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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Rapid Generation of Hierarchically Porous Metal–Organic Frameworks through Laser Photolysis

Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP‐MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP‐MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing‐cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP‐MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.

Wang, Kun‐Yu↗
DOE OSTI2024

Investigation of pyruvic acid photolysis at the air-liquid interface as a source of aqueous secondary organic aerosols

Pyruvic acid (PA) is a ubiquitous 2-oxocarboxylic acid in the atmosphere. Its photochemical process at the air-liquid (a-l) interface has been suggested as an important source of aqueous secondary organic aerosols. Here, we investigated the photochemical reaction pathways of PA at the a-l interface using synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) microreactor. Results from mass spectral analysis and the determination of appearance energies (AEs) indicate that photolysis of PA can generate radicals, then they recombine with carboxylic acids and simple molecular oligomers. Furthermore, the preliminary products could form larger oligomers via radical reaction or esterification in the presence of hydroxyl and carboxyl functional groups. Mass spectral comparison shows that most photochemical reactions would complete within 4 h. The expanded photochemistry-driven reaction flowchart of PA is proposed based on the newly discovered products. Our results reveal that the interfacial PA photochemical reactions have different mechanisms from the bulk liquid due to the interfacial properties, such as molecular density, composition, and ion concentration. Our findings show that in situ mass spectral analysis with bright photon ionization is useful to elucidate the contribution of a-l interfacial reactions leading to aqSOA formation.

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

Evolution of Radicals from the Photolysis of High Ionic Strength Alkaline Nitrite Solutions

Reactive nitrogen species (RNS), along with reactive oxygen species (ROS), are significant products from radiolysis in solution. While much research has been focused on biological systems, these species are also important products in the autoradiolysis that occurs in nuclear waste. In this work, we determine the correlation between solution constituents, particularly nitrite, and radical products in highly alkaline solutions relevant to liquid waste. Because these radicals tend to be very short-lived, we employ spin trapping in conjunction with electron paramagnetic resonance (EPR) to detect them and quantify their production. Most spin traps do not function in these conditions (>1 M NaOH); however, nitroalkanes such as nitromethane will act as spin traps in their aci form, which is dominant at high pH. To restrict the products to those originating from nitrite, we use 280–480 nm UV light to generate radicals, avoiding products from the photolysis of water. Under these circumstances, nitric oxide, nitrite radicals, and hydroxyl radicals are detected, and the trends with the concentration of the constituents of the solutions are tracked. These include nitrite, nitrate, hydroxide, and carbonate. We find that, while the equilibrium shifts with increasing pH from hydroxyl radicals to the more slowly reacting oxide radicals, the production of nitrite radicals does not decrease.

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

Visible Light Photolysis at Single Atom Sites in Semiconductor Perovskite Oxides

Designing catalysts with well-defined active sites with chemical functionality responsive to visible light has significant potential for overcoming scaling relations limiting chemical reactions over heterogeneous catalyst surfaces. Visible light can be leveraged to facilitate the removal of strongly bound species from well-defined single cationic sites (Rh) under mild conditions (323 K) when they are incorporated within a photoactive perovskite oxide (Rh-doped SrTiO 3 ). CO, a key intermediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh + (CO) 2 ), that could act as site blockers or poisons during a catalytic cycle. For the first time, we demonstrate that CO removal can occur at mild temperatures (323 K) under low-energy red light (635 nm) irradiation, which is not possible for supported isolated-site Rh catalysts (0.2 wt % Rh/γ-Al 2 O 3 ). Photolysis of supported Rh + (CO) 2 complexes (e.g., 0.2 wt % Rh/γ-Al 2 O 3 ) has been demonstrated but is limited to high energy UV photons. Rigorous kinetic experiments elucidate disparate mechanisms for CO photodepletion from Rh-doped SrTiO 3 and supported isolated site Rh/γ-Al 2 O 3 . CO photodepletion from supported isolated site Rh/γ-Al 2 O 3 involves a direct metal to ligand charge transfer mechanism, whereas Rh-doped SrTiO 3 is governed by electron–hole pair formation in the perovskite. In this work, we show that under visible, low-energy red light, surface Rh species in Rh-doped SrTiO 3 introduce midgap energy states above the valence band that facilitate electronic excitations leading to surface CO removal. Isolated Rh sites in Rh-doped SrTiO 3 also exhibit exceptional stability under multiple CO photodepletion cycles. Overall, incorporating single sites into photoactive perovskite oxides is an effective strategy to influence surface chemistries with visible light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