High-pressure response of vibrational properties of b-AsxP1-x:in situRaman studies.

The structural evolution of black arsenic-phosphorous (b-AsxP1-x) alloys with varying arsenic concentrations was investigated under hydrostatic pressure usingin situRaman spectroscopy. High-pressure experiments were conducted using a diamond anvil cell, which revealed pressure-induced shifts in vibrational modes associated with P-P bonds (A1g,A2g,B2g), As-As bonds (A1g,A2g,B2g), and As-P bonds in b-AsxP1-xalloys. Two distinct pressure regimes were observed. In the first regime (region I), all vibrational modes exhibited a monotonic upshift, indicating phonon hardening due to hydrostatic pressure. In the second regime (region II), As0.4P0.6and As0.6P0.4alloys displayed a linear blueshift (or negligible change in some modes) at a reduced rate, suggesting local structural reorganization with less compression on the bonds. Notably, the alloy with the highest As concentration, As0.8P0.2, exhibited anomalous behavior in the second pressure regime, with a downward shift observed in all As-As and As-P Raman modes (and some P-P modes). Interestingly, the emergence of new peaks corresponding to theEgmode andA1gmode of the gray-As phase was observed in this pressure range, indicating compressive strain-induced structural changes. The anomalous change in region II confirms the formation of a new local structure, characterized by elongation of the P-P, As-As, and As-P bonds along the zigzag direction within the b-AsxP1-xphase, possibly near the grain boundary. Additionally, a gray-As phase undergoes compressive structural changes. This study underscores the significance of pressure in inducing structural transformations and exploring novel phases in two-dimensional materials, including b-AsxP1-xalloys.

Ligand-Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands.

Herein, we developed the recyclable ligand-free iridium (Ir)-hydride based Ir0 nanoparticles (NPs) for the first regioselective partial hydrogenation of PV -substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal-surface-bound hydrides, most likely formed from Ir0 species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High-resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X-ray photoelectron spectroscopy confirmed the dominance of Ir0 in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (H8 -BINAP) and its derivatives without losing enantioselectivity during catalytic events.

Ultrasmall CuI Nanoparticles Stabilized on Surface of HPMC: An Efficient Catalyst for Fast and Organic Solvent-Free Tandem Click Chemistry in Water.

A simple and environmentally benign technology for synthesizing ultrasmall CuI nanoparticles (NPs) on the surface of the food additive hydroxypropyl methylcellulose (HPMC) and their application in completely organic solvent-free tandem alkyne-azide cycloaddition reactions were reported. The NP catalyst was thoroughly characterized by high-angle annular dark-field scanning transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis for its morphology, particle size distribution, chemical composition, and oxidation state analyses. The NP catalyst was highly efficient, affording products in 10-45 min. All products were obtained in high purity by simple filtration, obviating organic solvents from the reaction set-up to product isolation. The methodology is general and scalable as validated by a broad substrate scope.

Harnessing the cation-π interactions of metalated gold monolayer-protected clusters to detect aromatic volatile organic compounds.

The strong, non-covalent interactions between π-systems and cations have been the focus of numerous studies on biomolecule structure and catalysis. These interactions, however, have yet to be explored as a sensing mechanism for detecting trace levels of volatile organic compounds (VOCs). In this article, we provide evidence that cation-π interactions can be used to elicit sensitive and selective chemiresistor responses to aromatic VOCs. The chemiresistors are fitted with carboxylate-linked alkali metals bound to the surface of gold monolayer-protected clusters formulated on microfabricated interdigitated electrodes. Sensor responses to aromatic and non-aromatic VOCs are consistent with a model for cation-π interactions arising from association of electron-rich aromatic π-systems to metal ions with the relative strength of attraction following the order K+ > Na+ > Li+. The results point toward cation-π interactions as a promising research avenue to explore for developing aromatic VOC-selective sensors.

Metal-Micelle Interaction Leading to Spontaneous Formation of Ligand-Free Palladium(0) Nanoparticles: Highly Efficient Catalysis Enabling Biaryl Ketone Formation from Carboxylic Acid Derivatives.

