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Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS 2 crystals into Janus WSSe and WSe 2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS 2 transforms through WS 2(1–x) Se 2x alloys to WSe 2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

2D materials↗

Transition Core Planning and Safety Analyses in Support of LEU Fuel Conversion of the University of Missouri Research Reactor (MURR)

The University of Missouri Research Reactor (MURR®) is one of six U.S. High Performance Research Reactors (USHPRR), including one critical facility, that is working with the National Nuclear Security Administration (NNSA) Office of Material Management and Minimization (M3) Reactor Conversion Program to convert from highly enriched uranium (HEU) to low-enriched uranium (LEU) fuel. The M3 Reactor Conversion USHPRR Project objectives include the development of LEU fuel element designs that will ensure safe reactor operations and to maintain the existing experimental performance of each facility. The work is being conducted through many inter-related activities being completed by four Project Pillars: Fuel Qualification (FQ), Fuel Fabrication (FF), Reactor Conversion (RC), and Cross Cutting (CC). A new type of LEU fuel based on an alloy of uranium-10 wt% molybdenum (U-10Mo) is expected to allow the conversion of those USHPRR, like MURR, requiring higher density fuels. The very-high-density LEU U-10Mo monolithic fuel is currently undergoing irradiation testing and post-irradiation examination under a planned and documented fuel qualification effort. The FQ Pillar will document fuel property and fuel performance data and qualify the fuel for use in these reactors. The FF Pillar is fabricating fuel for ongoing and future irradiation tests, as well as conducting fabrication demonstrations to validate or update preliminary fabrication assumptions. The FF Pillar is also working to develop and install commercial manufacturing capacity with the U-10Mo monolithic fuel to produce prototypic fuel. Working with the RC Pillar at Argonne, MURR has progressed through a preliminary fuel element design using preliminary data for the proposed monolithic alloy of U-10Mo. Analyses were completed in previous work that found for typical equilibrium operations with the preliminary LEU fuel element design, in conjunction with a power uprate to 12 MW and appropriate changes to the MURR Limiting safety system settings (LSSS), MURR will have adequate margins to safety for steady-state operations and postulated transient accidents and will have experimental performance in key locations that meets or exceeds current operations with HEU fuel. The purpose of this work is to develop a sequence of transition cycles that will enable MURR to transition from operation with the reactor core loaded with fresh LEU fuel elements only to typical equilibrium operations with mixed-burnup cores following conversion while meeting operational requirements on safety and experimental performance. It is expected that the use of fresh LEU fuel at conversion and subsequent low burnup of the LEU fuel elements that will initially be available for use following conversion will result in critical control blade positions that will substantially change the axial power distribution in the core and the neutron flux available in key experimental locations relative to equilibrium LEU operations. Given the constraints of MURR safety margins, operational practices, and production and research, a novel method has been developed to identify a transition sequence that minimizes the time MURR operates atypically compared to the current prototypic cycles using HEU fuel. The proposed transition sequence moves quickly to the same sort of equilibrium cycles for the LEU fuel that have already been evaluated in documented preliminary safety analyses. Although shifting the neutron flux peak to the lower half of the core during initial cycles with LEU at 12 MW reduces the experiment performance in some key locations relative to current HEU operations at 10 MW, all LEU cores provide an average performance that meets or exceeds that of HEU. An LEU cycle is reached that meets or exceeds the level of experimental performance predicted for current HEU and equilibrium LEU operations in more than 450 key locations identified by a reactor specialist at MURR by the 23rd cycle following conversion and that afterwards will enable MURR to consistently meet its experimental performance requirements. The proposed transition sequence only requires the fabrication of 34 fresh LEU elements in the first year of operation and does not exceed the anticipated availability of fresh elements that can be produced by the fuel fabricator. By the third year after conversion, 22 fresh LEU elements will be required each year, which is the same as expected for equilibrium LEU operations and the same as current operations with HEU fuel. The proposed transition sequence thus combines a relatively short time period before equilibrium burnup is achieved, a temporary increase of fuel elements needed annually relative to typical operations that are within the production capabilities of the fuel fabricator, and demonstrates comparable experimental performance of the LEU cores relative to current HEU operations. Further measures may be taken to reduce any initial experimental performance penalty even further, where possible, by repositioning certain experiments to leverage the increased performance in the lower axial experimental positions in the initial cycles following conversion or leaving the experiments in the irradiation facilities longer in order to achieve the required neutron fluence. This analysis may require refinement depending on the experimental facilities in use at the time of conversion. Nonetheless, the results presented here, including the experimental performance, core burnup, and critical control blade positions throughout the transition cycles, show that the proposed transition cycle fuel management patterns are consistent with what is expected and desired for MURR operation with LEU U-10Mo fuel. Detailed core power distributions from the neutronics models were also used to evaluate safety margins during steady-state operations for the selected transition cycles and the equilibrium LEU core. It is shown that there are adequate safety margins for both steady-state operations and postulated accident scenarios. For the steady-state operations with the preliminary LEU fuel element design the analysis predicts at least 2.49 MW margin to the onset of flow instability at the LSSS power of 15 MW. Considering the LSSS power is 125% of full license power, the margin to OFI is sufficient. In addition, the critical heat flux ratio at LSSS power is well above the requirement of CHFR > 2.0 from NUREG-1537 for all considered cases. For postulated transient accidents, the minimum margin to the fuel temperature safety limit is at least 109 °C. In summary, the proposed sequence of core loadings for MURR operations following conversion to LEU fuel and a power uprate to 12 MW provides sufficient safety margins for both steady-state operations and postulated transient accidents during a proposed sequence of transition cycles to equilibrium operations. Analysis has shown that there are some local experimental performance penalties during the initial cycles. Although there are local shifts in the experimental performance, on average all LEU cores at 12 MW have equal or higher performance than HEU at 10 MW. Temporary adjustments are being planned that will produce suitable experimental performance during these cycles. The results indicate that for the equilibrium LEU core the experimental performance exceeds that of current HEU operations in all key locations while also demonstrating sufficient safety margins.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Targeted Adjusting Molecular Arrangement in Organic Solar Cells via a Universal Solid Additive

