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All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods

Abstract

Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H2 and O2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O2 generation from water was verified by 18O isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting.

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Fig. 1: Schematic representation of water splitting on decorated CdS nanorods.
Fig. 2: Preparation and characterization of the photocatalyst.
Fig. 3: Effect of decoration of CdS with RuDTC on photoluminescence, quenching and decay dynamics.
Fig. 4: Transient absorption measurements.
Fig. 5: Photocatalytic hydrogen and oxygen generation.

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Acknowledgements

This work was supported by the Bavarian State Ministry of Science, Research, and Arts through the grant ‘Solar Technologies go Hybrid (SolTech)’ and the ERANETMED programme (project Hydrosol, grant no. ENERG-11-132). The authors thank C. Hohmann (Nanosystems Initiative Munich) for his support with graphics design. P.D.F. thanks the Alexander von Humboldt Foundation for a postdoctoral fellowship.

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All authors contributed to the design of the experiments, interpretation of the results and discussion of the outline of the manuscript. C.M.W., P.D.F., M.S., B.J.B., R.W., P.L. and M.T.C. carried out the experiments. J.K.S. wrote the manuscript, with input and comments from the other authors. J.F., F.W. and J.K.S. supervised the work.

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Correspondence to Frank Würthner or Jacek K. Stolarczyk.

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Supplementary Methods, Supplementary Notes 1–2, Supplementary Tables 1–2, Supplementary Figures 1–20, Supplementary References 1–2

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Wolff, C.M., Frischmann, P.D., Schulze, M. et al. All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods. Nat Energy 3, 862–869 (2018). https://doi.org/10.1038/s41560-018-0229-6

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