Dispersion Of Nanocrystals Research Articles

Glass-ceramic materials: influence of fluoride nanocrystals on emission properties of lanthanide ions

In this work, the oxyfluoride glass-ceramic materials containing LaF3 nanocrystals, prepared by using the sol-gel method, were described. The influence of fluoride nanocrystals on the photoluminescence properties of selected lanthanide ions was determined. The experimental results obtained for nano-glass-ceramics were compared to the precursor xerogels. Those Ln3+-doped sol-gel materials with dispersed LaF3 nanocrystals exhibit several visible emission bands. It was observed that heat-treatment process caused the elongation of the lifetimes of the 5D0 state from τ = 0.22 ms to τ1 = 0.79 ms, τ2 = 9.76 ms (for Eu3+-doped materials) and of the 4F9/2 state from τ = 0.027 ms to τ1 = 0.034 ms, τ2 = 1.731 ms (for Dy3+‑doped materials). The performed studies clearly revealed that luminescence behaviour also depends on an activator concentration and a distribution of energy levels of lanthanide ions.

Cellulose nanocrystal dispersion-ability in polylactides with various molecular weights prepared in dichloromethane/dimethyl sulfoxide solvents for electrospinning applications

In this study, effects of polylactide molecular weight, i.e., high (HPLA), medium (MPLA), low (LPLA), and dichloromethane (DCM)/dimethyl sulfoxide (DMSO) blend ratio on cellulose nanocrystal (CNC) dispersion quality in solution casted PLA/CNC nanocomposites were investigated via small amplitude oscillatory shear rheological analysis, while crystallization behavior, thermal degradation, morphological structure of the nanocomposites were also reported. Due to its low dielectric constant, none of the nanocomposites with 100DCM indicated a change in their complex viscosity as a result of poor CNC dispersion. This is while the increase in DMSO content (50%vv−1) improved CNC dispersion. The superior CNC dispersion-ability in PLAs with lower molecular weight was confirmed. The poorer CNC dispersion in HPLA attributes to hindering effect of higher molecular weight on solvent and nanoparticle diffusion. The better dispersed CNCs influenced crystal nucleation behavior of PLAs and increased crystallinity degree. In addition, the impact of well-dispersed CNCs on fiber formation quality of nanocomposites was reported. Introducing finely dispersed CNCs (1 wt%) in LPLA refined fiber diameters around 1200 nm with more homogenous structure. Besides, the use of 100DCM and the use of DMSO at high contents (50%vv−1) deteriorated fiber formation, respectively, due to low conductivity of DCM and high boiling temperature of DMSO.

Using Rheology and Image Processing to Study the Effects of Cellulose Nanocrystal Sedimentation.

The effect of sedimentation on lyotropic liquid crystalline dispersions is both an interesting subject in colloidal science and is of practical importance for understanding changes that can occur during dispersion storage. This research explored how the seemingly subtle changes in average length resulting from a single sedimentation step affected the rheological properties and self-assembly of aqueous dispersions of sulfated cellulose nanocrystals. Sedimentation of a primarily isotropic aqueous cellulose nanocrystal dispersion for 1 month at ambient conditions resulted in an isotropic top phase and a biphasic bottom phase, which were separated for further study. Both atomic force microscopy measurements and intrinsic viscosities determined via Fedor's equation showed preferential fractionation of longer cellulose nanocrystals (CNCs) to the bottom phase. The effects of this fractionation on dispersion rheology and phase behavior were studied by preparing a range of concentrations from each phase. As expected, the concentration for the isotropic-biphasic phase transition was significantly lower for the bottom phase than for the top phase or parent dispersion. Rheological changes were generally subtle, but significant differences were seen in the storage modulus at concentrations approaching rheological gelation. Most notably, quantitative image processing showed that even this simple, single-step fractionation process had a significant impact on the relative proportion of tactoids and chiral helices with planar and homeotropic anchoring in self-assembled cellulose nanocrystal films. These results highlight the impact that changes in polydispersity due to sedimentation can have on the self-assembly of nanomaterial mesogens.

Innovative Air Cathode with Ni-Doped Cobalt Sulfide in Highly Ordered Macroporous Carbon Matrix for Rechargeable Zn-Air Battery.

