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Preventing Loss of Selectivity during the Oxidative Dehydrogenation of Propane over Supported Vanadium Catalysts
Supported vanadium materials are promising catalysts for the oxidative dehydrogenation of propane to propylene (ODHP), but a lack of mechanistic understanding limits the rational design of catalysts with improved propylene selectivity. Adding Ta to V/SiO 2 increases the propylene selectivity, as well as the activity, leading to superior performance compared to state-of-the-art boron-based systems. In this contribution, we utilize this surprising promotional effect of Ta to elucidate key elements of the mechanistic cycle. Through a combination of characterization techniques, computational modeling, and kinetic experiments, we show that the catalytic cycle over V/SiO 2 likely involves the formation of an isopropyl alcohol intermediate, the fate of which is in kinetic competition between subsequent dehydration to propylene or further oxidation. Furthermore, we show that the relatively facile propylene overoxidation observed for these materials occurs via the epoxidation of propylene by a proposed peroxovanadium intermediate, rather than the abstraction of propylene’s allylic C–H bond as previously assumed. Using these key mechanistic features, we rationalize the enhanced selectivity and activity of Ta promotion. In conclusion, our mechanistic framework offers avenues for future catalyst development to improve supported vanadium materials for ODHP.
Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments
Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.
Compound Meta-Optics for Complete and Loss-Less Field Control
Optical metasurfaces offer a compact platform for manipulation of the amplitude, phase, and polarization state of light. Independent control over these properties, however, is hindered by the symmetric transmission matrix associated with single-layer metasurfaces. Here, we utilize multilayer birefringent meta-optics to realize high-efficiency, independent control over the amplitude, phase, and polarization state of light. In this work, high-efficiency control is enabled by redistributing the wavefront between cascaded metasurfaces, while end-to-end inverse design is used to realize independent complex-valued functions for orthogonal polarization states. Based on this platform, we demonstrate spatial mode division multiplexing, optical mode conversion, and universal vectorial holograms, all with diffraction efficiencies over 80%. This meta-optic platform expands the design space of flat optics and could lead to advances in optical communications, quantum entanglement, and information encryption.
Reaching 90% Photoluminescence Quantum Yield in One-Dimensional Metal Halide C 4 N 2 H 14 PbBr 4 by Pressure-Suppressed Nonradiative Loss
Low-dimensional perovskite-related metal halides have emerged as a new class of light-emitting materials with tunable broadband emission from self-trapped excitons (STEs). Although various types of low-dimensional structures have been developed, fundamental understating of the structure–property relationships for this class of materials is still very limited, and further improvement of their optical properties remains greatly important. Here, we report a significant pressure-induced photoluminescence (PL) enhancement in a one-dimensional hybrid metal halide C 4 N 2 H 14 PbBr 4 , and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. Under a gigapascal pressure scale, the PL quantum yields (PLQYs) were quantitatively determined to show a dramatic increase from the initial value of 20% at ambient conditions to over 90% at 2.8 GPa. With in situ characterization of photophysical properties and theoretical analysis, we found that the PLQY enhancement was mainly attributed to the greatly suppressed nonradiative decay. Pressure can effectively tune the energy level of self-trapped states and increase the exciton binding energy, which leads to a larger Stokes shift. The resulting highly localized excitons with stronger binding reduce the probability for carrier scattering, to result in the significantly suppressed nonradiative decay. Overall, our findings clearly show that the characteristics of STEs in low-dimensional metal halides can be well-tuned by external pressure, and enhanced optical properties can be achieved.
Mediating Photochemical Reaction Rates at Lewis Acidic Rare Earths by Selective Energy Loss to 4f-Electron States
Manifesting chemical differences in individual rare earth (RE) element complexes is challenging due to the similar sizes of the tripositive cations and the corelike 4f shell. In this work, we disclose a new strategy for differentiating between similarly sized Dy 3+ and Y 3+ ions through a tailored photochemical reaction of their isostructural complexes in which the f-electron states of Dy 3+ act as an energy sink. Complexes RE(hfac) 3 (NMMO) 2 (RE = Dy (2-Dy) and Y (2-Y), hfac = hexafluoroacetylacetonate, and NMMO = N-methylmorpholine-N-oxide) showed variable rates of oxygen atom transfer (OAT) to triphenylphosphine under ultraviolet (UV) irradiation, as monitored by 1 H and 19 F NMR spectroscopies. Ultrafast transient absorption spectroscopy (TAS) identified the excited state(s) responsible for the photochemical OAT reaction or lack thereof. Competing sensitization pathways leading to excited-state deactivation in 2-Dy through energy transfer to the 4f electron manifold ultimately slows the OAT reaction at this metal cation. The measured rate differences between the open-shell Dy 3+ and closed-shell Y 3+ complexes demonstrate that using established principles of 4f ion sensitization may deliver new, selective modalities for differentiating the RE elements that do not depend on cation size.
Arctic Soil Governs Whether Climate Change Drives Global Losses or Gains in Soil Carbon
Not Available
Warm Arctic, Cold Siberia Pattern: Role of Full Arctic Amplification Versus Sea Ice Loss Alone
The effect of future Arctic amplification (AA) on the extratropical atmospheric circulation remains unclear in modeling studies. Using a collection of coordinated atmospheric and coupled global climate model perturbation experiments, we find an emergent relationship between the high-latitude 1,000–500 hPa thickness response and an enhancement of the Siberian High in winter. This wave number-1-like sea level pressure anomaly pattern is linked to an equatorward shift of the eddy-driven jet and a dynamical cooling response in eastern Asia. Additional simulations, where AA is imposed directly into the model domain by nudging, demonstrate how the sea ice forcing is insufficient by itself to capture the vertical extent of the warming and by extension the amplitude of the response in the Siberian High. Additionally, this study demonstrates the importance of the vertical extent of the tropospheric warming over the polar cap in revealing the “warm Arctic, cold Siberia” anomaly pattern in future projections.
