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At least 109 records · Page 6

Nitrogenase Bioelectrocatalysis: ATP-Independent Ammonia Production Using a Redox Polymer/MoFe Protein System

Nitrogenase is the only biological catalyst that is understood to be able to convert nitrogen gas to ammonia. In microorganisms, the MoFe catalytic protein of nitrogenase is reduced by a transient Fe protein binding and separate hydrolysis of ATP. Yet, the requirement of 16 ATP molecules by the Fe protein for the 8 electron transfer is an energy-intense caveat to the enzymatic synthesis of NH 3 and is challenging from an electrochemical perspective. Thus, we report the redox polymer-based ATP-free mediated electron-transfer system of MoFe nitrogenase using cobaltocene-functionalized poly(allylamine) (Cc-PAA), which is able to reduce the MoFe nitrogenase directly with a low redox potential of -0.58 V vs SHE. An efficient immobilization of MoFe nitrogenase via Cc-PAA allowed for the bioelectrocatalytic reduction of N 3 – , NO 2 – , and N 2 to NH 3 . Bulk bioelectrosynthetic experiments produced 7 ± 2 and 30 ± 5 nmol of NH 3 from NO 2 – and N 3 – reduction for 30 min, respectively. In addition, biosynthetic N 2 reduction to NH 3 was confirmed by 15 N 2 labeling experiments with NMR analysis. This mediated electron-transfer approach of the immobilized nitrogenase using the Cc-PAA redox polymer provides a valuable technological basis for scale-up and industrial uses in the future of bioelectrosynthesis.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Porous Two-dimensional Iron-Cyano Nanosheets for High-rate Electrochemical Nitrate Reduction

Ammonia (NH 3 ) is an essential ingredient in agriculture and a promising source of clean energy as a hydrogen carrier. The current major method for ammonia production, however, is the Haber–Bosch process that leads to massive energy consumption and severe environmental issues. Compared with nitrogen (N 2 ) reduction, electrochemical nitrate reduction reaction (NO 3 RR), with a higher NH 3 yield rate and Faradaic efficiency, holds promise for efficient NH 3 production under ambient conditions. To achieve efficient NO 3 RR, electrocatalysts should exhibit high selectivity and Faradaic efficiency with a high NH 3 yield rate. In this work, we developed two-dimensional (2D) iron-based cyano-coordination polymer nanosheets (Fe-cyano NSs) following in situ electrochemical treatment for high-rate NO 3 RR. Owing to the strong adsorption of nitrate on Fe0 active sites generated via topotactic conversion and in situ electroreduction, 2D Fe-cyano electrocatalyst exhibits high catalytic activity with a yield rate of 42.1 mg h –1 mgcat –1 and a Faradaic efficiency of over 90% toward NH 3 production at –0.5 V (vs reversible hydrogen electrode, RHE). Further electrochemical characterizations revealed that superhydrophilic surface and enhanced electrochemical surface area of the 2D porous nanostructures also contributed to the high-rate NO 3 RR activity. Finally, an electrolyzer toward NO 3 RR and oxygen evolution reaction (OER) in a two-electrode configuration is constructed based on 2D Fe-cyano, achieving an energy efficiency of 26.2%. This work provides an alternative methodology toward topotactic conversion of transition metal nanosheets for NO 3 RR and reveals the often-overlooked contribution of hydrophilicity of the catalysts for high-rate electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrotreatment of Nylon 66 and Amide Model Compounds Over Sulfided NiMo Catalysts

