Nanohybrids of 2D Black Phosphorus with Phthalocyanines: Role of Interfacial Interactions in Heterostructure Development.

New 2D black phosphorus (bP)-phthalocyanine (Pc) nanohybrids have been synthesized by liquid phase exfoliation of black phosphorus crystals in the presence of two organic dyes: phthalocyanine (Pc) and manganese phthalocyanine (MnPc). The key role of the metal cation in the interfacial interaction between the organic dye and bP nanosheets was demonstrated by X-ray absorption spectroscopy and associated with an electron transfer between the metal cation Mn and bP nanosheets, which resembles a coordinative chemical bond. On the other hand, the interaction between bP nanosheets and pure phthalocyanine is governed by van der Waals forces.

Black phosphorus-based nanoplatforms for cancer therapy: chemistry, design, biological and therapeutic behaviors.

Cancer, a significant threat to human lives, has been the target of research for several decades. Although conventional therapies have drawbacks, such as side effects, low efficacy, and weak targeting, they have been applied extensively due to a lack of effective alternatives. The emergence of nanotechnology in medicine has opened up new possibilities and offered promising solutions for cancer therapy.

Melting Curve of Black Phosphorus: Evidence for a Solid-Liquid-Liquid Triple Point.

Black phosphorus (bP) is a crystalline material that can be seen as an ordered stacking of two-dimensional layers, which results in outstanding anisotropic physical properties. The knowledge of its pressure ()-temperature () phase diagram, and in particular, of its melting curve is fundamental for a better understanding of the synthesis and stability conditions of this element. Despite the numerous studies devoted to this subject, significant uncertainties remain regarding the determination of the position and slope of its melting curve.

Mechanical Transfer of Black Phosphorus on a Silk Fibroin Substrate: A Viable Method for Photoresponsive and Printable Biomaterials.

Despite the technological importance of semiconductor black phosphorus (BP) in materials science, maintaining the stability of BP crystals in organic media and protecting them from environmental oxidation remains challenging. In this study, we present the synthesis of bulk BP and the exploitation of the viscoelastic properties of a regenerated silk fibroin (SF) film as a biocompatible substrate to transfer BP flakes, thereby preventing oxidation. A model based on the flow of polymers revealed that the applied flow-induced stresses exceed the yield stress of the BP aggregate.

Anisotropic thermo-mechanical response of layered hexagonal boron nitride and black phosphorus: application as a simultaneous pressure and temperature sensor.

Hexagonal boron nitride (hBN) and black phosphorus (bP) are crystalline materials that can be seen as ordered stackings of two-dimensional layers, which lead to outstanding anisotropic physical properties. Knowledge of the thermal equations of state of hBN and bP is of great interest in the field of 2D materials for a better understanding of their anisotropic thermo-mechanical properties and exfoliation mechanism towards the preparation of important single-layer materials like hexagonal boron nitride nanosheets and phosphorene. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the thermoelastic parameters of hBN and bP.

Stability, Chemical Bonding, and Electron Lone Pair Localization in AsN at High Pressure by Density Functional Theory Calculations.

The covalent bonding framework of crystalline single-bonded cubic AsN, recently synthesized under high pressure and high temperature conditions in a laser-heated diamond anvil cell, is here studied by means of density functional theory calculations and compared to single crystal X-ray diffraction data. The precise localization of the nonbonding electron lone pairs and the determination of their distances and orientations are related to the presence of characteristic structural motifs and space regions of the unit cell dominated by repulsive electronic interactions, with the relative orientation of the electron lone pairs playing a key role in minimizing the energy of the structure. We find that the vibrational modes associated with the expression of the lone pairs are strongly localized, an observation that may have implications for the thermal conductivity of the compound.

A theragenerative bio-nanocomposite consisting of black phosphorus quantum dots for bone cancer therapy and regeneration.

Recently, the term theragenerative has been proposed for biomaterials capable of inducing therapeutic approaches followed by repairing/regenerating the tissue/organ. This study is focused on the design of a new theragenerative nanocomposite composed of an amphiphilic non-ionic surfactant (Pluronic F127), bioactive glass (BG), and black phosphorus (BP). The nanocomposite was prepared through a two-step synthetic strategy, including a microwave treatment that turned BP nanosheets (BPNS) into quantum dots (BPQDs) with 5 ± 2 nm dimensions .

