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At least 433 records · Page 24

A Review of Diagnostic Techniques for ISHM Applications

System diagnosis is an integral part of any Integrated System Health Management application. Diagnostic applications make use of system information from the design phase, such as safety and mission assurance analysis, failure modes and effects analysis, hazards analysis, functional models, fault propagation models, and testability analysis. In modern process control and equipment monitoring systems, topological and analytic , models of the nominal system, derived from design documents, are also employed for fault isolation and identification. Depending on the complexity of the monitored signals from the physical system, diagnostic applications may involve straightforward trending and feature extraction techniques to retrieve the parameters of importance from the sensor streams. They also may involve very complex analysis routines, such as signal processing, learning or classification methods to derive the parameters of importance to diagnosis. The process that is used to diagnose anomalous conditions from monitored system signals varies widely across the different approaches to system diagnosis. Rule-based expert systems, case-based reasoning systems, model-based reasoning systems, learning systems, and probabilistic reasoning systems are examples of the many diverse approaches ta diagnostic reasoning. Many engineering disciplines have specific approaches to modeling, monitoring and diagnosing anomalous conditions. Therefore, there is no "one-size-fits-all" approach to building diagnostic and health monitoring capabilities for a system. For instance, the conventional approaches to diagnosing failures in rotorcraft applications are very different from those used in communications systems. Further, online and offline automated diagnostic applications are integrated into an operations framework with flight crews, flight controllers and maintenance teams. While the emphasis of this paper is automation of health management functions, striking the correct balance between automated and human-performed tasks is a vital concern.

Patterson-Hine, Ann↗

Data Movement Dominates: Final Report

Over the past three years in this project, what we have observed is that the primary reason for data movement in large-scale systems is that the per-node capacity is not large enough—i.e., one of the solutions to the data-movement problem (certainly not the only solution that is required, but a significant one nonetheless) is to increase per-node capacity so that inter-node traffic is reduced. This unfortunately is not as simple as it sounds. Today’s main memory systems for datacenters, enterprise computing systems, and supercomputers, fail to provide high per-socket capacity [Dirik & Jacob 2009; Cooper-Balis et al. 2012], except at extremely high price points (factors of 10–100x the cost/bit of consumer main-memory systems) [Stokes 2008]. The reason is that our choice of technology for today’s main memory systems—i.e., DRAM, which we have used as a main-memory technology since the 1970s [Jacob et al. 2007]—can no longer keep up with our needs for density and price per bit. Main memory systems have always been built from the cheapest, densest, lowest-power memory technology available, and DRAM is no longer the cheapest, the densest, nor the lowest-power storage technology out there. It is now time for DRAM to go the way that SRAM went: move out of the way for a cheaper, slower, denser storage technology, and become a cache instead. This inflection point has happened before, in the context of SRAM yielding to DRAM. There was once a time that SRAM was the storage technology of choice for all main memories [Tomasulo 1967; Thornton 1970; Kidder 1981]. However, once DRAM hit volume production in the 1970s and 80s, it supplanted SRAM as a main memory technology because it was cheaper, and it was denser. It also happened to be lower power, but that was not the primary consideration of the day. At the time, it was recognized that DRAM was much slower than SRAM, but it was only at the supercomputer level (For instance the Cray X-MP in the 1980s and its follow-on, the Cray Y-MP, in the 1990s) that could one afford to build ever- larger main memories out of SRAM—the reasoning for moving to DRAM was that an appropriately designed memory hierarchy, built of DRAM as main memory and SRAM as a cache, would approach the performance of SRAM, at the price-per-bit of DRAM [Mashey 1999]. Today it is quite clear that, were one to build an entire multi-gigabyte main memory out of SRAM instead of DRAM, one could improve the performance of almost any computer system by up to an order of magnitude—but this option is not even considered, because to build that system would be prohibitively expensive. It is now time to revisit the same design choice in the context of modern technologies and modern systems. For reasons both technical and economic, we can no longer afford to build ever-larger main memory systems out of DRAM. Flash memory, on the other hand, is significantly cheaper and denser than DRAM and therefore should take its place. While it is true that flash is significantly slower than DRAM, one can afford to build much larger main memories out of flash than out of DRAM, and we show that an appropriately designed memory hierarchy, built of flash as main memory and DRAM as a cache, will approach the performance of DRAM, at the price-per-bit of flash. In our studies as part of this project, we have investigated Non-Volatile Main Memory (NVMM), a new main-memory architecture for large-scale computing systems, one that is specifically designed to address the weaknesses described previously. In particular, it provides the following features: non-volatility: The bulk of the storage is comprised of NAND flash, and in this organization DRAM is used only as a cache, not as main memory. Furthermore, the flash is journaled, which means that operations such as checkpoint/restore are already built into the system. 1+ terabytes of storage per socket: SSDs and DRAM DIMMs have roughly the same form factor (several square inches of PCB surface area), and terabyte SSDs are now commonplace. performance approaching that of DRAM: DRAM is used as a cache to the flash system. price-per-bit approaching that of NAND: Flash is currently well under $0.50 per gigabyte; DDR3 SDRAM is currently just over $10 per gigabyte [Newegg 2014]. Even today, one can build an easily affordable main memory system with a terabyte or more of NAND storage per CPU socket (which would be extremely expensive were one to use DRAM), and our cycle- accurate, full-system experiments show that this can be done at a performance point that lies within a factor of two of DRAM.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Development of Preliminary Remediation Goals for Indoor Dust at the Colonie FUSRAP Site - 12273

