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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Energy and emissions saving potential of additive manufacturing: the case of lightweight aircraft components

Additive manufacturing (AM) holds great potential for improving materials efficiency, reducing life-cycle impacts, and enabling greater engineering functionality compared to conventional manufacturing (CM), and AM has been increasingly adopted by aircraft component manufacturers for lightweight, cost-effective designs. This study estimates the net changes in life-cycle primary energy and greenhouse gas emissions associated with AM technologies for lightweight metallic aircraft components through the year 2050, to shed light on the environmental benefits of a shift from CM to AM processes in the U.S. aircraft industry. A systems modeling framework is presented, with integrates engineering criteria, life-cycle environmental data, aircraft fleet stock and fuel use models under different AM adoption scenarios. Estimated fleet-wide life-cycle primary energy savings at most reach 70-173 million GJ/year in 2050, with cumulative savings of 1.2–2.8 billion GJ. Associated cumulative GHG emission reductions were estimated at 92.1–215.0 million metric tons. In addition, thousands of tons of aluminum, titanium and nickel alloys could be potentially saved per year in 2050. The results indicate a significant role of AM technologies in helping society meet its long-term energy use and GHG emissions reduction goals, and highlight barriers and opportunities for AM adoption for the aircraft industry.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2019

Field-to-farm gate greenhouse gas emissions from corn stover production in the Midwestern U.S.

Measured field data were used to compare two allocation methods on life cycle greenhouse gas emissions from corn (Zea mays L.) stover production in the Midwest U.S. We used publicly-available crop yield, nitrogen fertilizer, and direct soil nitrous oxide emissions data from the USDA-ARS Resilient Economic Agricultural Practices research program. Field data were aggregated from 9 locations across 26 site-years for 3 stover harvest rates (no removal; moderate removal – 3.1 Mg ha –1 ; high removal – 7.2 Mg ha –1 ) and 2 tillage practices (conventional; reduced/no-till). Net carbon uptake by crops was computed from measured plant carbon content. Monte Carlo simulations sampled input distributions to assess variability in farm-to-gate GHG emissions. The base analysis assumed no change in soil organic carbon stocks. In all cases, net CO 2 uptake during crop growth and soil-respired CO 2 dominated system emissions. Emissions were most sensitive to co-product accounting method, with system expansion emissions ~15% lower than mass allocation. Regardless of accounting method, lowest emissions occurred for a moderate removal rate under reduced/no-till management. The absence of correlations between N fertilization rate and stover removal rate or soil N 2 O emissions in this study challenges the use of such assumptions typically employed in life cycle assessments Storage of all carbon retained on the field as SOC could reduce emissions by an additional 15%. Furthermore, our results highlight how variability in GHG emissions due to location and weather can overshadow the impact of farm management practices on field-to-farm gate emissions. Graphical abstract

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Life cycle assessment of biochar produced from forest residues using portable systems

Forest fires are getting extreme and more frequent because of increased fuel loads in the forest and extended dry conditions. Fuel treatment (i.e., thinning) methods to mitigate forest fires will generate large volumes of forest residues together with available logging residues that can be used to produce biochar. It has been proposed that portable biochar systems are economical means to utilize forest residues as an alternative to slash burning. In this study, the environmental impacts of biochar produced from forest residues using three portable systems [1. Biochar Solutions Incorporated (BSI), 2. Oregon Kiln, and 3. Air-curtain Burner] were evaluated using a cradle-to-gate life-cycle assessment approach. Environmental impacts were analyzed considering the various quality of feedstock, biomass collection methods, different production sites, and various sources of power used in the production of biochar. The results illustrate that the global warming potential (GWP) of biochar production from forest residues through BSI, Oregon Kiln, and Air-Curtain Burner were 0.25–0.31, 0.11, and 0.16 tonne CO 2 eq./tonne of fixed carbon in biochar respectively. Compared to pile burn, biochar production from forest residues with a portable system at the landing, reduced global warming potential (GWP) by 1.92–2.83, 2.7, and 1.9 tonnes CO 2 eq./tonne of biochar through BSI, Oregon Kiln, and Air-Curtain Burner respectively. The Air-Curtain Burner and Oregon Kiln have minimal feedstock preparation, thus have lower environmental impacts than the BSI system. The BSI system requires feedstock preparation and power to operate the system. The use of the biomass-gasifier generator improved the environmental performance substantially (16–280%) compared with a diesel generator in biochar production. Overall, the net GWP in biochar produced (0.10–1.63 tonne CO 2 eq./tonne of residues) from forest residues can reduce environmental impacts (2–40 times lower net CO 2 eq. emissions) compared to slash burning.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

