Ordered Cationic Mixing in a 1D Organic–Inorganic Hybrid
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Cassingham, Megan A. [Department of Chemistry; Uni↗
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Solution and Active Site Speciation Drive Selectivity for Electrocatalytic Reactive Carbon Capture in Diethanolamine over Ni-N-C Catalysts (Lightning Talk)
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Chemistry↗
Methane pyrolysis by Joule heating for graphitic carbon and hydrogen production
The global energy transition toward sustainability requires technologies that can decarbonize energy carriers and fuels while producing valuable materials. Methane, a primary component of natural gas, is both a high-energy-density fuel and a significant greenhouse gas. This study reports an approach for methane pyrolysis utilizing Joule heating within the deposition substrate to drive the endothermic reaction. With electric current passing through a resistive porous carbon cloth, heat is generated to break C-H bonds of methane molecules. Here, the decomposition of methane as it flows through the cloth results in hydrogen production and the formation of conformally layered graphite around the carbon fibers. The effects of input power, chamber pressure, feedstock flow rate, and process duration on hydrogen and graphite production are characterized via in situ mass spectrometry and laser absorption spectroscopy, resulting in methane conversion rates up to 88%, with hydrogen and carbon yields of 82% and 72%, respectively. Material characterization verifies uniform high-quality graphite deposition, with a Raman I D /I G ratio of 0.1 and 3.38 Å d-spacing. This Joule heating method for catalyst-free methane pyrolysis offers the potential for advancing hydrogen production technology by simultaneously producing valuable materials such as solid graphite, thus enhancing the economic viability of the fuel decarbonization process.
Energy Resources↗
Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex
Here, the authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 (μ 3 -H)(PN) 3 ] 2+ (2-H, PN = (2-pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2-H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 (μ-H) 4 (PN) 3 ] + (5). Neutron crystallography and DFT-supported neutron vibrational spectroscopy of 2-H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2-H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra- and pentanuclear clusters [Ir 3 H 6 (μ 3 -AuPPh 3 )(PN) 3 ] 2+ (2-Au) and [Ag{Ir 2 H 4 (μ-OAc)(PN) 2 } 2 ] 3+ (6) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 (μ-X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 (μ-Cl) 2 (PN) 2 ] (11).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crack formation in strained β-(AlxGa 1−x ) 2 O 3 films grown on (010) β-Ga 2 O 3 substrates
The cracking and local strain relaxation in (010) (Al x Ga 1−x ) 2 O 3 films grown on Ga 2 O 3 substrates are assessed in terms of film composition and thickness. We utilize x-ray diffraction and electron microscopy techniques combined with simulation and modeling to investigate that film cracking on curvature (flatness) has a directly proportional relationship with film thickness and/or aluminum content. Cross section transmission electron microscopy reveals that cracks along both the (001) and (100) cleavage planes penetrate into the substrate. The diffuse scattered intensity observed in reciprocal space maps (RSMs) is directly correlated with the tilt that is introduced due to the change in the deformation conditions near the cracks. While asymmetric RSMs show that the layers are fully strained, the diffuse scattering distribution in reciprocal space can be interpreted to show that the cracking relaxes and locally tilts the lattice ∼350 nm from the crack edges, which is consistent with the larger radius of curvature associated with the films with higher crack densities. For example, a 200 nm (Al 0.13 Ga 0.87 ) 2 O 3 thick film has an average inter-crack spacing of 3.3 µm, so most of the epitaxial layer is fully strained except near the cracks where it deforms elastically and is consistent with the gallium oxide Poisson ratio. A reciprocal space model was developed, which imports the strain and tilt distributions (based on finite element modeling) to match the features observed in the experimental maps. We also note that previous studies involving (Al x Ga 1−x ) 2 O 3 films may show evidence of cracking as observed in their symmetric and asymmetric RSMs.
