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At least 1,171 records · Page 65

Data–driven model reduction for the Bayesian solution of inverse problems

One of the prime challenges in the Bayesian solution of inverse problems governed by partial differential equations (PDEs) is the computational cost of repeatedly evaluating numerical PDE models, as required by Markov chain Monte Carlo (MCMC) methods for posterior sampling. This paper presents a data-driven projection-based model reduction technique to reduce this computational cost. The proposed technique has two distinctive features. To begin, the model reduction strategy is tailored to inverse problems: the snapshots used to construct the reduced-order model are computed adaptively from the posterior distribution. Posterior exploration and model reduction are thus pursued simultaneously. Second, to avoid repeated evaluations of the full-scale numerical model as in a standard MCMC method, we couple the full-scale model and the reduced-order model together in the MCMC algorithm. This maintains accurate inference while reducing its overall computational cost. In numerical experiments considering steady-state flow in a porous medium, the data-driven reduced-order model achieves better accuracy than a reduced-order model constructed using the classical approach. It also improves posterior sampling efficiency by several orders of magnitude compared with a standard MCMC method.

97 MATHEMATICS AND COMPUTING↗

Kernel Manifolds: Nonlinear‐Augmentation Dimensionality Reduction Using Reproducing Kernel Hilbert Spaces

This paper generalizes recent advances on quadratic manifold (QM) dimensionality reduction by developing kernel methods-based nonlinear-augmentation dimensionality reduction. QMs, and more generally feature map-based nonlinear corrections, augment linear dimensionality reduction with a nonlinear correction term in the reconstruction map to overcome approximation accuracy limitations of purely linear approaches. While feature map-based approaches typically learn a least squares optimal polynomial correction term, we generalize this approach by learning an optimal nonlinear correction from a user-defined reproducing kernel Hilbert space. Our approach allows one to impose arbitrary nonlinear structure on the correction term, including polynomial structure, and includes feature map and radial basis function-based corrections as special cases. Furthermore, our method has relatively low training cost and has monotonically decreasing error as the latent space dimension increases. In conclusion, we compare our approach to proper orthogonal decomposition and several recent QM approaches on data from several example problems.

kernel methods↗

Neural Active Manifolds: Nonlinear Dimensionality Reduction for Uncertainty Quantification

We present a new approach for nonlinear dimensionality reduction, specifically designed for computationally expensive mathematical models. We leverage autoencoders to discover a one-dimensional neural active manifold (NeurAM) capturing the model output variability, through the aid of a simultaneously learnt surrogate model with inputs on this manifold. Our method only relies on model evaluations and does not require the knowledge of gradients. The proposed dimensionality reduction framework can then be applied to assist outer loop many-query tasks in scientific computing, like sensitivity analysis and multifidelity uncertainty propagation. In particular, we prove, both theoretically under idealized conditions, and numerically in challenging test cases, how NeurAM can be used to obtain multifidelity sampling estimators with reduced variance by sampling the models on the discovered low-dimensional and shared manifold among models. Several numerical examples illustrate the main features of the proposed dimensionality reduction strategy and highlight its advantages with respect to existing approaches in the literature.

Autoencoders↗

Effect of Si Addition on the Electrochemical Reduction Rate of SiO{sub 2} Granules in Molten CaCl{sub 2}

The effect of adding Si powder/granules on the electrochemical reduction rate of SiO{sub 2} granules in molten CaCl{sub 2} was investigated. Various starting materials were prepared by mixing different amounts (up to 80 mass pct) of Si powder/granules (four different sizes: < 5, 20 to 100, 100 to 250 µm, 0.5 to 1.0 mm) with SiO{sub 2} granules, with these materials then being electrochemically reduced for 20 minutes in molten CaCl{sub 2} at 0.6 V vs Ca{sup 2+}/Ca and a temperature of 1123 K (850 °C). The effects of the size and amount of Si added on the reaction rates were then studied. When the size of the Si powder added is less than 5 µm, the reaction rate decreases as more Si is added. When Si with a size of 20 to 100 or 100 to 250 µm is used, the reaction rate does not change substantially with the amount added. When 0.5 to 1.0 mm Si is used, the reduction rate is the largest when 40 mass pct Si is added. The reduction rate is influenced by the reaction surface and the diffusion of O{sup 2−} ions in the mixture.

