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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

An ultrahigh-resolution E3SM land model simulation framework and its first application to the Seward Peninsula in Alaska

The availability of supercomputers and state-of-science datasets has made it possible to conduct large-scale land simulations at an ultrahigh-resolution. This study reported a computational framework for land surface simulation using the E3SM land model (ELM) at an unprecedented resolution (1 km x 1 km gridcell). The ultrahigh-resolution ELM (uELM) simulation framework includes three parts: (1) high-resolution atmospheric forcing and surface properties dataset generation, (2) massive gridcell-based simulation, and (3) large-scale simulation results analysis. Additionally, we implemented the uELM simulation framework and completed the first 1 km x 1 km terrestrial ecosystem simulation (from 1850 to 2014) over the Seward Peninsula in Alaska (78,000 km 2 ). The experiment contained two phases: a spin-up simulation and a transient simulation, and required five weeks of calculations using 320 cores in a 44-node Linux HPC computer. It created approximately 1.3 TB of data from the transient simulation alone (1850 - present). We selected sample results (monthly and daily simulation outputs) to illustrate the temporal and spatial variations of several variables in high-latitude Arctic ecosystems’ water, energy, and carbon cycles. At last, we summarized the lessons learned and proposed new developments for full-scale uELM simulations over the entire North American continent (approximately 22,000,000 km 2 ).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Investigating the Influence of Hexanuclear Clusters in Isostructural Metal–Organic Frameworks on Toxic Gas Adsorption

The efficient capture of toxic gases, such as ammonia (NH 3 ) and sulfur dioxide (SO 2 ), can protect the general population and mitigate widespread air pollution. Metal–organic frameworks (MOFs) comprise a tunable class of adsorbents with high surface areas that can meet this challenge by selectively capturing these gases at low concentrations. In this work, we explored how modifying the metal ions in the node of an isostructural MOF series from a transition metal to a lanthanide or actinide influences the electronic environment of the node-based active site. Next, we investigated the adsorption properties of each MOF toward the relatively basic NH 3 and relatively acidic SO 2 gases. Within the NU-907 family of MOFs, we found that Zr 6 -NU-907 exhibits the best uptake toward NH 3 at low pressures, while Th 6 -NU-907 demonstrates the best low-pressure performance for SO 2 adsorption. Here, tracking the infrared (IR) stretching frequency of the node-based μ 3 -OH groups provides insights into the electronegativity of the metal ion and suggests that the most electronegative metal ion (Zr) affords the node with the best NH 3 uptake at low pressures. In contrast, the Th 6 node contains additional coordinated water groups relative to the other M 6 nodes, which appears to yield the MOF with the greatest affinity for SO 2 uptake that occurs predominately through reversible physisorption interactions. Finally, in situ NH3 IR spectroscopic studies indicate that both NH 4 + and Lewis-bound NH 3 species form during adsorption. Combined, these results suggest that tuning the electronic properties and structure of the node-based active site in an MOF presents a viable strategy to change the affinity of an MOF toward toxic gases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Direct implementation of metal-organic frameworks as the catalyst for CO 2 electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e - products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au 3+ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO 2 reduction reaction pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Field Trial of a Low-Cost, Distributed Plug Load Monitoring System

Researchers have struggled to inventory and characterize the energy use profiles of the ever-growing category of so-called miscellaneous electric loads (MELs) because plug-load monitoring is cost-prohibitive to the researcher and intrusive to the homeowner. However, these data represent a crucial missing link to our understanding of how homes use energy, and we cannot control what we do not understand. Detailed energy use profiles would enable the nascent automated home energy management (AHEM) industry to develop effective control algorithms that target consumer electronics and other plug loads. If utility and other efficiency programs are to incent AHEM devices, they need large-scale datasets that provide statistically meaningful justification of their investments by quantifying the aggregate energy savings achievable. To address this need, we have investigated a variety of plug-load measuring devices available commercially and tested them in the laboratory to identify the most promising candidates for field applications. The scope of this report centers around the lessons learned from a field validation of one proof-of-concept system, called Smartenit (formerly SimpleHomeNet). The system was evaluated based on the rate of successful data queries, reliability over a period of days to weeks, and accuracy. This system offers good overall performance when deployed with up to ten end nodes in a residential environment, although deployment with more nodes and in a commercial environment is much less robust. We conclude that the current system is useful in selected field research projects, with the recommendation that system behavior is observed over time.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2014

