Matching Items (19)

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CO2 Reduction via Functionalized Protein/Organometallic Complexes

Description

As prices for fuel along with the demand for renewable resources grow, it becomes of paramount importance to develop new ways of obtaining the energy needed to carry out the tasks we face daily. Costs of production due to energy

As prices for fuel along with the demand for renewable resources grow, it becomes of paramount importance to develop new ways of obtaining the energy needed to carry out the tasks we face daily. Costs of production due to energy and time constraints impose severe limitations on what is viable. Biological systems, on the other hand, are innately efficient both in terms of time and energy by handling tasks at the molecular level. Utilizing this efficiency is at the core of this research. Proper manipulation of even common proteins can render complexes functionalized for specific tasks. In this case, the coupling of a rhenium-based organometallic ligand to a modified myoglobin containing a zinc porphyrin, allow for efficient reduction of carbon dioxide, resulting in energy that can be harnessed and byproducts which can be used for further processing. Additionally, a rhenium based ligand functionalized via biotin is tested in conjunction with streptavidin and ruthenium-bipyridine.

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2014-12

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Carbonate-ceramic dual-phase membranes for high temperature carbon dioxide separation

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Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation

Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.

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2011

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Synthesis and stability of ceramic-carbonate dual-phase membrane for carbon dioxide separation

Description

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.

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2013

Is carbon sequestration "good" for the environment?: an evaluation based on current technology and methods

Description

Carbon capture and sequestration (CCS) is one of the important mitigation options for climate change. Numerous technologies to capture carbon dioxide (CO2) are in development but currently, capture using amines is the predominant technology. When the flue gas reacts with

Carbon capture and sequestration (CCS) is one of the important mitigation options for climate change. Numerous technologies to capture carbon dioxide (CO2) are in development but currently, capture using amines is the predominant technology. When the flue gas reacts with amines (Monoethanaloamine) the CO2 is absorbed into the solution and forms an intermediate product which then releases CO2 at higher temperature. The high temperature necessary to strip CO2 is provided by steam extracted from the powerplant thus reducing the net output of the powerplant by 25% to 35%. The reduction in electricity output for the same input of coal increases the emissions factor of Nitrogen Oxides, Mercury, Particulate matter, Ammonia, Volatile organic compounds for the same unit of electricity produced. The thesis questions if this tradeoff between CO2 and other emissions is beneficial or not. Three different methodologies, Life Cycle Assessment, Valuation models and cost benefit analysis are used to identify if there is a net benefit to the society on implementation of CCS to a Pulverized coal powerplant. These methodologies include the benefits due to reduction of CO2 and the disbenefits due to the increase of other emissions. The life cycle assessment using ecoindicator'99 methodology shows the CCS is not beneficial under Hierarchical and Egalitarian perspective. The valuation model shows that the inclusion of the other emissions reduces the benefit associated with CCS. For a lower CO2 price the valuation model shows that CCS is detrimental to the environment. The cost benefit analysis shows that a CO2 price of at least $80/tCO2 is required for the cost benefit ratio to be 1. The methodology integrates Montecarlo simulation to characterize the uncertainties associated with the valuation models.

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2012

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A density functional theory study of CO2 interaction with brookite TiO2

Description

Over the past years, an interest has arisen in resolving two major issues: increased carbon dioxide (CO2) emissions and depleting energy resources. A convenient solution would be a process that could simultaneously use CO2 while producing energy. The photocatalytic reduction

Over the past years, an interest has arisen in resolving two major issues: increased carbon dioxide (CO2) emissions and depleting energy resources. A convenient solution would be a process that could simultaneously use CO2 while producing energy. The photocatalytic reduction of CO2 to fuels over the photocatalyst titanium dioxide (TiO2) is such a process. However, this process is presently inefficient and unsuitable for industrial applications. A step toward making this process more effective is to alter TiO2 based photocatalysts to improve their activity. The interactions of CO2 with oxygen-deficient and unmodified (210) surfaces of brookite TiO2 were studied using first-principle calculations on cluster systems. Charge and spin density analyses were implemented to determine if charge transfer to the CO2 molecule occurred and whether this charge transfer was comparable to that seen with the oxygen-deficient and unmodified anatase TiO2 (101) surfaces. Although the unmodified brookite (210) surface provided energetically similar CO2 interactions as compared to the unmodified anatase (101) surface, the unmodified brookite surface had negligible charge transfer to the CO2 molecule. This result suggests that unmodified brookite is not a suitable catalyst for the reduction of CO2. However, the results also suggest that modification of the brookite surface through the creation of oxygen vacancies may lead to enhancements in CO2 reduction. The computational results were supported with laboratory data for CO2 interaction with perfect brookite and oxygen-deficient brookite. The laboratory data, generated using diffuse reflectance Fourier transform infrared spectroscopy, confirms the presence of CO2- on only the oxygen-deficient brookite. Additional computational work was performed on I-doped anatase (101) and I-doped brookite (210) surface clusters. Adsorption energies and charge and spin density analyses were performed and the results compared. While charge and spin density analyses showed minute charge transfer to CO2, the calculated adsorption energies demonstrated an increased affinity for CO2adsorption onto the I-doped brookite surface. Gathering the results from all calculations, the computational work on oxygen-deficient, I-doped, and unmodified anatase and brookite surface structures suggest that brookite TiO2 is a potential photocatalysts for CO2 photoreduction.

