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At least 19 records

Carbon Utilization: Electrochemical Approach Using Novel Catalyst and System Integration

The environmental footprint from power generation can be mitigated by capturing emitted carbon dioxide (CO2) and converting it to value-added fuel sources. A multitude of different fuels can be produced from CO2 depending on the chemical reaction catalysts. Typically, these pathways can be developed electrochemically, or through hydrogenation. In recent years the electrochemical reduction of CO2 has grown exponentially, as it has shown potential to decrease atmospheric pollution and provide an additional means of on-demand electricity storage. Formic acid (FA) in particular has industrial applications such as in fuel cells or as a hydrogen storage medium, and requires a lower thermodynamic energy input than any other fuel produced for electrochemical CO2 reduction. However, product selectivity remains a challenge for conventional electrocatalysts, making FA production efficiencies above 50% difficult. To address the challenge of catalytic selectivity, UK CAER employs enzymatic catalysts to facilitate the FA production and minimize unwanted byproducts. Our process couples the catalyst with a charge mediator which is necessary to shuttle electrons, and an electrolyte pH buffer to prevent the catalyst from degrading. Presently, production efficiencies have approached 60% at a rate of over 10 mM FA/hour. System design considerations (flow rate, bulk volume) will also be discussed.

01 COAL, LIGNITE, AND PEAT↗

Integration of Concentrating Solar Power with High Temperature Electrolysis for Hydrogen Production: Preprint

Hydrogen (H2) has been identified as a leading sustainable contender to replace fossil fuels in transportation and electricity generation. H2 production can be achieved by concentrating solar thermal power (CSP) systems collecting thermal energy from the sun to various chemical processes for fuel production. Fuel production via solar thermal chemical processes integrated with CSP uses the full spectrum of sunlight compared with photovoltaic power conversion and stores solar energy directly and efficiently [1]. The solar fuel production can be realized by thermochemical processes (e.g., water splitting for H2 production, carbon dioxide reduction, or methane reforming) or thermal electrochemical methods (e.g., integration with solid oxide electrolysis cell). Technology development for CSP-integrated solar fuel production requires broad technological bases from solar energy collection to chemical energy conversion. H2 generated from renewable sources can be an energy carrier for a carbon-free economy. Integrating CSP with high temperature electrolysis (HTE) using solid oxide electrolysis cells (SOEC) provides a renewable path for H2 generation. The CSP-HTE integration approach provides the benefit of thermal energy storage (TES) for continuous operation, improved capacity, and SOEC life. H2 gas has low energy density for transportation, pipeline networks are expensive, and H2 liquefaction is energy intensive. However, an alternative method for H2 distribution is to use carbon dioxide (CO2) capture and liquid hydrocarbon synthesis to convert solar energy into liquid fuels that are compatible with the existing fossil fuel infrastructure.

concentrating solar thermal power↗

Molecular-Level Overhaul of y-Aminopropyl Aminosilicone/Triethylene Glycol Post-Combustion CO2-Capture Solvents

Capturing carbon dioxide (CO2) from post-combustion gas streams is an energy-intensive process that is required prior to either converting or sequestering CO2. There are a few commercial offerings of 1st and 2nd generation aqueous amine technologies, however the cost of capturing CO2 with these technologies remains high. To decrease costs of capture, researchers are designing efficient solvent systems with the goal of being drop-in replacements for 1st and 2nd generation infrastructure. One approach has seen the development of water-lean solvents that aim to increase efficiency by reducing the water content in solution. Water-lean solvents such as GE’s GAP/TEG are promising technologies, with potential to halve the parasitic load to a coal-fired power plant, only if the intrinsically high solution viscosities and hydrolysis of the siloxane moieties could be mitigated. We present here, an integrated multidisciplinary approach to overhaul the GAP/TEG solvent system at the molecular level to mitigate hydrolysis while also reducing viscosity. We present molecular-level insights into chemical speciation of CO2-containing ions, showing that co-solvents and diluents have a negligible effect on reducing viscosity and are not needed. This finding allowed for the design of singlecomponent siloxane-free diamine derivatives with site-specific incorporation of selective chemical moieties for direct placement and orientation of hydrogen bonding to reduce viscosity. Ultimately, we present new single-component diamine formulations less susceptible to hydrolysis that exhibit up to a 98% reduction in viscosity compared to the initial GAP/TEG formulation.