Field Trial of a Low-Cost, Distributed Plug Load Monitoring System

Researchers have struggled to inventory and characterize the energy use profiles of the ever-growing category of so-called miscellaneous electric loads (MELs) because plug-load monitoring is cost-prohibitive to the researcher and intrusive to the homeowner. However, these data represent a crucial missing link to understanding how homes use energy. Detailed energy use profiles would enable the nascent automated home energy management (AHEM) industry to develop effective control algorithms that target consumer electronics and other plug loads. If utility and other efficiency programs are to incent AHEM devices, they need large-scale datasets that provide statistically meaningful justification of their investments by quantifying the aggregate energy savings achievable. To address this need, NREL researchers investigated a variety of plug-load measuring devices available commercially and tested them in the laboratory to identify the most promising candidates for field applications. This report centers around the lessons learned from a field validation of one proof-of-concept system, called Smartenit (formerly SimpleHomeNet). The system was evaluated based on the rate of successful data queries, reliability over a period of days to weeks, and accuracy. This system offers good overall performance when deployed with up to 10 end nodes in a residential environment, although deployment with more nodes and in a commercial environment is much less robust. NREL concludes that the current system is useful in selected field research projects, with the recommendation that system behavior is observed over time.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

A new dynamic zOnal model with air-diffuser (DOMA) - Application to thermal comfort prediction

A new Dynamic zOnal Model with Air-diffuser (DOMA) was developed. Several case studies were investigated and tested to evaluate and validate this program using measurement data. This new model was integrated into a TRaNsient SYstems Simulation program library and coupled with the multi-zone thermal model. The DOMA/TRNSYS coupled model was then used to predict room temperature distribution over an entire day of a single-zone building. The results show that increasing the heating outputs of the electric floor system, for example, from 75 to 200 W/m 2 , would not effectively improve the indoor thermal comfort, since the thermostat will reach the set point first and then turn off the system before the room gets enough heat and reach a comfortable level. This indicates the importance of selecting an appropriate location and set point for the thermostat when using a floor heating system. This potential thermal comfort issue can only be identified through the two-node model with a dynamic zonal model rather than the conventional PMV model, which thus suggests that for optimizing indoor thermal comfort of a building equipped with a time-sensitive control strategy and/or HVAC system, the TSENS results obtained from the two-node model integrated with DOMA are more appropriate than PMVs.

Construction & Building Technology↗
DOE OSTI2015

Mapping Patterns of Ipsilateral Supraclavicular Nodal Metastases in Breast Cancer: Rethinking the Clinical Target Volume for High-risk Patients

Purpose: To map the location of metastatic supraclavicular (SCV) lymph nodes (LNMs) in breast cancer patients with SCV node involvement and determine whether and where the radiation therapy clinical target volume (CTV) of this region could be modified in high-risk subsets. Methods and Materials: Fifty-five patients with metastatic SCV LNMs were eligible for geographic mapping and atlas coverage analysis. All LNMs and their epicenters were registered proportionally by referencing the surrounding landmarks onto simulation computed tomography images of a standard patient. CTVs based on selected SCV atlases, including the one by the Radiation Therapy Oncology Group (RTOG) were contoured. A modified SCV CTV was tried and shown to have better involved-node coverage and thus theoretically improved prophylaxis in this setting. Results: A total of 50 (91%) and 45 (81.8%) patients had LNMs in the medial and lateral SCV subregions, respectively. Also, 36 patients (65.5%) had LNMs located at the junction of the jugular-subclavian veins. All nodes were covered in only 25.5% to 41.8% of patients by different atlases. The RTOG atlas covered all nodes in 25.5% of patients. Stratified by the nodes in all the patients as a whole, 49.2% to 81.3% were covered, and the RTOG atlas covered 62.6%. The lateral and posterior borders were the most overlooked locations. Modification by extending the borders to natural anatomic barriers allowed the new CTV to cover all the nodes in 81.8% of patients and encompass 96.1% of all the nodes. Conclusions: According to the distribution of SCV LNMs, the extent of existing atlases might not be adequate for potential metastatic sites in certain groups of patients. The extension of the lateral and posterior CTV borders in high-risk or recurrent patients might be a reasonable approach for increasing coverage. However, additional data in more homogeneous populations with localized disease are needed before routine application.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2018

