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Description
A new analytical method is proposed for measuring the deuterium to hydrogen ratio (D/H) of non-stoichiometric water in hydrous minerals via pyrolysis facilitated gas-chromatography - isotope ratio mass spectrometry (GC-IRMS). Previously published analytical methods have reported a poorly understood nonlinear dependence of D/H on sample size, for which any accurate correction is difficult. This sample size effect been variously attributed to kinetic isotope fractionation within the mass spectrometer and peripheral instruments, ion source linearity issues, and an unstable H_3^+-factor or incorrect H_3^+-factor calculations. The cause of the sample size effect is here identified by examinations of individual chromatograms as well as bulk data from chromatographic peaks. It is here determined that it is primarily an artifact of the calculations employed by the manufacturer's computer program, used to both monitor the functions of the mass spectrometer and to collect data. Ancillary causes of the sample size effect include a combination of persistent background interferences and chromatographic separation of the isotopologues of molecular hydrogen. Previously published methods are evaluated in light of these findings. A new method of H_3^+-factor and D/H calculation is proposed which makes portions of the Isodat software as well as other published calculation methods unnecessary. Using this new method, D/H is measured in non-stoichiometric water in chert from the Cretaceous Edwards Group, Texas, as well as the Precambrian Kromberg Formation, South Africa, to assess hydrological conditions as well as to estimate the maximum average surface temperature during precipitation of the chert. Data from Cretaceous chert are consistent with previously published data and interpretations, based upon conventional analyses of large samples. Data from Precambrian chert are consistent with maximum average surface temperatures approaching 65°C during the Archean, instead of the much lower temperatures derived from erroneous methods of sample preparation and analysis. D/H is likewise measured in non-stoichiometric water in silicified basalt from the Precambrian Hooggenoeg Complex, South Africa. Data are shown to be consistent with D/H of the Archean ocean similar to present day values.
ContributorsSheehan, Michael Robert (Author) / Knauth, Leroy P (Thesis advisor) / Anbar, Ariel (Committee member) / Farmer, Jack (Committee member) / Arizona State University (Publisher)
Created2011
Description
In the United States, 95% of the industrially produced hydrogen is from natural gas reforming. Membrane-based techniques offer great potential for energy efficient hydrogen separations. Pd77Ag23 is the bench-mark metallic membrane material for hydrogen separation at high temperatures. However, the high cost of palladium limits widespread application. Amorphous metals with lower cost elements are one alternative to replace palladium-based membranes. The overall aim of this thesis is to investigate the potential of binary and ternary amorphous metallic membranes for hydrogen separation. First, as a benchmark, the influence of surface state of Pd77Ag23 crystalline metallic membranes on the hydrogen permeability was investigated. Second, the hydrogen permeability, thermal stability and mechanical properties of Cu-Zr and Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was evaluated.
Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences.
Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications.
The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize.
Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences.
Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications.
The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize.
ContributorsLai, Tianmiao (Author) / Lind, Mary Laura (Thesis advisor) / Lin, Jerry (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2015
Description
Layers of intrinsic hydrogenated amorphous silicon and amorphous silicon carbide
were prepared on a polished, intrinsic crystalline silicon substrate via plasma-enhanced chemical vapor deposition to simulate heterojunction device relevant stacks of various materials. The minority carrier lifetime, optical band gap and FTIR spectra were observed at incremental stages of thermal annealing. By observing the changes in the lifetimes the sample structure responsible for the most thermally robust surface passivation could be determined. These results were correlated to the optical band gap and the position and relative area of peaks in the FTIR spectra related to to silicon-hydrogen bonds in the layers. It was found that due to an increased presence of hydrogen bonded to silicon at voids within the passivating layer, hydrogenated amorphous silicon carbide at the interface of the substrate coupled with a hydrogenated amorphous silicon top layer provides better passivation after high temperature annealing than other device structures.
were prepared on a polished, intrinsic crystalline silicon substrate via plasma-enhanced chemical vapor deposition to simulate heterojunction device relevant stacks of various materials. The minority carrier lifetime, optical band gap and FTIR spectra were observed at incremental stages of thermal annealing. By observing the changes in the lifetimes the sample structure responsible for the most thermally robust surface passivation could be determined. These results were correlated to the optical band gap and the position and relative area of peaks in the FTIR spectra related to to silicon-hydrogen bonds in the layers. It was found that due to an increased presence of hydrogen bonded to silicon at voids within the passivating layer, hydrogenated amorphous silicon carbide at the interface of the substrate coupled with a hydrogenated amorphous silicon top layer provides better passivation after high temperature annealing than other device structures.