To realize the practical application of rechargeable Zn-Air batteries (ZABs), it is imperative to develop a non-noble metal-based electrocatalyst with high electrochemical performance for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, Ni-doped Co9S8 nanoparticles dispersed on an inverse opal-structured N, S co-doped carbon matrix (IO─NixCo9-xS8@NSC) as a bifunctional electrocatalyst is presented. The unique 3D porous structure, arranged in an inverse opal pattern, provides a large active surface area. Also, the conductive carbon substrate ensures the homogeneous dispersion of NixCo9-xS8 nanocrystals, preventing aggregation and increasing the exposure of active sites. The introduction of heteroatom dopants into the Co9S8 structure generates defect sites and enhances surface polarity, thereby improving electrocatalytic performance in alkaline solutions. Consequently, the IO─NixCo9-xS8@NSC shows excellent bifunctional activity with a high half-wave potential of 0.926V for ORR and a low overpotential of 289mV at 10mA cm-2 for OER. Moreover, the rechargeable ZAB assembled with prepared electrocatalyst exhibits a higher specific capacity (768 mAh gZn -1), peak power density (180.2mW cm-2), and outstanding stability (over 160h) compared to precious metal-based electrocatalyst.

Study on the preparation and magnetodielectric properties of ferrite composite Co2Z/LFO-LZT for broadband antenna application

Magnetic materials are anticipated to address the bandwidth and size limitations of dielectric resonant antennas (DRAs) to fulfill the application demands of 5G base station antennas. The present study focuses on the development of a novel Co2Z/LFO-LZT magnetic composite with exceptional microwave dielectric-magnetic properties through a hybrid ceramic process. The proposed ceramic achieves uniform dispersion of spinel magnetic nanocrystals at the grain boundary of Co2Z, resulting in the formation of a particular micro-concrete structure that significantly enhances ceramic densification and reduces magnetic-dielectric loss. The electromagnetic parameters of the ceramic optimized and used for antenna design are εr = 11; μr = 2; tanδε = 0.001; tanδμ = 0.08 at 5 GHz. A high-performance Magnetodielectric Resonant Antenna (MDRA) was designed, which exhibits a low profile of 11.4% λ0 at 5 GHz, and broadband performance covering 19.0% and 11.8% bandwidth at 5 and 8 GHz.

Revival of Degraded CsPbI3 Nanocrystals by Diselenide Ligand and Nanocrystal Self-Assembly on Nanofibrilar Ligand Template.

Among the lead halide perovskite (LHP) family, CsPbI3 is known to be significantly vulnerable to moisture, which hinders its use in real device applications. It is reported that chalcogen-based ligands can better stabilize CsPbI3 and revive nanocrystals (NCs). Here, diphenyl diselenide (DPhDSe) ligand is used to revive the degraded CsPbI3 NCs through a post-synthetic treatment of adding a small amount of DPhDSe in the degraded NC dispersion. DPhDSe in the dispersion formed nanofibrillar crystals at a low temperature through the π-π stacking of the phenyl ring. The nanofibrils played as a template on which the NCs self-assembled and they are attached side-by-side to form microfibers. The microfiber powder containing the NCs is optically stable at ambient conditions and morphologically self-healable by mild thermal annealing due to the dynamic Se─Se bond. The mechanism of the structural changes, optical transitions, and chemical changes has been systematically characterized through electron microscopy, diffraction, spectroscopy, and elemental analysis.

Enhancing luminescence from visible to mid-infrared: Controllable crystallization in ZnF2-AlF3 fluoride glass-ceramics

This study presents the synthesis of innovative fluoride glass-ceramics (GCs) via a melt-quenching technique followed by heat treatment, enabling the controlled formation of ZnF2 nanocrystals within an Er3+-doped ZnF2-AlF3 fluoride glass matrix. The uniform dispersion of ZnF2 nanocrystals throughout the glass matrix was confirmed through X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Remarkably, the crystallized glass samples retained high levels of transparency. Enhanced luminescence across visible to mid-infrared spectral regions was observed in the Er3+-doped ZnF2-AlF3 based fluoride glass-ceramics compared to their precursor glass, signaling a significant improvement. These findings underscore the potential of the developed fluoride glass-ceramics as promising materials for laser applications and mark a significant step forward in the development of fluoride crystallized fibers.

Synergistic Effect of UiO-66 Directly Grown on Kombucha-Derived Bacterial Cellulose for Dye Removal.