Sensitized photon upconversion in anthracene-based zirconium metal–organic frameworks

Sensitized upconversion is explored in three metal–organic frameworks (MOFs) constructed from the anthracene dicarboxylate (ADC) derivatives and zirconium nodes, 9,10-ADC (9,10-MOF), 2,6-ADC (2,6-MOF) and 1,4-ADC (1,4-MOF). Selective excitation of surface-bound Pd(II) mesoporphyrin IX (PdMP) gives rise to delayed fluorescence (τ = 370 ± 30 ns) from anthracene in the 9,10-MOF. The overall upconversion efficiency of the Pd@9,10-MOF is 0.46 ± 0.05% with a threshold intensity of 104 ± 26 mW cm -2 .

36 MATERIALS SCIENCE↗
DOE OSTI2016

Automated detection of vessel lumen and stent struts in intravascular optical coherence tomography to evaluate stent apposition and neointimal coverage

Purpose: Intravascular optical coherence tomography (IV-OCT) is a high-resolution imaging method used to visualize the microstructure of arterial walls in vivo. IV-OCT enables the clinician to clearly observe and accurately measure stent apposition and neointimal coverage of coronary stents, which are associated with side effects such as in-stent thrombosis. In this study, the authors present an algorithm for quantifying stent apposition and neointimal coverage by automatically detecting lumen contours and stent struts in IV-OCT images. Methods: The algorithm utilizes OCT intensity images and their first and second gradient images along the axial direction to detect lumen contours and stent strut candidates. These stent strut candidates are classified into true and false stent struts based on their features, using an artificial neural network with one hidden layer and ten nodes. After segmentation, either the protrusion distance (PD) or neointimal thickness (NT) for each strut is measured automatically. In randomly selected image sets covering a large variety of clinical scenarios, the results of the algorithm were compared to those of manual segmentation by IV-OCT readers. Results: Stent strut detection showed a 96.5% positive predictive value and a 92.9% true positive rate. In addition, case-by-case validation also showed comparable accuracy for most cases. High correlation coefficients (R > 0.99) were observed for PD and NT between the algorithmic and the manual results, showing little bias (0.20 and 0.46 μm, respectively) and a narrow range of limits of agreement (36 and 54 μm, respectively). In addition, the algorithm worked well in various clinical scenarios and even in cases with a low level of stent malapposition and neointimal coverage. Conclusions: The presented automatic algorithm enables robust and fast detection of lumen contours and stent struts and provides quantitative measurements of PD and NT. In addition, the algorithm was validated using various clinical cases to demonstrate its reliability. Therefore, this technique can be effectively utilized for clinical trials on stent-related side effects, including in-stent thrombosis and in-stent restenosis.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

5G integrated edge computing platform for efficient component monitoring in coal-fired power plants

