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At least 775 records · Page 43

Porosity as a Design Element for Developing Catalytic Molecular Materials for Electrochemical and Photochemical Carbon Dioxide Reduction

The catalytic reduction of carbon dioxide (CO 2 ) using sustainable energy inputs is a promising strategy for upcycling of atmospheric carbon into value-added chemical products. This goal has inspired the development of catalysts for selective and efficient CO 2 conversion using electrochemical and photochemical methods. Among the diverse array of catalyst systems designed for this purpose, two- and three-dimensional platforms that feature porosity offer the potential to combine carbon capture and conversion. Included are covalent organic frameworks (COFs), metal-organic frameworks (MOFs), porous molecular cages, and other hybrid molecular materials developed to increase active site exposure, stability, and water compatibility while maintaining precise molecular tunability. This mini-review showcases catalysts for the CO 2 reduction reaction (CO 2 RR) that incorporate well-defined molecular elements integrated into porous materials structures. Selected examples provide insights into how different approaches to this overall design strategy can augment their electrocatalytic and/or photocatalytic CO 2 reduction activity. This article is protected by copyright. All rights reserved.

36 MATERIALS SCIENCE↗

Manufactured Porous Ambient Surface Simulants

The planetary science decadal survey for 2013-2022 (Vision and Voyages, NRC 2011) has promoted mission concepts for sample acquisition from small solar system bodies. Numerous comet-sampling tools are in development to meet this standard. Manufactured Porous Ambient Surface Simulants (MPASS) materials provide an opportunity to simulate variable features at ambient temperatures and pressures to appropriately test potential sample acquisition systems for comets, asteroids, and planetary surfaces. The original "flavor" of MPASS materials is known as Manufactured Porous Ambient Comet Simulants (MPACS), which was developed in parallel with the development of the Biblade Comet Sampling System (Backes et al., in review). The current suite of MPACS materials was developed through research of the physical and mechanical properties of comets from past comet missions results and modeling efforts, coordination with the science community at the Jet Propulsion Laboratory and testing of a wide range of materials and formulations. These simulants were required to represent the physical and mechanical properties of cometary nuclei, based on the current understanding of the science community. Working with cryogenic simulants can be tedious and costly; thus MPACS is a suite of ambient simulants that yields a brittle failure mode similar to that of cryogenic icy materials. Here we describe our suite of comet simulants known as MPACS that will be used to test and validate the Biblade Comet Sampling System (Backes et al., in review).

Carey, Elizabeth M.↗

Progress of chemical characterization of asteroid Ryugu samples

It is believed that meteorites come from asteroids. Samples of asteroid (25143) Itokawa returned by the JAXA Hayabusa mission revealed that S-type asteroids are composed of materials consistent with the ordinary chondrite class[1,2]. The JAXA Hayabusa 2 [3]spacecraft launched on December 3rd, 2014 towards an asteroid (162173) Ryuguto clarify relationships between C-type asteroids and the carbonaceous chondrite class. Remote sensing observations from Hayabusa 2 show that (1) the albedo of Ryugu is darker than those of every known meteorite class[4, 5], (2) an absorption band at 2.72 μm indicates that phyllosilicates are ubiquitous on Ryugu [5],(3) the strength and shape of the absorption band feature suggests that Ryugu materials experienced heating above 300 °C[6], and (4) thermal inertia suggests that Ryugu materials are more porous than every known carbonaceous chondrite[7]. These results suggest that carbonaceous chondrite class materials are plausible for Ryugu materials, but no known carbonaceous chondrite completely matches the results obtained from Ryugu. *Complete abstract available in attached document