Cantu Cantu, David↗

A Novel Process for Carbon Dioxide Conversion to Fuel

In this project, TDA developed a new mixed metal oxide-based sorbent that converts CO2 (captured from coal fired power plants) to CO, which can then be combined with renewable H2 generated by water electrolysis or H2 from steam methane reforming to produce different liquid fuels. TDA’s absorbent-based CO2 conversion process uses a redox process, which splits the catalytic reforming of methane with CO2 reaction into two stages: CO2 reduction to CO and CH4 reforming into H2 and CO which eliminates the equilibrium limitations. The CO produced in the two-stage reactor system can then be further reacted with renewable H2 to produce methanol, naphtha, diesel, or gasoline. We worked with the Advanced Power & Energy Program (APEP) of University of California, Irvine (UCI) to design and develop the liquid fuel synthesis process that is built around this new material. We demonstrated the techno-economic viability of the new sorbent based redox process to convert CO2 into synthesis gas by demonstrating continuous carbon dioxide reduction in a prototype test system for over 585 hours while converting up to 10 kg CO2/day. With the successful completion of the R&D effort, the technology is now ready for a larger pilot-scale demonstration and the technology readiness has been raised from TRL 3 to TRL 5. In collaboration with UCI, we completed a high-fidelity process design and economic analysis. The required sale price (RSP) for gasoline (Case 1 NG-MTG) is $4.91/gal and naphtha and diesel (Case 2 NG-FT) are $4.23/gal and $6.07/gal, respectively, on a 2011 dollar basis. To put these costs in perspective, the California prices in current dollars (with its strict specifications) for regular grade gasoline from last year to current year have varied from a low of $3.10/gal in January 2021 to a high of $5.76/gal in March 2022, while prices for diesel from last year to current year have varied from a low of $3.40/gal in January 2021 to a high of $6.41/gal in May 2022 according to the U.S. Energy Information Agency data. It should be noted that the gasoline and diesel produced by these designs of Case 1 and Case 2 would be of very high quality and both nitrogen and sulfur free. These RSPs are based on a cost of imported electricity of $64/MWh based on the low-end current wind generated electricity cost (Genevieve 2011). This cost is by far the largest component of the variable costs used in computing the RSPs. A sensitivity analysis of these RSPs to the cost of imported electricity shows that the cost of the imported electricity has a significant effect on the RSPs. The life cycle analysis (LCA) shows that the total cradle-to-gate CO2 emissions for both liquid fuels (diesel and gasoline) were negative, indicating that overall more CO2 is consumed than released during production of the fuel from CO2 feed stack for both cases (-296 kgCO2 per MT gasoline for Case 1 and -705 kgCO2 per MT diesel for Case 2). On a cradle-to-grave comparison, the use of diesel produced using TDA’s process (2,457 kgCO2 per MT diesel) would release 37.6% less CO2 compared to petroleum based diesel (3,937 kgCO2 per MT diesel) while the use of gasoline produced using TDA’s process (2,792 kgCO2 per MT gasoline) would release 29.3% less CO2 compared to petroleum based gasoline (3,946 kgCO2 per MT gasoline). With the successful completion of the R&D effort, the technology is now ready for a bench-scale demonstration and the technology readiness has been raised from TRL 3 (Analytical and experimental critical function and/or characteristic proof of concept) to TRL 5 (Laboratory scale similar system validation in relevant environment).

