Heterogenous CO2 Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins

Hitoshi Izu; Hiroyasu Tabe; Yuji Namiki; Hiroki Yamada; Satoshi Horike

doi:10.1021/acs.inorgchem.3c00700

Heterogenous CO₂ Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins

Inorg Chem. 2023 Jul 24;62(29):11342-11349. doi: 10.1021/acs.inorgchem.3c00700. Epub 2023 Jul 11.

Authors

Hitoshi Izu¹, Hiroyasu Tabe¹, Yuji Namiki^{2

3}, Hiroki Yamada⁴, Satoshi Horike^{1

5

6}

Affiliations

¹ Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida-hommachi, Sakyo-ku, Kyoto 606-8501, Japan.
² Frontier Research Center, POLA Chemical Industries, Inc., Kashio-cho, Totsuka-ku, Yokohama, Kanagawa 244-0812, Japan.
³ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
⁴ Diffraction and Scattering Division, Japan Synchrotron Radiation Research Institute (JASRI), Sayo, Hyogo 679-5198, Japan.
⁵ Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand.
⁶ Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan.

PMID: 37432910
DOI: 10.1021/acs.inorgchem.3c00700

Abstract

Transparent and grain boundary-free substrates are essential to immobilize molecular photocatalysts for efficient photoirradiation reactions without unexpected light scattering and absorption by the substrates. Herein, membranes of coordination polymer glass immobilizing metalloporphyrins were examined as a heterogeneous photocatalyst for carbon dioxide (CO₂) reduction under visible-light irradiation. [Zn(HPO₄)(H₂PO₄)₂](ImH₂)₂ (Im = imidazolate) liquid containing iron(III) 5,10,15,20-tetraphenyl-21H,23H-porphine chloride (Fe(TPP)Cl, 0.1-0.5 w/w%) was cast on a borosilicate glass substrate, followed by cooling to room temperature, resulting in transparent and grain boundary-free membranes with the thicknesses of 3, 5, and 9 μm. The photocatalytic activity of the membranes was in proportion to the membrane thickness, indicating that Fe(TPP)Cl in the subsurface of membranes effectively absorbed light and contributed to the reactions. The membrane photocatalysts were intact during the photocatalytic reaction and showed no recrystallization or leaching of Fe(TPP)Cl.