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At least 685 records · Page 38

Synthesis and optical properties of ordered-vacancy perovskite cesium bismuth halide nanocrystals

Perovskite-phase cesium bismuth halide (Cs 3 Bi 2 X 9 ; X= Cl, Br, I) nanocrystals were synthesized using a hot-injection approach. These nanocrystals adopted ordered-vacancy perovskite crystal structures and demonstrated composition-tunable optical properties. Growth occurred by initial formation of Bi 0 seeds, and morphology was controlled by precursor and seed concentration. The Cs 3 Bi 2 I 9 nanocrystals demonstrated excellent stability under ambient conditions for several months. Contrary to previous reports, we find that photoluminescence originates from the precursor material as opposed to the perovskite nanocrystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A LINK BETWEEN STAR FORMATION QUENCHING AND INNER STELLAR MASS DENSITY IN SLOAN DIGITAL SKY SURVEY CENTRAL GALAXIES

We study the correlation between galaxy structure and the quenching of star formation using a sample of Sloan Digital Sky Survey central galaxies with stellar masses 9.75 < log M{sub *}/M{sub ☉} < 11.25 and redshifts z < 0.075. Galaxy Evolution Explorer UV data are used to cleanly divide the sample into star-forming and quenched galaxies and to identify galaxies in transition (the green valley). Despite a stark difference in visual appearance between blue and red galaxies, their average radial stellar mass density profiles are remarkably similar (especially in the outer regions) at fixed mass. The inner stellar mass surface density within a radius of 1 kpc, Σ{sub 1}, is used to quantify the growth of the bulge as galaxies evolve. When galaxies are divided into narrow mass bins, their distribution in the color-Σ{sub 1} plane at fixed mass forms plausible evolutionary tracks. Σ{sub 1} seems to grow as galaxies evolve through the blue cloud, and once it crosses a threshold value, galaxies are seen to quench at fixed Σ{sub 1}. The Σ{sub 1} threshold for quenching grows with stellar mass, Σ{sub 1}∝M{sub *}{sup 0.64}. However, the existence of some star-forming galaxies above the threshold Σ{sub 1} implies that a dense bulge is necessary but not sufficient to quench a galaxy fully. This would be consistent with a two-step quenching process in which gas within a galaxy is removed or stabilized against star formation by bulge-driven processes (such as a starburst, active galactic nucleus feedback, or morphological quenching), whereas external gas accretion is suppressed by separate halo-driven processes (such as halo gas shock heating). Quenching thus depends on an interplay between the inner structure of a galaxy and its surrounding dark matter halo, and lack of perfect synchrony between the two could produce the observed scatter in color versus Σ{sub 1}.

79 ASTRONOMY AND ASTROPHYSICS↗

Hierarchically Structured Materials for Lithium Batteries

Lithium-ion battery (LIB) is one of the most promising power sources to be deployed in electric vehicles (EV), including solely battery powered vehicles, plug-in hybrid electric vehicles, and hybrid electrical vehicles. With the increasing demand on devices of high energy densities (>500 Wh/kg) , new energy storage systems, such as lithium-oxygen (Li-O2) batteries and other emerging systems beyond the conventional LIB also attracted worldwide interest for both transportation and grid energy storage applications in recent years. It is well known that the electrochemical performances of these energy storage systems depend not only on the composition of the materials, but also on the structure of electrode materials used in the batteries. Although the desired performances characteristics of batteries often have conflict requirements on the micro/nano-structure of electrodes, hierarchically designed electrodes can be tailored to satisfy these conflict requirements. This work will review hierarchically structured materials that have been successfully used in LIB and Li-O2 batteries. Our goal is to elucidate 1) how to realize the full potential of energy materials through the manipulation of morphologies, and 2) how the hierarchical structure benefits the charge transport, promotes the interfacial properties, prolongs the electrode stability and battery lifetime.

energy storage↗

Design principles for heterointerfacial alloying kinetics at metallic anodes in rechargeable batteries

