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Electrocatalytic transformation of oxygenated aromatics to cycloalkanes on activated carbon cloth-supported ruthenium and platinum under mild conditions (≤60°, atmospheric pressure) using hydrogen equivalents producedin situby water splitting. 

Electrocatalytic transformation of furfural to tetrahydrofurfuryl alcohol on activated carbon cloth-supported ruthenium at mild conditions (≤ 50 °C under atmospheric pressure) using hydrogen equivalents producedin situby water splitting. 

Quantification of environmental impacts through life cycle assessment is essential when evaluating bioenergy systems as potential replacements for fossil-based energy systems. Bioenergy systems employing localized fast pyrolysis combined with electrocatalytic hydrogenation followed by centralized hydroprocessing (Py-ECH) can have higher carbon and energy efficiencies than traditional cellulosic biorefineries. A cradle-to-grave life cycle assessment was performed to compare the performance of Py-ECH versus cellulosic fermentation in three environmental impact categories: climate change, water scarcity, and eutrophication. Liquid hydrocarbon production using Py-ECH was found to have much lower eutrophication potential and water scarcity footprint than cellulosic ethanol production. Greater amounts of renewable electricity led to lower greenhouse gas emissions for the Py-ECH processing. When the renewable fraction of grid electricity is higher than 87%, liquid hydrocarbon production using Py-ECH has lower greenhouse gas emissions than cellulosic ethanol production. A sensitivity analysis illustrates the major role of annual soil carbon sequestration in determining system-wide net greenhouse gas emissions. 

Abstract We present 870μm polarimetric observations toward 61 protostars in the Orion molecular clouds with ∼400 au (1″) resolution using the Atacama Large Millimeter/submillimeter Array. We successfully detect dust polarization and outflow emission in 56 protostars; in 16 of them the polarization is likely produced by self-scattering. Self-scattering signatures are seen in several Class 0 sources, suggesting that grain growth appears to be significant in disks at earlier protostellar phases. For the rest of the protostars, the dust polarization traces the magnetic field, whose morphology can be approximately classified into three categories: standard-hourglass, rotated-hourglass (with its axis perpendicular to outflow), and spiral-like morphology. A total of 40.0% (±3.0%) of the protostars exhibit a mean magnetic field direction approximately perpendicular to the outflow on several × 10²–10³au scales. However, in the remaining sample, this relative orientation appears to be random, probably due to the complex set of morphologies observed. Furthermore, we classify the protostars into three types based on the C¹⁷O (3–2) velocity envelope’s gradient: perpendicular to outflow, nonperpendicular to outflow, and unresolved gradient (≲1.0 km s⁻¹arcsec⁻¹). In protostars with a velocity gradient perpendicular to outflow, the magnetic field lines are preferentially perpendicular to outflow, with most of them exhibiting a rotated hourglass morphology, suggesting that the magnetic field has been overwhelmed by gravity and angular momentum. Spiral-like magnetic fields are associated with envelopes having large velocity gradients, indicating that the rotation motions are strong enough to twist the field lines. All of the protostars with a standard-hourglass field morphology show no significant velocity gradient due to the strong magnetic braking. 

Maximizing fossil fuel displacement and limiting atmospheric carbon dioxide levels require a high efficiency of carbon incorporation in bioenergy systems. The availability of biomass carbon is a constraint globally, and strategies to increase the efficiency of bioenergy production and biogenic carbon use are needed. Previous studies have shown that “energy upgrading” of biomass by coupling with renewable electricity through electrocatalytic hydrogenation offers a potential pathway to near full petroleum fuel displacement in the U.S., even when annual U.S. biomass production is limited to 1.2 billion dry tonnes. Commercialization of such technology requires economic feasibility. A technoeconomic model of decentralized, depot-based pyrolysis with electrocatalytic hydrogenation and centralized upgrading (Py-ECH), producing liquid hydrocarbon fuel is presented and compared to a cellulosic ethanol pathway using consistent assumptions. Using a discounted cash flow approach, a minimum fuel selling price (MFSP) of $3.62 per gallon gasoline equivalent (GGE) or $0.96 per gasoline liter equivalent (GLE) is estimated for Py-ECH fuel derived from corn stover, considering n th plant economics and a fixed internal rate of return of 10%. This is comparable to the MFSP for cellulosic ethanol from fermentation with the same feedstock ($3.71 per GGE or $0.98 per GLE) and is in the range of gasoline prices over the last 20 years of $1 per GGE ($0.26 per GLE) to $4.44 per GGE ($1.17 per GLE) in 2018. Optimization studies on depot sizing identified a trade-off between transportation and economies-of-scale costs, with an optimum size of 500 tpd. Sensitivity analyses showed that electricity cost, raw material costs, bio-oil yields, and cell efficiencies are the key parameters that affect the Py-ECH MFSP. With system improvements, a pathway to less than $3 per GGE or $0.79 per GLE is articulated for liquid hydrocarbon fuel from corn stover using Py-ECH. 

A simple chiroptical solution for the absolute stereochemical determination for asymmetric phosphorus V stereocenters is presented. Strong coordination of the phosphorus oxide with the Zn-metallo center of the racemic host Zn-MAPOL 2 leads to an induced axial chirality of the host, yielding a strong ECCD signal. A mnemonic is proposed to correlate the asymmetry of the guest molecule with the observed ECCD signal. 

The significance of solvent structural factors in the excited-state proton transfer (ESPT) reactions of Schiff bases with alcohols is reported here. We use the super photobase FR0 -SB and a series of primary, secondary, and tertiary alcohol solvents to illustrate the steric issues associated with solvent to photobase proton transfer. Steady-state and time-resolved fluorescence data show that ESPT occurs readily for primary alcohols, with a probability proportional to the relative –OH concentration. For secondary alcohols, ESPT is greatly diminished, consistent with the barrier heights obtained using quantum chemistry calculations. ESPT is not observed in the tertiary alcohol. We explain ESPT using a model involving an intermediate hydrogen-bonded complex where the proton is “shared” by the Schiff base and the alcohol. The formation of this complex depends on the ability of the alcohol solvent to achieve spatial proximity to and alignment with the FR0 -SB* imine lone pair stabilized by the solvent environment.