ELECTROLYTIC PRODUCTION OF OXYGEN AND REDUCTION OF CARBON DIOXIDE.
Electrolytic production of oxygen and reduction of carbon dioxide
ELECTROLYSIS↗
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ELECTROLYTIC PRODUCTION OF OXYGEN AND REDUCTION OF CARBON DIOXIDE.
Electrolytic production of oxygen and reduction of carbon dioxide
OXYGEN↗
Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction
An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO 2 RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO 2 RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH 4 ) current density of -421.63 mA/cm 2 and a CH 4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W 2 C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO 2 to produce CH 4 in a 700-h process under one sun illumination with a CO 2 RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO 2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Projecting the Performance of a Continuous Bosch Carbon Dioxide Reduction System
Kinetic studies using a subscale reactor were used to develop power-law rate equations for the two primary reactions contributing to the Bosch carbon dioxide reduction process: the reverse water-gas shift reaction and the carbon monoxide hydrogenation reaction. An alloy catalyst in bead form was used in these studies, which investigated both the dependence on gas composition and the dependence on time as the beads gradually disintegrate during carbon formation. Bead disintegration impacts both the rates and the relative activities of the two primary reactions. Although the kinetic testing was conducted in a single-pass mode, the target Bosch application requires operation in a recycle mode to achieve high conversion. Further, the proposed design concept for a full-scale carbon dioxide reduction system would allow carbon to be removed continuously in contrast to previous Bosch processes that required replacement of expendable catalyst cartridges. The developed power-law kinetic rate equations were used in conjunction with a reactor model to project the operating conditions, performance, and sizing of a continuous Bosch system.
carbon dioxide reduction↗
Regional Carbon Emission Reduction Prediction via Retrofits of Commercial Buildings with a Case Study of US School Buildings in Hot Climates
Retrofitting commercial buildings has great potential to reduce carbon emissions as demonstrated by previous studies in some specific cities, but their regional carbon emission reduction potential is still unknown. Thus, we develop a method to predict the long-term regional carbon emission reduction potential by retrofitting commercial buildings. School buildings in hot climate zones in the continental U.S. are selected as an example. The results show that the aggregated carbon emission reduction potential of school buildings in that region reduces from 3.33 to 2.01 megatons from 2024 to 2050 due to the increased penetration of renewable energy.
building energy simulation↗
Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties
Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sabatier Carbon Dioxide Reduction Assembly Development for Closed Loop Water Recovery
The Sabatier Carbon Dioxide Reduction System (CRA) offers water recovery on a long duration space mission to reduce water resupply. Currently, NASA Johnson Space Center (JSC), NASA Marshall Space Flight Center (MSFC), Hamilton Sundstrand Space Systems International, Inc. (HSSSI), and Southwest Research Institute (SWRI) are working together to develop a Sabatier CRA for the International Space Station (ISS). This effort is being funded by the Office of Biological and Physical Research (Code U)/Advanced Life Support program which is administered by NASA JSC. The Sabatier CRA is the next step in closing the oxygen life support loop on future space missions. The Sabatier reaction combines the waste carbon dioxide (recovered from crew metabolism) with waste hydrogen (a byproduct of electrolysis to produce oxygen) to produce water and methane (CH4). On ISS, the methane would be vented overboard, however the methane can be utilized for propulsion during a planetary exploration mission. Based on a crew size of 7-equivalent people, the Sabatier CRA can produce as much a 2000 lb/year water. Use of the Sabatier CRA will significantly reduce the amount of water that needs to be resupplied to the ISS on a yearly basis, at a tremendous cost saving to the program. Additionally, by recycling this additional water, the Sabatier CRA enables additional launch capacity for science experiments to be brought up to the ISS. The NASA/Industry team noted above has been working to reduce technical risks associated with the Sabatier CRA system. To date the technical risks have been considerably reduced, bringing the Technology Readiness Level (TRL) from TRL 4 to TRL 5/6. In doing so, the team has developed the system schematic, system models, control scheme, produced engineering development unit (EDU) hardware, performed limited integration testing of the EDU's and verified system modeling through testing. Additionally, the system schematic has been evaluated for failure modes and hazards and had a successful technical review by the NASA Safety Board. The current focus is now related to development of the water/methane phase separator, liquid sensor and CO2 compressor piston seal life. The overall goal of the current effort is to bring the system up to a TRL6 by the end of GFY04. Although the Sabatier CRA is not currently baselined for use on the ISS, its benefits are significant enough such that volume within the Oxygen Generation System rack has been reserved for future installation. The value of the water the CRA recover will allow NASA the additional crew time and payload needed to pursue its mission of scientific research.
