Near-infrared two-photon excited photoluminescence from Yb3+-doped CsPbClxBr3-x perovskite nanocrystals embedded into amphiphilic silica microspheres.

Nonlinear absorption of metal-halide perovskite nanocrystals (NCs) makes them an ideal candidate for applications which require multiphoton-excited photoluminescence. By doping perovskite NCs with lanthanides, their emission can be extended into the near-infrared (NIR) spectral region. We demonstrate how the combination of Yb3+ doping and bandgap engineering of cesium lead halide perovskite NCs performed by anion exchange (from Cl- to Br-) leads to efficient and tunable emitters that operate under two-photon excitation in the NIR spectral region. By optimizing the anion composition, Yb3+-doped CsPbClxBr3-x NCs exhibited high values of two-photon absorption cross-section reaching 2.3 × 105 GM, and displayed dual-band emission located both in the visible (407-493 nm) and NIR (985 nm). With a view of practical applications of bio-visualisation in the NIR spectral range, these NCs were embedded into silica microspheres which were further wrapped with amphiphilic polymer shells to ensure their water-compatibility. The resulting microspheres with embedded NCs could be easily dispersed in both toluene and water, while still exhibiting a dual-band emission in visible and NIR under both one- and two-photon excitation conditions.

Synthesis and Study of Organic Nanostructures Fabricated by Inclusion of 2-Methylbenzimidazole Molecules in Nanotubes of Chrysotile Asbestos, Mesoporous Silica, and Nanopores of Borate Glasses.

New organic nanostructures were synthesized by introducing 2-methylbenzimidazole (MBI) molecules from a melt, gas phase, or alcoholic solution into nanosized voids of borate porous glasses (PG), nanotubes of chrysotile asbestos (ChA), and mesoporous silica (MS). The incorporation of MBI into borate glasses with different pore sizes is accompanied by the appearance of several phases formed by nanocrystallites which have a MBI crystal structure, but somewhat differ in lattice parameters. The size of some crystallites significantly exceeds the size of nanopores, which indicates the presence of long-scale correlations of the crystal structure. The size of MBI nanocrystallites in ChA was close to the diameter of nanotubes (D ~10 nm), which shows the absence of crystal structure correlations. The XRD pattern of mesoporous silica filled by MBI does not exhibit reflections caused by MBI and a presence of MBI was confirmed only by the analysis of correlation function. The incorporation of MBI molecules into matrices is observed through optical IR absorption spectroscopy (FTIR) and photoluminescence. Introducing MBI in ChA and MS is followed by the appearance of bright green photoluminescence, the spectral structure of which is analogous to MBI crystals but slightly shifted in the blue region, probably due to a quantum-size effect. The influence of MBI inclusion in PG and ChA on the permittivity, dielectric losses, conductivity, and parameters of their hopping conductivity is analyzed.

Special Issue "Application Progress and Insights of Nanoporous Materials".

Application Progress and Insights of Nanoporous Materials is an open Special Issue in International Journal of Molecular Sciences, which aims to publish original research and review papers concerning fundamental and applied aspects of nanoporous materials of various composition and morphology, investigation of their properties and underlying mechanisms for fabrication of porous media with the desired characteristics [...].

Special Issue "Applications of Porous Nanotubes".

"Applications of Porous Nanotubes" is an open Special Issue of Materials, which aims to publish original contributions and review papers on new fundamental and applied aspects of porous nanomaterials, and to investigate their properties and underlying mechanisms for development of various porous media with a desired functionality [...].

Carbon Dots with an Emission in the Near Infrared Produced from Organic Dyes in Porous Silica Microsphere Templates.

