3 years ago

Photocatalytic CO2 Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites

Photocatalytic CO2 Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites
Yoshifumi Maegawa, Yusuke Kuramochi, Hitoshi Ishida, Kyohei Kitamura, Shinji Inagaki, Masato Sekine, Soichi Shirai, Yasutomo Goto
A periodic mesoporous organosilica (PMO) containing 2,2′-bipyridine (bpy) ligands within the framework (BPy-PMO) has great potential for designing novel catalysts by modifying metal complexes. A photosensitizing site (Ru(PS)) was introduced by treating cis-[Ru(bpy)2(dimethylsulfoxide)Cl]Cl with BPy-PMO. Then a catalytic site (Ru(Cat)) was brought in Ru(PS)x-BPy-PMO by reaction with a ruthenium polymer [Ru(CO)2Cl2]n. The stepwise modification of BPy-PMO successfully affords a novel photocatalyst Ru(PS)x-Ru(Cat)y-BPy-PMO. The molar fractions (x, y) of Ru(PS) and Ru(Cat) were determined by energy dispersive X-ray (EDX) measurement and quantification of the amount of CO emitted in the photo-decarbonylation of Ru(Cat), respectively. Photochemical CO2 reduction (λex>430 nm) by Ru(PS)x-Ru(Cat)y-BPy-PMO in a CO2-saturated N,N-dimethylacetamide/water solution containing 1-benzyl-1,4-dihydronicotinamide catalytically produced CO and formate. The total turnover frequency of CO and formate reached more than 162 h−1 on x=0.11 and y=0.0055. The product selectivity (CO/formate) became large when the ratio of Ru(PS)-to-Ru(Cat) (x/y) was increased. The photocatalysts can be recycled at least three times without losing their catalytic activity, demonstrating that the Ru(PS) and Ru(Cat) units were strongly immobilized on the BPy-PMO framework. Two of a kind: A periodic mesoporous organosilica (PMO) containing 2,2′-bipyridine (bpy) ligands within the framework (BPy-PMO) has been modified in a stepwise fashion with two different functional ruthenium complexes to synthesize Ru(PS)-Ru(Cat)-BPy-PMO as a heterogeneous catalyst for photochemical CO2 reduction.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701466

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