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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