Marty Lail

Boosting catalytic performance of MOFs for steroid transformations by confinement within mesoporous scaffolds

Solid-state crystallization achieves selective confinement of metal-organic framework (MOF) nanocrystals within mesoporous materials, thereby rendering active sites more accessible compared to the bulk-MOF and enhancing the chemical and mechanical stability of MOF nanocrystals. (Zr)UiO-66(NH2 )/SiO2 hybrid materials were tested as efficient and reusable heterogeneous catalysts for the synthesis of steroid derivatives, outperforming the bulk (Zr)UiO-66(NH2 ) MOF. A clear correlation between the catalytic activity of the dispersed Zr sites present in the confined MOF, and the loading of the mesoporous SiO2 , is demonstrated for steroid transformations.

Synthesis of Fluidized CO2 Sorbents Based on Diamine Coordinated to Metal–Organic Frameworks by Direct Conversion of Metal Oxides Supported on Mesoporous Silica

A general and efficient method for shaping MOFs into fluidized forms has been developed by direct conversion of metal oxides supported on fluidized mesoporous silica. The resulting fluidized MOF hybrid materials containing diamines coordinated at the open metal sites have been studied as CO2 solid sorbents from post-combustion flue gas showing similar performance than their bulk counterparts. These new fluidized MOF hybrid materials can be used for other applications involving fluidized bed reactor configurations, in which MOFs have never been considered.

Mechanistic study of CO formation from CO2 using a mixed-metal oxide of tin, iron, and aluminum

A mechanistic study has been performed to show that a reduced mixed metal oxide derived from tin, iron, and aluminum oxides can remove oxygen from carbon dioxide. Thermogravimetric analysis confirms that reduction of the mixed-metal oxide likely involves the reduction of SnO2and Fe2O3 phases. The reduced mixed-metal oxide can remove oxygen from carbon dioxide and this is shown using isotopically labelled C18O2 and mass spectroscopy. The 18O-labelled mixed-metal oxide can transfer the abstracted oxygen to a different carbonaceous compound, in this case carbon monoxide. Oxygen is readily exchanged in the mixed-metal oxide. Under both oxidizing and reducing conditions 18O is exchanged with unlabelled O resulting in the observation of all isotopomers.

Transformation of single MOF nanocrystals into single nanostructured catalysts within mesoporous supports: a platform for pioneer fluidized-nanoreactor hydrogen carriers

Well-dispersed nanostructured catalysts along mesoporous materials have been systematically prepared via a novel multistep approach involving either the pyrolysis under nitrogen, the calcination under oxygen or the reduction under hydrogen of MOF nanocrystals decorated with transition metal complexes and previously confined within the mesoporous cavities via novel solid state synthesis. The resulting supported nanostructured catalysts can be composed of metals, metal oxides, heteroatom-doped carbons and combinations thereof depending on the transformation conditions. The pioneering concept of Fluidized-Nanoreactor Hydrogen Carriers has been proposed for the first time by using the resulting nanostructured catalysts within fluidized mesoporous silica.

Conversion of CO2 into Commercial Materials Using Carbon Feedstocks

In this project, our research focused on developing reaction chemistry that would support using carbon as a reductant for CO2 utilization that would permit CO2 consumption on a scale that would match or exceed anthropomorphic CO2 generation for energy production from fossil fuels. Armed with the knowledge that reactions attempting to produce compounds with an energy content greater than CO2 would be thermodynamically challenged and/or require significant amounts of energy, we developed a potential process that utilized a solid carbon source and recycled the carbon to effectively provide infinite time for the carbon to react. During testing of different carbon sources, we found a wide range of reaction rates. Biomass-derived samples had the most reactivity and coals and petcoke had the lowest. Because we had anticipated this challenge, we recognized that a catalyst would be necessary to improve reaction rates and conversion. From the data analysis of carbon samples, we recognized that alkali metals improved the reaction rate. Through parametric testing of catalyst formulations we were able to increase the reaction rate with petcoke by a factor of >70. Our efforts to identify the reaction mechanism to assist in improving the catalyst formulation demonstrated that the catalyst was catalyzing themorexa0» extraction of oxygen from CO2 and using this extracted oxygen to oxidize carbon. This was a significant discovery in that if we could modify the catalyst formulation to permit controlled the oxidation, we would have a very power selective oxidation process. With selective oxidation, CO2 utilization could be effective used as one of the process steps in making many of the large volume commodity chemicals that support our modern lifestyles. The key challenges for incorporating these functionalities into the catalyst formulation were to make the oxidation selective and lower the temperature required for catalytic activity. We identified four catalyst families that had the potential to meet these challenges. Initial screening of the catalyst families did show that the reduction/oxidation activity did occur at lower temperatures and that these catalysts were able to cause carbon chain growth as well as C—C cleavage. A preliminary techno-economic feasibility of using petcoke/catalyst to produce a CO-rich syngas product was completed and showed significant economic promise. Testing of the different catalyst families demonstrated that Catalyst A was able to stably produce 5 sccm of ethylene/gram of catalyst at 900°C for one hour. For dry methane reforming, our Catalyst 4 was able to achieve production rates of > 10 sccm of CO and > 3 sccm of H2 per gram of catalyst at 600°C and 350 psig. Based on these developments, the potential for CO2 utilization in the production of large volume commodity chemicals is very promising.«xa0less