A multi-product landscape life-cycle assessment approach for evaluating local climate mitigation potential

Increasing demand for land-based climate mitigation requires more efficient management of agricultural landscapes for competing objectives. Here we develop methods for assessing trade-offs and synergies between intensification and carbon-sequestering conservation measures in annual crop production landscapes using the DayCent ecosystem model and the Greenhouse Gases, Regulated Emissions, and Energy Use in Technologies (GREET) life-cycle assessment (LCA) model. We compiled county-scaled crop yields, fertilizer application rates, and tillage intensity for a corn–soybean farming case study landscape in the US state of Iowa. Using DayCent, we estimated a baseline soil organic carbon (SOC) accrual rate of 0.29 Mg C ha -1 y -1 driven by historical increases in crop productivity and reductions in tillage intensity. We then simulated the effects of management interventions targeted toward intensification (stover removal) and SOC sequestration (tillage intensity reduction and winter cover crop addition) individually and in combination. We propose a new multi-product landscape–LCA approach that analyzes marginal changes in corn grain, corn stover, and soybean production from the landscape in terms of their value for biofuel production (corn ethanol, soy biodiesel, and cellulosic ethanol from stover) and associated net displacement of conventional fossil-derived fuel use. This enables us to evaluate both intensification and sequestration effects in common CO 2 -equivalent mitigation units. We also used DayCent-simulated yields under the different land management scenarios to estimate farm-level costs and revenues. Our results show that intensification via collecting 30% of corn stover for biofuel production would increase the total greenhouse gas (GHG) mitigation potential of this landscape by 0.93 Mg CO 2 e ha -1 y -1 and provide $49 ha -1 y -1 of additional net revenue from biomass sales, but would reduce the baseline SOC accumulation rate by approximately 40%. In contrast, integrated approaches that include co-adoption of winter cover cropping and/or tillage intensity reduction would result in increased rates of SOC accumulation above the baseline, achieving simultaneous improvements in both farm profits and the overall GHG mitigation potential of the landscape.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Conversion of food waste to renewable energy: A techno-economic and environmental assessment

Increasing quantities of food waste have become a concern due to high disposal costs in landfills and high greenhouse gas emissions. With this increase in food waste generation, there is also an increasing demand for renewable natural gas to supplement traditional fossil fuel combustion and offset the impacts of climate change. Collecting food waste from landfills and turning it into renewable natural gas using anaerobic digestion could be a win-win option for both food waste disposal and renewable energy production. While some literature exists on the energy potential, economic feasibility, and environmental benefit of food waste disposal via anaerobic digestion, no existing study simultaneously evaluates the energy, economic and environmental effect of food waste to renewable energy via anaerobic digestion, especially on a plant and city scale. Further, this study is focused on the techno-economic and environmental assessment of food waste to energy via anaerobic digestion in order to fill this gap. Four anaerobic digestion pathways are considered in this study: flare, pipeline natural gas, combined heat and power, and combined cycle for efficient power generation. Using a city of 1M people the results show that renewable natural gas from food waste could supply the natural gas usage for 1.9% of residential use, 2.7% of commercial use, 1.1% of industrial use, 167.5% of the compressed natural gas vehicle fleet, 0.7% of electric power generation, or 2.5% of industrial high-temperature heating processes. All pathways except pipeline natural gas will have a positive net present value in the baseline scenario, and the pipeline natural gas pathway will become economically viable with a net present value of 31 USD/t of food waste with renewable energy credits. Lastly, all of the pathways achieve negative greenhouse gas emissions, which indicates that anaerobic digestion is a more environmentally friendly method for the handling of food waste than landfills.

