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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Does H 2 Temperature–Programmed Reduction Always Probe Solid–State Redox Chemistry? The Case of Pt/CeO 2

Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H 2 temperature-programmed reduction (H 2 -TPR) is commonly used to probe oxide reducibility by measuring the rate of H 2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H 2 dissociation and H-spillover, before surface reduction and H 2 O formation occur. In this study, we evaluated the kinetics of H 2 consumption over CeO 2 and Pt/CeO 2 with varying Pt loadings and structures to identify the elementary steps probed by H 2 -TPR. Literature often attributes changes in H 2 -TPR characteristics with Pt addition to increased CeO 2 reducibility. However, our analysis revealed that the H 2 consumption rate is measurement of the rate of H-spillover at Pt-CeO 2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H 2 . Furthermore, lower temperature H 2 consumption observed with Pt addition does not indicate higher CeO 2 reducibility. Measurements on samples with mixtures of Pt single-atoms and nanoclusters demonstrated that H 2 -TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H 2 -TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Inverse regression for ridge recovery: a data-driven approach for parameter reduction in computer experiments

Parameter reduction can enable otherwise infeasible design and uncertainty studies with modern computational science models that contain several input parameters. In statistical regression, techniques for sufficient dimension reduction (SDR) use data to reduce the predictor dimension of a regression problem. A computational scientist hoping to use SDR for parameter reduction encounters a problem: a computer prediction is best represented by a deterministic function of the inputs, so data comprised of computer simulation queries fail to satisfy the SDR assumptions. To address this problem, here we interpret SDR methods sliced inverse regression (SIR) and sliced average variance estimation (SAVE) as estimating the directions of a ridge function, which is a composition of a low-dimensional linear transformation with a nonlinear function. Within this interpretation, SIR and SAVE estimate matrices of integrals whose column spaces are contained in the ridge directions’ span; we analyze and numerically verify convergence of these column spaces as the number of computer model queries increases. Moreover, we show example functions that are not ridge functions but whose inverse conditional moment matrices are low-rank. Consequently, the computational scientist should beware when using SIR and SAVE for parameter reduction, since SIR and SAVE may mistakenly suggest that truly important directions are unimportant.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2019

The Influence of Sulfur Content on the Carbothermal Reduction of SiMn Slag

This article examines the influence of sulfur content on the carbothermal reduction of MnO and SiO{sub 2} in SiMn slag by carbon black. The sulfur content in the synthetic slag is varied from 0 to 1.0 wt pct. Reduction experiments are carried out in a thermogravimetric (TG) furnace at 1873 K (1600 °C) under CO atmospheric pressure. The reduction rates are measured based on the weight loss data, and the samples are characterized by SEM/EDS and ICP-MS. The wetting property of slag on carbon black is also studied with the sessile drop technique. The reaction rate on the slag-metal interface is one order higher than on the slag-carbon interface. A small amount of sulfur (0.2 and 0.44 wt pct) accelerates the slag-metal reaction rate constant by 2.2 and 4.2 times, respectively. Therefore, small amounts of sulfur in slag significantly improve the reduction of MnO and SiO{sub 2}. The MnS precipitation phenomenon during slag cooling is studied by FactSage simulation and experimental verification.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Microstructural Changes and Kinetics of Reduction of Hematite to Magnetite in CO/CO{sub 2} Gas Atmospheres

The microstructures of porous magnetite formed on gaseous reduction of dense hematite have been examined using high-resolution scanning electron microscopy. It has been shown that cellular pores are formed on reduction in the temperature range 573 K to 973 K (300 °C to 700 °C). Dendritic shaped gas pores are formed on reduction at temperatures between 1073 K and 1273 K (800 °C and 1000 °C). The apparent chemical reaction rate constant for the reduction of hematite to magnetite in CO/CO{sub 2} gas mixtures has been derived from measurements of product thickness against reaction time; the rate constant is described by the relation φ{sub CO} = 0.232exp(76,000/RT) µm s{sup −1} atm{sup −1}.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Interaction of Strain Refined Precipitates and Recrystallized Grains in Nb-Ti Microalloyed Steel during Continuous Casting, Hot-Core Heavy Reduction Rolling, and Reheating Process

