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At least 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Coupling CTF to MPACT for Improved Thermal-Hydraulic Feedback for Transients

As computational power and techniques continue to advance, reactor analysis codes are afforded the opportunity to employ a more detailed physics model. One area where this has manifested is with coupled neutron kinetics and thermal-hydraulics codes for transient analysis, in which the feedback is critical for accurate modeling. The Michigan Parallel Characteristics Transport (MPACT) code is a 3-D method of characteristics neutron transport code capable of generating sub-pin level power distributions being developed by the University of Michigan through the Consortium for Advanced Simulation of LWRs (CASL) program. Currently, MPACT handles thermal-hydraulic feedback with an internal 1-D radial heat transfer model assuming constant moderator temperature. While this relatively simple treatment of thermal-hydraulic feedback has been shown to accurately model transients where Doppler feedback is the dominant feedback mechanism, coupling MPACT to a detailed thermal-hydraulic code will greatly expand the range of transient problems that can be accurately modeled. COBRA-TF (CTF) is a 3-D two-phase flow, subchannel thermal-hydraulics code maintained by Penn State University through CASL. CTF is based upon the Semi-Implicit Method for Pressure-Linked Equations, and it is especially well suited to model heat transfer and fluid flow phenomena associated with a nuclear reactor through a wide range of conditions. We present an initial effort coupling MPACT to CTF for transients, which provides a wider range of transient problems that can be modeled with increased accuracy. We have successfully coupled the thermal-hydraulics code CTF to the neutronics code MPACT for transient calculations by implicit and Crank-Nicolson methods, which have been demonstrated with single pin and 3x3 configurations. This capability extends the ability of MPACT to accurately model transients through a wider range of conditions than the existing thermal-hydraulic feedback, which is severely limited by the assumption of constant moderator temperature and density. By employing CTF for the thermal- hydraulic feedback, the transient physics can be described more completely at minimal computational expense. (authors)

42 ENGINEERING↗
DOE OSTI2016

Ab initio generation of thermal neutron scattering law for uranium dioxide

Neutronic analysis of moderated nuclear fission systems, e.g. nuclear reactors, relies upon an accurate prediction of the thermal neutron spectrum. Thermal neutrons have wavelengths on the order of the interatomic spacing between atoms in matter. Consequently, the scattering cross-sections of these neutrons are affected by the scattering law of the material (i.e. S(α,β), where α and β are dimensionless momentum and energy transfer variables), which describes the atomic structure and thermodynamic motion of the atomic nuclei. Uranium-dioxide (UO{sub 2}) is the primary fuel source for nuclear power reactors moderated by light water. In such systems (e.g. nuclear power reactors, spent fuel pools, etc.) the nuclear fuel comprises a large fraction of the system volume, approximately 1/3 in light-water reactors. Therefore, the scattering law of the fuel material may impact the thermal neutron spectrum and criticality of these systems. In this work previously established ab initio lattice dynamics (AILD) methods were utilized to calculate the phonon density of states (DOS), which acts as a fundamental input to the scattering law. Subsequently, the S(α,β) of UO{sub 2} was generated for publication as an ENDF thermal scattering library (TSL), which will be available for use in standard neutronics computer applications. (authors)

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2016

Preliminary neutronic assessment of a novel fluoride-salt-cooled high-temperature reactor design

The Fluoride-Salt-Cooled High-Temperature Reactor (FHR) is a molten salt cooled, graphite moderated high temperature reactor. In this work, single-batch cycle length, block power distributions, and temperature-related reactivity effects were assessed using the SCALE code suite. Two types of parametric studies were performed. The first consisted of fixed temperature (isothermal) cases in which to determine the relationship between operation power and cycle length as well as pin power distributions. This second study calculates various isothermal reactivity coefficients based on heterogeneous temperature distributions. Reactivity coefficients with respect to the temperature of the fuel, coolant, and moderator were performed separately to determine their individual contributions. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2016

