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At least 1,081 records · Page 60

Powering OSCAR

Recycling waste has been an issue on Earth for decades. The OSCAR project seeks to find ways to make sure that it does not become an issue in space. The main focus of OSCAR is the combustion of waste and reclamation of gaseous products in microgravity. The first phase of testing relies on a ground rig that operates both under normal (Earth) gravity and in drop tower tests that briefly simulate a microgravity environment. In the second phase, a test will be performed during a suborbital flight were the experiment will be carried out in microgravity. Throughout the spring term, interns have played an integral part in continuing the progress made by the project. They performed work in upgrading the electrical and mechanical systems that make up OSCAR. They made multiple improvements to the test rig's operating software to improve readability and usability. They prepared and edited documents that were vital to the engineering process. And, they were responsible for performing lab tests and refining the lab operations document and procedure. The interns were a big help in maintaining the rigorous test schedule. OSCAR, which stands for Orbital Syngas Commodity Augmentation Reactor, is to find a way to turn astronaut waste into chemical energy. The two parts of this are important: finding a way to dispose of waste generated in space, and seeing if there is a way to recycle that waste into chemical energy. The importance of the disposal aspect is that there is currently no way to dispose of, or recycle, waste that is created in space other than jettisoning it (which is what the ISS does via empty supply capsules). As manned missions go deeper into space, that method will no longer be viable, as a craft would essentially be littering the space and planets that they visit. Energy reclamation is also important because of the high monetary and spatial costs of sending supplies on space missions. Every little bit extra that can be reused out of what is sent can save room and funds for other supplies. The facet of this problem that the OSCAR project is focusing on is how to combust waste in zero gravity. Combustion in the presence of gravity is one of those things that is taken for granted. When something burns on Earth, the flames rise above the fuel as oxygen flows from underneath. In microgravity, the flames surround the object completely, which restricts the amount of oxygen that can reach the fuel, and retards the combustion. OSCAR uses a vortex reaction chamber to counter this phenomenon. The OSCAR test rig will eventually be tested on a suborbital flight to see if it is an effective solution to the issue in real-world conditions. Currently, there is a prototype test rig that is fully functional. This rig has been previously tested in a 2 second drop test at Glenn Research Center’s (GRC) Zero Gravity Facility (ZGF). (The free-fall conditions of the drop mimic microgravity, if only for a brief period of time). This session’s focus was on upgrading the test rig and software, updating the paperwork, performing additional lab tests, and readying the rig for the five second drop test, again at GRC. II. Upgrades The state of the testing rig at the start of the session was in between its configurations for the two second drop tower and the five second drop tower. The rig needed upgrades to address various insufficiencies that either were discovered during the two second campaign or were a direct result of the differences between the two drop tower setups. The main differences that had to be handled were the increase in shock loads from 30g to 65g, a difference in drop indicating signal (on the falling edge of a pulse instead of a change from high to low), and the ambient pressure of the test apparatus (the two second tower dropped the rig in atmosphere, while the five second tower drops in vacuum).

Cauvel, Thomas↗

Cryobotics: Extreme Cold Environment Testing

The extreme cold environment test chamber was designed to conduct research in cryobotics; an area of study that focuses on robotic systems and rotating machinery operating in extreme cold environments including Earth, low Earth orbit, Mars, Moon, asteroids, Solar orbit, planetary orbit, or those encountered during travel among these destinations. The test chamber incorporates a modular dynamometer, consisting of a variety of brakes, torque sensors and motors to be easily interchanged between tests. Each test employs a unique test profile that incorporates different setpoints of applied torques and velocities for a given period or number of revolutions. The modularity of the dynamometer setup allows for any combination of motor, gearbox to be tested. The chamber has been used to run tests for various projects including Bulk Metallic Glass Gears (BMGG), Volatiles Investigating Polar Exploration Rover (VIPER), Intelligent Payload Experiment (IPEX), and Pilot Excavator. Various upgrades have been made to the extreme cold environment test chamber for the use of cryobotic research. These upgrades greatly increased the autonomous capabilities of the test set up by providing redundancies in the hardware and software. The redundancies were primarily added to protect the integrity of the cryohead. A new strapping and insulation method was performed to create the thermal conductive path from the actuators to the cryohead. The software was upgraded to include temperature setpoint control, further increasing the autonomous capabilities of the test. This paper goes into detail regarding the upgrades made to the extreme cold environment test chamber, as well as highlights the results from a COLDArm acceptance test.