03 NATURAL GAS↗
DOE OSTI2021

DeepM&Mnet: Inferring the electroconvection multiphysics fields based on operator approximation by neural networks

Electroconvection is a multiphysics problem involving coupling of the flow field with the electric field as well as the cation and anion concentration fields. Here, we use electroconvection as a benchmark problem to put forward a new data assimilation framework, the DeepM&Mnet, for simulating multiphysics and multiscale problems at speeds much faster than standard numerical methods using pre-trained neural networks. We first pre-train DeepONets that can predict independently each field, given general inputs from the rest of the fields of the coupled system. DeepONets can approximate nonlinear operators and are composed of two sub-networks, a branch net for the input fields and a trunk net for the locations of the output field. DeepONets, which are extremely fast, are used as building blocks in the DeepM&Mnet and form constraints for the multiphysics solution along with some sparse available measurements of any of the fields. We demonstrate the new methodology and document the accuracy of each individual DeepONet, and subsequently we present two different DeepM&Mnet architectures that infer accurately and efficiently 2D electroconvection fields for unseen electric potentials. Furthermore, the DeepM&Mnet framework is general and can be applied for building any complex multiphysics and multiscale models based on very few measurements using pre-trained DeepONets in a “plug-and-play” mode.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Using a coupled dispersion model to estimate depletion of a tritium oxide plume by a forest

Tritium processing facilities may release tritium oxide (HTO) to the atmosphere which poses potential health risks to exposed co-located workers and to offsite individuals. Most radiological consequence analyses determine HTO dose by applying Gaussian plume models to simulate the transport of HTO. Within these models, deposition velocity is used to assess the sum of all deposition processes acting on the plume. While this may account for vegetative and soil uptake or respiration processes, it may currently lack inclusion of the complex interactions within heterogeneous forested environments. In this complex morphology, dispersion patterns are significantly altered by changing flow regimes above and below the forest canopy and by the transfer of plume material across the canopy boundary. To determine the effects of a heterogeneous forest canopy on an airborne HTO plume, a Gaussian plume model coupled with an advection-diffusion plume model was applied to estimate transport in the free atmosphere above the forest and within the forest canopy and understory. During 2012, wind speed and wind direction measurements taken at 5 heights, ranging from 2-m to 28-m, on an instrumented meteorological tower located in a loblolly pine forest at the Department of Energy (DOE) Savannah River Site (SRS), near Aiken, SC. From these measurements, model predictions were made over a full spectrum of meteorological conditions. Deposition and resuspension velocities were calculated based on the model-predicted flux of plume material across the top of the forest canopy. Additionally, net deposition velocity of the plume material was calculated as the difference between the deposition and resuspension velocities. The 1st and 5th percentile net deposition velocities were estimated to be 0.7 cm s-1 and 1.2 cm s-1, respectively.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2022

A new algorithm for estimating radioxenon concentrations

A new algorithm (Xcounts) is introduced for estimating the activity concentrations of the xenon isotopes 131m Xe, 133m Xe, 133 Xe, and 135 Xe using beta-gamma coincidence data. The algorithm simultaneously estimates the decay counts associated with the four xenon isotopes, background, and radon in contrast to the net-counts method that uses sequential residual removal to account for background and interreferences. Calibration data for background counts are determined from gas-background measurements and simulation. In Xcounts, the false positive count rates for 131m Xe and 133m Xe are lower than the false positive rates for 133 Xe and 135 Xe. This algorithm appears to reliably detect the metastable isotopes at lower activity levels than the net-counts method and have similar performance for the other isotopes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Comparison of the photochemical properties of phthalocyanine and hemiporphyrazine Zn(II) complexes

