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At least 1,693 records · Page 94

Excitons: Energetics and spatiotemporal dynamics

The concept of an exciton as a quasiparticle that represents collective excited states was originally adapted from solid-state physics and has been successfully applied to molecular aggregates by relying on the well-established limits of the Wannier exciton and the Frenkel exciton. However, the study of excitons in more complex chemical systems and solid materials over the past two decades has made it clear that simple concepts based on Wannier or Frenkel excitons are not sufficient to describe detailed excitonic behavior, especially in nano-structured solid materials, multichromophoric macromolecules, and complex molecular aggregates. In addition, important effects such as vibronic coupling, the influence of charge-transfer (CT) components, spin-state interconversion, and electronic correlation, which had long been studied but not fully understood, have turned out to play a central role in many systems. This has motivated new experimental approaches and theoretical studies of increasing sophistication. This article provides an overview of works addressing these issues that were published for A Special Topic of the Journal of Chemical Physics on ``Excitons: Energetics and spatio-temporal dynamics" and discusses their implications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Analysis of Inorganic Species in Herbaceous Materials Using Laser-Induced Breakdown Spectroscopy [plus supplemental information]

Inorganic compounds in biomass, often referred to as ash, are known to be problematic in the thermochemical conversion of biomass to bio-oil or syngas and, ultimately, hydrocarbon fuels because they negatively influence reaction pathways, contribute to fouling and corrosion, poison catalysts, and impact waste streams. The most common ash-analysis methods, such as inductively coupled plasma-optical emission spectrometry/mass spectrometry (ICP-OES/MS), require considerable time and expensive reagents. Laser-induced breakdown spectroscopy (LIBS) is emerging as a technique for rapid analysis of the inorganic constituents in a wide range of biomass materials. This study compares analytical results using LIBS data to results obtained from three separate ICP-OES/MS methods for 12 samples, including six standard reference materials. Analyzed elements include aluminum, calcium, iron, magnesium, manganese, phosphorus, potassium, sodium, and silicon, and results show that concentrations can be measured with an uncertainty of approximately 100 parts per million using univariate calibration models and relatively few calibration samples. These results indicate that the accuracy of LIBS is comparable to that of ICP-OES methods and indicate that some acid-digestion methods for ICP-OES may not be reliable for Na and Al. These results also demonstrate that germanium can be used as an internal standard to improve the reliability and accuracy of measuring many elements of interest, and that LIBS can be used for rapid determination of total ash in biomass samples. Key benefits of LIBS include little sample preparation, no reagent consumption, and the generation of meaningful analytical data instantaneously.

09 BIOMASS FUELS↗

Thermoelectric properties of SnSe and SnSe 2 single crystals

Thermoelectric materials can serve for conversion between thermal and electrical energy. In the search for new thermoelectric materials, layered SnSe and SnSe 2 are promising candidates. Here we have successfully synthesized SnSe and SnSe 2 single crystals by the modified Bridgman method and studied their thermoelectric properties: thermopower (S), thermal conductivity (κ), and electrical conductivity (σ) in the temperature range between 2 K and 400 K, which are absent in the literature. In particular, the kink observed in the thermopower corresponds to the metallic-nonmetallic crossover temperature for both SnSe and SnSe 2 , reflecting their inherent electronic nature. Compared to SnSe 2 above 100 K, we find that SnSe exhibits higher electrical conductivity, higher thermopower, and lower thermal conductivity, thus resulting in the higher figure of merit. Hall effect measurements reveal that the Hall mobility in SnSe is an order higher than that in SnSe 2 , advancing its thermoelectric performance. These experimental results are supported by first principles calculations, which indicate that the inequivalent Sn-Se bonding lengths help improve the figure of merit of SnSe.

36 MATERIALS SCIENCE↗

Cyclization strategies of meditopes: affinity and diffraction studies of meditope–Fab complexes

An overview of cyclization strategies of a Fab-binding peptide to maximize affinity. Recently, a unique binding site for a cyclic 12-residue peptide was discovered within a cavity formed by the light and heavy chains of the cetuximab Fab domain. In order to better understand the interactions that drive this unique complex, a number of variants including the residues within the meditope peptide and the antibody, as well as the cyclization region of the meditope peptide, were created. Here, multiple crystal structures of meditope peptides incorporating different cyclization strategies bound to the central cavity of the cetuximab Fab domain are presented. The affinity of each cyclic derivative for the Fab was determined by surface plasmon resonance and correlated to structural differences. Overall, it was observed that the disulfide bond used to cyclize the peptide favorably packs against a hydrophobic ‘pocket’ and that amidation and acetylation of the original disulfide meditope increased the overall affinity ∼2.3-fold. Conversely, replacing the terminal cysteines with serines and thus creating a linear peptide reduced the affinity over 50-fold, with much of this difference being reflected in a decrease in the on-rate. Other cyclization methods, including the formation of a lactam, reduced the affinity but not to the extent of the linear peptide. Collectively, the structural and kinetic data presented here indicate that small perturbations introduced by different cyclization strategies can significantly affect the affinity of the meditope–Fab complex.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization

The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than $500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

09 BIOMASS FUELS↗

Solar Technology Validation Project - Hualapai Valley Solar (Met Station): Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Tri-State G&T: Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Loyola Marymount University: Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Solar Technology Validation Project - Solargen (Met Station): Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Southwest Solar (Met Station): Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - RES Americas: Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Amonix, Inc.: Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - USS Data, LLC: Cooperative Research and Development (Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Utah State Energy Program (Met Station) (CRADA Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Solar Technology Validation Project - Iberdrola Renewables, Inc. (CRADA Final Report)

Under this Agreement, NREL will work with Participant to improve concentrating solar power system performance characterizations. This work includes, but is not limited to, research and development of methods for acquiring renewable resource characterization information using site-specific measurements of solar radiation and meteorological conditions; collecting system performance data; and developing tools for improving the design, installation, operation, and maintenance of solar energy conversion systems. This work will be conducted at NREL and Participant facilities.