36 MATERIALS SCIENCE↗
High Multiplicity Trigger for long-lived particles in CMS detector
Searches for long-lived particles (LLPs) at the CMS experiment often involve unconventional event topologies that are difficult to efficiently select using standard trigger strategies. To improve sensitivity to such signatures during LHC Run 3 operation, a dedicated High Multiplicity Trigger (HMT) has been developed and deployed in the CMS trigger system. The trigger targets events containing unusually large numbers of hits in the CMS cathode strip chamber (CSC) muon detectors, a characteristic signature of several LLP scenarios involving displaced decays in the muon system. The HMT implementation, trigger logic, rate dependence with pileup, and operational stability are described. Optimized hit multiplicity thresholds are used to maintain acceptable trigger rates under high-luminosity and high-pileup conditions while preserving high efficiency across a broad range of LLP lifetimes and kinematic regimes. The trigger performance is evaluated using both simulated event samples and proton-proton collision data collected during Run 3 of the LHC. The HMT substantially extends the CMS sensitivity to non-standard signatures associated with LLP decays and provides a flexible platform for future searches for physics beyond the Standard Model.
47 OTHER INSTRUMENTATION↗
Whole genome sequence of the syntrophic benzoate-degrading bacterium, Syntrophus buswellii DSM 102354 T
The syntrophic obligate proton-reducing bacterium Syntrophus buswellii DSM 102354 T , isolated from anaerobic digester sludge, degrades benzoate and possibly hydrocinnamate (phenyl-3-propionate) when grown with a suitable hydrogenotrophic partner. The complete genome sequence data provide insight regarding aromatic compound degradation under thermodynamically limiting conditions when exogenous electron acceptors are absent.
Syntrophus↗
Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2
Abstract Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water‐gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine‐learning interatomic potentials (MLIPs) integrated with an active‐learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high‐resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.
Lee, Yonghyuk [Chemistry and Biochemistry Universi↗
Mitigating CaCO 3 crystal nucleation and growth through continuous ion displacement via alternating electric fields
Mineral crystal formation poses a challenge on surfaces (e.g., heat exchangers, pipes, membranes, etc.) in contact with super-saturated fluids. Applying alternating currents (AC) to such surfaces can prevent surface crystallization under certain conditions. Here, we demonstrate that ion displacement induced by periodic charging and discharging of the electrical double layer (EDL) inhibits both heterogeneous and homogeneous nucleation (and crystal growth) of CaCO 3 . Titanium sheets (meant to simulate metallic heat exchanger surfaces) are immersed in super-saturated CaCO 3 solutions with a saturation index >11. We show that at relatively high AC frequencies, incomplete EDL formation leads to an alternating electric field that propagates far into the bulk solution, inducing rapid ion migration that overwhelms the Brownian motion of ions. Electrochemical characterization reveals EDL charging/discharging under AC conditions that greatly inhibits precipitation. Operating at 4 V pp , 0.1–10 Hz reduces turbidity by over 96% and reduces CaCO 3 coverage on the metal plates by over 92%. Based on electrokinetic and crystallization models, the ion displacement velocity (exceeding the mean Brownian velocity) and displacement length disrupts ion collision and crystal nucleation. Overall, the technique has potential for preventing mineral crystal formation in heat exchangers and many other industrially relevant systems.
42 ENGINEERING↗
On the Structural Origin of Fast Li-Ion Cycling in Tetragonal Bronze-Type Nb 8 W 9 O 47
Bronze and bronze-derived, mixed metal oxides are materials of growing interest for lithium-ion battery anodes due to their high-rate capabilities and the potential for high energy densities via multielectron redox. We report on the synthesis and electrochemical properties of the tetragonal tungsten bronzetype phase Nb 8 W 9 O 47 and our investigation into the structural evolution of this phase upon lithium (de)intercalation, with particular attention to how it relates to the fast-cycling capabilities. Electrochemical cycling shows Nb 8 W 9 O 47 can achieve greater than one Li + per transition metal at rates of C/2 or slower and maintains a capacity equivalent to 0.65 Li + per transition metal at a rate of 20C. Sequential Rietveld analysis of operando X-ray diffraction data reveals anisotropic changes to the unit cell parameters during discharge, accompanied by an off-centering of the transition metals within their octahedral environments. While higher capacities can be accessed below 1.2 V, cells discharged to 1.0 V exhibit a significant expansion of the unit cell volume and reduced Coulombic efficiencies. This report suggests that rigid crystal structures incapable of undergoing polyhedral rotational deformations can instead exploit displacive distortions of the transition metal redox center to enable fast Li-ion cycling with minimal atomic rearrangements.
