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The Osiris-Rex Mission - Sample Acquisitions Strategy and Evidence for the Nature of Regolith on Asteroid (101955) 1999 RQ36

NASA selected the OSIRIS-REx Asteroid Sample Return Mission as the third New Frontiers mission in May 2011 [I]. The mission name is an acronym that captures the scientific objectives: Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer. OSIRIS-REx will characterize near-Earth asteroid (101955) 1999 RQ36, which is both the most accessible carbonaceous asteroid [2,3] and one of the most potentially hazardous asteroids known [4]. The primary objective of the mission is to return a pristine sample from this bod, to advance our understanding of the generation, evolution, and maturation of regolith on small bodies.

Lauretta, D. S.↗

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO 2

Abstract We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO 2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron‐hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO 2 to CO. The interfacial dynamics and catalytic behavior are clearly revealed by time‐resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine‐captured CO 2 , namely carbamates, for direct photochemical conversion without additional energy input.

Choi, Chungseok↗

Facilely Cross-Linking Polybenzimidazole with Polycarboxylic Acids to Improve H 2 /CO 2 Separation Performance

Polybenzimidazole (PBI) with a strong size-sieving ability exhibits attractive H 2 /CO 2 separation properties for blue H 2 production and CO 2 capture. Herein, we report that PBI can be facilely cross-linked with polycarboxylic acids, oxalic acid (OA), and trans-aconitic acid (TaA) to improve its separation performance. The acids react with the amines on the PBI chains, decreasing free volume and increasing size-sieving ability. The acid doping increases H 2 /CO 2 selectivity from 12 to as high as 45 at 35 °C. Here, the acid-doped samples demonstrate stable H 2 /CO 2 separation performance when challenged with simulated syngas containing water vapor at 150 °C, which surpasses state-of-the-art polymers and Robeson’s upper bound for H 2 /CO 2 separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Site Selection for Mars Exopaleontology in 2001