Smith, Frederick↗
A carbon dioxide reduction unit using Bosch reaction and expendable catalyst cartridges
Catalytic carbon dioxide reduction cartridge for oxygen recovery in life support systems of long term manned space flights
Holmes, R. F.↗
Methane Post-Processor Development to Increase Oxygen Recovery beyond State-of-the-Art Carbon Dioxide Reduction Technology
State‐of‐the‐art life support carbon dioxide (CO2) reduction technology, based on the Sabatier reaction, is theoretically capable of 50% recovery of oxygen from metabolic CO2. This recovery is constrained by the limited availability of reactant hydrogen. Post‐processing of the methane byproduct from the Sabatier reactor results in hydrogen recycle and a subsequent increase in oxygen recovery. For this purpose, a Methane Post‐Processor Assembly containing three sub‐systems has been developed and tested. The assembly includes a Methane Purification Assembly (MePA) to remove residual CO2 and water vapor from the Sabatier product stream, a Plasma Pyrolysis Assembly (PPA) to partially pyrolyze methane into hydrogen and acetylene, and an Acetylene Separation Assembly (ASepA) to purify the hydrogen product for recycle. The results of partially integrated testing of the sub‐systems are reported.
Abney, Morgan↗
Synthesis of Ethylene and Other Useful Products by Reduction of Carbon Dioxide
The synthesis of ethylene and other useful products by reduction of carbon dioxide is discussed. The synthesis of ethylene from carbon dioxide has been undertaken. A few different chemical reactions are presented for the production of ethylene. This ethylene can then form the basis for the manufacture of a variety of useful products. It can be used in the preparation of a variety of plastics that can be used for the fabrication of structural materials, and can be used in creating life support systems, which can lead to the development of closed life support systems based on the use of inorganic processes and chemical engineering principles.
Sanders D. Rosenberg↗
Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?
Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard properties of organic sulfur gases. However, a number of the properties for aqueous organic sulfur compounds have not been experimentally determined. Furthermore, most of thermodynamic data that are available are for 25 C and 1 bar. In order to determine reaction properties to temperatures and pressures appropriate to the hydrothermal conditions in which thermophilic organisms actually live, we use equations of state developed by Helgeson and co-workers (Helgeson et al., 1981, AJS 281, 1249). A key piece of information needed to go up in temperature is the partial molal heat capacity, which is one of the properties for which experimental data are unavailable for nearly all organic sulfur compounds. We have used correlation methods to determine the partial molal heat capacities and volumes of many organic solutes. These estimates allow us to asses the role of organic sulfur compounds during the reduction of carbon in hydrothermal settings. We will present these data, along with examples of the thermodynamic properties of reactions involving aqueous organic sulfur compounds.