Metal-Organic Frameworks (MOFs) are particularly attractive sorbents with great potential for the removal of toxic dye pollutants from industrial wastewaters. The uniform dispersion of MOF particles on suitable substrates then represents a key condition to improve their processability and provide good accessibility to the active sites. In this work, we investigate the efficiency of a natural bacterial cellulose material derived from Kombucha (KBC) as an active functional support for growing and anchoring MOF particles with UiO-66 structures. An original hierarchical microstructure was obtained for the as-developed Kombucha cellulose/UiO-66 (KBC-UiO) composite material, with small MOF crystals (~100 nm) covering the cellulose fibers. Promising adsorption properties were demonstrated for anionic organic dyes such as fluorescein or bromophenol blue in water at pH 5 and pH 7 (more than 90% and 50% removal efficiency, respectively, after 10 min in static conditions). This performance was attributed to both the high accessibility and uniform dispersion of the MOF nanocrystals on the KBC fibers together with the synergistic effects involving the attractive adsorbing properties of UiO-66 and the surface chemistry of KBC. The results of this study provide a simple and generic approach for the design of bio-sourced adsorbents and filters for pollutants abatement and wastewater treatment.

Stearic acid enhanced starch nanocrystal integration in cassava starch film

SummaryStarch nanocrystals (SNCs) have emerged as promising biodegradable nanomaterial for the enhancement of biopolymer films' properties. Nevertheless, using SNCs alone is difficult due to restricted capacity for nanocrystal integration within the film's matrix. The objective of this study was to enhance the properties of biopolymer films using waxy corn starch nanocrystals supplemented with stearic acid. Cassava starch films containing varying proportions of SNCs (0–20 wt.% starch) and steric acid (2%) were prepared and characterised. The inclusion of stearic acid substantially improved SNC integration from 5% to 15%, yielding nanocomposite films with better tensile strength, thermal stability and barrier properties than those prepared with native starch or starch‐fatty acid alone. The improvement in film properties was attributed to V‐amylose complexes formation, increased crystallinity and hydrophobicity. Microscopy images revealed homogenous film surfaces, depicting greater nanocrystal dispersibility. The supplementation of lipid additives offers a valuable strategy to improve the integration of SNCs in film matrices.

Cellulose nanocrystal dispersions conjugated with symmetric and asymmetric dialkylamine groups

The present study discusses the effect of symmetric and asymmetric grafting on the surface of CNCs (cellulose nanocrystals) on their dispersion properties using dialkyl azetidinium salts. Three dialkylamine of different size and chain length were successfully grafted to the sulfate groups on the surface of CNCs by conjugation of azetidinium salts. The coupling process resulted in the formation of 2-hydroxypropyl-N-dialkylamine conjugated to the CNC sulfate groups abbreviated as Cn\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_n$$\\end{document}-N-Cm\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_m$$\\end{document}-Prop-2-OH-CNC, where m, n are the number of carbons in the alkyl groups, each with a total of m+n=12\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$m+n=12$$\\end{document}, with (m,n)=(11,1);(9,3);(6,6)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$(m,n) = (11,1); (9,3); (6,6)$$\\end{document}. Molecular dynamics simulations were used to assess the probable morphology of the grafted chains and the interaction potential between CNCs. Steady shear simultaneously combined with polarized light imaging and oscillatory shear rheological measurements were used to evaluate for the first time the impact of the CNC surface modifications on their dispersion flow and optical properties. Overall, the results show that the different linker topologies could effectively promote different types of aggregation morphologies based on the size of the linker, their flexibility and their most probable conformation.

Forming a disordered atomic layer to bond TiN or AlN ceramic with Sn[sbnd]9Zn metal under ultrasonication

