Adsorption and Photochemical Properties of a Molecular CO2 Reduction Catalyst in Hierarchical Mesoporous ZSM-5: An In Situ FTIR Study

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• 作者：Kevin D. Dubois ; Anton Petushkov ; Elizabeth Garcia Cardona ; Sarah C. Larsen ; Gonghu Li
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2012
• 出版时间：February 16, 2012
• 年：2012
• 卷：3
• 期：4
• 页码：486-492
• 全文大小：303K
• 年卷期：v.3,no.4(February 16, 2012)
• ISSN：1948-7185

文摘

As part of our recent effort to attach well-defined molecular photocatalysts to solid-state surfaces, this present study investigates adsorption and photochemical properties of a tricarbonyl rhenium(I) compound, Re(bpy)(CO)₃Cl (bpy = 2,2鈥?bipyridine), in hierarchical mesoporous ZSM-5. The molecular Re(I) catalyst, a Ru(bpy)₃²⁺ photosensitizer, and an amine-based electron donor were coadsorbed in the mesopores of the hierarchical ZSM-5 through simple liquid-phase adsorption. The functionalized ZSM-5 was then characterized with infrared and UV鈥搗isible spectroscopies and was tested in CO₂ reduction photocatalysis at the gas鈥搒urface interface. In the mesoporous ZSM-5, CO₂ molecules were adsorbed on the amine electron-donor molecules as bicarbonate, which would release CO₂ upon light irradiation to react with the Re(I) catalyst. The formation of important reaction intermediates, particularly a Re-carboxylato species, was revealed with in situ Fourier transform infrared spectroscopy in combination with isotopic labeling. The experimental results indicate that hierarchical mesoporous zeolites are promising host materials for molecular photocatalysts and that zeolite mesopores are potential 鈥渞eaction vessels鈥?for CO₂ reduction photocatalysis at the gas鈥搒olid interface.

Keywords:

rhenium; mesoporous zeolite; CO₂ reduction; photocatalysis; FTIR spectroscopy