In DMF (dimethylformamide) solutions containing concentrations of (NEt 4 )Br (Et = ethyl) between 0.001 and 0.05 M both zinc phthalocyanine (Pc) and hemiporphyrazine (Hp) complexes are dissolved and form species [Zn(Hp)(Br)] – , and [Zn(Pc)(Br)] – . The increase in formation of the hemiporphyrazine bromide adduct is revealed by a linear dependence of the UV–Vis absorption spectrum on the Br – concentration whereas, over the same concentration range, absorption measurements indicate the formation of the phthalocyanine bromide adduct in solution. The x-ray and molecular structure of [NEt 4 ][Zn(Pc)(Br)](H 2 O) 0.33 has been determined showing the coordination of the Br – to the metal center. Photo-induced processes of the Zn complexes were investigated with deaerated solutions in a time scale t ≥10 ns. The 355 nm flash irradiation of [Zn(Hp)(Br)] – produced transient spectra which showed a bathochromic shift of the absorption maximum from 460 nm to 440 nm and an increase of the spectrum rate of decay with increasing Br – concentrations. The initial spectrum is attributed to the (nπ*–LLCT Br→Hp )[Zn(Hp)(Br)] – excited state which reacts with H-atom donors forming a radical [Zn(Hp-H)(Br)] •– . On the other hand, a transient spectrum, λ max ~600 nm, grows in a time t ≤0.6 µs when [Zn(Pc)(Br)] – is flash irradiated at 355 nm. The photoreactions of these complexes with SCN – and 2-propanol (IPA) were studied. Despite of the apparent similarity between both complexes, IPA was photo-oxidized by both complexes although by different mechanisms, an electron transfer with [Zn(Pc)(Br)] – and an H atom abstraction with [Zn(Hp)(Br)] – . Finally, the photo-oxidation of SCN– by [Zn(Pc)(Br)] – but not by [Zn(Hp)(Br)] – makes a remarkable difference between the photochemistries of these complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Demonstration of a Highly Efficient Solid Oxide Fuel Cell Power System Using Adiabatic Steam Reforming and Anode Gas Recirculation

Solid oxide fuel cells (SOFC) are currently being developed for a wide variety of applications because of their high efficiency at multiple power levels. Applications for SOFCs encompass a large range of power levels including 1-2 kW residential combined heat and power applications, 100-250 kW sized systems for distributed generation and grid extension, and MW-scale power plants utilizing coal. This paper reports on the development of a highly efficient, small-scale SOFC power system operating on methane. The system uses adiabatic steam reforming of methane and anode gas recirculation to achieve high net electrical efficiency. The anode exit gas is recirculated and all of the heat and water required for the endothermic reforming reaction are provided by the anode gas emerging from the SOFC stack. Although the single-pass fuel utilization is only about 55%, because of the anode gas recirculation the overall fuel utilization is up to 93%. The demonstrated system achieved gross power output of 1650 to 2150 watts with a maximum net LHV efficiency of 56.7% at 1720 watts. Overall system efficiency could be further improved to over 60% with use of properly sized blowers.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

A look into the voltage plateau signal for detection and quantification of lithium plating in lithium-ion cells

Voltage plateau during relaxation or discharge after charging is a distinct signal associated with stripping of deposited Li metal and hence a feasible tool for online detection of Li plating in Li-ion batteries. In this report we present a physics-based model with incorporation of Li plating and stripping to gain a fundamental understanding of the voltage plateau behavior. Specifically, we focus on the internal cell characteristics when voltage plateau occurs and on key factors affecting the shape and duration of voltage plateau. Furthermore, the validity of using the duration of voltage plateau for estimating Li plating amount is assessed. It is found that the duration of voltage plateau depends on the rate of Li stripping, while the stripping rate is restricted by the capability of Li+ intercalation into graphite. Parameters like intercalation kinetics, solid-state diffusivity of graphite and cell temperature can substantially influence the voltage curves even with the same amount of Li plating. Further, we report an interesting phenomenon that during Li stripping one part of anode near the separator has net oxidation current (local stripping rate > intercalation rate), providing Li+ ions and electrons to the other part of anode near the foil which has net reduction current.

25 ENERGY STORAGE↗
DOE OSTI2010

Synthesis and structural characterization of different topological coordination polymers based on tunable Cu{sub 4}Br{sub 4-m}I{sub m} secondary building units and macrocyclic azacalixaromatics