14 SOLAR ENERGY↗

Thermal Analysis and Thermal Properties of ANPZ and DNDMP

The thermal properties of ANPZ and DNDMP are reported here. These properties were measured upon request for Pantex. The following is a list of measurements requested: Density; Decomposition Energy; Pre-exponential Factor; Activation Energy; and, Thermal Conductivity. We have reported all most in SI units with the expectation that unit conversions can easily be performed by any individual reading this report. In many cases, we have provides more information than requested as it seemed relevant or necessary for performing safety calculations on these materials. The measurement methods and experimental details are described briefly in each section of this report.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SynTec Final Technical Report: Synthetic biology for Tailored Enzyme cocktails

Using a novel enzyme screening method inspired by synthetic biology, Novozymes developed new technology under SynTec which allows for more rapidly tailoring of enzyme cocktails. The methodology can be applied to specific feedstocks, and or coupled to address a specific hydrolytic conversion process context. Using combinatorial high throughput screening of libraries of enzyme domains, we can quickly assess which combination of catalytic modules delivers the best performance for a specific condition. To demonstrate the effectiveness of the screening process, we measured performance of the output catalytic cocktail compared to CTec3/HTec3. SynTec benchmark cocktail - blend of Cellic® CTec3 and HTec3. The test substrate was - ammonia fiber expansion pretreated corn stover (AFEX™ PCS).CTec3/HTec3 was assayed at the optimal pH and temperature, and also in the absence of any pH adjustment. The new enzyme cocktail discovered under SynTec was assayed in the absence of any pH adjustment and at the optimal temperature. Conversion is delivered by SynTec enzyme at significant dose reduction relative to CTec3/HTec3 at the controlled pH optimum, and without titrant required to maintain pH, which delivers additional cost savings relative to current state of the art process. In this 2.5 year $4M project, the team delivered an experimental cocktail that significantly outperformed CTec3/HTec3 for a specific substrate, and for specific hydrolysis conditions. As a means of comparing performance improvement delivered per research dollar spent, we note that SynTec delivered a similar performance improvement to the previous award, in a shorter time and with fewer resources than for the previously successful DOE project DECREASE, a 3.5 year, $25M project, though this project focused on a different substrate and used different hydrolysis conditions. The newly implemented technology for rapid sourcing of new cellulases and hemicellulases from nature is an example of Novozymes' continued innovation that results in more effective products for the advanced biofuel market.

09 BIOMASS FUELS↗

Engineering of Lead Selenide Quantum Dot Based Devices and Core/Shell Heterostructures

Near infrared (NIR) emitting colloidal quantum dots (QDs) such as PbSe are interesting materials for implementation in various optoelectronic devices such as solar cells, photodetectors, and radiation detectors. Material properties like size tunable emission wavelengths, facile solution processability, the possibility of carrier multiplication and Auger assisted up-conversion, and high Z number provide PbSe QDs with unique advantages over many currently available commercial materials used in these devices. In this dissertation, after an introduction to QDs in general, we first focus on synthesis of PbSe-based heterostructured QDs for study via optical spectroscopy. PbSe/CdSe QDs synthesized via cation exchange reaction were used as seeds to study the proper conditions for further CdSe or CdS shell growth. Optical spectroscopy studies show that growth of thicker CdSe shells leads to tunable visible emission, while growth of thick CdS shells can greatly increase the photoluminescence quantum yield (PLQY) observed from the intermediate CdSe shell. NIR PL lifetimes can be greatly enhanced by the growth of CdS shells, due to strong delocalization of the hole wavefunction within the PbSe core, while the electron is delocalized throughout the QD including in the CdS shell, resulting in radiative lifetimes in the tens of microseconds. Two pulse delay measurements show that Auger assisted up conversion is also taking place in these engineered QD dot heterostructures. In the sections that follow, we look at QD devices, first with a focus on novel devices fabricated from PbSe QDs, using an amine synthesis method that allows for facile in-solution ligand exchange. QD film mobilities are measured for PbSe QDs capped with various short ionic ligands. Carrier densities in PbSe QD films are calculated from C-V measurements, showing for the first time that carrier densities can be modulated by simply changing the capping ligand. vii Radiation detectors utilizing PbSe QDs capped with KI and NH4I ligands show tangible response to incident alpha radiation. Current output response to alpha radiation is dependent on strength of radiation source and amount of bias voltage applied. In the final section a critical review of hybrid layered 2D-QD photodetectors is presented. In a typical example, PbSe and PbS QDs act as the absorbing layer in phototransistor devices which utilize layered 2D materials such as graphene and transition metal dichalcogenides as transport layers. Resulting devices display high gains and improved directivities compared to QD only and 2D only devices.

36 MATERIALS SCIENCE↗