Jonathan Drew Smith↗

Experimental Capabilities and Achievements of the Space Environment Dynamometer (SED)

The Space Environment Dynamometer (SED) chamber was designed to conduct research in cryobotics; an area of study that focuses on robotic systems and rotating machinery operating in extreme cold environments including Earth, low Earth orbit, Mars, Moon, asteroids, Solar orbit, planetary orbit, or those encountered during travel among these destinations. The test chamber incorporates a modular dynamometer, consisting of a variety of brakes, torque sensors and motors to be easily interchanged between tests. Each test employs a unique test profile that incorporates different setpoints of applied torques and velocities for a given period or number of rev- olutions. The modularity of the dynamometer setup allows for any combination of motor, gearbox to be tested. This chamber is one of a kind and resides at the Swamp Works facility within the Granular Mechanics and Regolith Operations laboratory (GMRO) at NASA Kennedy Space Center. Other cold chambers exist, however they are project specific and do not simultaneously output real time torque, temperature and efficiency data. The modularity of this extreme cold environment test chamber, coupled with the custom software and instrumentation, makes it one of a kind. The chamber is capable of stabilizing cryogenic temperatures and pressures to commensurate moon environments. Tests have successfully been conducted on motors and gearboxes for various cryogenic temperature set points, torques, and angular velocities. Relevant internal temperatures of the test article and chamber were recorded using a variety of temperature sensors. The temperature setpoints, on the motors and gearboxes tested, were stabilized by using PID gain scheduling of the PWM signal for the various heaters. The heat removal for the motor was provided by creating a thermally conductive path from a cryohead directly to the test article using copper straps. A variety of strainwave gears (SWGs), also known as Harmonic drives, planetary gear systems and DC motor actuator configurations have been tested in the chamber. The experiments performed were for various projects including Bulk Metallic Glass Gears (BMGG), Volatiles Investigating Polar Exploration Rover (VIPER), In-Situ Resource Utilization Pilot Excavator (IPEX) . Various upgrades have been made to the extreme cold environment test chamber for the use of cryobotic research. These upgrades greatly increased the autonomous capabilities of the test set up by providing redundancies in the hardware and software. The redundancies were primarily added to protect the integrity of the cryohead. A new strapping and insulation method was performed to create the thermal conductive path from the actuators to the cryohead. The software was upgraded to include temperature setpoint control, further increasing the autonomous capabilities of the test. This paper goes into detail regarding the upgrades made to the extreme cold environment test chamber, as well as highlights the results from a COLDArm acceptance test.

Casey J. Clark↗

Modernizing the SNS Control System

The Spallation Neutron Source at Oak Ridge National Laboratory has been operating since 2006. An upgrade to double the machine power from 1.4 MW to 2.8 MW is currently underway and a project to add a second target station is in the preliminary design phase. While each project will add the controls needed for their specific scope, the existing control system hardware, software, and infrastructure require upgrades to maintain high availability and ensure the system will meet facility requirements into the future. While some systems have received new hardware due to obsolescence, much of the system is original apart from some maintenance and technology refresh. Software will also become obsolete and must be upgraded for sustainability. Further, requirements for system capacity can be expected to increase as more subsystems upgrade to smarter devices capable of higher data rates. This paper covers planned improvements to the integrated control system with a focus on reliability, sustainability, and future capability.