Schulte, Mitchell↗
Methane Post-Processor Development to Increase Oxygen Recovery beyond State-of-the-Art Carbon Dioxide Reduction Technology
State-of‐the‐art life support carbon dioxide (CO2) reduction technology, based on the Sabatier reaction, is theoretically capable of 50% recovery of oxygen from metabolic CO2. This recovery is constrained by the limited availability of reactant hydrogen. Post‐processing of the methane byproduct from the Sabatier reactor results in hydrogen recycle and a subsequent increase in oxygen recovery. For this purpose, a Methane Post‐Processor Assembly containing three sub‐systems has been developed and tested. The assembly includes a Methane Purification Assembly (MePA) to remove residual CO2 and water vapor from the Sabatier product stream, a Plasma Pyrolysis Assembly (PPA) to partially pyrolyze methane into hydrogen and acetylene, and an Acetylene Separation Assembly (ASepA) to purify the hydrogen product for recycle. The results of partially integrated testing of the sub‐systems are reported
Abney, Morgan B.↗
Assessing the sequestration time scales of some ocean-based carbon dioxide reduction strategies
Abstract Ocean-based carbon dioxide (CO 2 ) removal (CDR) strategies are an important part of the portfolio of approaches needed to achieve negative greenhouse gas emissions. Many ocean-based CDR strategies rely on injecting CO 2 or organic carbon (that will eventually become CO 2 ) into the ocean interior, or enhancing the ocean’s biological pump. These approaches will not result in permanent sequestration, because ocean currents will eventually return the injected CO 2 back to the surface, where it will be brought into equilibrium with the atmosphere. Here, a model of steady state global ocean circulation and mixing is used to assess the time scales over which CO 2 injected in the ocean interior remains sequestered from the atmosphere. There will be a distribution of sequestration times for any single discharge location due to the infinite number of pathways connecting a location at depth with the sea surface. The resulting probability distribution is highly skewed with a long tail of very long transit times, making mean sequestration times much longer than typical time scales. Deeper discharge locations will sequester purposefully injected CO 2 much longer than shallower ones and median sequestration times are typically decades to centuries, and approach 1000 years in the deep North Pacific. Large differences in sequestration times occur both within and between the major ocean basins, with the Pacific and Indian basins generally having longer sequestration times than the Atlantic and Southern Oceans. Assessments made over a 50 year time horizon illustrates that most of the injected carbon will be retained for injection depths greater than 1000 m, with several geographic exceptions such as the Western North Atlantic. Ocean CDR strategies that increase upper ocean ecosystem productivity with the goal of exporting more carbon to depth will have mainly a short-term influence on atmospheric CO 2 levels because ∼70% will be transported back to the surface ocean within 50 years. The results presented here will help plan appropriate ocean CDR strategies that can help limit climate damage caused by fossil fuel CO 2 emissions.
54 ENVIRONMENTAL SCIENCES↗
Rotary Drum Separator and Pump for the Sabatier Carbon Dioxide Reduction System
A trade study conducted in 2001 selected a rotary disk separator as the best candidate to meet the requirements for an International Space Station (ISS) Carbon Dioxide Reduction Assembly (CRA). The selected technology must provide micro-gravity gasfliquid separation and pump the liquid from 10 psia at the gasfliquid interface to 18 psia at the wastewater bus storage tank. The rotary disk concept, which has pedigree in other systems currently being built for installation on the ISS, failed to achieve the required pumping head within the allotted power. The separator discussed in this paper is a new design that was tested to determine compliance with performance requirements in the CRA. The drum separator and pump @SP) design is similar to the Oxygen Generator Assembly (OGA) Rotary Separator Accumulator (RSA) in that it has a rotating assembly inside a stationary housing driven by a integral internal motor. The innovation of the DSP is the drum shaped rotating assembly that acts as the accumulator and also pumps the liquid at much less power than its predecessors. In the CRA application, the separator will rotate at slow speed while accumulating water. Once full, the separator will increase speed to generate sufficient head to pump the water to the wastewater bus. A proof-of- concept (POC) separator has been designed, fabricated and tested to assess the separation efficiency and pumping head of the design. This proof-of-concept item was flown aboard the KC135 to evaluate the effectiveness of the separator in a microgravity environment. This separator design has exceeded all of the performance requirements. The next step in the separator development is to integrate it into the Sabatier Carbon Dioxide Reduction System. This will be done with the Sabatier Engineering Development Unit at the Johnson Space Center.
Holder, Don↗
Carbon dioxide reduction electro catalysts prepared for metal organic frameworks
A pyrolyzed MOF catalyst for in the carbon dioxide reduction reaction and methods of making the catalyst. The catalysts are composed of highly porous transition metal organic frameworks exhibiting large pores with regular distribution of transition metals within the structure.