This project developed a cutting-edge 5G-integrated edge computing framework to enhance operational efficiency and reliability in coal-fired power plants through real-time component monitoring and anomaly detection. The initiative focused on leveraging distributed machine learning, federated learning, and 5G-based dynamic network slicing to support scalable, fault-tolerant monitoring environments to meet the operational requirements in industrial control systems. With a Distributed Edge Computing Service (DECS) orchestration, this project enabled federated learning at edge for condition monitoring and introduced adaptive client selection strategies to minimize communication overhead. Scalable distributed training was achieved using the Horovod framework, thus enhancing performance across edge nodes. In the realm of 5G networking, the project designed and deployed reconfigurable, QoS-aware network slicing tailored for operational technology (OT) environments, integrating software-defined networks to bolster cyber-resilience and enabling dynamic slicing for federated learning workloads. A significant milestone was the development of a virtualized ICS environment with 5G core integration—which allowed elastic and fault tolerant distributed training on real-world datasets such as NASA Bearings, Hydraulic Systems, and TEP. To broaden the impact of the project, a TRL-3 virtualized ICS testbed for research and education was designed. This project engaged several graduate and undergraduate students to conduct research on the cutting-edge technology, and it resulted in one PhD dissertation, one MS thesis, and over 14 peer-reviewed publications. With the support of this project students also participated in national cybersecurity competitions to improve their professional development skills.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

A link-node reformulation of ridesharing user equilibrium with network design

Though the conventional network design is extensively studied, the network design problem for ridesharing, in particular, the deployment of high-occupancy toll (HOT) lanes, remains understudied. Here this paper focuses on one type of network design problem as to whether existing roads should be retrofit into HOT lanes. It is a continuous bi-level mathematical program with equilibrium constraints. The lower level problem is ridesharing user equilibrium (RUE). To reduce the problem size and facilitate computation, we reformulate RUE in the link-node representation. Then we extend the RUE framework to accommodate the presence of HOT lanes and tolls. Algorithms are briefly discussed and numerical examples are illustrated on the Braess network and the Sioux Falls network, respectively. Results show that carefully selecting the deployment of HOT lanes can improve the overall system travel time.

42 ENGINEERING↗
DOE OSTI2016

WE-FG-BRA-09: Using Graphene Oxide Nano Flakes During Image Guided Radiotherapy to Minimize the Potential of Cancer Recurrence Or Metastasis

Purpose: An increasing number of studies show that cancer stem cells (CSCs) become more invasive (metastatic) and may escape into the blood stream and lymph nodes during radiotherapy (RT), before they have received a lethal dose during RT. Other Studies have shown that Graphene oxide (GO) can selectively inhibit the proliferative expansion of CSCs across multiplicative tumor types. In this study we investigate the feasibility of using GO during radiotherapy (RT) to minimize the escape of CSCs towards preventing cancer metastasis or recurrence. Methods: We hypothesize that sufficient amount of GO nano-flakes (GONFs) released from new design radiotherapy biomaterials (fiducials or spacers) loaded with the GONFs can reach all tumor cells within typical times of 14 or 21days before the beginning of image-guided radiotherapy (IGRT) following implantation. To test this hypothesis, the space-time diffusion of the GONFs was investigated. Knudsen’s and Cunningham’s numbers were calculated to get the Stokes’ velocities and mobility values, according to these values, diffusion coefficients were calculated. In a previous study it was shown that GONFs concentration of 50 µg/ml were effective. In the diffusion study, 100 µg/ml was chosen as an initial concentration because it has been shown to be relatively non-toxic. Results: The 50 µg/ml concentration in a 2 cm diameter volume of lung tumor could be only achieved using 2 nm and 6 nm GONFs with respective diffusion times of 14 and 21 days. As expected, increased nanoflake size requires longer times to achieve the target 50 µg/ml concentration. Conclusion: The preliminary results indicate the potential of using GONFs delivered via new design radiotherapy biomaterials (e.g. fiducials) to inhibit the proliferative expansion of CSCs. The study avails ongoing in-vivo studies on using GONFs to enhance treatment outcomes for cancer patients.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization

Metal–organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr 6 ) offer new opportunities as supports for catalysts with well-defined, essentially molecular, structures. We used the precursor Rh(C 2 H 4 ) 2 (acac) (acac is acetylacetonate) to anchor Rh(I) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization in a once-through flow reactor at 298 K and 1 bar. The catalyst performance data are complemented with structural information determined by infrared and extended X-ray absorption fine structure spectroscopies and by calculations at the level of density functional theory, the latter carried out also to extend the investigation to a related MOF, NU-1000. The agreement between the experimental and calculated structural metrics is good, and the calculations have led to predictions of reaction mechanisms and associated energetics. Finally, the data demonstrate a correlation between the catalytic activity and selectivity and the electron-donor tendency of the supported rhodium (as measured by the frequencies of CO ligands bonded as probes to the Rh(I) centers), which is itself a measure of the electron-donor tendency of the support.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Metal–Organic Frameworks as Catalysts for (De)Hydrogenation: Progress, Challenges, and Perspectives