Hot-core heavy reduction rolling (HHR{sup 2}) is an energy-saving process that directly rolls continuously cast slabs at the end of solidification that have a large temperature gradient. Here, we elucidated the interaction of strain refined precipitates and recrystallized grains in Nb-Ti microalloyed steel during continuous casting, hot-core heavy reduction rolling, and reheating process. Furthermore, theoretical models were established to calculate recrystallization driving force and pinning force at temperatures in the range of 850-1300 °C by a two-stage interrupted compression test using a Gleeble-3800 thermomechanical simulator. The study indicated that a random dispersion of strain refined precipitates with a size range of ~ 6-10 nm was obtained in the hot-core heavy reduction rolled slab, which was different from the coarse and uneven distribution of precipitates in a conventional slab. Upon reheating, the austenite grains in the hot-core heavy reduction rolled slab were significantly refined and evenly distributed along the thickness direction. This is attributed to the random dispersion of strain refined precipitates formed in the HHR{sup 2} process.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Iron Oxide Reduction Rate Affects Iron Product Morphology

Magnetite concentrates from different parts of the Mesabi Range, exhibiting varying tendencies to encapsulate, were reduced using thermogravimetric analysis (TGA) and a high-temperature confocal scanning laser microscope (CSLM). Gas-phase mass-transfer conditions were intentionally varied by employing two reactors with different geometries: the TGA produced significantly slower reduction, whereas the CSLM setup yielded reduction rates up to 20 times faster under mass-transfer-controlled conditions. A preliminary mechanism is proposed to explain the transition from a porous iron product to a dense encapsulating layer. Encapsulation is interpreted as the outcome of competition between pore creation, driven by the reduction rate, and pore elimination, driven by surface diffusion. When pore formation is insufficient to counteract pore coarsening, a dense iron layer develops and restricts further reduction.

encapsulation↗
DOE OSTI2020

Peak load reduction and load shaping in HVAC and refrigeration systems in commercial buildings by using a novel lightweight dynamic priority-based control strategy

Reducing peak power demand in a building can reduce electricity expenses for the building owner and contribute to the efficiency and reliability of the electrical power grid. For the building owner, reduced expenses come from the reduction or elimination of peak power charges on electricity bills. For the power system operator, reducing peak power demand leads to a more predictable load profile and reduces stress on the electric grid system. Herein we present a computationally inexpensive, dynamic, and retrofit-deployable control strategy to effect peak load reduction and load shaping. The effectiveness of the control strategy is examined in a simulation with 80 air-conditioning units and 40 refrigeration units. The results show that a peak demand reduction of 60 kW can be achieved relative to peak demand in a typical set point–based approach. The proposed strategy was deployed in a gymnasium building with four rooftop HVAC units, where it showed over 15% peak demand (kW) reduction savings while maintaining or lowering energy consumption (in kilowatt-hours) relative to the set point–based thermostat controls.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2020

Reduction and potential remediation of U(VI) by dithionite at an in-situ recovery mine: Insights gained by δ 238 U

In-situ recovery is a common method of mining U ore. This technique involves injecting an oxidant to oxidize U deposited as insoluble U(IV) to soluble U(VI) and a complexing agent to form mobile U(VI) compounds, which are extracted from mining waters. Unfortunately, U concentrations often remain elevated in groundwater following this mining process. One promising technique to decrease U concentrations to acceptable levels is in-situ remediation where a reductant is injected into the mined area to reduce U(VI) back to insoluble U(IV). Here we assess the efficacy of the chemical reductant dithionite to reduce U(VI) concentrations. While dithionite can reduce environmental Cr(VI), dithionite has previously never been tested for reducing U(VI) in the environment. We determine how effectively dithionite remediates U(VI) contamination using aqueous U concentration and δ 238 U data. U concentrations and δ 238 U decrease during the dithionite experiment, demonstrating that dithionite induces U(VI) reduction. As dithionite is removed by pumping, U concentrations and δ 238 U increase towards background levels, but U(VI) reduction continues for an extended period. In conclusion, measurements demonstrate that re-oxidation and remobilization does not appear to occur due to the reducing condition of groundwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Effect of alumina incorporation on the sulfur tolerance of the dual-catalyst aftertreatment system for reduction of nitrogen oxides under lean conditions