The incorporation of solid additive has been considered as an effective strategy for developing organic photovoltaics with multi-components, which is independent of dynamics, playing unique roles in morphology adjustment. However, their complex working mechanisms involving specific chemical structures are selective to material systems, hence limiting their university and flexibility in application. Herein, an inert small-molecular compound naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) is introduced into the bulk-heterojunction blend as the solid additive, which can function with various material systems and solvents, depending on its simple π-conjugated structure and S⋯N interaction for adjusting molecular alignment. It is interesting to note that the introduced NT can not only improve device performance, but also simplify complicated pre- or post-processing methods, reduce impact from batch-to-batch differences, construct sufficient energy transfer channel as well as improve device stability. The resulting devices based on PTzBI-dF:Y6-BO system show an impressive power conversion efficiency of 17.4% with obviously enhanced T 80 lifetime of >1200 h. These findings provide useful guidelines for exploring potential universal solid additives benefitting toward commercial application.

36 MATERIALS SCIENCE↗

A Pseudo Planar Heterojunction Structure for Eco‐Friendly Printable Organic Solar Cells Achieving 19.05% Efficiency

Abstract Obtaining a well‐accurate vertical distribution active layer morphology through the air‐printing process is an essential task for achieving efficient scalable large‐area organic solar cells (OSCs). In this target, the desired and controllable pseudo planar heterojunction (PPHJ) active layer structure with suitable phase separation is developed by pre‐deposited D18‐Cl layer under the PM6:BTP‐eC9 film via an eco‐friendly manufacturing method. The addition of the D18‐Cl regulates molecular crystallization and leads to an ideal vertical stratification while simultaneously suppressing voltage loss, optimizing energetic disorder, and carrier management. Impressively, the optimal PPHJ devices perform superior power conversion efficiencies (PCEs) of 19.05% (100 nm), 17.33% (300 nm), and 14.14% (4 cm 2 ) compared to the BHJ devices. Importantly, the PPHJ OSCs also exhibit an impressive extrapolated T 80 (the time required to reach 80% of initial PCE) of long‐time storage and operational stability, as well as thermal stability.