Comparison of Proposed HANARO Fuel Assemblies in the WWR-SM Reactor

Fuel supply stability is crucial to all reactors. The WWRSM research reactor operated by the Institute of Nuclear Physics at the Academy of Sciences in Uzbekistan currently uses Russian-supplied IRT-4M fuel. The goal of this Oregon State/PNNL research collaboration is to investigate the potential use of the Korean-made High-flux Advanced Neutron Application Reactor (HANARO) fuel rods in the WWR-SM. Many research reactors use unique fuels made by single suppliers, like the WWR-SM. The WWR-SM is a pool-type, high power research reactor using IRT-4M fuel assemblies which are sold and manufactured by a single fuel supplier. Use of HANARO fuel rods has the potential to improve fuel supply stability and associated costs while maintaining high flux levels needed for continuing operations. In the course of the investigation to design an alternate fuel assembly for the WWR-SM, multiple designs have been evaluated. In particular, two assemblies using standard HANARO fuel rods were considered: one with the optimal fuel-to-moderator ratio in the fueled region of the assembly and one with an under-moderated fuel region. Each of these assemblies has had its neutronic performance characterized with MCNP6 system reactivity and flux distribution calculations. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Minimum critical masses and their uncertainties for several fissile nuclides and reflectors - 14296

A systematic effort was undertaken to reevaluate the minimum critical mass for several fissile nuclides and reflectors. This was done using MCNP6 in combination with several modern nuclear data libraries, viz. ENDF/B-VII.1, JENDL-4.0 and JEFF-3.1.1. This combination was benchmarked extensively against criticality safety benchmarks. The procedure to extract the minimum critical mass from the MCNP6 calculations was carefully implemented, so that it would have a negligible impact on the accuracy of the end results. All parts of the calculation, i.e. nuclear data processing, MCNP6 models, and post-processing, were applied consistently for all cases, involving varying fissile nuclides and reflectors. Results for the minimum critical mass were generated for {sup 233,235}U, {sup 236,239,241}Pu, {sup 242m}Am, {sup 243,245,247}Cm, and {sup 249,251}Cf, for the case of water moderation and water reflection. For {sup 235}U, the minimum critical mass was also calculated for cases with other reflectors, such as beryllium, heavy water, graphite, lead, and concrete. The results for the water reflection cases are in good agreement with most of the literature values, but for the cases with reflectors such as graphite, lead, or concrete, there are sizable differences. The accuracy of the results was assessed in two ways. First, a comparison was made with criticality safety benchmark results, by selecting benchmarks that resemble the minimum mass systems the most. It was clear that for {sup 233,235}U and {sup 239}Pu with water reflection, the differences in minimum critical masses between the libraries are consistent with the differences obtained for benchmark cases. The difference between the benchmark calculations and the benchmark values is then an indication of the accuracy with which one can simulate comparable systems. Secondly, sensitivity runs were performed with the new MCNP6 sensitivity option, based on ENDF/B-VII.1 nuclear data. For each fissile nuclide, the sensitivity of k{sub eff} to cross sections such as capture, fission, elastic, inelastic was calculated for the minimum critical mass case. The same was done for the {sup 1}H and {sup 16}O cross sections in the moderator and reflector. The uncertainty in k{sub eff} was calculated by combining the sensitivity profiles with the appropriate ENDF/B-VII.1 covariance matrix, using the SUSD code. As a final step, the uncertainty in k{sub eff} can be translated to an uncertainty in the minimum critical mass. (author)

42 ENGINEERING↗
DOE OSTI2015

Criticality calculation package and its use for a spent fuel storage pool with steam layer - 14324

Criticality studies need several calculations with small variations in a number of parameters. Therefore, a calculation package written at VTT in order to facilitate sensitivity studies in criticality calculations was used. This package is based on MCNP5 [1], and consists of a data transfer and analysis program written in Perl, and a set of pseudo inputs for the transport and storage systems including the fuel assembly. The pseudo inputs contain key words that are replaced by a given value for the specific parameter. In this paper, the package is described in more detail including the new modifications needed for this study. The usability will be demonstrated with a study of the fuel pool in the case of steam gathered under the support plates of the pool. In the new pool model the steam layer was added as a water layer with a very low density. The density of this layer, i.e. the steam density, could be varied as well as the thickness of the layer. This package was then used to study the reactivity effect of the moderator density, the steam density and the thickness of the steam layer. As can be expected the strongest effect was obtained with the moderator density. However, the steam density seemed not to affect the reactivity while the thickness of the layer had a small effect. (author)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Coolant density and control blade history effects in extended BWR burnup credit - 14494