The Colonie FUSRAP Site is located in the Town of Colonie, Albany County, New York. The U.S. Army Corps of Engineers is currently addressing environmental contamination associated with the Site under the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) process as part of the Formerly Utilized Sites Remedial Action Program (FUSRAP). Soil remediation activities have been substantially completed at the Colonie FUSRAP Site and its vicinity properties under the FUSRAP. A study unrelated to FUSRAP was recently performed by an independent party to establish the distribution of DU contamination in various media in the environs of the Site. As part of this study, dust samples were collected in residencies and businesses in the immediate vicinity of the Site. These samples were collected in non-living areas such as basement window sills and garages. Many of these samples tested positive for DU. An assessment was performed to establish preliminary remediation goals (PRGs) for indoor dust in non-living areas of residential homes and businesses in the vicinity of the Site. The results of this assessment provide estimates of dose-based, carcinogenic risk-based, and noncarcinogenic-based PRGs derived from a hypothetical exposure scenario with reasonable levels of conservatism. Ultimately, the PRGs will be compared to results of dust sampling and analyses in residences and businesses in proximity of the Site to determine whether a response action is appropriate. This assessment estimates PRGs for DU contaminated dust in non-living areas of residences in the vicinity of the Colonie FUSRAP site based on a reasonably conservative exposure scenario. Estimated PRGs based on residential receptors are considered to be conservatively representative of workers in nearby businesses based on the considerably longer exposure duration of residents relative to workers. This assessment provides reasonably conservative estimates of PRGs for DU contaminated dust in non-living areas within residences in the vicinity of the Site. It should be noted that the PRGs include hypothetical exposures resulting from activities in both the living areas and non-living areas of a residence. The PRGs are derived and presented in terms of DU dust concentration in non-living areas to facilitate comparison to results of a planned Site Investigation that will characterize concentrations of DU in dust in non-living areas. It is important to recognize that the exposure assumptions used to derive these PRGs are based on average dust DU concentrations in non-living areas. It is inappropriate to compare these PRGs to the dust DU concentration in an isolated small area. The ongoing Site Investigation addresses this consideration and is designed to provide reasonable estimates of average dust DU concentrations in non-living areas of vicinity properties. In order to accomplish this, sampling is conducted in accordance with EPA Guidance for the Sampling and Analysis of Lead in Indoor Residential Dust for Use in the Integrated Exposure Uptake Biokinetic (IEUBK) Model, (EPA 2008), which specifically addresses estimating average contaminant concentrations in dust. Four (4) large-area samples are collected from each VP in accordance with this guidance. It is anticipated that the results of the Site Investigation will be used in conjunction with the results of this assessment, and/or subsequent assessments, to establish whether or not a response action is appropriate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Can Large Language Models Understand Intermediate Representations?

