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At least 397 records · Page 22

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2 P, Rh 2 P, and Pd 3 P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2 P NPs was shown to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3 P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2 . The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2 P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.

09 BIOMASS FUELS↗

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

The drive to reduce consumption of fossil resources, coupled with expanding capacity for renewable electricity, invites the exploration of new routes to utilize this energy for the sustainable production of fuels, chemicals, and materials. Biomass represents a possible source of platform precursors for such commodities due to its inherent ability to fix CO2 in the form of multi-carbon organic molecules. Electrochemical methods for the valorization of biomass are thus intriguing, but there is a need to objectively evaluate this field and define the opportunity space by identifying pathways suited to electrochemistry. In this contribution we offer a comprehensive, critical review of recent advances in low-temperature (liquid phase), electrochemical reduction and oxidation of biomass-derived intermediates (polyols, furans, carboxylic acids, amino acids, and lignin), with emphasis on identifying the state-of-the-art for each documented reaction. Progress in computational modeling is also reviewed. We further suggest a number of possible reactions that have not yet been explored but which are expected to proceed based on established routes to transform specific functional groups. We conclude with a critical discussion of technological challenges for scale-up, fundamental research needs, process intensification opportunities (e.g., by pairing compatible oxidations and reductions), and new benchmarking standards that will be necessary to accelerate progress toward application in this still-nascent field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Diel Cycling Temperature, Relative Humidity, and Synthetic Route on the Surface Morphology and Hydrolysis of α -U 3 O 8

The speciation and morphological changes of α-U 3 O 8 following aging under diel cycling temperature and relative humidity (RH) have been examined. This work advances the knowledge of U-oxide hydration as a result of synthetic route and environmental conditions, ultimately giving novel insight into nuclear material provenance. α-U 3 O 8 was synthesized via the washed uranyl peroxide (UO 4 ) and ammonium uranyl carbonate (AUC) synthetic routes to produce unaged starting materials with different morphologies. α-U 3 O 8 from UO 4 is comprised of subrounded particles, while α-U 3 O 8 from AUC contains blocky, porous particles approximately an order of magnitude larger than particles from UO 4 . For aging, a humidity chamber was programmed for continuous daily cycles of 12 “high” hours of 45 °C and 90% RH, and 12 “low” hours of 25 °C and 20% RH. Samples were analyzed at varying intervals of 14, 24, 36, 43, and 54 days. At each aging interval, crystallographic changes were measured via powder X-ray diffraction coupled with whole pattern fitting for quantitative analysis. Morphologic effects were studied via scanning electron microscopy and 12-way classification via machine learning. While all samples were found to have distinguishing morphologic characteristics (93.2% classification accuracy), α-U 3 O 8 from UO 4 had more apparent change with increasing aging time. Nonetheless, α-U 3 O 8 from AUC was found to hydrate more quickly than α-U 3 O 8 from UO 4 , which can likely be attributed to its larger surface area and porous starting material morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent-Free Dimerization of Isoprene at Ambient Temperature: A Green Route to Biofuel-Range Hydrocarbons

In order to achieve a net-zero carbon footprint by 2050, the global aviation industry must reduce its dependence on fossil fuels. In this regard, there is a global challenge to produce sufficient sustainable aviation fuel (SAF) from renewable sources. Isoprene is an intermediate molecule that can be derived from multiple biomass-based or biosynthetic routes. Here, in this work, we report a green route for the catalytic conversion of isoprene to hydrocarbons that are suitable for aviation fuel. By using an Amberlyst-15 catalyst without metal loading at ambient temperature (19–23 °C), as well as 40 °C, 50 °C, and 60 °C, isoprene was converted into olefinic precursors for SAF and/or blending with conventional aviation fuels. Specifically, at ambient temperature, the process achieved approximately 70 wt % conversion of isoprene with over 50 mol % carbon selectivity toward the aviation fuel range. The resulting SAF-range hydrocarbons were composed of iso-alkenes, branched olefinic monocyclic compounds, and bicyclic compounds, covering a wide range of aviation fuel components. Our work demonstrates, for the first time, the formation of diverse hydrocarbon families for SAF and/or aviation fuel blending at ambient temperature from isoprene.