Lan Anh Ngoc Nguyen↗

Updates on the Predictive Materials Modeling Software Tools

Updates on NASA‘s efforts to build a Predictive Material Modeling (PMM) framework from the micro-scale to the macro-scale are presented in this abstract. The PMM effort is part of the Entry Systems Modeling (ESM) project under NASA’s Game Changing Development (GCD) program. To reduce the need for extensive testing and accelerate the design cycle process, ESM is developing simulation and modeling tools that enable the characterization of the properties of thermal protection materials and their response to extremely hot plasma. The Porous Microstructure Analysis (PuMA) software has been developed to compute effective material properties and perform material response simulations on digitized microstructures of porous media. PuMA is able to import three-dimensional digital images obtained from X-ray microtomography or to generate artificial microstructures that mimic real materials. PuMA also provides a module for interactive 3D visualizations. Version 3, which was recently released as open-source, includes modules to compute simple morphological properties such as porosity, volume fractions, pore diameter, and specific surface area. Additional capabilities include the determination of effective thermal and electrical conductivity (both radiative and solid conduction - including the ability to simulate local anisotropy for the latter); effective diffusivity and tortuosity from the continuum to the rarefied regime; techniques to determine the local material orientation, as well as mechanical properties (elasticity coefficients), and permeability. Computed properties are then used to inform a macro-scale material response model, such as those implemented in the Porous material Analysis Toolbox based on OpenFOAM (PATO) software developed within ESM. The computational model in PATO is a generic heat and mass transfer model for porous reactive materials containing several solid phases and a single gas phase. The detailed chemical interactions occurring between the solid phases and the gas phase are modeled at the pore scale, assuming Local Thermal Equilibrium. Recent efforts include the development of a mechanical erosion model as well as a unified model allowing an intrinsic coupling between fluid and material. Comparison to flight data (Mars Science Laboratory [MSL] Entry Descent and Landing Instrument [MEDLI] and Mars 2020 MEDLI2) is critical in order to validate these computational tools. Examples of ablative material response using the code will be presented, including 3D simulations of the full-scale heatshield of the MSL capsule. The simulations demonstrated the ability of the modern material response code, PATO, to handle the material response of geometrically complex and large domains through the use of massively parallel computations.

material modeling↗

Cocontinuous Nanostructures by Microphase Separation of Statistically Cross-Linked Polystyrene/Poly(2-vinylpyridine) Networks

Cocontinuous polymeric nanostructures have drawn considerable attention due to their ability to combine distinct, percolation-dependent properties of two different polymer domains. Randomly end-linked copolymer networks (RECNs) have previously been shown to support the formation of disordered cocontinuous nanostructures across wide composition windows in a robust way. However, achieving highly efficient linking of telechelic polymers with excellent end-group fidelity often requires complex synthetic routes. As an alternative, we study here statistically cross-linked copolymer networks (SCCNs) composed of polystyrene and poly(2-vinylpyridine) (PS and P2VP) with cross-linkable allyl pendent groups that are conveniently synthesized by controlled radical copolymerization. Via selective extraction of P2VP, coupled with gravimetry, small-angle X-ray scattering, and electron microscopy, we find disordered cocontinuous phases across wide composition ranges (up to ≈ 35 wt %), approaching values previously determined for RECNs. Remarkably, even for samples that appear to exhibit full percolation, a substantial fraction of P2VP (≈ 20–30 wt %) cannot be removed, which we ascribe to short strands between nearby cross-linkers that are physically embedded within PS domains. Here, the resulting PS porous monoliths with residual surface P2VP layers enable facile surface modification to resist protein adsorption and templating of porous gold nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porous and Microporous Honeycomb Composites as Potential Boundary-Layer Bleed Materials

Results of an experimental investigation are presented in which the use of porous and microporous honeycomb composite materials is evaluated as an alternate to perforated solid plates for boundary-layer bleed in supersonic aircraft inlets. The terms "porous" and "microporous," respectively, refer to bleed orifice diameters roughly equal to and much less than the displacement thickness of the approach boundary-layer. A Baseline porous solid plate, two porous honeycomb, and three microporous honeycomb configurations are evaluated. The performance of the plates is characterized by the flow coefficient and relative change in boundary-layer profile parameters across the bleed region. The tests were conducted at Mach numbers of 1.27 and 1.98. The results show the porous honeycomb is not as efficient at removing mass compared to the baseline. The microporous plates were about equal to the baseline with one plate demonstrating a significantly higher efficiency. The microporous plates produced significantly fuller boundary-layer profiles downstream of the bleed region for a given mass flow removal rate than either the baseline or the porous honeycomb plates.

Davis, D. O.↗

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

36 MATERIALS SCIENCE↗

Environment-Conscious Ceramics (Ecoceramics) Technology Received 2001 R&D 100 Award

Since the dawn of human civilization, there has been a delicate balance between the use of resources as human frontiers expanded and the need to have a minimum influence on the ecosystem. The first 200 years of the industrial revolution essentially solved the problem of production. However, the massive production of goods also generated tremendous amounts of byproducts and wastes. In the new millennium, to sustain a healthy life in harmony with nature, it will be extremely important for us to develop various materials, products, and processes that minimize any harmful influence on the environment. Environment-conscious ceramics (ecoceramics) are a new class of materials that can be fabricated with renewable resources (wood) and wood waste material (wood sawdust). Wood is a "lignocellulosic" material formed by the photosynthetic reaction within the needles or leaves of trees. The photosynthesis process uses sunlight to take carbon dioxide from air and convert it into oxygen and organic materials. Wood has been known to be one of the best and most intricate engineering materials created by nature and known to mankind. In addition, natural woods of various types are available throughout the world. On the other hand, wood sawdusts are generated in abundant quantities by sawmills. Environment-conscious ceramic materials, fabricated via the pyrolysis and infiltration of natural wood-derived preforms, have tailorable properties with numerous potential applications. The experimental studies conducted to date on the development of materials based on biologically derived structures indicate that these materials behave like ceramic materials manufactured by conventional approaches. These structures have been shown to be quite useful in producing porous or dense materials having various microstructures and compositions.