Molybdenum sulfide-based catalysts, such as nickel–molybdenum on alumina (NiMoS x /Al 2 O 3 ), are widely used in hydrotreating and have potential for catalyzing waste plastic conversion via hydrogenolysis, yet their performance, such as reaction kinetics and network, for amide-rich polymer feeds is poorly defined. Here we combine Nylon 66 with the amide model compound, N,N-dibutylhexanediamide (DBDAD), to quantify hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) chemistry in a stirred batch reactor (53 bar H 2 , 280–320°C). DBDAD conversion is near-linear with time, indicating strong adsorption of the substrates on the active sites. Time-resolved product identification indicates parallel C─O first-cleavagedeoxygenation (DO) and C─N first-cleavagedenitrogenation (DN) sequences proceeding through amine and diol intermediates, respectively, to C 4 ─C 6 alkanes. Increasing temperature shifts selectivity toward DN, decreasing the initial r(DO)/r(DN) from 1.38 (280°C) to 0.69 (320°C), with an apparent activation energy of 173 kJ mol −1 for DBDAD conversion. At 300°C, nylon 66 converts faster than DBDAD, producing a complex mixture of oxygen- and nitrogen-containing species and an initial rate ratio r(DO)/r(DN) of 1.6. No heteroaromatic nitrogen products are detected by the method used. These results provide reaction pathways and product signatures relevant to hydro-processing catalysts exposed to polyamide-derived streams.

Nylon 66↗

Selective semihydrogenation of acetylene in ethylene using defect-rich boron nitride catalyst from flux reconstruction

Efficient removal of trace acetylene from ethylene streams is essential for producing polymer-grade ethylene, yet achieving highly selective semihydrogenation without over-hydrogenation remains a long-standing challenge. A key barrier is the lack of a simple, low-cost catalyst that can activate hydrogen effectively while preventing ethylene from reacting further. Here we show that defect-rich boron nitride, prepared through a straightforward flux reconstruction method, serves as a highly selective and metal-free catalyst for acetylene semihydrogenation. The catalyst contains abundant open boron and nitrogen sites that enable efficient hydrogen activation and rapid release of ethylene, thereby avoiding over-hydrogenation. Experiments combined with isotope labeling and theoretical analysis reveal that these defects lower the energy barrier for hydrogen activation while accelerating product desorption. Our findings demonstrate a scalable strategy for defect engineering in boron nitride and highlight its potential as a robust, sustainable alternative to metal-based catalysts in industrial ethylene purification.

Wang, Tao [Oak Ridge National Laboratory (ORNL), O↗

Microbial extracellular polysaccharide production and aggregate stability controlled by switchgrass ( Panicum virgatum ) root biomass and soil water potential

Deep-rooting perennial grasses are promising feedstocks for biofuel production, especially in marginal soils lacking organic material, nutrients, and/or that experience significant water stress. Perennial grass roots influence surrounding soil conditions and microbial activities, and produce extracellular polymeric substances (EPS) composed primarily of extracellular polysaccharides (EPSac). These polymers can alleviate microbial moisture and nutrient stress, and enhance soil characteristics through improved water retention and aggregate stability—which may in turn enhance carbon persistence. Here, we used a 13 CO 2 greenhouse tracer experiment to examine the effect of switchgrass cultivation on EPSac production and origin in a marginal soil with five fertilization/water treatments (control, +N, +NP, +P, low water), and compared these results with measurements of field soils collected after long-term switchgrass cultivation. Soils with added nitrogen and phosphorus (+NP) had the highest root biomass, EPSac and percentage of water-stable soil aggregates. Multiple linear regression analyses revealed that root biomass and soil water potential were important determinants of soil EPSac production, potentially by controlling carbon supply and diurnal changes in moisture stress. Path analysis showed that soil aggregation was positively correlated with bulk soil EPSac content and also regulated by soil water potential. High mannose content indicated the majority of EPSac was of microbial origin and 13 CO 2 labeling indicated that 0.18% of newly fixed plant carbon was incorporated into EPSac. Analysis of field soils suggests that EPSac is significantly enhanced after long-term switchgrass cultivation. Taken as a whole, our greenhouse and field results demonstrate that switchgrass cultivation can promote microbial production of EPSac, providing a mechanism to enhance aggregation in marginal soils.

