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At least 649 records · Page 36

Gd-Ni-Sb-SnO 2 electrocatalysts for active and selective ozone production

Direct electrochemical production of dissolved ozone could potentially provide economic wastewater treatment and sanitation or a valuable chemical oxidant. Although Ni-Sb-SnO 2 electrocatalysts have the highest known faradaic efficiencies for electrochemical ozone production, the activity and selectivity are not yet sufficient for commercial implementation. This report finds that co-doping Ni and Gd increases the ozone selectivity by a factor of three over Ni alone. These findings are the first demonstration of an active dopant other than Ni in SnO 2 . Electrochemical and physical characterization show that trends in ozone activity are caused by chemical catalysis, not morphology effects, and that conduction band alignment is not a catalytic descriptor for the system. Selective radical quenching experiments and quantum chemistry calculations of thermodynamic energies suggest that the kinetic barriers to form solution-phase intermediates are important for understanding the role of dopants in electrochemical ozone production.

42 ENGINEERING↗

A thermochemical database from high-throughput first-principles calculations and its application to analyzing phase evolution in AM-fabricated IN718

A comprehensive thermochemical database is constructed based on high–throughput first-principles phonon calculations of over 3000 atomic structures in limited concentrations in Ni, Fe, and Co alloys involving a total of 26 elements including Al, B, C, Cr, Cu, Hf, La, Mn, Mo, N, Nb, O, P, Re, Ru, S, Si, Ta, Ti, V, W, Y, and Zr, providing thermochemical data largely unavailable from existing experiments. Here, the database can be employed to predict the equilibrium phase compositions and fractions directly from first-principles by minimizing the chemical potential of a multicomponent system with a fixed overall chemical composition and a fixed temperature. It is applied to the additively manufactured nickel-based IN718 superalloy to analyze the phase evolution with temperature. IN718 is known for its great performance in tensile, fatigue, creep, and rupture strength, combined with easy fabrication and corrosion resistance. In particular, we successfully predicted the formation of L1 0 -FeNi, γ’-Ni 3 (Fe,Al), α-Cr, δ-Ni 3 (Nb,Mo), γ”-Ni 3 Nb, and η-Ni 3 Ti at low temperatures (below 680 K), γ’-Ni 3 Al, δ-Ni 3 Nb, γ”-Ni 3 Nb, α-Cr, and γ-Ni(Fe,Cr,Mo) at intermediate temperatures (between 680 and 1140 K), and δ-Ni 3 Nb and γ-Ni(Fe,Cr,Mo) at high temperatures (above 1140 K) in IN718. These predictions are validated by EDS mapping of compositional distributions and corresponding identifications of phase distributions. The database is expected to be a valuable source for future thermodynamic analysis and microstructure prediction of alloys involving the 26 elements.

36 MATERIALS SCIENCE↗

A scoping review of non-destructive testing (NDT) techniques in building performance diagnostic inspections

Understanding building envelope thermodynamics is an essential foundation of building sciences, mainly due to the envelope’s role as a boundary layer for exterior environments, as well as a container and regulator of internal microclimates. This paper presents a scoping literature review of select Non-destructive Testing (NDT) techniques for building envelope scanning and surveying for thermodynamic diagnostics. The investigation focuses specifically on reviewing six NDT techniques: Ground Penetrating Radar (GPR), Light Detection and Ranging (LiDAR)/Laser Scanning, Thermography, Ultrasound, Close-Range Photogrammetry and Through Wall Imaging Radar (TWIR). The aim is to identify knowledge gaps in terms of their use in accurately characterizing envelope compositions for further integration in Building Energy Modeling (BEM). Each technique was evaluated according to set categories imbibed from the American Society of Heating, Refrigerating, and Air Conditioning Engineering (ASHRAE) Standard 211P that showcase the technique’s ability to extract various relevant information. A framework is then developed to inform users on how to use hybrid NDT-based workflows applied in building envelope energy audits. The study concludes by discussing possibilities of utilizing NDT in large-scale audit automation, BEM integration, and developing built environment policies focusing on increasing existing building performance through retrofitting design.

