Immobilizing photocatalysts in polyampholytic graft copolymers enables prolonged catalyst lifetime and improved repair capability

in: ChemRxiv (2025)
Utievskyi, Yurii; Mengele, Alexander; Puthanagady, Mariet Sibi; Vashistha, Nikita; Zedler, Linda; Neumann, Christof; Müssler, Marius; Turchanin, Andrey; Dietzek-Ivanšić, Benjamin; Rau, Sven; Schacher, Felix H.
The incorporation of the natural photosynthetic apparatus into a (soft matter) environment highly restricts the number of degradation possibilities and furthermore enables targeted repair of key molecular components. Intrigued by this design-principle of the natural blueprint, we postulate that balancing the interplay between polymeric matrices and photocatalytically active centers prolongs and sustains photocatalytic activity as well as repair-capability in molecular artificial photosynthesis. There are few systems where active repair has been demonstrated, and one prominent example is the Ru(tpphz)PtI2 hydrogen-evolving photocatalyst, where hydrogenation of the pyrazine ring in the tpphz bridging ligand has been shown to lead to an end of photocatalytic activity. Subsequent in-situ repair by persulfate enabled catalyst reactivation, but so far at the cost of decreasing catalytic activity over several repair cycles. We now show that tailored polyampholytic graft copolymers allow to electrostatically immobilize the photocatalyst in a unimolecular soft matter matrix, can prolong (photo)catalytic activity, and facilitate active repair without significant loss of activity over several cycles. We attribute this to a decreased propensity for hydrogenation of the pyrazine ring and, with that, slower degradation of the bridge and improved long term HER activity, as evidenced by a holistic spectroscopic characterization of molecular and electronic structure of the photoredox catalyst. We therefore regard this as a novel blueprint for a synergistic molecule-in-matrix combination for sustainable light-driven catalysis.

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