Matching Items (3)
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- All Subjects: Interfaces
- All Subjects: Surface Functionalization
- Creators: Cay, Pinar
- Creators: Dhamdhere, Ajit
- Creators: Moore, Gary F.
Description
The molecular modification of semiconductors has applications in energy
conversion and storage, including artificial photosynthesis. In nature, the active sites of
enzymes are typically earth-abundant metal centers and the protein provides a unique
three-dimensional environment for effecting catalytic transformations. Inspired by this
biological architecture, a synthetic methodology using surface-grafted polymers with
discrete chemical recognition sites for assembling human-engineered catalysts in three-dimensional
environments is presented. The use of polymeric coatings to interface cobalt-containing
catalysts with semiconductors for solar fuel production is introduced in
Chapter 1. The following three chapters demonstrate the versatility of this modular
approach to interface cobalt-containing catalysts with semiconductors for solar fuel
production. The catalyst-containing coatings are characterized through a suite of
spectroscopic techniques, including ellipsometry, grazing angle attenuated total reflection
Fourier transform infrared spectroscopy (GATR-FTIR) and x-ray photoelectron (XP)
spectroscopy. It is demonstrated that the polymeric interface can be varied to control the
surface chemistry and photoelectrochemical response of gallium phosphide (GaP) (100)
electrodes by using thin-film coatings comprising surface-immobilized pyridyl or
imidazole ligands to coordinate cobaloximes, known catalysts for hydrogen evolution.
The polymer grafting chemistry and subsequent cobaloxime attachment is applicable to
both the (111)A and (111)B crystal face of the gallium phosphide (GaP) semiconductor,
providing insights into the surface connectivity of the hard/soft matter interface and
demonstrating the applicability of the UV-induced immobilization of vinyl monomers to
a range of GaP crystal indices. Finally, thin-film polypyridine surface coatings provide a
molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto
GaP. In all constructs, photoelectrochemical measurements confirm the hybrid
photocathode uses solar energy to power reductive fuel-forming transformations in
aqueous solutions without the use of organic acids, sacrificial chemical reductants, or
electrochemical forward biasing.
conversion and storage, including artificial photosynthesis. In nature, the active sites of
enzymes are typically earth-abundant metal centers and the protein provides a unique
three-dimensional environment for effecting catalytic transformations. Inspired by this
biological architecture, a synthetic methodology using surface-grafted polymers with
discrete chemical recognition sites for assembling human-engineered catalysts in three-dimensional
environments is presented. The use of polymeric coatings to interface cobalt-containing
catalysts with semiconductors for solar fuel production is introduced in
Chapter 1. The following three chapters demonstrate the versatility of this modular
approach to interface cobalt-containing catalysts with semiconductors for solar fuel
production. The catalyst-containing coatings are characterized through a suite of
spectroscopic techniques, including ellipsometry, grazing angle attenuated total reflection
Fourier transform infrared spectroscopy (GATR-FTIR) and x-ray photoelectron (XP)
spectroscopy. It is demonstrated that the polymeric interface can be varied to control the
surface chemistry and photoelectrochemical response of gallium phosphide (GaP) (100)
electrodes by using thin-film coatings comprising surface-immobilized pyridyl or
imidazole ligands to coordinate cobaloximes, known catalysts for hydrogen evolution.
The polymer grafting chemistry and subsequent cobaloxime attachment is applicable to
both the (111)A and (111)B crystal face of the gallium phosphide (GaP) semiconductor,
providing insights into the surface connectivity of the hard/soft matter interface and
demonstrating the applicability of the UV-induced immobilization of vinyl monomers to
a range of GaP crystal indices. Finally, thin-film polypyridine surface coatings provide a
molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto
GaP. In all constructs, photoelectrochemical measurements confirm the hybrid
photocathode uses solar energy to power reductive fuel-forming transformations in
aqueous solutions without the use of organic acids, sacrificial chemical reductants, or
electrochemical forward biasing.
ContributorsBeiler, Anna Mary (Author) / Moore, Gary F. (Thesis advisor) / Moore, Thomas A. (Thesis advisor) / Redding, Kevin E. (Committee member) / Allen, James P. (Committee member) / Arizona State University (Publisher)
Created2018
Description
Zeolite thin films and membranes are currently a promising technology for pervaporation, gas separation and water purification. The main drawback with these technologies is that the synthesis is not consistent leading to varied and unreproducible results. The Langmuir-Blodgett technique is a robust method for transferring monolayers of molecules or crystals to a solid substrate. By measuring the surface pressure and controlling the area, reliable results can be achieved by transferring monolayers to different solid substrates. It has been shown previously that various types of zeolites can be functionalized and dispersed on the top of water. This is done by using an alcohol to form a hydrophobic coating on the surface of zeolite. The Langmuir-Blodgett can be used to create thin, compact films of zeolites for synthesizing and growing zeolite films. For the first reported time, cubic LTA Zeolites monolayers have been assembled with the Langmuir-Blodgett technique with multiple solvents and different sizes of zeolites. These films were characterized with Scanning Electron Microscopy and Pressure-Area Isotherms generated from the Langmuir-Blodgett. It was found that linoleic acid is a required addition to the zeolite dispersions to protect the mechanical stability during agitation. Without this addition, the LTA zeolites are broken apart and lose their characteristic cubic structure. This effect is discussed and a theory is presented that the interparticle interactions of the long alkane chain of the linoleic acid help reduce the shear stress on the individual zeolite particles, thus preventing them from being broken. The effect of size of the zeolites on the monolayer formation was also discussed. There seemed to be little correlation between the monolayer quality and formation as size was changed. However, to optimize the process, different concentrations and target pressures are needed. Lastly, the effect of the solvent was explored and it was found that there is a different between monolayer formations for different solvents likely due to differing interparticle interactions. Overall, LTA zeolites were successfully fabricated and the important factors to consider are the zeolite size, the solvent, and the amount of surfactant stabilizer added.
ContributorsDopilka, Andrew Michael (Author) / Lind, Mary Laura (Thesis director) / Cay, Pinar (Committee member) / Materials Science and Engineering Program (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS). Oxide thin films grown on SrTiO3/Si pseudo-substrate showed the presence of amorphised SrTiO3 (STO) at the STO/Si interface. Oxide/oxide interfaces were observed to be atomically clean with very few defects.
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
ContributorsDhamdhere, Ajit (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Chamberlin, Ralph (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015