The Crystal Structure of 5-Aminouracil and the Ambiguity of Alternative Polymorphs
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Watts, T.A.↗
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Results for “RAMAN SPECTROSCOPY”
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An insight into microscopy and analytical techniques for morphological, structural, chemical, and thermal characterization of cellulose
Cellulose obtained from plants is a bio-polysaccharide and the most abundant organic polymer on earth that has immense household and industrial applications. Hence, the characterization of cellulose is important for determining its appropriate applications. In this article, we review the characterization of cellulose morphology, surface topography using microscopic techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Additionally, other physicochemical characteristics like crystallinity, chemical composition, and thermal properties are studied using techniques including X-ray diffraction, Fourier transform infrared, Raman spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This review may contribute to the development of using cellulose as a low-cost raw material with anticipated physicochemical properties.
59 BASIC BIOLOGICAL SCIENCES↗
SERS and the scientific career of Richard P. Van Duyne (1945–2019)
This article describes the scientific career of our dear friend Richard P. Van Duyne. Rick was the discoverer of surface-enhanced Raman spectroscopy (SERS), and over the period from the mid-1970s until his death in 2019, he served as both the intellectual leader of the field, and the technical genius who pushed the field forward through his numerous inventions and discoveries. Rick's work went through many phases, and even involved a significant period of inactivity that Rick was able to break out of, but especially after 2000, there was a period of incredible creativity that ultimately led to a detailed understanding of what the SERS enhancement factor is all about and also led to fabrication techniques for making optimum SERS substrates such that applications of SERS to a wide variety of real-world problems in sensing became possible. In addition, Rick's SERS work spawned numerous related technologies, including index of refraction sensing based on localized surface plasmon resonance (LSPR) measurements, and the extension of SERS to its tip-enhanced cousin TERS, to electrochemical versions of SERS and TERS, and to ultrafast nonlinear techniques. The practical applications he pursued included diagnostics for diseases such as cancer, hand-held glucose sensing, and SERS studies related to art conservation. Furthermore, Rick's legacy will probably be best known through the numerous students, postdocs, and collaborators that passed through his lab and who are now active researchers in areas related to SERS at universities and industrial labs around the world.
47 OTHER INSTRUMENTATION↗
Microstructure changes during failure of PVDF-based photovoltaic backsheets
The backsheet layer of a solar module provides a safety and environmental barrier to the high voltages running through the photovoltaic (PV) cells and electrical contacts within the core of the module. However, in the past decade, backsheet cracking has become one of the most observed failure modes in PV module field surveys. In this work, the degradation of polyvinylidene fluoride (PVDF)-based backsheets is explored. Backsheet samples are either exposed to accelerated laboratory aging (UV light, heat, and moisture) or collected from the field. Fourier transform infrared and Raman spectroscopy, fragmentation testing, atomic force and scanning electron microscopy, and small-angle neutron scattering are combined to develop an understanding of how chemistry and microstructure evolve during aging. Chemical degradation, surface pitting, polymer phase changes, and anisotropic polymer domains are all observed in aged backsheet samples. The results provide insight into the degradation mechanisms that lead to cracking and field failure of PVDF-based backsheets. The comparison of aged PVDF-based backsheets helps to lay the groundwork for limiting polymer-based failure modes in PV modules.
PVDF↗
High‐Pressure Characterization of Melt‐Castable Energetic Materials: Bis(Nitroxymethylisoxazolyl) Furoxan (DNDIF)
Abstract The high‐pressure behavior of bis(nitroxymethylisoxazolyl) furoxan (DNDIF) was studied at ambient temperature and pressures approaching 30 GPa by Raman spectroscopy and powder X‐ray diffraction. There was no evidence of a phase change observed over this pressure range, indicating that the ambient structure of DNDIF remains stable up to conditions similar to the detonation pressure of the material. Such findings suggest that this melt‐castable explosive may be used in the replacement of 2,4,6‐trinitrotoluene (TNT) in energetic formulations without the concern of uncontrolled polymorphism that might otherwise affect the performance and safety of the munition. Additionally, empirical understanding of the effect of different structural motifs in the crystal packing builds on understanding of what macroscale features are desirable for future materials and gets us closer to the design of future novel energetics.