How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest. Here, we consider the relation between the surface chemistry at interfaces and the reversibility of electrochemical transformations at rechargeable battery electrodes. Using Zn as a model system, we report that a moderate strength of chemical interaction between the deposit and the substrate—neither too weak nor too strong—enables highest reversibility and stability of the plating/stripping redox processes. Focused ion beam and electron microscopy were used to directly probe the morphology, chemistry, and crystallography of heterointerfaces of distinct natures. Analogous to the empirical Sabatier principle for chemical heterogeneous catalysis, our findings arise from competing interfacial processes. Using full batteries with stringent negative electrode–to–positive electrode capacity (N:P) ratios, we show that such knowledge provides a powerful tool for designing key materials in highly reversible battery systems based on Earth-abundant, low-cost metals such as Zn and Na.

25 ENERGY STORAGE↗

Assessment of Cementitious Composites for High-Temperature Geothermal Wells

High-temperature (HT) geothermal wells can provide green power 24 hours a day, 7 days a week. Under harsh environmental and operational conditions, the long-term durability requirements of such wells require special cementitious composites for well construction. This paper reports a comprehensive assessment of geothermal cement composites in cyclic pressure function laboratory tests and field exposures in an HT geothermal well (300–350 °C), as well as a numerical model to complement the experimental results. Performances of calcium–aluminate cement (CAC)-based composites and calcium-free cement were compared against the reference ordinary Portland cement (OPC)/silica blend. The stability and degradation of the tested materials were characterized by crystalline composition, thermo-gravimetric and elemental analyses, morphological studies, water-fillable porosity, and mechanical property measurements. All CAC-based formulations outperformed the reference blend both in the function and exposure tests. The reference OPC/silica lost its mechanical properties during the 9-month well exposure through extensive HT carbonation, while the properties of the CAC-based blends improved over that period. The Modified Cam-Clay (MCC) plasticity parameters of several HT cement formulations were extracted from triaxial and Brazilian tests and verified against the experimental results of function cyclic tests. These parameters can be used in well integrity models to predict the field-scale behavior of the cement sheath under geothermal well conditions.

15 GEOTHERMAL ENERGY↗

Growth and characterization of epitaxially stabilized ceria(001) nanostructures on Ru(0001)

We have studied (001) surface terminated cerium oxide nanoparticles grown on a ruthenium substrate using physical vapor deposition. Their morphology, shape, crystal structure, and chemical state are determined by low-energy electron microscopy and micro-diffraction, scanning probe microscopy, and synchrotron-based X-ray absorption spectroscopy. Square islands are identified as CeO 2 nanocrystals exhibiting a (001) oriented top facet of varying size; they have a height of about 7 to 10 nm and a side length between about 50 and 500 nm, and are terminated with a p(2 × 2) surface reconstruction. Micro-illumination electron diffraction reveals the existence of a coincidence lattice at the interface to the ruthenium substrate. The orientation of the side facets of the rod-like particles is identified as (111); the square particles are most likely of cuboidal shape, exhibiting (100) oriented side facets. Lastly, the square and needle-like islands are predominantly found at step bunches and may be grown exclusively at temperatures exceeding 1000 °C.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Radiative Transfer, Non-transparency, Stability Against Quench in Superconductors and Their Correlations

Radiative transfer calculations are presented for multi-filamentary BSCCO 2212 and 2223 and for thin film-coated YBaCuO 123 superconductors. A strictly radiative view allows conductor morphology of these superconductors to be interpreted as particulate or quasi-particulate objects. Problems then arising from non-regular particle shape, missing refractive indices, dependent scattering and superconductor material (diamagnetic) properties are solved in a multi-step, approximation approach. Both types of conductors are shown to be non-transparent to mid-IR radiation. Non-transparency may become critical for superconductor stability. The obtained extinction cross sections converge near the phase transition. A substantial difference of extinction properties between the superconducting and normal conducting state thus cannot be observed. As a first corollary from non-transparency, application of the additive approximation for the total thermal conductivity used in previous numerical calculations of the BSCCO and YBaCuO superconductors is confirmed. Second, within transit time intervals, the length of which depends on optical thickness, no uniform equilibrium conditions of electron pair density within the conductor cross section and near critical temperature are observed. Phase transition does not proceed uniformly, neither spatial nor temporal, and the order (succession on time scales) of local events (temperature variations, quench), in extreme cases, is completely dissolved. As another corollary, non-transparency even makes the existence of uniquely defined, physical time scales doubtful in a superconductor. The obtained results are expected to improve existing stability models and will be of practical value for future materials development.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing the Stability and Band Gaps of Cs 2 AgInCl 6 and Cs 2 AgSbCl 6 Lead-Free Double Perovskite Nanocrystals