Presence of sulfur or sulfur additives in natural gas lead to the formation of sulfur dioxide in the exhaust stream of natural gas-fired lean-burn engines. The sulfur tolerance and hydrothermal stability of the dual-catalyst aftertreatment system comprising a reduction catalyst (palladium supported on sulfated zirconia- Pd/SZ) and an oxidation catalyst (cobalt oxide supported on ceria- CoO x /CeO 2 ) for NOx reduction under lean-burn conditions has been tested under simulated engine exhaust conditions. Alumina-incorporated Pd/SZ (Pd/SZ(Alumina)) reduction catalyst as part of the dual catalyst bed demonstrated superior sulfur tolerance in the presence of 5 ppm SO 2 in the feed. The ratio of the reduction to oxidation catalyst was also seen to affect the hydrothermal stability under wet conditions with SO 2 in the reaction medium. The effect of hydrocarbon and water concentration in the reaction mixture on the sulfur tolerance of the dual-catalyst bed was studied. Increasing the reaction temperature from 450°C to 500°C demonstrated very stable NO x conversion and improved CH 4 conversions when the dual-catalyst bed was kept on-stream for 40 h -1 . X-ray photoelectron spectroscopy on samples poisoned with SO 2 ex-situ revealed the deposition of surface sulfates on the Pd/SZ catalyst samples and a combination of sulfates and sulfites on the CoO x /CeO 2 on treatment with SO 2 . The presence of alumina in the Pd/SZ sample protects the support from SO 2 poisoning as the oxidation state of the zirconia support remained largely unchanged on poisoning while in the CoO x /CeO 2 sample, sulfur poisoning likely affects the cerium redox cycle (Ce 3+ -Ce 4+ ). 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) revealed redistribution of the octahedral and tetrahedral Al-O coordination on SO 2 poisoning. Due to association with deposited sulfates on the catalyst, shielding effect on the Al nuclei resulted in an increased octahedral Al-O coordination in the poisoned sample.

03 NATURAL GAS↗
DOE OSTI2021

Reduction and bacterial adsorption of dissolved mercuric ion by indigenous bacteria at the Oak Ridge Reservation site

Mercury exists in various forms in the environment and the indigenous bacteria mediated processes have the potential to be used for mercury remediation. In this study, two mixed cultures of indigenous bacteria at the Oak Ridge Reservation site (i.e., ORR soil culture and ORR sediment culture) were selected to study the microbial mediated mercuric reduction under an aerobic condition as well as mercury adsorption onto bacterial surfaces. PCR analysis was performed to provide insights into the microbial community. The mercuric volatilizing experiment demonstrated the mercuric reducing capacity for both ORR cultures, in which the Pseudomonas genus was the dominating Hg 0 producer. The investigation of the impact of the sole carbon source revealed the energy-dependent characteristics of the mercuric reduction in this study. Namely, the mercuric reduction was nearly not impacted by the type of carbon source but positively related to the energy that a unit amount of substrate could provide. The study also indicated that the mercury adsorption competed with the reduction. According to the fitting of the Langmuir isotherm, the ORR soil culture was found to have a higher mercury adsorption capacity (i.e., 67.5 mg Hg/g dry biomass) than the ORR sediment culture (i.e., 53.1 mg Hg/g dry biomass). The negative correlation between the reduced mercury mass and adsorbed mercury mass was identified for both ORR cultures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Photoelectrocatalytic reduction of CO 2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon

The reduction of carbon dioxide (CO 2 ) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type ( R bpy)Mn(CO) 3 Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO x -porSi). SiO x -porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO x -porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO 2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm 2 ), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. Here, the applied potential is close to the equilibrium potential for CO 2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO 2 reduction to formate and the first on semiconducting silicon.

13 HYDRO ENERGY↗
DOE OSTI2020

Assessment of peak power demand reduction available via modulation of building ventilation systems.

