Ulm University, Ulm, Germany

    Sebastian Amthor, Sebastian Knoll, Magdalena Heiland, Djawed Nauroozi, Alexander K. Mengele, Montaha Anjass, Sven Rau & Carsten Streb

  2. Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena (Leibniz IPHT), Jena, Germany

    Linda Zedler & Benjamin Dietzek-Ivanšić

  3. Institute of Physical Chemistry, Friedrich Schiller University Jena, Jena, Germany

    Chunyu Li & Benjamin Dietzek-Ivanšić

  4. Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Jena, Germany

    Willi Tobaschus & Ulrich S. Schubert

  5. Jena Center of Soft Matter (JCSM), Friedrich Schiller University Jena, Jena, Germany

    Willi Tobaschus & Ulrich S. Schubert

  6. Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Jena, Germany

    Willi Tobaschus, Ulrich S. Schubert & Benjamin Dietzek-Ivanšić

  7. Helmholtz-Institute Ulm (HIU), Ulm, Germany

    Montaha Anjass & Carsten Streb

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Contributions

S.A., S.K., A.K.M., S.R., B.D. and C.S. conceived the experiments and performed data analyses. S.A. and S.K. performed syntheses and characterization. S.A. and M.H. performed catalytic tests. C.L., L.Z. and B.D. performed time-resolved spectroscopy and provided data interpretation. D.N. and M.A. performed electrochemistry. W.T. and U.S.S. provided mass-spectrometric data. A.K.M. performed crystallography. All authors cowrote the manuscript.

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Correspondence to Benjamin Dietzek-Ivanšić, Sven Rau or Carsten Streb.

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Supplementary Information

Supplementary Figs. 1–27; Tables 1–3; Discussion; instrumentation, synthesis and characterization details; and spectroscopic, electrochemical, spectro-electrochemical, mass-spectrometric and single-crystal X-ray diffraction data.

Supplementary Data 1

Crystallographic data for (mPO3Et2)bpy; CCDC no. 2045447.

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Amthor, S., Knoll, S., Heiland, M. et al. A photosensitizer–polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production. Nat. Chem. 14, 321–327 (2022). https://doi.org/10.1038/s41557-021-00850-8

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