Lead toxicity has sparked interest into alternative halide nanomaterials with properties similar to CsPbX 3 perovskites. A promising alternative predicted from bulk studies is the family of double perovskites of the form Cs 2 AgMX 6 . In this work, we report the synthesis of colloidal CsCs 2 AgInCl 6 and Cs 2 AgSbCl 6 nanocrystals via injection of acyl halides into a metal acetate solution under atmospheric conditions and relatively mild temperatures. We reflect the synthesis of single-crystalline cubic nanocrystals of ca. 10 nm side length and their morphological similarities to other double perovskite nanostructures in terms of their [200] facet termination and decoration with Ag (o) smaller nanocrystallites. To contrast the stabilities of the synthesized materials, we develop a titration assay based on the degradation of nanocrystals with amines as a proxy for degradation by humidity, which provides a quantifiable stability metric. This measurement shows that Cs 2 AgSbCl 6 releases more than twice the decomposition energy compared to Cs 2 AgInCl 6 or CsPbCl 3 and degrades in the presence of approximately one molar equivalent of amine, whereas the other two materials require more than a 100-fold excess. Using facile chemical titration to quantitatively determine chemical stability provides an additional tool to aid in the basic understanding of what makes some of these materials more environmentally stable than others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

Hurwitz, Frances I.↗

Hydrothermal synthesis of hollow SnO{sub 2} spheres with excellent electrochemical performance for anodes in lithium ion batteries

Highlights: • Hollow SnO{sub 2} spheres were synthesized by NaF via employing hydrothermal method. • The microstructure of hollow spheres can be judiciously controlled by adjusting the amount of NaF. • Their high capacity reversibility and long-term cycling stability were demonstrated. • Their excellent rate performance was also exhibited. - Abstract: Hollow SnO{sub 2} spheres with oriented cone-like SnO{sub 2} nanoparticle shells were synthesized by a one-step hydrothermal process using NaF as the morphology controlling agent. The resulting hollow SnO{sub 2} sphere electrode exhibits high reversible capacity (initial charge and discharge capacities of 1342.9 and 1947.6 mAh/g at 0.1 C and 1235.4 and 1741.3 mAh/g at 1 C) and good cycling stability (discharge capacities maintained 758.1 and 449.6 mAh/g after 100 cycles at 0.1 C and 1 C, respectively). Good rate performance was also obtained (1234.5 mAh/g at 0.1 C, 884.2 mAh/g at 0.2 C, 692.4 mAh/g at 0.5 C, 497.6 mAh/g at 1 C, 315.8 mAh/g at 2 C and 80.6 mAh/g at 5 C, and more importantly, when the current density returns to 0.1 C, a capacity of 869.6 mAh/g can be recovered. The observed electrochemical performance can attributed to the hollow structure, the use of NaF for morphology control and the unique oriented cone-like shell of the particles.

36 MATERIALS SCIENCE↗

Characterization of Hydrophobic Silane Film Deposited on AISI 304 Stainless Steel for Corrosion Protection