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2012

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Examining a sustainable approach to global climate change policy

Description

The United Nation's Framework Convention on Climate Change (UNFCCC) recognizes development as a priority for carbon dioxide (CO2) allocation, under its principle of "common but differentiated responsibilities". This was codified in the Kyoto Protocol, which exempt developing nations from binding

The United Nation's Framework Convention on Climate Change (UNFCCC) recognizes development as a priority for carbon dioxide (CO2) allocation, under its principle of "common but differentiated responsibilities". This was codified in the Kyoto Protocol, which exempt developing nations from binding emission reduction targets. Additionally, they could be the recipients of financed sustainable development projects in exchange for emission reduction credits that the developed nations could use to comply with emission targets. Due to ineffective results, post-Kyoto policy discussions indicate a transition towards mitigation commitments from major developed and developing emitters, likely supplemented by market-based mechanisms to reduce mitigation costs. Although the likelihood of achieving substantial emission reductions is increased by the new plan, there is a paucity of consideration to how an ethic of development might be advanced. Therefore, this research empirically investigates the role that CO2 plays in advancing human development (in terms of the Human Development Index or HDI) over the 1990 to 2010 time period. Based on empirical evidence, a theoretical CO2-development framework is established, which provides a basis for designing a novel policy proposal that integrates mitigation efforts with human development objectives. Empirical evidence confirms that CO2 and HDI are highly correlated, but that there are diminishing returns to HDI as per capita CO2 emissions increase. An examination of development pathways reveals that as nations develop, their trajectories generally become less coupled with CO2. Moreover, the developing countries with the greatest gains in HDI are also nations that have, or are in the process of moving toward, outward-oriented trade policies that involve increased domestic capabilities for product manufacture and export. With these findings in mind, future emission targets should reduce current emissions in developed nations and allow room for HDI growth in developing countries as well as in the least developed nations of the world. Emission trading should also be limited to nations with similar HDI levels to protect less-developed nations from unfair competition for capacity building resources. Lastly, developed countries should be incentivized to invest in joint production ventures within the LDCs to build capacity for self-reliant and sustainable development over the long-term.

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Date Created
2013

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Energy and carbon dioxide impacts from lean logistics and retailing systems: a discrete-event simulation approach for the consumer goods industry

Description

Consumer goods supply chains have gradually incorporated lean manufacturing principles to identify and reduce non-value-added activities. Companies implementing lean practices have experienced improvements in cost, quality, and demand responsiveness. However certain elements of these practices, especially those related to transportation

Consumer goods supply chains have gradually incorporated lean manufacturing principles to identify and reduce non-value-added activities. Companies implementing lean practices have experienced improvements in cost, quality, and demand responsiveness. However certain elements of these practices, especially those related to transportation and distribution may have detrimental impact on the environment. This study asks: What impact do current best practices in lean logistics and retailing have on environmental performance? The research hypothesis of this dissertation establishes that lean distribution of durable and consumable goods can result in an increased amount of carbon dioxide emissions, leading to climate change and natural resource depletion impacts, while lean retailing operations can reduce carbon emissions. Distribution and retailing phases of the life cycle are characterized in a two-echelon supply chain discrete-event simulation modeled after current operations from leading organizations based in the U.S. Southwest. By conducting an overview of critical sustainability issues and their relationship with consumer products, it is possible to address the environmental implications of lean logistics and retailing operations. Provided the waste reduction nature from lean manufacturing, four lean best practices are examined in detail in order to formulate specific research propositions. These propositions are integrated into an experimental design linking annual carbon dioxide equivalent emissions to: (1) shipment frequency between supply chain partners, (2) proximity between decoupling point of products and final customers, (3) inventory turns at the warehousing level, and (4) degree of supplier integration. All propositions are tested through the use of the simulation model. Results confirmed the four research propositions. Furthermore, they suggest synergy between product shipment frequency among supply chain partners and product management due to lean retailing practices. In addition, the study confirms prior research speculations about the potential carbon intensity from transportation operations subject to lean principles.