Singh, Mrityunjay↗

Reactive Processing of Environment Conscious, Biomorphic Ceramics: A Novel and Eco-friendly Route to Advanced Ceramic

Environment-conscious, biomorphic ceramics (Ecoceramics) are a new class of materials that can be produced with renewable resources (wood) and wood wastes (wood sawdust). These materials have tailorable properties with numerous potential applications. Silicon carbide-based ecoceramics have been fabricated by the infiltration of wood-derived carbonaceous preforms with oxide and silicon based materials. The wood-derived carbonaceous preforms have been shown to be quite useful in producing porous or dense materials with different microstructures and compositions. The microstructure and mechanical properties (flexural strength, fracture toughness, elastic modulus, and compressive strength) of a wide variety of Sic-based ecoceramics have been measured. Ecoceramics have tailorable properties and behave like ceramic materials manufactured by conventional approaches. In this presentation the fabrication approach, microstructure, and thermomechanical properties of a wide variety of Sic-based Ecoceramics will be reported.

Singh, M.↗

Glassy embedded solid-state electrode assemblies, solid-state batteries and methods of making electrode assemblies and solid-state batteries

Batteries, component structures and manufacturing methods, in particular including a glassy embedded battery electrode assembly having a composite material structure composed of interpenetrating material components including a porous electroactive network including a solid electroactive material, and a continuous glassy medium including a Li ion conducting sulfide glass, can achieve enhanced power output, reduced charging time and/or improved cycle life.

Visco, Steven J.↗

Carbide-based fuel assembly for thermal propulsion applications

Carbide-based fuel assembly includes outer structural member of ceramic matrix composite material, the interior surface of which is lined in higher temperature regions with an insulation layer of porous refractory ceramic material. Continuous insulation layer extends the length of the fuel assembly or separate insulation layer sections have a thickness increasing step-wise along the length of the fuel assembly from upper (inlet) section towards bottom (outlet) section. A fuel element positioned inward of the insulation layer and between support meshes has a fuel composition including HALEU and the form of a plurality of individual elongated fuel bodies or one or more fuel monolith bodies containing coolant flow channels. Fuel assemblies are distributively arranged in a moderator block, with upper end of the outer structural member attached to an inlet for propellant and lower end of the outer structural member operatively interfaced with a nozzle forming a nuclear thermal propulsion reactor.

Barringer, Eric A.↗

When Pore Met Semi: Charting the Rise of Porous Metal Halide Semiconductors

Metal halide semiconductors (MHS) are a versatile class of materials with fully customizable mechanical and optoelectronic properties that have proven to be prominent candidates in numerous impactful applications. Finding a way to generate porosity in MHS would bestow upon them an additional node in property engineering, thus allowing them to be utilized in uncharted technologies. Motivated by this promise, we developed a general strategy to render the MHS porous. We employed molecular cages as structure-directing agents and countercations, which fostered a new family of materials: porous metal halide semiconductors (PMHS). The presence of molecular cages gave rise to ultramicroporous structures imposed by the organic part cavities and a record water stability performance of 27 months so far. In this Perspective, we discuss the principles and promises of PMHS, which combine the merits of porous and electronic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sol-gel processing of a covalent organic framework for the generation of hierarchically porous monolithic adsorbents

Covalent organic frameworks (COFs) have emerged as a versatile material platform for such applications as chemical separations, chemical reaction engineering, and energy storage. Their inherently low mechanical stability, however, frequently renders existing methods of pelletization ineffective, contributing to pore collapse, pore blockage, or insufficient densification of crystallites. Here, we present a process for the shaping and densifying of COFs into robust centimeter-scale porous monoliths without the need for templates, additives, or binders. This process minimizes mechanical damage from shear-induced plastic deformation and further provides a network of interparticle mesopores that we exploit in accessing analyte capacities above those achievable from the intrinsic COF structure. Using a lattice-gas model, we accurately capture the monolithic structure across the mesoporous range and tie pore architecture to performance in both gas-storage and -separation applications. Collectively, these results represent a substantial step in the practical applicability of COFs and other mechanically weak porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TRIDENT Drill Validation at Mars and Lunar Analog Field Sites