36 MATERIALS SCIENCE↗

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH

A thorough comprehension of the mechanism underlying the methanol oxidation reaction (MOR) on Ni-based catalysts is critical for future electrocatalytic design and development. However, the mechanism of MOR on these materials remains a matter of controversy. Herein, we combine in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) calculations to identify the active sites and determine the mechanism of MOR on monometallic Ni-based catalysts in alkaline media. The SEIRAS results show that formate and (bi)carbonate are formed after the commencement of the MOR with potential-dependent relative distributions. These spectroscopic results are in good agreement with the DFT-computed reaction profiles over an oxygen vacancy, suggesting that the MOR mainly proceeds through the formate-involving pathway, in which the early consumption of methanol yields formate as the major product, while increasing potential drives further oxidation of formate to (bi)carbonate. We also find a parallel pathway for the generation of (bi)carbonate at high potentials that bypasses the formation of formate. The two main pathways are thermodynamically more feasible than the one predominantly reported in the literature for MOR on NiOOH that involves CHO and/or CO as key intermediates. These DFT results are supported by spectroscopic evidence showing that no band associated with CHO or CO can be detected by SEIRAS, which is attributed to the nature of the oxygen vacancies as the active sites, suppressing deep dehydrogenation of CH 2 O to CHO. Furthermore, this work thus shows the promising role of defect engineering in promoting the electrocatalytic MOR activity and selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing the Thermodynamic Driving Force of the Phosphofructokinase Reaction in Clostridium thermocellum

Glycolysis is an ancient, widespread, and highly conserved metabolic pathway that converts glucose into pyruvate. In the canonical pathway, the phosphofructokinase (PFK) reaction plays an important role in controlling flux through the pathway. Clostridium thermocellum has an atypical glycolysis and uses pyrophosphate (PP i ) instead of ATP as the phosphate donor for the PFK reaction. The reduced thermodynamic driving force of the PP i -PFK reaction shifts the entire pathway closer to thermodynamic equilibrium, which has been predicted to limit product titers. Here, in this study, we replace the PP i -PFK reaction with an ATP-PFK reaction. We demonstrate that the local changes are consistent with thermodynamic predictions: the ratio of fructose 1,6-bisphosphate to fructose-6-phosphate increases, and the reverse flux through the reaction (determined by 13 C labeling) decreases. The final titer and distribution of fermentation products, however, do not change, demonstrating that the thermodynamic constraints of the PP i -PFK reaction are not the sole factor limiting product titer.

59 BASIC BIOLOGICAL SCIENCES↗

Extension of Solvent-Assisted Linker Exchange to Supported Metal–Organic Framework Thin Films

Solvent-assisted linker exchange (SALE) is a common postsynthetic approach used to accommodate metal–organic frameworks (MOFs) for targeted applications. As this technique is relatively untested in immobilized MOF structures, we repeated the generalized SALE approach with ZIF-8 deposited directly onto solid substrates and assessed the results with a variety of techniques, including time-of-flight secondary-ion mass spectrometry (ToF-SIMS). Our methods confirm that the supported films maintain their key structural properties while allowing for linker substitution with foreign species. Alongside experiments, we used computational modeling to quantify the relative energetics of SALE reactions with a variety of linkers. These techniques together reveal that SALE is translatable to immobilized MOFs. Additionally, we recognize how various aspects of the postsynthetic approach can bear consequences for the material’s final micro- and macroscopic properties. Furthermore, the results uncover basic yet critical details needed to inform future efforts to engineer MOF films with functional properties.