09 BIOMASS FUELS↗

Crystal and Electronic Structures of Neptunium Nitrides Synthesized Using a Fluoride Route

A low-temperature fluoride route was utilized to synthesize neptunium mononitride, NpN. Through the development of this process, two new neptunium nitride species, NpN{sub 2} and Np{sub 2}N{sub 3}, were identified. The NpN{sub 2} and Np{sub 2}N{sub 3} have crystal structures isomorphous to those of UN{sub 2} and U{sub 2}N{sub 3}, respectively. NpN{sub 2} crystallizes in a face-centered cubic CaF{sub 2}-type structure with a space group of Fm3m and a refined lattice parameter of 5.3236(1) {angstrom}. The Np{sub 2}N{sub 3} adopts the body-centered cubic Mn{sub 2}O{sub 3}-type structure with a space group of Ia{bar 3}. Its refined lattice parameter is 10.6513(4) {angstrom}. The NpN synthesis at temperatures {le} 900 C using the fluoride route discussed here was also demonstrated. Previous computational studies of the neptunium nitride system have focused exclusively on the NpN phase because no evidence was reported experimentally on the presence of NpN{sub x} systems. Here, the crystal structures of NpN{sub 2} and Np{sub 2}N{sub 3} are discussed for the first time, confirming the experimental results by density functional calculations (DFT). These DFT calculations were performed within the local-density approximation (LDA+U) and the generalized-gradient approximation (GGA+U) corrected with an effective Hubbard parameter to account for the strong on-site Coulomb repulsion between Np 5f electrons. The effects of the spin-orbit coupling in the GGA+U calculations have also been investigated for NpN{sub 2} and NpN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precursor-Dependent Routing of Aromatic Amino Acids Determines Lignin Structure in Grasses by Sensitivity-Enhanced Solid-State NMR

Lignin biosynthesis in grasses exhibits unique metabolic flexibility, yet the precursor-specific routing of carbon into lignin polymers remains poorly resolved in planta. Here, we combine 13 C-isotope labeling with solid-state NMR under sensitivity-enhancement by dynamic nuclear polarization (DNP), to directly track phenylalanine- and tyrosine-derived carbon incorporation into the lignin polymer in Brachypodium distachyon. Precursor-specific 13 C labeling reveals that phenylalanine is the dominant contributor to canonical guaiacyl and syringyl lignins, whereas tyrosine preferentially enriches hydroxyphenyl lignin and hydroxycinnamates, including ferulates characteristic of grass cell walls. Two-dimensional 13 C− 13 C correlation NMR resolves distinct lignin moieties arising from each precursor. Disruption of pcoumarate 3-hydroxylase (C3H) selectively impairs phenylalanine-derived lignification, while tyrosine-derived lignin remains comparatively unchanged, maintaining polymer assembly through alternative metabolic routes. These findings show precursordependent control of lignin composition and reveal tyrosine-mediated lignification as a compensatory pathway in grasses. This work also establishes precursor-resolved solid-state NMR and DNP as a powerful framework for dissecting lignin biosynthesis and metabolic plasticity in plant cell walls.

Biopolymers↗

Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route

Synthesis of nucleobases in nonaqueous environments is an alternative way for the emergence of terrestrial life, which could solve the fundamental problem connected to the hydrolytic instability of nucleic acid components in an aqueous environment. In this contribution, we present a plausible reaction route for the prebiotic synthesis of nucleobases in formamide, which does not require participation of the formamide trimer and aminoimidazole-carbonitrile intermediates. The computed activation energy of the proposed pathway is noticeably higher than that of the HCN-based synthetic route, but it is still feasible under the experimental conditions of the Saladino synthesis. We show that, albeit both the pyrimidine and purine ring formation utilizes the undissociated form of formamide, the dehydration product of formamide, HCN, may also play a key role in the mechanism. The rate determining step of the entire reaction path is the cyclization of the diaza-pentanimine precursor. The subsequent formation of the imidazole ring proceeds with a moderate activation energy. Our calculations thus demonstrate that the experimentally suggested reaction path without the involvement of aminoimidazole-carbonitrile intermediates is also a viable alternative for the nonaqueous synthesis of nucleobases.

