Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science.
Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis.
The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts.
The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands:
-One with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and,
-Anotheronewithvicinalbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15.
The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis.
The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials.
A fairly good turn over number (TON = 43) has been obtained following hydrogen treatment of tungsten alkylidyne supported on [N,O] SBA151100, in comparison with TON of zero in the obtained with [N,N] SBA15 and classical SiO2 silica support. Therefore, the cooperation between silylamine and silanol in close vicinity are required to improve the efficiency of the catalyst in the metathesis of propane.
|Date of Award||Apr 2014|
|Original language||English (US)|
- Physical Science and Engineering
|Supervisor||Jean-Marie Basset (Supervisor)|
- Surface organometallic chemistry
- propane metathesis
- nitrogen ligands
- tungsten alkylidyne