Stable Water‐dispersed CdTe Nanocrystals Dependent on Stoichiometric Ratio of Cd to Te Precursor

The improved properties of CdTe nanocrystals (NCs) synthesized by hydrothermal method were introduced. The experimental results indicated that the NCs properties could be dramatically influenced by means of changing Cd‐to‐Te molar ratio (the molar ratio of CdCl₂ and NaHTe in the precursor) of the MPA‐capped CdTe NCs. With the increase of the ratio from 2:1 to 10:1, the formation time of near‐infrared‐emitting CdTe NCs was shortened. In particular, high Cd‐to‐Te molar ratio brought about MPA‐capped CdTe NCs of superior radical oxidation‐resistance and photostability. As a result, the optimum ratio was found to be 8:1 or 10:1 in the study in order to efficiently attain stable, water‐dispersed CdTe NCs.     

Counterion‐Assisted Shaping of Nanocluster Supracrystals

Ag₄₄(p‐MBA)₃₀^4? (p‐MBA=para‐mercaptobenzoic acid) nanocluster (NC) supracrystals (SCs) with customizable shapes can be obtained by simply altering the type and concentration of the counterions of the p‐MBA ligands in the dimethylsulfoxide (DMSO)/water crystallization system. Changing the counterion of the p‐MBA ligand from H⁺ to Cs⁺ eliminates the directional hydrogen bonds in the SCs, resulting in the packing of deprotonated Ag₄₄(p‐MBA)₃₀^4? NCs into octahedral SCs, which is in stark contrast to the rhombohedral SCs that were formed by the packing of protonated Ag₄₄(p‐MBA)₃₀^4? NCs in previous studies. Furthermore, the double layer of deprotonated Ag₄₄(p‐MBA)₃₀^4? NCs is sensitive to charge screening induced by increasing the Cs⁺ concentration, thereby providing a means to regulate the precipitation kinetics of the Ag₄₄(p‐MBA)₃₀^4? NCs for SC shape engineering. Slow precipitation kinetics was found to favor over‐growth at the corners and edges of the octahedral SC nuclei, shaping the SCs into concave octahedra.     

Synthesis of Aqueous CdTe Nanocrystals with High Efficient Blue‐Green Emission of Exciton

As one of the most popular nanocrystals (NCs), aqueous CdTe NCs have very weak green emission under conventional synthesis conditions. In this work, we report the first example of blue‐emitting CdTe NCs directly synthesized in aqueous solution by slowing down the growth rate after nucleation. The key for the synthesis is the optimization of NC growth conditions, namely pH range of 7.5 to 8.5, TGA/Cd ratio of 3.6, Cd/Te ratio of 10, and Te concentration of 2×10^?5 mol/L, to get a slow growth rate after nucleation. The as‐prepared blue‐emitting CdTe NCs have small size (as small as 1.9 nm) and bright emission [with 4% photoluminescence quantum yield (PL QY) at 486 nm and 17% PLQY at 500 nm]. Transmission electron microscopy (TEM) images of the as‐prepared CdTe show monodispersed NCs which exhibit cubic zinc blend structure. Moreover, time‐resolved PL decay and X‐ray photoelectron spectroscopy (XPS) results show the as‐prepared NCs have better surface modification by ligand, which makes these luminescent small CdTe NCs have higher photoluminescence quantum yield, compared with NCs synthesized under conventional conditions.     

Carbon Monoxide: A Mild and Efficient Reducing Agent towards Atomically Precise Gold Nanoclusters

In recent years, thiolate‐protected gold nanoclusters (or thiolated Au NCs) with a core size below 2 nm have emerged as a new class of multifunctional nanoparticles because of their unique molecular‐like properties and the potential to use these properties in many practical applications. A general synthesis of Au NCs may involve the use of a strong reducing agent (e.g., sodium borohydride (NaBH₄)), which often leads to the formation of mix‐sized Au NCs if no delicate control is applied. To obtain atomically precise Au NCs, additional physical or chemical selection processes (e.g., high‐resolution separation or size‐focusing) are required, which are difficult to be scaled up or are limited to only thermodynamically stable products. By introducing a milder reducing agent – carbon monoxide (CO) – both stable and metastable thiolated Au NCs, including Au_10–12, Au₁₅, Au₁₈, Au₂₅, and Au₂₉, can be synthesized in a one‐pot manner. In addition, CO reduction also enables the synthesis of a highly luminescent Au₂₂(SG)₁₈ NC. Furthermore, the intermediates of Au NC growth can be tracked in the CO‐reduction system due to the mild and readily stoppable nature of CO reduction. Therefore, the use of CO reduction may bring new flexibilities in designing synthetic strategies and understanding the growth mechanism of atomically precise Au NCs, which could contribute to a better design of functional Au NCs, further paving their way towards practical applications in various fields.     

