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In situ catalyst activation and regeneration enable energy-efficient high-current CO 2 reduction to ethanol-rich C 2+ mixtures

Electrochemical conversion of dissolved CO 2 in bicarbonate electrolytes, i.e., bicarbonate electrolysis, offers distinct advantages over gas diffusion electrode systems by enabling direct utilization of the CO 2 capture electrolyte while bypassing the energy-intensive CO 2 release step. However, bicarbonate electrolysis faces challenges such as CO 2 mass-transfer limitation, local pH-driven CO 2 depletion, and high cathodic potentials. The higher potential often causes catalyst surface reorganization, leading to a gradual loss of active sites and variations in selectivity during CO 2 reduction. Here, we report a directed, in situ activation and regeneration method that allows precatalysts to equilibrate under dynamic (pulsed) electrolysis conditions. We demonstrate in situ activation of a scalable Cu 2 O/Cu mesh that, under short-width (t = 4 s) pulsed electrolysis, provides stable mixed oxidation states of Cu, favoring the formation of an ethanol-rich crude mixture. The pulsed electrolysis waveform, consisting of six distinct segments, is tuned to form Cu + oxides, which are then reduced to generate local alkaline conditions favoring C–C coupling. This synergistic effect results in FEs of 73% for C2+ products and 39% for ethanol at an applied current density of −150 mA cm −2 and a cathodic potential of −1.45 V (vs. RHE). The overall half-cell energy efficiency is ∼30% for C 2+ products. The in situ Raman experiments confirm the role of pCO 2 R in dynamically regenerating Cu+-containing surface species during pulsed operation, thereby steering selectivity towards C 2+ products. A comprehensive multiscale, multiphysics model is developed to investigate the dynamic behavior of copper surface species (Cu, Cu + , and Cu 2+ ) and local microenvironmental conditions during the pCO 2 R. The results reveal that the coexistence of different copper oxidation states, especially the Cu+ intermediate, is critical in steering selectivity towards multicarbon (C 2+ ) products. The dynamic modulation of surface redox states via tailored pulsing strategies favors C–C coupling pathways by inducing localized alkaline conditions and stabilizing reactive intermediates. This work establishes a predictive modeling platform that links pulse waveform design with mechanistic insights into catalyst state evolution and product selectivity. Overall, this study provides valuable insights into the synergistic effect of in situ activation of pre-catalysts and pulsed electrolysis for higher selectivity towards C 2+ products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pyrite (001) Interface Chemistry is Controlled by a Sulfoxy Termination

Pyrite (FeS 2 ) is the most common sulfide mineral on Earth, forming through inorganic reactions in the crust and oceanic hydrothermal systems and via microbially driven processes in anaerobic sediments. The pyrite–water interface is the site of a wide range of adsorption and reaction processes in Earth systems including oxidation that dramatically affects the geochemistry of surface waters and influences global carbon and oxygen cycles. Mechanistic geochemical models of pyrite interfacial reactivity, however, are limited by the lack of experimentally derived atomistic structures of the reduced and reacting surfaces. Here, in this work, we reveal the atomic-scale structure of the pyrite (001)-water interface that forms at very low oxygen partial pressures, relevant to suboxic environments in Earth. The interface structure and surface speciation were obtained using the crystal truncation rod method supported by ambient-pressure photoelectron spectroscopy and density functional theory calculations. The surface is dominantly composed of disulfide groups bound to a single oxygen atom, forming a sulfoxy group that has no known molecular or bulk mineral analog. This surface is interpreted as the first step in the oxidative dissolution of pyrite. The sulfoxy group is readily protonated through surface acid–base reactions that alter the structure of interfacial water and the free energy of interfacial reactions. Surface iron sites are not oxidized. Surprisingly, this interface can likely develop in equilibrium with bulk pyrite in some reducing and acidic solutions. This termination is therefore likely representative of pyrite surfaces under a vast range of experimental, industrial and Earth conditions.

oxidation↗

The origin of KREEP

KREEP is a lunar material having very high concentrations of incompatible elements; its name is an acronym for the incompatibles K, rare-earth elements (REE), and P. Although a few pristine (endogenously igneous) KREEPy samples were returned from the Apollo 15 and 17 sites, most KREEPy samples are polymict breccias. Most models of KREEP petrogenesis have been based on partial melting of a variety of sources. Such models fail to explain the veritable absence of variations in incompatible element patterns over the sampled portion of the moon. We have defined a KREEP component based on the average composition of Apollo 14 breccias having extremely high concentrations of incompatible elements. Normalization of accurate incompatible data for KREEPy samples from the Apollo 12, 14, 15, 16, and 17 sites to this component virtually always shows no resolvable fractionation (e.g., <10% variation in the La/Lu ratio), whereas partial melting models typically produce larger fractionations (±20–25% in La/Lu) from a factor of 2 difference in degree of partial melting. Required is a single major source that could provide KREEP to widely separated locations on the nearside of the moon. The anorthositic crust of the moon is commonly attributed to the flotation of plagioclase on a deep, moon-wide magma ocean. Fractional crystallization of this magma ocean would have produced large enrichments of incompatibles in a residual liquid. No other plausible major source of incompatibles has been proposed. We borrow the German prefix ur—meaning primeval and designate this residual liquid ‘urKREEP.’ We propose that all KREEPy rocks originated by dilution of urKREEP with crustal or mantle materials during assimilation, or zone-refining (pristine samples), or impact-induced brecciation (breccias and melt rocks). The formation of urKREEP cannot be dated precisely. Correction of breccia Rb-Sr model ages for Rb loss or gain during the early intense bombardments yields ages that cluster in the range 4.4–4.5 Gy. This implies that crystallization of the magma ocean was essentially complete at this time and is in general agreement with U-Pb evidence indicating crustal formation at 4.4 Gy. Assuming that the moon had the composition of an H-group chondrite depleted in Fe-Ni and FeS and that half the incompatibles fractionated into materials other than urKREEP, the thickness of a moon-wide urKREEP layer was <2 km. Thorium concentrations determined by gamma ray spectroscopy indicate that about 4% of the incompatibles in an H chondritic moon are now in the outermost kilometer.

