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Ordered Pt 3 Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction

Highly ordered Pt alloy structures are proved effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt 3 Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt 3 Co structures. It is very crucial for the formation of the ordered Pt 3 Co to carefully control the doping content of Co into the MOFs and the heating temperatures for Co diffusion. The optimal Pt 3 Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs. RHE and only losing 12 mV after 30,000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests evidenced by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt 3 Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt 3 Co intermetallic catalysts. Finally, the new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen doping.

25 ENERGY STORAGE↗

Synthesis of Nitrogen and Sulfur Codoped Nanoporous Carbons from Algae: Role in CO 2 Separation

Nitrogen and sulfur codoped and completely renewable carbons were synthesized from two types of algae, Spirulina Platensis and Chlorella Vulgaris, without any additional nitrogen fixation reaction. The type of activation agents, char-forming temperature, activation agent-to-char ratio, and activation temperature were all varied to optimize the reaction conditions for this synthesis. The maximum Brunauer–Emmett–Teller surface area and total pore volumes of the carbons were 2685 m 2 /g and 1.4 cm 3 /g, respectively. The nitrogen and sulfur contents of the carbons were in the range of 0.9–5.69 at. % and 0.05–0.2 at. %, respectively. The key nitrogen functionalities were pyridinic, amino, and pyridonic/pyrrolic groups, whereas the key sulfur functionalities were S–C, O–S–C, and SO x groups. CO 2 adsorption isotherms were measured at 273, 298, and 313 K, and the ideal adsorbed solution theory was employed to calculate the selectivity of adsorption of CO 2 over N 2 and simulate binary adsorption isotherms. The adsorption results demonstrated that the CO 2 adsorption amount and the heat of CO 2 adsorption were higher for carbons with higher nitrogen content, confirming the influence of nitrogen functionality in CO 2 adsorption. The overall results suggested that these algae-derived renewable carbons can serve as potential adsorbents for CO 2 separation from N 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface energies of elemental crystals

The surface energy is a fundamental property of the different facets of a crystal that is crucial to the understanding of various phenomena like surface segregation, roughening, catalytic activity, and the crystal's equilibrium shape. Such surface phenomena are especially important at the nanoscale, where the large surface area to volume ratios lead to properties that are significantly different from the bulk. Here, we present the largest database of calculated surface energies for elemental crystals to date. This database contains the surface energies of more than 100 polymorphs of about 70 elements, up to a maximum Miller index of two and three for non-cubic and cubic crystals, respectively. Well-known reconstruction schemes are also accounted for. The database is systematically improvable and has been rigorously validated against previous experimental and computational data where available. We will describe the methodology used in constructing the database, and how it can be accessed for further studies and design of materials.

36 MATERIALS SCIENCE↗

Mitigation of PtCo/C Cathode Catalyst Degradation via Control of Relative Humidity

Maintaining the high performance of proton-exchange membrane fuel cells (PEMFC) over the course of its lifetime is a key enabling factor for its successful commercialization as a primary power source in zero-emission transportation applications. In this context, it is important to mitigate the degradation of PtCo-alloy based cathode catalysts used for oxygen reduction reaction (ORR). PtCo-alloy catalysts exhibit high activity at beginning-of-life (BOL) which tends to decrease during operation due to loss of electrochemical surface area (ECSA) and dissolution-contamination related effects of the Co-alloying component. Here, we demonstrate the use of relative humidity (RH) of the inlet gases as a controllable parameter to mitigate the degradation of PtCo-alloy catalyst degradation. We employ a catalyst-specific voltage cycling accelerated stress test (AST) durability protocol as a function of inlet RH to degrade PtCo catalysts. A series of in situ electrochemical diagnostics and ex situ characterizations have been carried out to investigate the catalyst layer characteristics at end-of-test (EOT). Our results show that at sub-saturated conditions of durability protocol operation, PtCo catalyst sustains higher EOT H 2 /air performance due to better retention of ECSA and smaller impact of Co 2+ dissolution/contamination.