The microbial fossil record encompasses a wide range of information, including cellular remains, stromatolites, biofabrics, trace fossils, biominerals and chemofossils. The preservation of fossils is strongly influenced by the physical, chemical and biological factors of the environment which, acting together, ultimately determine the types of information that will be captured and retained in the rock record. The critical factor in assessing the suitability of a site for a microbial fossil record is the paleoenvironment. The reconstruction of ancient sedimentary environments usually requires the integration of a wide variety of geological information, including the shape, geometry and internal structure of sedimentary deposits, their mineralogy, and geochemistry. For Mars, much of our knowledge about past environments is based on orbital imaging of geomorphic features. This evidence provides an important context and starting point for site selection. However, our knowledge of the martian surface is quite limited, and a major goal of the upcoming exploration effort is to reconstruct the history of Martian volatiles, climate, and hydrology as a context for the exploration for past or present life. Mineralogical mapping from orbit will be an important key in this effort. In exploring for evidence of past life, terrestrial experience suggests that the long-term preservation of biological information as fossils occurs under a fairly narrow range of geological conditions that are well known to paleontologists (1). In detrital sedimentary systems, microbial fossilization is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long term preservation, host rocks must be composed of stable minerals that resist chemical weathering, and which form an impermeable matrix and closed chemical system that can protect biosignatures from alteration during subsequent diagenetic change or metamorphism. In this context, host rocks composed of highly ordered, chemically-stable mineral phases, like silica (forming cherts) or phosphate (forming phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and (along with carbonates and shales), are the most common host rocks for the Precambrian microfossil record on Earth. If we assume that a subsurface hydrosphere has been present throughout martian history, then life could have originated there at any time, perhaps emerging at the surface periodically when climate changes, induced by external forcing or endogenous processes (e.g. volcanism), allowed liquid water to exist at the surface. The recent discovery of subsurface chemolithoautotrophic organisms which are capable of synthesizing organic substrates from C02 and H2 liberated from the aqueous weathering of basalt, is especially. relevant as a model for martian life. While a subsurface habitable zone may yet exist on Mars, access to such environments will likely require drilling to depths of several kilometers. Given the technological challenge of deep drilling, this is unlikely to occur prior to human missions. So, even if there is extant life on Mars today in subsurface habitats, it may be much easier to find its fossil counterparts in ancient deposits exposed at the surface. In exploring for a fossil record in subsurface environments on Mars there are several geological situations that may provide access to the appropriate materials. These include 1) ejecta from impact craters, 2) talus slopes, debris flows or alluvial fans developed below the walls of deep canyons, and 3) the deposits of outflood channels. Examples of aqueous mineral deposits of formed in subsurface environments that could harbor a microbial fossil record include such things as cements in detrital sedimentary rocks, low temperature diagenetic minerals deposited in veins, or filling vesicles in volcanic rocks, and hydrothermal deposits formed below the upper temperature limit for life (about 160 degrees C). There are many sites within the present latitudinal constraints for the 2001 mission (15 deg S to 30 deg N) that meet these requirements. But the practical problem with these kinds of deposits is that they tend to be disseminated, making up only a small percentage of a host rock. Even with mineralogical information provided by the Thermal Emission Spectrometer (TES) presently in orbit around Mars, predicting their occurrence ahead of time may be quite difficult. The deposits of surficial aqueous sedimentary systems are likely to provide the largest targets for site selection in 2001. Of these, the deposits of hydrothermal systems (subaerial and subaqueous thermal springs) have been discussed previously. It is likely that hydrothermal systems were widespread on Mars early in its history and a number of common geo-tectonic settings on Mars are likely to have hosted hydrothermal activity. Most of these are represented within the latitudinal constraints presently identified for 2001. However, the deposits of surface spring systems are likely to be difficult to find as well. On Earth, exposure areas for hydrothermal spring mounds are typically a few square kms, less than a single TES pixel. But such deposits may be quite abundant within some volcanic terrains, It is estimated, for example, that between 15-20% of the floor of Yellowstone caldera is covered by thermal spring deposits. In such abundances, subaerial sinters could well be detected by TES. Where exposed, the shallow subsurface portions of these systems may be quite a lot larger (perhaps tens of square kms), although (as noted above) mineralization may be finely disseminated in the basement rock, making remote detection more difficult. Paleolake Basins. There are a large number of potential paleolake basins on Mars (inclusive of impact craters and volcanic calderas) that have been previously identified using Viking images. Most of these lie in the southern highlands beyond the l5 deg S constraint for 2001. However, deposits of paleolakes may offer the largest and most easily identified exopaleontological targets from orbit. Based on a variety of arguments, some workers have suggested that there was once an ancient ocean on the northern plains, and some sites of interest (potential shoreline terraces) fall within the 30 deg N constraint. From a paleontological standpoint the most interesting places of this type are terminal paleolake basins which are likely to have been both saline and alkaline. Models by Schaefer suggest such environments could be widespread on Mars. The conditions in terminal lake basin settings favor widespread chemical sedimentation, an important condition for microbial fossilization. Important lithological targets for a microbial fossil record in terminal lake basins include spring-deposited carbonates, shoreline cements, a wide variety of evaporite minerals and fine-grained detrital sediments including shales, marls, and water-lain volcanic ash deposits. In developing a strategy to explore for ancient hydrothermal deposits on Mars, we can learn from the methods that have been developed by explorationists to explore for economic mineral deposits on Earth. Due to their simple mineralogy, hydrothermal deposits can often be detected using remote sensing methods. Common thermal spring mineral assemblages include silica, carbonate, and various metallic oxides and sulfides. But there are also a number of diagnostic silicate minerals, including clays, formed by the hydrothermal alteration of country rocks. These hydrothermal minerals have characteristic spectral signatures that could be detected from Mars orbit using high resolution infrared remote sensing methods. In playa lake settings, evaporite deposits often form a predictable "bull's eye" pattern with carbonates being deposited in marginal basin areas, and sulfates and halides occurring progressively more basinward. The floors of some impact craters on Mars, such as "White Rock" and Bequeral Crater (see Oxia Palus NE, Site 148), have floor deposits that could be evaporites, inclusive of carbonates. Evaporite minerals possess characteristic spectral signatures in the infrared and could similarly be identified from Mars orbit using high resolution remote sensing methods. Clearly, utilization of TES data will be important for optimizing site selection for Exopaleontology, and every effort should be made to benefit from that data before a final decision is made.

