The production of separate streams of pure hydrogen and carbon dioxide from coal via an iron-oxide redox cycle

A chemical looping process using the redox reactions of iron oxide has been used to produce separate streams of pure H2 and CO2 from a solid fuel. An iron oxide carrier prepared using a mechanical mixing technique and comprised of 100wt.% Fe2O3 was used. It was demonstrated that hydrogen can be produced from three representative coals - a Russian bituminous, a German lignite and a UK sub-bituminous coal. Depending on the fuel, pure H2 with [CO] ≲50vol.ppm can be obtained from the proposed process. The cyclic stability of the iron oxide carrier was not adversely affected by contaminants found in syngas which are gaseous above 273K. Stable quantities of H2 were produced over five cycles for all three coals investigated. Independent of the fuel, SO2 was not formed during the oxidation with steam, i.e. the produced H2 was not contaminated with SO2. Since oxidation with air removes contaminants and generates useful heat and pure N2 for purging, it should be included in the operating cycle. Overall, it was demonstrated that the proposed process may be an attractive approach to upgrade crude syngas produced by the gasification of low-rank coals to pure H2, representing a substantial increase in calorific value, whilst simultaneous capturing CO2, a greenhouse gas. © 2010 Elsevier B.V.

Evaluation of bioactive sphingolipids in 4-HPR-resistant leukemia cells

Background -- N-(4-hydroxyphenyl)retinamide (4-HPR, fenretinide) is a synthetic retinoid with potent pro-apoptotic activity against several types of cancer, but little is known regarding mechanisms leading to chemoresistance. Ceramide and, more recently, other sphingolipid species (e.g., dihydroceramide and dihydrosphingosine) have been implicated in 4-HPR-mediated tumor cell death. Because sphingolipid metabolism has been reported to be altered in drug-resistant tumor cells, we studied the implication of sphingolipids in acquired resistance to 4-HPR based on an acute lymphoblastic leukemia model. Methods -- CCRF-CEM cell lines resistant to 4-HPR were obtained by gradual selection. Endogenous sphingolipid profiles and in situ enzymatic activities were determined by LC/MS, and resistance to 4-HPR or to alternative treatments was measured using the XTT viability assay and annexin V-FITC/propidium iodide labeling. Results -- No major crossresistance was observed against other antitumoral compounds (i.e. paclitaxel, cisplatin, doxorubicin hydrochloride) or agents (i.e. ultra violet C, hydrogen peroxide) also described as sphingolipid modulators. CCRF-CEM cell lines resistant to 4-HPR exhibited a distinctive endogenous sphingolipid profile that correlated with inhibition of dihydroceramide desaturase. Cells maintained acquired resistance to 4-HPR after the removal of 4-HPR though the sphingolipid profile returned to control levels. On the other hand, combined treatment with sphingosine kinase inhibitors (unnatural (dihydro)sphingosines ((dh)Sph)) and glucosylceramide synthase inhibitor (PPMP) in the presence or absence of 4-HPR increased cellular (dh)Sph (but not ceramide) levels and were highly toxic for both parental and resistant cells. Conclusions -- In the leukemia model, acquired resistance to 4-HPR is selective and persists in the absence of sphingolipid profile alteration. Therapeutically, the data demonstrate that alternative sphingolipid-modulating antitumoral strategies are suitable for both 4-HPR-resistant and sensitive leukemia cells. Thus, whereas sphingolipids may not be critical for maintaining resistance to 4-HPR, manipulation of cytotoxic sphingolipids should be considered a viable approach for overcoming resistance.

