Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO[subscsript 2] Reduction: Mechanistic
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Li, Yi↗
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Data-driven multi-element substitution of TiFe alloys for tunable thermodynamics and enhanced activation behaviour for hydrogen storage
Due to their high volumetric hydrogen storage capacity under moderate storage conditions, TiFe alloys have been widely investigated as candidates for practical solid-state hydrogen storage. Partially substituting Ti or Fe sites can improve the key characteristics of TiFe alloys, such as the first hydrogen absorption step (activation) and the equilibrium hydrogen pressure (thermodynamic properties). However, the selection of substitution elements has heavily relied on intuition and trial-and-error. Also, conventional substitution strategies have mainly focused on single-element substitution within the TiFe alloy, limiting the design space and tunability for target applications. Here, to address this limitation, we report a multi-element substitution strategy motivated by an efficient, data-driven machine learning (ML) approach combined with corroborating density functional theory (DFT) calculations. Our models successfully predict experimentally measured hydride stability in five selected alloys using only compositional descriptors. Most importantly, the multi-element substitution leads to enhanced activation properties compared to pure TiFe, achieving near room-temperature activation behaviour. This work provides a method for on-demand tuning of hydrogen storage and activation properties, which may have broad implications for data-driven discovery of energy storage materials.
Cho, YongJun [Korea Advanced Institute Science and↗
Operation of helium sub-atmospheric multistage cryogenic centrifugal compressor trains: Part 2 – Transient modeling and pump-down path selection
Low-pressure conditions required for operation of helium cryogenic systems below the normal boiling point (i.e. 4.2 K) are established through a transient process, commonly referred to as ‘pump-down’. This process is defined as the transition from pressures above atmospheric conditions to the saturation pressure which corresponds to a specified operational temperature. The FRIB 2 K system consists of five cryogenic centrifugal compressors which are operated in series. Historically, the pump-down process path has been established through empirical methods and system operator experience. Investigation into the pump-down process at FRIB aimed to develop a pump-down methodology which relies on theoretical model predictions rather than empirically developed process paths. Ensuring stable operation during the pump-down process involved application of a centrifugal compressor performance prediction model, which is described in Part 1 of this paper. Compressor performance maps can be directly used to evaluate the stability of a selected pump-down path and anticipate the overall reliability of the selected path. In conjunction with the compressor performance maps, a system pressure model was developed to estimate the transient pressure response during the pump-down process. Lastly, an explicit equation was developed to establish a mass flow rate profile for the pump-down process. Implementation of the presented methodology (including the developed models) allows for the system operator to determine a continuous pump-down path which maintains compressor stability while conforming to overall system capabilities. Altogether, the methodology presented has resulted in simplification of transient pump-down operations and increased the reliability, stability and efficiency of the pump-down process.
Compressor train control↗
Decoupling plasma, catalyst, and gaseous mechanisms for non-oxidative methane conversion
Direct non-oxidative methane (CH 4 ) conversion to value-added hydrogen (H 2 ) and C 2 products remains hindered by fundamental catalytic scaling constraints and rapid surface deactivation at elevated temperatures. Plasma-enabled catalysis offers a promising route to overcome the thermodynamic and kinetic barriers of direct non-oxidative methane upgrading at mild conditions, yet control over C–C product selectivity and catalyst stability remains elusive. Here, we establish a unified mechanistic framework including Langmuir–Hinshelwood (L–H) and Langmuir–Rideal (L–R) mechanisms that disentangles the roles of plasma excitation (including vibrationally activated species and radicals), surface temperature (T sur ), and catalyst binding energy in steering CH 4 conversion to H 2 and C 2 hydrocarbons. Through a combination of density functional theory (DFT) informed microkinetic modeling, in situ and ex situ surface characterization, and product quantification under dielectric barrier discharge conditions, we show that vibrationally excited CH 4 lowers activation barriers selectively for dissociative chemisorption, enabling surface activation across a wide range of transition metal catalysts at low thermal energy input. We find that once CH 4 is dissociatively chemisorbed, the branching between C 2 H 2 , C 2 H 4 , and C 2 H 6 is governed by surface properties (carbon binding energy, T sur , etc), regardless of plasma excitation. The DFT informed microkinetic model decouples the effects of molecular activation from surface properties and indentifies operating windows that maximize target yields while suppressing carbon accumulation and subsequent catalytic inactivation. Experiments on polycrystalline Cu/Al 2 O 3 , Ni/Al 2 O 3 , and Pt/Al 2 O 3 validate these predictions, revealing catalyst-dependent branching toward ethane or ethylene and distinct deactivation profiles. We unify these trends into a generalized three-dimensional plasma-thermal-catalytic design space, from which reduced descriptors such as T vib /T sur in the limit of vibrationally excited L–H pathways emerge as predictive metrics. These results enable rational tuning of methane conversion pathways and unlock selective C 2 formation using earth-abundant metals under mild plasma conditions.