Farmer, Jack↗

Life Cycle Greenhouse Gas Emissions of Coal-Biomass Co-Firing Power Plants with Carbon Capture and Storage

The United States has set a target to achieve the net-zero economy by 2050. Bioenergy with Carbon Capture and Sequestration (BECCS) is one of the promising negative-emission routes in the mitigation portfolio to help meet this goal. Coal-biomass co-firing with carbon capture and storage (CCS) is a key BECCS technology to realize the carbon mitigation at fossil-fuel power plants. The mitigation potential of co-firing option is affected by numerous critical factors, such as biomass properties, co-firing level, and carbon capture rate. The objectives of the study are to characterize and estimate the life cycle greenhouse gas (GHG) emissions and performance of coal-biomass co-firing power plants with CCS, determine the breakeven co-firing level at power plants necessary to achieve net-zero life cycle emissions, and quantify the variabilities and uncertainties in life cycle emissions. The scope of the life cycle assessment includes the fuel supply, combustion-based power generation, and CO2 transport and storage. A fuel-based life cycle module is developed and embedded in the Integrated Environmental Control Model (IECM), a fossil-fuel power plant modeling tool. This study then applies the enhanced IECM to conduct the process-based life cycle assessment for an array of biomass co-firing scenarios. Deterministic analysis indicates that reaching net-zero life cycle emissions in a biomass co-firing plant without CCS deployment is challenging. Combining biomass co-firing and CCS deployment can significantly lower the overall life cycle emissions of power plants. Net-zero life cycle emissions can be achieved with a 20 wt.% co-firing level and 90% CCS when the Powder River Basin coal is co-fired with energy crops or forestry residues. However, the breakeven co-firing level for net-zero emissions depend on the selected fuel properties. Fuel supply and plant operation are the critical stages influencing the life cycle emissions of power plants with 90% CCS. Deployment of deep CCS beyond 90% CO2 capture can remarkably reduce operational emissions and the breakeven co-firing level. With 99% CCS, the breakeven co-firing rate can be reduced to 12% on average. These findings highlight the trade-offs between technical performance and environmental impact of biomass co-firing at coal-fired power plants and emphasize the role of deep CCS in achieving a net-zero emissions future.

Wu, Wanying↗

Strategy for Ranking the Science Value of the Surface of Asteroid 101955 Bennu for Sample Site Selection for Osiris-REx

OSRIS-REx is NASA's New Frontiers 3 sample return mission that will return at least 60 g of pristine surface material from near-Earth asteroid 101955 Bennu in September 2023. The scientific value of the sample increases enormously with the amount of knowledge captured about the geological context from which the sample is collected. The OSIRIS-REx spacecraft is highly maneuverable and capable of investigating the surface of Bennu at scales down to the sub-cm. The OSIRIS-REx instruments will characterize the overall surface geology including spectral properties, microtexture, and geochemistry of the regolith at the sampling site in exquisite detail for up to 505 days after encountering Bennu in August 2018. The mission requires at the very minimum one acceptable location on the asteroid where a touch-and-go (TAG) sample collection maneuver can be successfully per-formed. Sample site selection requires that the follow-ing maps be produced: Safety, Deliverability, Sampleability, and finally Science Value. If areas on the surface are designated as safe, navigation can fly to them, and they have ingestible regolith, then the scientific value of one site over another will guide site selection.