A disordered atomic layer instead of traditional intermetallic compounds is formed in the bonding interface of ceramic and metal in the metallization of ceramics under ultrasonication. A deep understanding of the bonding mechanism between poor-wetted ceramics and low-temperature metals remains limited with regard to high metallization efficiency and nanoscale bonding structure. In this work, the metallization of AlN and TiN ceramics was realized using Sn9Zn metal with the aid of ultrasonication. The microstructure, energy, and element sources of the ceramic/metal interface were analyzed. Results show that a nanoscale amorphous layer is formed between the ceramics and the metal, and this layer can bond easily with AlN or TiN and Sn9Zn because of the irregular arrangement of its atoms. Some dispersed nanocrystals are also present in the amorphous bonding layer. The thermal effect of ultrasonic cavitation produces a high temperature above 106 K, which provides the energy for the bonding of AlN or TiN with Sn9Zn. O and Zn accumulate in the Sn-9Zn/AlN bonding layer. Zn originates from Sn9Zn. O could be from the O2 dissolved in the liquid solder or the O2 adhering to the ceramic. A small amount of AlN decomposes because of its high ΔG of decomposition. However, TiN decomposes into Ti and N2 under the extreme condition caused by ultrasonic cavitation. The accumulated Ti in the Sn-9Zn/TiN bonding layer originates from TiN. The source of the accumulated O is the same as that of Sn-9Zn/AlN bonding layer.

Enhanced oxidation resistance of HfB2‐SiC‐ZrSi2 coating at 1700°C through low‐loss film‐forming treatment

AbstractTo enhance the oxidation resistance of HfB2‐SiC‐ZrSi2 coating, low‐loss film‐forming treatment (LFT) was employed to generate high‐quality oxygen barrier glass layers, and the modification effect of varying formation temperature on the oxidation resistance was investigated at 1700°C. The results demonstrated that, with LFT at 1500°C, the relatively modest oxidation activity and complete dispersion of metal oxide nanocrystals generated a compact and continuous composite glass layer, which caused a decreased oxidation activity at 1700°C. The excessive formation temperature might result in oxidized and porous coatings, while lower temperatures could lead to poor fluidity of the glass layer, rendering it challenging to achieve compact composite glass layers. The coating sample with LFT at 1500°C exhibited a carbon loss rate of 0.33 × 10−6 g·cm−2·s−1 and an oxygen permeability level of 0.28%, respectively, when oxidized at 1700°C. These results provide fundamental insights into the oxidation resistance mechanisms within the modified HfB2‐SiC‐ZrSi2 coating system.

Tailored gradient nanocrystallization in bulk metallic glass via ultrasonic vibrations

To advance materials with superior performance, the construction of gradient structures has emerged as a promising strategy. In this study, a gradient nanocrystalline-amorphous structure was induced in Zr46Cu46Al8 bulk metallic glass (BMG) through ultrasonic vibration (UV) treatment. Applying a 20 kHz ultrasonic cyclic loading in the elastic regime, controllable gradient structures with varying crystallized volume fractions can be achieved in less than 2 s by adjusting the input UV energy. In contrast to traditional methods of inducing structural gradients in BMGs, this novel approach offers distinct advantages: it is exceptionally rapid, requires minimal stress, and allows for easy tuning of the extent of structural gradients through precise adjustment of processing parameters. Nanoindentation tests reveal higher hardness near the struck surface, attributed to a greater degree of nanocrystal formation, which gradually diminishes with depth. As a result of the gradient dispersion of nanocrystals, an increased plasticity was found after UV treatment, characterized by the formation of multiple shear bands. Microstructural investigations suggest that UV-induced nanocrystallization originates from local atomic rearrangements in phase-separated Cu-rich regions with high diffusional mobility. Our study underscores the tunability of structural gradients and corresponding performance improvements in BMGs through ultrasonic energy modulation, offering valuable insights for designing advanced metallic materials with tailored mechanical properties.

VOx Matrix Confinement Approach to Generate Sub-3nm L10-Pt-Based Intermetallic Catalysts for Fuel Cell Cathode.

Pt-based intermetallic compounds (IMCs) are considered as a class of promising fuel cell electrocatalysts, owing to their outstanding intrinsic activity and durability. However, the synthesis of uniformly dispersed IMCs with small sizes presents a formidable challenge during the essential high-temperature annealing process. Herein, a facile and generally applicable VOx matrix confinement strategy is demonstrated for the controllable synthesis of ordered L10-PtM (M = Fe, Co, and Mn) nanoparticles, which not only enhances the dispersion of intermetallic nanocrystals, even at high loading (40 wt%), but also simplifies the oxide removal and acid-washing procedures. Taking intermetallic PtCo as an example, the as-prepared catalyst displays a high-performance oxygen reduction activity (mass activity of 1.52 A mgPt -1) and excellent stability in the membrane electrode assemblies (MEAs) (the ECSA has just 7% decay after durability test). This strategy provides an economical and scalable route for the controlled synthesis of Pt-based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies.