25 ENERGY STORAGE↗

Low Cost, High Capacity Regenerable Sorbent for Carbon Dioxide Capture from Existing Coal-fired Power Plants

In this project TDA Research, Inc (TDA) has developed a new post combustion carbon capture technology based on a vacuum swing adsorption system that uses a steam purge and demonstrated its technical feasibility and economic viability in laboratory-scale tests and tests in actual coal derived flue gas. TDA uses an advanced physical adsorbent to selectively remove CO 2 from the flue gas. The sorbent exhibits a much higher affinity for CO 2 than N 2 , H 2 O or O 2 , enabling effective CO 2 separation from the flue gas. We also carried out a detailed process design and analysis of the new system as part of both sub-critical and super-critical pulverized coal fired power plants. The new technology uses a low cost, high capacity adsorbent that selectively removes CO 2 in the presence of moisture at the flue gas temperature without a need for significant cooling of the flue gas or moisture removal. The sorbent is based on a TDA proprietary mesoporous carbon that consists of surface functionalized groups that remove CO 2 via physical adsorption. The high surface area and favorable porosity of the sorbent also provides a unique platform to introduce additional functionality, such as active groups to remove trace metals (e.g., Hg, As). In collaboration with the Advanced Power and Energy Program of the University of California, Irvine (UCI), TDA developed system simulation models using Aspen PlusTM simulation software to assess the economic viability of TDA’s VSA-based post-combustion carbon capture technology. The levelized cost of electricity including the TS&M costs for CO 2 is calculated as $116.71/MWh and $113.76/MWh for TDA system integrated with sub-critical and super-critical pulverized coal fired power plants; much lower than the $153.03/MWhand $147.44/MWh calculated for the corresponding amine based systems. The cost of CO 2 captured for TDA’s VSA based system is $38.90 and $39.71 per tonne compared to $65.46 and $66.56 per tonne for amine based system on 2011 $ basis, providing 40% lower cost of CO 2 captured. In this analysis we have used a sorbent life of 4 years. If a longer sorbent life can be maintained (which is not unreasonable for fixed bed commercial PSA systems), this would lower the cost of CO 2 captured by $0.05 per tonne (e.g., to $38.85 and $39.66 per tonne at 5 years sorbent replacement). These system analysis results suggest that TDA’s VSA-based post-combustion capture technology can substantially improve the power plant’s thermal performance while achieving near zero emissions, including greater than 90% carbon capture. The higher net plant efficiency and lower capital and operating costs results in a substantial reduction in the cost of carbon capture and cost of electricity for the power plant equipped with TDA’s technology.

20 FOSSIL-FUELED POWER PLANTS↗

Mining Air for Fuels and Fine Chemicals

The Intergovernmental Panel on Climate Change’s 2021 report underscores that Direct Air Capture (DAC) is an essential component to limiting global warming to 2 °C, yet separating CO 2 from air and its subsequent concentration for conversion into carbon neutral fuels/chemicals or permanent storage remains energy intensive and costly. Further, most DAC technologies rely on repetitive capture and release cycles that reduces the amount of time the DAC materials are able to collect CO 2 and increases wear and tear. Moisture swing (MS) sorption within anion exchange materials utilizes differences in relative humidity to capture and concentrate CO 2 up to 500-fold with negligible energy inputs and low-cost sorbents. Molecular modeling predicts that membranes with a dry and wet side would actively transport CO 2 from its dry side to its wet side against a counter flow of H 2 O evaporating on the dry side, however, existing MS materials are too brittle to be processed into membranes to test this hypothesis. This project brought together experts in DAC materials and design, techno-economic analysis and project management at Arizona State University (ASU), polymer processing at University of Texas at Austin (UTA) and modeling gas transport and exchange at Norther Arizona University (NAU) to develop hollow fiber membranes that use energy from water evaporation to continuously pump CO 2 from air against a concentration gradient to the membranes interior and requiring significantly less energy than current DAC technologies. While this project did not meet its ultimate objectives of demonstrating an active CO 2 pumping membrane, a number of key accomplishments were made in developing low-cost, flexible anion exchange membranes (AEM) at 3.5 m 2 scale, characterizing the ionic and molecular transport within MS materials, and developing several analytical and mathematical models of the MS and pumping process leading to new fundamental knowledge about key rate limiting steps of CO 2 flux in anion exchange membranes at low water activity. Technoeconomic models show that if CO 2 fluxes ≥ 25 µmol CO 2 m -2 s -1 (membrane surface area) are achieved that cost ≤ $\$$100/tonne CO 2 captured, purified and compressed to pipeline quality is possible. The knowledge gained in this research will guide future research in developing new materials toward overcoming these rate limiting steps that in turn could enable transformative and disruptive DAC technologies needed for capturing gigatons of CO 2 per year needed to limiting global warming to 2 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active microwave remote sensing research program plan. Recommendations of the Earth Resources Synthetic Aperture Radar Task Force