Chemistry↗

A Parallel Computing Framework for Finding the Supported Solutions to a Biobjective Network Optimization Problem

Abstract Solving multi‐objective combinatorial optimization problems can quickly become computationally challenging when applied to large networks generated from big data. Present‐day first‐rate Mixed Integer Programming (MIP) solvers have parallelism built‐in to take advantage of multicore architectures; but specialized network optimization algorithms that can often solve graph problems more efficiently than a general MIP solver are typically programmed serially. Thus, these network algorithm implementations do not take full advantage of modern multicore computer capabilities. Many parallel computing languages include a fork/join framework into their concurrency packages that allow for simple conversion of recursive serial algorithms to operate in parallel without having to use complicated low‐level message‐passing interfaces. Fork/join is particularly well suited to divide and conquer algorithms such as Non‐Inferior Set Estimation (NISE) method for computing the supported Pareto front of a multi‐objective optimization problem. This work develops a simple general parallel NISE (pNISE) implementation using the Java 7 concurrency tools, and then offers results from a specific implementation of solving a bi‐objective shortest path problem. The results indicate that this method is capable of sizeable speed‐ups on both small‐scale personal computers as well as large‐scale shared memory supercomputers. Finally, other network problems suitable to this method are discussed, including multi‐objective variants of the minimum spanning tree problem, transportation problem, assignment problem, maximum flow problem, and the minimum‐cost flow problem. Copyright © 2015 John Wiley & Sons, Ltd.

Medrano, Fernando Antonio↗

Synthesis and Photophysical Properties of Light-Harvesting Gold Nanoclusters Fully Functionalized with Antenna Chromophores

The development of efficient light-harvesting systems is important to understand the key aspects of solar-energy conversion processes and to utilize them in various photonic applications. In this study, atomically well-defined gold nanoclusters are reported as a new platform to fabricate artificial light-harvesting systems. An efficient amide coupling method is developed to synthesize water-soluble Au 22 clusters fully protected with pyrene chromophores by taking advantage of their facile phase-transfer reaction. The synthesized Au 22 clusters with densely packed 18 pyrene chromophores (Au 22 –PyB 18 ) exhibit triple-emission in blue, green, and red wavelength regions arising respectively from pyrene monomer, pyrene excimer, and Au 22 emission, producing bright white light emission together. The photoluminescence of Au 22 is enhanced by more than tenfold, demonstrating that pyrenes at the periphery efficiently channel the absorbed energy to the luminescent Au 22 at the center. A combination of femtosecond transient absorption and anisotropy measurements of Au 22 –PyB 18 explicitly reveals three main decay components of 220 fs, 3.5 ps, and 160 ps that can be assigned to energy migration between pyrenes and energy transfer processes from pyrene monomer and excimer to the central Au 22 , respectively.

14 SOLAR ENERGY↗

Predicting the evolution of biomass bulk density through feedstock preprocessing: Discrete element modeling, regression analysis, and pilot-scale validation

Bulk density is an important material property of biomass feedstocks, influencing handling, storage, transport costs, and conversion efficiency. In this study, predictive regression models for loose and tapped bulk densities of Alamo and Cave-in-Rock switchgrass are developed using a comprehensive dataset generated via calibrated bonded-sphere discrete element method (DEM) simulations. Here, a key contribution of this study is the use of a DEM-based approach, which correlates density with moisture content and particle size distribution parameters and enables analysis across a continuous particle size range, overcoming limitations of purely experimental data. For comparison, regression models are also developed using only experimental data from pilot-scale runs at the Biomass Feedstock National User Facility at Idaho National Laboratory. Validation against pilot-scale data showed reasonable prediction accuracy for both model types, particularly for smaller particle sizes (post-secondary grinding). While the experimental model showed slightly better performance matching the validation data in some cases, the DEM-based model benefits from a much larger dataset, reduced predictor multicollinearity, and continuous parameter coverage, highlighting the utility of validated simulation models for developing robust predictive tools for biomass preprocessing applications.

09 - BIOMASS FUELS↗

Palladium was supported on superparamagnetic nanoparticles: A magnetically recoverable catalyst for Heck reaction

Highlights: Black-Right-Pointing-Pointer Palladium-based heterogeneous catalyst was prepared facilely via the co-precipitation method. Black-Right-Pointing-Pointer The particles are nearly spherical in shape with an average size of 20 {+-} 1.0 nm. Black-Right-Pointing-Pointer The developed magnetic catalyst showed high activity for Heck reaction. Black-Right-Pointing-Pointer The catalyst was easily recovered from the reaction mixture with external magnetic field. Black-Right-Pointing-Pointer The catalytic efficiency for Heck reaction remains unaltered even after 6 repeated cycles. -- Abstract: A novel and high-performance palladium-based catalyst for Heck reaction was prepared easily by the co-precipitation method. The catalyst was characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS) and atomic absorption spectrophotometry (AAS). The catalyst afforded a fast conversion of the 4-bromonitrobenzene to 4-nitrostilbene at a catalyst loading of 5 mol%, and the efficiency of the catalyst remains unaltered even after 6 repeated cycles. The excellent catalytic performance of the Pd/Fe{sub 3}O{sub 4} catalyst might be attributed to the enhanced synergistic effect between Pd nanoparticles and magnetite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Colorful Perovskite Solar Cells Using a Top Polymer Electrode Simultaneously as Spectrally Selective Antireflection Coating