20 FOSSIL-FUELED POWER PLANTS↗

A Model of Large Scale Electrochemical Direct Ocean Capture Under Variable Power

Since limiting warming to 1.5 degrees C by 2100 will not only require an energy transition but also billions of tons of carbon dioxide (CO2) removal per year, it is essential to expand these efforts. This can be done offshore via electrochemical direct ocean capture (eChem DOC) which extracts CO2 from seawater that can later be stored underground or converted to products. Deployments of eChem DOC will be powered by renewable energy and therefore need to function with variable power inputs. This project aims to support future large-scale deployments by developing a model of eChem DOC operation, informed by industry and literature, and assessing its performance under variable power and varying designs. Initial analysis suggests that discretizing the eChem system has a higher impact on increasing overall capture than storing the chemical solutions to continue capture during periods of lower power availability, but this is likely situation dependent. Future work will use more realistic power profiles.

direct ocean capture↗

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Ru/Al2O3 Catlayst↗

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Catlayst↗

Engineering Enzymes for Environmental Sustainability

The development and implementation of more efficient and sustainable technologies is key to delivering our net–zero targets. Here we review how engineered enzymes, with a focus on those developed using directed evolution, can be deployed to improve the sustainability of numerous processes and help to conserve our environment. Efficient and robust biocatalysts have been engineered to capture carbon dioxide (CO2) and have been embedded into new efficient metabolic CO2 fixation pathways. Enzymes have been refined for bioremediation, enhancing their ability to degrade toxic and harmful pollutants. Biocatalytic recycling is gaining momentum, with engineered cutinases and PETases developed for the depolymerization of the abundant plastic, PET. Finally, biocatalytic approaches for accessing petroleum–based feedstocks and chemicals are expanding, using optimized enzymes to convert plant biomass into biofuels or other high value products. Finally, through these examples, we hope to illustrate how enzyme engineering and biocatalysis can contribute to the development of more environmentally sustainable approaches, in order to protect our planet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Depolarized Electro-Membrane System (EDEMS) for Direct Capture of Carbon Dioxide from Ambient Air (Final Report)

The goal of this final project report is to summarize the work conducted on project DE-FE0031962. In accordance with the Statement of Project Objectives (SOPO), the University of Kentucky Center for Applied Energy Research (UK CAER) (Recipient) developed an intensified process to capture CO2 from ambient conditions (400 ppm CO2). The process combines low-temperature solvent-aided membrane capture with electrochemically-mediated solvent regeneration to simultaneously capture ambient CO2 while regenerating the solvent. The technology employs only two primary units (regenerator and absorber/contactor) while generating high purity hydrogen as a co-product that can be sold, used for energy storage, or cost-saving depolarization of the direct air capture (DAC) system during the grid peak demand, allowing for flexible operation. When depolarization is employed, the operating voltage is reduced by more than 1 V. Since the technology is powered directly by DC electricity, it can seamlessly tie in with power sources like solar cells without the need for AC/DC converters, therefore allowing for a remote operation to further mitigate greenhouse gas generation toward deploying a negative carbon emissions technology that is completely decoupled from the carbon emissions from the power source for the DAC unit. The project results verified that UK CAER’s integrated approach addressed the complexities of incumbent DAC systems by demonstrating at ambient conditions, including (1) low gas-side pressure-drop facile CO2 capture via a membrane contactor with in-situ generated hydroxide as capture solvent, (2) multi-functional electrochemical regenerator for hydroxide regeneration, CO2 concentration and hydrogen production, and (3) depolarization using cathode-produced hydrogen to reduce energy requirement. The EH&S Assessment of the process did not identify any obvious concern for the bench-scale operation and no apparent barriers to implementing UK CAER’s carbon capture and solvent regeneration system at a larger scale.