Bennion, Jonathan C.↗
High-Pressure Characterization of Two Stereoisomers of Tetranitroester Cyclobutane
The high-pressure behavior of two stereoisomeric cyclobutane nitric ester materials were studied at room temperature to near 25 GPa via Raman spectroscopy and powder X-ray diffraction. The materials investigated included [cis-trans-cis]- and [all-cis]-tetranitrate ester cyclobutanes. Over the course of these studies no evidence of polymorphism was observed, highlighting the stability of the ambient pressure crystal structures of the cyclobutanes to conditions near the detonation pressure of the material. Differences were observed between the bulk moduli of the two stereoisomers, suggesting potential tunability in materials response under dynamic conditions through the use of isomeric materials. Finally, such findings suggest that these high-performance materials can serve as TNT replacement in novel melt-castable energetic formulations without the concern of uncontrolled polymorphism that might otherwise affect the performance and safety of a munition.
45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
Testing and Modeling of Functionally Graded Aluminum-Doped Zinc Oxide Using Spark Plasma Sintering and Discrete Powder Layers of Varying Composition
Functionally graded material (FGM) ZnO is made via spark plasma sintering/field-assisted sintering technique (SPS/FAST) by varying the Al dopant content along the z-axis or pressing direction. A wide range of Al content (0–5 wt%) is used by adding Al powder to nanosized ZnO powder. Thermoelectric (TE) measurements are done on the FGM and individual layers made separately. X-ray diffraction (XRD) shows two phases, ZnO and spinel phase (ZnAl 2 O 4 ). High-resolution Raman spectroscopy reveals doped ZnO and spinel phase (ZnAl 2 O 4 ) spatially and shows segregation in the layer with highest Al content. Electron backscatter diffraction (EBSD) reveals noticeable grain growth with decreasing Al content, and there is a common, random preferred orientation in all layers. The tested properties are used to simulate efficiency curves for a discretely graded, five-layer FGM as well as a homogenous material, where both graded structures provide an opportunity to widen the current density ranges and therefore the temperature range of useful energy conversion.
36 MATERIALS SCIENCE↗
Effect of Ion Irradiation on Amorphous and Crystalline Ge–Se and Their Application as Phase Change Temperature Sensor
Research on phase change materials is predominantly focused on their application as memory devices or for temperature control which requires low phase change temperature. The Ge–Se binary chalcogenide glass system with its wide glass-forming region is a potential candidate for high-temperature and high-radiation phase change applications. In this study, the concept of employing Ge x Se 100– x glasses to monitor high temperature (450–528 °C) using the phase change effect, is reported. Materials selection, device structure, and performance of prototype sensors are analyzed. In addition, the effect of heavy ion irradiation by Xe ions with energies of 200, 600, and 1000 keV (fluence ≈10 14 cm –2 ) on the Ge x Se 100– x ( x = 30, 33, 40) thin films and phase change devices is studied. The irradiation effect on the amorphous and crystalline structure of the thin films is evaluated by Raman spectroscopy and X-ray diffraction (XRD). Although the changes in the structural units of amorphous films are negligible, in crystalline films orthorhombic-GeSe 2 crystals are found to be most affected by irradiation and a new phase, orthorhombic GeSe is found in the thin films after irradiation. The performance of a sensor with an active film of Ge 40 Se 60 is also shown as an example.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Using Neural Networks to Identify Mixture Components in Hyperspectral Reflectance Data
Neural networks have been employed to identify materials of interest from hyperspectral data (generally imagery) based on their unique spectral signatures. This approach assumes that there is a single material that is standing out from the rest of the spectrum to be identified. However, pixels often contain more than one material, or a material of interest may itself be a mixture of multiple materials. Neural networks are only as good as the data used to train them, and it takes a great deal of work in the laboratory to identify, make, and measure all potential mixtures of interest. Thus, researchers often calculate synthetic spectra using algorithms with varying degrees of fidelity to the physics that govern the interactions between light and multiple materials. In this work, we have (1) adapted a neural network designed to identify mixture components from Raman spectroscopy to work with visible to near‐infrared reflectance data and (2) tested three common mixture algorithms to determine the most accurate and least computationally expensive method to build synthetic training datasets. With our initial test dataset, we have achieved accuracies of > 90% and found that the synthetic training dataset produced using the Hapke mixture model provides the best results.