Drilling on Earth is typically a human-intensive activity. Drilling on other planets is further complicated by the lack of prior local field surveys of their target area, hence blindly drilling into uncertain target rocks. Field conditions on the Moon or Mars are also different than for shallow drilling on Earth: lower temperatures and pressures, less power available, low masses (hence less weight-on-bit). Given the cost of transport from Earth, no drilling muds or working fluids are likely to be available to carry away cuttings. And impact-gardened regolith and dust vary mechanically and texturally from most terrestrial soils. The Regolith and Ice Drill for Exploration of New Terrains (TRIDENT) is a rotary-percussive 1m-class drill from Honeybee Robotics. It is low-power (rotary and percussive actuators are 200 W each) and lightweight (<20 kg) with the maximum weight on bit limited to 200 N. TRIDENT has been manifested for the Volatiles Investigating Polar Exploration Rover (VIPER) and PRIME-1 lunar south pole missions in 2024, has previously been field tested at a hot, dry analog site in the Atacama Desert, and in lunar conditions in thermal vacuum chamber tests. TRIDENT was also part of the 2019 Icebreaker Mars Discovery proposal, as well as in the Mars Life Explorer concept. During ARADS tests, drill control and fault recovery automation software enabled hands-off operations of a rover-mounted TRIDENT drill. TRIDENT Drill Analog Site Validation: Past TRIDENT tests in thermal vacuum (TVAC) chambers targeted containers of manufactured lunar simulants with added volatiles. 2022 TRIDENT ambient testing at NASA Ames drilled into cemented lunar simulant materials. Low cuttings-permeability led to cuttings buildup, and drill choking and binding was observed. The Atacama analog site in ARADS had desiccated unconsolidated sediments that did not challenge the TRIDENT design. However, lunar polar regolith is expected to be diverse and heterogeneous with varying clast sizes, with abundant impactites and perhaps subsurface ice deposits. Neither the simulants nor Atacama testing had completely covered the TRIDENT-targeted field characteristics, motivating further analog tests prior to the planned lunar missions. To gain more insight into the behavior of the TRIDENT hardware in diverse impactites and subsurface ice, and to verify the software automation in that environment, in August 2023 TRIDENT was brought to Haughton Crater, a field analog site in the Canadian Arctic. In September 2023 the same drill was brought to the Bishop Tuff in southern California to verify whether drilling binding behaviors previously seen in lunar simulant testing would be observed in naturally occurring fine-grained massive layers. The ~22 Ma Haughton Crater impact structure is located at 75 ̊22’ N, 89 ̊41’ W, on northwestern Devon Island, Nunavut, Canada. Numerous deposits of pale-grey crater-fill polymictic impact-melt breccia are found within the crater with a typical thickness reaching ~125 m or greater and covering ~60 km -2 . An approximately 600m-thick permafrost layer is also present with ice typically found within 0.5-0.6m of the surface. The volcanic tableland north of Bishop, CA exposes densely welded tuff laid down during the eruption that created the Long Valley Caldera at approximately 0.76 Ma. Extensional faults and the Owens River gorge expose cross-sections across the plateau. The area is viewed as an analog site for Mars features believed to be of pyroclastic origin. Results: Haughton Crater.Drilling tests were conducted 8-13 August 2023 at a previously undisturbed area separated 5-10 m from past years’ Drill Hill test sites (75.4208, -089.7613). In six days, TRIDENT drilled 8 holes to nearly 1 m depth each, totaling 7.80 m. The active layer/ice boundary was at ~67 cm depth, with a total of approximately 2.4 m drilled into ice or ice-cemented impact breccia. During drilling, five drill fault states were observed and successfully recovered. Holes 23-1, 4 and 7 were drilled under manual control, using Honeybee’s Thorax user interface. Holes 23-5, 6, and 8 were drilled with the Ames IBexec automated drilling control software. TRIDENT was observed to have little difficulty in the thawed uncemented impact breccia above the active layer boundary, but required percussion to make slower headway in the ice-cemented breccia. In Hole 23-7 (Fig.1), drilling slowed down in a massive unit just above the active-layer boundary (perhaps a large rock extending into the ice-cementation?), with only 7cm progress made in 27 minutes of high auger torque and constant percussion, leading to a choking fault and then a binding fault. A similar pattern had been observed in TRIDENT Rio Tinto test data from 2017 [6] as well as in the 2022laboratory tests.Bishop Tuff.A team from NASA Ames and the US Geological Survey deployed the same TRIDENT drill to Bishop Sites 1B and 1C (37.4203, -118.4289; 37.4265, -118.4215) on 13-16 September 2023, on the Bishop Tuff plateau. A third drill site was used 17-18 September 2023(37.4598, -118.3667) in an abandoned pumice mine. Four holes (totaling 2.5m depth) were drilled into the fine-grained, meters-thick tuff units at Sites 1B and 1C, and a further two boreholes (totaling 1.98m depth) were made at the pumice site. Drill behavior in the tuff below 10 cm depth was similar to that seen at 65-74 cm depth in Haughton Hole 23-7 (Fig. 1) and that seen in the 2022 lab simulant drilling. Drill safety torque limits were exceeded multiple times resulting in drill stops downhole. These freezes then required external added torques (with a pipe wrench) to resume rotation, to unstick the drill for withdrawal. To prevent this choking and binding behavior we found that more-frequent cuttings removal was necessary, e.g., reducing the “drill bite” size from the nominal 10 cm to 2 cm per bite --bringing the auger up to the surface more frequently, as seen in Bishop Site 1C Hole 2 (Fig.2). This permitted slow progress without drill binding and without external interventions. Conversely, TRIDENT drilling in the more porous pumice target material showed no cuttings buildup issue, and single bites as large as 40 cm were demonstrated. Discussion: We observed that TRIDENT easily penetrated unconsolidated heterogeneous soils (both above the active layer boundary at Haughton and previously in the Atacama). Cemented or consolidated targets that were cuttings-permeable (icy impact breccia, pumice) required more energy applied and percussion. However, in non-cuttings-permeable targets (welded microporous tuff, cemented simulants, boulder) TRIDENT was observed to be prone to excessive cuttings accumulation leading to choking/binding faults and stalling. The wedge cutting bit, used by TRIDENT in field tests and in its flight versions, pulverizes the target rock and creates fine cuttings that ideally are transported up the auger spirals for removal. In porous, fractured or vesicular target materials (such as at the Bishop pumice site) a significant portion of the cuttings are pushed aside, but for non-fractured, microporous targets the cuttings remain in the borehole and accumulate. Rock powder is relatively incompressible as a working fluid at only 100-200N downward force (TRIDENT limits) and hence eventual drilling progress slows or stops. Our recommended strategy for improving TRIDENT cuttings removal in massive target units with low cuttings-permeability is to reduce TRIDENT bite sizes when encountering these units, from 10cm to as little as 1-2cm, to effectively bail the accumulating cuttings. This approach was demonstrated to reduce choking and allowed slow progress to continue in cuttings-impermeable microporous target units (viz. the Bishop tuff in our September 2023 tests or cemented simulants in 2022 ambient tests).