High-pressure and high-temperature synthesis of crystalline Sb N.

A chemical reaction between Sb and N was induced under high-pressure (32-35 GPa) and high-temperature (1600-2200 K) conditions, generated by a laser heated diamond anvil cell. The reaction product was identified by single crystal synchrotron X-ray diffraction at 35 GPa and room temperature as crystalline antimony nitride with Sb N stoichiometry and structure belonging to orthorhombic space group Cmc2 . Only Sb-N bonds are present in the covalent bonding framework, with two types of Sb atoms respectively forming SbN distorted octahedra and trigonal prisms and three types of N atoms forming NSb distorted tetrahedra and NSb trigonal pyramids.

Unraveling the Role of Nickel Nanoparticles Functionalization in the Electronic Properties and Structural Features of 2D Black Phosphorene Exposed to Ambient Conditions.

Layered black phosphorus (BP) is endowed with peculiar chemico-physical properties that make it a highly promising candidate in the field of electronics. Nevertheless, as other 2D materials with atomic scale thickness, it suffers from easy degradation under ambient conditions. Herein, it is shown that the functionalization of BP with preformed and in situ grown Ni NPs, affects the electronic properties of the material.

Black or red phosphorus yields the same blue phosphorus film.

After the discovery of graphene, many other 2D materials have been predicted theoretically and successfully prepared. In this context, single-sheet black phosphorus - phosphorene - is emerging as a viable contender in the field of (2D) semiconductors. Phosphorene offers high carrier mobility and an anisotropic structure that gives rise to a modulation of physical and chemical properties.

High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-PN.

The direct chemical reactivity between phosphorus and nitrogen was induced under high-pressure and high-temperature conditions (9.1 GPa and 2000-2500 K), generated by a laser-heated diamond anvil cell and studied by synchrotron X-ray diffraction, Raman spectroscopy, and DFT calculations. α-PN and γ-PN were identified as reaction products.

Label-Free Morpho-Molecular Imaging for Studying the Differential Interaction of Black Phosphorus with Tumor Cells.

Black phosphorus nanosheets (2D BP) are emerging as very promising, highly selective chemotherapeutic agents due to their fast degradation in the intracellular matrix of cancer cells. Here, optical diffraction tomography (ODT) and Raman spectroscopy were exploited as a powerful label-free approach to achieve integrated insights into the processes accompanying the administration of exfoliated 2D BP flakes in human prostatic adenocarcinoma and normal human prostate epithelial cells. Our ODT experiments provided unambiguous visualization of the 2D BP internalization in cancer cells and the morphological modifications of those cells in the apoptotic phase.

Evidence of Josephson Coupling in a Few-Layer Black Phosphorus Planar Josephson Junction.

Setting up strong Josephson coupling in van der Waals materials in close proximity to superconductors offers several opportunities both to inspect fundamental physics and to develop cryogenic quantum technologies. Here we show evidence of Josephson coupling in a planar few-layer black phosphorus junction. The planar geometry allows us to probe the junction behavior by means of external gates, at different carrier concentrations.

Single-Bonded Cubic AsN from High-Pressure and High-Temperature Chemical Reactivity of Arsenic and Nitrogen.

Chemical reactivity between As and N , leading to the synthesis of crystalline arsenic nitride, is here reported under high pressure and high temperature conditions generated by laser heating in a diamond anvil cell. Single-crystal synchrotron X-ray diffraction at different pressures between 30 and 40 GPa provides evidence for the synthesis of a covalent compound of AsN stoichiometry, crystallizing in a cubic P2 3 space group, in which each of the two elements is single-bonded to three atoms of the other and hosts an electron lone pair, in a tetrahedral anisotropic coordination. The identification of characteristic structural motifs highlights the key role played by the directional repulsive interactions between non-bonding electron lone pairs in the formation of the AsN structure.

Air Stable Nickel-Decorated Black Phosphorus and Its Room-Temperature Chemiresistive Gas Sensor Capabilities.

In the rapidly emerging field of layered two-dimensional functional materials, black phosphorus, the P-counterpart of graphene, is a potential candidate for various applications, e.g., nanoscale optoelectronics, rechargeable ion batteries, electrocatalysts, thermoelectrics, solar cells, and sensors.

Dispersion of Few-Layer Black Phosphorus in Binary Polymer Blend and Block Copolymer Matrices.