Carbon dots (CDs) with an emission in the near infrared spectral region are attractive due to their promising applications in bio-related areas, while their fabrication still remains a challenging task. Herein, we developed a template-assisted method using porous silica microspheres for the formation of CDs with optical transitions in the near infrared. Two organic dyes, Rhodamine 6G and IR1061 with emission in the yellow and near infrared spectral regions, respectively, were used as precursors for CDs. Correlation of morphology and chemical composition with optical properties of obtained CDs revealed the origin of their emission, which is related to the CDs' core optical transitions and dye-derivatives within CDs. By varying annealing temperature, different kinds of optical centers as derivatives of organic dyes are formed in the microsphere's pores. The template-assisted method allows us to synthesize CDs with an emission peaked at 1085 nm and photoluminescence quantum yield of 0.2%, which is the highest value reported so far for CDs emitting at wavelengths longer than 1050 nm.

Micro-mesoporous submicron silica particles with pore size tunable in a wide range: synthesis, properties and prospects for LED manufacturing.

An approach has been developed that allows the synthesis of submicron spherical silica particles with a controlled micro-mesoporous structure possessing a large specific surface area (up to 1300 m2g-1). Particle synthesis is carried out by the hydrolysis of a mixture of various organosilanes mostly associated either with CTAB or with each other. A change in the concentration of CTAB in the reaction mixture apparently leads to a change in the formation mechanism of nuclei for the silica particle growth, which allows for varying the diameter of the synthesized particles in the range from 40-450 nm. The effect of the composition of the silica precursor ([3-(methacryloyloxy)propyl]trimethoxysilane, (3-aminopropyl)triethoxysilane and tetraethoxysilane) on the formation process and porosity of the resulting particles is studied. It was shown that by simply varying the ratio of organosilanes in the composition of the precursor, one can control the pore diameter of the particles in a wide range from 0.6-15 nm. The large-pore (up to 15 nm) silica particles are used as a matrix for the spatial distribution of luminescent carbon dots. The incorporation of carbon dots into SiO2particles prevents their aggregation leading to emission quenching after drying, thus allowing us to obtain highly luminescent composite particles. LEDs based on the obtained composite material show bright visible luminescence with spectral characteristics similar to that of a commercial cold white LED.

Interface Chemical Modification between All-Inorganic Perovskite Nanocrystals and Porous Silica Microspheres for Composite Materials with Improved Emission.

In recent years, there has been rapid progress in the development of photonic devices based on lead halide perovskite nanocrystals since they possess a set of unique optical and charge transport properties. However, the main limiting factor for their subsequent application is poor stability against exposure to adverse environmental conditions. In this work, a study of a composite material based on perovskite CsPbBr3 nanocrystals embedded in porous silica microspheres is presented. We developed two different approaches to change the interface between nanocrystals and the surface of the microsphere pores: surface treatment of (i) nanocrystals or (ii) microspheres. The surface modification with tetraethylorthosilicate molecules not only increased stability but also improved the optical responses of the composite material. The position of the emission band remained almost unchanged, but its lifetime increased significantly compared to the initial value. The improvement of the optical performance via surface modification with tetraethylorthosilicate molecules also works for the lead-free Bi-doped Cs2AgInCl6 double perovskite nanocrystals leading to increased stability of their optical responses at ambient conditions. These results clearly demonstrate the advantage of a composite material that can be used in novel photonic devices with improved performance.

Strongly Luminescent Composites Based on Carbon Dots Embedded in a Nanoporous Silicate Glass.

Luminescent composites based on entirely non-toxic, environmentally friendly compounds are in high demand for a variety of applications in photonics and optoelectronics. Carbon dots are a recently developed kind of luminescent nanomaterial that is eco-friendly, biocompatible, easy-to-obtain, and inexpensive, with a stable and widely tunable emission. Herein, we introduce luminescent composites based on carbon dots of different chemical compositions and with different functional groups at the surface which were embedded in a nanoporous silicate glass. The structure and optical properties of these composites were comprehensively examined using electron microscopy, Fourier transform infrared transmission, UV-Vis absorption, and steady-state and time-resolved photoluminescence. It is shown that the silicate matrix efficiently preserved, and even enhanced the emission of different kinds of carbon dots tested. The photoluminescence quantum yield of the fabricated nanocomposite materials reached 35-40%, which is comparable to or even exceeds the values for carbon dots in solution.