A research program plan developed by the Office of Space and Terrestrial Applications to provide guidelines for a concentrated effort to improve the understanding of the measurement capabilities of active microwave imaging sensors, and to define the role of such sensors in future Earth observations programs is outlined. The focus of the planned activities is on renewable and non-renewable resources. Five general application areas are addressed: (1) vegetation canopies, (2) surface water, (3) surface morphology, (4) rocks and soils, and (5) man-made structures. Research tasks are described which, when accomplished, will clearly establish the measurement capabilities in each area, and provide the theoretical and empirical results needed to specify and justify satellite systems using imaging radar sensors for global observations.

Source record↗

Making Fuel-Cell Electrodes By Electrodeposition

Electrodes for direct oxidation of methanol in fuel cells fabricated in process involving room-temperature electro-chemical deposition of platinum-alloy catalysts on commercially available high-surface-area carbon support structures containing polytetrafluoroethylene (PTFE). Process takes 30 to 50 minutes and results in electrodes catalytically active as prepared; no need for additional activation step. Composition of catalytic platinum alloy and sizes of particles in catalytic layers on electrodes varied by changing operating conditions during electrodeposition; process affords additional flexibility in design of electrocatalysts.

Narayanan, Sekharipuram R.↗

Tack Measurements of Prepreg Tape at Variable Temperature and Humidity

NASA’s Advanced Composites Project has established the goal of achieving a 30 percent reduction in the timeline for certification of primary composite structures for application on commercial aircraft. Prepreg tack is one of several critical parameters affecting composite manufacturing by automated fiber placement (AFP). Tack plays a central role in the prevention of wrinkles and puckers that can occur during AFP, thus knowledge of tack variation arising from a myriad of manufacturing and environmental conditions is imperative for the prediction of defects during AFP. A full design of experiments was performed to experimentally characterize tack on 0.25-inch slit-tape tow IM7/8552-1 prepreg using probe tack testing. Several process parameters (contact force, contact time, retraction speed, and probe diameter) as well as environmental parameters (temperature and humidity) were varied such that the entire parameter space could be efficiently evaluated. Mid-point experimental conditions (i.e., parameters not at either extrema) were included to enable prediction of curvature in relationships and repeat measurements were performed to characterize experimental error. Collectively, these experiments enable determination of primary dependencies as well as multi-parameter relationships. Slit-tape tow samples were mounted to the bottom plate of a rheometer parallel plate fixture using a jig to prevent modification of the active area to be interrogated with the top plate, a polished stainless steel probe, during tack testing. The probe surface was slowly brought into contact with the pre-preg surface until a pre-determined normal force was achieved (2-30 newtons). After a specified dwell time (0.02-10 seconds), during which the probe substrate interaction was maintained under displacement control, the probe was retracted from the surface (0.1-50 millimeters per second). Initial results indicated a clear dependence of tack strength on several parameters, with a particularly strong dependence on temperature and humidity. Although an increase in either of these parameters reduces tack strength, a maximum in tack was predicted to occur under conditions of low temperature and moderate humidity.

Wohl, Christopher↗

Big Sky Regional Carbon Sequestration Partnership (Phase III Final Scientific/Technical Report)