Chemistry↗

Dynamically reconfigurable topological routing in nonlinear photonic systems

The propagation path of topologically protected states is bound to the interface between regions with different topology, and as such, the functionality of linear photonic devices leveraging these states is fixed during fabrication. Here, we propose a mechanism for dynamic control over a driven dissipative system’s local topology, yielding reconfigurable topological interfaces and thus tunable paths for protected routing. We illustrate our approach in non-resonantly pumped polariton lattices, where the nonlinear interaction between the polaritons and the exciton reservoir due to non-resonant pumping can yield picosecond-scale changes in the propagation paths of the chiral edge states. To analytically confirm the numerically observed topological dynamics, we generalize the spectral localizer framework to non-linear non-Hermitian Chern materials and apply this framework to a continuous model of the polariton system based on a driven-dissipative Gross-Pitaevskii equation. In doing so, we show that the local changes in the polariton lattice’s topology are captured by a local Chern marker. Looking forward, we anticipate such reconfigurable topological routing will enable the realization of novel classes of topological photonic devices.

Wong, Stephan [Sandia National Laboratories (SNL-N↗

Route to high-energy density polymeric nitrogen t-N via He-N compounds

Polymeric nitrogen, stabilized by compressing pure molecular nitrogen, has yet to be recovered to ambient conditions, precluding its application as a high-energy density material. Here we suggest a route for synthesis of a tetragonal polymeric nitrogen, denoted t-N, via He-N compounds at high pressures. Using first-principles calculations with structure searching, we predict a class of nitrides with stoichiometry HeN 4 that are energetically stable (relative to a mixture of solid He and N 2 ) above 8.5 GPa. At high pressure, HeN 4 comprises a polymeric channel-like nitrogen framework filled with linearly arranged helium atoms. The nitrogen framework persists to ambient pressure on decompression after removal of helium, forming pure polymeric nitrogen, t-N. t-N is dynamically and mechanically stable at ambient pressure with an estimated energy density of ~11.31 kJ/g, marking it out as a remarkable high-energy density material. As a result, this expands the known polymeric forms of nitrogen and indicates a route to its synthesis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simplified synthetic routes for low cost and high photovoltaic performance n-type organic semiconductor acceptors

The application of polymer solar cells (PSCs) with n-type organic semiconductor as acceptor requires further improving powder conversion efficiency, increasing stability and decreasing cost of the related materials and devices. Here we report a simplified synthetic route for 4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno [1,2-b:5,6-b’] dithiophene by using the catalyst of amberlyst15. Based on this synthetic route and methoxy substitution, two low cost acceptors with less synthetic steps, simple post-treatment and high yield were synthesized. In addition, the methoxy substitution improves both yield and efficiency. The high efficiency of 13.46% was obtained for the devices with MO-IDIC-2F (3,9-bis(2-methylene-5 or 6-fluoro-(3-(1,1- dicyanomethylene)-indanone)-4,4,9,9-tetrahexyl-5,10-dimethoxyl-4,9-dihydro-s-indaceno [1,2-b:5,6-b’] dithiophene) as acceptor. Based on the cost analysis, the PSCs based on MOIDIC-2F possess the great advantages of low cost and high photovoltaic performance in comparison with those PSCs reported in literatures. Therefore, MO-IDIC-2F will be a promising low cost acceptor for commercial application of PSC

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultrafast narrowband exciton routing within layered perovskite nanoplatelets enables low-loss luminescent solar concentrators

In luminescent solar concentrator (LSC) systems, broadband solar energy is absorbed, down-converted and waveguided to the panel edges where peripheral photovoltaic cells convert the concentrated light to electricity. Achieving a low-loss LSC requires reducing the reabsorption of emitted light within the absorbing medium while maintaining high photoluminescence quantum yield (PLQY). Here we employ layered hybrid metal halide perovskites—ensembles of two-dimensional perovskite domains—to fabricate low-loss large-area LSCs that fulfil this requirement. Here, we devised a facile synthetic route to obtain layered perovskite nanoplatelets (PNPLs) that possess a tunable number of layers within each platelet. Efficient ultrafast non-radiative exciton routing within each PNPL (0.1 ps –1 ) produces a large Stokes shift and a high PLQY simultaneously. Using this approach, we achieve an optical quantum efficiency of 26% and an internal concentration factor of 3.3 for LSCs with an area of 10 × 10 cm 2 , which represents a fourfold enhancement over the best previously reported perovskite LSCs.