Nakamura-Messenger, K.↗

Discovery of Multiple Light-Harvesting States of the Photosynthetic Protein PE545

Cryptophytes are photosynthetic microalga that flourish in a remarkable diversity of natural environments by using pigment-containing proteins with absorption maxima tuned to each ecological niche. While this diversity in the absorption has been well established, the subsequent photophysics is highly sensitive to the local protein environment and so may exhibit similar variation. Thermal fluctuations of the protein conformation are expected to introduce photophysical heterogeneity of the pigments that may have evolved important functional properties in a manner similar to that of the absorption. However, such heterogeneity is averaged out in ensemble measurements and, therefore, has not yet been probed. Here, we report single-molecule measurements of phycoerythrin 545 (PE545), the prototypical cryptophyte antenna protein, in its native dimeric form. A conformational ensemble was resolved consisting of distinct photophysical states with different light-harvesting properties. Proteins that did not quench, partially quenched, or fully quenched absorbed light were observed. Light intensity increased the quenched-state population of the dimer, potentially as a mechanism to deal with the extreme light intensities found in aqueous environments. Cross-linking, which mimics local interactions, introduces this light-dependent functionality while also suppressing other conformational dynamics. The cellular organization can, therefore, actively modulate the protein conformation and dynamics, selecting for distinct levels of light harvesting. Furthermore, the complex conformational equilibrium provides an additional mechanism for cryptophytes and likely other photosynthetic organisms to optimize solar energy capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ligand modulation of the conformational dynamics of the A 2A adenosine receptor revealed by single-molecule fluorescence

G protein-coupled receptors (GPCRs) are the largest class of transmembrane proteins, making them an important target for therapeutics. Activation of these receptors is modulated by orthosteric ligands, which stabilize one or several states within a complex conformational ensemble. The intra- and inter-state dynamics, however, is not well documented. Here, we used single-molecule fluorescence to measure ligand-modulated conformational dynamics of the adenosine A 2A receptor (A 2A R) on nanosecond to millisecond timescales. Experiments were performed on detergent-purified A 2R in either the ligand-free (apo) state, or when bound to an inverse, partial or full agonist ligand. Single-molecule Förster resonance energy transfer (smFRET) was performed on detergent-solubilized A 2A R to resolve active and inactive states via the separation between transmembrane (TM) helices 4 and 6. The ligand-dependent changes of the smFRET distributions are consistent with conformational selection and with inter-state exchange lifetimes ≥ 3 ms. Local conformational dynamics around residue 229 6.31 on TM6 was measured using fluorescence correlation spectroscopy (FCS), which captures dynamic quenching due to photoinduced electron transfer (PET) between a covalently-attached dye and proximal aromatic residues. Global analysis of PET-FCS data revealed fast (150–350 ns), intermediate (50–60 μs) and slow (200–300 μs) conformational dynamics in A 2A R, with lifetimes and amplitudes modulated by ligands and a G-protein mimetic (mini-G s ). Most notably, the agonist binding and the coupling to mini-G s accelerates and increases the relative contribution of the sub-microsecond phase. Molecular dynamics simulations identified three tyrosine residues (Y112, Y288 7.53 , and Y290 7.55 ) as being responsible for the dynamic quenching observed by PET-FCS and revealed associated helical motions around residue 229 6.31 on TM6. As a result, this study provides a quantitative description of conformational dynamics in A 2A R and supports the idea that ligands bias not only GPCR conformations but also the dynamics within and between distinct conformational states of the receptor.

59 BASIC BIOLOGICAL SCIENCES↗

Selective Whole-Genome Amplification as a Tool to Enrich Specimens with Low Treponema pallidum Genomic DNA Copies for Whole-Genome Sequencing