Olefin cyclopropanation and carbon-hydrogen amination via carbene and nitrene transfers catalyzed by engineered cytochrome P450 enzymes

Synthetic biology promises to transform organic synthesis by enabling artificial catalysis in living cells. I start by reviewing the state of the art in this young field and recognizing that new approaches are required for designing enzymes that catalyze nonnatural reactions, in order to expand the scope of biocatalytic transformations. Carbene and nitrene transfers to C=C and C-H bonds are reactions of tremendous synthetic utility that lack biological counterparts. I show that various heme proteins, including cytochrome P450BM3, will catalyze promiscuous levels of olefin cyclopropanation when provided with the appropriate synthetic reagents (e.g., diazoesters and styrene). Only a few amino acid substitutions are required to install synthetically useful levels of stereoselective cyclopropanation activity in P450BM3. Understanding that the ferrous-heme is the active species for catalysis and that the artificial reagents are unable to induce a spin-shift-dependent increase in the redox potential of the ferric P450, I design a high-potential serine-heme ligated P450 (P411) that can efficiently catalyze cyclopropanation using NAD(P)H. Intact E. coli whole-cells expressing P411 are highly efficient asymmetric catalysts for olefin cyclopropanation. I also show that engineered P450s can catalyze intramolecular amination of benzylic C-H bonds from arylsulfonyl azides. Finally, I review other examples of where synthetic reagents have been used to drive the evolution of novel enzymatic activity in the environment and in the laboratory. I invoke preadaptation to explain these observations and propose that other man-invented reactions may also be transferrable to natural enzymes by using a mechanism-based approach for choosing the enzymes and the reagents. Overall, this work shows that existing enzymes can be readily adapted for catalysis of synthetically important reactions not previously observed in nature.

Earth-abundant materials for solar hydrogen generation

A critical challenge for the 21st century is shifting from the predominant use of fossil fuels to renewables for energy. Among many options, sunlight is the only single renewable resource with sufficient abundance to replace most or all of our current fossil energy use. However, existing photovoltaic and solar thermal technologies cannot be scaled infinitely due to the temporal and geographic intermittency of sunlight. Therefore efficient and inexpensive methods for storage of solar energy in a dense medium are needed in order to greatly increase utilization of the sun as a primary resource. For this purpose we have proposed an artificial photosynthetic system consisting of semiconductors, electrocatalysts, and polymer membranes to carry out photoelectrochemical water splitting as a method for solar fuel generation.

This dissertation describes efforts over the last five years to develop critical semiconductor and catalyst components for efficient and scalable photoelectrochemical hydrogen evolution, one of the half reactions for water splitting. We identified and developed Ni–Mo alloy and Ni₂P nanoparticles as promising earth-abundant electrocatalysts for hydrogen evolution. We thoroughly characterized Ni–Mo alloys alongside Ni and Pt catalysts deposited onto planar and structured Si light absorbers for solar hydrogen generation. We sought to address several key challenges that emerged in the use of non-noble catalysts for solar fuels generation, resulting in the synthesis and characterization of Ni–Mo nanopowder for use in a new photocathode device architecture. To address the mismatch in stability between non-noble metal alloys and Si absorbers, we also synthesized and characterized p-type WSe₂ as a candidate light absorber alternative to Si that is stable under acidic and alkaline conditions.

