Photocatalytic Recovery of Noble Metals by Covalent Silyl Polyoxophosphotungstate–Porphyrin Copolymers
The photocatalytic recovery of noble metals on photosensitive semiconductors such as TiO<sub>2</sub> is well-established for forming M/TiO<sub>2</sub> but has notable drawbacks. TiO<sub>2</sub> suffers from low conversion efficiency due to significant recombination of photogenerated electron-hole pairs. Its wide energy band gap (3.2 eV) also restricts excitation to high-energy UV light, limiting its use with solar energy. This study proposes an efficient alternative using hybrid polyoxometalate (POM)-porphyrin copolymers for the photocatalytic recovery of Ag and Pt under visible light. Copolymeric films composed of hybrid polyoxometalates and porphyrins have been obtained by the electrooxidation of 5,15-(di-<i>p</i>-tolyl)porphyrin (<b>H<sub>2</sub>T<sub>2</sub>P</b>) or 2,3,7,8,12,13,17,18-octaethylporphine zinc(II) (<b>ZnOEP</b>) together with Keggin or Wells-Dawson-type organosilyl polyoxophosphotungstate ([PW<sub>11</sub>Si<sub>2</sub>O<sub>40</sub>C<sub>26</sub>H<sub>16</sub>N<sub>2</sub>]TBA<sub>3</sub> or [P<sub>2</sub>W<sub>17</sub>Si<sub>2</sub>O<sub>62</sub>C<sub>26</sub>H<sub>16</sub>N<sub>2</sub>]TBA<sub>6</sub>). In these films, porphyrin subunits can be excited under visible illumination, acting as photosensitizers that transfer electrons to the polyoxometalate catalysts. Notably, POM-porphyrin films demonstrated high efficiency in Pt(IV) photoreduction over repeated cycles without catalyst degradation.
Authors
- Guillaume Izzet (ORCID: https://orcid.org/0000-0002-9849-4939)
- Min Zheng (ORCID: https://orcid.org/0000-0002-4985-2680)
- Brahim Akhsassi (ORCID: https://orcid.org/0000-0001-6777-1246)
- Anna Proust (ORCID: https://orcid.org/0000-0002-0903-6507)
- Corinne Boudon (ORCID: https://orcid.org/0000-0003-4640-0475)
- Laurent Ruhlmann (ORCID: https://orcid.org/0000-0003-1154-2422)
- Qianjun He (ORCID: https://orcid.org/0000-0003-0689-8838)
- Zhaohui Huo
- Guojun Xu
- Tian Lan (ORCID: https://orcid.org/0000-0002-0339-4418)
- Jiamin Yu
Institutions
- Centre National de la Recherche Scientifique (FR)
- Guangdong University Of Finances and Economics (CN)
- Guangdong University of Education (CN)
- Sorbonne Université (FR)
- Institut de Chimie de Strasbourg (FR)
- Environmental Protection Engineering (Greece) (GR)
- Institut Parisien de Chimie Moléculaire (FR)
- Laboratoire Médiations (FR)
- Université de Strasbourg (FR)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-02-12
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c04890
- Citations
- 6
- Primary Topic
- Polyoxometalates: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 3.11
Funders
- Government of Guangdong Province
- Université de Strasbourg
- Centre National de la Recherche Scientifique
- Sorbonne Université
- Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province