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2011

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Synthesis of amine-modified aerogel sorbents and metal-organic framework-5 (MOF-5) membranes for carbon dioxide separation

Description

Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified

Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects.

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Date Created
2010

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Towards biohybrid artificial photosynthesis

Description

A vast amount of energy emanates from the sun, and at the distance of Earth, approximately 172,500 TW reaches the atmosphere. Of that, 80,600 TW reaches the surface with 15,600 TW falling on land. Photosynthesis converts 156 TW in the

A vast amount of energy emanates from the sun, and at the distance of Earth, approximately 172,500 TW reaches the atmosphere. Of that, 80,600 TW reaches the surface with 15,600 TW falling on land. Photosynthesis converts 156 TW in the form of biomass, which represents all food/fuel for the biosphere with about 20 TW of the total product used by humans. Additionally, our society uses approximately 20 more TW of energy from ancient photosynthetic products i.e. fossil fuels. In order to mitigate climate problems, the carbon dioxide must be removed from the human energy usage by replacement or recycling as an energy carrier. Proposals have been made to process biomass into biofuels; this work demonstrates that current efficiencies of natural photosynthesis are inadequate for this purpose, the effects of fossil fuel replacement with biofuels is ecologically irresponsible, and new technologies are required to operate at sufficient efficiencies to utilize artificial solar-to-fuels systems. Herein a hybrid bioderived self-assembling hydrogen-evolving nanoparticle consisting of photosystem I (PSI) and platinum nanoclusters is demonstrated to operate with an overall efficiency of 6%, which exceeds that of land plants by more than an order of magnitude. The system was limited by the rate of electron donation to photooxidized PSI. Further work investigated the interactions of natural donor acceptor pairs of cytochrome c6 and PSI for the thermophilic cyanobacteria Thermosynechococcus elogantus BP1 and the red alga Galderia sulphuraria. The cyanobacterial system is typified by collisional control while the algal system demonstrates a population of prebound PSI-cytochrome c6 complexes with faster electron transfer rates. Combining the stability of cyanobacterial PSI and kinetics of the algal PSI:cytochrome would result in more efficient solar-to-fuel conversion. A second priority is the replacement of platinum with chemically abundant catalysts. In this work, protein scaffolds are employed using host-guest strategies to increase the stability of proton reduction catalysts and enhance the turnover number without the oxygen sensitivity of hydrogenases. Finally, design of unnatural electron transfer proteins are explored and may introduce a bioorthogonal method of introducing alternative electron transfer pathways in vitro or in vivo in the case of engineered photosynthetic organisms.

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Date Created
2014

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Synthesis and carbon dioxide adsorption properties of amine modified particulate silica aerogel sorbents

Description

Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including

Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including metal organic frameworks, zeolites, and carbon based materials. One particular group of capable materials are amine based solid sorbents that has shown to possess high adsorption capacities and favorable adsorption kinetics. A key variable in the synthesis of an amine based sorbent is the support which acts as the platform for the amine modification. Aerogels, due to their high porosities and surface areas, appear to be a promising support for an amine modified CO2 sorbent. Therefore, in order to develop a commercially viable CO2 sorbent, particulate aerogels manufactured by Cabot Corporation through an economical and proprietary ambient drying process were modified with amines using a variety of functionalization methods. Two methods of physical impregnation of the amino polymer TEPA were performed in order to observe the performance as well as understand the effects of how the TEPA distribution is affected by the method of introduction. Both samples showed excellent adsorption capacities but poor cyclic stability for lack of any covalent attachment. Furthermore the method of TEPA impregnation seems to be independent on how the polymer will be distributed in the pore space of aerogel. The last two methods utilized involved covalently attaching amino silanes to the surface silanols of the aerogel. One method was performed in the liquid phase under anhydrous and hydrous conditions. The materials developed through the hydrous method have much greater adsorption capacities relative to the anhydrous sample as a result of the greater amine content present in the hydrous sample. Water is another source of silylation where additional silanes can attach and polymerize. These samples also possessed stable cyclic stability after 100 adsorption/regeneration cycles. The other method of grafting was performed in the gas phase through ALD. These samples possessed exceptionally high amine efficiencies and levels of N content without damaging the microstructure of the aerogel in contrast to the liquid phase grafted sorbents.

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Date Created
2014