The Big Sky Carbon Sequestration Partnership (BSCSP) pursued a Phase III demonstration project at Kevin Dome in north central Montana. Kevin Dome covers approximately 700 square miles and is a naturally occurring CO 2 reservoir that is flanked by oil and gas fields. The carbon dioxide (CO 2 ) is in the upper Devonian Duperow (carbonate) formation and does not reach the spill point of the dome; therefore, the dome has potential as a CO 2 sequestration reservoir, a CO 2 supply, or as both if anthropogenic sources and enhanced oil recovery (EOR) operations are associated with the dome. Kevin Dome could potentially act as a buffer to continue accepting anthropogenic CO 2 when EOR flooding operations are interrupted or completed. The project objective was to produce one million tonnes of CO 2 from the gas cap of Kevin Dome, pipe it laterally, inject, and re-store it in the brine leg of the same formation to test the hub / buffer storage concept. This was to be accomplished by drilling up to five production wells, building a short pipeline and compression facilities, and drilling an injection well and several monitoring wells. BSCSP commenced outreach and site characterization activities including acquiring baseline data for near-surface insurance monitoring, acquiring 3-dimensional, 9-component surface seismic over the project area, drilling two test wells (one in the production area and one in the injection area), coring key intervals, and performing comprehensive logging. Well tests of those wells revealed two barriers to the project. The production (Danielson 33-17) well was perforated in multiple zones but failed to produce any significant CO 2 . This was despite being drilled in the near vicinity of a historic well that had produced 3700 MCF per day in a drill stem test. Modeling indicated that this was likely due to a phase change during production causing a temperature drop resulting in hydrate and/or water ice formation that clogged the formation. Tests of the injection zone (Wallewein 22-1) well indicated total dissolved solids (TDS) slightly below the EPA required 10,000 parts per million (ppm) for a Class VI underground injection control permit. While the project was initiated before Class VI rules were promulgated, and this was an experimental project (seemingly qualified for a Class V permit), the Environmental Protection Agency (EPA) indicated that injection would require a Class VI permit. The low salinity result was unexpected as contours plotted based on regional formation water quality data indicated an expected TDS above 20,000 ppm, and wells between the recharge zone and the Wallewein well tested above 10,000 ppm. Faced with the inability to obtain an injection permit, the demonstration project could not proceed. However, the project had generated valuable samples and data on a large natural analog including 32 sq. mi. of 3-D, 9-C seismic, 430 ft. of carbonate core covering seven different depositional environments taken from areas with, and without the presence of CO 2 , 30 ft. of core of two caprocks, a tight carbonate and an anhydrite, a full set of modern logs on both wells, and well tests. DOE decided to re-scope the project around completing studies utilizing this data. This report covers both the initial scope and the re-scope (Task / Section numbers preceded with an R). While the report covers a wide range of project activities, highlights of this work include: Development of a geostatic model using neural nets to match well logs to facies and using multi-waveform seismic to inform reservoir heterogeneity; Unique mechanical testing of permeability – stress relationship in two caprock materials; Development of full waveform inversion to generate a high resolution velocity model; Model development for dual permeability (fracture and matrix) systems to better account for matrix-matrix interactions; Joint seismic wave inversion (including the first quadr-joint inversion) exhibiting better imaging of a challenging reservoir zone in stiff rock; Core flow and core flood results on a reactive carbonate; and Innovative laboratory measurements of seismic response of fractured core as a function of fluid fill.

54 ENVIRONMENTAL SCIENCES↗

Highly Crystalline and Porous Borocarbonitrides as Metal‐Free Catalysts for Boosted N‐Heterocycle Dehydrogenation

Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. In this work, we report a metal‐free catalyst design that overcomes the long‐standing trade‐off between crystallinity and surface area in two‐dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux‐assisted reconstruction strategy transforms amorphous borocarbonitrides (AM‐BCN) into highly crystalline, defect‐rich BCN nanosheets (C‐BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x‐ray, and neutron analyses. C‐BCN catalyzes the acceptor‐less dehydrogenation of aza‐fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM‐BCN and previously reported metal‐free scaffolds. Mechanistic insights from x‐ray, neutron scattering, and theoretical calculations identify open C‐B‐N and N‐B‐N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect‐rich two‐dimensional lattices and demonstrates a highly active metal‐free platform for LOHC dehydrogenation with high‐purity H 2 generation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dismantling Rubble Pile Asteroids with AoES (Area-of-Effect Soft-bots)

Area-of-Effect Softbots (AoES) are soft-robotic spacecraft that are designed with a large, flexible surface area to leverage the dynamical environment at rubble pile asteroids. In particular, this surface area allows AoES to use adhesive forces, both naturally arising from van der Waals forces between the AoES and the asteroid regolith, and by using active electroadhesion, as well as using SRP forces to provide fuel free orbit and hopping trajectory control. The main purpose of the bus structure is to house a digging and launching mechanism that can liberate and launch asteroid regolith off the surface of the asteroid to be collected in orbit.

