Elucidation of Diels–Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst
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bio-inspired↗
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COLDz: KARL G. JANSKY VERY LARGE ARRAY DISCOVERY OF A GAS-RICH GALAXY IN COSMOS
The broad spectral bandwidth at millimeter and centimeter wavelengths provided by the recent upgrades to the Karl G. Jansky Very Large Array (VLA) has made it possible to conduct unbiased searches for molecular CO line emission at redshifts, z > 1.31. We present the discovery of a gas-rich, star-forming galaxy at z = 2.48 through the detection of CO J = 1-0 line emission in the COLDz survey and through a sensitive, Ka-band (31-39 GHz) VLA survey of a 6.5 arcmin{sup 2} region of the COSMOS field. We argue that the broad line (FWHM ∼ 570 ± 80 km s{sup –1}) is most likely to be CO J = 1-0 at z = 2.48, as the integrated emission is spatially coincident with an infrared-detected galaxy with a photometric redshift estimate of z {sub phot} = 3.2 ± 0.4. The CO J = 1-0 line luminosity is L{sub CO}{sup ′}=(2.2±0.3)×10{sup 10} K km s{sup –1} pc{sup 2}, suggesting a cold molecular gas mass of M {sub gas} ∼ (2-8) × 10{sup 10} M {sub ☉} depending on the assumed value of the molecular gas mass to CO luminosity ratio α{sub CO}. The estimated infrared luminosity from the (rest-frame) far-infrared spectral energy distribution (SED) is L {sub IR} = 2.5 × 10{sup 12} L {sub ☉} and the star formation rate is ∼250 M {sub ☉} yr{sup –1}, with the SED shape indicating substantial dust obscuration of the stellar light. The infrared to CO line luminosity ratio is ∼114 ± 19 L {sub ☉}/(K km s{sup –1} pc{sup 2}), similar to galaxies with similar SFRs selected at UV/optical to radio wavelengths. This discovery confirms the potential for molecular emission line surveys as a route to study populations of gas-rich galaxies in the future.
79 ASTRONOMY AND ASTROPHYSICS↗
Synergistic effect of acidity and extraframework position in faujasite on renewable $p$-xylene production
p-Xylene is a commodity chemical used for the manufacture of plastic bottles and textiles. For the biomass-based route from 2,5-dimethylfuran (DMF) and ethylene, the properties of the catalyst such as acidity effect, product selectivity and catalyst activity play an important role. To determine the effect of acidity and extraframework position in faujasite zeolite on p-xylene selectivity, type Y (Si/Al = 40 and Si/Al = 2.55) and X (Si/Al = 1.25) zeolites containing the extraframework Lewis acids Na+, K+, Li+, Ag+ and Cu+, and a Brønsted acid-containing zeolite, HY (Si/Al = 40), were prepared and tested for p-xylene production under solvent-free conditions and at low conversions (less than 35%). Here it is reported that NaX zeolite catalyses DMF and ethylene conversion to p-xylene with 91% selectivity at 30% conversion, which is better than the 25% p-xylene selectivity obtained when using HY at similar conversion. ANOVA was used to show that there is a synergistic effect between acidity and extraframework position on the rate of p-xylene production. At 7% DMF conversion, Lewis acids were more selective than the Brønsted acid tested (50 versus 30% p-xylene selectivity). p-Xylene selectivity is optimal when using Lewis acids with moderate acidity and extraframework positions located in the faujasite supercage (sites II and III).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Composition Quantification of SiGeSn Alloys Through Time-of-Flight Secondary Ion Mass Spectrometry: Calibration Methodologies and Validation With Atom Probe Tomography
Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) is a powerful technique for elemental compositional analysis and depth profiling of materials. However, it encounters the problem of matrix effects that hinder its application. In this work, we introduce a pioneering ToF-SIMS calibration method tailored for SixGeySnz ternary alloys. SixGe1-x and Ge1-zSnz binary alloys with known compositions are used as calibration reference samples. Through a systematic SIMS quantification study of SiGe and GeSn binary alloys, we unveil a linear correlation between secondary ion intensity ratio and composition ratio for both SiGe and GeSn binary alloys, effectively mitigating the matrix effects. Extracted relative sensitivity factor (RSF) value from SixGe1-x (0.07 < x < 0.83) and Ge1-zSnz (0.066 < z < 0.183) binary alloys are subsequently applied to those of SixGeySnz (0.011 < x < 0.113, 0.863 < y < 0.935 and 0.023 < z < 0.103) ternary alloys for elemental compositions quantification. These values are cross-checked by Atom Probe Tomography (APT) analysis, an indication of the great accuracy and reliability of as-developed ToF-SIMS calibration process. Furthermore, the proposed method and its reference sample selection strategy in this work provide a low-cost as well as simple-to-follow calibration route for SiGeSn composition analysis, thus driving the development of next-generation multifunctional SiGeSn-related semiconductor devices.