36 MATERIALS SCIENCE↗

Transient Interaction Between Reduction and Slagging Reactions of Wustite in Simulated Cohesive Zone of Blast Furnace

The blast furnace cohesive zone plays an important role in the gas flow distribution and heat-transfer efficiency. Previous work mainly employed temperature-based indices to evaluate and predict the shape and thickness of the cohesive zone, whereas the internal reactions and related effects on the softening and melting properties of a complex burden are ignored. In this study, an innovative index, namely, shrinkage rate (SR), is first proposed to directly estimate the shrinkage behavior of wustite (FeO)-packed bed inside a simulated cohesive zone. The index is applied as the temperature increases to elucidate the transient interaction between reduction and slagging reactions. Results show that the thermally induced slagging reaction causes the packed bed to shrink at lower temperature, and the SR doubles when compounds with low melting temperature are generated by adding a reasonable concentration of CaO or SiO{sub 2}. The reduction reaction becomes the driving force during the shrinkage of the packed bed between 1173 K and 1273 K when CO is introduced in the mixture gas. Then, the dominating factors for further shrinkage include slagging, reduction, or both factors. These factors vary with respect to the added compounds or temperature.

36 MATERIALS SCIENCE↗

Damring Formation During Rotary Kiln Chromite Pre-reduction: Effects of Pulverized Carbonaceous Fuel Selection and Partial Pellet Melting

Electricity consumption is the largest cost contributing factor in the production of ferrochrome. Currently the pelletized chromite pre-reduction process (solid-state reduction of chromite) is the process option with the lowest specific electricity consumption (MWh/ton). In this process, pelletized chromite is fed into a rotary kiln at 1573 K (1300 °C), where partial pre-reduction takes place. Damring formation (material build-up) in the rotary kiln causes routine shutdowns, resulting in loss of revenue. The damring formation is possibly caused by melting of the ash of the pulverized coal used to fire the kiln and/or the partial melting of the chromite pellets. Ash fusion temperatures of twenty different samples were evaluated to assess the temperature at which the pulverized coal ash will start to contribute to damring formation. Sessile drop tests were used to assess the softening behavior of different ore types (e.g., UG2, MG, and LG metgrade), as well as softening of composite chromite pellets made from these ores. Actual damrings were also analyzed using scanning electron microscopy with energy dispersive X-ray spectroscopy. Results indicate that it is mainly the pulverized coal ash that will contribute to damring formation, and not ore or pellet softening. Multiple-linear regression was used to derive equations to predict the ash fusion temperatures of the pulverized coal ash, which can be used by ferrochrome producers to optimize pulverized coal selection.

36 MATERIALS SCIENCE↗

Hydrogen Plasma Smelting Reduction of Fe{sub 2}O{sub 3}

The paper reports successful smelting reduction of iron ore (hematite) in thermal hydrogen plasma. A specially designed reactor with water cooled copper crucible and a plasma torch was used to demonstrate the process in 1-kg scale. The number of stoichiometric requirement of hydrogen is a better parameter, instead of time, for determining the rate of the process. This parameter, along with the degree of reduction, is also helpful to determine the degree of hydrogen utilization. The ratio of the height of the molten bath to the diameter of the reactor is found to be an important parameter for effective hydrodynamics and the resultant degree of reduction. This is also an important parameter for scaling up of the process.

36 MATERIALS SCIENCE↗

Influence of Aluminum-Carbon Composite Pellets on FeO Reduction and Iron Recovery from Electric Arc Furnace Slag

We investigated the effect of Al-C composite pellets (ACCP) on the reduction behavior of FeO in electric arc furnace (EAF) slag and the iron recovery at different n{sub Al}/(n{sub Al} + n{sub C}) at 1823 K (1550 °C). A carbothermic reaction was the dominant process at n{sub Al}/(n{sub Al} + n{sub C}) < 0.4, whereas aluminothermic reduction was the major process at n{sub Al}/(n{sub Al} + n{sub C}) > 0.6; these observations are based on the final content of FeO and Al{sub 2}O{sub 3} in the molten slag. The aluminum and carbon present in the ACCP competitively affected the reaction stoichiometry (i.e., the material balance) between the production of CO + Al{sub 2}O{sub 3} and the consumption of FeO. Iron recovery increased up to a yield of approx. 90 pct as the n{sub Al}/(n{sub Al} + n{sub C}) ratio increased. Because Al in the ACCP readily reacts to reduce FeO in the molten slag, iron recovery is proportional to the n{sub Al}/(n{sub Al} + n{sub C}) ratio. The precipitation of solid compounds in the slag phase, such as monoxide ([Mg,Fe]·O) and spinel (MgO·Al{sub 2}O{sub 3}), occurred during FeO reduction; this was experimentally confirmed as well as by thermochemical computation. Furthermore, we proposed a schematic reaction mechanism in the present study.