A novel strategy has been developed to spontaneously form ligand-free Pd(0) nanoparticles (NPs) from water- and air-sensitive Pd2dba3 in water. These NPs are thoroughly characterized by IR, NMR, and mass spectrometry, revealing that the metal-micelle binding plays a critical role in their stability and activity. High-resolution transmission electron microscopy supported the ultrasmall nature of NPs, whereas X-ray photoelectron spectroscopy analysis confirmed the zero-oxidation state of Pd. The shielding effect of micelles and enhanced stability of NPs enabled fast cross-couplings of water-sensitive triazine adducts of carboxylic acid to form nonsymmetrical biaryl ketones. These naturally formed NPs are more efficient than new synthetic NPs formed under a hydrogen atmosphere and traditional NPs formed using the air-sensitive Grignard reagent as a reductant. The activity of naturally formed NPs is compared with that of synthetic NPs over 34 substrates, revealing that naturally formed NPs are much more efficient than synthetic NPs.

Ultra-Narrow Phosphorene Nanoribbons Produced by Facile Electrochemical Process.

Phosphorene nanoribbons (PNRs) have inspired strong research interests to explore their exciting properties that are associated with the unique two-dimensional (2D) structure of phosphorene as well as the additional quantum confinement of the nanoribbon morphology, providing new materials strategy for electronic and optoelectronic applications. Despite several important properties of PNRs, the production of these structures with narrow widths is still a great challenge. Here, a facile and straightforward approach to synthesize PNRs via an electrochemical process that utilize the anisotropic Na+ diffusion barrier in black phosphorus (BP) along the [001] zigzag direction against the [100] armchair direction, is reported. The produced PNRs display widths of good uniformity (10.3 ± 3.8 nm) observed by high-resolution transmission electron microscopy, and the suppressed B2g vibrational mode from Raman spectroscopy results. More interestingly, when used in field-effect transistors, synthesized bundles exhibit the n-type behavior, which is dramatically different from bulk BP flakes which are p-type. This work provides insights into a new synthesis approach of PNRs with confined widths, paving the way toward the development of phosphorene and other highly anisotropic nanoribbon materials for high-quality electronic applications.

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the first time, we report F-doped Li5+yPS5Fy argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li6PS5F0.5Cl0.5 exhibits the highest Li-ion conductivity of 3.5 × 10-4 S cm-1 at room temperature (RT). Furthermore, Li symmetric cells using Li6PS5F0.5Cl0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li6PS5F0.5Cl0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li3P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

Phosphine Ligand-Free Bimetallic Ni(0)Pd(0) Nanoparticles as a Catalyst for Facile, General, Sustainable, and Highly Selective 1,4-Reductions in Aqueous Micelles.

Phosphine ligand-free bimetallic nanoparticles (NPs) composed of Ni(0)Pd(0) catalyze highly selective 1,4-reductions of enones, enamides, enenitriles, and ketoamides under aqueous micellar conditions. A minimal amount of Pd (Ni/Pd = 25:1) is needed to prepare these NPs, which results in reductions without impacting N- and O-benzyl, aldehyde, nitrile, and nitro functional groups. A broad range of substrates has been studied, including a gram-scale reaction. The metal-micelle binding is supported by surface-enhanced Raman spectroscopy data on both the NPs and their individual components. Optical imaging, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy analyses reveal the formation of NP-containing micelles or vesicles, NP morphology, particle size distribution, and chemical composition. X-ray photoelectron spectroscopy measurements indicate the oxidation state of each metal within these bimetallic NPs.

A scalable approach to topographically mediated antimicrobial surfaces based on diamond.

Bio-inspired Topographically Mediated Surfaces (TMSs) based on high aspect ratio nanostructures have recently been attracting significant attention due to their pronounced antimicrobial properties by mechanically disrupting cellular processes. However, scalability of such surfaces is often greatly limited, as most of them rely on micro/nanoscale fabrication techniques. In this report, a cost-effective, scalable, and versatile approach of utilizing diamond nanotechnology for producing TMSs, and using them for limiting the spread of emerging infectious diseases, is introduced. Specifically, diamond-based nanostructured coatings are synthesized in a single-step fabrication process with a densely packed, needle- or spike-like morphology. The antimicrobial proprieties of the diamond nanospike surface are qualitatively and quantitatively analyzed and compared to other surfaces including copper, silicon, and even other diamond surfaces without the nanostructuring. This surface is found to have superior biocidal activity, which is confirmed via scanning electron microscopy images showing definite and widespread destruction of E. coli cells on the diamond nanospike surface. Consistent antimicrobial behavior is also observed on a sample prepared seven years prior to testing date.