Storing hydrogen through chemical bonding in liquid-organic hydrogen carriers (LOHCs) offers a safer and more practical approach for hydrogen transportation compared to physical liquefaction, which is limited by low volumetric efficiency and gas release. The efficiency of LOHC systems is highly dependent on effective catalysts, which are typically composed of transition metals supported on metal oxides. However, these materials often rely upon costly noble metals, and their nonuniform nature limits mechanistic insights and structure–function relationships that could improve catalyst design. Metal–organic frameworks (MOFs) are promising alternatives to existing catalysts due to their crystalline, tunable, and porous nature. However, their use as catalysts for (de)hydrogenation reactions remains largely underexplored. Related to this, we identify two general classes of MOFs reported as catalysts for (de)hydrogenation reactions: MOFs as scaffolds for catalytically active species and MOFs that function as reactive materials themselves. MOF composites anchor reactive nanoparticles or homogeneous species, imparting reactivity to the framework. The confinement effects experienced by the affixed species, combined with favorable substrate adsorption interactions or acid sites provided by the MOF, enhance the stability, selectivity, and activity of these catalysts for (de)hydrogenation reactions. Additionally, catalytically active MOFs often feature open metal sites at the node or undergo postsynthetic modification at either node or linker to impart reactivity. Here, taking inspiration from these materials, we outline the current state and key challenges of utilizing MOFs as (de)hydrogenation catalysts and propose research pathways to advance materials in this field for energy applications.

Catalysts↗
DOE OSTI2019

Ultrafast manipulation of topologically enhanced surface transport driven by mid-infrared and terahertz pulses in Bi 2 Se 3

Topology-protected surface transport of ultimate thinness in three-dimensional topological insulators (TIs) is breaking new ground in quantum science and technology. Yet a challenge remains on how to disentangle and selectively control surface helical spin transport from the bulk contribution. Here we use the mid-infrared and terahertz (THz) photoexcitation of exclusive intraband transitions to enable ultrafast manipulation of surface THz conductivity in Bi 2 Se 3 . The unique, transient electronic state is characterized by frequency-dependent carrier relaxations that directly distinguish the faster surface channel than the bulk with no complication from interband excitations or need for reduced bulk doping. We determine the topological enhancement ratio between bulk and surface scattering rates, i.e., γ BS /γ SS ~3.80 in equilibrium. As a result, the ultra-broadband, wavelength-selective pumping may be applied to emerging topological semimetals for separation and control of the protected transport connected with the Weyl nodes from other bulk bands.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

N-terminal additions to the WE14 peptide of chromogranin A create strong autoantigen agonists in type 1 diabetes

Chromogranin A (ChgA) is an autoantigen for CD4 + T cells in the nonobese diabetic (NOD) mouse model of type 1 diabetes (T1D). The natural ChgA-processed peptide, WE14, is a weak agonist for the prototypical T cell, BDC-2.5, and other ChgA-specific T-cell clones. Mimotope peptides with much higher activity share a C-terminal motif, WXRM(D/E), that is predicted to lie in the p5 to p9 position in the mouse MHC class II, IA g7 binding groove. This motif is also present in WE14 (WSRMD), but at its N terminus. Therefore, to place the WE14 motif into the same position as seen in the mimotopes, we added the amino acids RLGL to its N terminus. Like the other mimotopes, RLGL-WE14, is much more potent than WE14 in T-cell stimulation and activates a diverse population of CD4 + T cells, which also respond to WE14 as well as islets from WT, but not ChgA –/– mice. The crystal structure of the IA g7 –RLGL–WE14 complex confirmed the predicted placement of the peptide within the IA g7 groove. Fluorescent IA g7 –RLGL–WE14 tetramers bind to ChgA-specific T-cell clones and easily detect ChgA-specific T cells in the pancreas and pancreatic lymph nodes of NOD mice. Here, the prediction that many different N-terminal amino acid extensions to the WXRM(D/E) motif are sufficient to greatly improve T-cell stimulation leads us to propose that such a posttranslational modification may occur uniquely in the pancreas or pancreatic lymph nodes, perhaps via the mechanism of transpeptidation. This modification could account for the escape of these T cells from thymic negative selection.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