White, Karen S.↗

Systems and methods for producing fuel intermediates

The present disclosure relates to a method that includes pyrolyzing a biomass to produce a pyrolysis oil and upgrading the pyrolysis oil to yield a first upgraded pyrolysis oil, where the pyrolysis oil is in at least one of a liquid phase and/or a vapor phase, the pyrolyzing is performed in a pyrolysis reactor at a first temperature between 400° C. and 600° C., the biomass has a residence time of less than five seconds in the pyrolysis reactor, the upgrading is performed in a fluidized bed reactor, and the upgrading is catalyzed using a zeolite.

09 BIOMASS FUELS↗

Integrated Operations for Nuclear: Work Reduction Opportunity Demonstration Strategy

EXECUTIVE SUMMARY The Light Water Reactor Sustainability Program Plant Modernization Pathway has been working with industry for a number of years to leverage digital technology to extend the life and improve the performance of the existing fleet through modernized technologies and improved processes for plant operation and power generation. This includes development of modernization solutions to improve reliability and economic performance while addressing US nuclear industry’s aging and obsolescence challenges. The objective of these efforts is to deliver a sustainable business model that enables US nuclear industry to remain competitive. Digital Infrastructure (DI) research has established a technical foundation for these efforts. This effort began with technical analysis and support for a safety-related instrumentation and control (I&C) pilot upgrade being performed at Constellation Energy Generation’s Limerick Nuclear Plant. The following publicly available reports were produced as part of this effort. • INL/EXT-20-61079, Vendor-Independent Design Requirements for a Boiling Water Reactor Safety System Upgrade [1] • INL/EXT-20-59371, Business Case Analysis for Digital Safety-Related Instrumentation & Control System Modernizations [2] • INL/EXT-20-59809, “Safety-Related Instrumentation and Control Pilot Upgrade: Initial Scoping Phase Implementation Report and Lessons Learned [3] • INL/RPT-23-72105, Safety-Related Instrumentation and Control Upgrade: Conceptual – Detailed Design Phase Report and Lessons Learned [4]

99 GENERAL AND MISCELLANEOUS↗

Quality Control of Silicon Sensor Modules for Particle Detectors

The High-Luminosity Large Hadron Collider (HL-LHC) will produce a higher rate of particle collisions than the current Large Hadron Collider (LHC), requiring significant upgrades to the Compact Muon Solenoid (CMS) to handle the increased amount of data. An important upgrade is the Phase-2 Outer Tracker Upgrade, which consists of 13,000 silicon sensor modules made of two parallel silicon sensors and readout electronics. These modules undergo careful quality control checks both during and after module assembly to ensure precise and reliable detector performance. This project focuses on precision testing for quality control of silicon sensor modules at Fermilab. Hands-on work includes visual inspection, current-voltage testing, module testing, and ultraviolet (UV) light exposure of modules showing abnormal current-voltage behavior. The ultraviolet exposure process improves the abnormal sensor readout data by placing the selected sensor side of the module directly under the UV light inside a controlled box. In addition to laboratory testing and ultraviolet experiments, I developed a Python-based data tool that connects to a module database and allows selected testing conditions and module information to be retrieved and displayed efficiently. These different testing procedures, experimental processes, and computational tools support the broader goal of identifying module issues and improving modules that will be used in the CMS Outer Tracker Phase-2 Upgrade.

Siddiqui, Hooriya [DuPage Coll.; Fermilab] (ORCID:↗

TRTR NRAD NRS Beamline Abstract

The Neutron Radiography (NRAD) Reactor is a 250kW TRIGA housed under the largest hot cell in the United States, making it the foremost location to perform neutron imaging of irradiated nuclear fuels and materials, including those intended for use with advanced reactors. Currently, NRAD has two radial beamlines that are used for neutron radiography and tomography. Upgrades to the North neutron beamline include the replacement of the in-tank beam chamber, through-the-wall collimator, and neutron shutter. These beamline upgrades will not only improve image quality for current capabilities but will also condition the beam to be more suitable for advanced methods such as neutron powder diffraction. These upgrades will increase the excess reactivity of the core, reduce unnecessary activation and exposure to workers, and significantly reduce the amount of shielding required around the beam. This presentation will describe how these upgrades improve beam quality, increase utilization of the reactor, and reduce radiation exposure to personnel.