25 ENERGY STORAGE↗
Decoding α-MoC 1− x Nanoparticle Formation in Continuous Flow via Machine Learning
Molybdenum carbide nanoparticles (α-MoC 1−x NPs) are promising catalysts that offer noble-metal-like performance at lower cost. We report a mild continuous-flow synthesis of α-MoC 1−x NPs from Mo(CO) 6 , coupled with in-line spectroscopic monitoring and machine learning (ML)-based analysis to quantify precursor conversion and product formation in real time. A multilayer perceptron ML model was found to accurately deconvolute complex, nonlinear spectral patterns, enabling identification of a two-step reaction pathway, involving precursor conversion to an amorphous intermediate followed by intraparticle crystallization to α-MoC 1−x NPs, with the first step being rate limiting. Ex situ small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) validation confirm the predicted concentration profiles and crystallization behavior. This integrated approach showcases how ML can empower insights into NP nucleation and growth, paving the way for self-driving, flow-based platforms for NP synthesis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Solution and Active Site Speciation Drive Selectivity for Electrocatalytic Reactive Carbon Capture in Diethanolamine over Ni-N-C Catalysts
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Chemistry↗
Strategic Lifetime Tuning of Visible-Light Absorbing Two-Coordinate Metal Complexes
This paper highlights how the singlet and triplet amide ligand centered ( 1,3 LC) and interligand charge transfer ( 1,3 ICT) states in (carbene)M(amide), M = Cu, Au (cMa) complexes influence the excited state properties when the triplet states are close in energy. To that end we prepared a set of five cMa complexes, in which the amide (i.e., 5H-benzo[b]carbazole, H-BnCz) was kept constant giving a 3 LC energy of ca. 2.15 eV. Four different carbene ligands were selected to develop M BnCz Carbene complexes which have energies for the ICT state that vary from being either markedly higher, lower, or close to the energy of the 3 LC state on the amide ligand. Steady-state and time-resolved spectroscopic studies show that the emission spectrum of the cMa complex mirrors the phosphorescence of the parent H-BnCz amide and has a luminescence decay lifetime in the millisecond regime when the lowest energy excited state is 3 LC. When the lowest energy states are 1,3 ICT in nature, the emission band is broad and featureless, giving a lifetime in the nanosecond regime. As the 3 LC and 1,3 ICT states have comparable energies, dynamic equilibrium between the states is observed with the luminescence consisting of a mixture of 3 LC and 1,3 ICT transitions. The measured lifetime of this equilibrating system is between 45 and 350 μs depending on the solvent, for both copper- and gold-based cMa complexes. Furthermore, these complexes demonstrate the ability to “park” the excited state population in the 3 LC state, allowing it to act as a reservoir for thermally activated emission, while still maintaining a very rapid equilibrium between LC and ICT states.
14 SOLAR ENERGY↗
Uncovering the True Active Sites in Ni–N–C Catalysts for CO 2 Electroreduction
Understanding and designing active sites in single-atom catalysts (SACs) requires going beyond static models to capture their dynamic evolution under realistic electrochemical conditions. Here, in this work, we develop an integrated theoretical framework that accounts for operational conditions, by combining grand canonical density functional theory (GC-DFT) with machine-learning-accelerated sampling, to uncover structure–activity–stability relationships in Ni–N–C SACs for the CO 2 reduction reaction (CO 2 RR). A library of NiN x C 4–x (x = 0–4) motifs─representing coordination defects likely formed during high-temperature synthesis─was systematically evaluated. Under working conditions, these sites were found to undergo hydrogenation, and NiN 3 C 1_ H 1 was identified as the most probable active site. At reducing potentials, hydrogen adsorbs spontaneously at C–Ni bridge sites rather than Ni top sites, while subsurface hydrogen facilitates bent CO 2 adsorption crucial for activation. High CO 2 RR selectivity toward CO arises from site separation: Ni centers drive CO2RR, while the hydrogen evolution reaction (HER) occurs at the C–Ni bridge or N sites and from thermodynamic suppression of HER at moderate hydrogen coverage. At more negative potentials, a shift in the CO 2 RR rate-determining process (RDP) and Ni out-of-surface displacement induced by coadsorption of H and H 2 O jointly reduce activity and selectivity. Thus, both the high CO2RR selectivity of Ni–N–C catalysts and its reversal with more negative potentials can be rationalized by accounting for hydrogenated surfaces. This highlights the necessity of modeling realistic; in situ conditions. This framework provides generalizable insights into the dynamic behavior of active sites in SACs, offering guidance for the rational design of active and robust catalysts for a wide range of electrochemical reactions.