Paul H. Warren↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

Search for Fluid Inclusions in a Carbonaceous Chondrite Using a New X-Ray Micro-Tomography Technique Combined with FIB Sampling

Early solar system aqueous fluids are preserved in some H chondrites as aqueous fluid inclusions in halite (e.g., [1]). Although potential fluid inclusions are also expected in carbonaceous chondrites [2], they have not been surely confirmed. In order to search for these fluid inclusions, we have developped a new X-ray micro-tomography technique combined with FIB sampling and applied this techniqu to a carbanaceous chondrite. Experimental: A polished thin section of Sutter's Mill meteorite (CM) was observed with an optical microscope and FE-SEM (JEOL 7001F) for chosing mineral grains of carbonates (mainly calcite) and sulfides (FeS and ZnS) 20-50 microns in typical size, which may have aqueous fluid inclusions. Then, a "house" similar to a cube with a roof (20-30 microns in size) is sampled from the mineral grain by using FIB (FEI Quanta 200 3DS). Then, the house was atached to a thin W-needle by FIB and imaged by a SR-based imaging microtomography system with a Fresnel zone plate at beamline BL47XU, SPring-8, Japan. One sample was imaged at two X-ray energies, 7 and 8 keV, to identify mineral phases (dual-enegy microtomography: [3]). The size of voxel (pixel in 3D) was 50-80 nm, which gave the effective spatial resolution of approx. 200 nm. A terrestrial quartz sample with an aqueous fluid inclusion with a bubble was also examined as a test sample by the same method. Results and discussion: A fluid inclusion of 5-8 microns in quartz was clearly identified in a CT image. A bubble of approx. 4 microns was also identified as refraction contrast although the X-ray absorption difference between fluid and bubble is small. Volumes of the fluid and bubble were obtained from the 3D CT images. Fourteen grains of calcite, two grains of iron sulfide and one grain of (Zn,Fe)S were examined. Ten calcite, one iron sulfide and one (Zn,Fe)S grains have inclusions >1 micron in size (the maximum: approx. 5 microns). The shapes are spherical or irregular. Tiny inclusions (<1 micron) are also present in all the grains examined. These results show that mineral grains have more inclusions than expected from 2D observations. The X-ray absorption of the inclusions shows that they are not solid inclusions. No bubbles were observed inside, indicating that we cannot determine whether they are really aqueous fluids or merely voids. One calcite grain has an inclusion approx. 2 microns in size, which seems to have a bubble and a tiny solid daughter crystal inside (three-phase inclusion). As we know the exact 3D position of the inclusion, we will anlyze the inclusion by SIMS after freezing the sample as has been done for a halite sample [3]. The present technique is useful for finding small inclusions not only in carbonaceous chondrites but also for terrestrial materials.

Tsuchiyama, A.↗

Design and Performance Improvements of the Prototype Open Core Flywheel Energy Storage System

A prototype magnetically suspended composite flywheel energy storage (FES) system is operating at the University of Maryland. This system, designed for spacecraft applications, incorporates recent advances in the technologies of composite materials, magnetic suspension, and permanent magnet brushless motor/generator. The current system is referred to as an Open Core Composite Flywheel (OCCF) energy storage system. This paper will present design improvements for enhanced and robust performance. Initially, when the OCCF prototype was spun above its first critical frequency of 4,500 RPM, the rotor movement would exceed the space available in the magnetic suspension gap and touchdown on the backup mechanical bearings would occur. On some occasions it was observed that, after touchdown, the rotor was unable to re-suspend as the speed decreased. Additionally, it was observed that the rotor would exhibit unstable oscillations when the control system was initially turned on. Our analysis suggested that the following problems existed: (1) The linear operating range of the magnetic bearings was limited due to electrical and magnetic saturation; (2) The inductance of the magnetic bearings was affecting the transient response of the system; (3) The flywheel was confined to a small movement because mechanical components could not be held to a tight tolerance; and (4) The location of the touchdown bearing magnifies the motion at the pole faces of the magnetic bearings when the linear range is crucial. In order to correct these problems an improved design of the flywheel energy storage system was undertaken. The magnetic bearings were re-designed to achieve a large linear operating range and to withstand load disturbances of at least 1 g. The external position transducers were replaced by a unique design which were resistant to magnetic field noise and allowed cancellation of the radial growth of the flywheel at high speeds. A central rod was utilized to ensure the concentricity of the magnetic bearings, the motor/generator, and the mechanical touchdown bearings. In addition, the mechanical touchdown bearings were placed at two ends of the magnetic bearing stack to restrict the motion at pole faces. A composite flywheel was made using a multi-ring interference assembled design for a high specific energy density. To achieve a higher speed and better efficiency, a permanent magnet DC brushless motor was specially designed and fabricated. A vacuum enclosure was constructed to eliminate windage losses for testing at high speeds. With the new improvements the OCCF system was tested to 20,000 RPM with a total stored energy of 15.9 WH and an angular momentum of 54.8 N-m-s (40.4 lb-ft-s). Motor current limitation, caused by power loss in the magnetic bearings, was identified as causing the limit in upper operating speed.

Pang, D.↗