Shielding Effect of Nanomicelles: Stable and Catalytically Active Oxidizable Pd(0) Nanoparticle Catalyst Compatible for Cross-Couplings of Water-Sensitive Acid Chlorides in Water.

Under the shielding effect of nanomicelles, a sustainable micellar technology for the design and convenient synthesis of ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) and their subsequent catalytic exploration for couplings of water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays a crucial role in stabilizing these NPs, preventing their aggregation and oxidation state changes. These NPs were characterized using 13C nuclear magnetic resonance (NMR), infrared (IR), and surface-enhanced Raman scattering (SERS) spectroscopy to evaluate the carbonyl interactions of PS-750-M with Pd. High-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDX) studies were performed to reveal the morphology, particle size distribution, and chemical composition, whereas X-ray photoelectron spectroscopy (XPS) measurements unveiled the oxidation state of the metal. In the cross-couplings of water-sensitive acid chlorides with boronic acids, the micelle's shielding effect and boronic acids plays a vital role in preventing unwanted side reactions, including the hydrolysis of acid chlorides under basic pH. This approach is scalable and the applications are showcased in multigram scale reactions.

Active Targeting Significantly Outperforms Nanoparticle Size in Facilitating Tumor-Specific Uptake in Orthotopic Pancreatic Cancer.

Nanoparticles are widely studied as theranostic vehicles for cancer; however, clinical translation has been limited due to poor tumor specificity. Features that maximize tumor uptake remain controversial, particularly when using clinically relevant models. We report a systematic study that assesses two major features for the impact on tumor specificity, i.e., active vs passive targeting and nanoparticle size, to evaluate relative influences in vivo. Active targeting via the V7 peptide is superior to passive targeting for uptake by pancreatic tumors, irrespective of nanoparticle size, observed through in vivo imaging. Size has a secondary effect on uptake for actively targeted nanoparticles in which 26 nm nanoparticles outperform larger 45 and 73 nm nanoparticles. Nanoparticle size had no significant effect on uptake for passively targeted nanoparticles. Results highlight the superiority of active targeting over nanoparticle size for tumor uptake. These findings suggest a framework for optimizing similar nonaggregate nanoparticles for theranostic treatment of recalcitrant cancers.

Metal-Micelle Cooperativity: Phosphine Ligand-Free Ultrasmall Palladium(II) Nanoparticles for Oxidative Mizoroki-Heck-type Couplings in Water at Room Temperature.

The amphiphile PS-750-M generates stable, phosphine ligand-free, and catalytically active ultrasmall Pd(II) nanoparticles (NPs) from Pd(OAc)2, preventing their precipitation, polymerization, and oxidation state changes. PS-750-M directly interacts with Pd(II) NP surfaces, as confirmed by high-resolution mass spectrometry and IR spectroscopy, resulting in their high stability. The Pd cations in NPs are most likely held together by hydroxides and acetate ions. The NPs were characterized by HRTEM, revealing their morphology and particle size distribution, and by HRMS and IR, providing evidence for NP-amphiphile interaction. The NP catalytic activity was examined in the context of oxidative Mizoroki-Heck-type couplings in water at room temperature. Hot filtration, hot extraction, and three-phase tests indicate heterogeneous catalysis occurring at the micellar interface rather than homogeneous catalysis occurring in the solution. NMR studies indicate that the catalytic activity stems from metal cation-π interactions of the styrene along with transmetalation by the arylboronic acid, followed by insertion and ß-H elimination to furnish the coupled product along with the reoxidation of Pd by benzoquinone to complete the catalytic cycle. This method is very mild and sustainable, both in terms of NP synthesis and subsequent catalysis, and shows broad substrate scope while circumventing the need for organic solvents for this important class of couplings.

Surface Modification of Nanocrystalline LiMn2O4 Using Graphene Oxide Flakes.