Downstream next-generation sequencing (NGS) of the syphilis spirochete Treponema pallidum subspecies pallidum (T. pallidum) is hindered by low bacterial loads and the overwhelming presence of background metagenomic DNA in clinical specimens. In this study, we investigated selective whole-genome amplification (SWGA) utilizing multiple displacement amplification (MDA) in conjunction with custom oligonucleotides with an increased specificity for the T. pallidum genome and the capture and removal of 5'-C-phosphate-G-3' (CpG) methylated host DNA using the NEBNext Microbiome DNA enrichment kit followed by MDA with the REPLI-g single cell kit as enrichment methods to improve the yields of T. pallidum DNA in isolates and lesion specimens from syphilis patients. Sequencing was performed using the Illumina MiSeq v2 500 cycle or NovaSeq 6000 SP platform. These two enrichment methods led to 93 to 98% genome coverage at 5 reads/site in 5 clinical specimens from the United States and rabbit-propagated isolates, containing >14 T. pallidum genomic copies/μL of sample for SWGA and >129 genomic copies/μL for CpG methylation capture with MDA. Variant analysis using sequencing data derived from SWGA-enriched specimens showed that all 5 clinical strains had the A2058G mutation associated with azithromycin resistance. SWGA is a robust method that allows direct whole-genome sequencing (WGS) of specimens containing very low numbers of T. pallidum, which has been challenging until now.

59 BASIC BIOLOGICAL SCIENCES↗

Recovery of Forest Structure Following Large-Scale Windthrows in the Northwestern Amazon

The dynamics of forest recovery after windthrows (i.e., broken or uprooted trees by wind) are poorly understood in tropical forests. The Northwestern Amazon (NWA) is characterized by a higher occurrence of windthrows, greater rainfall, and higher annual tree mortality rates (~2%) than the Central Amazon (CA). We combined forest inventory data from three sites in the Iquitos region of Peru, with recovery periods spanning 2, 12, and 22 years following windthrow events. Study sites and sampling areas were selected by assessing the windthrow severity using remote sensing. At each site, we recorded all trees with a diameter at breast height (DBH) ≥ 10 cm along transects, capturing the range of windthrow severity from old-growth to highly disturbed (mortality > 60%) forest. Across all damage classes, tree density and basal area recovered to >90% of the old-growth values after 20 years. Aboveground biomass (AGB) in old-growth forest was 380 (±156) Mg ha -1 . In extremely disturbed areas, AGB was still reduced to 163 (±68) Mg ha -1 after 2 years and 323 (± 139) Mg ha -1 after 12 years. This recovery rate is ~50% faster than that reported for Central Amazon forests. The faster recovery of forest structure in our study region may be a function of its higher productivity and adaptability to more frequent and severe windthrows. These varying rates of recovery highlight the importance of extreme wind and rainfall on shaping gradients of forest structure in the Amazon, and the different vulnerabilities of these forests to natural disturbances whose severity and frequency are being altered by climate change.

54 ENVIRONMENTAL SCIENCES↗

Onboard Detection of Active Canadian Sulfur Springs: A Europa Analogue

We discuss a current, ongoing demonstration of insitu onboard detection in which the Earth Observing-1 spacecraft detects surface sulfur deposits that originate from underlying springs by distinguishing the sulfur from the ice-rich glacial background, a good analogue for the Europan surface. In this paper, we describe the process of developing the onboard classifier for detecting the presence of sulfur in a hyperspectral scene, including the use of a training/testing set that is not exhaustively labeled, i.e.not all true positives are marked, and the selection of 12, out of 242, Hyperion instrument wavelength bands to use in the onboard detector. This study aims to demonstrate the potential for future missions to capture short-lived science events, make decisions onboard, identify high priority data for downlink and perform onboard change detection. In the future, such capability could help maximize the science return of downlink bandwidth-limited missions, addressing a significant constraint in all deep-space missions.

autonomy↗

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO 2

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO 2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron-hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO 2 to CO. Here, the interfacial dynamics and catalytic behavior are clearly revealed by time-resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine-captured CO 2 , namely carbamates, for direct photochemical conversion without additional energy input.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CFD Modeling of Concentration Polarization in High-Performance Flat-Sheet Modules