McMahon, Jay↗

Canopy reflectance, photosynthesis, and transpiration. II - The role of biophysics in the linearity of their interdependence

The ability of satellite sensor systems to estimate area-averaged canopy photosynthetic and transpirative properties is evaluated. The near linear relationship between the simple ratio (SR) and normalized difference (ND) and the surface biophysical properties of canopy photosynthetically active radiation (PAR) absorption, photosynthesis, and bulk stomatal resistance is studied. The models utilized to illustrate the processes of canopy reflectance, photosynthesis, and resistance are described. The dependence of SR, the absorbed fraction of PAR, and canopy photosynthesis and resistance on total leaf area index is analyzed. It is noted that the SR and ND vegetation indices and vegetation-dependent qualities are near-linearly related due to the proportion of leaf scattering coefficient in visible and near IR wavelength regions. The data reveal that satellite sensor systems are useful for the estimation of photosynthesis and transpirative properties.

Sellers, P. J.↗

Zero-Valent Iron Permeable Reactive Barrier to Remediate Volatile Organic Compounds in Groundwater - 20209

The US DOE-SRS, the US EPA, and the South Carolina Department of Health and Environmental Control determined it was appropriate to perform a non-time critical removal action at the P-Area Groundwater Operable Unit at the SRS to reduce the mass and downgradient transport of trichloroethylene in the P-Area groundwater plume. Contaminated groundwater discharges to a nearby stream, Steel Creek, within the SRS boundaries, resulting in trichloroethylene concentrations above the maximum contaminant level. Impact to surface water is limited in areal extent and supported by recently collected characterization data. The P-Area Groundwater Operable Unit encompasses the groundwater beneath an industrial area within SRS, P Area, where the P-Reactor once operated. The boundaries of the P-Area Groundwater Operable Unit extend northwest to Steel Creek, northeast toward PAR Pond, and southeast to Meyers Branch. Groundwater in the Upper Three Runs Aquifer of the P-Area Groundwater Operable Unit has been impacted by reactor and facility operations between 1954 and 1991, including tritium and volatile organic compounds. The P-Area surface units contributing to groundwater contamination were remediated as part of the P-Area Operable Unit in 2011. The P-Reactor closure is one of the first of its kind in the DOE Complex and is one of only a few full-sized production reactors in the US to undergo completion of final closure activities. The nature and extent of groundwater contamination was determined using a variety of investigative approaches such as groundwater monitoring wells, direct-push technology, and surface water samples. Groundwater contamination associated with trichloroethylene is primarily exhibited in a narrow plume that extends from the source area at P-Reactor and west to Steel Creek. Maximum contaminant level exceedances in groundwater occur over an area of ∼6.9 hectares for trichloroethylene with concentrations as high as 7.7 milligrams per liter. To the west of the P-Area facility area, the trichloroethylene groundwater plume is controlled by a buried geologic feature, assumed to be an old stream bed, that further narrows the groundwater plume in what has been designated as the 'neck area.' This narrowing of the groundwater plume provides an ideal location for a treatment barrier. The non-time critical removal action alternative chosen is to install a zero-valent iron permeable reactive barrier within the neck area of the trichloroethylene groundwater plume, perpendicular to groundwater flow direction. This technology will provide a treatment barrier that will reduce trichloroethylene groundwater concentrations by 90% and has an anticipated useful life of at least 25 years. A pre-design investigation was performed in the neck area to confirm site lithology, hydrogeology, geochemistry, and extent of trichloroethylene contamination prior to a final design. A treatability study, conducted as part of the pre-design investigation, indicated that the subsurface and groundwater in the PArea Groundwater Operable Unit is compatible with the zero-valent iron and will not lead to excessive buildup from mineralization/precipitation or biofouling. Probabilistic modeling was conducted using field and laboratory data to determine the expected performance of the zero-valent iron permeable reactive barrier. The model simulations indicated that a 3.81-centimeter thick barrier would provide greater than 90% reduction of trichloroethylene groundwater concentration. The final design of the zero-valent iron permeable reactive barrier is a barrier that will extend 80.5 linear meters in a 'zigzag' orientation to best transect the trichloroethylene plume and account for varying groundwater flow. The barrier will be installed from 13.7 meters below ground surface to 41.1 meters below ground surface for 65.8 linear meters and from 13.7 meters below ground surface to 36.6 meters below ground surface for 14.6 linear meters, the base of which is 'keyed' into a low permeability zone. The barrier is designed to a thickness of 10.2 centimeters, which was determined to reduce the trichloroethylene groundwater concentrations by greater than 90% with a safety factor of 2.67. A total of approximately 689 metric tons of zero-valent iron will be injected through 22 injection wells spaced 3.66 meters apart, using guar to suspend the zero-valent iron. Zero-valent iron permeable reactive barrier construction will be monitored through 23 installed resistivity receivers offset 7.32 meters from the zerovalent iron permeable reactive barrier. The zero-valent iron will be energized with a low-voltage 100 Hertz signal during injection and will be monitored using the resistivity receivers to ensure complete coalescence of the zero-valent iron permeable reactive barrier. The zero-valent iron was sized to have a hydraulic conductivity greater than the natural subsurface, thus promoting groundwater flow through the barrier. As contaminated groundwater contacts the zero-valent iron, volatile organic compounds, including trichloroethylene, are immediately degraded to harmless compounds such as ethylene. The performance of the zero-valent iron permeable reactive barrier will be monitored using three upgradient monitoring well clusters, six downgradient monitoring well clusters, and four in-wall monitoring wells. The in-wall monitoring wells will indicate immediate reduction of trichloroethylene mass in the groundwater and allow analyses of the zero-valent iron permeable reactive barrier health. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tracer Methods for Characterizing Fracture Creation in Engineered Geothermal Systems