36 MATERIALS SCIENCE↗
Flexible silicon photonic architecture for accelerating distributed deep learning
The increasing size and complexity of deep learning (DL) models have led to the wide adoption of distributed training methods in datacenters (DCs) and high-performance computing (HPC) systems. However, communication among distributed computing units (CUs) has emerged as a major bottleneck in the training process. In this study, we propose Flex-SiPAC, a flexible silicon photonic accelerated compute cluster designed to accelerate multi-tenant distributed DL training workloads. Flex-SiPAC takes a co-design approach that combines a silicon photonic hardware platform with a tailored collective algorithm, optimized to leverage the unique physical properties of the architecture. The hardware platform integrates a novel wavelength-reconfigurable transceiver design and a micro-resonator-based wavelength-reconfigurable switch, enabling the system to achieve flexible bandwidth steering in the wavelength domain. The collective algorithm is designed to support reconfigurable topologies, enabling efficient all-reduce communications that are commonly used in DL training. The feasibility of the Flex-SiPAC architecture is demonstrated through two testbed experiments. First, an optical testbed experiment demonstrates the flexible routing of wavelengths by shuffling an array of input wavelengths using a custom-designed spatial-wavelength selective switch. Second, a four-GPU testbed running two DL workloads shows a 23% improvement in job completion time compared to a similarly sized leaf-spine topology. We further evaluate Flex-SiPAC using large-scale simulations, which show that Flex-SiPAC is able to reduce the communication time by 26% to 29% compared to state-of-the-art compute clusters under representative collective operations.
Wu, Zhenguo (ORCID:0000000322847985)↗
Direct ink writing techniques for in situ gelation and solidification
Direct ink writing (DIW) is an extrusion-based 3D printing method which prints near ambient temperatures and has one of the broadest printable material selections among additive manufacturing techniques. However, DIW uses viscoelastic materials susceptible to collapse during printing. Overall, one promising route to improve the structural integrity of viscoelastic inks is using in situ curing methods to increase the yield strength of the printed structures after deposition. This review summarizes progress in three representative methods of in situ curing for DIW, including ultra-violet-induced crosslinking, rapid cure of reactive ingredients, and flash vaporization of a solution’s solvent to coagulate dissolved polymers.
36 MATERIALS SCIENCE↗
Design of a signal conditioner for the Fermilab Magnet Test Facility
This thesis describes the design of a remotely-programmable signal conditioner for the harmonic measurement of accelerator magnets. A 10-channel signal conditioning circuit featuring bucking capabilities was designed from scratch and implemented to the level of the printed circuit board layout. Other system components were chosen from those available on the market. Software design was started with the definition of routine procedures. This thesis is part of an upgrade project for replacing obsolescent automated test equipment belonging to the Fermilab Magnet Test Facility. The design started with a given set of requirements. Using a top-down approach, all the circuits were designed and their expected performances were theoretically predicted and simulated. A limited prototyping phase followed. The printed circuit boards were laid out and routed using a CAD software and focusing the design on maximum electromagnetic interference immunity. An embedded board was selected for controlling and interfacing the signal conditioning circuitry with the instrumentation network. Basic low level routines for hardware access were defined. This work covered the entire design process of the signal conditioner, resulting in a project ready for manufacturing. The expected performances are in line with the requirements and, in the cases where this was not possible, approval of trade-offs was sought and received from the end users. Part I deals with the global structure of the signal conditioner and the subdivision in functional macro-blocks. Part II treats the hardware design phase in detail, covering the analog and digital circuits, the printed circuit layouts, the embedded controller and the power supply selection. Part III deals with the basic hardware-related routines to be implemented in the final software.