Electrospray Ionization Mass Spectrometry: A Powerful Platform for Noble‐Metal Nanocluster Analysis

Electrospray ionization mass spectrometry (ESI‐MS) is an analytical technique that measures the mass of a sample through “soft” ionization. Recent years have witnessed a rapid growth of its application in noble‐metal nanocluster (NC) analysis. ESI‐MS is able to provide the mass of a noble‐metal NC analyte for the analysis of their composition (n, m, q values in a general formula [M_nL_m]^q), which is crucial in understanding their properties. This review attempts to present various developed techniques for the determination of the composition of noble metal NCs by ESI‐MS. Additionally, advanced applications that use ESI‐MS to further understand the reaction mechanism, complexation behavior, and structure of noble metal NCs are introduced. From the comprehensive applications of ESI‐MS on noble‐metal NCs, more possibilities in nanochemistry can be opened up by this powerful technique.     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation‐Induced Emission of Gold Nanoclusters

Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]^?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the Au^I‐SR motifs on the NC surface. Decreasing the length of Au^I‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au⁰‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

SnFe2O4 Nanocrystals as Highly Efficient Catalysts for Hydrogen‐Peroxide Sensing

SnFe₂O₄ nanocrystals (NC), prepared with a simple one‐step carrier‐solvent‐assisted interfacial reaction process, were developed as highly efficient catalysts for hydrogen peroxide sensing. These NCs, with a size of around 7 nm, served as the sensing catalyst and were decorated onto the pore surfaces of a porous fluorine‐doped tin oxide (PFTO) host electrode, prepared from commercial FTO glass with a simple anodic treatment, to form the sensing electrode for hydrogen peroxide. The SnFe₂O₄ NCs‐loaded PFTO electrode exhibited an ultra‐high sensitivity of 1027 mA m ^?1 cm^?2 toward hydrogen peroxide, outperforming Pt NCs‐loaded PFTO electrodes. The SnFe₂O₄ NCs‐loaded PFTO electrode proved a promising relatively low cost, high performance sensing electrode for hydrogen peroxide.     

Lead‐Free Silver‐Bismuth Halide Double Perovskite Nanocrystals

Lead‐free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb²⁺ cation with a divalent cation or substituting three Pb²⁺ cations with two trivalent cations. The substitution of two Pb²⁺ cations with one monovalent Ag⁺ and one trivalent Bi³⁺ cations was used to synthesize Cs₂AgBiX₆ (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs₂AgBiBr₆ NCs exhibit ultrafast hot‐carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs₂AgBiCl₆ NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.     

Control of the Fluorescence of DNA‐templated Silver Nanoclusters by Adenosine Triphosphate and Mercury(II)

Several DNA templates with the sequence 5′‐T _n TAACCCCTAACCCCT ‐3′ (n = 0, 15, 30, and 45) were used to prepare DNA template–silver nanoclusters (DNA –Ag NCs ). The T _n sequence acts as a recognition element for Hg²⁺, while the rest of the sequence acts as a template for DNA –Ag NCs . At pH 3.0, the fluorescence intensity of DNA –Ag NCs is enhanced by ATP , and the enhanced fluorescence is quenched by Hg²⁺. The length of polyT shows a slight effect on the sensitivity for the detection of Hg²⁺ but almost no effect on the optical properties of DNA –Ag NCs . The fluorescence response of DNA –Ag NCs (T₁₅‐DNA –Ag NCs ) vs. Hg²⁺ concentration shows two linear ranges over 10–100 and 100–1000 nM , mainly because of the fluorescence quenching due to DNA conformational changes through T–Hg²⁺–T coordination and the formation of an amalgam with Ag NCs , respectively. The sensitivity of the T₁₅‐DNA –Ag NC probe was validated through the analysis of Hg²⁺ in spiked pond water. Based on the switch‐on and switch‐off fluorescence properties of T₁₅‐DNA –Ag NCs , an IMPLICATION logic gate was fabricated using the concentrations of ATP and Hg²⁺ as inputs and the fluorescence intensity at 585 nm as output.     