42 ENGINEERING↗

Techno-economic analysis and life-cycle greenhouse gas mitigation cost of five routes to bio-jet fuel blendstocks

Decarbonizing the air transportation sector remains one of the most challenging hurdles to mitigating climate change. Lignocellulosic biomass-derived jet fuel blendstocks can contribute to the shift toward renewable, low-carbon energy sources for aircrafts. Producing these renewable jet fuel molecules from biomass requires advanced pathways with the potential for efficient and affordable conversion routes. Here, this paper presents a detailed techno-economic analysis and sensitivity analysis, including estimated minimum selling price (MSP), and life-cycle greenhouse gas (GHG) mitigation costs for five routes to four potential bio-jet fuel molecules – limonane via limonene, limonane via 1,8-cineole, tetrahydromethylcyclopentadiene dimer (RJ-4), bisabolane, and epi-isozizaane. The simulated biorefineries utilize biomass sorghum and an integrated high-gravity ionic liquid-based biomass deconstruction process. We present results reflecting the current state of the technology and potential future scenarios with improved yields. Among the conversion pathways and the fuel molecules evaluated in this study, limonane, bisabolane, and epi-isozizaane could reach an MSP of 0.73–0.91 dollars per L-Jet A (2.75–3.45 dollars per gal-Jet A) in optimized future cases, without a hypothetical lignin-derived co-product. RJ-4 requires a more costly upgrading process and catalysts, resulting in a comparatively higher MSP (1.33 dollars per L-Jet A or 5.04 dollars per gal-jet A). Based on the GHG footprints of each fuel, the minimum achievable carbon mitigation cost relative to conventional Jet-A is 29 dollars per metric ton CO 2e , which is just under double the current cap-and-trade market price in California. In the absence of any policy support, the economics could be improved through high-value uses for lignin. To reach a target selling price of 0.66 dollars per L-Jet A (2.50 dollars per gal), lignin-derived products would need to be sold for at least 1.9 dollars per kg. However, the higher energy density of these bio-based blendstocks offers valuable improvements in aircraft efficiency/range; we find that commercial airlines may be willing to pay a 4–14 cent per L premium for these bio-jet fuels. In conclusion, our results highlight the need for improvements beyond currently-reported yields for the biologically produced intermediates, identification of ideal microbial hosts, selection of metabolic pathways to achieve competitive production costs, and a focus on fuels with attractive properties that increase their value.

09 BIOMASS FUELS↗

Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials

Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg −1 ) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. Here, to address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li 1.25 Mn 0.5 Ti 0.3 O 1.95 F 0.05 and Li 1.35 Mn 0.7 Ti 0.1 O 1.85 F 0.15 . More specifically, a glycine–nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80–90% pure DRX after annealing for 1 h at 800–1000 °C, and 19 F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F− anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li 1.35 Mn 0.7 Ti 0.1 O 1.85 F 0.15 attaining reversible capacities ∼210 mA h g −1 and moderate cycling stability in half cells (65% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.

25 ENERGY STORAGE↗

A divergent synthetic route to functional copolymer libraries via modular polymers

High-throughput polymer synthesis enables rapid exploration of chemical space but remains limited by batch-to-batch inconsistencies that can obscure structure–property relationship trends. To address this challenge, we developed a synthetic approach to produce multifunctional copolymers using post-polymerization modification of activated ester modular polymers with commercially available amines. Easily derivitized parent polymers—poly(tetrafluorophenyl acrylate) and poly(tetrafluorophenyl styrene sulfonate)—were synthesized by RAFT polymerization to yield single polymer batches containing highly reactive tetrafluorophenyl esters or sulfonate esters on each repeat unit. Tuning post-polymerization modification reaction conditions enabled the addition of sub-stoichiometric amounts of amines (relative to the repeat unit) to yield partially functionalized intermediates that could then be further derivatized. Reaction monitoring by 19 F NMR spectroscopy confirmed good control over these sequential post-polymerization modifications. This synthetic route produced a variety of copolymers with defined comonomer ratios while preserving the underlying polymer structure (degree of polymerization, dispersity, tacticity) for both the acrylate and styrene sulfonate backbones. We further applied this approach in a divergent manner to create a small library of structurally distinct copolymers from a single parent batch in three synthetic steps. This modular, divergent synthesis demonstrates a general route to structurally consistent copolymer libraries that enable systematic studies of structure–property relationships and can accelerate functional materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global reaction route mapping of isomerization pathways of exotic C{sub 6}H molecular species

