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At least 937 records · Page 52

Surface Chemistry and Particle Morphology Changes in Pine Biomass under Indirect Thermal Gradients: Implications for Feed Screw Design

The conversion of biomass feedstocks into fuels and chemicals using fast pyrolysis is a promising approach to renewable energy. Feed screws that convey biomass to pyrolysis reactors, however, often encounter plugging. Indirect heating of the feed screw occurs due to contact with the pyrolysis chamber, resulting in a heating gradient ranging from ambient temperature (22 °C) to reactor temperature (500 °C). Given that major cell wall macromolecules, such as lignin, cellulose, and hemicellulose, begin to produce bio-oils and volatile resin acid compounds within this temperature gradient, we hypothesized that indirect heating during feed screw conveyance is sufficient to cause premature degradation of biomass. We characterized this degradation by observing increases in surface roughness, changes in overall particle morphology, and the production and deposition of bio-oils on biomass particle surfaces. Correlative analysis between optical in situ hot-stage microscopy, confocal Raman spectroscopy, and SEM analysis revealed that heating at temperatures as low as 375 °C caused significant increases in surface roughness, with large fissures forming between and within cell walls. Additionally, droplets of bio-oil were observed on particles, especially in the bark and cambium samples. This work suggests that these phenomena contribute to particle agglomeration, leading to feed screw plugging, and that engineering a solution to cool the feed screw could prevent particle agglomeration and reduce plugging incidents, thereby increasing biomass processing efficiency.

09 BIOMASS FUELS↗

High-Throughput Screening and Accurate Prediction of Ionic Liquid Viscosities Using Interpretable Machine Learning

Ionic liquids (ILs) are a novel group of green solvents with great promise for various industrial applications, including carbon capture and lignocellulosic biomass deconstruction. However, the use of ILs at the industrial scale remains challenging due to their high viscosities at ambient temperatures. To develop ILs with lower viscosities, a systematic study of their quantitative structure–property relationship (QSPR) is desirable. Here, we developed four machine learning (ML) models to predict viscosity at various temperature and pressure ranges, trained over a wide range of ILs consisting of various cationic and anionic families. ML methods including two-factor polynomial regression (two-factor PR), support vector regression (SVR), feed-forward neural networks (FFNN), and categorical boosting (CATBoost) were developed based on features that have proven useful in previous ML studies: COSMO-RS (conductor-like screening model for real solvents)-derived surface screening charge densities (sigma profiles). FFNN and CATBoost were the most accurate in predicting IL viscosities with lower average absolute relative deviation and higher R2 values on the test set. Tanimoto similarity scores were calculated to characterize the chemical space and structural similarity of the investigated ions. Furthermore, SHapley Additive exPlanation (SHAP) analysis was employed to interpret the ML results. Temperature, the polar area of ILs, and the nonpolar regions of ions are key features that influence the viscosity predictions. Importantly, the IL viscosity prediction here is the most accurate reported to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermostable Enzyme Variants in the Lower Mevalonate Pathway Improve Isoprenoid Production by Cell-Free Biocatalysis

Cell-free biocatalysis is a rapidly evolving field with great potential for sustainably producing valuable chemicals. Some challenges in cell-free biocatalysis include reaction longevity, enzyme stability, and the cost of the biocatalysts. Here, the challenge of enzyme instability was addressed by employing thermophilic enzymes to improve the productivity of the lower mevalonate pathway, using limonene as an example isoprenoid product. The Classical mesophilic mevalonate pathway was compared to a newly assembled set of thermophilic enzymes comprising the Archaea I mevalonate pathway. The thermophilic pathway enzymes were thermostable to at least 60 °C and exhibited a 6× longer operating lifetime at 22 °C. Thus, despite lower initial activity rates at ambient temperature, the thermophilic pathway was longer-lived and resulted in a more productive cell-free reaction overall, achieving 1.7× higher yield of limonene compared to using enzymes from mesophiles. Moreover, the thermostable pathway retained activity for longer with the challenge of solvent exposure, namely, ethanol and isoprenol, which broadens the scope of accessible substrates and/or products in cell-free reactions employing this pathway. Altogether, we showed significant improvement in the stability and productivity of the lower mevalonate pathway, which will enable more efficient cell-free biosynthesis of isoprenoid products. This represents a valuable strategy to increase the robustness of cell-free systems by carefully sourcing biocatalysts from thermophilic organisms, which have proven to be resilient to challenges unique to cell-free reaction systems.