25 ENERGY STORAGE↗
Polymorphic Control of CsGaE 2 (E = S, Se) Using Diorganyl Dichalcogenide Precursors
Diorganyl dichalcogenides (R–E–E–R; R = organyl, E = S, Se, Te) are widely employed for the polymorphic control of diamond-like crystal structures owing to their tunable C–E bond reactivity. In this work, we extend their application to non-close-packed alkali metal-based chalcogenides by demonstrating the selective synthesis of CsGaE 2 (E = S, Se) polymorphs. Weaker C–E bonds or higher temperatures promote the formation of the thermodynamically stable mC64 phases, while stronger C–E bonds or lower temperatures allow for the isolation of the metastable mC16 phases. Furthermore, heat-treatment studies reveal the pronounced metastability of CsGaSe 2 -mC16 particles and the irreversible phase transition of CsGaS 2 analogous to its bulk counterpart.
Cancer↗
Multi-purpose quantum laboratories from superconducting circuits
Superconducting circuits (SCs) are the cornerstone of modern quantum technology, enabling scalable computing through coherent control of macroscopic quantum states. Through a legacy that predates modern quantum computing, SCs have emerged as high-precision instruments for discovery. In this review, we highlight the role of SCs as general-purpose quantum laboratories, outlining the emerging landscape of correlated matter-circuit science. We review and unify the capabilities of superconducting quantum hardware across condensed matter, high energy and quantum information sciences. We trace the technical evolution of these architectures, illustrating how their foundational development has culminated in a toolkit for resolving the complexities of macroscopic quantum states.
Arora, Arpit [UCLA, Los Angeles (main); UCLA; Haim↗
Ultrahigh pressure compaction-resistant thin film crosslinked composite reverse osmosis membranes
In this study, we present a class of thin-film crosslinked (TFX) composite reverse osmosis (RO) membranes that resist physical compaction at ultrahigh pressures (up to 200 bar). Since RO membranes experience compaction at virtually all pressure ranges, the ability to resist compaction has widespread implications for RO membrane technology. The process described herein involves crosslinking a phase inverted porous polyimide (PI) support membrane followed by interfacial polymerization of a polyamide layer, thereby forming a fully thermoset composite membrane structure. We explore a range of phase inversion membrane formation parameters such as PI concentration, solvent-cosolvent ratios, coagulation bath composition, and crosslinking methods in addition to interfacial polymerization reaction chemistry and conditions. Overall, TFX membranes exhibit significantly less compaction compared to hand-cast and commercial high-pressure RO membranes, experiencing less than 10% decline in water permeance and maintaining salt rejection over 99% for NaCl solutions up to 180,000 mg/L with 200 bar applied pressure.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Demonstration of tokamak vertical stability control based on non-inductive Faraday-effect polarimetry measurements
Long-pulse or steady-state fusion reactors are envisioned to control vertical stability based on non-inductive measurements, i.e. that do not rely on temporal change of magnetic field. For the first time, vertical stability control using non-inductive Faraday-effect polarimetry measurements has been demonstrated. The Radial Interferometer-Polarimeter system on DIII-D is capable of microsecond resolution and was used to absolutely determine the vertical position of the plasma magnetic axis Z 0 . A vertical stability controller was developed to robustly stabilize diverted plasmas using Faraday-based measurements. The system was able to stabilize against vertical displacement events with growth rates up to 350 s -1 in elongated and elliptical plasma shapes, and instabilities with even higher growth rates are likely to be controllable with further improvements to controller tuning. Tests show that the Faraday-based controller remains effective and is capable of recovering from loss of control even when the plasma vertical position is far from the region where the linear model used to calculate Z 0 is most valid. Faraday control has also been activated during plasma ramp-up, demonstrating the robustness of the technique to larger systematic diagnostic uncertainty at low electron density.
Faraday-effect polarimetry↗