The aim of this proposal is to develop, through novel high-temperature-tracing approaches, three technologies for characterizing fracture creation within Engineered Geothermal Systems (EGS). The objective of a first task is to identify, develop and demonstrate adsorbing tracers for characterizing interwell reservoir-rock surface areas and fracture spacing. The objective of a second task is to develop and demonstrate a methodology for measuring fracture surface areas adjacent to single wells. The objective of a third task is to design, fabricate and test an instrument that makes use of tracers for measuring fluid flow between newly created fractures and wellbores. In one method of deployment, it will be used to identify qualitatively which fractures were activated during a hydraulic stimulation experiment. In a second method of deployment, it will serve to measure quantitatively the rate of fluid flowing from one or more activated fracture during a production test following a hydraulic stimulation.

15 GEOTHERMAL ENERGY↗

Improving Durability of Fuel Cells with Platinum-rich Alloy Cathode Catalysts

Pt 3 Co-alloy based nanoparticle catalysts are very active for oxygen reduction reaction (ORR) thereby enabling high performance of proton exchange membrane fuel cells (PEMFC) for automotive propulsion. However, these catalyst materials degrade due to a combination of electrochemical surface area (ECSA) loss and dissolution of cobalt-alloying element from the nanoparticles. Dissolution of cobalt has a two-fold impact on the durability of fuel cells—i) a loss in the low-current density kinetic region due to a decrease in specific activity and ii) a loss in the high-current density transport region due to Co 2+ contamination of the ionomer phase. Cobalt dissolution-contamination needs to be mitigated as it limits fuel cell performance and lifetime for heavy-duty automotive applications. In this article, we study the use of PtCo-alloy catalysts with Pt-rich compositions using catalyst-specific accelerated stress test measurement in membrane electrode assemblies to decrease the amount of dissolved Co and mitigate its subsequent contamination effects. We demonstrate Pt 5 Co and Pt 7 Co compositions to enable significant improvements in durability (∼50 mV and ∼100 mV with respect to Pt 3 Co after 30,000 voltage cycles) with a minor but acceptable compromise in the initial specific activity of the catalyst.

08 HYDROGEN↗

Activity and stability of mesoporous CeO 2 and ZrO 2 catalysts for the self-condensation of cyclopentanone

Metal oxides containing acid-base pairs are widely used as catalysts for aldol condensation reactions, but they are often prone to secondary condensation and fast deactivation. In this contribution, high-surface area mesoporous CeO 2 and ZrO 2 have been synthesized and tested as catalysts for the self-condensation of cyclopentanone, an attractive molecular building block for several biomass upgrading strategies. Here, the catalytic activity, stability, and overall kinetics behavior of these two catalysts have been compared in the liquid phase. A detailed kinetics analysis shows that on both oxides, the reaction is controlled by the initial unimolecular α-H abstraction step, in which cyclopentanone forms the crucial enolate intermediate. Subsequently, the enolate couples with another cyclopentanone molecule in a bimolecular C-C coupling step. CO 2 -TPD analysis and site titration with probe molecules indicate that initially the most active catalyst is the mesoporous ZrO 2 sample with strong base character. However, this catalyst exhibits a very rapid deactivation. By contrast, the mesoporous CeO 2 prepared in this study has lower basicity strength, which results in lower initial activity, but enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO 2 surface area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