robotic drilling↗

Breaking the trade-off between selectivity and adsorption capacity for gas separation

It is generally recognized that porous solids (sorbents) with high selectivity and high adsorption capacity offer potential for energy-efficient gas separations. Unfortunately, there is generally a trade-off between capacity and selectivity, which represents a roadblock to the utility of sorbents in key industrial processes. For example, acetylene (C 2 H 2 ), an important fuel and chemical intermediate, is produced with CO 2 as an impurity, and the similar physicochemical properties of C 2 H 2 and CO 2 mean that most sorbents are poorly selective. Hybrid ultramicroporous materials (HUMs) are candidates for gas separations as they exhibit benchmark selectivity for several key gas pairs. Unfortunately, existing HUMs are handicapped by low capacity. Here, we report a new HUM, SIFSIX-21-Ni, that addresses the trade-off between selectivity and capacity that has plagued sorbents, as its high uptake and high selectivity renders it the new benchmark for C 2 H 2 /CO 2 separation performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of very-low-density, high-stiffness carbon fiber/aluminum hybridized composite with ultra-low density and high stiffness (M-11)

Fabrication of a composite material with ultra-low density and high stiffness in microgravity is the objective of the investigation. The composite structure to be obtained is a random three-dimensional array of high modulus, short carbon fibers bonded at contact points by an aluminum alloy coated on the fibers. The material is highly porous and thus has a very low density. The motivation toward the investigation, simulation experiments, choice of the component materials, and on-flight experiment during ballistic trajectory of a NASDA rocket, are described.

Suzuki, Tomoo↗

Metastable carbon in two chondritic porous interplanetary dust particles

An understanding of carbonaceous matter in primitive extraterrestrial materials is an essential component of studies on dust evolution in the interstellar medium and the early history of the Solar System. Analytical Electron Microscopy (AEM) on carbonaceous material in two Chondritic Porous (CP) aggregrates is presented. The study suggests that a record of hydrocarbon carbonization may also be preserved in these materials.

Rietmeijer, F. J. M.↗