Two-Dimensional Perovskite Oxynitride K2 LaTa2 O6 N with an H+ /K+ Exchangeability in Aqueous Solution Forming a Stable Photocatalyst for Visible-Light H2 Evolution

Takayoshi Oshima; Tom Ichibha; Kenji Oqmhula; Keisuke Hibino; Hiroto Mogi; Shunsuke Yamashita; Kotaro Fujii; Yugo Miseki; Kenta Hongo; Daling Lu; Ryo Maezono; Kazuhiro Sayama; Masatomo Yashima; Koji Kimoto; Hideki Kato; Masato Kakihana; Hiroshi Kageyama; Kazuhiko Maeda

doi:10.1002/anie.202002534

Two-Dimensional Perovskite Oxynitride K₂ LaTa₂ O₆ N with an H⁺ /K⁺ Exchangeability in Aqueous Solution Forming a Stable Photocatalyst for Visible-Light H₂ Evolution

Angew Chem Int Ed Engl. 2020 Jun 8;59(24):9736-9743. doi: 10.1002/anie.202002534. Epub 2020 Apr 2.

Authors

Takayoshi Oshima^{1

2}, Tom Ichibha³, Kenji Oqmhula³, Keisuke Hibino¹, Hiroto Mogi¹, Shunsuke Yamashita⁴, Kotaro Fujii¹, Yugo Miseki⁵, Kenta Hongo^{6

7

8

9}, Daling Lu¹⁰, Ryo Maezono³, Kazuhiro Sayama⁵, Masatomo Yashima¹, Koji Kimoto⁴, Hideki Kato¹¹, Masato Kakihana¹¹, Hiroshi Kageyama¹², Kazuhiko Maeda¹

Affiliations

¹ Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1-NE-2 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan.
² Japan Society for the Promotion of Science, Kojimachi Business Center Building, 5-3-1 Kojimachi, Chiyoda-ku, Tokyo, 102-0083, Japan.
³ School of Information Science, JAIST, Asahidai 1-1, Nomi, Ishikawa, 923-1292, Japan.
⁴ Research Center for Advanced Measurement and Characterization, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.
⁵ Research Center for Photovoltaics (RCPV) and Global Zero Emission Research Center (GZR), National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan.
⁶ Research Center for Advanced Computing Infrastructure, JAIST, Asahidai 1-1, Nomi, Ishikawa, 923-1292, Japan.
⁷ Center for Materials Research by Information Integration, Research and Services Division of Materials Data and Integrated System, National Institute for Materials Science, Tsukuba, 305-0047, Japan.
⁸ PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi-shi, Saitama, 322-0012, Japan.
⁹ Computational Engineering Applications Unit, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
¹⁰ Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8503, Japan.
¹¹ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan.
¹² Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.

PMID: 32134159
DOI: 10.1002/anie.202002534

Abstract

Undoped layered oxynitrides have not been considered as promising H₂ -evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K₂ LaTa₂ O₆ N, as an exceptional example of a water-tolerant photocatalyst for H₂ evolution under visible light. The material underwent in-situ H⁺ /K⁺ exchange in aqueous solution while keeping its visible-light-absorption capability. Protonated K₂ LaTa₂ O₆ N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H₂ evolution in the presence of I^- as an electron donor and under visible light; the activity was six times higher than Pt/ZrO₂ /TaON, one of the best-performing oxynitride photocatalysts for H₂ evolution. Overall water splitting was also achieved using the Ir-loaded, protonated K₂ LaTa₂ O₆ N in combination with Cs-modified Pt/WO₃ as an O₂ evolution photocatalyst in the presence of an I₃ ^- /I^- shuttle redox couple.

Keywords: artificial photosynthesis; layered materials; mixed anion compound; solar fuels; water splitting.

Abstract

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