Ligands↗

Multiplexed characterization of rationally designed promoter architectures deconstructs combinatorial logic for IPTG-inducible systems

Abstract A crucial step towards engineering biological systems is the ability to precisely tune the genetic response to environmental stimuli. In the case of Escherichia coli inducible promoters, our incomplete understanding of the relationship between sequence composition and gene expression hinders our ability to predictably control transcriptional responses. Here, we profile the expression dynamics of 8269 rationally designed, IPTG-inducible promoters that collectively explore the individual and combinatorial effects of RNA polymerase and LacI repressor binding site strengths. We then fit a statistical mechanics model to measured expression that accurately models gene expression and reveals properties of theoretically optimal inducible promoters. Furthermore, we characterize three alternative promoter architectures and show that repositioning binding sites within promoters influences the types of combinatorial effects observed between promoter elements. In total, this approach enables us to deconstruct relationships between inducible promoter elements and discover practical insights for engineering inducible promoters with desirable characteristics.

59 BASIC BIOLOGICAL SCIENCES↗

A Cost-Performance Analysis of a Sodium Heat Engine for Distributed Concentrating Solar Power

We present that a sodium thermal electrochemical converter (Na-TEC) generates electricity directly from heat through isothermal expansion of sodium ions across a beta"-alumina solid-electrolyte. This heat engine has been considered for use with conventional concentrating solar power (CSP) systems before. However, unlike previous single-stage devices, the improved design uses two stages with an interstage reheat, allowing more economical and efficient conversion up to 29% at a hot side temperature of 850 °C. Herein, a cost-performance analysis for this improved design assesses opportunities for distributed-CSP in the context of micro-combined heat and power systems. A high-level techno-economic analysis (TEA) is presented that explores four scenarios where a Na-TEC is used as the heat engine for a distributed-CSP system. Overnight capital cost and levelized cost of electricity (LCOE) are estimated for a system lifetime of 30 years, revealing that overnight capital costs in a range from $3.57 to $17.71 per W e are feasible, which equate to LCOEs from 6.9 to 17.2 cents kWh e -1 . This analysis makes a significant contribution by concurrently quantifying the efficiency and unit costs for a range of multistage configurations, and demonstrating that a Na-TEC may be a promising alternative to Stirling engines for distributed-CSP systems at residential scale of 1–5 kW e .

14 SOLAR ENERGY↗

An analysis of alcohol compression ignition strategies on different engine platforms

Strategies that enable ignition of the low cetane alcohol fuels (methanol and ethanol) include intake heating (direct or via hot residual trapping), increased compression ratio (CR), multi-injection strategies, ignition enhancers, and active prechambers. The literature consistently shows alcohol compression ignition (CI) is more efficient than diesel at high loads irrespective of ignition strategy but shows contradictory results at low loads. To understand this, this work combines data from four different engine platforms ranging from a displaced volume of 0.4 to 2.1 L/cyl. using different alcohol CI ignition strategies. Using modeling to support experimental analysis, alcohol-specific efficiency penalties are highlighted to inform alcohol combustion system development. The alcohols’ lower energy density means more fuel must be injected near top dead center to achieve a given load, increasing the relative penalty of sensible/latent heating. Pilot injections help reduce this penalty. Intake heating incurs both a heat transfer penalty and a thermodynamic penalty due to a reduced ratio of specific heats during compression. A strategy that combines elevated CR, large pilot injections, and ignition enhancers can avoid this penalty. Alternatively, a prechamber strategy can achieve this without changing the CR, nor needing ignition enhancers in the fuel. At low loads, diesel burns in a partially premixed mode characterized by high burn rates and low heat losses, reducing alcohol-specific combustion benefits. Alcohol CI on the light-duty platform showed abnormally high heat transfer over diesel compared to other platforms, favoring a more premixed/partially premixed strategy despite a combustion efficiency tradeoff.