36 MATERIALS SCIENCE↗

Mechanisms and Kinetics of Reduction of Solid NiO in CO/CO{sub 2} and CO/Ar Gas Mixtures

Experimental studies have been carried out on the reduction of dense nickel oxide in CO/CO{sub 2} and CO/Ar gas mixtures at temperatures between 873 K and 1273 K (600 °C and 1000 °C). Examination of the nickel product microstructures of partially reduced samples has been undertaken using high-resolution scanning electron microscopy. It has been shown that the reduction can result in the formation of a dense nickel layer at the sample surface, continuous gas pore growth in the NiO, or the discontinuous growth of the porous nickel product. The product morphologies formed, and the microstructures of the gas/metal oxide/metal interfaces, are functions of reaction temperature and gas conditions. The microstructural and kinetic evidence indicates direct links between the reduction rates, nickel product growth mechanisms, and product microstructures.

36 MATERIALS SCIENCE↗

Closure of Internal Porosity in Continuous Casting Bloom During Heavy Reduction Process

To investigate the closure behavior of internal porosity (also referred to as internal void) in continuous casting bloom during heavy reduction (HR) and thus provide theoretical guidance for minimizing this kind of internal defect more effectively with HR, a three-dimensional (3D) mechanical model was developed based on the predicted temperature field by a 2D heat transfer model. With this 3D mechanical model, closure behaviors of internal porosity in continuous casting bloom during HR at and after the strand solidification end under different process conditions were numerically studied. It was found that the void axis length decreased significantly along the bloom thickness direction and increased slightly along the casting and bloom width directions after HR, and the influence of the initial void size on the void closure was not obvious. With a decrease of temperature difference between the bloom surface and center, HR efficiency for minimizing internal void decreased, while the required reduction force significantly increased. Compared with blooms with a uniform temperature distribution of 1100 °C, the void closure index after HR implemented at the strand solidification end was increased by ~ 25 pct. Compared with a conventional flat roll, the application of a convex roll during HR could contribute to minimizing the internal porosity more effectively and significantly enhance the reduction capacity of the withdrawal and straightening units. The void closure index of η{sub s} and η{sub v} (where η{sub s} and η{sub v} were defined based on the variation of the void aspect ratio and the void volume, respectively) was closely related to the equivalent strain (ε{sub eq}) and the hydrostatic integration parameter (Q), respectively, and two mathematical equations were derived to quantitatively describe the relationship of η{sub s} − ε{sub eq} and η{sub v} − Q.

36 MATERIALS SCIENCE↗

Carbon flowers as electrocatalysts for the reduction of oxygen to hydrogen peroxide

Small-scale and decentralized production of H 2 O 2 via electrochemical reduction of oxygen is of great benefit, especially for sanitization, air and water purification, as well as for a variety of chemical processes. The development of low-cost and high-performance catalysts for this reaction remains a key challenge. Carbon-based materials have drawn substantial research efforts in recent years due to their advantageous properties, such as high chemical stability and high tunability in active sites and morphology. Deeper understanding of structure–activity relationships can guide the design of improved catalysts. We hypothesize that mass transport to active sites is of great importance, and herein we use carbon materials with unique flower-like superstructures to achieve high activity and selectivity for O 2 reduction to H 2 O 2 . The abundance of nitrogen active sites controlled by pyrolysis temperature resulted in high catalytic activity and selectivity for oxygen reduction reaction (ORR). The flower superstructure showed higher performance than the spherical nanoparticles due to greater accessibility to the active sites. Chemical activation improves the catalysts’ performances further, driving the production of H 2 O 2 to a record-setting rate of 816 mmol·g cat -1 ·h -1 using a bulk electrolysis setup. In conclusion, this work demonstrates the development of a highly active catalyst for the sustainable production of H 2 O 2 through rational design and synthetic control. The understanding from this work provides further insight into the design of future carbon-based electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regulating the product distribution of CO reduction by the atomic-level structural modification of the Cu electrode surface