Ab initio study of anharmonicity in high pressure Cmca-4 metallic hydrogen

Hydrogen is the only atom for which the Schr odinger equation is solvable. Consisting only of a proton and an electron, hydrogen is the lightest element and, nevertheless, is far from being simple. Under ambient conditions, it forms diatomic molecules H2 in gas phase, but di erent temperature and pressures lead to a complex phase diagram, which is not completely known yet. Solid hydrogen was rst documented in 1899 [1] and was found to be isolating. At higher pressures, however, hydrogen can be metallized. In 1935 Wigner and Huntington predicted that the metallization pressure would be 25 GPa [2], where molecules would disociate to form a monoatomic metal, as alkali metals that lie below hydrogen in the periodic table. The prediction of the metallization pressure turned out to be wrong: metallic hydrogen has not been found yet, even under a pressure as high as 320 GPa. Nevertheless, extrapolations based on optical measurements suggest that a metallic phase may be attained at 450 GPa [3]. The interest of material scientist in metallic hydrogen can be attributed, at least to a great extent, to Ashcroft, who in 1968 suggested that such a system could be a hightemperature superconductor [4]. The temperature at which this material would exhibit a transition from a superconducting to a non-superconducting state (Tc) was estimated to be around room temperature. The implications of such a statement are very interesting in the eld of astrophysics: in planets that contain a big quantity of hydrogen and whose temperature is below Tc, superconducting hydrogen may be found, specially at the center, where the gravitational pressure is high. This might be the case of Jupiter, whose proportion of hydrogen is about 90%. There are also speculations suggesting that the high magnetic eld of Jupiter is due to persistent currents related to the superconducting phase [5]. Metallization and superconductivity of hydrogen has puzzled scientists for decades, and the community is trying to answer several questions. For instance, what is the structure of hydrogen at very high pressures? Or a more general one: what is the maximum Tc a phonon-mediated superconductor can have [6]? A great experimental e ort has been carried out pursuing metallic hydrogen and trying to answer the questions above; however, the characterization of solid phases of hydrogen is a hard task. Achieving the high pressures needed to get the sought phases requires advanced technologies. Diamond anvil cells (DAC) are commonly used devices. These devices consist of two diamonds with a tip of small area; for this reason, when a force is applied, the pressure exerted is very big. This pressure is uniaxial, but it can be turned into hydrostatic pressure using transmitting media. Nowadays, this method makes it possible to reach pressures higher than 300 GPa, but even at this pressure hydrogen does not show metallic properties. A recently developed technique that is an improvement of DAC can reach pressures as high as 600 GPa [7], so it is a promising step forward in high pressure physics. Another drawback is that the electronic density of the structures is so low that X-ray di raction patterns have low resolution. For these reasons, ab initio studies are an important source of knowledge in this eld, within their limitations. When treating hydrogen, there are many subtleties in the calculations: as the atoms are so light, the ions forming the crystalline lattice have signi cant displacements even when temperatures are very low, and even at T=0 K, due to Heisenberg's uncertainty principle. Thus, the energy corresponding to this zero-point (ZP) motion is signi cant and has to be included in an accurate determination of the most stable phase. This has been done including ZP vibrational energies within the harmonic approximation for a range of pressures and at T=0 K, giving rise to a series of structures that are stable in their respective pressure ranges [8]. Very recently, a treatment of the phases of hydrogen that includes anharmonicity in ZP energies has suggested that relative stability of the phases may change with respect to the calculations within the harmonic approximation [9]. Many of the proposed structures for solid hydrogen have been investigated. Particularly, the Cmca-4 structure, which was found to be the stable one from 385-490 GPa [8], is metallic. Calculations for this structure, within the harmonic approximation for the ionic motion, predict a Tc up to 242 K at 450 GPa [10]. Nonetheless, due to the big ionic displacements, the harmonic approximation may not su ce to describe correctly the system. The aim of this work is to apply a recently developed method to treat anharmonicity, the stochastic self-consistent harmonic approximation (SSCHA) [11], to Cmca-4 metallic hydrogen. This way, we will be able to study the e ects of anharmonicity in the phonon spectrum and to try to understand the changes it may provoque in the value of Tc. The work is structured as follows. First we present the theoretical basis of the calculations: Density Functional Theory (DFT) for the electronic calculations, phonons in the harmonic approximation and the SSCHA. Then we apply these methods to Cmca-4 hydrogen and we discuss the results obtained. In the last chapter we draw some conclusions and propose possible future work.

Non-catalytic multi-fuel reformer for syngas production for fuel cell applications

Rich combustion of n-heptane, diesel oil, jet A-1 kerosene, and bio-diesel (rapeseed-oil methyl ester) were studied to produce hydrogen enriched gas, ready for the cleanup stages for fuel cell applications. n-heptane was successfully reformed up to an equivalence ratio of 3:1, reaching a conversion efficiency up to 83% for a packed bed of alumina bead burner. Diesel, kerosene and bio-diesel were reformed to synthesis gas with conversion efficiency up to 65%. At equivalence ratio of 2:1 and P=7 kw, stability, low HC formation, high conversion efficiency, and low soot emission were achieved. A common synthesis gas composition around this condition was 15 and 13% H2, 15 and 17% CO, and 4 and 4.5% CO2 for n-heptane and diesel, jet A-1 and bio-diesel, respectively, for burner A. This is an abstract of a paper presented at the 2010 Spring National Meeting (San Antonio, TX 3/21-25/2010).