Oak Ridge National Laboratory and the US Nuclear Regulatory Commission have initiated a multiyear project to investigate the application of burnup credit (BUC) for boiling water reactor (BWR) fuel in storage and transportation casks. This project includes two phases. The first phase investigates the applicability of peak reactivity methods currently used for spent fuel pools to spent fuel storage and transportation casks and the validation of reactivity (k{sub eff}) calculations and predicted spent fuel compositions. The second phase focuses on extending BUC beyond peak reactivity. This paper documents work performed to date investigating some aspects of extended BUC. The technical basis for application of peak reactivity methods to BWR fuel in storage and transportation systems is presented in a companion paper. Two reactor operating parameters are being evaluated to establish an adequate basis for extended BWR BUC: (1) the effect of axial void profile and (2) the effect of control blade utilization during operation. A detailed analysis of core simulator data for one cycle of a modern operating BWR plant was performed to determine the range of void profiles and the variability of the profile experienced during irradiation. Although a single cycle does not provide complete data, the data obtained are sufficient to determine the primary effects and to identify conservative modeling approaches. These data were used in a study of the effect of axial void profile. The first stage of the study was determination of the necessary moderator density temporal fidelity in depletion modeling. After the required temporal fidelity was established, multiple void profiles were used to examine the effect on cask reactivity. The results of these studies are being used to develop recommendations for conservatively modeling the void profile effects for BWR depletion calculations. The second operational parameter studied was control blade history. Control blades are inserted in various locations and at varying degrees during BWR operation based on the core loading pattern. When present during depletion, control blades harden the neutron spectrum locally because they displace the moderator and absorb thermal neutrons. The investigation of the effect of control blades on post operational cask reactivity is documented herein, as is the effect of multiple (continuous and intermittent) exposure periods with control blades inserted. The coupled effects of control blade presence on power density, void profile, or burnup profile will be addressed in future work. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2016

On the time needed to reach an equilibrium structure of the radiation belts

In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as the radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τ Diffusion /τ loss ), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E ~ [200, 300] keV for L = [3.7, 4] at Kp = 1, E ~ [0.6, 1] MeV for L = [3, 4] at Kp = 3, and E ~ 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Precise relative locations for earthquakes in the northeast Pacific region

We report that double-difference methods applied to cross-correlation measured Rayleigh wave time shifts are an effective tool to improve epicentroid locations and relative origin time shifts in remote regions. We apply these methods to seismicity offshore of southwestern Canada and the U.S. Pacific Northwest, occurring along the boundaries of the Pacific and Juan de Fuca (including the Explorer Plate and Gorda Block) Plates. The Blanco, Mendocino, Revere-Dellwood, Nootka, and Sovanco fracture zones host the majority of this seismicity, largely consisting of strike-slip earthquakes. The Explorer, Juan de Fuca, and Gorda spreading ridges join these fracture zones and host normal faulting earthquakes. Our results show that at least the moderate-magnitude activity clusters along fault strike, supporting suggestions of large variations in seismic coupling along oceanic transform faults. Our improved relative locations corroborate earlier interpretations of the internal deformation in the Explorer and Gorda Plates. North of the Explorer Plate, improved locations support models that propose northern extension of the Revere-Dellwood fault. Relocations also support interpretations that favor multiple parallel active faults along the Blanco Transform Fault Zone. Seismicity of the western half of the Blanco appears more scattered and less collinear than the eastern half, possibly related to fault maturity. We use azimuthal variations in the Rayleigh wave cross-correlation amplitude to detect and model rupture directivity for a moderate size earthquake along the eastern Blanco Fault. Lastly, the observations constrain the seismogenic zone geometry and suggest a relatively narrow seismogenic zone width of 2 to 4 km.