20 FOSSIL-FUELED POWER PLANTS↗

Carbon Dioxide Conversion to Nanomaterials: Methods, Applications, and Challenges

Anthropogenic carbon dioxide (CO 2 ) emission is one of the biggest global threats that we are confronted with in the 21st century. A lack of prompt action to mitigate the atmospheric CO 2 level could lead to global catastrophic events. As a result of the significance of the aforementioned threat, multiple nations have agreed to enact carbon capture, storage, utilization, and sequestration (CCUS) technologies at academic and industrial scales with the aim of lowering the atmospheric CO 2 level. Although there are many reviews on CCUS technologies, there is a lack of comprehensive review on CO 2 conversion to more economically valuable products, such as nanomaterials. Carbon dioxide capture and conversion into nanomaterials is an interesting research topic in many ways because it contributes to our fundamental knowledge of material conversion, provides alternative ways to reduce atmospheric pollution, and yields lucrative products, which has not been explored broadly. Aside from the positive outcomes, we have a moral obligation to rectify a global threat caused by anthropogenic emission. Herein, we present current methods of converting CO 2 into organic and inorganic nanomaterials with a focus on operating conditions and challenges as well as the potential of nanomaterials in specifically biomedical applications as opposed to extensively reviewed energy-related uses. Furthermore, our review emphasizes the toxicity issues related to using such nanomaterials in biological settings based on literature and other comparable studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods and systems for the electrochemical reduction of carbon dioxide using switchable polarity materials

A method of electrochemically reducing CO2 comprises introducing a first feed stream comprising H2O to a positive electrode of an electrolysis cell comprising the positive electrode, a negative electrode, and a proton conducting membrane. A second feed stream comprising a solvent and a non polar form of a switchable polarity material is directed into a CO2 capture apparatus. A third feed stream comprising CO2 is directed into the CO2 capture apparatus to interact with the second feed stream and form a first product stream comprising the solvent and a polar form of the switchable polarity material. The first product stream is introduced to the negative electrode. A potential difference is applied between the positive electrode and the negative electrode to convert the polar form of the switchable polarity material into CO2 and the non-polar form and to form products from the CO2 and the solvent. A CO2 treatment system is also described.

Lister, Tedd E.↗

Carbon Management Projects (CONNECT) Database and Explorer

Overview The Carbon Management Projects (CONNECT) Toolkit is an online exploratory visualization tool developed by the U.S. Department of Energy's (DOE) Office of Fossil Energy and Carbon Management (FECM) with support from other federal agencies such as the U.S. Environmental Protection Agency (EPA) and the U.S. Department of Transportation (DOT). It provides a single point of access to authoritative information on federal agency investment in a portfolio of research, development, and demonstration (RD&D) projects that have been publicly announced to advance technologies for point source carbon capture, carbon dioxide removal, transport, storage, and conversion, collectively referred to as carbon management. The RD&D programs covered in this tool are authorized by annual congressional appropriations ("Base Program") and the 2021 Infrastructure Investment and Jobs Act (IIJA). The tool also incorporates public information on other federal initiatives, such as the Regional Clean Hydrogen Hubs, and public information released by other government agencies, such as the Environmental Protection Agency's (EPA) and Primacy States’ Underground Injection Control Class VI permits and EPA’s facility level greenhouse gas (GHG) emissions. Developed in a geographic information system, the tool organizes carbon management projects into five groups based on the primary technology that a project aims to advance, each visually represented as a digital layer ("carbon management project layer"). Only federally funded projects are included, which can be awarded projects that are completed or ongoing, or projects that have been selected but are currently under negotiation. Project information can be viewed in the map or in the attribute table below it when turned on. In the map view, each project is displayed at either its host site (for field work), where available, or its performer site (project lead's location, further explained in the table below). Host sites and performer sites are represented in distinct icons. Several reference layers offer additional public information on infrastructural and natural resource environment for carbon management. These reference layers, combined with multiple geographical basemaps, enable users to visualize the carbon management project layers in context. Carbon management project information will be updated monthly based on feedback and information availability. Carbon management project layers Point Source Carbon Capture (PSC) This layer contains DOE-funded projects focused on capturing carbon dioxide (CO2) from power plants or industrial facilities. Carbon Dioxide Removal (CDR) This layer contains DOE-funded projects focused on capturing CO2 from the atmosphere, including direct air capture (DAC) and DAC hubs, direct ocean capture, enhanced mineralization, and biomass carbon removal and storage. For projects with multiple host sites, each of the sites are displayed individually with the project cost and cost sharing information representing the total for the entire project. Carbon Transport This layer contains DOE- and DOT-funded projects focused on CO2 transport. The Transport Research and Development sublayer contains projects that do not involve physical infrastructure; the Proposed Transport Corridor sublayer contains projects for which either a route for the transport infrastructure has been proposed or a general area for the transport infrastructure has been identified. Carbon Storage This layer contains DOE-funded key projects focused on CO2 storage. For projects with multiple field-work sites, each of the sites are displayed individually on the map with the project cost and cost sharing information representing the overall total for the entire project. Carbon Conversion This layer contains DOE-funded projects focused on converting CO2 into economically valuable products. Reference layers The following layers provide additional information in the geographic proximity of carbon management projects. Users should reference the original sources for more details (weblinks provided below and in pop-up windows on the map). Regional Clean Hydrogen Hub and Facility These layers illustrate the approximate areas of the Regional Clean Hydrogen Hubs announced by DOE's Office of Clean Energy Demonstrations (OCED) and the approximate locations of individual facilities that constitute the hubs (see "Where are the H2Hubs located?" on the webpage linked above). EPA Facility Level GHG Emissions (direct emitter) This layer shows direct CO2 emissions from stationary sources in 2022, using data extracted from EPA's Facility Level Information on GreenHouse gases Tool (FLIGHT). Captured and injected CO2 are not deducted from direct emitters’ total emissions. Contact EPA for additional details. Underground Injection Control Class VI permit/permit application This layer shows the locations of CO2 injection wells that are granted or in the process of applying for an Underground Injection Control Class VI permit by EPA or a Primacy State (currently Louisiana, North Dakota, and Wyoming). The URLs for the permits or permit applications are provided in the pop-up windows associated with the well locations. Contact EPA for additional details. Carbon Storage Resource This layer contains information on prospective CO2 storage resources in saline formations and oil and gas reservoirs provided by the National Carbon Sequestration Database and Geographic Information System (NATCARB) spatial database. Contact NETL for additional details. Existing CO2 pipeline This layer shows active CO2 pipelines based on information digitized from the map issued by the Pipeline and Hazardous Materials Safety Administration (PHMSA). Contact PHMSA for additional details.

