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At least 289 records · Page 16

An Americium-Containing Metal-Organic Framework: A Platform for Studying Transplutonium Elements

The synthesis, structural and spectroscopic characterization of the first transplutonium metal-organic framework (MOF) is described. The preparation and structure of Am GWMOF-6, [Am2(C6H8O4)3(H2O)2][(C10H8N2)], is analogous to that of the isostructural trivalent lanthanide-only containing material GWMOF-6. The presented MOF architecture is used as a plat-form to probe Am3+ coordination chemistry and guest-enhanced luminescent emission, whereas the framework itself provided a means to monitor the effects of self-irradiation upon crystallinity over time. Presented here is a discussion of these properties and the opportunities that metal-organic frameworks provide in the structural and spectroscopic study of actinides.

Ridenour, James A.↗

Contribution of Metal-Organic-Heat Carrier nanoparticles in a R245fa low-grade heat recovery Organic Rankine Cycle

This paper presents an in-depth investigation of the applications of an innovative nanofluid – suspensions of nanoparticles in a base fluid- in the ORC field, based on a new class of nanoparticles – termed Metal-Organic Heat Carriers (MOHCs) – molecularly engineered to reversibly uptake and release the working fluid molecules in which they are suspended. Unlike standard nanoparticles (i.e. Al2O3, Al, …), these MOHCs make it possible to extract additional heat from the endothermic enthalpy of desorption which can be as much as twice the level of the latent heat of vaporization of the pure fluid phase alone. The paper illustrates the development of a numerical model for assessing the MOHC-based nanofluid gain in ORC systems. More specifically, the possible combination of the base fluid R245fa with the nanoparticle MIL101, a robust Metal Organic Heat Carrier, was considered. To properly model the reversible adsorption/desorption process, experimental analyses were carried out to study the uptake of the R245fa in MIL101 at different operating conditions and departing from the experimental results, proper semi-empirical correlations were defined and adopted within the numerical model. The resulting performance of the MIL101/R245fa were compared with those of pure organic fluids, whose cycle was optimized in order to maximize the area-to-power ratio. Promising results were achieved in terms of system efficiency increase and heat exchanger area reduction.

Cavazzini, Giovanna↗

Oriented Covalent Organic Framework Film on Graphene for Robust Ambipolar Vertical Organic Field-Effect Transistor

Periodically eclipsed π-stacking columns in two-dimensional covalent organic frameworks (2D COFs) could function as direct channel paths for charge carrier transport. Incorporating a welldefined 2D COF into organic electronic devices, however, is still a challenge. Herein, we reported the solvothermal synthesis of a COF TFPy-PPDA film on single layer graphene (SLG), which was constructed via covalent imine-type linkage by employing 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPy) and p-phenylenediamine (PPDA) as building blocks. A vertical field-effect transistor (VFET) based on the heterostructure of COF TFPy-PPDA film and SLG shows ambipolar charge carrier behavior under lower modulating voltages. Work-function-tunable contact between SLG and COFTFPy-PPDA film and suitable injection barriers of charge carriers lead to the ambipolar transport with high current density on/off ratio (>10 5 ) and high on-current density (>4.1 Acm -2 ). Interfacing 2D COF with graphene for VFET could shed the promising application prospect of 2D COFs in organic electronics and optoelectronics.

36 MATERIALS SCIENCE↗

Evolution of Pore Structure in Organic-Lean and Organic-Rich Mudrocks

The pore structure of mudrocks is a key characteristic to evaluate flow behavior through these rocks. Although significant advances have been made to resolve pore characteristics, porosity evolution, or pore connectivity, there is still insufficient knowledge linking porosity evolution to flow and transport in mudrocks. To better understand these links, we conducted very small-angle (VSANS) and small-angle neutron scattering (SANS) experiments on 13 sets of mudrocks from global locations, characterized by differences in composition, maturity, and depositional environment. Our results indicate that a homogeneous pore structure reflects a stable and low-energy depositional environment. Organic-lean mudrocks mainly contain pores <10 nm, which restricts flow and is beneficial for, e.g., caprock seal integrity. Increasing maturity as a result of increasing burial depth, and therefore, temperature leads to porosity evolution. In organic-rich mudrocks (ORMs), this happens through the generation of organic matter pores and pore preservation around diagenetically formed carbonates. ORMs mainly contain macropores (>50 nm), favoring production from, e.g., unconventional reservoirs. SANS-derived pore size distributions will help to better understand fluid imbibition and flow properties in mudrocks through comprehensive quantitative characterization of the nano- to micron scale pore network conduits and their relationships to burial diagenesis.