A Novel Risk Stratification to Predict Local-Regional Failures in Urothelial Carcinoma of the Bladder After Radical Cystectomy

Purpose: Local-regional failures (LF) following radical cystectomy (RC) plus pelvic lymph node dissection (PLND) with or without chemotherapy for invasive urothelial bladder carcinoma are more common than previously reported. Adjuvant radiation therapy (RT) could reduce LF but currently has no defined role because of previously reported morbidity. Modern techniques with improved normal tissue sparing have rekindled interest in RT. We assessed the risk of LF and determined those factors that predict recurrence to facilitate patient selection for future adjuvant RT trials. Methods and Materials: From 1990-2008, 442 patients with urothelial bladder carcinoma at University of Pennsylvania were prospectively followed after RC plus PLND with or without chemotherapy with routine pelvic computed tomography (CT) or magnetic resonance imaging (MRI). One hundred thirty (29%) patients received chemotherapy. LF was any pelvic failure detected before or within 3 months of distant failure. Competing risk analyses identified factors predicting increased LF risk. Results: On univariate analysis, pathologic stage {>=}pT3, <10 nodes removed, positive margins, positive nodes, hydronephrosis, lymphovascular invasion, and mixed histology significantly predicted LF; node density was marginally predictive, but use of chemotherapy, number of positive nodes, type of surgical diversion, age, gender, race, smoking history, and body mass index were not. On multivariate analysis, only stage {>=}pT3 and <10 nodes removed were significant independent LF predictors with hazard ratios of 3.17 and 2.37, respectively (P<.01). Analysis identified 3 patient subgroups with significantly different LF risks: low-risk ({<=}pT2), intermediate-risk ({>=}pT3 and {>=}10 nodes removed), and high-risk ({>=}pT3 and <10 nodes) with 5-year LF rates of 8%, 23%, and 42%, respectively (P<.01). Conclusions: This series using routine CT and MRI surveillance to detect LF confirms that such failures are relatively common in cases of locally advanced disease and provides a rubric based on pathological stage and number of nodes removed that stratifies patients into 3 groups with significantly different LF risks to simplify patient selection for future adjuvant radiation therapy trials.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2023

Bioinspired Cu(II) Defect Sites in ZIF-8 for Selective Methane Oxidation

Activating the C–H bonds of alkanes without further oxidation to more thermodynamically stable products, CO and CO 2 , is a long-sought goal of catalytic chemistry. Here, inspired by the monocopper active site of methane monooxygenase, we synthesized a Cu-doped ZIF-8 metal–organic framework with 25% Cu and 75% Zn in the nodes and activated it by heating to 200 °C and dosing in a stepwise fashion with O 2 , methane, and steam. We found that it does oxidize methane to methanol and formaldehyde. The catalysis persists through at least five cycles, and beyond the third cycle, the selectivity improves to the extent that no CO 2 can be detected. Experimental characterization and analysis were carried out by PXRD, DRUV–vis, SEM, and XAS (XANES and EXAFS). The reaction is postulated to proceed at open-coordination copper sites generated by defects, and the mechanism of methanol production was explicated by density functional calculations with the revMO6-L exchange–correlation functional. The calculations reveal a catalytic cycle of oxygen-activated Cu I involving the conversion of two molecules of CH 4 to two molecules of CH 3 OH by a sequence of hydrogen atom transfer reactions and rebound steps. For most steps in the cycle, the reaction is more favored by singlet species than by triplets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