Formulation and characterization of ibuprofen solid dispersions using native and modified starches

Background: Ibuprofen is an anti-inflammatory analgesic drug that is weakly water-soluble with a poor bioavailability.Objectives: The aim of this study is to formulate ibuprofen solid dispersions by solvent evaporation method using natural polymers (native cassava and genetically modified cassava (GMS), Cassava nanocrystal and corn starches) as possible hydrophilic carriers at varying weight proportions to optimize ibuprofen solubility and dissolution.Material and Methods: Solvent evaporation method was used to formulate the ibuprofen solid dispersions at different drug polymer ratios. The pure drug and solid dispersions were characterized using Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), particle size, and in vitro drug release.Results: Solid dispersions formulated with starch nanocrystals showed the highest solubility. All solid dispersions prepared with drug:polymer ratio 1:2 generally showed highest solubility. According to the FTIR, the chemical structure of ibuprofen remained intact in the amorphous solid dispersion, but the structure changed from crystalline to amorphous, according to the XRD and the DSC also confirmed this. The scanning electron microscopy showed the solid dispersions were more porous than the pure drug. Higher dissolution rate was observed with nanocrystal solid dispersions with T50 (time required for 50% of the medication to be released) between 1.8 and 4.1 minutes.Conclusion: This study has shown that using these natural polymers increased the solubility and dissolution rate of ibuprofen.

Microstructure and EMW absorption properties of PDCs-SiCN(Ti) ceramics with adjustable SiC nanowires and TiC nanocrystallines

Herein, a novel type of ceramic material exhibiting tunable electromagnetic properties was synthesized using the polymer-derived ceramics (PDCs) method. The precursor employed in this process was a tetrabutyl titanate-modified polysilazane, which ultimately led to the formation of PDCs-SiCN(Ti) ceramics. High-temperature annealing (1400 °C-1500 °C) was used to prepare PDCs-SiCN(Ti) ceramics, which exhibited a unique dual nanostructure comprising SiC nanowires and TiC nanocrystals and served as effective nanoabsorbents. The SiC and TiC contents are closely related to the annealing temperature and induced Ti content. After annealing at 1500 °C, the PDCs-SiCN(Ti) ceramics with the typical A + B + C electromagnetic absorbing structure exhibited excellent electromagnetic wave (EMW) absorption properties. The PDCs-SiCN(Ti) ceramics, with a Ti content of 5 wt%, demonstrated an effective absorption bandwidth (EAB) of 3.8 GHz, which encompassed 90.5 % of the X band, despite having a relatively thin impedance matching thickness of only 2.1 mm. The outstanding EMW attenuation capability of the PDC-SiCN(Ti) ceramics can be ascribed to their large specific surface area and defects combined with the high permittivity of dispersed TiC nanocrystals, which facilitates multiple reflections of EMW within the SiCN matrix. Therefore, this work provides a controllable preparation method for PDCs-SiCN(Ti) ceramics with various microwave absorbing phases.

Ultrasmall Pd nanocrystals confined into Co-based metal organic framework-decorated MXene nanoarchitectures for efficient methanol electrooxidation

The natural scarcity and insufficient utilization of noble metal-based catalysts bring a heavy block in the way of the widespread applications of direct methanol fuel cells. Herein, we propose a feasible bottom-up approach to the construction of ultrasmall Pd nanocrystals confined into Co-based metal organic framework-decorated Ti3C2Tx MXene (Pd/MOF-MX) nanoarchitectures via a controllable solvothermal process. The ultrathin MXene nanolamellas and porous Co-based MOFs constitute an ideal hybrid carrier with high electron conductivity and large accessible surface areas, which not only facilitates the size restriction and uniform dispersion of Pd nanocrystals, but also ameliorates their intrinsic catalytic activity through the direct electronic interactions. By virtue of the pronounced synergistic coupling effects, the newly-developed Pd/MOF-MX nanoarchitectures exhibit markedly enhanced electrocatalytic properties towards the methanol oxidation reaction, including a large electrochemically active surface area of 116.7 m2 g−1, a high mass activity of 1700.4 mA mg−1 as well as a satisfactory long-term durability, which are superior to those of traditional Pd electrocatalysts anchored on carbon blacks, carbon nanotubes, graphene, and undecorated MXene matrixes.