The coordination self-assembly between the macrocyclic ligand tetraazacalix[4]pyrimidine (TAPM) with cubane-like copper halides (Cu{sub 4}X{sub 4}) produced five coordination polymers 1-5 {l_brace}Cu{sub 4}Br{sub 4-m}I{sub m}(TAPM){r_brace}{sub n} (m=0 (1), 1 (2), 2 (3), 3 (4) and 4 (5)). X-ray single crystal analysis revealed that the Br:I ratio in the Cu{sub 4}X{sub 4} cores serves as a controlling factor to fine-tune the geometries of Cu{sub 4}X{sub 4} and therefore induce the conformation variation of tetraazacalix[4]pyrimidine. Consequently, two different topological nets, dia and lcs, were successfully constructed based on tetrahedrally coordinated Cu{sub 4}X{sub 4} secondary building units and the flexible macrocyclic quadridentate ligand TAPM. The structure details of 1-5 as porous materials are analyzed, which shows a solvent accessible volume within the range of 27-35%. Compounds 1-5 exhibit luminescence properties with the peak maximum at around 476-488 nm. -- Graphical Abstract: Five luminescent coordination polymers 1-5 were obtained via the reaction of tetrahedral Cu{sub 4}Br{sub 4-m}I{sub m} SBUs and a flexible macrocyclic ligand tetraazacalix[4] pyrimidine (TAPM), wherein the Br/I ratio serves as a controlling factor to fine-tune the geometries of Cu{sub 4}Br{sub 4-m}I{sub m} and induce the conformation variation of TAPM, thus constructing two different dia and lcs topological nets. Display Omitted Research highlights: > The ratio of Br/I in the Cu{sub 4}X{sub 4} cores fine-tunes the geometries of Cu{sub 4}X{sub 4}. > Variation of Cu{sub 4}X{sub 4} induces the conformation change of the ligand TAPM. > Two different coordination polymeric structures were successfully constructed. > The five coordination polymers show good luminescent properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Two new frameworks of potassium saccharate obtained from acidic and alkaline solution

Two chiral K(I) complexes based on D-saccharic acid (H{sub 2}sac), [K(Hsac)]{sub n} (1) and [K{sub 2}(sac)]{sub n} (2) were obtained from acidic and alkaline solution. The 3D framework of 1 includes K(I) polyhedral rods and typical pairwise coaxial right- and left-handed helical chains, and displays binodal 6-connected pcu topology. 2 contains 2D polyhedral sheets consisting of left-handed helical chains, and generates 3D network with an unprecedented (7,11)-connected net. Cyclic voltammetry tests and charge-discharge tests indicate that the addition of complex 2 to the electrolyte could improve the electrochemical properties of the nickel hydroxide electrode. -- Graphical abstract: Two K(I) complexes based on D-saccharic acid (H{sub 2}sac), [K(Hsac)]{sub n} (1) and [K{sub 2}(sac)]{sub n} (2) were obtained and characterized. Electrochemical studies indicate the potential use of 2 in Ni-MH battery. Display Omitted highlights: > Two novel chiral K(I) frameworks based on D-saccharic acid were obtained. > The structure of 1 includes K(I) polyhedral rods and typical helical chains. > 2 contains 2D polyhedral sheets and generates an unprecedented (7,11)-connected net. > Addition of 2 to electrolyte could improve the nickel hydroxide electrode's property.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}

New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Nd{sub 25}B{sub 12}C{sub 28}: space group P1-bar, a=8.3209(7) A, b=8.3231(6) A, c=29.888(2) A, {alpha}=83.730(9){sup o}, {beta}=83.294(9){sup o}, {gamma}=89.764(9){sup o}. Pr{sub 25}B{sub 14}C{sub 26}: space group P2{sub 1}/c, a=8.4243(5) A, b=8.4095(6) A, c=30.828(1) A, {beta}=105.879(4){sup o}, V=2100.6(2) A{sup 3}, (R1=0.048 (wR2=0.088) from 2961 reflections with I{sub o}>2{sigma}(I{sub o})); for Nd{sub 25}B{sub 14}C{sub 26} space group P2{sub 1}/c, Z=2, a=8.3404(6) A, b=8.3096(6) A, c=30.599(2) A, {beta}=106.065(1){sup o}. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Accordingly, extended Hueckel tight-binding calculations indicate that the compounds are metallic in character. - Graphical Abstract: New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms, respectively. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Highlights: > New rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}. > Structures contain 1-D finite B{sub 3}C{sub 3}, B{sub 2}C{sub 4}, BC{sub 2} units as well as isolated C atoms. > B/C distribution in the crystal structures was approved by EH-TB calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Unprecedented {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains and four novel organic-inorganic hybrids based on Mo-POMs and azaheterocycles templates