catalyst inactivation↗
Catalytic oxidative coupling of arenes and alkanes: applications for efficient chemical synthesis and for hydrocarbon oligomerization. Progress Report 2016-7. Final report
This is the final report for DE-FG02-08ER15997 with a grant period of 8/15/2008-8/14/2018 (plus 1 year NCE); Program: Basic Energy Sciences; PI: Melanie S. Sanford; co-PI: Adam J. Matzger. The project resulted in 20 publications, 12 supported entirely by this grant and 8 supported substantially by this grant. The overall goals of this project were design catalysts (both homogeneous catalysts and MOF-supported catalysts) to control reactivity and selectivity in energy relevant C–H bond functionalization reactions. The proposed research led to a variety of new catalysts and catalytic processes which are currently finding application in organic synthesis. These efforts were well aligned with the goals of the DOE BES Catalysis Science Program. C–H functionalization reactions have extensive applications in energy-related industries, including petroleum and biofuels processing. The research activities also matched many of the priority areas identified by the Catalysis Science Program, including: investigating problems at the interface of heterogeneous and homogeneous catalysis as a means to derive new catalysts; incorporating 2° interactions to modulate catalyst stability, reactivity, and selectivity; using these new catalysts to tune molecular-level catalytic activity and selectivity; and studying structure-reactivity relationships of inorganic, organic, or hybrid catalytic materials in solution.
02 PETROLEUM↗
The interaction of reactants, intermediates and products with Cu ions in Cu-SSZ-13 NH3 SCR catalysts: An energetic and ab initio X-ray absorption modeling study
Copper-exchanged SSZ-13 (Cu-SSZ-13) provides excellent catalytic activity and hydrothermal stability in the selective catalytic reduction (SCR) of NOx by using NH3 as a reductant. In this contribution, we compare the most likely positions for Cu with a single charge compensating Al atom (ZCu), including the effect of the adsorption of reactants, intermediates and products of a NH3 SCR reaction by using first-principles calculations based on density functional theory. We find that the 6-membered ring (6MR) site is the most energetically favorable while the 8-membered ring (8MR) sites are less favorable with energy differences about 0.5 eV with respect to the 6MR site. Upon molecular adsorption, the energy differences between Cu in the 8MR and 6MR sites decreases and almost disappears, which means that the thermodynamic stability of ZCu with molecularly adsorbed species is nearly identical for Cu in different sites. Considering more complicated scenarios of NO (or CO) adsorption, we find that the co-adsorption of 2 NO (or 2 CO) molecules weakens their interaction with Cu, as well as their co-adsorption with OH and H2O. The X-ray absorption near edge structure (XANES) of Cu in Cu-SSZ-13 under different conditions was also modeled from first principles. We find that the pre-edge feature in the K-edge XANES of Cu in clean Cu-SSZ-13 with Cu in a 8MR site is induced by a 1s to 4s transition while there is no pre-edge peak when Cu is in a 6MR site. Molecular adsorption onto Cu in a 6MR or a 8MR site results in the same K-edge XANES. When NO is adsorbed onto Cu in SSZ-13, we find that the origin of the small pre-edge peak in the K-edge XANES lies in a 1s to 3d electron transition. On the other hand, when CO or N2 is adsorbed onto an isolated Cu atom in SSZ-13, a transition from the 1s state to the hybridized state of 3d and 4p results in a pre-edge peak in the K-edge of the XANES spectrum. It is also found that the edge position and intensity of the maximum peak of Cu K-edge XANES depend on the Cu locations and the adsorbed molecules. By studying the Cu K-edge XANES of ZCu with adsorption of species of different oxidizing power, we conclude that a higher oxidation state of Cu will result in a higher energy edge position in the Cu K-edge XANES. These results are expected to greatly aid our understanding of Cu-SSZ-13 SCR catalysts. This work was supported by institutional funds provided to JSM from the Voiland School of Chemical Engineering and Bioengineering. Financial support was also provided by the National Science Foundation GOALI program under contract Nos. CBET-1258717, CBET-1258715 and CBET-1258690. We thank Prof. Fabio Ribeiro, Mr. Atish Parekh, Prof. W. F. Schneider, Mr. Christopher Paolucci, Mr. Trunjoyo Anggara and Prof. Jeff Miller for stimulating discussions on the modeling of the XANES spectrum and Ms. Alyssa Hensley for her comments on the manuscript. J.Sz. acknowledges the financial support of this work by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. A portion of the computer time for the computational work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL. PNNL is a multi-program national laboratory operated for the US DOE by Battelle.