C{sub 6}H radical is known to exist in the astrophysical environment in linear form; however, it may originate from nonlinear isomeric forms. Potential energy surface of C{sub 6}H is explored to search isomers of C{sub 6}H and transition states connecting them. This work reports first-ever identification of reaction pathways for isomerization of C{sub 6}H. The reaction route search is performed through global reaction route mapping method, which utilizes an uphill walking technique based on an anharmonic downward distortion following approach to search intermediates and transition states. The computations performed at the CASSCF/aug-cc-pVTZ, CCSD(T)/6-311++G(d,p)//DFT/B3LYP/6-311++G(d,p), and DFT/B3LYP/aug-cc-pVTZ levels of the theory identified 14 isomers (including 8 new isomeric forms of C{sub 6}H) and 28 transition states. Most of the identified isomers are found to have significant multireference character. The kinetic stability and natural bond orbital analysis of the identified isomers is also investigated. The isomeric forms are further characterized using spectral analysis involving rotational constants, vibrational frequencies, and Raman scattering activities as well as analyzing the effect of isotopic substitution of hydrogen on the spectral features. This study proposes that the linear-C{sub 6}H can readily isomerize to a six-member ring isomer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modified chemical route for deposition of molybdenum disulphide thin films

Molybdenum disulphide (MoS{sub 2}) thin films were deposited on quartz substrates using a modified chemical route. Sodium molybdate and sodium sulphide were used as precursors for molybdenum and sulphur respectively. The route involves formation of tetrathiomolybdate ions (MoS{sub 4}{sup 2−}) and further reduction by sodium borohydride to form MoS{sub 2}. The deposition was performed at room temperature. The deposited films were annealed in argon atmosphere at 1073 K for 1 hour to improve its crystallinity. The deposited films were characterized using scanning electron microscopy (SEM) for morphology, UV-Vis absorption spectroscopy for optical studies and X-ray diffraction (XRD) for structure determination.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A novel process route for the production of spherical SLS polymer powders

Currently, rapid prototyping gradually is transferred to additive manufacturing opening new applications. Especially selective laser sintering (SLS) is promising. One drawback is the limited choice of polymer materials available as optimized powders. Powders produced by cryogenic grinding show poor powder flowability resulting in poor device quality. Within this account we present a novel process route for the production of spherical polymer micron-sized particles of good flowability. The feasibility of the process chain is demonstrated for polystyrene e. In a first step polymer microparticles are produced by a wet grinding method. By this approach the mean particle size and the particle size distribution can be tuned between a few microns and several 10 microns. The applicability of this method will be discussed for different polymers and the dependencies of product particle size distribution on stressing conditions and process temperature will be outlined. The comminution products consist of microparticles of irregular shape and poor powder flowability. An improvement of flowability of the ground particles is achieved by changing their shape: they are rounded using a heated downer reactor. The influence of temperature profile and residence time on the product properties will be addressed applying a viscous-flow sintering model. To further improve the flowability of the cohesive spherical polymer particles nanoparticles are adhered onto the microparticles’ surface. The improvement of flowability is remarkable: rounded and dry-coated powders exhibit a strongly reduced tensile strength as compared to the comminution product. The improved polymer powders obtained by the process route proposed open new possibilities in SLS processing including the usage of much smaller polymer beads.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

On-chip electrically controlled routing of photons from a single quantum dot

Electrical control of on-chip routing of photons emitted by a single InAs/GaAs self-assembled quantum dot (SAQD) is demonstrated in a photonic crystal cavity-waveguide system. The SAQD is located inside an H1 cavity, which is coupled to two photonic crystal waveguides. The SAQD emission wavelength is electrically tunable by the quantum-confined Stark effect. When the SAQD emission is brought into resonance with one of two H1 cavity modes, it is preferentially routed to the waveguide to which that mode is selectively coupled. This proof of concept provides the basis for scalable, low-power, high-speed operation of single-photon routers for use in integrated quantum photonic circuits.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