A 5-step reduced mechanism for combustion of CO/H2/H2O/CH4/CO2 mixtures with low hydrogen/methane and high H2O content

In this study a 5-step reduced chemical kinetic mechanism involving nine species is developed for combustion of Blast Furnace Gas (BFG), a multi-component fuel containing CO/H2/CH4/CO2, typically with low hydrogen, methane and high water fractions, for conditions relevant for stationary gas-turbine combustion. This reduced mechanism is obtained from a 49-reaction skeletal mechanism which is a modified subset of GRI Mech 3.0. The skeletal and reduced mechanisms are validated for laminar flame speeds, ignition delay times and flame structure with available experimental data, and using computational results with a comprehensive set of elementary reactions. Overall, both the skeletal and reduced mechanisms show a very good agreement over a wide range of pressure, reactant temperature and fuel mixture composition. © 2012 The Combustion Institute..

Magneto-Optical Imaging of Superconductors for Liquid Hydrogen Applications

Restricted deposits of fossil fuels and ecological problems created by their extensive use require a transition to renewable energy resources and clean fuel free from emissions of CO2. This fuel is likely to be liquid hydrogen. An important feature of liquid hydrogen is that it allows wide use of superconductivity. Superconductors provide compactness, high efficiency, savings in energy and a range of new applications not possible with other materials. The benefits of superconductivity justify use of low temperatures and facilitate development of fossil-free energy economy. The widespread use of superconductors requires a simple and reliable technique to monitor their properties. Magneto-optical imaging (MOI) is currently the only direct technique allowing visualization of the superconducting properties of materials. We report the application of this technique to key superconducting materials suitable for the hydrogen economy: MgB2 and high temperature superconductors (HTS) in bulk and thin-film form. The study shows that the MOI technique is well suited to the study of these materials. It demonstrates the advantage of HTS at liquid hydrogen temperatures and emphasizes the benefits of MgB2, in particular. © 2012 Springer Science+Business Media New York.

Light water breeding with nitride fuel

This scoping study proposes using mixed nitride fuel in Pu-based high conversion LWR designs in order to increase the breeding ratio. The higher density fuel reduces the hydrogen-to-heavy metal ratio in the reactor which results in a harder spectrum in which breeding is more effective. A Resource-renewable Boiling Water Reactor (RBWR) assembly was modeled in MCNP to demonstrate this effect in a typical high conversion LWR design. It was determined that changing the fuel from (U,TRU)O2 to (U,TRU)N in the assembly can increase its fissile inventory ratio (fissile Pu mass divided by initial fissile Pu mass) from 1.04 to up to 1.17. © 2011 Elsevier Ltd. All rights reserved.

Transition films from amporphous to microcrystalline silicon and solar cells

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasmaenhanced chemical vapor deposition (VHF-PECVD)from a mixture of SiH4 diluted in H-2. The effect of hydrogen dilution ratios R = [H-2]/[SiH4] on the microstructure of the films was investigated. The photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that the diphasic films gain both the fine photoelectric properties like a-Si: H and high stability like mu w-Si:H. By using the diphasic silicon films as the intrinsic layer, p-i-n junction solar cells were prepared. Current-voltage (J-V) characteristics and stability of the solar cells were measured under an AM1.5 solar simulator. We observed a light-induced increase of 5.2% in the open-circuit voltage (V-oc) and a light-induced degradation of similar to 2.9% inefficiency.