43 PARTICLE ACCELERATORS↗
Microprogramable module
Device is small lightweight selective circuit/function panel that utilizes microelectronic circuits in flat packs to eliminate hard wiring and heavy-harness routing to various subsystems.
Stringer, E. J.↗
The role of catalyst acidity and microstructure on light olefin selectivity in polyethylene deconstruction in short contact time pulse Joule-heated reactors
The growing volume of plastics waste, compounded with a low recycling rate, has led to an alarming amount of plastics ending up in landfills or being incinerated. While pyrolysis offers a route for plastic waste deconstruction, its product distribution is often broad and poorly controlled due to unselective radical chemistry at high temperatures. We recently demonstrated that rapid pulse Joule-heated catalytic cracking over HZSM-5, combined with small fractions of steam, can achieve high selectivity (>80 %) toward C 2 -C 4 olefins, while significantly reducing coking compared to continuous Joule heating. Here, we investigate how acid catalyst properties, such as silica/alumina ratio, zeolite topology, and catalyst porosity, influence light olefin selectivity during polyethylene deconstruction via rapid pulse Joule heating. We demonstrate that silica-to-alumina ratios of ∼30 yield high light olefin selectivity, and small-pore zeolites favor light olefins at the expense of increased coke formation. To mitigate coking, we synthesize HZSM-5 nanosheets and hierarchical zeolites (MFI, FAU, and CHA). Furthermore, these catalysts achieve an ethylene selectivity of approximately 35 %, a twofold increase over prior catalytic pyrolysis. Additionally, co-feeding steam and incorporating hierarchical porosity reduce coke formation and enhance catalyst stability.
Catalytic cracking↗
Phase Discovery and Selected Synthesis of Subvalent Niobium Tellurides Using a Polytelluride Flux Strategy
Transition metal subchalcogenides involve electron-rich metals and can facilitate an in-depth understanding of the relationships among quantum properties such as superconductivity, charge density wave, and topological band structures. However, effective experimental routes toward synthesizing transition metal subchalcogenides are still lacking, hindering the development of new quantum materials. Herein, we propose a eutectic polytelluride flux strategy as an excellent solution to address phase discovery and crystal growth in transition metal subtelluride systems. We report new phases easily and selectively synthesized using a eutectic “K 3 Te 4 ” polytelluride flux upon adjusting the ratio of Nb metal to flux in the starting materials (K/Nb/Te = 3:x:4). Using a high Nb content in the solvent (x = 2 and 1), crystals of KNb 3 Te 3 O 0.38 and K 0.9 Nb 3 Te 4 are obtained. Both subtellurides exhibit diverse Nb clusters, including face-sharing and edge-sharing Nb 6 octahedral columns and zig-zag Nb chains. Reducing the Nb content to x = 0.33 leads to the formation of a layered compound, K 1.06 NbTe 2 . This compound comprises a NbTe 6 trigonal prism with K intercalated between the layers. Single crystals of known binary Nb tellurides can also be grown using another eutectic flux “KTe 3 . 2 ”, and the obtained NbTe 2 exhibits a new polymorphism with extra trimerization along the b-axis in the Nb–Nb bonded double zig-zag cluster. Finally, precise control over the structural dimensionality and oxidation state, combined with the facile crystal growth process, makes our synthetic strategy an efficient route to explore quantum materials in transition metal subchalcogenides.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes
The introduction of sp 3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show that such selectivity can be obtained through aryl functionalization of so-called ‘zigzag’ nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. Finally, we show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Identifying Critical Electrode Metrics for Efficient, Selective CO 2 Electrochemical Conversion
Low-temperature electrochemical CO 2 reduction (CO 2 R) in zero-gap membrane electrode assembly (MEA) reactors presents a scalable route to fuels and carbon utilization. However, performance at industrially relevant current densities hinges on mesoscale catalyst layer integration, particularly at the ionomer|catalyst interface. Here, we demonstrate a generalizable in situ electrochemical impedance spectroscopy (EIS) method. We utilize this technique to decouple electrode-level parameters that are correlated to the overall MEA performance. By performing this ex situ EIS method on CO 2 -to-CO catalyst-coated membranes with systematically varied ionomer-to-catalyst (I:C) ratios, we reveal a pronounced dependence of performance, ion transport resistance, and catalyst utilization on the I:C ratio as well as the electrode conditioning. We demonstrate that an optimal I:C ratio exists at which ion transport resistance is minimized and Faradaic efficiency for CO production is maximized. Beyond the electrodes examined, here we compare ion transport resistance to MEA selectivity/Faradaic efficiency obtained in prior studies, revealing a clear correlation between the two. These results suggest that ion transport resistance within the catalyst layer may be a quantitative predictor of MEA performance which underscores the importance of mesoscale integration in achieving scalable CO 2 R technologies.