Peak power demand strains electrical grids and increases cost of electricity generation, transmission and distribution infrastructure. Many studies have examined ways of reducing peak power demand, including modification of room air temperature setpoints or reduction of lighting levels. However, very few or no studies have examined the peak power reduction resource offered by temporary curtailment of building ventilation systems. For this reason, we conducted a simulation campaign in which we examined the resource offered by temporary ventilation curtailment in commercial buildings of different use types across the United States and in residences in the state of California, with the essential constraint that any changes resulted in air quality acceptable to occupants through additional ventilation to compensate for the curtailment. To do this, we employed previously validated building models implemented in the airflow and contaminant transport tool CONTAM and building thermal and systems modeling tool EnergyPlus, in some cases co-simulated. Overall, results show savings are highly dependent on building type and climate but range from 0–2 W/ft 2 and up to 40% of total peak building power demand. Depending on building type, this power shed can be conducted for 1.5–8 h before acute exposure or odor concerns are expected, assuming a safety factor of 2. This reduction is of the same magnitude as that offered by thermal control strategies such as setpoint increase, or from lighting reduction strategies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2015

Reduction in Tumor Volume by Cone Beam Computed Tomography Predicts Overall Survival in Non-Small Cell Lung Cancer Treated With Chemoradiation Therapy

Purpose: We sought to evaluate whether tumor response using cone beam computed tomography (CBCT) performed as part of the routine care during chemoradiation therapy (CRT) could forecast the outcome of unresectable, locally advanced, non-small cell lung cancer (NSCLC). Methods and Materials: We manually delineated primary tumor volumes (TV) of patients with NSCLC who were treated with radical CRT on days 1, 8, 15, 22, 29, 36, and 43 on CBCTs obtained as part of the standard radiation treatment course. Percentage reductions in TV were calculated and then correlated to survival and pattern of recurrence using Cox proportional hazard models. Clinical information including histologic subtype was also considered in the study of such associations. Results: We evaluated 38 patients with a median follow-up time of 23.4 months. The median TV reduction was 39.3% (range, 7.3%-69.3%) from day 1 (D1) to day 43 (D43) CBCTs. Overall survival was associated with TV reduction from D1 to D43 (hazard ratio [HR] 0.557, 95% CI 0.39-0.79, P=.0009). For every 10% decrease in TV from D1 to D43, the risk of death decreased by 44.3%. For patients whose TV decreased ≥39.3 or <39.3%, log-rank test demonstrated a separation in survival (P=.02), with median survivals of 31 months versus 10 months, respectively. Neither local recurrence (HR 0.791, 95% CI 0.51-1.23, P=.29), nor distant recurrence (HR 0.78, 95% CI 0.57-1.08, P=.137) correlated with TV decrease from D1 to D43. Histologic subtype showed no impact on our findings. Conclusions: TV reduction as determined by CBCT during CRT as part of routine care predicts post-CRT survival. Such knowledge may justify intensification of RT or application of additional therapies. Assessment of genomic characteristics of these tumors may permit a better understanding of behavior or prediction of therapeutic outcomes.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2020

Impact of zero valent iron aging on reductive removal of technetium-99

Zero valent iron (ZVI) is a promising material for reductive removal of technetium from industrial waste streams. An example application of this method could be to treatment of low activity aqueous waste that is currently stored in tanks at the Hanford site. However, there is still a lack of understanding of the useful lifetime of ZVI for treatment and the changes in reductive removal of Tc over time. In this research, we studied the reductive removal of Tc from aqueous solutions by ZVI aged with up to 30 days by contact with 0.08 M NaCl solutions. These results show that ZVI could be used to remove Tc(VII) from aqueous solutions by its reduction to the less soluble and relatively immobile Tc(IV) with greater than 99% removal in three hours. Still, greater than 90% of Tc is removed with ZVI aging up to one week. However, after 10 days of aging of zero valent iron, a significant decrease in removal of Tc occurs (55% removal at three hours) followed by negligible removal after aging for two weeks or more which is consistent with formation of iron oxides on the surface. Further, these results correlate with XRD and FTIR analysis showing an increase in magnetite followed by maghemite and goethite with aging time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

A Parametric Study of Operating Carbon Anodes in the Oxide Reduction Process

A parametric study of the electrolytic reduction of uranium dioxide in molten lithium chloride – lithium oxide using carbon anodes was conducted to determine the operational parameter values necessary for high yields. Operational parameters evaluated in this study include anode and cathode current densities, anodic polarization, UO 2 batch size, and method of electrochemical control. Seven oxide reduction experiments were conducted with between 25 g and 100 g UO 2 . The current density on the cathode was the critical parameter, which indicates the reduction process is kinetically controlled by cathodic reactions. High cell currents were achieved without the application of high anodic potentials by using a large anode surface area. As a result, this approach facilitates efficient reduction at high throughput without production of chlorine or other corrosive gasses.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Reduction mechanism of sulfur in lithium-sulfur battery: From elemental sulfur to polysulfide