Consistent Timing of Arctic Permafrost Loss Across the CESM1 Large Ensemble
Abstract The Arctic is especially vulnerable to climate change and is warming faster than the global average. Changes in this region pose a heightened threat due to the immense amount of carbon frozen as organic material in the soil. When permafrost thaws, organic material decays and releases as greenhouse gases into the atmosphere, contributing to further warming. A better understanding of the processes that influence permafrost degradation is needed to inform climate adaptation and mitigation planning. This study assesses changes to Arctic permafrost across 35 ensemble member simulations from the Community Earth System Model 1 Large Ensemble Project, under the Representative Concentration Pathway 8.5 21st century scenario. Most Arctic near‐surface permafrost is lost by 2100, but timing varies across regions and with soil depth. Internal climate variability, represented by differences between ensemble members, has a constrained influence on degradation timing due to relative consistency of summer temperature increases and insulation by winter snow cover.
Stratospheric Climate Anomalies and Ozone Loss Caused by the Hunga Tonga-Hunga Ha'apai Volcanic Eruption
We report the Hunga Tonga-Hunga Ha'apai (HTHH) volcanic eruption in January 2022 injected unprecedented amounts of water vapor (H 2 O) and a moderate amount of the aerosol precursor sulfur dioxide (SO 2 ) into the Southern Hemisphere (SH) tropical stratosphere. The H 2 O and aerosol perturbations have persisted during 2022 and early 2023 and dispersed throughout the atmosphere. Observations show large-scale SH stratospheric cooling, equatorward shift of the Antarctic polar vortex and slowing of the Brewer-Dobson circulation. Satellite observations show substantial ozone reductions over SH winter midlatitudes that coincide with the largest circulation anomalies. Chemistry-climate model simulations forced by realistic HTHH inputs of H 2 O and SO 2 qualitatively reproduce the observed evolution of the H 2 O and aerosol plumes over the first year, and the model exhibits stratospheric cooling, circulation changes and ozone effects similar to observed behavior. The agreement demonstrates that the observed stratospheric changes are caused by the HTHH volcanic influences.
Recent Upper Colorado River Streamflow Declines Driven by Loss of Spring Precipitation
Abstract Colorado River streamflow has decreased 19% since 2000. Spring (March‐April‐May) weather strongly influences Upper Colorado River streamflow because it controls not only water input but also when snow melts and how much energy is available for evaporation when soils are wettest. Since 2000, spring precipitation decreased by 14% on average across 26 unregulated headwater basins, but this decrease did not fully account for the reduced streamflow. In drier springs, increases in energy from reduced cloud cover, and lowered surface albedo from earlier snow disappearance, coincided with potential evapotranspiration (PET) increases of up to 10%. Combining spring precipitation decreases with PET increases accounted for 67% of the variance in post‐2000 streamflow deficits. Streamflow deficits were most substantial in lower elevation basins (<2,950 m), where snowmelt occurred earliest, and precipitation declines were largest. Refining seasonal spring precipitation forecasts is imperative for future water availability predictions in this snow‐dominated water resource region.
Shrub Expansion Can Counteract Carbon Losses From Warming Tundra
Arctic warming is causing substantial compositional, structural, and functional changes in tundra vegetation including shrub and tree-line expansion and densification. However, predicting the carbon trajectories of the changing Arctic is challenging due to interacting feedbacks between vegetation composition and structure, and surface characteristics. We conduct a sensitivity analysis of the current-date to 2100 projected surface energy fluxes, soil carbon pools, and CO 2 fluxes to different shrub expansion rates under future emission scenarios (intermediate—RCP4.5, and high—RCP8.5) using the Arctic-focused configuration of E3SM Land Model (ELM). We focus on Trail Valley Creek (TVC), an upland tundra site in the western Canadian Arctic, which is experiencing shrub densification and expansion. We find that shrub expansion did not significantly alter the modeled surface energy and water budgets. However, the carbon balance was sensitive to shrub expansion, which drove higher rates of carbon sequestration as a consequence of higher shrubification rates. Thus, at low shrub expansion rates, the site would become a carbon source, especially under RCP8.5, due to higher temperatures, which deepen the active layer and enhance soil respiration. At higher shrub expansion rates, TVC would become a net CO 2 sink under both Representative Concentration Pathway scenarios due to higher shrub productivity outweighing temperature-driven respiration increase. Our simulations highlight the effect of shrub expansion on Arctic ecosystem carbon fluxes and stocks. We predict that at TVC, shrubification rate would interact with climate change intensity to determine whether the site would become a carbon sink or source under projected future climate.
Author Correction: Transcription Factor 4 loss-of-function is associated with deficits in progenitor proliferation and cortical neuron content
Correction to: Nature Communicationshttps://doi.org/10.1038/s41467-022-29942-w, published online 02 May 2022 In the version of the article initially published, the text “UCSD has filed a patent application (WO2022072709A1), in which F.P. and A.R.M. are inventors, containing some results regarding the TCF4 correction overexpression strategy described in this paper. The patent was published on 04-07-2022” was missing from the Competing interests section and has now been added to the HTML and PDF versions of the article.