58 GEOSCIENCES↗
DOE OSTI2017

Large CO 2 and CH 4 emissions from polygonal tundra during spring thaw in northern Alaska: Spring Pulse Emission

The few prethaw observations of tundra carbon fluxes suggest that there may be large spring releases, but little Is lmown about the scale and underlying mechanisms of this phenomenon. To address these questions, we combined ecosystem eddy flux measurements from two towers near Barrow, Alaska, with mechanistic soil-core thawing experiment During a 2week period prior to snowmelt In 2014, large fluxes were measured, reducing net summer uptake of CO2 by 46% and adding 6% to cumulative CH4 emissions. Emission pulses were linked to unique rain-on-snow events enhancing soli cracking. Controlled laboratory experiment revealed that as surface Ice thaws, an immediate, large pulse of trapped gases Is emitted. These results suggest that the Arctic C02 and CH4 spring pulse is a delayed release of biogenic gas production from the previous fall and that the pulse can be large enough to offset a significant fraction of the moderate Arctic tundra carbon sink.

Raz-Yaseef, Naama↗
DOE OSTI2017

Aerosol and cloud microphysics covariability in the northeast Pacific boundary layer estimated with ship-based and satellite remote sensing observations: NE Pacific Aerosol-Cloud Interactions

Ship measurements collected over the northeast Pacific along transects between the port of Los Angeles (33.7°N, 118.2°W) and Honolulu (21.3°N, 157.8°W) during May to August 2013 were utilized to investigate the covariability between marine low cloud microphysical and aerosol properties. Ship-based retrievals of cloud optical depth (τ) from a Sun photometer and liquid water path (LWP) from a microwave radiometer were combined to derive cloud droplet number concentration Nd and compute a cloud-aerosol interaction (ACI) metric defined as ACICCN = ∂ ln(Nd)/∂ ln(CCN), with CCN denoting the cloud condensation nuclei concentration measured at 0.4% (CCN0.4) and 0.3% (CCN0.3) supersaturation. Analysis of CCN0.4, accumulation mode aerosol concentration (Na), and extinction coefficient (σext) indicates that Na and σext can be used as CCN0.4 proxies for estimating ACI. ACICCN derived from 10 min averaged Nd and CCN0.4 and CCN0.3, and CCN0.4 regressions using Na and σext, produce high ACICCN: near 1.0, that is, a fractional change in aerosols is associated with an equivalent fractional change in Nd. ACICCN computed in deep boundary layers was small (ACICCN = 0.60), indicating that surface aerosol measurements inadequately represent the aerosol variability below clouds. Satellite cloud retrievals from MODerate-resolution Imaging Spectroradiometer and GOES-15 data were compared against ship-based retrievals and further analyzed to compute a satellite-based ACICCN. Satellite data correlated well with their ship-based counterparts with linear correlation coefficients equal to or greater than 0.78. Combined satellite Nd and ship-based CCN0.4 and Na yielded a maximum ACICCN = 0.88–0.92, a value slightly less than the ship-based ACICCN, but still consistent with aircraft-based studies in the eastern Pacific.

Painemal, David↗
DOE OSTI2016

A computationally efficient parallel Levenberg-Marquardt algorithm for highly parameterized inverse model analyses

Inverse modeling seeks model parameters given a set of observations. However, for practical problems because the number of measurements is often large and the model parameters are also numerous, conventional methods for inverse modeling can be computationally expensive. We have developed a new, computationally-efficient parallel Levenberg-Marquardt method for solving inverse modeling problems with a highly parameterized model space. Levenberg-Marquardt methods require the solution of a linear system of equations which can be prohibitively expensive to compute for moderate to large-scale problems. Our novel method projects the original linear problem down to a Krylov subspace, such that the dimensionality of the problem can be significantly reduced. Furthermore, we store the Krylov subspace computed when using the first damping parameter and recycle the subspace for the subsequent damping parameters. The efficiency of our new inverse modeling algorithm is significantly improved using these computational techniques. We apply this new inverse modeling method to invert for random transmissivity fields in 2D and a random hydraulic conductivity field in 3D. Our algorithm is fast enough to solve for the distributed model parameters (transmissivity) in the model domain. The algorithm is coded in Julia and implemented in the MADS computational framework (http://mads.lanl.gov). By comparing with Levenberg-Marquardt methods using standard linear inversion techniques such as QR or SVD methods, our Levenberg-Marquardt method yields a speed-up ratio on the order of ~10 1 to ~10 2 in a multi-core computational environment. Furthermore, our new inverse modeling method is a powerful tool for characterizing subsurface heterogeneity for moderate- to large-scale problems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Comparisons of Ice Water Path in Deep Convective Systems Among Ground-Based, GOES, and CERES-MODIS Retrievals