Liu, Di-Jia↗
Evaluation of Rail Decarbonization Alternatives: Framework and Application
The Northwestern University Freight Rail Infrastructure & Energy Network Decarbonization (NUFRIEND) framework is a comprehensive industry-oriented tool for simulating the deployment of new energy technologies including biofuels, e-fuels, battery-electric, and hydrogen locomotives. By classifying fuel types into two categories based on deployment requirements, the associated optimal charging/fueling facility location and sizing problem are solved with a five-step framework. Life-cycle analysis (LCA) and techno-economic analysis (TEA) are used to estimate carbon reduction, capital investments, cost of carbon reduction, and operational impacts, enabling sensitivity analysis with operational and technological parameters. Here, the framework is illustrated on lower-carbon drop-in fuels as well as battery-electric technology deployments for the US Eastern and Western Class I railroad networks. Drop-in fuel deployments are modeled as admixtures with diesel in existing locomotives, while battery-electric deployments are shown for varying technology penetration levels and locomotive ranges. When mixed in a 50% ratio with diesel, results show biodiesel’s capacity to reduce emissions at 36% with a cost of $\$$ 0.13 per kilogram of CO 2 reduced, while e-fuels offer a potential reduction of 50% of emissions at a cost of $\$$ 0.22 per kilogram of CO 2 reduced. Battery-electric results for 50% deployment over all ton-miles highlight the value of future innovations in battery energy densities as scenarios assuming 800-mi range locomotives show an estimated emissions reduction of 46% with a cost of $\$$ 0.06 per kilogram of CO 2 reduced, compared with 16% emissions reduction at a cost of $\$$ 0.11 per kilogram of CO 2 reduced for 400-mi range locomotives. The NUFRIEND framework provides a systematic method for comparing different alternative energy technologies and identifying potential challenges and benefits in their future deployments.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
Vapor–Fed Electrolyzers for Carbon Dioxide Reduction Using Tandem Electrocatalysts: Cuprous Oxide Coupled with Nickel–Coordinated Nitrogen–Doped Carbon
We report ethylene is particularly attractive due to its major importance as a feedstock for various applications including the polymer industry. As such, catalyst and electrolyzer developments are crucial to achieve industrially relevant ethylene production and efficiency levels. In this work, a tandem electrocatalyst composed of copper nanocubes and nickel-coordinated nitrogen-doped carbon (NiNC) is presented, which is integrated into gas diffusion electrodes (GDEs) for direct conversion of vapor-fed CO 2 into ethylene. Evaluation of tandem GDEs in the vapor-fed flow electrolyzer shows significantly increased ethylene selectivity in terms of faradaic efficiency and C 2 H 4 /CO ratio compared to a non-tandem copper GDE. The enhancements are attributed to the increased local CO availability near the copper surface via effective CO 2 to CO conversion on neighboring NiNC. The experimental results are validated by 3D resolved continuum simulations, which show increased flux of higher-order prod-ucts with the added CO flux from NiNC. The practical viability of Cu/NiNC catalyst is further evaluated in a membrane electrode assembly electrolyzer, achieving 40% FE toward ethylene at 150 mA cm -2 and 3.2 V. These find-ings highlight the high selectivity and formation rate of ethylene achieved by successful device integration of the Cu/NiNC catalyst, demonstrating the potential for implementation in large-scale sustainable CO 2 electrolyzers.
36 MATERIALS SCIENCE↗
Carbon Dioxide Reduction Post-Processing Sub-System Development
The state-of-the-art Carbon Dioxide (CO2) Reduction Assembly (CRA) on the International Space Station (ISS) facilitates the recovery of oxygen from metabolic CO2. The CRA utilizes the Sabatier process to produce water with methane as a byproduct. The methane is currently vented overboard as a waste product. Because the CRA relies on hydrogen for oxygen recovery, the loss of methane ultimately results in a loss of oxygen. For missions beyond low earth orbit, it will prove essential to maximize oxygen recovery. For this purpose, NASA is exploring an integrated post-processor system to recover hydrogen from CRA methane. The post-processor, called a Plasma Pyrolysis Assembly (PPA) partially pyrolyzes methane to recover hydrogen with acetylene as a byproduct. In-flight operation of post-processor will require a Methane Purification Assembly (MePA) and an Acetylene Separation Assembly (ASepA). Recent efforts have focused on the design, fabrication, and testing of these components. The results and conclusions of these efforts will be discussed as well as future plans.
Abney, Morgan B.↗