09 BIOMASS FUELS↗

3 d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni( t-Bu bpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV–Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3 d-d rather than 3 MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1 H NMR techniques, supporting that this 3 d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3 d-d state was determined to lie ~0.5 eV (12 kcal/mol) above the ground state. Because the 3 d-d state features a weak Ni–aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni–aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State

In the solid state the properties of organic radicals depend heavily on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4- dimethoxyphenylene), and outline how its bisradical dicationic redox state associates with the methyl viologen radical cation (MV •+ ) to give a trisradical tricationic inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid-state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments with a range of guests reveal that the methoxy substituents on the para-xylenyl do not influence significantly of the binding affinity of the cyclophane for small neutral guests, whereas the affinity decreases by an order of magnitude for larger radical cationic guests such as MV •+ . X-Ray diffraction reveals that the solid- state structures of the tricationic trisradical complexes to be a discrete entity with weak intermolecular orbital overlap between the neighboring complexes. Transient nutation EPR experiment and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap within the complex, while the quartet-state spin configuration is higher in energy and so is inaccessible at ambient temperature. The superconducting quantum interference device (SQUID) measurement reveals that trisradical tricationic complexes interact antiferromagnetically (J/k = - 2.33 K) and form a 1D Heisenberg antiferromagnetic chain along the a-axis in the crystal. Furthermore, these results offer new insights into the design and synthesis of organic magnetic materials based on host-guest inclusion complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO 2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO 2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at a 97% conversion of NO 2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h-1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO 2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO 2 } adducts promoting the conversion of NO 2 to N 2 . This study will inspire the further design and study of new efficient single-atom catalysts for NO 2 abatement via detailed unravelling of their role in catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Depolymerization of Hydroxylated Polymers via Light-Driven C–C Bond Cleavage

The accumulation of persistent plastic waste in the environment is widely recognized as an ecological crisis. New chemical technologies are necessary both to recycle existing plastic waste streams into high-value chemical feedstocks and to develop next-generation materials that are degradable by design. Here, we report a catalytic methodology for the depolymerization of a commercial phenoxy resin and high molecular weight hydroxylated polyolefin derivatives upon visible light irradiation near ambient temperature. Proton-coupled electron transfer (PCET) activation of hydroxyl groups periodically spaced along the polymer backbone furnishes reactive alkoxy radicals that promote chain fragmentation through C–C bond β-scission. The depolymerization produces well-defined and isolable product mixtures that are readily diversified to polycondensation monomers. In addition to controlling depolymerization, the hydroxyl group modulates the thermomechanical properties of these polyolefin derivatives, yielding materials with diverse properties. Furthermore, these results demonstrate a new approach to polymer recycling based on light-driven C–C bond cleavage that has the potential to establish new links within a circular polymer economy and influence the development of new degradable-by-design polyolefin materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Acid Catalysis over Low-Silica Faujasite Zeolites