Impact of hydrogen dilution on microstructure and optoelectronic properties of silicon films deposited using tirisilane

We explored the deposition of hydrogenated amorphous silicon (a-Si: H) using trisilane (Si3H8) as a gas precursor in a radiofrequency plasma enhanced chemical vapour deposition process and studied the suitability of this material for photovoltaic applications. The impact of hydrogen dilution on the deposition rate and microstructure of the films is systematically examined. Materials deposited using trisilane are compared with that using disilane (Si2H6). It is found that when using Si3H8 as the gas precursor the deposition rate increases by a factor of similar to 1.5 for the same hydrogen dilution (R = [H-2]/[Si3H8] or [H-2]/[Si2H6])- Moreover, the structural transition from amorphous to nanocrystalline occurs at a higher hydrogen dilution level for Si3H8 and the transition is more gradual as compared with Si2H6 deposited films. Single-junction n-i-p a-Si: H solar cells were prepared with intrinsic layers deposited using Si3H8 or Si2H6. The dependence of open circuit voltage (V-oc) on hydrogen dilution was investigated. V-oc greater than 1 V can be obtained when the i-layers are deposited at a hydrogen dilution of 180 and 100 using Si3H8 and Si2H6, respectively.

Light-induced changes in diphasic nanocrystalline silicon films and solar cells

A series of diphasic nanocrystalline silicon films and solar cells was prepared using different hydrogen dilution ratios of silane by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). It was observed that after light soaking the open circuit voltage (V-oc) of the diphasic solar cells increased, while that of amorphous silicon solar cells decreased. Raman scattering spectroscopy was performed on the series of diphasic silicon films before and after light soaking. It was found that after light soaking the nanostruclures in the diphasic nanocrystalline silicon films were changed. Both the grain sizes and grain volume fraction reduced, while the grain boundary components increased. These results provide experimental evidence for the conjecture that the light-induced increase in V-oc of the diphasic nanocrystalline solar cells might be induced by the changes in the nanostructure of the intrinsic layer. (c) 2006 Elsevier B.V. All rights reserved.

Heterojunction solar cells with n-type nanocrystalline silicon emitters on p-type c-Si wafers

Hydrogenated nanocrystalline silicon (nc-Si:H) n-layers have been used to prepare heterojunction solar cells on flat p-type crystalline silicon (c-Si) wafers. The nc-Si:H n-layers were deposited by radio-frequency (RF) plasma enhanced chemical vapor deposition (PECVD), and characterized using Raman spectroscopy, optical transmittance and activation energy of dark-conductivity. The nc-Si:H n-layers obtained comprise fine grained nanocrystallites embedded in amorphous matrix, which have a wider bandgap and a smaller activation energy. Heterojunction solar cells incorporated with the nc-Si n-layer were fabricated using configuration of Ag (100 nm)/1T0 (80 nm)/n-nc-Si:H (15 nm)/buffer a-Si:H/p-c-Si (300 mu m)/Al (200 nm), where a very thin intrinsic a-Si:H buffer layer was used to passivate the p-c-Si surface, followed by a hydrogen plasma treatment prior to the deposition of the thin nanocrystalline layer. The results show that heterojunction solar cells subjected to these surface treatments exhibit a remarkable increase in the efficiency, up to 14.1% on an area of 2.43 cm(2). (c) 2006 Elsevier B.V. All rights reserved.

Light-induced changes in diphasic nanocrystalline silicon films and solar cells

A series of diphasic nanocrystalline silicon films and solar cells was prepared using different hydrogen dilution ratios of silane by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). It was observed that after light soaking the open circuit voltage (V-oc) of the diphasic solar cells increased, while that of amorphous silicon solar cells decreased. Raman scattering spectroscopy was performed on the series of diphasic silicon films before and after light soaking. It was found that after light soaking the nanostruclures in the diphasic nanocrystalline silicon films were changed. Both the grain sizes and grain volume fraction reduced, while the grain boundary components increased. These results provide experimental evidence for the conjecture that the light-induced increase in V-oc of the diphasic nanocrystalline solar cells might be induced by the changes in the nanostructure of the intrinsic layer. (c) 2006 Elsevier B.V. All rights reserved.