21 - SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLAN↗

A Machine Learning Model for Predicting Composition of Catalytic Coprocessing Products from Molecular Beam Mass Spectra

Demand for the development of an automated and integrated refining process for biofuels has increased in recent years due to the lack of generalized process inspection tools. In bio-oil upgrading processes, all process variables are maintained based on the offline specification of intermediates and products. A lack of real-time product specifications in batch-wise monitoring can cause process failure and wasted resources. Therefore, there is a need for a fast and accurate intermediates/product specification tool that can be used for real-time specification to reduce waste and mitigate the risk of process failure. Here, to address this gap, we developed a machine learning (ML) model for predicting speciated bio-oil composition, including paraffin, iso-paraffins, olefins, naphthene, and aromatics. The model is trained using the mass spectra from upgraded products collected in the vapor phase before condensation and predicts the composition of the condensed product. Training ML models using raw mass spectra is challenging due to numerous overlapped peaks originating from different parent compounds. With this in mind, we propose a protocol that (i) transforms raw mass spectra to chemistry-inspired predefined features and (ii) trains decision tree-based models using these features. Our results show that the random forest model was robust against overfitting and had the highest accuracy compared to other models. Moreover, a stochastic ablation method determined the eight most significant features while maximizing the accuracy. Our protocol facilitates real-time compositional analysis of upgraded bio-oils and thus real-time process monitoring. Additionally, this protocol enables the rational design of efficient catalysts and the determination of optimal process conditions.

09 BIOMASS FUELS↗

Report on the deployment of the National Geothermal Data System 2.0

This reports includes a video description of recent upgrades and changes to the National Geothermal Data System (geothermaldata.org) and a text report of its relevant security upgrades. Improvements include a new operating system, implementation of HTTPS, implementation of a standard firewall, PostgreSQL upgrades, an ESRI ArcGIS server, new registration policies, and a non-public API.

15 GEOTHERMAL ENERGY↗

Bioblendstocks to Optimize Mixing Controlled Compression Ignition (MCCI) Engines

In this project, a team of researchers from the University of Massachusetts Lowell, the University of Maine, and Mainstream Engineering developed an integrated process for the product of bioblendstocks to optimize mixing controlled compression ignition (MCCI) engines. The objective was to improve the energy density, sooting propensity, and cetane number of base diesel fuel while maintaining cold weather behavior. The process converts woody biomass (e.g. sawmill residues) into bio-oil through selective fast pyrolysis; the bio-oil is then selectively upgraded to form selectively oxygenated, minimally-branched hydrocarbons using non-noble metal catalysts in combination with metal-catalyzed hydrogenation. Advanced predictive models, in conjunction with existing property databases, and experimental testing are used to evaluate overall bioblendstock properties and their impact on base diesel fuel. An iterative, targeted upgrading approach was implemented to optimize the proposed bioblendstock’s properties. Assessment methodologies included techno-economic analysis, life-cycle assessment, property testing, and engine testing. Ultimately, the project team successfully produced a viable bioblendstock while identifying critical process points related to scale-up efforts. It was found that producing pyrolysis oils at 500 degrees C and with pine particle sizes of 1-2 mm led to bio-oil with a higher yield (of approximately 45 wt%) and rich amounts of aromatic alcohols. The resultant pyrolysis oil was then upgraded using a sequence of mild hydrotreating, followed by catalytic etherification and esterification, followed by another final mild hydrotreating to produce a blendstock containing saturated species with a limited, but non-zero, amount of oxygen. The aromatic alcohols produced by pyrolysis were especially helpful in this regard, as the resulting bicycloethers and derivatives exhibited high cetane numbers. While most bulk properties of the bioblendstock met or exceeded targeted thresholds, viscosity and cloud point notably fell outside the expected range; this could be addressed by blending limits and/or through the use of additives that are commonplace in current refinding practices. Identification of a bioblendstock that can be produced economically at scale while improving the performance and emissions characteristics of internal combustion engines positively affects the economy by boosting domestic fuel production and the environment by decreasing harmful emissions and increasing efficiency.

