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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water

Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour-1) at pH 7 with an overpotential of –0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Establishing a sustainable regulatory framework for the security of radioactive sources through harmonization with a safety regulatory framework

In order to establish and maintain sustainable nuclear security regulatory infrastructures for radioactive sources, it is important for States to develop nuclear security regulations with regulatory requirements and relevant criteria for security, which are consistent and well integrated with those for radiation safety. In establishing national regulations, experts worldwide follow the international recommendations on safety and security of radioactive sources published by the International Atomic Energy Agency (IAEA). Within the IAEA publications on safety and security of radioactive sources, some international recommendations are identical or very similar for both safety and security, for example, the requirement for the establishment of a national registry of radioactive sources. However, some other international recommendations are unique to the security area, such as the recommendation to examine the trustworthiness of employees, or to the safety area, such as the need to establish public exposure controls. Additionally, many international recommendations fall somewhere in between, such as the need for effective authorization of facilities and activities, a regulatory inspection and enforcement regime and the graded approach to establish and apply regulatory requirements. This paper examines how the IAEA international recommendations for establishing regulatory frameworks for safety and security relate to one another.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2022

Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra–Framework Anions in Pore–Space–Partitioned Metal–Organic Frameworks

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. Herein the effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co 3 -cpt-tph-Cl (Hcpt=4-(p-carboxyphenyl)-1,2,4-triazole, H-tph=(2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C 2 H 2 uptake capacity (200 cm 3 /g at 298 K), also exhibits (desirably) the lowest CO 2 uptake and hence the highest C 2 H 2 /CO 2 selectivity. The successful boost in both C 2 H 2 capacity and IAST selectivity allows Co 3 -cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C 2 H 2 uptake and C 2 H 2 /CO 2 experimental breakthrough separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Adsorption of a catalytically accessible polyoxometalate in a mesoporous channel-type metal–organic framework

A Keggin-type polyoxometalate (H 3 PW 12 O 40 ) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW 12 @NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW 12 @NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Splitting Mono- and Di-Branched Alkane Isomers by a Robust Aluminum-Based Metal-Organic Framework Material with Optimal Pore Dimensions

The separation of alkanes with different degrees of branching, particularly mono- and dibranched isomers, represents a challenging yet important industrial process for the production of premium gasoline blending components with high octane number. We report here the separation of linear/monobranched and dibranched alkanes through complete molecular sieving by a robust aluminum-based MOF material, Al-bttotb (H 3 bttotb = 4,4',4"-(benzene-1,3,5-triyltris(oxy))tribenzoicacid). Single- and multicomponent adsorption experiments reveal that the material adsorbs linear and monobranched alkanes, but fully excludes their dibranched isomers. Adsorption sites of alkanes within the MOF channels have been identified by single-crystal X-ray diffraction studies, and the adsorption mechanism was explored through computational calculations and modeling. The highly selective adsorption of the MOF should be attributed to its optimal pore dimensions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal–Organic Frameworks

Abstract Cooperative cluster metalation and ligand migration were performed on a Zr‐MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr 6 M 4 (M=Ni, Co) clusters. The M 2+ reacts with the μ 3 ‐OH and terminal H 2 O ligands on an 8‐connected [Zr 6 O 4 (OH) 8 (H 2 O) 4 ] cluster to form a bimetallic [Zr 6 M 4 O 8 (OH) 8 (H 2 O) 8 ] cluster. Along with the metalation of Zr 6 cluster, ligand migration is observed in which a Zr–carboxylate bond dissociates to form a M–carboxylate bond. Single‐crystal to single‐crystal transformation is realized so that snapshots for cooperative cluster metalation and ligand migration processes are captured by successive single‐crystal X‐ray structures. In 3+ was metalated into the same Zr‐MOF which showed excellent catalytic activity in the acetaldehyde cyclotrimerization reaction. This work not only provides a powerful tool to functionalize Zr‐MOFs with other metals, but also structurally elucidates the formation mechanism of the resulting heterometallic MOFs.

Yuan, Shuai↗
DOE OSTI2016

Controlled Generation of Singlet Oxygen in Living Cells with Tunable Ratios of the Photochromic Switch in Metal–Organic Frameworks

Abstract Development of a photosensitizing system that can reversibly control the generation of singlet oxygen ( 1 O 2 ) is of great interest for photodynamic therapy (PDT). Recently several photosensitizer–photochromic‐switch dyads were reported as a potential means of the 1 O 2 control in PDT. However, the delivery of such a homogeneous molecular dyad as designed (e.g., optimal molar ratio) is extremely challenging in living systems. Herein we show a Zr‐MOF nanoplatform, demonstrating energy transfer‐based 1 O 2 controlled PDT. Our strategy allows for tuning the ratios between photosensitizer and the switch molecule, enabling maximum control of 1 O 2 generation. Meanwhile, the MOF provides proximal placement of the functional entities for efficient intermolecular energy transfer. As a result, the MOF nanoparticle formulation showed enhanced PDT efficacy with superior 1 O 2 control compared to that of homogeneous molecular analogues.

Park, Jihye↗