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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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Closure of Earth’s Global Seasonal Cycle of Energy Storage

Abstract The global seasonal cycle of energy in Earth’s climate system is quantified using observations and reanalyses. After removing long-term trends, net energy entering and exiting the climate system at the top of the atmosphere (TOA) should agree with the sum of energy entering and exiting the ocean, atmosphere, land, and ice over the course of an average year. Achieving such a balanced budget with observations has been challenging. Disagreements have been attributed previously to sparse observations in the high-latitude oceans. However, limiting the local vertical integration of new global ocean heat content estimates to the depth to which seasonal heat energy is stored, rather than integrating to 2000 m everywhere as done previously, allows closure of the global seasonal energy budget within statistical uncertainties. The seasonal cycle of energy storage is largest in the ocean, peaking in April because ocean area is largest in the Southern Hemisphere and the ocean’s thermal inertia causes a lag with respect to the austral summer solstice. Seasonal cycles in energy storage in the atmosphere and land are smaller, but peak in July and September, respectively, because there is more land in the Northern Hemisphere, and the land has more thermal inertia than the atmosphere. Global seasonal energy storage by ice is small, so the atmosphere and land partially offset ocean energy storage in the global integral, with their sum matching time-integrated net global TOA energy fluxes over the seasonal cycle within uncertainties, and both peaking in April.

54 ENVIRONMENTAL SCIENCES↗

Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, Are Intrinsically Correlated to the Structural Disorder

Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pK a or band gaps (E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.

Bond dissociation free energy↗