09 BIOMASS FUELS↗

Community-scale interaction of energy efficiency and demand flexibility in residential buildings

Demand-side management (DSM) strategies, including energy efficiency (EE) and demand flexibility (DF), contribute to cost-effective operation of the electricity grid. From a system-level perspective, such programs reduce costs, enhance reliability, and reduce network issues. Similarly, DSM programs help participating customers reduce utility bills while maintaining occupant comfort. Understanding the relationship between EE and DF is key to realizing the full potential of DSM programs. In this study, we modeled an all-electric residential community based on a 498-home community that is planned for construction in Fort Collins, Colorado in the United States. We used this community model to study the relationship between different EE measures, including building envelope upgrades and smart appliances, and DF enabled by a home energy management system (HEMS) responding to a time-varying tariff. Various EE levels in the homes – code-minimum, zero energy ready, and even higher levels of envelope efficiency – were simulated. DF is enabled by the HEMS, which coordinates behind-the-meter resources, including flexible building loads, PV, and home battery systems, to minimize utility bills while maintaining occupant comfort. When comparing to the code-minimum homes, EE upgrades alone reduce HVAC energy use during peak hours by up to 50% and the HVAC utility bill by up to $312/year. With the addition of HEMS, the average daily peak demand can be reduced by up to 0.58 MW or 1.2 kW/home in the higher envelope efficiency homes. The combination of EE upgrades, HEMS, and home battery systems is expected to save homeowners up to $590/year while increasing community load flexibility. However, HEMS and home battery systems are less effective in increasing the DF in the more efficient homes due to the lower load.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Improving anaerobic digestion of sewage sludge to renewable natural gas by the Advanced Pretreatment & Anaerobic Digestion technology (APAD): Pilot testing

Conventional anaerobic digestion (AD) of sewage sludge in wastewater treatment facilities suffers from low carbon conversion efficiency (CCE = 40%) and requires costly CO2 removal for injection of the produced CH4 into the natural gas grid. To address these limitations, we developed the Advanced Pretreatment and Anaerobic Digestion (APAD) process. This integrates Advanced Wet Oxidation & Steam Explosion (AWOEx) pretreatment of residual sludge after conventional AD, followed by biogas upgradation using a novel methanogenic strain, Methanothermobacter wolfeii BSEL, converting CO2 with H2 into CH4 or RNG (renewable natural gas). Pilot-scale results demonstrated that AWOEx pretreatment achieved a CCE of 62% for the residual sludge, 68% higher than the conventional AD process. The CH4 production was further increased by 79%. Subsequent biogas upgrading in a trickling bed reactor with H2 further enhanced total methane output by 100% and resulted in a final CO2 concentration of =3%. The integrated APAD process achieved a remarkable overall CCE of 83%, resulting in a 200% increase in RNG output when compared to conventional AD. Techno-economic analysis revealed that AWOEx pretreatment alone reduced sludge treatment costs from $494 to $253 per ton of dry solids. The complete APAD process incurred a higher cost of treatment of $530 per ton, driven by prices for bottled H2. The process did, however, show gains in energy recovery and decarbonization. Renewable H2, which may reduce in price in the near future, can positively improve the economics of biogas upgrading for the APAD process.

Life Cycle Assessment (LCA)↗

The impact of behavioral and geographic heterogeneity on residential-sector carbon abatement costs

Analyses of monetary and emissions savings from residential efficiency upgrades usually neglect behavioral differences between consumers. Variations in behavior are frequently large: 13% of the U.S. population sets thermostats for cooling at 20 °C (68 °F) or lower and 15% at 25.5 °C (78 °F) or higher. Efficiency analyses should account for behavioral heterogeneity as well as variations in climate and housing characteristics. We model energy and economic savings of efficiency upgrades for U.S. single-family detached houses, accounting for differences in thermostat settings, climate zone, fuel prices, and home characteristics. We consider five efficiency interventions: wall insulation, attic insulation, air sealing, high-efficiency furnaces, and high-efficiency air conditioners. Energy and economic savings vary widely by consumer; the average net present value for wall insulation is $3,020 United States Dollar (USD), but considering heterogeneity, it has a 10th percentile value of -$231 and 90th percentile value of $5,000. Neglecting heterogeneity, technology upgrades can be prioritized from lower to higher carbon abatement costs: air conditioners, wall insulation, furnace, air sealing, and attic insulation. Accounting for heterogeneity reorders this prioritization, and consumer-specific conditions affect mitigation costs such that technologies are mixed in with one another and are no longer arranged one after another. These results indicate that interventions to improve efficiency should consider differences between consumers.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Nexus of electrification and energy efficiency retrofit of commercial buildings at the district scale