33 ADVANCED PROPULSION SYSTEMS↗

Substitution-Mediated Calcination of Nickel-Based Cathodes: Decoupling Lithiation and Crystallization

Nickel-based layered cathodes such as LiNiO 2 offer high energy density for lithium-ion batteries, yet improvements in cycling performance and safety are required for practical use–often achieved through manganese and cobalt substitution as in LiNi 0.80 Mn 0.10 Co 0.10 O 2 (NMC811). However, how such substitution impacts calcination, the key process that governs lithiation, structural ordering, crystallization, and ultimately the resulting material properties, remains unclear. Here, in this study, we investigate substitution-mediated calcination dynamics in NMC811 compared to LiNiO 2 using multiscale-correlated in situ spectroscopy and atomistic-to-mesoscale modeling. While both systems progress through the same sequence of intermediates toward the thermodynamically favored layered phase, NMC811 exhibits an earlier onset of layering, concurrent with hydroxide decomposition followed by sluggish crystallization. Modeling reveals that Mn and Co lower the energy barrier for lithium incorporation and ordering but increase the penalty for interlayer gliding, thereby slowing crystal growth at elevated temperatures. This substitution-mediated decoupling of lithiation and crystallization explains the fine-grained microstructure observed in NMC811 versus coarsened particles in LiNiO 2 and establishes a mechanistic framework for predictive microstructure engineering of Ni-based cathodes.

Calcination↗

Bandgap engineering of SrZrS 3 chalcogenide perovskite via substitutional doping for photovoltaic applications: a first-principles DFT study

Strontium zirconium sulfide (SrZrS 3 ) has garnered significant attention for photovoltaic (PV) applications due to its excellent optoelectronic properties, high chemical and moisture stability, and non-toxicity. However, the bandgaps of both the α- and β-phases lie outside the optimum ranges for both single-junction solar cells (SJSCs) and tandem solar cells (TSCs), thereby limiting their applications in PV technologies. In this study, we employed hybrid density functional theory to engineer the band gaps of α- and β-SrZrS 3 through substitutional doping. We considered three dopants (Hf, Sn, and Ti) at the Zr site of SrZrS 3 with varying doping concentrations and investigated their effects on the structural, electronic, and optical properties of the materials. We found that Sn and Ti doping effectively lowers the band gaps of both α- and β-SrZrS 3 , whereas Hf doping increases them. For x values up to 0.25, the band gaps of the α-SrZr 1−x Sn x S 3 and α-SrZr 1−x Ti x S 3 are within the optimum range for SJSCs, and those of β-SrZr 1−x Sn x S 3 and β-SrZr 1−x Ti x S 3 lie within the optimum range for Si/perovskite as well as perovskite/perovskite TSCs. The three dopants exhibited significant effects on the optical properties of both α- and β-SrZrS 3 , including the absorption coefficient, energy-loss functions, reflectivity, and refractivity spectra. Thermodynamic stability analysis revealed that for both phases, SrZr 1−x Hf x S 3 can be synthesized via exothermic processes, whereas the formation of SrZr 1−x Ti x S 3 and SrZr1−xSn x S 3 is endothermic and hence, not thermodynamically favorable. Further analysis showed that SrZr 1−x Ti x S 3 in both α- and β-phases are stable under thermodynamic equilibrium conditions, whereas SrZr 1−x Sn x S 3 is prone to dissociation into ternary phases (SrZrS 3 and SrSnS 3 ), especially at higher doping concentrations. These results show that Ti doping is effective in tuning the band gaps of α- and β-SrZrS 3 toward the optimal values for PV applications.