13c labeling↗

Contrasting geochemical and fungal controls on decomposition of lignin and soil carbon at continental scale

Lignin is an abundant and complex plant polymer that may limit litter decomposition, yet lignin is sometimes a minor constituent of soil organic carbon (SOC). Accounting for diversity in soil characteristics might reconcile this apparent contradiction. Tracking decomposition of a lignin/litter mixture and SOC across different North American mineral soils using lab and field incubations, here we show that cumulative lignin decomposition varies 18-fold among soils and is strongly correlated with bulk litter decomposition, but not SOC decomposition. Climate legacy predicts decomposition in the lab, and impacts of nitrogen availability are minor compared with geochemical and microbial properties. Lignin decomposition increases with some metals and fungal taxa, whereas SOC decomposition decreases with metals and is weakly related with fungi. Decoupling of lignin and SOC decomposition and their contrasting biogeochemical drivers indicate that lignin is not necessarily a bottleneck for SOC decomposition and can explain variable contributions of lignin to SOC among ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Silane-modified polyester blends and methods of preparation

A silane-modified polyester blend comprising a polyester polymer homogeneously blended with silane molecules containing two or three alkoxy groups bound to the silicon atom, wherein said silane molecules are present in said polyester blend in an amount of 0.05-20 wt % (or, e.g., 0.05-10 wt %, 0.05-5 wt %, or 0.05-2 wt %). The polyester polymer may, in particular embodiments, be a polyhydroxyalkanoate, terephthalate-based polyester, adipate-based, or succinate-based polyester. The silane molecule may be according to the formula (R2O)2SiR3R4, wherein R2 groups are independently selected from alkyl groups containing 1-4 carbon atoms; and R3 and R4 are independently selected from OR2 groups and alkyl groups containing 1-12 carbon atoms, provided that at least one of R3 and R4 is an alkyl group, wherein the alkyl group optionally includes one or more heteroatoms selected from oxygen, nitrogen, halogen, sulfur, phosphorus, and silicon. Methods for producing the silane-modified polyester blend are also described.

Meng, Xiangtao↗

Accelerated Synthesis of Ordered Mesoporous Carbons Using Plasma

Conventional ordered mesoporous carbon (OMC) production usually requires long processing times in the carbonization step to achieve desired temperatures through controlled ramps. To enable expedited materials discovery, developing advanced manufacturing capability with significantly improved throughput is highly desired. Current approaches for accelerating the synthesis of OMCs include using microwave and Joule heating. However, both methods rely on the introduction of additional components, such as microwave absorbers and electrically conductive agents, within the bulk materials to impart the ability to reach high carbonization temperatures. This work demonstrates accelerated synthesis and functionalization of OMCs through the use of a dielectric barrier discharge plasma, where carbonization can be accomplished within 15 min using 30 W plasma sources, representing more than an order of magnitude increase in polymer-to-carbon conversion kinetics compared to that of a traditionally pyrolyzed analogue. Particularly, the ability of performing rapid carbonization without the use of additional substrates within the OMC precursor systems is advantageous. A systematic investigation of how plasma power, time, and gas atmosphere impact the resulting OMC pore textures and properties is performed, demonstrating the broad applicability of plasma-enabled carbonization methods. Furthermore, we demonstrate that the plasma treatment strategy can be extended to incorporate heteroatoms into the carbon framework by introducing ammonia gas, resulting in OMCs with a nitrogen content up to 4.7 at %, as well as non-Pluronic templating systems for synthesizing OMC with pore sizes larger than 10 nm. As employing a plasma source for materials pyrolysis is an industrially relevant approach, our system can be extended toward scaled synthesis of OMCs with much faster production rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling of Nondegenerate Topological Modes in Nitrogen Core-Doped Graphene Nanoribbons