In this work, a facile, wet chemical synthesis was utilized to achieve a series of lithium manganese oxide (LiMn2O4, (LMO) with 1-5%wt. graphene oxide (GO) composites. The average crystallite sizes estimated by the Rietveld method of LMO/GO nanocomposites were in the range of 18-27 nm. The electrochemical performance was studied using CR2013 coin-type cell batteries prepared from pristine LMO material and LMO modified with 5%wt. GO. Synthesized materials were tested as positive electrodes for Li-ion batteries in the voltage range between 3.0 and 4.3 V at room temperature. The specific discharge capacity after 100 cycles for LMO and LMO/5%wt. GO were 84 and 83 mAh g-1, respectively. The LMO material modified with 5%wt. of graphene oxide flakes retained more than 91% of its initial specific capacity, as compared with the 86% of pristine LMO material.

Chemical Vapor Transport Route toward Black Phosphorus Nanobelts and Nanoribbons.

Chemical vapor transport (CVT) method is widely used for bulk black phosphorus (BP) fabrication. In this work, we demonstrate that CVT provides a route for the fabrication of BP nanoribbons and nanobelts. This method consists of a two-step procedure, including initial BP column growth using the CVT technique, followed by ultrasonic treatment and centrifugation. The obtained nanostructures preserve BP column dimensions, forming ultralong ribbon-like structures with the length to the width aspect ratio of up to 500. Computational modeling of the growth mechanism of a BP flake is also presented in support of the observed columnar growth. Calculation of the average energy of the molecule in the asymmetric flakes shows that the growth of the structure in the zigzag direction is more energetically favorable than in the armchair direction.

Effect of Metal Nanoparticle Aggregate Structure on the Thermodynamics of Oxidative Dissolution.

Here, we compare the electrochemical oxidation potential of 15 nm diameter citrate-stabilized Au NPs aggregated by acid (low pH) to those aggregated by tetrakis(hydroxymethyl) phosphonium chloride (THPC). For acid-induced aggregation, the solution changes to a blue-violet color, the localized surface plasmon resonance (LSPR) band of Au NPs at 520 nm decreases along with an increase in absorbance at higher wavelengths (600-800 nm), and the peak oxidation potential (Ep) in anodic stripping voltammetry (ASV) obtained in bromide has a positive shift by as large as 200 mV. For THPC-induced aggregation (Au/THPC mole ratio = 62.5), the solution changes to a blue color as the LSPR band at 520 nm decreases and a new distinct peak at 700 nm appears, but the Ep does not exhibit a positive shift. Scanning transmission electron microscopy (STEM) images reveal that acid-induced aggregates are three-dimensional with strongly fused Au NP-Au NP contacts, while THPC-induced aggregates are linear or two-dimensional with ∼1 nm separation between Au NPs. The surface area-to-volume ratio (SA/V) decreases for acid-aggregated Au NPs due to strong Au NP-Au NP contacts, which leads to lower surface free energy and a higher Ep. The SA/V does not change for THPC-aggregated Au NPs since space remains between them and their SA is fully accessible. These findings show that metal NP oxidative stability, as determined by ASV, is highly sensitive to the details of the aggregate structure.

Insight the process of hydrazine gas adsorption on layered WS2: a first principle study.

The process of hydrazine gas adsorption on layered WS2 has been systematically studied from first principle calculations. Our results demonstrate that this adsorption process is exothermic, and hydrazine molecules are physically adsorbed. The layer-dependent adsorption energy and interlayer separation induced by van der Waals interaction exerted by hydrazine molecules lead to the difficulty in desorbing hydrazine molecules from layered WS2 as the number of layers increases. The most interesting finding is the emergence of localized impurity states below the Fermi level upon the hydrazine adsorption, irrespective of the number of WS2 layers, resulting in a significant effect on the band structures and subsequently changing its electrical conductivity. Furthermore, a layer-dependent small charge transfer occurs between hydrazine and layered WS2, leading to a charge redistribution and considerable polarization in the adsorbed systems. The existence of defects and the humidity, on the other hand, influences the sensitivity of layered WS2 to the hydrazine adsorption. Obtained results show that a perfectly layered WS2 might be a promising candidate as an efficient nanosensor to detect such toxic gas in dry environment.

ZnO ALD-Coated Microsphere-Based Sensors for Temperature Measurements.