Here, Cu catalyzes the electrochemical reduction of CO 2 or CO to an assortment of products, a behavior that is a detriment when only one reduced compound is desired. The present article provides an example in which, through the atomic-level control of the structure of the Cu electrode surface, the yield distribution is regulated to generate only one product. The reaction investigated was the preferential reduction of CO to C 2 H 5 OH on Cu at a low overpotential in alkaline solution. Experimental measurements combined electrochemical scanning tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS). An atomically ordered Cu(100) surface, prepared from either a single crystal or by Cu(pc)-to-Cu(100) reconstruction, did not produce ethanol. When the surfaces were subjected to monolayer-limited Cu↔Cu 2 O cycles, only the reconstructed surface underwent an additional structural transformation that spawned the selective production of ethanol at a potential 645 mV lower than that which generates multiple products. Quasi-operando ECSTM indicated transformation to an ordered stepped surface, Cu(S) [3(100)×(111)], or Cu(511). The non-selective, multiple-product Cu-catalyzed reduction of CO had thus been regulated to yield only one liquid fuel by an atomic-level structural modification of the electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A New One-Pot Sequential Reduction-Deposition Method for the synthesis of Silica-supported NiPt and CuPt Bimetallic Catalysts

A one-pot redox deposition method is described to prepare silica-supported bimetallic NiPt and CuPt catalysts using differences in standard reduction potentials. The synthesis involved the initial reduction of non-noble metal ions (Ni 2+ and Cu 2+ ) by NaBH 4 , followed by reduction of Pt ions by these reduced metals. Alloy formation and phase purity were established by X-ray diffraction (XRD), bulk composition by X-ray fluorescence (XRF), and surface composition by X-ray photoelectron spectroscopy (XPS). Alloy formation was enhanced by increase in the amount of base metals available to reduce Pt, or through the use of excess NaBH 4 after redox deposition. The catalysts were evaluated for methane oxidation at 300-400 °C and atmospheric pressure. Reference samples prepared using the incipient wetness impregnation (IW) method had inferior performance and characteristics. The redox deposition method provides a simple and versatile protocol for the preparation of bimetallic alloys between noble metals and base metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sequentially prepared Mo-V-Based SCR catalyst for simultaneous Hg 0 oxidation and NO reduction

Molybdenum (Mo)-vanadium (V)-based selective catalytic reduction (SCR) catalyst synthesized by the sequential impregnation of Mo and W followed by V was investigated for simultaneous elemental mercury (Hg 0 ) oxidation and nitrogen oxide (NO) reduction in an existing SCR unit with respect to different TiO 2 phases, calcination temperatures, flue gas constituents, gas velocities, and reaction temperatures. Anatase phase TiO 2 and the calcination temperatures of 400 and 500 degrees C resulted in similar to 69% Hg 0 oxidation at 10 ppmv HCl and 350 degrees C. The high calcination temperature of 700 degrees C resulted in TiO 2 phase transformation from anatase to rutile and agglomeration. The modified SCR catalyst prepared with the impregnation sequence of Mo and W followed by V using anatase TiO 2 and calcination temperature 500 degrees C showed similar to 99% Hg 0 oxidation and 87% NO reduction conversions at an NH 3 /NO molar ratio of 0.9 under 350 degrees C and 5,000 hr -1 space velocity in typical sub-bituminous and lignite coal simulated flue gases. Finally, the effects of these parameters and conditions were further investigated using various characterization techniques including BET, TEM, XRD, NH 3 TPD and XAFS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly active subnanometer Rh clusters derived from Rh-doped SrTiO 3 for CO 2 reduction