Zhang, Renqin↗
Characterization of a selective, zero power sensor for distributed sensing of hydrogen in energy applications
The use of hydrogen as a clean and renewable energy source is increasing rapidly for both vehicle and stationary applications. There are safety concerns for the locations in which hydrogen is made, used, and transported (i.e., pipelines and tanker trucks). Sensors are needed to comply with safety regulations and to enable a smooth and safe rollout of hydrogen as an alternative energy. However, hydrogen sensors do not yet exist that have the combined features of small size and low power for easy deployment coupled with high-volume manufacturability and low cost. This is necessary to accommodate the emerging fixed and mobile markets while retaining critical metrological metrics, including measurement range, detection limits, selectivity, fast response, stability, and long lifetime. An amperometric gas sensor for hydrogen (AGS) has been developed using an innovative manufacturing method. The sensor was designed using scalable fabrication strategies based on “Printed Electronics” (PE) methodology which are compatible with large-scale production. Prototype sensors were batch fabricated with multiple individual elements on a substrate compatible in size with a standard 8-inch wafer to enable high-volume, low-cost manufacturing, thereby leveraging PE and semiconductor fabrication infrastructure. This novel AGS was instrumented with control circuitry and evaluated for hydrogen detection in the range of 0–5000 ppmv H2 in air. Specific performance evaluations included assessment of the sensor measurement range, repeatability, and selectivity.
08 HYDROGEN↗
SPF/DB primary structure for supersonic aircraft (T-38 horizontal stabilizer)
The structural integrity and potential cost savings of superplastic forming/diffusion bonding (SPF/DB) titanium structure for future Supersonic Cruise Research (SCR) and military aircraft primary structure applications was demonstrated. Using the horizontal stabilizer of the T-38 aircraft as a baseline, the structure was redesigned to the existing criteria and loads, using SPF/DB titanium technology. The general concept of using a full-depth sandwich structure which is attached to a steel spindle, was retained. Trade studies demonstrated that the optimum design should employ double-truss, sinewave core in the deepest section of the surface, making a transition to single-truss core in the thinner areas at the leading and trailing edges and at the tip. At the extreme thin edges of the surface, the single-truss core was changed to dot core to provide for gas passages during the SPF/DB process. The selected SPF/DB horizontal stabilizer design consisted of a one-piece SPF/DB sinewave truss core panel, a trunnion fitting, and reinforcing straps. The fitting and the straps were mechanically fastened to the SPF/DB panel.
Delmundo, A. R.↗
Synthesis and characterization of Sn-doped hematite as visible light photocatalyst
Highlights: • Sn-doped hematite nanoparticles are prepared by SCS in one step. • The Sn doping have the ability to inhibit particle growth of hematite. • Sn can enhance visible light harvesting and e{sup −}/h{sup +} separation. • Sn-doped hematite degrades MB under visible light effectively. • The products with 5 mol% Sn have the highest photocatalytic activity. - Abstract: Sn-doped hematite nanoparticles are prepared by solution combustion synthesis. The products are characterized with various analytical and spectroscopic techniques to determine their structural, morphological, light absorption and photocatalytic properties. The results reveal that all the samples consist of nanocrystalline hematite with mesoporous structures, and Sn has the ability to inhibit the growth of hematite particle. Compared to pure hematite, the doped hematite samples with appropriate amount of Sn show better activities for degradation of methylene blue under visible light irradiation. The highest activity is observed for 5% Sn doped hematite and this product has long-term stability and no selectivity for dye degradation. The enhanced performance of 5% Sn doped hematite is ascribed to the smaller particle size, increased ability to absorb in visible light, efficient charge separation as well as improved e{sup −} transfer associated with the effects of appropriate amount of Sn doped sample.