Abstrct: Four novel organic-inorganic hybrid materials based on Mo-POMs and organic templates, namely [DEB] [{beta}-Mo{sub 8}O{sub 26}] [NH{sub 4}]{sub 2} (1), [BMIM] [{beta}-Mo{sub 8}O{sub 26}]{sub 0.5}{center_dot}H{sub 2}O (2), [BMIM] [1D-Mo{sub 8}O{sub 26}]{sub 0.5} (3) and {l_brace}3D-[Cu(DIE){sub 2}] [1D-Mo{sub 8}O{sub 26}]{sub 0.5}{r_brace}{sub {infinity}} (4) [DEB= 1,1 Prime -diethyl-4,4 Prime -bipyridinium, BMIM=1,1 Prime -bis(1-methylimidazolium)methylene, DIE=1,2-diimidazoloethane] have been hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermal gravimetric analysis(TGA) and single-crystal X-ray diffraction. Both compounds 1 and 2 are POMs-based supramolecular compounds consisted of independent [{beta}-Mo{sub 8}O{sub 26}]{sup 4-} anions and [DEB]{sup 2+} or [BMIM]{sup 2+} organic cations. Compound 3 is the first external template example of Mo-POMs-based supramolecular network incorporated with novel {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains. Compound 4 is a rare supramolecular structure that contains octamolybdate {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains interconnected via DIE ligands to form a 3D net. Moreover, it was indicated that these polyacid compounds had definite catalytic activities on the probe reaction of acetaldehyde oxidation to acetic acid with H{sub 2}O{sub 2}. - Graphical abstract: Four novel organic templated polyoxometalates comprising of 0D, 1D and 3D supramolecular frameworks together with the catalytic activities on the acetaldehyde oxidation to acetic acid were reported. Highlights: Using cation templated self-assembly four novel polyoxometalates were prepared. Compounds 1 and 2 consisted of independent [{beta}-Mo{sub 8}O{sub 26}]{sup 4-} anions and organic cations. Compound 3 is the first external template-assisted POMs with {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} chain. Compound 4 is a rare 3D net containing {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} 1D chain and DIE ligands. These compounds had definite catalytic activities on the acetaldehyde oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Local structure of Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot}2H{sub 2}O by the modeling of X-ray diffuse scattering - from average-structure to microdomain model

Local structure of dirubidium tetralithium tris(selenate(VI)) dihydrate - Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot} 2H{sub 2}O has been determined basing on the modeling of X-ray diffuse scattering. The origin of observed structured diffuse streaks is SeO{sub 4} tetrahedra switching between two alternative positions in two quasi-planar layers existing in each unit cell and formation of domains with specific SeO{sub 4} tetrahedra configuration locally fulfilling condition for C-centering in the 2a Multiplication-Sign 2b Multiplication-Sign c superstructure cell. The local structure solution is characterized by a uniform distribution of rather large domains (ca. thousand of unit cells) in two layers, but also monodomains can be taken into account. Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming two-string ribbons. Inside the ribbons SeO{sub 4} and LiO{sub 4} tetrahedra share the oxygen corners, whereas ribbons are bound to each other by a net of hydrogen bonds and fastened by corner sharing SeO{sub 4} tetrahedra of the neighboring layers. - Graphical abstract: Experimental sections of the reciprocal space showing diffraction effects observed for RLSO. Bragg spots are visible on sections with integer indices (1 kl section - on the left), streaks - on sections with fractional ones (1.5 kl section - on the right). At the center: resulting local structure of the A package modeled as a microdomain: two-string ribbons of ordered oxygen-corners-sharing SeO{sub 4} and LiO{sub 4} terahedra extended along ab-diagonal are seen; ribbons are bound by hydrogen bonds (shown in pink); the multiplied 2a Multiplication-Sign 2b unit cell is shown. Highlights: Black-Right-Pointing-Pointer X-ray diffuse scattering in RLSO was registered and modeled. Black-Right-Pointing-Pointer The origin of diffuse streaks is SeO{sub 4} tetrahedra switching in two structure layers. Black-Right-Pointing-Pointer The local structure is characterized by a uniform distribution of microdomains. Black-Right-Pointing-Pointer Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming ribbons. Black-Right-Pointing-Pointer The ribbons are bound to each other by a net of hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