In this paper, the application of a microsphere-based fiber-optic sensor with a 200 nm zinc oxide (ZnO) coating, deposited by the Atomic Layer Deposition (ALD) method, for temperature measurements between 100 and 300 °C, is presented. The main advantage of integrating a fiber-optic microsphere with a sensing device is the possibility of monitoring the integrity of the sensor head in real-time, which allows for higher accuracy during measurements. The study has demonstrated that ZnO ALD-coated microsphere-based sensors can be successfully used for temperature measurements. The sensitivity of the tested device was found to be 103.5 nW/°C when the sensor was coupled with a light source of 1300 nm central wavelength. The measured coefficient R2 of the sensor head was over 0.99, indicating a good fit of the theoretical linear model to the measured experimental data.

Stable and Flexible Sulfide Composite Electrolyte for High-Performance Solid-State Lithium Batteries.

Sulfide-based lithium (Li)-ion conductors represent one of the most popular solid electrolytes (SEs) for solid-state Li metal batteries (SSLMBs) with high safety. However, the commercial application of sulfide SEs is significantly limited by their chemical instability in air and electrochemical instability with electrode materials (metallic Li anode and oxide cathodes). To address these difficulties, here, we design and successfully demonstrate a novel sulfide-incorporated composite electrolyte (SCE) through the combination of inorganic sulfide Li argyrodite (Li7PS6) with poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) polymer. In this composite structure, Li7PS6 is embedded in PVDF-HFP polymer matrix, making the SCE flexible and air-stable and achieve great chemical and electrochemical stability. Meanwhile, the presence of sulfide facilitates Li-ion transport in SCE, leading to a superior room-temperature ionic conductivity of 1.1 × 10-4 S cm-1. Using the SCE with enhanced stability while maintaining high conductivity, Li||Li symmetric cells achieved stable cycling up to 1000 h at 0.2 mA cm-2. In addition, LiFePO4 (LFP)||SCE||Li cells can deliver an impressive specific capacity of 160 mAh g-1 over 150 cycles. These features indicate that Li7PS6/PVDF-HFP SCE is a promising candidate to contribute to the practical development of SSLMBs.

Strain-induced vibrational properties of few layer black phosphorus and MoTe2 via Raman spectroscopy.

We studied and compared the effect of tensile strain on the Raman spectra of black phosphorus (BP) and molybdenum ditelluride (MoTe2) crystals by using a simple custom strain device. In-situ Raman spectroscopy on BP revealed clear red shifting of all three phonon modes, A1 g, B2g and A2 g, under tensile stress. From our theoretical analyses, we found that such red shifting strongly depends on the direction of the strain exerted on the system even within the elastic deformation limit (i.e. strain ≤ 1 %). In particular, calculated results for the strain along the armchair direction are consistent with our experimental data, confirming that the strain applied to the sample acts effectively along the armchair direction. In a comparative study, we found that the effect of strain on the Raman shifting is larger for BP than that for MoTe2, presumably due to the smaller Young's modulus of BP. We also see a remarkable resemblance between donor-type intercalation induced vibrational properties and tensile stress-induced vibrational properties in BP. We anticipate that our method of in-situ Raman spectroscopy can be an effective tool that can allow observation of strain effect directly which is critical for future flexible electronic devices.

Iodine activation: a general method for catalytic enhancement of thiolate monolayer-protected metal clusters.

To enhance catalytic activity, the present study details a general approach for partial thiolate ligand removal from monolayer-protected clusters (MPCs) by straightforward in situ addition of iodine. Two model reactions are examined to illustrate the effects on the catalytic activity of glutathione (SG)-capped Au MPCs serving as a catalyst for the NaBH4 reduction of 4-nitrophenol to 4-aminophenol and SG-capped Pd MPCs serving as a catalyst for the hydrogenation/isomerization of allyl alcohol. Iodine addition promoted partial thiolate ligand removal from both MPCs and improved the catalytic properties, presumably due to greater surface exposure of the metal cores as a result of ligand dissociation. The rate of 4-nitrophenol reduction increased from 0.066 min-1 in the absence of I2 to 0.505 min-1 in the presence of 2.0 equivalents I2 (equivalents based on total ligated glutathione). The reaction of allyl alcohol to produce 1-propanol and propanal was similarly accelerated as indicated by the increase in turnover frequency from 131 to 230 moles products per moles catalyst per h by addition of 0.2 equivalents I2. In both reactions, as the amount of I2 added increases the catalyst recyclability decreases due to catalyst instability. Low equivalents of I2 are optimal when considering both reaction rate and catalyst recyclability.