Rapid electrification of buildings at the district scale is needed for cities to achieve climate change mitigation goals. However, most electrification studies focus on either the single building level or the city/region building stock level, and depend on the slow and uncertain process of requesting personally identifiable customer energy usage data from utilities. To answer a key question facing local policymakers: “Where can electrification proceed at scale without first upgrading the grid?” this study aims to quantify and inform building electrification impacts at the district scale using detailed building energy modeling and based on public records datasets. We explore how energy efficiency retrofits can help mitigate increased peak electric demand, and quantify impacts to energy use and carbon emissions. Building energy models of a baseline, and scenarios of simple electrification, energy retrofits, and electrification in combination with retrofits were created and simulated for 54 commercial buildings in two contiguous districts of San Francisco. A simple electrification scenario increased annual electricity consumption but reduced annual site energy usage by 15% to 17%, mainly due to replacing inefficient gas furnaces and boilers with more efficient heat pumps. Peak demand increased 7.4% for Fisherman's Wharf (e.g. within the capacity of the existing power grid), while the Design District showed a marginal decrease. Annual carbon emissions were reduced by 46% and 37%. Combining electrification with efficiency upgrades reduced peak demand by 26% and 40%, and annual carbon emissions by 63% and 64% for the two districts. Furthermore, these results indicate that impacts of electrification depend on the mix of building uses within a district, and coupling electrification with energy efficiency upgrades is an effective strategy to decarbonize buildings while maintaining or reducing the peak electric demand.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Techno-economic assessment of distributed wellhead RO water treatment for nitrate removal and salinity reduction: A field study in small disadvantaged communities

Techno-economic analysis of distributed wellhead water treatment and desalination (DWTD) systems was carried out based on a three-year field study in three small, disadvantaged communities (DACs) to evaluate the reliability and affordability of upgrading their impaired well water. The local water supplies of the three study DACs, located in Salinas Valley, California, were contaminated with nitrate at levels (~ 12–87 mg/L NO$^{-}_{3}$ - N) ) above the California maximum contaminant level (MCL) of 10 mg/L NO$^{-}_{3}$ - N , and had elevated water salinity (~600–1,600 mg/L total dissolved solids(TDS)) above its secondary MCL (SMCL) of 500 mg/L TDS. Well water nitrate removal and salinity reduction were accomplished via reverse osmosis (RO) based DWTD systems that operated autonomously, supported by remote monitoring and supervisory cyberinfrastructure. Reliable DWTD operation provided treated water quality, with respect to nitrate and salinity, in the range of 0.5–6.3 mg/L NO$^{-}_{3}$ - N and 57–161 mg/L TDS, respectively, which were well below the respective MCL and SMCL. The levelized cost of water treatment was in the range of ~$$2/m 3 - $$2.9/m 3 which aligns with typical residential water costs in California and in the study region, and monthly residential water costs (39 dollars-74 dollars/residential unit/month) were also within the range in California. The study showcased the DWTD approach as a viable and potentially scalable solution for upgrading impaired local potable water supply of communities lacking centralized water delivery infrastructure. However, streamlined permitting processes and standardized regulatory frameworks are critical to promoting wider adoption and maximizing the socio-economic benefits of the DWT approach. Moreover, DACs are likely to require government subsidies in order to cover the CapEx of DWTD systems in addition to upgrade of site infrastructure.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Engineered Pseudomonas putida simultaneously catabolizes five major components of corn stover lignocellulose: Glucose, xylose, arabinose, p-coumaric acid, and acetic acid