Organometal halide perovskites have demonstrated excellent optoelectronic properties and have been used to demonstrate a variety of semiconductor devices. Colorful solar cells are desirable for photovoltaic integration in buildings and other aesthetically appealing applications. Yet, the realization of colorful perovskite solar cells is challenging because of their broad and large absorption coefficient that commonly leads to cells with dark-brown colors. Herein, for the first time, we report a simple and efficient strategy to achieve colorful perovskite solar cells by using the transparent conducting polymer (poly(3,4-ethylenedioxythiophene):poly- (styrenesulfonate), PEDOT:PSS) as a top electrode and simultaneously as an spectrally selective antireflection coating. Vivid colors across the visible spectrum are attained by engineering optical interference effects among the transparent PEDOT:PSS polymer electrode, the hole-transporting layer and the perovskite layer. The colored perovskite solar cells display power conversion efficiency values from 12.8 to 15.1% (from red to blue) when illuminated from the FTO glass side and from 11.6 to 13.8% (from red to blue) when illuminated from the PEDOT:PSS side. The new method offers an advanced solution for fabricating colorful perovskite solar cells with easy processing and high efficiency.

42 ENGINEERING↗

Thienopyrroledione-Based Photosensitizers as Strong Photoinduced Oxidants: Oxidation of Fe(bpy) 3 2+ in a >1.3 V Dye-Sensitized Solar Cell

The creation of visible light absorbing organic dyes as strong photoinduced oxidants is needed for many potential applications in energy production and storage. In order to access more positive potentials, the electron deficient thienopyrroledione building block is promising as a π-bridge combined with weak aryl-ether donor groups and the phenyl-cyanoacetic acid acceptor group. The thienopyrroledione (TPD) building block is compared to the ubiquitous benzothiadiazole (BTD) building block which was recently used in a dye-sensitized solar cell (DSC) device with >1.4 V photovoltage output. The variation in dye donor group is studied through UV-Vis absorption spectroscopy and electrochemical methods both in solution and on TiO2 films. The TPD building block resulted in a more positive ground state and excited state oxidation potential, a higher photocurrent (up to 3.5 mA/cm 2 ), and a higher power conversion efficiency (up to 2.9%) than a BTD analogue while retaining comparable photovoltages (~1.3 V versus ~1.4 V). Computational analysis was used to better understand the optical properties of the thienopyrroledione-based dyes showing overlap of orbitals at the TPD bridge in the S 0 and S 1 states. The dyes were analyzed in high voltage-DSC devices with a challenging to oxidize redox shuttle, [Fe(bpy) 3 ] 2+ , at 1.37 V versus NHE.

25 ENERGY STORAGE↗

Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites

Transition metal-oxo centers in zeolites are known to be active in the conversion of methane to methanol. In this work, we examine this reaction over Fe-oxo sites in the zeolite SSZ-13. By comparing calculations for the fully periodic structure and a cluster for two different methods—the standard van der Waals corrected semilocal density functional PBE-D2 and ACFDT-RPA, which is a method where correlation is calculated fully nonlocally—we find that it is actually the confining environment in the zeolite that reduces the barrier for this reaction, by more than 50%, and we find that the two applied methods lead to qualitatively different ends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast Photoflash Synthesis of High-Entropy Oxide Nanoparticles