We report low-silica faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.2–1.8) sustain framework integrity and porosity upon moderate ion exchange (0.01 M NH 4 NO 3 solution for 1 h at ambient temperature), which introduces two kinds of protons, distinctive in reactivity and coordination to the zeolite framework, within supercages (H SUP ). Moderate ion exchange limited within supercages transpires while maintaining full occupancy of Na + cations within associated sodalite cages; this in turn helps stabilize the framework of low-silica H-FAU zeolites. Protons located on site II (H 3630 ) and site III (H 3650 ) within supercages on low-silica FAU zeolites can be classified and enumerated by virtue of infrared spectroscopy, providing an opportunity to compare reactivities of these distinct protons for monomolecular protolytic reactions of propane. Protons on site II exhibit prominently higher reactivity for monomolecular propane dehydrogenation and cracking than protons on site III. Low-silica proton-form FAU zeolites (zeolite X) upon moderate ion exchange possess protons on site III that are unavailable on high-silica FAU zeolites (zeolite Y) and limit ion exchange within supercages, providing unprecedented high-temperature structural and chemical stability (>773 K) and enabling their application as solid-acid catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 ( R PDI = 2,6-(2,6-R 2 -C 6 H 3 N=CMe) 2 C 5 H 3 N), and the alkyl-substituted examples, ( Cy APDI)FeCH 3 ( Cy APDI = 2,6-(C 6 H 11 N=CMe) 2 C 5 H 3 N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, ( iPr PDI)FeCH 3 , has an idealized planar geometry and exhibits spin crossover behavior from S = 1/2 to S = 3/2 states. At 23 °C under an N 2 atmosphere, both ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [( Me PDI)Fe(N 2 )] 2 (μ-N 2 ) and [( Et PDI)Fe(N 2 )] 2 (μ-N 2 ), respectively, while ( iPr PDI)FeCH 3 proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, ( R PDI)Fe(η 4 -C 4 H 6 ) (R = Me, Et, i Pr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N 2 or butadiene to access a catalytically active iron compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Recycling of Thiol Epoxy Thermosets via Light-Driven C–C Bond Cleavage

Epoxy thermosets are high-volume materials that play a central role in a wide range of engineering applications; however, technologies to recycle these polymers remain rare. Here, we present a catalytic, light-driven method that enables chemical recycling of industrially relevant thiol epoxy thermosets to their original monomer at ambient temperature. This strategy relies on the proton-coupled electron transfer (PCET) activation of hydroxy groups within the polymer network to generate key alkoxy radicals that promote the fragmentation of the polymer through C–C bond β-scission. The method fully depolymerizes insoluble thiol epoxy thermosets into well-defined mixtures of small-molecule products, which can collectively be converted into the original monomer via a one-step dealkylation process. Notably, this process is selective and efficient even in the presence of other commodity plastics and additives commonly found in commercial applications. Finally, these results constitute an important step toward making epoxy thermosets recyclable and more generally exemplify the potential of PCET to offer a more sustainable end-of-life for a diverse array of commercial plastics.

36 MATERIALS SCIENCE↗

Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3 MC Excited State in an Fe(II) Carbene Complex

The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered ( 3 MC) excited states - recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls - have to date remained elusive, with temporally isolable examples limited to the picosecond regime. Here, with this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived 3 MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn−Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a 3 MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.

carbene compounds↗

Toward Hydrogen Isotope Separations through Strong Hydrogen Adsorption at Open Copper(I) Sites in an Ultramicroporous Metal-Organic Framework

Metal-organic frameworks with coordinatively unsaturated metal sites (open metal sites) capable of engaging in orbital interactions with pi-acidic gases are of interest for enabling ambient-temperature gas separations, such as hydrogen isotope separations. In view of the weakly pi-acidic nature of H2, we sought to strengthen pi-backbonding-mediated H2 adsorption through pore confinement effects. Toward that end, we synthesized and characterized the ultramicroporous metal-organic framework CuxZn5-xCl4-yHz(bbta)3 (CuIZn-MFU-4; H2bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole), featuring pi-basic trigonal pyramidal CuI sites that reside within 7 A of one another at their closest. Gas adsorption measurements reveal an H2 adsorption enthalpy of -38 kJ/mol, exceeding that of the larger-pore analog (CuIZn-MFU-4l; -33 kJ/mol) and representing the strongest H2 adsorption yet achieved in a metal-organic framework. The stronger H2 adsorption in CuIZn-MFU-4 is attributed to a combination of pore confinement effects and the increased ..sigma..-accepting nature of the CuI sites caused by a more electron-withdrawing bbta2- linker, as supported by structural, spectroscopic, and computational evidence. With the strongest H2 adsorption, equilibrium isotope effects in CuIZn-MFU-4 lead to a D2/H2 selectivity (as estimated by ideal adsorbed solution theory) of 1.35 even at 298 K, approaching the values reported below 200 K for conventional porous materials.