This present study was conducted to determine the aptitude of hydrophobic silane coating in corrosion resistance of AISI 304 stainless steel substrate at the nanoscale. Three newly developed hydrophobic silane-based compounds of compositions, namely [tris(trimethylsiloxy)silyethyl]dimethylchlorosilane (alkyl); tridecafloro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS); and henicosyl-1,1,2,2-tetrahydrododecyltricholrosilane (FDDTS), were used as precursors to coat AISI 304 stainless steel surfaces. Prior to deposition, the substrate surfaces were pretreated with plasma oxide via a multi-step treatment to serve as adhesion. The plasma oxide and the silane precursors were deposited by using a hybrid atomic layer deposition and chemical vapor deposition process. The structural, chemical and electrochemical stabilities were investigated using SEM, AFM, XRD, ATR-FTIR, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the microstructures and morphology of the coated samples were similar, due to the chlorosilane functionalization. The FTIR indicated complete hydrolysis at the nanoscale while the polarization results showed that nano-coating can hamper the corrosion propagation mechanisms. Furthermore, the EIS results revealed that all the precursors acted as a barrier to AISI 304 dissolution into the electrolyte. The electrochemical effect was observed in the microstructural transformation of the coatings. Although all the precursors were shown to have been effective at few nanoscales, the stability of the FDDTS showed to have superseded that of alkyl and FOTS.

36 MATERIALS SCIENCE↗

Quaternary M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (M = Ni, Zn, Co, Mn) ferrite oxides: Synthesis, characterization and magnetic properties

Highlights: • Superparamagnetic quaternary nanoferrite (M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4,} where M = Mn, Zn, Co, Ni) were obtained. • C, O, H and metals were observed by XPS analysis. • Phases purity were confirmed by XRD diffraction and crystallite size (3–10 nm) were determind. - Abstract: We report the synthesis of M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (where M = Mn, Zn, Co, Ni) nanoparticles using the coprecipitation method in the presence of carboxymethyl cellulose (CMC) as the in-situ surfactant. The crystalline structure and surface morphology were examined by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM) and it was established that the average diameter of the magnetic nanoparticles (MNPs) is in the range of 3–10 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) show that the MNPs are activated by the hydrophilic groups of the surfactant, which coat them and enhance their stability. The vibrating sample magnetometry measurements show the superparamagnetic behavior of the nanoparticles. Due to their small crystallite size, which implies large surface area, and their functionalization with organic groups, the obtained nanoparticles could have medical and catalytic applications.

36 MATERIALS SCIENCE↗

Water stable molecular n-doping produces organic electrochemical transistors with high transconductance and record stability

From established to emergent technologies, doping plays a crucial role in all semiconducting devices. Doping could, theoretically, be an excellent technique for improving repressively low transconductances in n-type organic electrochemical transistors – critical for advancing logic circuits for bioelectronic and neuromorphic technologies. However, the technical challenge is extreme: n-doped polymers are unstable in electrochemical transistor operating environments, air and water (electrolyte). Here, the first demonstration of doping in electron transporting organic electrochemical transistors is reported. The ammonium salt tetra-n-butylammonium fluoride is simply admixed with the conjugated polymer poly(N,N’-bis(7-glycol)-naphthalene-1,4,5,8-bis(dicarboximide)-co-2,2’-bithiophene-co-N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide), and found to act as a simultaneous molecular dopant and morphology-additive. The combined effects enhance the n-type transconductance with improved channel capacitance and mobility. Furthermore, operational and shelf-life stability measurements showcase the first example of water-stable n-doping in a polymer. Overall, the results set a precedent for doping/additives to impact organic electrochemical transistors as powerfully as they have in other semiconducting devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local Cation-Ordered Superlattice Stabilizing Ni-Rich Single-Crystalline Cathodes

Ni-rich single-crystalline cathodes are pivotal for advancing lithium-ion battery technology due to their high energy density and mechanical stability. However, Ni-rich single-crystalline particles face intrinsic structural heterogeneity due to excessively high sintering temperature required to shape micron-sized morphologies─typically over 150 °C above the polycrystalline optimum, leading to rapid electrochemical decay and unsatisfied rate performance that hinder their practical application. Here, in this work, we propose a lithium-deficient presintering strategy to synthesize cation-ordered single-crystalline LiNi 0.83 Co 0.12 Mn 0.05 O 2 (S-NCM83), effectively minimizing lattice chemical heterogeneity and defect formation. The resulting cation-ordered percolation network enhances the structural stability of the bulk, reduces the energy barrier for Li + migration, and stabilizes Li + diffusion pathways. Consequently, S-NCM83 demonstrates significantly improved cycling stability across various operating temperatures and achieves exceptional rate performance, delivering 206 mAh g –1 at 0.1 C and 170 mAh g –1 at 5 C, without requiring surface coatings or doping. This work introduces a universal strategy to address the long-standing structural instability issues in single-crystalline cathodes, paving the way for simplified and scalable approaches to long-life and high-energy lithium-ion batteries.