Exfoliated black phosphorus (bP) embedded into a polymer is preserved from oxidation, is stable to air, light, and humidity, and can be further processed into devices without degrading its properties. Most of the examples of exfoliated bP/polymer composites involve a single polymer matrix. Herein, we report the preparation of biphasic polystyrene/poly(methyl methacrylate) (50/50 wt.

Easy and fast in situ functionalization of exfoliated 2D black phosphorus with gold nanoparticles.

Heterostructures of single- and few-layer black phosphorus (2D bP) functionalized with gold nanoparticles (Au NPs) have been recently reported in the literature, exploiting their intriguing properties and biocompatibility for catalytic, therapeutical and diagnostic applications. However, a deeper insight on the structural and electronic properties at the interface of the 2D bP/Au NP heterostructure is still lacking. In this work, 2D bP is functionalized with Au nanoparticles (NPs) through in situ deposition-precipitation heterogeneous reaction.

Interlayer Coordination of Pd-Pd Units in Exfoliated Black Phosphorus.

The chemical functionalization of 2D exfoliated black phosphorus (2D BP) continues to attract great interest, although a satisfactory structural characterization of the functionalized material has seldom been achieved. Herein, we provide the first complete structural characterization of 2D BP functionalized with rare discrete Pd units, obtained through a mild decomposition of the organometallic dimeric precursor [Pd(η-CH)Cl]. A multitechnique approach, including HAADF-STEM, solid-state NMR, XPS, and XAS, was used to study in detail the morphology of the palladated nanosheets (Pd/BP) and to unravel the coordination of Pd units to phosphorus atoms of 2D BP.

Large-Area Oxidized Phosphorene Nanoflakes Obtained by Electrospray for Energy-Harvesting Applications.

Bidimensional (2D) materials are nowadays being developed as outstanding candidates for electronic and optoelectronic components and devices. Targeted applications include sensing, energy conversion, and storage. Phosphorene is one of the most promising systems in this context, but its high reactivity under atmospheric conditions and its small-area/lab-scale deposition techniques have hampered the introduction of this material in real-world applications so far.

2D exfoliated black phosphorus influences healthy and cancer prostate cell behaviors.

Nowadays, prostate cancer is the most widespread tumour in worldwide male population. Actually, brachytherapy is the most advanced radiotherapy strategy for the local treatment of prostate cancer. It consists in the placing of radioactive sources closed to the tumour side thus killing cancer cells.

High pressure synthesis of phosphine from the elements and the discovery of the missing (PH)H tile.

High pressure reactivity of phosphorus and hydrogen is relevant to fundamental chemistry, energy conversion and storage, and materials science. Here we report the synthesis of (PH)H, a crystalline van der Waals (vdW) compound (I4cm) made of PH and H molecules, in a Diamond Anvil Cell by direct catalyst-free high pressure (1.2 GPa) and high temperature (T ≲ 1000 K) chemical reaction of black phosphorus and liquid hydrogen, followed by room T compression above 3.

First exfoliated Ru-Ru-Au organometallic polymer with layered structure.

A new water soluble heterometallic polymeric complex [{(PTA)2CpRu-μ-CN-1κC:2κ2N-RuCp(PTA)2}-μ-{Au(CN)4}4]n·2H2O (1) is synthesized and characterized by single crystal X-ray diffraction. This complex self-assembles forming 3D polymeric structures with large scale hexagonal conformation. They also organize as 3D stacks of polymer sandwiches that can be exfoliated providing mono heterometallic-3D layers, as shown by electron microscopy.

Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles.

Since its discovery, the environmental instability of exfoliated black phosphorus (2D bP) has emerged as a challenge that hampers its wide application in chemistry, physics, and materials science. Many studies have been carried out to overcome this drawback. Here we show a relevant enhancement of ambient stability in few-layer bP decorated with nickel nanoparticles as compared to pristine bP.

Anisotropic thermal expansion of black phosphorus from nanoscale dynamics of phosphorene layers.

Black phosphorus (bP) is a crystalline material which can be seen as an ordered stacking of two-dimensional layers, referred to as phosphorene. The knowledge of the linear thermal expansion coefficients (LTECs) of bP is of great interest in the field of 2D materials for a better understanding of the anisotropic thermal properties and exfoliation mechanism of this material. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the LTECs of bP.