99 GENERAL AND MISCELLANEOUS↗
Integration of Highly Luminescent Lead Halide Perovskite Nanocrystals on Transparent Lead Halide Nanowire Waveguides through Morphological Transformation and Spontaneous Growth in Water
The integration of highly luminescent CsPbBr 3 quantum dots on nanowire waveguides has enormous potential applications in nanophotonics, optical sensing and quantum communications. On the other hand, CsPb 2 Br 5 nanowires have also attracted a lot of attention due to their unique water stability and controversial luminescent property. Here we first report the growth of CsPbBr 3 nanocrystals on CsPb 2 Br 5 nanowires by simply immersing CsPbBr 3 powder into pure water, CsPbBr 3-γ X γ (X = Cl, I) nanocrystals on CsPb 2 Br 5-γ X γ nanowires are then synthesized for tunable light sources. Systematic structure and morphology studies, including in-situ monitoring, revealed that CsPbBr 3 powder was first converted to CsPb 2 Br 5 microplatelets in water, followed by a morphological transformation from CsPb 2 Br 5 microplatelets to nanowires, which is a kinetic dissolution-recrystallization process controlled by electrolytic dissociation and supersaturation of CsPb 2 Br 5 . CsPbB r3 nanocrystals are spontaneously formed on CsPb 2 Br 5 nanowires when nanowires are collected from the aqueous solution. Raman spectroscopy, combined photoluminescence and SEM imaging confirm that the bright emission originates from CsPbBr 3-γ X γ nanocrystals while CsPb 2 Br 5-γ X γ nanowires are transparent waveguides. In conclusion, the intimate integration of nanoscale light sources with a nanowire waveguide is demonstrated through the observation of the wave guiding of light from nanocrystals and Fabry-Perot interference modes of the nanowire cavity.
42 ENGINEERING↗
Co-Assembly of Carbon Nanotube Porins into Biomimetic Peptoid Membranes
Robust and cost-effective membrane-based separations are essential to solving many global crises, such as the lack of clean water. Even though the current polymer-based membranes are widely used for separations, their performance and precision can be enhanced by using a biomimetic membrane architecture that consists of highly permeable and selective channels embedded in a universal membrane matrix. Researchers have shown that artificial water and ion channels, such as carbon nanotube porins (CNTPs), embedded in lipid membranes can deliver strong separation performance. However, their applications are limited by the relative fragility and low stability of the lipid matrix. In this work, we demonstrate that CNTPs can co-assemble into two-dimension (2D) peptoid membrane nanosheets, opening up a way to produce highly programmable synthetic membranes with superior crystallinity and robustness. A combination of molecular dynamics (MD) simulations, Raman spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) measurements to verify the co-assembly of CNTP and peptoids are used and show that it does not disrupt peptoid monomer packing within the membrane. In conclusion, these results provide a new option for designing affordable artificial membranes and highly robust nanoporous solids.
36 MATERIALS SCIENCE↗
Atomically Dispersed Silver Atoms Embedded in NiCo Layer Double Hydroxide Boost Oxygen Evolution Reaction
Abstract Bimetallic layered double hydroxides (LDHs) are promising catalysts for anodic oxygen evolution reaction (OER) in alkaline media. Despite good stability, NiCo LDH displays an unsatisfactory OER activity relative to the most robust NiFe LDH and CoFe LDH. Herein, a novel NiCo LDH electrocatalyst modified with single‐atom silver grown on carbon cloth (Ag SA ‐NiCo LDH/CC) that exhibits exceptional OER activity and stability in 1.0 m KOH is reported. The Ag SA ‐NiCo LDH/CC catalyst only requires a low overpotential of 192 mV to reach a current density of 10 mA cm −2 , obviously boosting the OER activity of NiCo LDH/CC (410 mV@10 mA cm −2 ). Inspiringly, Ag SA ‐NiCo LDH/CC can maintain its high activity for up to 500 h at a large current density of 100 mA cm −2 , exceeding most single‐atom OER catalysts. In situ Raman spectroscopy studies uncover that the in situ formed NiCoOOH during OER is the real active species. Hard X‐ray absorption spectrum (XAS) and density functional theory (DFT) calculations validate that single‐atom Ag occupying Ni site increases the chemical valence of Ni elements, and then weakens the adsorption of oxygen‐contained intermediates on Ni sites, fundamentally accounting for the enhanced OER performance.
