Date of Completion

12-2-2019

Embargo Period

12-1-2022

Keywords

Porous materials, Heterogenous catalysis, Methane activation, Supercritical, Renewable energy

Major Advisor

Dr. Steven L. Suib

Associate Advisor

Dr. Alfredo Angeles-Boza

Associate Advisor

Dr. Gaël Ung

Associate Advisor

Dr. Jose Gascon

Associate Advisor

Dr. Fatma Selampinar

Field of Study

Chemistry

Degree

Doctor of Philosophy

Open Access

Campus Access

Abstract

Nickel incorporated (mol. 30%), high surface area (423 m2 g-1), mesoporous (3.8-4.3 nm) TiO2, bare NiO, and bare TiO2 were synthesized with surfactant-assisted metal dissolution techniques. Ethanol is successfully converted to higher energy density compounds including hexanol (yield 63%), acetic acid (39%), and furan (54%) with bare titanium dioxide (300-500°C), whereas C10 decanoic acid (63%), acetaldehyde (50%) is synthesized on Ni/TiO2 at different temperatures.

Meso-microporous hexagonal and monoclinic defective tungsten oxide (WOx) materials were synthesized using a surfactant-assisted metal dissolution methodology. The C(sp2)-C(sp2) cross-coupling of cyclo-pentene, hexane, and heptene with aromatic compounds was achieved with a maximum of 95% yield in 2 hours at 110°C using (max. TOF 7.9 h-1) proton incorporated WOx. When Li+, Na+, and K+ incorporated WOx were used, the reaction was completely stopped. Lower but significant yield (37%) compared to H-WOx (67%) was observed in the presence of cobalt incorporated WOx

Mesoporous spinel cobalt oxide (Co3O4) with fine-tuned pore size distributions (9.6-17.6 nm) were synthesized using a series of nonionic surfactants. Tandem synthesis strategy to synthesize amine homo-coupled imine and amine-alcohol cross-coupled imine was introduced. Light-induced singlet oxygen and hydroxyl radical-mediated reaction mechanism was proposed.

Metal-free methane conversion with high methanol yield (17% O2 based) at mild temperatures (275°C) was achieved with sub-supercritical acetonitrile cluster assisted boron nitride initiation mechanism. Experimental and theoretical evidence supporting acetonitrile-O2 cluster formation and oxygen activation have been presented. Reaction temperature, dwell time, methane-oxygen and solvent-oxygen molar ratio were identified as other critical factors controlling the methane activation and methanol yield.

Available for download on Thursday, December 01, 2022

Share

COinS