Intermediate Representations (IRs) are essential in compiler design and program analysis, yet their comprehension by Large Language Models (LLMs) remains underexplored. This paper presents a pioneering empirical study to investigate the capabilities of LLMs, including GPT-4, GPT-3, Gemma 2, LLaMA 3.1, and Code Llama, in understanding IRs. We analyze their performance across four tasks: Control Flow Graph (CFG) reconstruction, decompilation, code summarization, and execution reasoning. Our results indicate that while LLMs demonstrate competence in parsing IR syntax and recognizing high-level structures, they struggle with control flow reasoning, execution semantics, and loop handling. Specifically, they often misinterpret branching instructions, omit critical IR operations, and rely on heuristic-based reasoning, leading to errors in CFG reconstruction, IR decompilation, and execution reasoning. The study underscores the necessity for IR-specific enhancements in LLMs, recommending fine-tuning on structured IR datasets and integration of explicit control flow models to augment their comprehension and handling of IR-related tasks.

Jiang, Hailong↗

Framing Potential Wildfire Opportunities for DRF

A Data & Reasoning Fabric (DRF) is envisioned to enable the full potential of air mobility by providing all data and reasoning where they are needed. The DRF provides a marketplace based on an open foundational ecosystem of data and reasoning exchange between the many systems that must seamlessly interplay to manage the complex and dense airspace operations required to achieve advanced air mobility goals. The DRF marketplace is decentralized and will not be owned by any single party. To deliver reference designs and development environments that catalyze broad private and public sector buy-in and self-sustaining development of DRF and associated standards, DRF activities will collaboratively test these technologies, open standards and architectures, and an integrated framework with end-users.

Aeronautics↗

A Two-length Scale Turbulence Model for Single-phase Multi-fluid Mixing

A two-length scale, second moment turbulence model (Reynolds averaged Navier-Stokes, RANS) is proposed to capture a wide variety of single-phase flows, spanning from incompressible flows with single fluids and mixtures of different density fluids (variable density flows) to flows over shock waves. The two-length scale model was developed to address an inconsistency present in the single-length scale models, e.g. the inability to match both variable density homogeneous Rayleigh-Taylor turbulence and Rayleigh-Taylor induced turbulence, as well as the inability to match both homogeneous shear and free shear flows. The two-length scale model focuses on separating the decay and transport length scales, as the two physical processes are generally different in inhomogeneous turbulence. This allows reasonable comparisons with statistics and spreading rates over such a wide range of turbulent flows using a common set of model coefficients. The specific canonical flows considered for calibrating the model include homogeneous shear, single-phase incompressible shear driven turbulence, variable density homogeneous Rayleigh-Taylor turbulence, Rayleigh-Taylor induced turbulence, and shocked isotropic turbulence. The second moment model shows to compare reasonably well with direct numerical simulations (DNS), experiments, and theory in most cases. The model was then applied to variable density shear layer and shock tube data and shows to be in reasonable agreement with DNS and experiments. Additionally, the importance of using DNS to calibrate and assess RANS type turbulence models is highlighted.

04 OIL SHALES AND TAR SANDS↗

A Bayesian View on the Dr. Evil Scenario

Abstract In Defeating Dr. Evil with Self-Locating Belief , Adam Elga proposes and defends a principle of indifference for self-locating beliefs: if an individual is confident that his world contains more than one individual who is in a state subjectively indistinguishable from his own, then he should assign equal credences to the hypotheses that he is any one of these individuals. Through a sequence of thought experiments, Elga in effect claims that he can derive the credence function that should apply in such situations, thus justifying his principle of indifference. Here we argue, using a Bayesian approach, that Elga’s reasoning is circular: in analyzing the third of his thought experiments, he uses an assertion that is justifiable only if one assumes, from the start, the principle of indifference that he is attempting to justify. We agree with Elga that the assumption of equal credences is a very reasonable principle, in the absence of any reason to assign unequal credences, but we do not agree that the equality of credences can be so derived.