36 MATERIALS SCIENCE↗
A Study on Effect of Tuning Capacitor in Dynamic Radioisotope Power Systems
This study presents the effect of the tuning capacitor on the stability and electrical power output of a gas spring-based free-piston Stirling convertor (FPSC) when the FPSC runs on a forced-oscillation type controller. It has been widely accepted that the tuning capacitor is an important circuit component of the FPSC to stabilize piston amplitude and maximize electrical power output by correcting the power factor. Recent modeling analysis, however, suggests that while the effect on the stability is significant, the effect on the electrical power output is almost negligible as long as the operating frequency the FPSC is fixed by a forced-oscillation controller and operating conditions, such as the hot-end/cold-end temperatures, piston amplitude, and pressure, are unchanged. To verify the modeling analysis results, Advanced Stirling Convertor (ASC) is controlled by an AC power supply and the piston amplitude, hot-end temperature, cold-end temperature, and pressure are actively controlled to 4.3mm, 760˚C, 40˚C and 485psig, respectively, while the tuning capacitor value is changed from 840μF to 1040μF and 1240μF. Furthermore, the vibration test results of the ASC with the three tuning capacitor values are also presented to show the effect of the tuning capacitor on stability. The test results suggest that when the FPSC operates at a fixed frequency, the effect of tuning capacitor on electrical power output is negligible while the effect on stability is rather significant. Therefore, the tuning capacitor value should be selected toward the highest stability.
Free-Piston Stirling Convertor Controller↗
Measuring and directing charge transfer in heterogenous catalysts
Abstract Precise control of charge transfer between catalyst nanoparticles and supports presents a unique opportunity to enhance the stability, activity, and selectivity of heterogeneous catalysts. While charge transfer is tunable using the atomic structure and chemistry of the catalyst-support interface, direct experimental evidence is missing for three-dimensional catalyst nanoparticles, primarily due to the lack of a high-resolution method that can probe and correlate both the charge distribution and atomic structure of catalyst/support interfaces in these structures. We demonstrate a robust scanning transmission electron microscopy (STEM) method that simultaneously visualizes the atomic-scale structure and sub-nanometer-scale charge distribution in heterogeneous catalysts using a model Au-catalyst/SrTiO 3 -support system. Using this method, we further reveal the atomic-scale mechanisms responsible for the highly active perimeter sites and demonstrate that the charge transfer behavior can be readily controlled using post-synthesis treatments. This methodology provides a blueprint for better understanding the role of charge transfer in catalyst stability and performance and facilitates the future development of highly active advanced catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe 2 (dobdc) Analogues
Abstract not provided
Xiao, Dianne J.↗
Transition correlations in three-dimensional boundary layers
The stability and transition characteristics of three-dimensional boundary-layer flows are examined. First, the flow over a rotating cone is considered computationally. An increase of stagnation temperature is found to be only slightly stabilizing. Parameter studies on the simple rotating-cone geometry provide a large database of three-dimensional boundary-layer profiles and associated stability characteristics. To determine the possibility of correlating transition location with parameters based purely on basic-state three-dimensional boundary-layer profile characteristics, an empirical transition location of N = 9 is assumed. Transition location does not correlate with the traditional crossflow Reynolds number. A more appropriate definition for crossflow Reynolds number is found and termed R(sub cf(new)). This new parameter appears to correlate for transition location when plotted against maximum crossflow velocity. Then, the flow over a yawed cone is considered experimentally. The correlation results obtained from the rotating-cone work are applied to the actual measured transition locations on two different yawed-cone models under various angle-of-attack conditions in two different experimental facilities and are verified. This correlation is only suggested as a tool for preliminary transition prediction and design in three-dimensional boundary layers; once a preliminary shape is selected, further linear stability theory or parabolized stability equation calculations are strongly urged.