Zeta Potential and Size Analysis of Zeolitic Imidazolate Framework-8 Nanocrystals Prepared by Surfactant-Assisted Synthesis.

The crystal nucleation and growth mechanism of monodispersed metal-organic framework nanoparticles were studied using time-resolved light dynamic, electrokinetic, and powder X-ray diffraction methods. We confirmed that zeolitic imidazolate framework-8 (ZIF-8) nanocrystals follow a nonclassical crystal growth pathway, where a fast nucleation occurs with dense liquid clusters or nanocrystals forming spontaneously when two precursors are mixed. We also explored the zeta potential and solvodynamic size changes of ZIF-8 prepared by a surfactant-assisted synthesis. Three modulators, including 1-methylimidazole (1-mIm), tris(hydroxymethyl)aminomethane (THAM), and (1-hexadecyl)trimethylammonium bromide (CTAB), were studied. We found that 1-mIm dramatically increases the rate of nucleation of ZIF-8. With an increasing amount of 1-mIm, which functions as a coordination modulator, the size increases, and the zeta potential of ZIF-8 decreases. Whereas THAM, as both a coordination and a deprotonation modulator, increases the size and zeta potential of ZIF-8 simultaneously, CTAB, as a long alkyl cationic surfactant, mainly adsorbs on the surface of ZIF-8, and the zeta potential of the formed ZIF-8 is controlled by the amount of CTAB in solution compared with its critical micelle concentration. Overall, we reveal that the modulator type and concentration can be used to control the size and zeta potential of the dispersed ZIF-8 nanocrystals in a colloid system. The experiments also enable identification of the nucleation and crystal growth processes of ZIF-8. The findings will be applicable to other nanocrystals in colloid systems, which are used for heterogeneous catalysis and guest molecular loadings.

Conjugated Zwitterionic Oligomers as Ligands on Perovskite Nanocrystals: Hybrid Structures with Tunable Interparticle Spacing.

Conventional ligands for CsPbBr3 perovskite nanocrystals (NCs), composed of polar, coordinating head groups (e.g., ammonium or zwitterionic) and aliphatic tails, are instrumental in stabilizing the NCs against sintering and aggregation. Nonetheless, the aliphatic (insulating) nature of these ligands represents drawbacks with respect to objectives in optoelectronics, and yet removing these ligands typically leads to a loss of colloidal stability. In this paper, we describe the preparation of CsPbBr3 NCs in the presence of discrete conjugated oligomers that were prepared by an iterative synthetic approach and capped at their chain ends with sulfobetaine zwitterions for perovskite coordination. Notably, these zwitterionic oligofluorenes are compatible with the hot injection and ligand exchange conditions used to prepare CsPbBr3 NCs, yielding stable NC dispersions with high photoluminescence quantum yields (PLQY, >90%) and spectral features representative of both the perovskite core and conjugated ligand shell. Controlling the chain length of these capping ligands effectively regulated inter-NC spacing and packing geometry when cast into solid films, with evidence derived from both transmission electron microscopy (TEM) and grazing incidence X-ray scattering measurements.

Feasible preparation of preferentially oriented (111) Pd nanocrystals supported on cyano-COFs for ultrahigh activity in C-C cross-couplings

It is much challenging to synthesize highly dispersed noble metal nanocrystals (MNCs) and prevent their aggregation during the catalytic cycles. Choosing suitable solid supports to mediate the growth of MNCs can provide stable yet ultra-highly active heterogenous catalysts. However, very few studies have provided the controllable preparation of ultrafine MNCs. Herein, cyano-functionalized covalent organic frameworks (cyano-COFs)-mediated ultrafine preferentially oriented (111) PdNCs with particle diameter of 2.88 ± 0.60 nm were easily prepared in MeOH without any other external reducing agent. The obtained Pd/cyano-COFs presented ultrahigh activity in Suzuki-Miyaura couplings, with TOF of 2578 h−1 and chemo-selectivity of > 99 % for the cross-coupling between p-iodotoluene and phenylboronic acid at room temperature in the air. Furthermore, outstanding catalytic performance of Pd/cyano-COFs was found in Heck couplings as well. This study provides a new idea for the controllable preparation of metallic nanomaterials with high performance, which could facilitate the research on the regulation of catalytic performance by the chemical composition of supports.