Azhar, Feraz↗

Frequency-Dependent Enhancement of Fluid Intelligence Induced by Transcranial Oscillatory Potentials

Everyday problem solving requires the ability to go beyond experience by efficiently encoding and manipulating new information, i.e., fluid intelligence (Gf) [1]. Performance in tasks involving Gf, such as logical and abstract reasoning, has been shown to rely on distributed neural networks, with a crucial role played by prefrontal regions [2]. Synchronization of neuronal activity in the gamma band is a ubiquitous phenomenon within the brain; however, no evidence of its causal involvement in cognition exists to date [3]. Here, we show an enhancement of Gf ability in a cognitive task induced by exogenous rhythmic stimulation within the gamma band. Imperceptible alternating current [4] delivered through the scalp over the left middle frontal gyrus resulted in a frequency-specific shortening of the time required to find the correct solution in a visuospatial abstract reasoning task classically employed to measure Gf abilities (i.e., Raven’s matrices) [5]. Crucially, gamma-band stimulation (γ-tACS) selectively enhanced performance only on more complex trials involving conditional/logical reasoning. The finding presented here supports a direct involvement of gamma oscillatory activity in the mechanisms underlying higher-order human cognition.

59 BASIC BIOLOGICAL SCIENCES↗

Contribution of climate and land cover changes to reduction in soil erosion rates within small cultivated catchments in the eastern part of the Russian Plain during the last 60 years

Highlights: • The soil erosion has decreased at least 2–3 times over the last 30 years at the RP. • The increase in winter air temperature is the key reason for the soil loss reduction. • The crop rotation changes is the factor of erosion rate reduction at the forest zone. The eastern part of the Russian Plain is an important agricultural region of European Russia with high proportion of cultivated lands in the steppe, forest-steppe and forest (southern part) landscape zones. Soil erosion is the main process of land degradation and surface water contamination there. Climate and land cover changes have been observed in this region during the last 30 years. However, field quantitative assessments of soil erosion rates are not available for the eastern part of European Russia due to the lack of monitoring data as well as the evaluation of erosion/deposition processes in cultivated catchments using other field methods. Three representative small cultivated catchments with high (> 80%) proportion of cultivated lands were selected in the forest (southern part), forest-steppe and steppe zones of the study region to evaluate sedimentation rates in dry valley bottoms of the catchments for two-time intervals (1963–1986 and 1987–2016) based on the application of the bomb-derived and Chernobyl-derived {sup 137}Cs isotope for sediment dating. The 3–4 depth {sup 137}Cs profiles were used to assess the sedimentation rates within the each investigated catchment. It was established that the sedimentation rates have considerably decreased (at least 2–3 times) over the last 30 years compared to 1963–1986 in all the investigated catchments. This is in agreement with results of erosion rate calculations using erosion models for the forest zone, however not consistent with erosion rates assessments for the forest-steppe and steppe zones. According to the model calculations, erosion rates show a slight decrease in the forest-steppe zone and increase in the steppe zone. The reduction in surface runoff during snowmelt period is one of the reasons for decrease in erosion rates within cultivated slopes for all the investigated catchments. The increase in proportion of perennial grasses in the regional crop rotation is another important reason for the decrease in erosion rates for the catchment located in the south of the forest zone. The importance of land cover changes in a major decrease of soil losses from the cultivated fields of the investigated catchments located in the forest-steppe and steppe zones cannot be identified due to the lack detailed information about crop rotation for those particular sites. However, available regional information about crop rotation changes for the two-time intervals (1960–1980 and 1996–2012) do not explain very high reduction in sedimentation rates in the dry valley bottoms after 1986.

54 ENVIRONMENTAL SCIENCES↗

Advanced manufacturing—A transformative enabling capability for fusion

Additive Manufacturing (AM) can create novel and complex engineered material structures. Features such as controlled porosity, micro-fibers and/or nano-particles, transitions in materials and integral robust coatings can be important in developing solutions for fusion subcomponents. A realistic understanding of this capability would be particularly valuable in identifying development paths. Major concerns for using AM processes with lasers or electron beams that melt powder to make refractory parts are the power required and residual stresses arising in fabrication. A related issue is the required combination of lasers or e-beams to continue heating of deposited material (to reduce stresses) and to deposit new material at a reasonable built rate while providing adequate surface finish and resolution for meso-scale features. Some Direct Write processes that can make suitable preforms and be cured to an acceptable density may offer another approach for PFCs.