Here, sub-nanometer Rh clusters derived from Rh-doped SrTiO 3 , demonstrated by in-situ X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements, are applied as highly active catalysts for CO 2 reduction. Compared to the supported Rh/SrTiO 3 , the catalyst synthesized by a doping-segregation method exhibits a higher space-time yield (STY) to CO with a selectivity of 95% for CO 2 reduction by hydrogen; it also shows a higher activity with a larger turnover frequency (TOF) for CO 2 reduction by ethane. According to the in-situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) experiments, the higher CO selectivity for CO 2 hydrogenation is attributed to the lower CO binding strength resulted by the strong interactions (e.g., charge transfer) between Rh atoms and the oxide support with surface defects. The superior activity is suggested to be originated from the cooperative effect between the highly dispersed sub-nanometer Rh clusters for efficient dissociation of H 2 /C 2 H 6 and the reconstructed SrTiO 3 with oxygen vacancies for preferential adsorption/activation of CO 2 . Finally, the doping-segregation method provides a unique opportunity to tune the size of active metal clusters and the physicochemical properties of the oxide support, offering the potential for applications in a variety of chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of four-mode hydrothermal aging on three-way catalysts for passive selective catalytic reduction to control emissions from lean-burn gasoline engine

Passive selective catalytic reduction (SCR) is a promising approach for the control of NOX emissions in lean burn gasoline exhausts. It requires ammonia (NH 3 ) to be produced over a three-way catalyst (TWC) during periods of fuel-rich operation for the reduction of NO X during periods of fuel-lean operation. Previous research has shown the viability of this system but has not examined the effects of hydrothermal degradation. This work is focused on evaluating the effects of hydrothermal aging on the TWC in a passive SCR system. Two catalysts were studied: a Pd-TWC, and a NO X storage and reduction (NSR) TWC. Samples were aged at 920 °C for 100 h using a four-mode hydrothermal aging procedure. This causes the catalyst to be oxidized and reduced, as it would in a real system. The effects of aging were evaluated using simulated exhaust under both steady state and lean-rich cycling conditions. Hydrothermal aging caused significant changes in catalyst activity, leading to a decrease in low temperature conversion of carbon monoxide (CO) and propane (C 3 H 8 ) on both catalysts, and degradation of oxygen storage and NO X storage components. Furthermore, the catalysts maintained their activity for NO X conversion and NH 3 production, showing sufficient activity for the operation of a passive SCR with an optimum projected fuel consumption of 92–98% compared to stoichiometric operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of transition metal formyl intermediates in the reduction of CO and CO 2

Transition-metal formyl (metalloformyl) complexes occupy a central position in the activation of small molecules, particularly in the reduction of carbon monoxide (CO) and carbon dioxide (CO 2 ). This review examines five decades of progress in the synthesis of metalloformyl complexes and investigations into their structure and reactivity. The bonding in the M–CHO unit is best described as a resonance hybrid between a classical σ-bound formyl ligand and an oxycarbene-like electronic structure, which governs their distinctive spectroscopic signatures and versatile reactivity. Established synthetic routes are summarized, including pathways involving hydride addition and CO insertion, alongside a discussion of the thermodynamic and kinetic factors that control formyl stability. Decomposition pathways and Lewis-acid stabilization strategies are analyzed as key design principles for extending metalloformyl lifetimes under catalytic conditions. Particular attention is given to hydride transfer processes and the role of metalloformyl intermediates as both reactive substrates and hydride sources in reduction chemistry. Lastly, emerging catalytic strategies that exploit metalloformyl intermediates in CO 2 and CO reduction are evaluated, highlighting how control of hydricity, redox potential, and secondary-sphere interactions enables selective C—H bond formation under comparatively mild conditions. Collectively, these studies establish metalloformyl complexes as mechanistically informative and functionally relevant intermediates that bridge fundamental organometallic chemistry with modern approaches to small-molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction kinetics of hercynite redox materials for solar thermochemical water splitting

Solar thermochemical water splitting (STWS) using a hercynite redox cycle is a promising technology for producing renewable H 2 . Here, the reduction kinetics of hercynite (FeAl 2 O 4 ) is evaluated using thermogravimetric and XRD analyses. The results indicate that as-prepared hercynite materials undergo reduction via two different reaction mechanisms. The reaction first proceeds by a nucleation and growth mechanism (AE1), followed by a third-order kinetic model (F3). XRD analyses show the occurrence of superstoichiometric oxygen in the spinel structure of FeAl 2 O 4+δ in the second reaction mechanism, which indicates the formation of cationic vacancies. TGA and XRD analyses confirm that hercynite maintains its spinel structure when the materials are thermally reduced and oxidized with steam. Differential scanning calorimetry (DSC) performed on FeAl 2 O 4 particles shows two heats of reaction in agreement with the two observed mechanisms. This is the first kinetics study to report on the thermal reduction of hercynite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