Membrane-based gas separation is a promising, regeneration-free route for industrial CO₂ capture, but its performance is often limited by concentration polarization (CP). Classical 1-D models neglect CP and thus overpredict fluxes, especially for today’s high-permeance, high-selectivity membranes. Therefore, we built a 3-D CFD model that resolves local species transport, boundary-layer resistance, permeate-side effects, and pressure drop in flat-sheet modules. Using the Concentration Polarization Coefficient (CPC) and the overall Effective Membrane CP Index (EAC), the model quantifies how geometry and operating conditions shape CP intensity. Simulations show CP becomes pronounced for advanced membranes, with feed-channel height emerging as the dominant geometric lever: shrinking the gap mitigates CP but raises pressure drop, forcing a trade-off between mass-transfer enhancement and energy cost. These insights emphasize the need for CFD-level analysis in next-generation module design, where 1-D treatments can severely underestimate required membrane area and misguide scale-up.

carbon capture↗

Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Water-gas shift (WGS) reaction followed by carbon dioxide (CO 2 ) separation is a critical step in the integrated gasification combined cycle (IGCC) process for fossil-fuel-fired electrical power generation with CO 2 capture. To intensify the IGCC process hydrogen-permselective zeolite membrane reactor offers promise to replace the conventional energy-intensive fixed-bed reactors and solvent-based CO 2 capture units. The objectives of this project were to develop a bench-scale zeolite membrane reactor (total membrane area: 932 cm 2 for a 21-tube membrane bundle) for the water-gas-shift reaction of raw syngas from an oxygen-blown coal-gasifier for H 2 production with simultaneous CO 2 separation at the capability of about 2 kilograms H 2 per day (equivalent to 2 kW IGCC power plant) and to demonstrate significant progress toward achieving overall performance goal of 90% CO 2 capture rate with 95% CO 2 purity at the cost of electricity 30% less than the baseline carbon capture approaches. This report summarizes results obtained in this project on scaling up the zeolite membrane reactor by a factor of 200 in membrane area, tests of the bench-scale zeolite membrane reactor for the water-gas-shift reaction at high temperature and high-pressure, and techno-economic analysis of the integration of the zeolite membrane reactor in IGCC power plant for the electrical generation with CO 2 capture. With effective pore modification by catalytic cracking deposition of MDES (methyldiethoxysilane), fabrication of MFI-type zeolite membranes was successfully scaled-up from a lab-scale disk type to bench-scale multiple-tube bundles on low-cost alumina supports. A Co-Mo based sour shift catalyst was evaluated and used in the zeolite membrane reactors for water-gas-shift reaction. The reaction kinetic and gas-permeation equations were developed and employed in mathematic models to guide/predict experiments/performance of zeolite membrane reactors for water-gas shift reaction. Multiple-tube zeolite membrane bundles and reactors were designed, fabricated and tested for gas separation and water-gas-shift reactions with real raw syngas from a coal-fired gasifier operated at high temperature and pressure. The zeolite membrane reactors demonstrated good long-term thermal and chemical stability and constant H 2 permeance (>300 GPU) together with a Knudsen selectivity (~4.7) for H 2 over CO 2 in the field test (cumulative time >28 hours) with high-sulfur coal-derived syngas. The zeolite-membrane-reactor integrated IGCC process was designed using the performance experimentally measured by the University of Cincinnati team with a single-tube zeolite membrane reactor that offers a CO conversion >98% with more than 90% of CO 2 and H 2 captured. With the above integrative approaches, a techno-economic analysis for a cost-benefit comparison was performed to uncover features that determine the power output, capital expenditure, operating expenditure, cost of electricity and cost of CO 2 capture in a 550-MW zeolite-membrane-reactor integrated IGCC process. The integration of the zeolite membrane reactor in IGCC could provide a significant reduction of 80% and 27% in the power consumption for Selexol™ Acid Gas Removal and CO 2 compression, respectively, which lowers the total auxiliary power consumption by 12.5%. However, the low pressure required at permeate stream for maintaining the driving force of hydrogen permeation through the zeolite membrane costs a huge power in permeate compressor, compensating the power consumption reduction achieved with the membrane reactor. Thus, for coal-fired IGCC for electricity generation with 90% CO 2 captured, the integration of the membrane reactor could provide a CO conversion ~99% and a significant drop in cost-of-electricity using zeolite membrane with H 2 permeance >600 GPU and the H 2 /CO 2 selectivity over 70.

