Polyampholytic Graft Copolymers as Matrix for TiO2 /Eosin Y/[Mo3 S13 ]2- Hybrid Materials and Light-Driven Catalysis

Afshin Nabiyan; Johannes Bernhard Max; Christof Neumann; Magdalena Heiland; Andrey Turchanin; Carsten Streb; Felix Helmut Schacher

doi:10.1002/chem.202100091

Polyampholytic Graft Copolymers as Matrix for TiO₂ /Eosin Y/[Mo₃ S₁₃ ]^2- Hybrid Materials and Light-Driven Catalysis

Chemistry. 2021 Dec 6;27(68):16924-16929. doi: 10.1002/chem.202100091. Epub 2021 Mar 8.

Authors

Afshin Nabiyan^{1

2

3}, Johannes Bernhard Max^{1

2

3}, Christof Neumann^{2

3

4}, Magdalena Heiland⁵, Andrey Turchanin^{2

3

4}, Carsten Streb⁵, Felix Helmut Schacher^{1

2

3}

Affiliations

¹ Institute of Organic Chemistry and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Lessingstraße 8, 07743, Jena, Germany.
² Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany.
³ Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Philosophenweg 7a, 07743, Jena, Germany.
⁴ Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena, Lessingstr. 10, 07743, Jena, Germany.
⁵ Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.

Abstract

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core-shell hybrid materials based on a TiO₂ core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO₂ ). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO₂ core. This resulted in high visible-light-driven H₂ generation. The enhanced light-driven catalytic activity is attributed to the unique core-shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO₂ was possible by introducing [Mo₃ S₁₃ ]^2- cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.

Keywords: hybrid materials; hydrogen evolution reaction; photocatalysis; polyampholytes; thiomolybdates.

Abstract

Grants and funding