Valorization of all major lignocellulose components, including lignin, cellulose, and hemicellulose is critical for an economically viable bioeconomy. In most biochemical conversion approaches, the standard process separately upgrades sugar hydrolysates and lignin. Here, we present a new process concept based on an engineered microbe that could enable simultaneous upgrading of all lignocellulose streams, which has the ultimate potential to reduce capital cost and enable new metabolic engineering strategies. Specifically, we engineered Pseudomonas putida, a robust microorganism capable of catabolizing aromatic compounds, organic acids, and D-glucose, to utilize D-xylose and L-arabinose by tuning D-xylose transport and pentose phosphate pathway flux. Distinct L-arabinose pathways enabled D-glucose, D-xylose, and L-arabinose co-utilization in minimal medium using model compounds as well as corn stover hydrolysate. After modifying catabolite repression, our engineered P. putida simultaneously co-utilized five representative compounds from cellulose, hemicellulose, and lignin, demonstrating the feasibility of simultaneously upgrading total lignocellulosic biomass to value-added chemicals.

Elmore, Joshua R.↗

Bimetallic-Derived Catalytic Structures for CO 2 -Assisted Ethane Activation

In recent years, the simultaneous upgrading of CO 2 and ethane has emerged as a promising approach for generating valuable gaseous (CO, H 2 , and ethylene) and liquid (aromatics and C 3 oxygenates) chemicals from the greenhouse gas CO 2 and large-reserved shale gas. The key challenges for controlling product selectivity lie in the selective C-H and C-C bond cleavage of ethane with the assistance of CO 2 . Bimetallic-derived catalysts likely undergo alloying or oxygen-induced segregation under reaction conditions, thus providing diverse types of interfacial sites, e.g., metal/support (M/M'O x ) interface and metal oxide/metal (M'O x /M) inverse interface, that are beneficial for selective CO 2 -assisted ethane upgrading. The alloying extent can be initially predicted by cohesive energy and atomic radius (or Wigner-Seitz radius), while the preference for segregation to form the on-top suboxide can be approximated using the work function, electronegativity, and binding strength of adsorbed oxygen. Furthermore, bimetallic-derived catalysts are typically supported on high surface area oxides. Modifying the reducibility and acidity/basicity of the oxide supports and introducing surface defects facilitate CO 2 activation and oxygen supplies for ethane activation. Using in situ synchrotron characterization and density functional theory (DFT) calculations, we found that the electronic properties of oxygen species influence the selective cleavage of C-H/C-C bonds in ethane, with electron-deficient oxygen over the metal (or alloy) surface promoting nonselective bond scission to produce syngas and electron-enriched oxygen over the metal oxide/metal interface enhancing selective C-H scission to yield ethylene. Here, we further demonstrate that the preferred structures of the catalyst surfaces, either alloy surfaces or metal oxide/metal inverse interfaces, can be controlled through the appropriate choice of metal combinations and their atomic ratios. Through a comprehensive comparison of experimental results and DFT calculations, the selectivity of C-C/C-H bond scission is correlated with the thermodynamically favorable bimetallic-derived structures (i.e., alloy surfaces or metal oxide/metal inverse interfaces) under reaction conditions over a wide range of bimetallic catalysts. These findings not only offer structural and mechanistic insights into bimetallic-derived catalysts but also provide design principles for selective catalysts for CO 2 -assisted activation of ethane and other light alkanes. This Account concludes by discussing challenges and opportunities in designing advanced bimetallic-derived catalysts, incorporating new reaction chemistries for other products, employing precise synthesis strategies for well-defined structures with optimized site densities, and leveraging time/spatial/energy-resolved in situ spectroscopy/scattering/microscopy techniques for comprehensive structural analysis. The research methodologies established here are helpful for the investigation of dynamic alloy and interfacial structures and should inspire more efforts toward the simultaneous upgrading of CO 2 and shale gas.

03 NATURAL GAS↗