ContributorsJackson, Alec James (Author) / Holman, Zachary (Thesis advisor) / Bertoni, Mariana (Committee member) / Kozicki, Michael (Committee member) / Arizona State University (Publisher)
Created2016
Description
This thesis is devoted to the theoretical and computational study of electron transport in molecular junctions where one or more hydrogen bonds are involved in the process. While electron transport through covalent bonds has been extensively studied, in recent work the focus has been shifted towards hydrogen-bonded systems due to their ubiquitous presence in biological systems and their potential in forming nano- junctions between molecular electronic devices and biological systems.
This analysis allows us to significantly expand our comprehension of the experimentally observed result that the inclusion of hydrogen bonding in a molecular junc- tion significantly impacts its transport properties, a fact that has important implications for our understanding of transport through DNA, and nano-biological interfaces in general. In part of this work I have explored the implications of quasiresonant transport in short chains of weakly-bonded molecular junctions involving hydrogen bonds. I used theoretical and computational analysis to interpret recent experiments and explain the role of Fano resonances in the transmission properties of the junction.
In a different direction, I have undertaken the study of the transversal conduction through nucleotide chains that involve a variable number of different hydrogen bonds, e.g. NH···O, OH···O, and NH···N, which are the three most prevalent hydrogen bonds in biological systems and organic electronics. My effort here has fo- cused on the analysis of electronic descriptors that allow a simplified conceptual and computational understanding of transport properties. Specifically, I have expanded our previous work where the molecular polarizability was used as a conductance de- scriptor to include the possibility of atomic and bond partitions of the molecular polarizability. This is important because it affords an alternative molecular descrip- tion of conductance that is not based on the conventional view of molecular orbitals as transport channels. My findings suggest that the hydrogen-bond networks are crucial in understanding the conductance of these junctions.
A broader impact of this work pertains the fact that characterizing transport through hydrogen bonding networks may help in developing faster and cost-effective approaches to personalized medicine, to advance DNA sequencing and implantable electronics, and to progress in the design and application of new drugs.
This analysis allows us to significantly expand our comprehension of the experimentally observed result that the inclusion of hydrogen bonding in a molecular junc- tion significantly impacts its transport properties, a fact that has important implications for our understanding of transport through DNA, and nano-biological interfaces in general. In part of this work I have explored the implications of quasiresonant transport in short chains of weakly-bonded molecular junctions involving hydrogen bonds. I used theoretical and computational analysis to interpret recent experiments and explain the role of Fano resonances in the transmission properties of the junction.
In a different direction, I have undertaken the study of the transversal conduction through nucleotide chains that involve a variable number of different hydrogen bonds, e.g. NH···O, OH···O, and NH···N, which are the three most prevalent hydrogen bonds in biological systems and organic electronics. My effort here has fo- cused on the analysis of electronic descriptors that allow a simplified conceptual and computational understanding of transport properties. Specifically, I have expanded our previous work where the molecular polarizability was used as a conductance de- scriptor to include the possibility of atomic and bond partitions of the molecular polarizability. This is important because it affords an alternative molecular descrip- tion of conductance that is not based on the conventional view of molecular orbitals as transport channels. My findings suggest that the hydrogen-bond networks are crucial in understanding the conductance of these junctions.
A broader impact of this work pertains the fact that characterizing transport through hydrogen bonding networks may help in developing faster and cost-effective approaches to personalized medicine, to advance DNA sequencing and implantable electronics, and to progress in the design and application of new drugs.