14 SOLAR ENERGY↗

Carbon Negative Synthesis of Amino Acids Using a Cell-Free-Based Biocatalyst

Biological systems can directly upgrade carbon dioxide (CO 2 ) into chemicals. The CO 2 fixation rate of autotrophic organisms, however, is too slow for industrial utility, and the breadth of engineered metabolic pathways for the synthesis of value-added chemicals is too limited. Biotechnology workhorse organisms with extensively engineered metabolic pathways have recently been engineered for CO 2 fixation. Yet, their low carbon fixation rate, compounded by the fact that living organisms split their carbon between cell growth and chemical synthesis, has led to only cell growth with no chemical synthesis achieved to date. Here, we engineer a lysate-based cell-free expression (CFE)-based multienzyme biocatalyst for the carbon negative synthesis of the industrially relevant amino acids glycine and serine from CO 2 equivalents–formate and bicarbonate–and ammonia. The formate-to-serine biocatalyst leverages tetrahydrofolate (THF)-dependent formate fixation, reductive glycine synthesis, serine synthesis, and phosphite dehydrogenase-dependent NAD(P)H regeneration to convert 30% of formate into serine and glycine, surpassing the previous 22% conversion using a purified enzyme system. We find that (1) the CFE-based biocatalyst is active even after 200-fold dilution, enabling higher substrate loading and product synthesis without incurring additional cell lysate cost, (2) NAD(P)H regeneration is pivotal to driving forward reactions close to thermodynamic equilibrium, (3) balancing the ratio of the formate-to-serine pathway genes added to the CFE is key to improving amino acid synthesis, and (4) efficient THF recycling enables lowering the loading of this cofactor, reducing the cost of the CFE-based biocatalyst. To our knowledge, this is the first synthesis of amino acids that can capture CO 2 equivalents for the carbon negative synthesis of amino acids using a CFE-based biocatalyst. Looking ahead, the CFE-based biocatalyst process could be extended beyond serine to pyruvate, a key intermediate, to access a variety of chemicals from aromatics and terpenes to alcohols and polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Orientation-Controlled Large-Area Epitaxial PbI 2 Thin Films with Tunable Optical Properties

Lead iodide (PbI 2 ) as a layered material has emerged as an excellent candidate for optoelectronics in the visible and ultraviolet regime. Micrometer-sized flakes synthesized by mechanical exfoliation from bulk crystals or by physical vapor deposition have shown a plethora of applications from low-threshold lasing at room temperature to high-performance photodetectors with large responsivity and faster response. However, large-area centimeter-sized growth of epitaxial thin films of PbI 2 with well-controlled orientation has been challenging. Additionally, the nature of grain boundaries in epitaxial thin films of PbI 2 remains elusive. Here, we use mica as a model substrate to unravel the growth mechanism of large-area epitaxial PbI 2 thin films. The partial growth leading to uncoalesced domains reveals the existence of inversion domain boundaries in epitaxial PbI 2 thin films on mica. Combining the experimental results with first-principles calculations, we also develop an understanding of the thermodynamic and kinetic factors that govern the growth mechanism, which paves the way for the synthesis of high-quality large-area PbI 2 on other substrates and heterostructures of PbI 2 on single-crystalline graphene. Here, the ability to reproducibly synthesize high-quality large-area thin films with precise control over orientation and tunable optical properties could open up unique and hitherto unavailable opportunities for the use of PbI 2 and its heterostructures in optoelectronics, twistronics, substrate engineering, and strain engineering.

2D materials↗

Numerical Investigation of Wall-Cooling Effect on Aero-Optical Distortions for Hypersonic Boundary Layer

Compressible wall-modeled large-eddy simulations of Mach 8 turbulent boundary-layer flows over a flat plate were carried out for the conditions of the hypersonic wind tunnel at Sandia National Laboratories. The simulations provide new insight into the effect of wall cooling on the aero-optical path distortions for hypersonic turbulent boundary-layer flows. Four different wall-to-recovery temperature ratios, 0.3, 0.48, 0.71, and 0.89, are considered. Despite the much lower grid resolution, the mean velocity, temperature, and resolved Reynolds stress profiles from the simulation for a temperature ratio of 0.48 are in good agreement with those from a reference direct numerical simulation. The normalized root-mean-square optical path difference obtained from the present simulations is compared with that from reference direct numerical simulations, Sandia experiments, as well as predictions obtained with a semi-analytical model by Notre Dame University. Here the present analysis focuses on the effect of wall cooling on the wall-normal density correlations, on key underlying assumptions of the aforementioned model such as the strong Reynolds analogy, and on the elevation angle effect on the optical path difference. Wall cooling is found to increase the velocity fluctuations and decrease the density fluctuations, resulting in an overall reduction of the normalized optical path distortion. Compared to the simulations, the basic strong Reynolds analogy overpredicts the temperature fluctuations for cooled walls. Also different from the strong Reynolds analogy, the velocity and temperature fluctuations are not perfectly anticorrelated. Finally, as the wall temperature is raised, the density correlation length, away from the wall but inside the boundary layer, increases significantly for beam paths tilted in the downstream direction.