Carbon Conversion↗

Summary Report of the Reactive CO 2 Capture: Process Integration for the New Carbon Economy Workshop, February 18-19, 2020

This report provides a summary of feedback from the “Reactive CO 2 Capture: Process Integration for the New Carbon Economy” workshop held February 18-19, 2020. The focus of this workshop was to discuss approaches for merging carbon dioxide (CO 2 ) capture and CO 2 conversion/utilization systems into an integrated "reactive capture" strategy. By the workshop’s definition, reactive capture (RC) of CO 2 is the coupled process of capturing CO 2 from a mixed gas stream and converting it into a valuable product without going through a purified CO 2 intermediate. Participants were able to identify four key themes and associated calls to action for the reactive capture community: (1) essential role of partnerships; (2) critical challenges; (3) defining the value proposition; and (4) approach to support technological advancement.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

The status and prospects of materials for carbon capture technologies

In order to combat climate change, carbon dioxide (CO 2 ) emissions from industry, transportation, buildings, and other sources need to be captured and long-term stored. Decarbonization of these sources requires special types of materials that have high affinities for CO 2 . Potassium hydroxide is a benchmark aqueous sorbent that reacts with CO 2 to convert it into K 2 CO 3 and subsequently precipitated as CaCO 3 . Another class of carbon capture materials is solid sorbents that are usually functionalized with amines or have natural affinities for CO 2 . The next wave of materials for carbon capture under investigation includes activated carbon, metal–organic frameworks, zeolites, carbon nanotubes, and ionic liquids. In this issue of MRS Bulletin, some of these materials are highlighted, including solvents and sorbents, membranes, ionic liquids, and hydrides. Other materials that can capture CO2 from low concentrations of gas streams, such as air (direct air capture) are also discussed. Also covered in this issue are machine learning-based computer algorithms developed with the goal to speed up the progress of carbon capture materials development, and to design advanced materials with high CO 2 capacity, improved capture and release kinetics, and improved cyclic durability.