08 HYDROGEN↗

Atomic Evolution of Hydrogen Intercalation Wave Dynamics in Palladium Nanocrystals Revealed by Liquid-Phase Transmission Electron Microscopy

Solute-intercalation-induced phase separation creates spatial heterogeneities in host materials, a phenomenon ubiquitous in batteries, hydrogen storage, and other energy devices. Despite many efforts, probing intercalation processes at the atomic scale has been a significant challenge. By utilizing liquid-phase transmission electron microscopy (TEM), we study hydrogen (de)intercalation in palladium nanocrystals as a model system and have achieved unprecedented atomic-resolution imaging of hydrogen intercalation wave dynamics. Our observations reveal that intercalation wave mechanisms, instead of shrinking-core mechanisms, prevail at ambient temperature for palladium nanocubes ranging from ∼60 nm down to ∼10 nm. Systematic image analysis uncovers the atomic evolution of the hydrogen intercalation wave, transitioning from nonplanar and inclined boundaries to those closely aligned with {100} planes. Our kinetic Monte Carlo simulations demonstrate that the observed intercalation wave dynamics correspond to sorption pathways minimizing the lattice mismatch strain at the phase boundary. In conclusion, unveiling the atomic intercalation pathways holds profound implications for engineering intercalation-mediated devices and advancements in energy sciences.

Lee, Daewon [Lawrence Berkeley National Laboratory↗

A novel network-based approach to determining measurement representation error for model evaluation of aerosol microphysical properties

Atmospheric aerosol size and abundance influence radiative effects and climate change. To date, efforts to constrain global climate models’ radiative forcing with in situ aerosol observations have been hamstrung by uncertainty. One source of error, the regional “representation error,” arises when accurate but sparse single-point measurements of atmospheric aerosol distributions are compared with a model value, assuming that the single-point measurement is representative of the model domain. The Portable Optical Particle Spectrometer network in the Southern Great Plains (POPSnet-SGP) campaign has demonstrated that a network of nearly autonomous aerosol instruments operating at ambient temperature and relative humidity (with low measurement error) may be used to quantify measurement representation error and investigate the factors introducing heterogeneity in aerosol distributions across a rural, continental background region. Measurements were made using Portable Optical Particle Spectrometer (POPS) instruments at several sites for five months across the Department of Energy’s Aerosol Radiation Measurement Southern Great Plains (ARM-SGP) User Facility in the central USA. Measurement representation error decreased with longer averaging periods (20-40 % between 1 sec and 1 day), varied between sites by 10 – 20 % for aerosol concentration 140 – 2500 nm in diameter (N_140), and was higher for aerosols > 400 nm in diameter (N_400). Our measurements also show the influence of local meteorology on aerosol surface area (A_140) and size distributions: A_140 is positively correlated with wind speed and relative humidity, negatively correlated with precipitation, and lower given westerly winds. Based on this study, we conclude that the POPSnet approach provides considerably more insight into the spatial variability in the aerosol population that can be used to constrain climate models than would be available from similar networks of PM 2.5 monitors.

