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Near-infrared photon upconversion and solar synthesis using lead-free nanocrystals

Abstract

Near-infrared-to-visible photon upconversion holds great promise for a diverse range of applications. Current photosensitizers for triplet-fusion upconversion across this spectral window often contain either precious or toxic elements and have relatively low efficiencies. Although colloidal nanocrystals have emerged as versatile photosensitizers, the only family of nanocrystals discovered for near-infrared upconversion is the highly toxic lead chalcogenides. Here we report zinc-doped CuInSe2 nanocrystals as a low-cost and lead-free alternate, enabling near-infrared-to-yellow upconversion with an external quantum efficiency reaching 16.7%. When directly merged with photoredox catalysis, this system enables efficient near-infrared-driven organic synthesis and polymerization, which in turn solves the issue of reabsorption loss for nanocrystal-sensitized upconversion. Moreover, the broadband light capture of these nanocrystals enables very rapid reactions under indoor sunlight. Extending the reach of ‘solar synthesis’ into the near-infrared may realize the century-long dream of conducting high-added-value chemical transformations using sunlight.

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Fig. 1: Excited-state dynamics and energy transfer of the ZCISe NCs.
Fig. 2: NIR-to-visible TTA-UC.
Fig. 3: NIR and solar-driven photoredox using TTA-UC.
Fig. 4: NIR and solar-driven photopolymerization using TTA-UC.

Data availability

All data are available in the Article or the Supplementary Information and can be obtained upon request from the corresponding author. These data are also available via Figshare at https://figshare.com/articles/figure/Data_for_CISe_TTA-UC_and_photoredox/21701204. Source data are provided with this paper.

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Acknowledgements

K.W. acknowledges financial support from the Chinese Academy of Sciences (YSBR-007), the National Natural Science Foundation of China (22173098, 21975253 and 22209180), the Ministry of Science and Technology of China (2018YFA0208703), the Dalian Institute of Chemical Physics (DICP I 202106) and the Fundamental Research Funds for the Central Universities (20720220009).

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Authors

Contributions

K.W. conceived the ideas and designed the project. W.L. and J.D. synthesized the samples and characterized them. C.N. and W.L. carried out the photoredox reactions. W.L. and G.L. carried out the spectroscopic measurements. Y.H. and G.Z. participated in discussions. F.Y. carried out the GC-MS and LC-MS measurements. K.W. wrote the manuscript with contributions from all authors. W.L., C.N. and J.D. contributed equally.

Corresponding author

Correspondence to Kaifeng Wu.

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Nature Photonics thanks Mohammad Khaja Nazeeruddin, Yasuhiro Tachibana and Michael Walter for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Texts 1–4, Table 1, Figs. 1–17 and refs. 1–26.

Supplementary Data 1

Raw data for the TTA-UC parameters listed in Table 1.

Source data

Source Data Fig. 1

Fig. 1 source data in spreadsheet.

Source Data Fig. 2

Fig. 2 source data in spreadsheet.

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Liang, W., Nie, C., Du, J. et al. Near-infrared photon upconversion and solar synthesis using lead-free nanocrystals. Nat. Photon. 17, 346–353 (2023). https://doi.org/10.1038/s41566-023-01156-6

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