Retrievals of convective cloud microphysical properties based on passive satellite imagery are difficult. To help quantify their uncertainties, ice water paths (IWPs) retrieved from the NASA Clouds and the Earth's Radiant Energy System project using Geostationary Operational Environmental Satellite (GOES) and Terra/Aqua MODerate-resolution Imaging Spectroradiometer observations are compared with IWPs retrieved from Next-Generation Radar (NEXRAD) observations over a large domain (32°N to 40°N and 105°W to 91°W) during the 2011 Midlatitude Continental Convective Clouds Experiment field campaign. Based on comparisons of pixel-level (4 km × 4 km) daytime IWP retrievals from NEXRAD and GOES, it is found that NEXRAD- and GOES-retrieved mean IWPs are 2.03 and 1.83 kg m -2 , respectively, for ice-phase cloud in thick anvil area. Their mean difference of 0.20 kg m -2 (with 95% confidence interval: 0.14-0.26 kg m -2 ) is within the uncertainty of NEXRAD retrievals. However, the low correlation between pixel-to-pixel comparisons indicates a large variation in GOES-retrieved IWP. For mixed-phase clouds in thick anvil areas, in addition to IWPs, total water paths (TWPs, sum of ice and liquid water path) are estimated with aid of aircraft measurements for NEXRAD retrievals and corrected using a TWP parameterization for GOES retrievals. The mean values of estimated TWPs from NEXRAD (corrected using aircraft in situ measurements) and GOES are similar. GOES and Clouds and the Earth's Radiant Energy System-MODerate-resolution Imaging Spectroradiometer-retrieved IWPs/TWPs generally do not exceed 5 kg m - 2. Large differences and low correlations exist between satellite and NEXRAD retrievals in stratiform rain areas. Possible reasons for the differences between retrievals are discussed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Multistate and On-Demand Smart Windows

Composite films consisting of wrinkles on top of the elastomeric poly(dimethylsiloxane) film and a thin layer of silica particles embedded at the bottom is prepared as on-demand mechanoresponsive smart windows. By carefully varying the wrinkle geometry, silica particle size, and stretching strain, different initial optical states and a large degree of optical transmittance change in the visible to near infrared range with a relatively small strain (as small as 10%) is achieved. The 10% pre-strain sample has shallow wrinkles with a low amplitude and shows moderate transmittance (60.5%) initially and the highest transmittance of 86.4% at 550 nm when stretched at the pre-strain level. Stretching beyond the pre-strain level leads to a drastic decrease of the transmittance at 550 nm, 39.7% and 70.8% with an additional 10% and 30% strain, respectively. The large drop of optical transmittance is the result of combined effects from the formation of secondary wrinkles and nanovoids generated around the particles. The 20% pre-strain sample has wrinkles with a moderate amplitude, showing 36.9% transmittance in the initial state, and the highest transmittance of 71.5% at 550 nm when stretched to the pre-strain level. Lastly, further stretching leads to increased opacity similar to that seen from the 10% pre-strain sample.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Spin‐Orbit Effects in a Thallium Borohydride Stabilized by Coordination to Bis(diisopropylamino)Cyclopropenylidene (BAC)

The reaction of Tl(OTf) with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in THF results in formation of [Tl(BAC) 2 (OTf)] (1) in moderate yields. Subsequent reaction of 1 with [K][H 2 -9-BBN] ([H 2 -9-BBN] − = dihydrido 9-boratabicyclo[3.3.1]nonane) in THF results in formation of [Tl(BAC)(μ-H 2 -9-BBN)] 2 (3), also in moderate yield. Complex 3 is the first reported thallium borohydride. We attribute its thermal stability to the strong donor ability of the BAC co-ligand. Both 1 and 3 exhibit trigonal pyramidal geometries about Tl + in the solid-state, indicative of the presence of stereochemically active lone pairs. The hydride environment in 3 is calculated to exhibit a 3.9 ppm downfield shift attributed to spin-orbit effects from the adjacent Tl center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Light rain events change over North America, Europe, and Asia for 1973-2009