42 ENGINEERING↗

Engineering Evaluation of Barium Buildup in a Decayed CsCl Sealed Source and Potential Impact for Cesium Release from a Breached Source

For more than 50 years, radioactive 137 Cs has been a major source material for radioactive sealed sources, usually constructed as cesium chloride (CsCl) salt loaded into double-walled, stainless-steel capsules. A complication develops as 137 Cs decays to 137 Ba since this process creates a strongly reducing environment inside the capsule. A potential hazard exists if the capsule is breached and air ingress induces rapid exothermic oxidation, and this mechanism is suspected to be responsible for the well-known contamination incident at the Harbor View facility in Washington state. For this study, many thermodynamic evaluations were performed to assess the internal state of capsules after several decades of decay and to describe the potential oxidation if the capsule contents were to suddenly be exposed to air. Results suggest that reduction of impurities such as Cu, Fe, Pb, and Cr to metal will occur. If these impurities are lacking, it is possible that even Ba metal will form. In most cases, rapid oxidation can occur, and the exothermic reactions are sufficient to vaporize portions of the contents, which would include the remaining 137 Cs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Selection of solvents for integrated CO 2 absorption and electrochemical reduction systems

Abstract Solvent‐based electrochemical CO 2 reduction (CO 2 R) enables the production of chemicals or fuels using CO 2 from a preceding absorption process. Employing previously tested CO 2 capture solvents does not ensure their suitability for either CO 2 R or integrated CO 2 absorption‐reduction. We propose solvent selection criteria that include the CO 2 solubility, kinetic constant, ionic conductivity, concentration of the bicarbonate, carbamate, and solvent cation in the CO 2 ‐loaded solution, and sustainability indicators. They are implemented for solvent selection (a) from novel, aqueous mixtures of N ‐methylcyclohexylamine (MCA) with piperazine (PZ), 2‐amino‐2‐methyl‐1‐propanol (AMP), potassium hydroxide (KOH), and potassium chloride (KCl) and (b) from aqueous monoethanolamine (MEA), AMP, KOH, MCA, and PZ solutions. Versions of a modified Kent‐Eisenberg model for strong bases, carbamate, and non‐carbamate‐forming amine solutions are developed and parameterized through experimental equilibrium measurements. CO 2 R experimental results are presented for solutions of KOH and MCA + KOH, as these indicate desired trade‐offs for CO 2 absorption and reduction.

Amines↗

Engineering Multi-scale B2 Precipitation in a Heterogeneous FCC Based Microstructure to Enhance the Mechanical Properties of a Al0.5Co1.5CrFeNi1.5 High Entropy Alloy

While ordered L12 or gamma prime precipitates in face centered cubic (FCC) based microstructures have been extensively used for strengthening Nickel or Cobalt base superalloys, and more recently in high entropy alloys (HEAs) or complex concentrated alloys (CCAs), the possibility of exploiting ordered B2 precipitates in FCC-based systems has been relatively less investigated. The present study shows the propensity of developing a heterogeneous microstructure, consisting of two different distributions of FCC grain sizes, and two different size scales of B2 precipitates, within an FCC-based Al0.5Co1.5CrFeNi1.5 HEA/CCA. This alloy composition has been designed using solution thermodynamics-based modeling such that it has a high phase fraction and solvus temperature of the B2 phase. The resulting heterogenous microstructure exhibited an approximately 400% increase in yield strength with respect to the single-phase FCC solid solution condition of the same alloy while maintaining very good tensile ductility ~20 %.

Dasari, Sriswaroop↗