Chemistry↗
Multi-Functional Applications of H-Glass Embedded with Stable Plasmonic Gold Nanoislands
Metal nanoparticles (MNPs) are synthesized using various techniques on diverse substrates that significantly impact their properties. However, among the substrate materials investigated, the major challenge is the stability of MNPs due to their poor adhesion to the substrate. Herein, it is demonstrated how a newly developed H-glass can concurrently stabilize plasmonic gold nanoislands (GNIs) and offer multifunctional applications. The GNIs on the H-glass are synthesized using a simple yet, robust thermal dewetting process. The H-glass embedded with GNIs demonstrates versatility in its applications, such as i) acting as a room temperature chemiresistive gas sensor (70% response for NO 2 gas); ii) serving as substrates for surface-enhanced Raman spectroscopy for the identifications of Nile blue (dye) and picric acid (explosive) analytes down to nanomolar concentrations with enhancement factors of 4.8 × 10 6 and 6.1 × 10 5 , respectively; and iii) functioning as a nonlinear optical saturable absorber with a saturation intensity of 18.36 × 10 15 W m -2 at 600 nm, and the performance characteristics are on par with those of materials reported in the existing literature. In conclusion, this work establishes a facile strategy to develop advanced materials by depositing metal nanoislands on glass for various functional applications.
36 MATERIALS SCIENCE↗
Photonics in Multimaterial Lateral Heterostructures Combining Group IV Chalcogenide van der Waals Semiconductors
Abstract Lateral heterostructures combining two multilayer group IV chalcogenide van der Waals semiconductors have attracted interest for optoelectronics, twistronics, and valleytronics, owing to their structural anisotropy, bulk‐like electronic properties, enhanced optical thickness, and vertical interfaces enabling in‐plane charge manipulation/separation, perpendicular to the trajectory of incident light. Group IV monochalcogenides support propagating photonic waveguide modes, but their interference gives rise to complex light emission patterns throughout the visible/near‐infrared range both in uniform flakes and single‐interface lateral heterostructures. Here, this work demonstrates the judicious integration of pure and alloyed monochalcogenide crystals into multimaterial heterostructures with unique photonic properties, notably the ability to select photonic modes with targeted discrete energies through geometric factors rather than band engineering. SnS‐GeS 1− x Se x ‐GeSe‐GeS 1− x Se x heterostructures with a GeS 1− x Se x active layer sandwiched laterally between GeSe and SnS, semiconductors with similar optical constants but smaller bandgaps, were designed and realized via sequential vapor transport synthesis. Raman spectroscopy, electron microscopy/diffraction, and energy‐dispersive X‐ray spectroscopy confirm a high crystal quality of the laterally stitched components with sharp interfaces. Nanometer‐scale cathodoluminescence spectroscopy provides evidence for a facile transfer of electron–hole pairs across the lateral interfaces and demonstrates the selection of photon emission at discrete energies in the laterally embedded active (GeS 1− x Se x ) part of the heterostructure.
2D layered crystals↗
Synthesis‐Related Nanoscale Defects in Mo‐Based Janus Monolayers Revealed by Cross‐Correlated AFM and TERS Imaging
2D Janus transition metal dichalcogenides (TMDs) are promising candidates for various applications including non-linear optics, energy harvesting, and catalysis. These materials are usually synthesized via chemical conversion of pristine TMDs. Nanometer-scale characterization of the obtained Janus materials’ morphology and local composition is crucial for both the synthesis optimization and the future device applications. In this work, we present the results of cross-correlated atomic force microscopy (AFM) and tip-enhanced Raman spectroscopy (TERS) study of Janus monolayers synthesized by the hydrogen plasma-assisted chemical conversion of MoSe 2 and MoS 2 . We demonstrate that the choice of both the growth substrate and the starting TMD influences the residual strain, thereby shaping the nanoscale morphology of the resulting Janus material. Furthermore, by employing TERS imaging, we show the presence of nanoscale islands (≈20 nm across) of MoSe 2 - ${\mathrm{Mo}}_{{\mathrm{Se}}}^{\mathrm{S}}$ (MoS 2 -${\mathrm{Mo}}_{\mathrm{S}}^{{\mathrm{Se}}}$) vertical heterostructures originating from the bilayer nanoislands in the precursor monolayer crystals. The understanding of the origins of nanoscale defects in Janus TMDs revealed in this study can help with further optimization of the Janus conversion process towards uniform and wrinkle-/crack-free Janus materials. Moreover, this work shows that cross-correlated AFM and TERS imaging is a powerful and accessible method for studying nanoscale composition and defects in Janus TMD monolayers.