High-entropy metal oxides (HEOs) have recently received growing attention for broad energy conversion and storage applications due to their tunable properties. HEOs typically involve the combination of multiple metal cations in a single oxide lattice, thus bringing distinctive structures, controllable elemental composition, and tunable functional properties. Many synthesis methods for HEOs have been reported, such as solid-state reactions and carbon thermal shock methods. These methods frequently are energy-intensive or require relatively expensive heating equipment. In this work, we report an ultrafast photoflash synthesis method for HEO nanoparticles on diverse substrates. The energy input is provided by a commercial Xe photoflash unit, which triggers exothermic reactions to convert metal salt precursors to HEO nanoparticles within tens of milliseconds. The formation of HEO nanoparticles is attributed to the ultrafast heating (∼106 K/s) and cooling (∼105 K/s) rates of the photoflash and overall high temperature (>1000 K) during the ultrafast synthesis process. When the synthesized CoNiFeCrMn oxide (HEO) is tested as an oxygen evolution reaction electrocatalyst, it shows similar activity to similar materials prepared by other methods. We believe this photoflash synthesis provides a simple method for many others to synthesize diverse HEOs and explore their properties and potential applications.

exothermic reaction synthesis↗

Fabrication and characterization of photovoltaic devices based on perovskite compounds with TiO{sub 2} nanoparticles

Perovskite-type photovoltaic devices were fabricated by a spin-coating method using a mixture solution. The compact and meso-porous TiO{sub 2} of the solar cells were fabricated from TiO{sub 2} nanoparticles and sol, and the photovoltaic properties and microstructures were characterized. The conversion efficiencies were improved by the combination of TiO{sub 2} nanoparticles and sol. Current density was also improved by increasing numbers of spin-coatings of meso-porous TiO{sub 2}. Thick meso-porous TiO2 layers would assist the construction of perovskite layers and block of the leak current.

36 MATERIALS SCIENCE↗

Numerical investigation of non-perturbative kinetic effects of energetic particles on toroidicity-induced Alfvén eigenmodes in tokamaks and stellarators

The resonant interaction of shear Alfvén waves with energetic particles is investigated numerically in tokamak and stellarator geometry using a non-perturbative MHD-kinetic hybrid approach. The focus lies on toroidicity-induced Alfvén eigenmodes (TAEs), which are most easily destabilized by a fast-particle population in fusion plasmas. While the background plasma is treated within the framework of an ideal-MHD theory, the drive of the fast particles, as well as Landau damping of the background plasma, is modelled using the drift-kinetic Vlasov equation without collisions. Building on analytical theory, a fast numerical tool, STAE-K, has been developed to solve the resulting eigenvalue problem using a Riccati shooting method. The code, which can be used for parameter scans, is applied to tokamaks and the stellarator Wendelstein 7-X. High energetic-ion pressure leads to large growth rates of the TAEs and to their conversion into kinetically modified TAEs and kinetic Alfvén waves via continuum interaction. To better understand the physics of this conversion mechanism, the connections between TAEs and the shear Alfvén wave continuum are examined. It is shown that, when energetic particles are present, the continuum deforms substantially and the TAE frequency can leave the continuum gap. The interaction of the TAE with the continuum leads to singularities in the eigenfunctions. To further advance the physical model and also to eliminate the MHD continuum together with the singularities in the eigenfunctions, a fourth-order term connected to radiative damping has been included. The radiative damping term is connected to non-ideal effects of the bulk plasma and introduces higher-order derivatives to the model. Thus, it has the potential to substantially change the nature of the solution. For the first time, the fast-particle drive, Landau damping, continuum damping, and radiative damping have been modelled together in tokamak- as well as in stellarator geometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Theory, observations, and simulations of kinetic entropy in a magnetotail electron diffusion region

In this work, we examine velocity-space kinetic entropy, a spatially local measure of entropy for systems out of thermal equilibrium, during an encounter of an electron diffusion region at a magnetic reconnection site in Earth’s magnetotail by the Magnetospheric Multiscale (MMS) mission. We start by generalizing the theory of kinetic entropy to the case of non-uniform velocity space grids and transforming the equations into spheri- cal energy coordinates useful to experimental plasma detectors. The theory is then applied to MMS data and compared to particle-in-cell simulations of reconnection. We demonstrate that the entropy-based non-Maxwellianity measure from the MMS data is of sufficiently high precision to reliably identify non-Maxwellian distributions and therefore the measurements when kinetic effects are most significant. By comparing two different non-Maxwellian measures, we show that total entropy density suffers from “information loss” because it lacks a dependence on the velocity space grid, and so has lost information about how well a distribution function is resolved. Local velocity-space kinetic entropy density recovers this information. We quantify information loss and argue that the considerations needed to minimize it are crucial for instruments designed to measure distribution functions in situ.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

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↗