Metal Oxide Catalysis | Wiley Online Books
This conversion involves the removal of hydrogen atoms and insertion of a more reactive carbon-carbon double bond. To perform this conversion at low temperatures requires use of a catalyst, and one such example is a mixed metal oxide catalyst.
The objective of this project is to understand how the size and shape of pores within the mixed metal oxide may be engineered to more selectivity catalyze the oxidative alkane to alkene reaction. This project will probe the role of micropores in ordered bulk transition metal oxide catalysts in the selective hydrocarbon oxidation of small alkanes and alkanols. Ordered M1 phase mixed oxides contain one dimensional pores that are similar in size to the kinetic diameters of the reactants; examples include M1 phase mixed oxides of Mo V, Te and Nb and octahedral molecular sieves of Mn oxides.
The project will correlate the oxidation rate ratios of linear versus branched alkanes to cycloalkanes to pore dimension, with consideration of pore sizes that exhibit size exclusivity.
- Metal Oxide Catalysis.
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Kinetic and density functional theory DFT will probe selectivity with variations in pore geometry, reactant geometry, and surface reactivity. It is anticipated van der Walls stabilizations and steric hindrance may limit conversion to secondary byproducts, which may enhance selectivity by bypassing the thermodynamic driving forces for secondary oxidation reactions to secondary byproducts.
Planned education and outreach activities will promote understanding of heterogeneous catalysis and its role in meeting the challenges of sustainable chemical production and energy efficiency. These activities will target students from underprivileged backgrounds, with an aim to increase their retention in science and engineering fields. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.
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Concepts in Catalysis by Transition Metal Oxides
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How to Manage Your Award. Typical oxidation catalysts are metal oxides and metal carboxylates.
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- Catalytic oxidation.
Oxidation catalysis is conducted by both heterogeneous catalysis and homogeneous catalysis. In the heterogeneous processes, gaseous substrate and oxygen or air are passed over solid catalysts. Typical catalysts are platinum, and redox-active oxides of iron, vanadium, and molybdenum. In many cases, catalysts are modified with a host of additives or promoters that enhance rates or selectivities. Important homogeneous catalysts for the oxidation of organic compounds are carboxylates of cobalt, iron, and manganese.
Electron Microscopy in Heterogeneous Catalysis
To confer good solubility in the organic solvent, these catalysts are often derived from naphthenic acids and ethylhexanoic acid , which are highly lipophilic. These catalysts initiate radical chain reactions , autoxidation that produce organic radicals that combine with oxygen to give hydroperoxide intermediates. Generally the selectivity of oxidation is determined by bond energies.
For example, benzylic C-H bonds are replaced by oxygen faster than aromatic C-H bonds.
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Many selective oxidation catalysts have been developed for producing fine chemicals of pharmaceutical or academic interest. Nobel Prize—winning examples are the Sharpless epoxidation and the Sharpless dihydroxylation.
Role of mixed metal oxides in catalysis science—versatile applications in organic synthesis
Catalytic oxidations are common in biology, especially since aerobic life subsists on energy obtained by oxidation of organic compounds by air. In contrast to the industrial processes, which are optimized for producing chemical compounds, energy-producing biological oxidations are optimized to produce energy. Many metalloenzymes mediate these reactions. Fuel cells rely on oxidation of organic compounds or hydrogen using catalysts.