Nitrogen core-doping of graphene nanoribbons (GNRs) allows trigonal planar carbon atoms along the backbone of GNRs to be substituted by higher-valency nitrogen atoms. The excess valence electrons are injected into the π-orbital system of the GNR, thereby changing not only its electronic occupation but also its topological properties. We have observed this topological change by synthesizing dilute nitrogen core-doped armchair GNRs with a width of five atoms (N 2 -5-AGNRs). The incorporation of pairs of trigonal planar nitrogen atoms results in the emergence of topological boundary states at the interface between doped and undoped segments of the GNR. These topological boundary states are offset in energy by approximately ΔE = 300 meV relative to the topological end states at the termini of finite 5-AGNRs. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal that for finite GNRs the two types of topological states can interact through a linear combination of orbitals, resulting in a pair of asymmetric hybridized states. This behavior is captured by an effective Hamiltonian of nondegenerate diatomic molecules, where the analogous interatomic hybridization interaction strength is tuned by the distance between GNR topological modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Performance of Pt Nanoparticles on Ni-N Co-Doped Graphitized Carbon for Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Since the reaction rate and cost for cathodic catalyst in polymer electrolyte membrane fuel cells are obstacles for commercialization, the high-performance catalyst for oxygen reduction reaction is necessary. The Ni encapsulated with N-doped graphitic carbon (Ni@NGC) prepared with ethylenediamine and carbon black is employed as an efficient support for the oxygen reduction reaction. Characterizations show that the Ni@NGC has a large surface area and mesoporous structure that is suitable to the support for the Pt catalyst. The catalyst structure is identified and the size of Pt nanoparticles distributed in the narrow range of 2–3 nm. Four different nitrogen species are doped properly into graphitic carbon structure. The Pt/Ni@NGC shows higher performance than the commercial Pt/C catalyst in an acidic electrolyte. The mass activity of the Pt/Ni@NGC in fuel cell tests exhibits over 1.5 times higher than that of commercial Pt/C catalyst. The Pt/Ni@NGC catalyst at low Pt loading exhibits 47% higher maximum power density than the Pt/C catalyst under H2-air atmosphere. These results indicate that the Ni@NGC as a support is significantly beneficial to improving activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The phototrophic purple non‐sulfur bacteria Rhodomicrobium spp. are novel chassis for bioplastic production

Abstract Petroleum‐based plastics levy significant environmental and economic costs that can be alleviated with sustainably sourced, biodegradable, and bio‐based polymers such as polyhydroxyalkanoates (PHAs). However, industrial‐scale production of PHAs faces barriers stemming from insufficient product yields and high costs. To address these challenges, we must look beyond the current suite of microbes for PHA production and investigate non‐model organisms with versatile metabolisms. In that vein, we assessed PHA production by the photosynthetic purple non‐sulfur bacteria (PNSB) Rhodomicrobium vannielii and Rhodomicrobium udaipurense. We show that both species accumulate PHA across photo‐heterotrophic, photo‐hydrogenotrophic, photo‐ferrotrophic, and photo‐electrotrophic growth conditions, with either ammonium chloride (NH 4 Cl) or dinitrogen gas (N 2 ) as nitrogen sources. Our data indicate that nitrogen source plays a significant role in dictating PHA synthesis, with N 2 fixation promoting PHA production during photoheterotrophy and photoelectrotrophy but inhibiting production during photohydrogenotrophy and photoferrotrophy. We observed the highest PHA titres (up to 44.08 mg/L, or 43.61% cell dry weight) when cells were grown photoheterotrophically on sodium butyrate with N 2 , while production was at its lowest during photoelectrotrophy (as low as 0.04 mg/L, or 0.16% cell dry weight). We also find that photohydrogenotrophically grown cells supplemented with NH 4 Cl exhibit the highest electron yields – up to 58.89% – while photoheterotrophy demonstrated the lowest (0.27%–1.39%). Finally, we highlight superior electron conversion and PHA production compared to a related PNSB, Rhodopseudomonas palustris TIE‐1. This study illustrates the value of studying non‐model organisms like Rhodomicrobium for sustainable PHA production and indicates future directions for exploring PNSB metabolisms.

59 BASIC BIOLOGICAL SCIENCES↗

Direct Conversion of MnO2 into Atomic Mn Sites for Oxygen Reduction

Development of platinum group metal (PGM)-free catalysts has been investigated to replace the platinum group metal catalyst in future inexpensive polymer electrolyte membrane (PEM) fuel cells. Usually, synthetic methods for these PGM-free catalysts involve introducing transition-metal salts or molecules. Herein, we demonstrate a facile synthetic method to prepare PGM-free Mn-N-C catalysts by directly converting manganese oxides into highly active MnN4 sites. Typically, MnO2 is used as a Mn source. Ammonium chloride and benzimidazole are introduced during high-temperature treatment to enhance catalytic activity and stability further. Ammonia generated from the decomposition of ammonium chloride can improve the intrinsic ORR activity of MnNx moieties through chemical or electronic effects by introducing additional nitrogen groups. The Mn-N-C catalyst exhibits promising ORR activity, achieving a half-wave potential of 0.83 V in 0.5 M H2SO4, outperforming most PGM-free ORR catalysts. The robust carbon structure resulting from organic-molecule treatment is also verified by electrochemical and physical characterization, thereby improving the catalyst's durability.

