Ruthenium(II)−Bipyridine/NanoC3N4 Hybrids: Tunable Photochemical Properties by Using Exchangeable Alkali Metal Cations |
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| Authors: | Prof. Dr. Kohsuke Mori Daisuke Tatsumi Tomoyuki Iwamoto Prof. Dr. Yoichi Masui Prof. Dr. Makoto Onaka Prof. Dr. Hiromi Yamashita |
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| Affiliation: | 1. Graduate School of Engineering, Osaka University, Suita, Osaka, Japan;2. Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, Katsura, Kyoto, Japan;3. JST, PRESTO, Kawaguchi, Saitama, Japan;4. Department of Chemistry, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan |
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| Abstract: | A series of nanoporous carbon nitrides that contained a range of alkali metal cations (M@nanoC3N4: M=Li+, Na+, K+, Rb+, and Cs+) have been successfully synthesized from as‐synthesized g‐C3N4 by delamination with concentrated sulfuric acid, followed by neutralization with aqueous solutions of the corresponding alkali metal hydroxides. Tris(2,2′‐bipyridine)ruthenium(II) complexes, [Ru(bpy)3]2+, were grafted onto the carbon nitrides in an effort to explore the physicochemical properties of the deposited [Ru(bpy)3]2+, as well as its photocatalytic activity in the aerobic photooxidation of phenylboronic acid and H2 production from aqueous media in the presence of a Pt co‐catalyst under visible‐light irradiation. Highly porous nanoC3N4 could significantly enhance photocatalytic activity, because of its high surface area, owing to its unique porous structure. More interestingly, the photoluminescence intensities of [Ru(bpy)3]2+ complexes that were associated with M@nanoC3N4 increased in the presence of lighter alkali metal cations, which correlated with increased photocatalytic activities for both reactions. This study demonstrates that M@nanoC3N4 are fascinating supports, in which the local environment of an immobilized metal complex can be precisely controlled by varying the alkali metal cation from Li+ to Cs+. |
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| Keywords: | alkali metals immobilization photochemistry ruthenium supported catalysts |
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