In this study, the polysulfide ions formed during the first reduction wave of sulfur in Li–S battery were determined through both in-situ and ex-situ derivatization of polysulfides. By comparing the cyclic voltammetric results with and without the derivatization reagent (methyl triflate) as well as the in-situ and ex-situ derivatization results under potentiostatic condition, in-situ derivatization was found to be more appropriate than its ex-situ counterpart, since subsequent fast chemical reactions between the polysulfides and sulfur may occur during the timeframe of ex-situ procedures. It was found that the major polysulfide ions formed at the first reduction wave of elemental sulfur were the S 4 2– and S 5 2– species, while the widely accepted reduction products of S 8 2– and S 6 2– for the first reduction wave were in low abundance.

25 ENERGY STORAGE↗
DOE OSTI2014

Synthesis, characterization and electrochemical studies of nanostructured CaWO{sub 4} as platinum support for oxygen reduction reaction

Highlights: • Nanostructured CaWO{sub 4} was fabricated by co-precipitation method. • Platinum was electrodeposited onto the surface prepared nanostructured CaWO{sub 4}. • Pt/CaWO{sub 4}-graphite demonstrate good oxygen reduction reaction activity. - Abstract: In the present work, we employed nanostructured calcium tungstate as a supporting material for platinum, a well-known electrocatalyst for oxygen reduction. The co-precipitation method has been utilized to synthesize nanostructured calcium tungstate from aqueous solution. The structure and morphology of the obtained CaWO{sub 4} were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Preparation of the Pt/CaWO{sub 4}-graphite catalyst was carried out by electrodeposition of Pt onto the surface of CaWO{sub 4}/graphite electrode. The physical properties of the catalyst were determined by scanning electron microscopy analysis and energy dispersive X-ray (SEM/EDX). The electrochemical activity of the Pt/CaWO{sub 4}-graphite for the oxygen reduction reaction (ORR) was investigated in acid solution by cyclic voltammetry measurements, linear sweep voltammetry, and electrochemical impedance spectroscopy. The results revealed that the Pt/CaWO{sub 4}-graphite has higher electrocatalytic activity for oxygen reduction in comparison with Pt/graphite catalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The influence of a silica pillar in lamellar tetratitanate for selective catalytic reduction of NO{sub x} using NH{sub 3}

Highlights: • Potassium ions significantly affected the SCR. • The introduction of silica in the catalyst promotes the NH{sub 3}-SCR reaction. • The catalysts activities were not significantly influenced by SO{sub 2} addition. - Abstract: Silica-pillared layered titanate (SiO{sub 2}–Ti{sub 4}O{sub 9}) was prepared by intercalating organosilanes into the interlayers of a layered K{sub 2}Ti{sub 4}O{sub 9} followed by calcination at 500 °C. The lamellar titanates produced were used as a support to prepare vanadium catalysts (1 and 2 wt%) through wet impregnation for selective catalytic reduction (SCR) of NO. The catalysts were characterized using nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (H{sub 2}-TPR), nuclear magnetic resonance ({sup 29}Si NMR), and infrared spectroscopy (FT-IR). Reduction of NO by NH{sub 3} was studied in a fixed-bed reactor packed with the catalysts and fed a mixture comprising 1% NH{sub 3}, 1% NO, 10% O{sub 2}, and 34 ppm SO{sub 2} (when used) in helium. The results demonstrate that activity is correlated with the support, i.e., with acidic strength of catalysts. The potassium in the support, K{sub 2}Ti{sub 4}O{sub 9}, significantly affected the reaction and level of vanadium species reduction. The catalyst (1VSiT) with 1 wt% vanadium impregnated on the SiO{sub 2}–Ti{sub 4}O{sub 9} support reduced ∼80% of the NO. Approximately the same conversion rate was generated on the catalyst (2VSiT) with 2 wt% vanadium using the same support. The increased NH{sub 3} adsorption demonstrate that introduction of silica in the catalyst promotes the NH{sub 3}-SCR reaction. More importantly, 2VSiT and 1VSiT were strongly resistant to SO{sub 2} poisoning.

36 MATERIALS SCIENCE↗