Yang, Xiaoxuan↗

Catalytic degradation of waste rubbers and plastics over zeolites to produce aromatic hydrocarbons

Catalytic conversion of waste rubbers and plastics into aromatic hydrocarbons is a promising approach to waste management and energy recovery. In the present study, acidic HY zeolites were supported by cobalt, iron, and zirconium, and the catalysts were characterized by powder X-ray diffraction, nitrogen adsorption-desorption, ammonia temperature programmed desorption, X-ray photoelectron spectroscopy, and pyridine-Fourier transform infrared spectroscopy. Here, the catalytic degradation of waste polybutadiene rubbers (BR) was conducted to investigate the degradation mechanism and evaluate the catalytic activity of supported zeolites. Experimental results indicated that HY loaded by zirconium and iron led to a higher content of Lewis acid sites as opposed to cobalt supported one. Compared with the non-catalytic pyrolysis of BR, the zirconium supported HY (Zr/HY) led to a 10-fold increase in aromatic hydrocarbons production with a distinctively high selectivity of 97.9%. A series of waste polymers including waste tires (WT), polyethylene (PE), polycarbonate (PC), and BR, were subjected to catalytic pyrolysis to explore the effects of polymer type on aromatic hydrocarbons generation, and BR was the most effective substrate, with yield enhancement reaching 2.4 over Zr/HY. Catalytic co-pyrolysis of waste rubbers and plastics was conducted to probe the effect of polymer structure on aromatic hydrocarbons formation, where a significant synergistic effect was observed in the PE co-fed with PC run.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helical Organic and Inorganic Polymers

Despite being a staple of synthetic plastics and biomolecules, helical polymers are scarcely studied with Gaussian-basis-set ab initio electron-correlated methods on an equal footing with molecules. This article introduces an ab initio second-order many-body Green’s-function [MBGF(2)] method with nondiagonal, frequency-dependent Dyson self-energy for infinite helical polymers using screw-axis-symmetry-adapted Gaussian-spherical-harmonics basis functions. Together with the Gaussian-basis-set density-functional theory for energies, analytical atomic forces, translational-period force, and helical-angle force, it can compute correlated energy, quasiparticle energy bands, structures, and vibrational frequencies of an infinite helical polymer, which smoothly converge at the corresponding oligomer results. These methods can handle incommensurable structures, which have an infinite translational period and are hard to characterize by any other method, just as efficiently as commensurable structures. We apply them to polyethylene (2/1 helix), polyacetylene (Peierls’ system), and polytetrafluoroethylene (13/6 helix) to establish the quantitative accuracy of MBGF(2)/cc-pVDZ in simulating their (angle-resolved) ultraviolet photoelectron spectra, and of B3LYP/cc-pVDZ or 6-31G** in reproducing their structures, infrared and Raman band positions, phonon dispersions, and (coherent and incoherent) inelastic neutron scattering spectra. We then predict the same properties for infinitely catenated chains of nitrogen or oxygen and discuss their possible metastable existence under ambient conditions. They include planar zigzag polyazene (N2)x (Peierls’ system), 11/3-helical isotactic polyazane (NH)x, 9/4-helical isotactic polyfluoroazane (NF)x, and 7/2-helical polyoxane (O)x as potential high-energy-density materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth-associated polyhydroxybutyrate accumulation in Azospira suillum PS during aerobic and perchlorate respiration