08 HYDROGEN↗
Preliminary Routing for a National Laboratory Lab-Wide Commuting Program
There is a growing interest in reducing the amount of vehicle miles traveled (VMT), both in public and private sector organizations, in an effort to reduce overall carbon emissions. The Oak Ridge National Laboratory (ORNL), located in Oak Ridge, Tennessee, and located within close proximity to Knoxville, Tennessee, has more than 4,500 employees, most of which live in and around Knoxville. ORNL is currently developing a pilot commuting program for all employees, which incorporates the use of park-and-ride facilities. This study outlines the methodology behind the preliminary geoanalysis and routing used in developing a lab-wide commuting program. Due to privacy concerns, the data used for the study included numbers of employee residences per zip code rather than actual residential addresses. Commuting configurations by clustered zip code area and vehicle type were developed based on number of residences in a limited area, and the desire to minimize VMT. Central locations were selected using ArcGIS software. Satellite imagery was used to locate actual, suitable parking facilities to accommodate the specified number of residents involved in each commuting configuration. Optimized routing, and estimations of travel times, were performed using TransCAD GIS software. Energy estimates in kilowatt-hours (kwh) and gallons of gasoline, and gallons of gasoline equivalent, were all determined based on the scenarios. Standard petroleum-fueled vehicles were used in the initial estimates. Standard electric vehicles were also used in alternative scenarios to estimate potential additional energy and fuel savings. Furthermore the initial findings from this work will be used to develop a pilot program for ORNL.
99 GENERAL AND MISCELLANEOUS↗
Developing reactors for electrifying bio-methanation: a perspective from bio-electrochemistry
The integration of microbial synthesis with renewable electricity is an emerging route for both CO 2 utilization and seasonal energy storage in the form of stored bio-electrofuels. The major benefits of electrifying bioreactors include: using highly selective bio-catalysts for CO 2 conversion under mild reaction conditions; decoupling the production of more facile electrochemical intermediates, such as hydrogen, at the electrode from the production of bio-catalyzed multi-electron and/or carbon products, such as methane or acetate; using microbes as robust and self-regenerating catalysts enabling higher efficiency and durability in CO 2 conversion systems compared to inorganic catalysis. In this Perspective, we propose research aimed at developing electro-bioreactor components that will increase the productivity of the reactor while maintaining high energy efficiency and biocompatible reaction conditions to fully realize the benefits of electrified bioreactors. Furthermore, these developments include: flow reactors with tailored 3D electrodes to optimally use the reactor volume, electrocatalysts designed for peak performance in neutral pH electrolytes, high conductivity microbial media, and new membrane separator materials with high ion conductivity and low gas permeability. Production of methane via a hybrid electrical-biological approach is taken as a case study to motivate these developments. Finally, an iterative design–manufacture–test cycle, enabled by additive manufacturing and 3D printing technologies, is proposed to rapidly prototype components prior to large-scale manufacturing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Biphenyl dicarboxylates from ethene and bifuran dimethyl esters
The substrate scope of the Diels-Alder-Dehydration reaction was expanded to the deactivated bifuran structure. Dimethyl biphenyl-4,4'-dicarboxylate (1) and methyl 5- [4-(methoxycarbonyl)phenyl]-2-furoate (2) were synthesized from dimethyl 2,2'-bifuran-5,5'-dicarboxylate (3) via metal-triflate-catalyzed Diels-Alder-Dehydration reaction with ethene. A 31% yield of (1) was obtained using Sc(OTf)3 catalyst, and a 76.6% yield of (2) was obtained using La(OTf)3 catalyst under moderate reaction conditions. This approach is inherently selective to the 4,4'-dicarboxylates, and bypasses the methyl-group oxidation step of the dimethyl-biphenyl route.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Low Temperature Oxygen Activation on the NiAg(100) Single-Atom Alloy Surface