36 MATERIALS SCIENCE↗

Improved stability and efficiency of perovskite solar cells with submicron flexible barrier films deposited in air

Here in this paper, we report on submicron organosilicate barrier films produced rapidly in air by a scalable spray plasma process that improves both the stability and efficiency of perovskite solar cells. The plasma is at sufficiently low temperature to prevent damage to the underlying layers. Oxidizing species and heat from the plasma improve device performance by enhancing both interfacial contact and the conductivity of the hole transporting layer. The thickness of the barrier films is tunable and transparent over the entire visible spectrum. The morphology and density of the barrier are shown to improve with the addition of a fluorine-based precursor. Devices with submicron coatings exhibited significant improvements in stability, maintaining 92% of their initial power conversion efficiencies after more than 3000 h in dry heat (85 °C, 25% RH) while also being resistant to degradation under simulated operational conditions of continuous exposure to light, heat, and moisture. X-ray diffraction measurements performed while heating showed the barrier film dramatically slows the formation of PbI 2 . The barrier films also are compatible with flexible devices, exhibiting no signs of cracking or delamination after 10000 bending cycles on a 127 μm substrate with a bending radius of 1 cm.

36 MATERIALS SCIENCE↗

In‐Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO 2 Reduction to Ethylene

Abstract Bridging homogeneous molecular systems with heterogeneous catalysts is a promising approach for the development of new electrodes, combining the advantages of both approaches. In the context of CO 2 electroreduction, molecular enhancement of planar copper electrodes has enabled promising advancement towards high Faradaic efficiencies for multicarbon products. Besides, nanostructured copper electrodes have also demonstrated enhanced performance at comparatively low overpotentials. Herein, we report a novel and convenient method for nanostructuring copper electrodes using N , N ′‐ethylene‐phenanthrolinium dibromide as molecular additive. Selectivities up to 70 % for C ≥2 products are observed for more than 40 h without significant change in the surface morphology. Mechanistic studies reveal several roles for the organic additive, including: the formation of cube‐like nanostructures by corrosion of the copper surface, the stabilization of these nanostructures during electrocatalysis by formation of a protective organic layer, and the promotion of C ≥2 products.

Thevenon, Arnaud↗

Thin-film semiconductor perspective of organometal trihalide perovskite materials for high-efficiency solar cells

Organolead trihalide perovskites (OTPs) are arising as a new generation of low-cost active materials for solar cells with efficiency rocketing from 3.5% to over 20% within only five years. From “dye” in dye sensitized solar cells to “hole conductors” and “electron conductors” in mesoscopic heterojunction solar cells, there has been a dramatic conceptual evolution on the function of OTPs in photovoltaic devices. OTPs were originally used as dyes in Gratzel cells, achieving a high efficiency above 15% which, however, did not manifest the excellent charge transport properties of OTPs. An analogy of OTPs to traditional semiconductors was drawn after the demonstration of highly efficient planar heterojunction structure OTP devices and the observation of their excellent bipolar transport properties with a large diffusion length exceeding 100 nm in CH 3 NH 3 PbI 3 (MAPbI 3 ) polycrystalline thin films. Here, this review aims to provide the most recent advances in the understanding of the origin of the high OTP device efficiency. Specifically we will focus on reviewing the progress in understanding 1) the characterization of fantastic optoelectronic property of OTPs, 2) the unusual defect physics that originate the optoelectronic property; 3) morphology control of the perovskite film from fabrication process and film post-treatment, and 4) device interface and charge transport layers that dramatically impact device efficiency in the OTP thin film devices; 5) photocurrent hysteresis; 6) tandem solar cells; 7) stability of the perovskite materials and solar cell devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