Polyhydroxyalkanoates (PHAs) are widespread microbial storage polymers increasingly recognized for roles beyond carbon and energy storage, including redox homeostasis and stress physiology. While PHA accumulation is classically associated with stationary-phase metabolism under severe nutrient imbalance, comparatively little is known about growth-associated PHA synthesis in facultative anaerobes with unusual respiratory strategies. Here, we investigated polyhydroxybutyrate (PHB) metabolism in Azospira suillum PS, a genetically tractable perchlorate-reducing bacterium capable of both aerobic and anaerobic respiration. Using physiological growth experiments, targeted gene deletions, PHB extractions, and intracellular redox measurements, we examined PHB accumulation under varying respiratory and nutrient conditions. We demonstrate that PHB accumulates during exponential growth under moderately nitrogen-limited conditions, both aerobically and during perchlorate respiration, representing a rare example of growth-associated PHB synthesis under anaerobic conditions. Genomic analysis revealed four phaC homologs, one of which could not be deleted under the experimental conditions tested and co-localized with phaB and phaR. Redox profiling further revealed a strong positive correlation between PHB accumulation and intracellular NADPH/NADP+ ratios. Together, these findings expand the physiological contexts in which PHB synthesis is known to occur and highlight perchlorate-respiring bacteria as underexplored model systems for studying growth-integrated carbon and redox storage strategies.

Meier, David A O↗

The Molecular Structures of Liquid and Glassy Nifedipine and Felodipine and Their Incorporation into PVP

Background: Amorphous drug formulations are commonly used to improve the solubility and bioavailability of poorly soluble molecular pharmaceuticals, yet less is known about their molecular conformations and local bonding interactions than their crystalline phases. Methods: High-energy X-ray diffraction structure factor measurements have been made on liquid and glassy nifedipine (NIF), felodipine (FEL), NIF 1:3 polyvinylpyrrolidone (PVP), and FEL 1:3 PVP wt.% mixtures. The corresponding X-ray pair distribution functions have been interpreted using empirical potential structure refinement using different models and density functional theory conformer calculations. Results: In both NIF and FEL, the NH···O inter-molecular hydrogen bonds between the pyridyl nitrogen and ester carbonyls are found to be considerably weaker than those observed in the crystalline polymorphs. For nifedipine, it is proposed that either inter-molecular NH…ON nitro bonds are present and/or a fraction (<20%) of conformational changes, with the aryl ring flipped, occur in the liquid state. For felodipine, the models indicate significant disorder associated with the methyl and ethyl side chains in the liquid state, with the main peak intensity at 3.0 Å arising from intra-molecular Cl-Cl atom pairs. When nifedipine molecules are incorporated into PVP, our models show they possess stronger NH···O bonds to the PVP polymer than felodipine molecules, which have stronger affinity for bonding to the polymer than to other felodipine molecules. Conclusions: The amorphous forms of both NIF and FEL show much weaker hydrogen bonding than found in their crystalline phases. Liquid NIF also exhibits configurations which are not observed in the crystal phases.

Amorphous Solid Dispersion↗

Electrodes with Electrodeposited Water-excluding Polymer Coating Enable High-Voltage Aqueous Supercapacitors

Aqueous supercapacitors are powerful energy sources, but they are limited by energy density that is much lower than lithium-ion batteries. Since raising the voltage beyond the thermodynamic potential for water splitting (1.23 V) can boost the energy density, there has been much effort on water-stabilizing salvation additives such as Li 2 SO 4 that can provide an aqueous electrolyte capable of withstanding ~1.8 V. Guided by the first-principles calculations that reveal water can promote hydrogen and oxygen evolution reactions, here, we pursue a new strategy of covering the electrode with a dense electroplated polymerized polyacrylic acid, which is an electron insulator but a proton conductor and proton reservoir. The combined effect of salvation and coating expands the electrochemical window throughout pH 3 to pH 10 to 2.4 V for both fast and slow proton-mediated redox reactions. This allows activated carbon to quadruple the energy density, a kilogram of nitrogen-doped graphene to provide 127 Watt-hour, and both to have improved endurance because of suppression of water-mediated corrosion. Therefore, aqueous supercapacitors can now achieve energy densities quite comparable to that of a lithium-ion battery, but at 100 times the charging/discharging speed and cycle durability.

Dong, Wujie↗