Additive Manufacturing, fusion energy, Fusion Mate↗

Advective gas flow in bentonite: Development and comparison of enhanced multi-phase numerical approaches

Understanding the impact of repository gas, generated from degradation of waste and its interaction with the host rock, is essential when assessing the performance and safety function of long-term disposal systems for radioactive waste. Numerical models based on conventional multi-phase flow theory have historically been applied to predict the outcome and impact of gas flow on different repository components. However, they remain unable to describe the full complexity of the physical processes observed in water-saturated experiments (e.g., creation of dilatant pathways) and thus, the development of novel representations for their description is required when assessing fully saturated clay-based systems. This was the primary focus of Task A within the international cooperative project DECOVALEX-2019 (D-2019) and refinement of these approaches is the primary focus of this study (Task B in the current phase of DECOVALEX-2023). This paper summarises development of enhanced numerical representations of key processes and compares the performance of each model against high-quality laboratory test data. Experimental data reveals that gas percolation in water-saturated compacted bentonite is characterised by four key features: (i) a quiescence phase, followed by (ii) the gas breakthrough, which leads to a (iii) peak value, which is then followed by (iv) a negative decay. Three models based on the multiphase flow theory have been developed. These models can provide good initial values and reasonable responses for gas breakthrough (although some of them still predict a too-smooth response). Peak gas pressure values are in general reasonably well captured, although maximum radial stress differences are observed at 48 mm from the base of the sample. Here, numerical peak values of 12.8 MPa are predicted, whereas experimental values are about 11 MPa. These models are also capable of providing a reasonable representation of the negative pressure decay following peak pressure. However, other key specific features (such as the timing of gas breakthrough) still require a better representation. The model simulations and their comparison with experimental data show that these models need to be further improved with respect to model parameter calibration, the numerical representation of spatial heterogeneities in material properties and flow localisation, and the upscaling of the related physical processes and parameters. To further understand gas flow localisation, a new conceptual model has been developed, which shows that discrete channels can possibly be induced through the instability of gas-bentonite interface during gas injection, thus providing a new perspective for modeling gas percolation in low-permeability deformable media.

58 GEOSCIENCES↗

Experimental workflow to estimate model parameters for evaluating long term viscoelastic response of CO2 storage caprocks

Understanding the time-dependent behavior of reservoir and sealing formations is critical to assessing risks associated with geological carbon storage since time-dependent deformation strongly influences mechanical responses of some rock types. Many studies have evaluated the risk of CO2 leakage and induced seismicity by assuming poroelastic rheology in sealing formations. Few have considered viscoelastic or other time-dependent responses, where the existing literature adopts 1D models to represent long-term time-dependent responses. This is primarily because to date, the general form of a reasonable 3D time-dependent model for rocks remains unclear. In this paper, we address this unclear issue by proposing a new workflow to select constitutive modeling parameters to evaluate if a 3D viscoelastic model is reasonable using several-hour-long experimental data and a power-law response to extrapolate to the decades-long time frames of interest in geologic carbon storage. To provide experimental data, we conducted multi-level loading/unloading triaxial relaxation tests with four rock types. The experimental results showed that the maximum load relaxation observed is approximately 49%, with some rock types showing as little as 1.4%. Using a simple linear viscoelastic model, parameters were chosen such that a maximum deviation of 1.5 MPa in axial stress and 7 MPa in radial stress was attained with the extrapolated 30-year data. We found that a reasonable parameter range for the normalized elastic modulus is 0.1~2 for rocks with significant time-dependent responses and 0.01~0.06 for those with small time-dependent responses. No matter how significant time-dependent responses are for rocks considered, our results showed that the relaxation time has a general range of 1~10^10 s, whose time scale can be one or two orders higher than a time frame typically envisioned for CO2 injection projects.

Stress relaxation, 3D time-dependent model, viscoe↗

Bayesian Inversion of Seismic and Electromagnetic Data for Marine Gas Reservoir Characterization Using Multi-chain Markov Chain Monte Carlo Sampling

In this study we developed an efficient Bayesian inversion framework for interpreting marine seismic amplitude versus angle (AVA) and controlled source electromagnetic (CSEM) data for marine reservoir characterization. The framework uses a multi-chain Markov-chain Monte Carlo (MCMC) sampler, which is a hybrid of DiffeRential Evolution Adaptive Metropolis (DREAM) and Adaptive Metropolis (AM) samplers. The inversion framework is tested by estimating reservoir-fluid saturations and porosity based on marine seismic and CSEM data. The multi-chain MCMC is scalable in terms of the number of chains, and is useful for computationally demanding Bayesian model calibration in scientific and engineering problems. As a demonstration, the approach is used to efficiently and accurately estimate the porosity and saturations in a representative layered synthetic reservoir. The results indicate that the seismic AVA and CSEM joint inversion provides better estimation of reservoir saturations than the seismic AVA-only inversion, especially for the parameters in deep layers. The performance of the inversion approach for various levels of noise in observational data was evaluated – reasonable estimates can be obtained with noise levels up to 25%. Sampling efficiency due to the use of multiple chains was also checked and was found to have almost linear scalability.