ContributorsWimmer, Michael (Author) / Mujica, Vladimiro (Thesis advisor) / Wolf, George (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2017
Description
Past experiments have revealed several unusual properties about interstitial hydrogen atoms in niobium. Absorption isotherms showed that niobium absorbs a large amount of hydrogen without changing its crystal structure. These isotherms also revealed that the interactions between hydrogen atoms in niobium are a combination of long-range attraction and short-range repulsion and exhibit many-body characteristics. Other experiments reported the facile thermal diffusion of hydrogen and deuterium in niobium. Contrary to the classical theory of diffusion, these experiments revealed a break in the activation energy of hydrogen diffusion at low temperatures, but no such break was reported for deuterium. Finally, experiments report a phenomenon called electromigration, where hydrogen atoms inside niobium respond to weak electric fields as if they had a positive effective charge. These experimental results date back to when tools like density functional theory (DFT) and modern high-performance computing abilities did not exist. Therefore, the current understanding of these properties is primarily based on inferences from experimental results. Understanding these properties at a deeper level, besides being scientifically important, can profoundly affect various applications involving hydrogen separation and transport. The high-level goal of this work is to use first-principles methods to explain the discussed properties of interstitial hydrogen in niobium. DFT calculations were used to study hydrogen atoms' site preference in niobium and its effect on the cell shape and volume of the host cell. The nature and origin of the interactions between hydrogen atoms were studied through interaction energy, structural, partial charge, and electronic densities of state analysis. A phenomenological model with fewer parameters than traditional models was developed and fit to the experimental absorption data. Thermodynamic quantities such as the enthalpy and entropy of hydrogen dissolution in niobium were derived from this model. The enthalpy of hydrogen dissolution in niobium was also calculated using DFT by sampling different geometric configurations and performing an ensemble-based averaging. Further work is required to explain the observed isotope effects for hydrogen diffusion in niobium and the electromigration phenomena. Applications of the niobium-hydrogen system require studying hydrogen's behavior on niobium's surface.
ContributorsRamcahandran, Arvind (Author) / Lackner, Klaus S. (Thesis advisor) / Zhuang, Houlong (Thesis advisor) / Muhich, Christopher (Committee member) / Singh, Arunima (Committee member) / Arizona State University (Publisher)
Created2021
Description
The conversion of H2S enables the recycling of a waste gas into a potential source of hydrogen at a lower thermodynamic energy cost as compared to water splitting. However, studies on the photocatalytic decomposition of H2S focus on traditional deployment of catalyst materials to facilitate this conversion, and operation only when a light source is available. In this study, the efficacy of Direct Ink Written (DIW) luminous structures for H2S conversion has been investigated, with the primary objective of sustaining H2S conversion when a light source has been terminated. Additionally, as a secondary objective, improving light distribution within monoliths for photocatalytic applications is desired. The intrinsic illumination of the 3D printed monoliths developed in this work could serve as an alternative to monolith systems that employ light transmitting fiber optic cables that have been previously proposed to improve light distribution in photocatalytic systems. The results that were obtained demonstrate that H2S favorable adsorbents, a wavelength compatible long afterglow phosphor, and a photocatalyst can form viscoelastic inks that are printable into DIW luminous monolithic contactors. Additionally, rheological, optical and porosity analyses conducted, provide design guidelines for future studies seeking to develop DIW luminous monoliths from compatible catalyst-phosphor pairs. The monoliths that were developed demonstrate not only improved conversion when exposed to light, but more significantly, extended H2S conversion from the afterglow of the monoliths when an external light source was removed. Lastly, considering growing interests in attaining a global circular economy, the techno-economic feasibility of a H2S-CO2 co-utilization plant leveraging hydrogen from H2S photocatalysis as a feed source for a downstream CO2 methanation plant has been assessed. The work provides preliminary information to guide future chemical kinetic design characteristics that are important to strive for if using H2S as a source of hydrogen in a CO2 methanation facility.