36 MATERIALS SCIENCE↗

A Novel Framework to Evaluate the Costs and Potential of Bioenergy in Decarbonization of the U.S. Economy

The long-term strategy of the United States targets reaching economy-wide net-zero emissions by 2050 and a carbon-neutral electricity grid by 2035 (U.S. Department of State and U.S. Executive Office of the President, 2021). Meeting these targets would require considerable changes to the energy system. Some key characteristics of illustrative net-zero energy systems include increased penetration of renewable energy and carbon sources, use of CO2 capture and storage (CCS) in hard-to-abate sectors, and a greater role for energy carriers such as electricity and hydrogen (Davis et al, 2018). Another common feature of such energy systems is the need for carbon dioxide removal (CDR) approaches (Horowitz et al, 2022). Across all these characteristics of net-zero energy systems, bioenergy and biomass feedstock is anticipated to play an important role. Biomass feedstock serves as a renewable carbon source. This can enable conversion of such feedstock into fuels and energy carriers for hard-to-abate sectors such as aviation. Indeed, the U.S. Government has a target to meet all jet fuel demand by 2050 from sustainable aviation fuel (SAF), where biofuel pathways are likely to have an important role (EERE, 2020). Bioenergy is also highly versatile with the possibility to convert feedstock into electricity, hydrogen, liquid fuels, heat or high-value products, based on biomass type, demand and technology availability (Clarke et al, 2022). Combination of bioenergy with CCS can also nominally deliver CDR (Fuhrman et al, 2023). As such, the share of bioenergy is expected to grow by at least five time across scenarios studied for the long-term strategy of the U.S. between 2020 and 2050 (Horowitz et al, 2022). Notwithstanding the role of bioenergy in the energy systems, its deployment, costs and scalability are influenced by a number of factors. Some of these factors pertain to policy interventions such as imposition of a binding decarbonization target either at an economy-wide level or the sectoral level. Resource availability and type of biomass feedstock also varies considerably across regions. From a technological perspective, the readiness of bioenergy conversion pathways is subject to high variability. This influences the costs of deployment. Moreover, the sourcing of feedstock, grid carbon intensity, and co-product handling approaches all affect the life cycle efficacy of bioenergy. The latter, in turn, is particularly important in determining the extent to which bioenergy with CCS or BECCS can effectively deliver CDR (Fajardy and Mac Dowell, 2017).

air emission↗

The Role of Alkalis in Orchestrating Uranyl-Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, in this work, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb + and Cs + salts (Cs-U 1 and Rb-U 1 ). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li + , Na + and K + analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U 1 , the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO 2 in the solid-state, converting to Cs 4 [U VI O 2 (CO 3 ) 3 ], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U 1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsU V O 3 , where the parent phase has been computationally predicted, but not yet synthesized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Synthetic Natural Gas Production from Direct Air Capture Using Titania-Based Dual Function Materials

Converting atmospheric CO2 into methane offers a compelling pathway to store intermittent renewable electricity and enhance energy security using existing natural gas infrastructure. However, current CO2 utilization approaches remain energy- and capital-intensive, largely due to the need for separate capture, purification, and conversion steps. Integrating CO2 capture with catalytic methanation represents a transformative strategy for process intensification on both the unit operation and molecular levels. We report a series of Ru-Na/TiO2 dual function materials (DFMs) for a reactive carbon capture (RCC) process consisting of simulated direct air capture and subsequent CO2 methanation (DACM). Superior methane desorption purity was observed on TiO2-based DFMs (>94 %) relative to state-of-the-art Al2O3-supported DFMs (77 %). Modifying the process to begin CO2 adsorption immediately following the methanation stage, rather than beginning adsorption near ambient temperature, resulted in >97 % methane desorption purity, suitable for injection into the natural gas pipeline without additional CO2 separation steps.

organic↗