Fluorescence enhancement of monodisperse carbon nanodots treated with aqueous ammonia and hydrogen peroxide.

The treatment of monodisperse carbon nanodots (MCNDs) with a combination of aqueous ammonia and hydrogen peroxide is found to result in a prominent enhancement of their fluorescence efficiency. Depending on the hydrogen peroxide concentration, an increase of the MCNDs quantum yield of up to seven-fold has been achieved. Considering the absence of prominent changes in fluorescence lifetime and fluorescence spectra upon the treatment it is suggested that the observed rise of fluorescence efficiency originates from additional formation of new isolated sp2 domains surrounded by defect sites. The structural modification of MCNDs induced by their treatment with combination of aqueous ammonia and hydrogen peroxide is indicated by both transmission electron microscopy images and infrared spectra. The applied method has insignificant effect on the aggregation properties and size distribution of the studied MCNDs. Taking into account the proposed mechanism, the applied treatment procedure can serve as a basis for a facile approach for modification of emissive properties of various nanocarbon structures.

Enhanced stability of the optical responses from all-inorganic perovskite nanocrystals embedded in a synthetic opal matrix.

Nanostructured luminescent materials based on perovskite nanocrystals (p-NCs) are attractive since their optical properties can be tuned in a wide spectral range with high luminescence quantum yields and lifetimes, however, they lack stability. In this work, the optical properties of highly luminescent colloidal p-NCs (CsPbX3, where X = Cl/Br, Br, I) embedded in porous opal matrices are presented. It is shown that the photoluminescence of the p-NCs embedded into opal matrices possess increased longtime stability of its spectral and kinetic parameters under ambient conditions. LEDs based on the developed materials show pure color p-NC emission with stability of its parameters. The results of this work may expand the knowledge of interactions between luminescent nanoparticles within multicomponent nanostructured materials for further photonic applications.

Controllable spherical aggregation of monodisperse carbon nanodots.

Monodisperse carbon nanodots (MCNDs) having an identical composition, structure, shape and size possess identical chemical and physical properties, making them highly promising for various technical and medical applications. Herein, we report a facile and effective route to obtain monodisperse carbon nanodots 3.5 ± 0.9 nm in size by thermal decomposition of organosilane within the pores of monodisperse mesoporous silica particles with subsequent removal of the silica template. Structural studies demonstrated that the MCNDs we synthesized consist of ∼7-10 defective graphene layers that are misoriented with respect to each other and contain various oxygen-containing functional groups. It was demonstrated that, owing to their identical size and chemical composition, the MCNDs are formed via coagulation primary aggregates ∼10-30 nm in size, which are, in turn, combined into secondary porous spherical aggregates ∼100-200 nm in diameter. The processes of coagulation of MCNDs and peptization of their hierarchical aggregates are fully reversible and can be controlled by varying the MCND concentration or the pH value of the hydrosols. Submicrometer spherical aggregates of MCNDs are not disintegrated as the hydrosol is dried. The thus obtained porous spherical aggregates of MCNDs are promising for drug delivery as a self-disassembling container for medicinal preparations.

Ni-functionalized submicron mesoporous silica particles as a sorbent for metal affinity chromatography.

In this research, a novel IMAC sorbent with high specificity for chlorine-containing compounds was developed. Ni-functionalized monodisperse spherical mesoporous silica particles of 500±25nm diameter were synthesized and their metal affinity properties were studied with the use of diclofenac as the model substance. The particles were aggregatively stable in the pH range of 3-12. The sorbent demonstrated a high adsorption capacity (0.60±0.06µg of DCF per 1mg of the sorbent) and high adsorption/desorption rate (20 and 5min was enough for the sorbent saturation and desorption of DCF, correspondingly). A mixture of eluents with addition of PFOS providing the almost complete recovery (98%) of diclofenac was first proposed. The monodispersity and the high sedimentation and aggregative stability of the particles provide the formation of a stable hydrosol even under ultrasound treatment which makes the mSiO2/Ni particles suitable for batch chromatography.