Silver-catalyzed ethylene epoxidation remains the only industrially viable route for ethylene oxide (EO) production. However, this process requires chlorine and other promoters to achieve a high EO selectivity while still generating substantial CO 2 emissions. A recent theory-guided approach identified Ni, in single-atom alloy (SAA) form, as a new promoter of this reaction. Specifically, the addition of Ni to Ag nanoparticles supported on α-Al 2 O 3 at a highly diluted ratio (1 Ni per 200 Ag atoms) increased catalyst selectivity to EO by ∼25%, the same increase afforded by the ubiquitous industrial promoter chlorine. To better understand the effect of Ni, we investigated the interaction of O 2 with NiAg(100) SAA surfaces by using scanning tunneling microscopy (STM) and density functional theory (DFT). While only molecular O 2 was present when pure Ag(100) was exposed to O 2 at 78 K, a distinct NiO 2 species, indicative of O 2 dissociation at Ni atom sites, was identified on the NiAg(100) SAA under the same conditions. High-resolution STM imaging backed by DFT simulations elucidated the formation of an O−Ni−O species with the oxygen atoms in 4-fold hollow sites. These findings provide direct experimental evidence that Ni atoms are very effective at O 2 activation, even at cryogenic temperatures. This suggests that, in addition to the known role of Ni in stabilizing the unselective nucleophilic oxygen on Ag, it could also accelerate O 2 dissociation, which can be rate limiting.
Catalysts↗
Dimensional Control of Octahedral Tilt in SrRuO 3 via Infinite-Layered Oxides
Manipulation of octahedral distortion at atomic scale is an effective means to tune the ground states of functional oxides. Previous work demonstrates that strain and film thickness are variable parameters to modify the octahedral parameters. However, selective control of bonding geometry by structural propagation from adjacent layers is rarely studied. Here we propose a new route to tune the ferromagnetism in SrRuO 3 (SRO) ultrathin layers by oxygen coordination of adjacent SrCuO 2 (SCO) layers. The infinite-layered CuO 2 exhibits a structural transformation from “planar-type” to “chain-type” with reduced film thickness. Two orientations dramatically modify the polyhedral connectivity at the interface, thus altering the octahedral distortion of SRO. The local structural variation changes the spin state of Ru and orbital hybridization strength, leading to a significant change in the magnetoresistance and anomalous Hall resistivity. Furthermore, these findings could launch investigations into adaptive control of functionalities in quantum oxide heterostructures using oxygen coordination.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Investigating the Effect of Lamination on FAMACs: Toward a New Phase Space of Perovskite Solar Cell Fabrication
The rapid progress in the field of perovskite solar cells has led to efficiencies approaching that of crystalline silicon in single junction devices, and increasing emphasis is now being placed on scalable fabrication strategies that have the potential to truly impact the photovoltaics industry. The standard fabrication route of sequential, layer-bylayer depositions to form the device stack is limited by the small range of selective materials that can withstand successive solvent exposures and thermal annealings. In order to overcome this limitation, we have developed a method to fabricate the device stacks through mechanical lamination under moderate pressures and temperatures. The procedure involves fabricating two transparent conductive oxide/transport material/perovskite half stacks and laminating them together at the perovskite/perovskite interface. This procedure previously achieved 10% efficiency in initial attempts based on methyl ammonium lead iodide (MAPI) perovskite compositions. Herein, we reported the fabrication conditions to achieve a reproducible lamination with a complex, multi-cation perovskite, [Cs0.05(MA0.17F A0.83)0.95P b(I0.83Br0.17)3] (FAMACs), laminated at 18 degrees C and with a pressure of 350 psi for 30 minutes. The resulting material showed a sharpening of the optical absorption edge and a slight reduction in the band gap from 1.622 eV to 1.616 eV, indicative of improved ordering and reduced defects. Concurrently, time resolved photoluminescence measurements revealed an increased luminescence lifetime from 85 ns to 123 ns.
14 SOLAR ENERGY↗