54 ENVIRONMENTAL SCIENCES↗

Exploring the Meteorological Impacts of Surface and Rooftop Heat Mitigation Strategies Over a Tropical City

Different heat mitigation technologies have been developed to improve the thermal environment in cities. However, the regional impacts of such technologies, especially in the context of a tropical city, remain unclear. The deployment of heat mitigation technologies at city-scale can change the radiation balance, advective flow, and energy balance between urban areas and the overlying atmosphere. We used the mesoscale Weather Research and Forecasting model coupled with a physically based single-layer urban canopy model to assess the impacts of five different heat mitigation technologies on surface energy balance, standard surface meteorological fields, and planetary boundary layer (PBL) dynamics for premonsoon typical hot summer days over a tropical coastal city in the month of April in 2018, 2019, and 2020. Results indicate that the regional impacts of cool materials (CMs), super-cool broadband radiative coolers, green roofs (GRs), vegetation fraction change, and a combination of CMs and GRs (i.e., “Cool city (CC)”) on the lower atmosphere are different at diurnal scale. Results showed that super-cool materials have the maximum potential of ambient temperature reduction of 1.6°C during peak hour (14:00 LT) compared to other technologies in the study. During the daytime hours, the PBL height was considerably lower than the reference scenario with no implementation of strategies by 700 m for super-cool materials and 500 m for both CMs and CC cases; however, the green roofing system underwent nominal changes over the urban area. During the nighttime hours, the PBL height increased by CMs and the CC strategies compared to the reference scenario, but minimal changes were evident for super-cool materials. The changes of temperature on the vertical profile of the heat mitigation implemented city reveal a stable PBL over the urban domain and a reduction of the vertical mixing associated with a pollution dome. This would lead to crossover phenomena above the PBL due to the decrease in vertical wind speed. Therefore, assessing the coupled regional impact of urban heat mitigation over the lower atmosphere at city-scale is urgent for sustainable urban planning.

54 ENVIRONMENTAL SCIENCES↗

Dual heterogeneous structures lead to ultrahigh strength and uniform ductility in a Co-Cr-Ni medium-entropy alloy

Alloys with ultra-high strength and sufficient ductility are highly desired for modern engineering applications but difficult to develop. Here we report that, by a careful controlling alloy composition, thermomechanical process, and microstructural feature, a Co-Cr-Ni-based medium-entropy alloy (MEA) with a dual heterogeneous structure of both matrix and precipitates can be designed to provide an ultra-high tensile strength of 2.2 GPa and uniform elongation of 13% at ambient temperature, properties that are much improved over their counterparts without the heterogeneous structure. Electron microscopy characterizations reveal that the dual heterogeneous structures are composed of a heterogeneous matrix with both coarse grains (10~30 μm) and ultra-fine grains (0.5~2 μm), together with heterogeneous L1 2 -structured nanoprecipitates ranging from several to hundreds of nanometers. The heterogeneous L1 2 nanoprecipitates are fully coherent with the matrix, minimizing the elastic misfit strain of interfaces, relieving the stress concentration during deformation, and playing an active role in enhanced ductility.

36 MATERIALS SCIENCE↗

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na 3-x Y 1-x Zr x Cl 6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na + ) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10 –5 S cm –1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl 6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO 2 + NYZC composite cathode, Na 3 PS 4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room emperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

99 GENERAL AND MISCELLANEOUS↗

Electrochemical reduction of acetonitrile to ethylamine

Electrifying chemical manufacturing using renewable energy is an attractive approach to reduce the dependence on fossil energy sources in chemical industries. Primary amines are important organic building blocks; however, the synthesis is often hindered by the poor selectivity because of the formation of secondary and tertiary amine byproducts. Herein, we report an electrocatalytic route to produce ethylamine selectively through an electroreduction of acetonitrile at ambient temperature and pressure. Among all the electrocatalysts, Cu nanoparticles exhibit the highest ethylamine Faradaic efficiency (~96%) at -0.29 V versus reversible hydrogen electrode. Under optimal conditions, we achieve an ethylamine partial current density of 846 mA cm -2 . A 20-hour stable performance is demonstrated on Cu at 100 mA cm -2 with an 86% ethylamine Faradaic efficiency. Moreover, the reaction mechanism is investigated by computational study, which suggests the high ethylamine selectivity on Cu is due to the moderate binding affinity for the reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