Rhodium complex-anchored and supramolecular polymer-grafted CdS nanoflower for enhanced photosynthesis of H₂O₂ and photobiocatalytic C–H bond oxyfunctionalization

Abstract

Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp³)–H bonds using only H₂O₂ as a clean oxidant, while also exhibiting sensitivity to H₂O₂ concentration. CdS-based semiconductors are promising for the photosynthesis of H₂O₂ owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process, however, they suffer from fast H₂O₂ decomposition on the surface of pristine CdS. Therefore, [Cp*Rh(bpy)H₂O]²⁺, a highly selective proton-coupled electron transfer catalyst, was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H₂O₂, mitigating the surface issue of pristine CdS, increasing light absorption, accelerating photonic carrier separation, and enhancing oxygen reduction reaction selectivity to H₂O₂. This photocatalyst promoted the light driven H₂O₂ generation rate up to 1345 μmol·L^–1·g^–1·h^–1, which was 2.4 times that of pristine CdS. The constructed heterojunction photocatalyst could supply H₂O₂ in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene, achieving a yield of 81% and an ee value of 99% under optimum conditions. A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system, achieving the corresponding chiral alcohols in good yield (51%–88%) and excellent enantioselectivity (90%–99% ee).

Graphical abstract

Keywords

cadmium sulfide / unspecific peroxygenases / photobiocatalysis / hydrogen peroxide / oxyfunctionalization

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This study was supported by the National Natural Science Foundation of China (Grant No. 22378096), the Natural Science Foundation of Hebei Province (Grant No. B2023202014), the Science Technology Research Project of Higher Education of Hebei Province (Grant Nos. QN2021045, and QN2023207), and the Tianjin Science and Technology Project (Grant No. 22KPHDRC00260).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2465-6 and is accessible for authorized users.

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