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.
Recommended Citation
Kankanam Kapuge, Tharindu Madusanka Premalal, "The Function of High Surface Area Mesoporous Metal Oxides in Heterogeneous Catalysis and Partial Oxidation of Methane to Methanol in Near Supercritical Acetonitrile" (2019). Doctoral Dissertations. 2356.
https://digitalcommons.lib.uconn.edu/dissertations/2356