58 GEOSCIENCES↗

River Organic Carbon Fluxes Modulated by Hydrodynamic Sorting of Particulate Organic Matter

Rivers regulate the global carbon cycle by transferring particulate organic carbon (POC) from terrestrial landscapes to marine sedimentary basins, but the processes controlling the amount and composition of fluvially exported POC are poorly understood. We propose that hydrodynamic sorting processes modify POC fluxes during fluvial transit. We test this hypothesis by studying POC transported along a ~1,200 km reach of the Rio Bermejo, Argentina. Nanoscale secondary ion mass spectrometry revealed that POC was either fine, mineral-associated organic matter, or coarse discrete organic particles. Mineral-associated POC is more resistant to oxidation and has a lower particle settling velocity than discrete POC. Consequently, hydraulic sorting and downstream fining amplify the proportion of fine, mineral-associated POC from ~55% to ~78% over 1,220 km of downstream transit. This suggests that mineral-associated POC has a greater probability of export and preservation in marine basins than plant detritus, which may be oxidized to CO 2 during transit.

58 GEOSCIENCES↗

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO 2 fluxes (up to 6x), and caused rapid and persistent changes in bacterial community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO 2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. As a result, we identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.

54 ENVIRONMENTAL SCIENCES↗

Solution-grown small-molecule organic semiconductor with enhanced crystal alignment and areal coverage for organic thin film transistors

Drop casting of small-molecule organic semiconductors typically forms crystals with random orientation and poor areal coverage, which leads to significant performance variations of organic thin-film transistors (OTFTs). In this study, we utilize the controlled evaporative self-assembly (CESA) method combined with binary solvent system to control the crystal growth. A small-molecule organic semiconductor,2,5-Di-(2-ethylhexyl)-3,6-bis(5"-n-hexyl-2,2',5',2"]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH), is used as an example to demonstrate the effectiveness of our approach. By optimizing the double solvent ratios, well-aligned SMDPPEH crystals with significantly improved areal coverage were achieved. As a result, the SMDPPEH based OTFTs exhibit a mobility of 1.6 × 10 -2 cm 2 /V s, which is the highest mobility from SMDPPEH ever reported.

59 BASIC BIOLOGICAL SCIENCES↗

Organic-inorganic proximity effect in the magneto-conductance of vertical organic field effect transistors

Vertical organic field effect transistors having a patterned source electrode and an a-SiO{sub 2} insulation layer show high performance as a switching element with high transfer characteristics. By measuring the low field magneto-conductance under ambient conditions at room temperature, we show here that the proximity of the inorganic a-SiO{sub 2} insulation to the organic conducting channel affects considerably the magnetic response. We propose that in n-type devices, electrons in the organic conducting channel and spin bearing charged defects in the inorganic a-SiO{sub 2} insulation layer (e.g., O{sub 2} = Si{sup +·}) form oppositely charged spin pairs whose singlet-triplet spin configurations are mixed through the relatively strong hyperfine field of {sup 29}Si. By increasing the contact area between the insulation layer and the conducting channel, the ∼2% magneto-conductance response may be considerably enhanced.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Evaluation of the Current State of Knowledge for Thermolysis of Organics within SRS Waste Forming Volatile Organic Compounds (VOCs)

The 2017 report Flammable Gas Generation Mechanisms for High Level Liquid Waste Facilities , X-ESRG- 00062 Rev. 1, assessing mechanisms for flammable gas generation acknowledged the presence of flammable organics, concluding that available data indicated their concentrations pose a minor contribution (e.g., <5%) to the composite lower flammable limit. Savannah River Remediation (SRR) chartered the Savannah River National Laboratory (SRNL) to perform a more detailed assessment of available and emerging data to assess the current state of knowledge for formation of Volatile Organic Compounds (VOCs) from thermolysis of organics in Savannah River Site (SRS) caustic tank waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