The selective reduction of carbon dioxide (CO2) is one of the greatest challenges towards the development of secure and carbon-neutral fuels. This has led to significant advances in the development of homogeneous molecular CO2reduction catalysts. However, there exists a dearth of reports extending the advances in homogeneous molecular systems to heterogeneous systems despite there being several practical advantages to heterogeneous catalysis. Among heterogenization methodologies, the incorporation of active molecular catalysts in the matrix of hybrid materials gives access to advantageous catalytic solids. The ordered crystalline nature of metal-organic frameworks (MOFs) makes this class of porous solids promising model materials for the grafting of single-site organometallic catalysts.The water stable framework Zr-UiO-67, formulated Zr6(OH)4(O)4(O2C-C6H4-C6H4-CO2)6, has been modified to incorporate CO2 reduction catalysts that have previously been studied as homogeneous electrocatalysts. Upon treatment with photosensitizers and irradiated with visible light, the new materials have been assayed for photocatalytic activity toward CO2 reduction. Compared to homogeneous control systems, the heterogeneous systems displayed remarkably consistent turnover frequencies and product selectivity as well as enhanced stability. The results are extended to other MOF systems and indicate that principles and advances develop within homogeneous CO2? reduction systems can be extended to heterogeneous systems in a generalized manner. The enhanced stability has been attributed to a unique interaction between the MOF and the photosensitizer and the nature of this interaction has been further explored. This highlighted the importance of light absorption within the systems investigated and therefore alternative methods of direct light absorption via modifications of MOFs have been investigated.The presentation will focus on photochemical assays and the quantification of CO2 reduction products. The characterization of the new catalytic materials as well as the development of new strategies for light absorption will be discussed in the context of CO2 reduction.

Photochemical reduction of CO<sub>2</sub> via heterogenization of catalysts within metal-organic frameworks: Evaluation of catalytic performance and light absorption strategies

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Photochemical reduction of CO2 via heterogenization of catalysts within metal-organic frameworks: Evaluation of catalytic performance and light absorption strategies

Photochemical reduction of CO₂ via heterogenization of catalysts within metal-organic frameworks: Evaluation of catalytic performance and light absorption strategies