2D materials↗
SnSe 1-x S x Alloys: Anisotropic Van der Waals Semiconductors with Tunable Bandgaps
Alloying is one of the main tools of bandgap engineering, allowing the tuning of crystal structure, lattice parameters, and electronic structure of 3D and 2D/layered semiconductors. Among the latter, it can play a key role in tailoring the properties of tin monochalcogenides, a class of van der Waals semiconductors of interest for optoelectronics, thermoelectrics, ferroelectrics, and valleytronics. Here, the study investigates the synthesis and properties of large flakes of the anion substitution alloys SnSe 1-x S x . Alloy flakes across a wide range of compositions are obtained systematically by repeated growth from the same mixed (SnS, SnSe) powder precursor. Combined experiment and theory show full miscibility for all compositions, along with tunable lattice constants, bandgaps, and vibrational modes. Atomic resolution imaging demonstrates the accumulation of S and Se in alternating layers in the SnSe 1-x S x unit cell, attributed to growth kinetics. Polarized Raman spectroscopy confirms anisotropic vibrational modes; the calculated and measured band structure shows systematic changes in the band edge energies and anisotropic electronic structure due to the anisotropic in-plane lattice of the monochalcogenides. Cathodoluminescence, finally, indicates that a unique configuration of two non-degenerate, direct valleys along orthogonal k-space directions persists all the way from SnS to SnSe, making SnSe 1-x S x alloys interesting for valleytronics.
36 MATERIALS SCIENCE↗
Rigidity‐Driven Structural Isomers in the NaCl–Ga 2 S 3 System: Implications for Energy Storage
Alternative energy sources require the search for innovative materials with promising functionalities. Systems with unusual chemical properties represent an insufficiently explored domain, concealing unexpected features. Using diffraction and Raman spectroscopy over a wide temperature range, supported by first‐principles simulations, a rare phenomenon is unveiled: phase‐dependent chemical interactions between binary components in the NaCl–Ga 2 S 3 system. In this unique occurrence, previously intact binary crystalline species transform upon melting into mixed liquid structural isomers, forming bonds with new partners. The chemical combinatorics appears to be fully reversible for stable crystals and liquids. Despite this, rapidly frozen glasses out of thermodynamic equilibrium remain in a metastable isomeric state, offering remarkable properties, particularly a high room‐temperature Na + conductivity, comparable to the best sodium halide superionic conductors and therefore encouraging for sodium solid‐state batteries and energy applications. A rigidity paradigm is responsible for the observed phenomenon, as the extremely constrained Ga 2 S 3 crystal lattice does not survive viscous flow, breaking up at a short‐range level. The removal of rigidity constraints and dense packing leads to a significant increase in empty space, which is the origin of high sodium diffusivity. Broadly, the rigidity‐driven structural isomerism opens up an inspiring path to the discovery of atypical materials.
25 ENERGY STORAGE↗
Direct determination of cellulosic glucan content in starch-containing samples
A simple and highly selective analytical procedure is presented for the determination of cellulosic glucan content in samples that contain both cellulose and starch. This method eliminates the unacceptably large compounding errors of current two-measurement methods. If both starch and cellulose are present before analytical hydrolysis, both will be hydrolyzed to glucose causing bias and inaccuracy in the method. To prevent this interference, the removal of starch prior to cellulosic quantification is crucial. The method presented here is a concise in-series procedure with minimal measurements, eliminating large compounding errors. Sample preparation consists of a starch extraction employing enzymatic hydrolysis followed by a simple filtration and wash. The samples are then subjected to a two-stage acid hydrolysis. The concentration of glucose is determined by ion exchange high-performance liquid chromatography with a Pb 2+ column and a refractive index detector. The cellulosic glucan content is calculated based on the initial dry weight of the starting material. Data for the native biomass materials studied show excellent reproducibility, with coefficients of variance of 3.0% or less associated with the method. This selectivity for cellulosic glucan by the procedure was validated with several analytical techniques such as liquid chromatography coupled with mass spectrometry (LC–MS), Raman spectroscopy, and nuclear magnetic resonance.
09 BIOMASS FUELS↗