Ren, Huiying↗

Voltammetry measurements in lithium chloride-lithium oxide (LiCl–Li 2 O) salt: An evaluation of working electrode materials

Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

90° Rotation of orbital stripes in bilayer manganite PrCa{sub 2}Mn{sub 2}O{sub 7} studied by in situ transmission electron microscopy

We present an in situ transmission electron microscopy study on the half-doped bilayer manganite PrCa{sub 2}Mn{sub 2}O{sub 7} to reveal the rotation process of the orbital stripes. Between the reported initial and final ordering phases, we identified an intermediate state with two sets of satellite spots to bridge the 90° rotation of the orbital stripes. Furthermore, we determined that the rotation of the orbital stripes does not always occur. Some restricted conditions for the orbital rotation to occur were found and reasons are discussed. - Graphical abstract: The intermediate state of the thermally induced 90° rotation of orbital stripes between two charge/orbital ordering CO1 and CO2 phase in the bilayer manganite PrCa{sub 2}Mn{sub 2}O{sub 7} is revealed by in situ TEM. A new state with two sets of satellite spots in the [001] electron diffraction patterns is found to bridge this transition. The reasons to this transition are explained. Highlights: ► Intermediate states to bridge the 90° rotation of the orbital stripes in bilayer manganite PrCa{sub 2}Mn{sub 2}O{sub 7} were identified. ► Some restricted conditions for the orbital rotation to occur were found and reasons were discussed. ► The reported CO2 phase at high temperatures in PrCa{sub 2}Mn{sub 2}O{sub 7} can also exist at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of aluminum substitution on photocatalytic property of BiVO{sub 4} under visible light irradiation

Graphical abstract: Visible-light-driven Al/BiVO{sub 4} photocatalyst was prepared by a hydrothermal process. After introducing Al, the BiVO{sub 4} particles retain monoclinic scheelite structures and the ability of visible light absorption is enhanced. XPS and FTIR results reveal that the Al ions influence the local structure of the BiVO{sub 4}. The photocatalytic experiments demonstrate that the Al species incorporation can effectively enhance the photocatalytic activity of BiVO{sub 4} due to the existence of distorted VO{sub 4}{sup 3-} tetrahedron and the stronger optical absorption intensity. Highlights: Black-Right-Pointing-Pointer The visible-light-driven Al/BiVO{sub 4} photocatalysts are first prepared in our study. Black-Right-Pointing-Pointer It is found that Al is introduced into the BiVO{sub 4} lattice successfully. Black-Right-Pointing-Pointer The Al-doped BiVO{sub 4} shows a far higher photocatalytic activity than undoped BiVO{sub 4}. Black-Right-Pointing-Pointer One of the reason for the higher activity is the distorted VO{sub 4}{sup 3-} tetrahedron. Black-Right-Pointing-Pointer Another reason for the higher activity is the strong optical absorption intensity. -- Abstract: Novel visible-light-driven Al/BiVO{sub 4} photocatalysts were synthesized via a facile hydrothermal method for the first time. The samples were characterized by X-ray diffraction, N{sub 2}-sorption, UV-vis diffuse reflectance spectra, scanning electron microscopy, high-resolution transmission electron microscopy, Fourier transformed infrared spectra and X-ray photoelectron spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of methylene blue under visible light irradiation (400 nm < {lambda} <580 nm) and was compared with that of single-phase BiVO{sub 4}. The results revealed that the introduction of Al can improve photocatalytic performance greatly and different concentration of Al resulted in different photocatalytic activity. The highest activity is obtained by the sample with a doping concentration of 12 at%. The reason for the enhanced photocatalytic activities of Al/BiVO{sub 4} samples was also discussed in this paper.