ContributorsAbdullahi, Adnan (Author) / Andino, Jean (Thesis advisor) / Phelan, Patrick (Thesis advisor) / Bhate, Dhruv (Committee member) / Wang, Robert (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2023
Description
Hydrogen is the main constituent of stars, and thus dominates the protoplanetary disc from which planets are born. Many planets may at some point in their growth have a high-pressure interface between refractory planetary materials and ahydrogen-dominated atmosphere. However, little experimental data for these materials at the relevant pressure-temperature conditions exists. I have experimentally explored the interactions between planetary materials and hydrogen at high P-T conditions utilizing the pulsed laser-heated diamond-anvil cell. First, I found that ferric/ferrous iron (as Fe2O3 hematite and (Mg,Fe)O ferropericlase) are reduced to metal by hydrogen: Fe2O3 + 4H2 → 2FeO + H2O + 3H2 → 2FeH + 3H2O and (Mg1−xFex) O + 3/2 xH2 → xFeH + (1 − x) MgO + xH2O respectively. This reduction of iron by hydrogen is important because it produces iron metal and water from iron oxide. This can partition H into the core (as FeH) or mantle (as H2O/OH−) of a growing planet.
Next, I expanded my starting materials to silicates. I conducted experiments on San Carlos Olivine at pressures of 5-42 GPa. In the presence hydrogen, I observed the breakdown of molten magnesium silicate and the reduction of both iron and silicon to metal, forming alloys of both Fe-H and Fe-Si: Mg2SiO4 + 2H2 + 3Fe →
2MgO + FeSi + 2FeH + 2H2O.
Similar experiments using natural fayalite (Fe2SiO4) as a starting material at pressures of 5-21 GPa yielded similar results. Hydrogen reduced iron to metal as it did in experiments with iron oxides. Unlike with San Carlos olivine, above 10 GPa silicon remained oxidized, implying the following reaction: Fe2SiO4 + 3H2 → 2FeH+2H2O +SiO2. However, below 7 GPa, silicon reduces and alloys with iron. The formation of Fe-Si alloys from silicates facilitated by hydrogen could have important effects for core composition in growing planets. I also observed at low pressures (<10 GPa), quenched iron melt can trap more hydrogen than previously thought (H/Fe nearly 2 instead of 1). This may have important effects for the chemical sequestration of a hydrogen atmosphere at shallow depths in an early magma ocean.
All of the experimental work presented herein show that the composition, chemical partitioning, and phase stability of the condensed portion of growing planets can be modified via interaction with overlaying or ingassed volatile species.
ContributorsAllen-Sutter, Harrison (Author) / Shim, Sang-Heon Dan (Thesis advisor) / Li, Mingming (Committee member) / Leinenweber, Kurt D (Committee member) / Tyburczy, James A (Committee member) / Gabriel, Travis S.J. (Committee member) / Arizona State University (Publisher)
Created2022
Improving cyanobacterial hydrogen production through bioprospecting of natural microbial communities
Description
Some cyanobacteria can generate hydrogen (H2) under certain physiological conditions and are considered potential agents for biohydrogen production. However, they also present low amounts of H2 production, a reaction reversal towards H2 consumption, and O2 sensitivity. Most attempts to improve H2 production have involved genetic or metabolic engineering approaches. I used a bio-prospecting approach instead to find novel strains that are naturally more apt for biohydrogen production. A set of 36, phylogenetically diverse strains isolated from terrestrial, freshwater and marine environments were probed for their potential to produce H2 from excess reductant. Two distinct patterns in H2 production were detected. Strains displaying Pattern 1, as previously known from Synechocystis sp. PCC 6803, produced H2 only temporarily, reverting to H2 consumption within a short time and after reaching only moderately high H2 concentrations. By contrast, Pattern 2 cyanobacteria, in the genera Lyngbya and Microcoleus, displayed high production rates, did not reverse the direction of the reaction and reached much higher steady-state H2 concentrations. L. aestuarii BL J, an isolate from marine intertidal mats, had the fastest production rates and reached the highest steady-state concentrations, 15-fold higher than that observed in Synechocystis sp. PCC 6803. Because all Pattern 2 strains originated in intertidal microbial mats that become anoxic in dark, it was hypothesized that their strong hydrogenogenic capacity may have evolved to aid in fermentation of the photosynthate. When forced to ferment, these cyanobacteria display similarly desirable characteristics of physiological H2 production. Again, L. aestuarii BL J had the fastest specific rates and attained the highest H2 concentrations during fermentation, which proceeded via a mixed-acid pathway to yield acetate, ethanol, lactate, H2, CO2 and pyruvate. The genome of L. aestuarii BL J was sequenced and bioinformatically compared to other cyanobacterial genomes to ascertain any potential genetic or structural basis for powerful H2 production. The association hcp exclusively in Pattern 2 strains suggests its possible role in increased H2 production. This study demonstrates the value of bioprospecting approaches to biotechnology, pointing to the strain L. aestuarii BL J as a source of useful genetic information or as a potential platform for biohydrogen production.