Long-term daily precipitation data from NCDC are used to investigate the changes of light rain events from 1973-2009 over North America, Europe and Asia. Results reveal that the trend of light rain events presents a remarkably diverse feature in different regions, while an overall decrease trend can be found over the continents in northern hemisphere. In North America, most of stations show a decrease trend for light rain on the annual basis but a decrease trend can also be found for moderate and heavy rain. The opposite trends are observed over the stations in Europe and the trend of light rain is not significant when averaged for all the stations. In Asia, especially East Asia, the light rain days show an overwhelming decrease trend with high spatial coherency. Meanwhile the moderate and heavy rain events (> 10 mm/day) have increased, suggesting a remarkable shift of precipitation from light to heavy rain in East Asia. While both the warming at a global scale and increased atmospheric aerosols due to air pollution at a regional scale (e.g. East Asia) may have affected the light rain changes, it remains a challenging task to quantitatively detect and separate the cause of light rain changes in different regions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Methane combustion over Ni/Ce x Zr 1-x O 2 catalysts: impact of ceria/zirconia ratio

In this work, a series of Ce x Zr 1–x O 2 (x=1, 0.83, 0.17, 0) supports and 2 wt.% Ni/Ce x Zr 1–x O 2 catalysts were synthesized and evaluated for CH 4 oxidation. The Ce x Zr 1–x O 2 supports showed moderate activity (T 50 =519-638°C) with CO by-product formation. Additionally, nickel incorporation onto Ce x Zr 1–x O 2 lowered the T 50 to 438–477°C and eliminated the formation of CO. The results indicated that moderate Zr doping improved the support oxygen storage capacity (OSC) and reducibility of the catalyst at low temperatures (H 2 -TPR) leading to an enhanced CH 4 combustion turnover frequency: Ni/ZrO 2 <Ni/Ce 0.17 Zr 0.83 O 2 <Ni/CeO 2 <Ni/Ce 0.83 Zr 0.17 O 2 . The apparent activation energies of Ni/Ce x Zr 1–x O 2 catalysts (87-92 kJ/mol) were much lower than the ones of Ce x Zr 1–x O 2 supports and Ni/quartz sand (111-120 kJ/mol) indicating that CH 4 oxidation is facilitated when Ni is deposited on Ce x Zr 1–x O 2 . Moreover, stability tests with H 2 O and CO 2 showed that Zr doping can improve the catalyst stability, while H 2 O had a stronger reversible inhibition effect than CO 2 for CH 4 combustion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Molecular‐Level Insight into the Chlorofluorocarbons Adsorption by Defective Covalent Organic Polymers

Abstract Halocarbons have important industrial applications, but because of their contribution to global warming and the fact that they can cause ozone depletion, they are considered highly toxic. Hence, the techniques that can capture and recover the used halocarbons with energy‐efficient methods have been recently received greater attention. In this contribution, we report the capture of dichlorodifluoromethane (R12), which has high global warming and ozone depletion potential, using covalent organic polymers (COPs). The defect‐engineered COPs were synthesized and demonstrated outstanding sorption capacities, ~226 wt % of R12 combined with linear‐shaped adsorption isotherms. We further identified the plausible microscopic adsorption mechanism of the investigated COPs via grand canonical Monte Carlo simulations applied to non‐defective and a collection of atomistic models of the defective COPs. The modeling work suggests that significant R12 adsorption performance is attributed to a gradual increment of porosities due to isolated/interconnected micro‐/meso‐pore channels and the change of the long‐range ordering of both COPs. The successive hierarchical‐pore‐filling mechanism promotes R12 molecular adsorption via moderate van der Waals adsorbate‐adsorbent interactions in the micropores of both COPs at low pressure followed by adsorbate‐adsorbate interactions in the extra‐voids created at moderate to high pressure ranges. This continuous pore‐filling mechanism makes defective COPs as promising sorbents for halocarbon adsorption.

Shen, Jian↗