36 MATERIALS SCIENCE↗

Development of photocatalyst by combined nitrogen and yttrium doping

Graphical abstract: The simulated compensated YN{sub SUB} co-doped TiO{sub 2} model can reasonably explain the experimental observations. Calculation results show that substitutional Y at Ti sites and substitutional N at O sites with an oxygen vacancy give stable configuration, reduced band gap, better visible light absorption and enhance separations of photoexcited charge carriers. The experimental observations confirmed the theoretical findings. - Highlights: • (Y, N) codoped TiO{sub 2} was synthesized by mild one pot hydrothermal method. • The Y doping concentration was varied from 0.01 to 1.38 at%. • 0.05% (Y, N) codoped TiO{sub 2} shows enhanced visible light photocatalytic activity. • Compensated and noncompensated ab-initio calculations were performed. • Calculation results reasonably explained the experimental findings. - Abstract: Titanium dioxide co-doped with yttrium and nitrogen with different yttrium doping concentration has been synthesized by mild one pot hydrothermal method without any post calcination for crystallization. Irrespective of the yttrium doping concentration, all the synthesized samples were composed of pure anatase phase with good crystallinity. And the synthesized co-doped samples have spherical morphology with uniform particle size distribution. The absorption edge of the co-doped TiO{sub 2} was shifted toward visible light region depicting that the intrinsic band gap of TiO{sub 2} was affected by the co-doping. Among the different samples, the co-doped sample with 0.05% yttrium doping concentration exhibits enhanced visible light photocatalytic activity by degradation of methylene blue in aqueous solution. Compensated and non-compensated yttrium–nitrogen co-doped TiO{sub 2} models were simulated using density functional theory to explain the experimental findings. The calculation results show that the compensated yttrium–nitrogen co-doped TiO{sub 2} model may reasonably explain the experimental observations due to its stable configuration, narrowed band gap and enhanced separation of photoexcited carriers.

36 MATERIALS SCIENCE↗

25 Mg NMR and Computational Modeling Studies of the Solvation Structures and Molecular Dynamics in Magnesium Based Liquid Electrolytes

There is increasing evidence that the solvation structure of the active components in a liquid electrolyte solution strongly impacts the performance in electrochemical applications. In this work, the nanoscale solvation structures and dynamics of Mg(BH 4 ) 2 and Mg(TFSI) 2 dissolved in diglyme (DGM) at various concentrations and ratios of Mg(BH 4 ) 2 /Mg(TFSI) 2 were investigated using a combination of natural abundance 25 Mg NMR, quantum chemistry calculations of 25 Mg NMR chemical shifts, classical molecular dynamics (MD) calculations, and electrochemical performance tests. By mixing two competing Mg salts, we were able to reduce the strong covalent interactions between Mg 2+ and BH 4 – anions. A small increase is observed in the coordination number of Mg-TFSI and a significant increase in the interaction of Mg 2+ ions with glymes. Through a combination of NMR, DFT and MD simulations, various stable species around 1 nm in size were detected in the mixed salt solution, which play key roles in the enhanced electrochemical performance of the mixed electrolyte. It is established that for the neat Mg(TFSI) 2 in DGM electrolyte at dilute concentrations the TFSI - is fully dissociated from Mg 2+ . At higher concentrations, Mg 2+ and TFSI - are only partially dissociated as contact ion pairs are formed. In contrast, at 0.01 M Mg(BH 4 ) 2 (saturated concentration) in DGM, the first solvation shell of a Mg 2+ ion contains two BH 4 - anions and one DGM molecule, while the second solvation shell consists of five to six DGM molecules. An exchange mechanism between the solvation structures in the combined electrolyte containing both Mg(BH 4 ) 2 and Mg(TFSI) 2 in DGM was found to result in the observation of a single 25 Mg NMR peak. This exchange is responsible for an increase in uncoordinated anions, as well as improved stability and ionic conductivity as compared to single anion solution. Solvent molecule rearrangement and direct Mg-ion exchange between the basic solvation structures are hypothesized as likely reasons for the exchange. We elucidate that the solvent rearrangement is energetically much more favorable than direct Mg-ion hopping and is thus suggested as the dominant exchange mechanism.

Magnesium battery, electrolytes, Mg(BH4)2, Mg(TFSI↗