ContributorsKothari, Ankita (Author) / Garcia-Pichel, Ferran (Thesis advisor) / Vermaas, Willem F J (Committee member) / Rittmann, Bruce (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2013
Description
Water-soluble, adenosine triphosphate (ATP)-stabilized palladium nanoparticles have been synthesized by reduction of palladium salt in the presence of excess ATP. They have been characterized by electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and X-ray diffraction in order to determine particle size, shape, composition and crystal structure. The particles were then subsequently attached to a glassy carbon electrode (GCE) in order to explore their electrochemical properties with regard to hydrogen insertion in 1 M sodium hydroxide. The particles were found to be in the size range 2.5 to 4 nm with good size dispersion. The ATP capping ligand allowed the particles to be air-stable and re-dissolved without agglomeration. It was found that the NPs could be firmly attached to the working electrode via cycling the voltage repeatedly in a NP/phosphate solution. Further electrochemical experiments were conducted to investigate the adsorption and absorption of hydrogen in the NPs in 1 M sodium hydroxide. Results for cyclic voltammetry experiments were consistent with those for nanostructured and thin-film palladium in basic solution. Absorbed hydrogen content was analyzed as a function of potential. The maximum hydrogen:Pd ratio was found to be ~0.7, close the theoretical maximum value for β phase palladium hydride.
ContributorsLamb, Timothy (Author) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeffery (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2013
Description
The transport of hydrogen to the Earth’s deep interior remains uncertain. The upper mantle minerals have very low hydrogen solubilities (hundreds of ppm). The hydrogen storage capability in the transition zone minerals (2 wt%) is high compared to those of the upper mantle. The hydrogen storage in the lower mantle is not well known. The main minerals in the lower mantle bridgmanite and ferropericlase have very low hydrogen storage capacities (less than 20 ppm). In order to further understand the hydrogen storage in the lower mantle, a series of experiments had been conducted to simulate the environment similar to the Earth’s mantle. The experiments with hydrous Mg2SiO4 ringwoodite (Rw) show that it converts to crystalline dense hydrous silica, stishovite (Stv) or CaCl2-type SiO2(mStv), containing ∼1 wt% H2O together with bridgmanite (Brd) and MgO at the pressure-temperature conditions expected for lower mantle depths between approximately 660 to 1600 km. Brd would break down partially to dense hydrous silica (6–25 mol%) and(Mg,Fe)O in mid-mantle regions with 0.05–0.27 wt% H2O. The hydrous stishovite has a CaCl2 structure, which is common among hydrous minerals in the lower mantle. Based on this observation, I hypothesize the existence of hydrous phases in the lower mantle. The experiments found a new hexagonal iron hydroxide (η-Fe12O18+x/2Hx) between the stability fields of the epsilon and pyrite-type FeOOH at 60–80 GPa and high temperature. The new phase contains less H2O, limiting the H2O transport from the shallow to the deep mantle in the Fe–O–H system. Possible hydrogen storage in Ca-perovskite was studied. CaPv could contain 0.5–1 wt% water and the water in CaPv could distort the crystal structure of CaPv from cubic to tetragonal structure. In conclusion, hydrogen can be stored in hydrous stishovite in the shallower depth of the lower mantle. At greater depth, the new η phase and pyrite-type phase would take over the hydrogen storage. The role of CaPv in deep water storage needs to be considered in future studies.
ContributorsChen, Huawei (Author) / Shim, Sang-Heon (Thesis advisor) / Garnero, Edward (Committee member) / Bose, Maitrayee (Committee member) / Li, Mingming (Committee member) / Leinenweber, Kurt (Committee member) / Arizona State University (Publisher)
Created2019