Reed, Helen L.↗
Promoting propane dehydrogenation over PtFe bimetallic catalysts by optimizing the state of Fe species
Optimizing the structure of Pt-based bimetallic catalysts is of utmost importance toward improving the propane dehydrogenation performance. It is challenging to precisely synthesize uniform PtFe alloy nanoparticles without excess unalloyed Fe species on the support as these Fe species lead to low propylene selectivity, coke deposition, and poor stability. Herein, we report an effective strategy to optimize the structure of PtFe bimetallic catalysts with minimal coke and high turnover frequency (8.2 s -1 ). For the optimized catalyst, 1Pt3Fe@S-1, most Fe species is in the framework of the zeolite S-1, which significantly suppresses the formation of coke. In addition, the extra-framework Fe and Pt species encapsulated in the channel of zeolite form uniform PtFe alloy nanoparticles, which significantly improves the C 3 H 6 selectivity, catalytic stability, and recycling performance. In conclusion, these findings provide insights into the structure-performance relationship of PtFe bimetallic catalysts and shall be beneficial to future design and optimization of similar catalytic materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
On BWR regional oscillations with rotational symmetry line using SIMULATE-3K
A new stability analysis methodology is being developed at the Paul Scherrer Institute (PSI) using the best-estimate coupled neutronic/thermal- hydraulics code, SIMULATE-3K (S3K). This methodology has so far been validated against Leibstadt NPP (KKL) stability tests of C10, C13 and C19, which all show global (in-phase) oscillations. However, the methodology has not yet been validated for regional instabilities and to that aim, a special KKL cycle 07 stability test was selected. Indeed, during this test, the core not only showed growing power oscillation amplitudes in an out-of-phase regime but also an oscillating and rotating symmetry line. Thereby, it was selected in order to verify the S3K capability to predict regional instabilities and on that basis, obtain more insights towards understanding the causes for the oscillatory and rotational behaviour of symmetry lines. The results obtained so far are presented in this paper. First, it is found that the S3K results are in good agreement with measurements both qualitatively and quantitatively, although the resonance frequency is slightly over-predicted. Secondly, the excitation of the out-of-phase mode with oscillations as well as rotation of the symmetry line is also well captured i.e. in accordance to the experimental observations. Related to this, an in-depth analysis of LPRM signals indicates that two out-of-phase oscillation modes associated to two azimuthal neutronic modes are simultaneously excited. Furthermore, it is found that a superposition of these two modes will trigger the symmetry line dynamics and that the behaviour will be guided by the dominance ratio between these two modes. More precisely, the oscillatory behaviour is due to the superposition of the two azimuthal modes but with one dominant mode. The rotational behaviour is however due to the superposition of the two modes with comparable strengths. (authors)
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
Stabilization of Cu 2 O through Site-Selective Formation of a Co 1 Cu Hybrid Single-Atom Catalyst
Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co 1 Cu SAC centers on a Cu 2 O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu 2 O(111) surface, forming a Co 1 Cu SAA with no direct Co–O x bonds. The centers, here referred to as Co 1 Cu hybrid SACs, are found to stabilize the active Cu + sites of the low-cost Cu 2 O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu 2 O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results.
36 MATERIALS SCIENCE↗
A Semiconducting Two‐Dimensional Polymer as an Organic Electrochemical Transistor Active Layer
Abstract Organic electrochemical transistors (OECTs) are devices with broad potential in bioelectronic sensing, circuits, and neuromorphic hardware. Their unique properties arise from the use of organic mixed ionic/electronic conductors (OMIECs) as the active channel. Typical OMIECs are linear polymers, where defined and controlled microstructure/morphology, and reliable characterization of transport and charging can be elusive. Semiconducting two‐dimensional polymers (2DPs) present a new avenue in OMIEC materials development, enabling electronic transport along with precise control of well‐defined channels ideal for ion transport/intercalation. To this end, a recently reported 2DP, TIIP, is synthesized and patterned at 10 µm resolution as the channel of a transistor. The TIIP films demonstrate textured microstructure and show semiconducting properties with accessible oxidation states. Operating in an aqueous electrolyte, the 2DP‐OECT exhibits a device‐scale hole mobility of 0.05 cm 2 V –1 s –1 and a µ C * figure of merit of 1.75 F cm –1 V –1 s –1 . 2DP OMIECs thus offer new synthetic degrees of freedom to control OECT performance and may enable additional opportunities such as ion selectivity or improved stability through reduced morphological modulation during device operation.
2D-polymer↗
Electronic Structure Distortions in Chromium Chelates Impair Redox Kinetics in Flow Batteries
Aminopolycarboxylate chelates are emerging as a promising class of electrolyte materials for aqueous redox flow batteries, offering tunable redox potentials, solubility, and pH stability through careful selection of ligands and transition metal ions. Despite their potential, the impact of molecular structure modifications on the electronic and electrochemical properties of these chelates remains underexplored. Here, in this study, we examine how introducing a hydroxyl group, often employed for its solubilizing properties, to the backbone of CrPDTA, a reference chelate material, significantly changes the thermodynamics and kinetics of the chelate's redox process. We correlate changes in molecular and electronic structures to different electrochemical responses resulting from the hydroxyl addition and show that the introduction of this functional group leads to a distortion in the octahedral coordination of chromium. Furthermore, increased anisotropic spin density and nonintegral oxidation state changes in the Cr metal center result in a larger barrier for electron transfer in CrPDTA‐OH. It is demonstrated that preserving a hexacoordinate chelate structure across a broad pH range is crucial for efficient flow battery application and it is emphasized that ligand modifications must avoid distorting the octahedral coordination of the transition metal.
25 ENERGY STORAGE↗