Date of Completion


Embargo Period



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



Doctor of Philosophy

Open Access

Campus Access


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