01 COAL, LIGNITE, AND PEAT↗

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

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

Cantu Cantu, David↗

Encapsulation of Nanoparticle Organic Hybrid Materials within Electrospun Hydrophobic Polymer/Ceramic Fibers for Enhanced CO 2 Capture

Liquid-like nanoparticle organic hybrid materials (NOHMs) consisting of a silica core with ionically grafted branched polyethyleneimine chains (referred to as NIPEI) are encapsulated within submicron-scale polyacrylonitrile (PAN)/polymer-derived-ceramic electrospun fibers. The addition of a room-temperature curable, liquid-phase organopolysilazane (OPSZ) ceramic precursor to the PAN/NOHM solution enhances the internal dispersion of NOHMs and forms a thin ceramic sheath layer on the fiber exterior, shielding the hydrophilic NIPEI to produce near-superhydrophobic non-woven fiber mats with contact angles exceeding 140°. 60:40 loadings of NOHMs to PAN/OPSZ can be reliably achieved with low OPSZ percentages required, and up to 4:1 NOHM:polymer loadings are possible before losing hydrophobicity. These fibers demonstrate up to ≈2 mmol CO 2 g -1 fiber capture capacities in a pure CO 2 atmosphere through the nonwoven fibrous networks and the permeability of the OPSZ shell. In conclusion, the hybrid fibers additionally show enhanced capture kinetics under pure CO 2 and 400 ppm CO 2 conditions, indicating their promising application as a direct air capture platform.

36 MATERIALS SCIENCE↗

Chemical Design of Pb-Free Relaxors for Giant Capacitive Energy Storage

Dielectric capacitors have captured substantial attention for advanced electrical and electronic systems. Developing dielectrics with high energy density and high storage efficiency is challenging owing to the high compositional diversity and the lack of general guidelines. Herein, we propose a map that captures the structural distortion ($\delta$) and tolerance factor (t) of perovskites to design Pb-free relaxors with extremely high capacitive energy storage. Our map shows how to select ferroelectric with large $\delta$ and paraelectric components to form relaxors with a t value close to 1 and thus obtaining eliminated hysteresis and large polarization under a high electric breakdown. Taking the Bi 0.5 Na 0.5 TiO 3 -based solid solution as an example, we demonstrate that composition-driven predominant order-disorder characteristic of local atomic polar displacements endows the relaxor with a slushlike structure and strong local polar fluctuations at several nanoscale. This leads to a giant recoverable energy density of 13.6 J cm -3 , along with an ultrahigh efficiency of 94%, which is far beyond the current performance boundary reported in Pb-free bulk ceramics. In conclusion, our work provides a solution through rational chemical design for obtaining Pb-free relaxors with outstanding energy-storage properties.

25 ENERGY STORAGE↗

Machine learning with persistent homology and chemical word embeddings improves prediction accuracy and interpretability in metal-organic frameworks

Machine learning has emerged as a powerful approach in materials discovery. Its major challenge is selecting features that create interpretable representations of materials, useful across multiple prediction tasks. We introduce an end-to-end machine learning model that automatically generates descriptors that capture a complex representation of a material’s structure and chemistry. This approach builds on computational topology techniques (namely, persistent homology) and word embeddings from natural language processing. It automatically encapsulates geometric and chemical information directly from the material system. We demonstrate our approach on multiple nanoporous metal–organic framework datasets by predicting methane and carbon dioxide adsorption across different conditions. Our results show considerable improvement in both accuracy and transferability across targets compared to models constructed from the commonly-used, manually-curated features, consistently achieving an average 25–30% decrease in root-mean-squared-deviation and an average increase of 40–50% in R 2 scores. A key advantage of our approach is interpretability: Our model identifies the pores that correlate best to adsorption at different pressures, which contributes to understanding atomic-level structure–property relationships for materials design.

97 MATHEMATICS AND COMPUTING↗