Sensitively Electrochemical Sensing for Sequence‐Specific Detection of Phosphinothricin Acetyltransferase Gene: Layer‐by‐Layer Films of Poly‐L‐Lysine and Au‐Carbon Nanotube Hybrid

An electrochemical DNA sensing film was constructed based on the multilayers comprising of poly‐L ‐lysine (pLys) and Au‐carbon nanotube (Au‐CNT) hybrid. A precursor film of mercaptopropionic acid (MPA) was firstly self‐assembled on the Au electrode surface. pLys and Au‐CNT hybrid layer‐by‐layer assembly films were fabricated by alternately immersing the MPA‐modified electrode into the pLys solution and Au‐CNT hybrid solution. Cyclic voltammetry was used to monitor the consecutive growth of the multilayer films by utilizing [Fe(CN)₆]^3?/4? and [Co(phen)₃]^3+/2+ as the redox indicators. The outer layer of the multilayer film was the positively charged pLys, on which the DNA probe was easily linked due to the strong electrostatic affinity. The hybridization detection of DNA was accomplished by using methylene blue (MB) as the indicator, which possesses different affinities to dsDNA and ssDNA. Differential pulse voltammetry was employed to record the signal response of MB and determine the amount of the target DNA sequence. The established biosensor has high sensitivity, a relatively wide linear range from 1.0×10^?10 mol/L to 1.0×10^?6 mol/L and the ability to discriminate the fully complementary target DNA from single or double base‐mismatched DNA. The sequence‐specific DNA related to phosphinothricin acetyltransferase gene from the transgenically modified plants was successfully detected.     

Selective water‐permeable channels induced by polystyrene brushes within hairy nanocellulose/cellulose acetate membrane

Hairy nanocellulose (NC) was prepared by in‐situ admicellar polymerization of styrene on NC surface in the presence of cetyltrimethylammonium bromide through a stepwise fashion. It was also tried to achieve three hairy NCs with different polystyrene (PS) brush contents (i.e. 40, 50, and 80%) through altering monomer initial concentration. Then, NC and three hairy NCs were separately added into cellulose acetate (CA) solutions to fabricate membranes via the phase inversion technique. Transmission electron microscope images show that NC and three hairy NCs are spherical‐shaped nanoparticles. Results of Fourier transform infrared spectra provide clear evidence of PS brush being attached to the NC surfaces. Thermal gravimetric analysis confirms that increasing styrene initial concentration leads to enhanced PS content of hairy NCs. Results also elucidate that dispersions of prepared hairy NCs are highly stable even at high loading levels. It was found that incorporation of 1 wt% hairy NC with optimum brush content of 50% within CA membranes results in the increasing membrane water permeability from 7 to 40 l/m² hr with no change in its selectivity. Indeed, new interactions induced by PS brushes at hairy NC/CA interfaces result in the creation of connected channels at the interfaces which facilitate water transport through the membrane. This study provides insights into the key role that PS brushes play in overcoming the dispersion problems of NC in nonpolar media and offers guidelines to tailor channels within hairy NC/CA membrane for enhanced filtration performance. Copyright © 2017 John Wiley & Sons, Ltd.     

Carboxylic‐Acid‐Passivated Metal Oxide Nanocrystals: Ligand Exchange Characteristics of a New Binding Motif

Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO₂ and ZrO₂ NCs using ¹H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self‐adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X‐type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X‐type ligands yielding a combined X₂ binding motif that allows for self‐adsorption and exchange for L‐type ligands.     

Crystal structure of a NIR‐Emitting DNA‐Stabilized Ag16 Nanocluster

DNA has been used as a scaffold to stabilize small, atomically monodisperse silver nanoclusters, which have attracted attention due to their intriguing photophysical properties. Herein, we describe the X‐ray crystal structure of a DNA‐encapsulated, near‐infrared emitting Ag₁₆ nanocluster (DNA–Ag₁₆NC). The asymmetric unit of the crystal contains two DNA–Ag₁₆NCs and the crystal packing between the DNA–Ag₁₆NCs is promoted by several interactions, such as two silver‐mediated base pairs between 3′‐terminal adenines, two phosphate–Ca²⁺–phosphate interactions, and π‐stacking between two neighboring thymines. Each Ag₁₆NC is confined by two DNA decamers that take on a horse‐shoe‐like conformation and is almost fully shielded from the solvent environment. This structural insight will aid in the determination of the structure/photophysical property relationship for this class of emitters and opens up new research opportunities in fluorescence imaging and sensing using noble‐metal clusters.     

Templated‐Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr₃ perovskite NC colloids into large area (1 cm²) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr₃ 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.     

Efficient Solid‐State Light‐Emitting CuCdS Nanocrystals Synthesized in Air

Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long‐range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25 eV. Overcoating the NCs leads to a high solid‐state PL quantum yield (QY) of ca. 55 % measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X‐ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu‐rich surface and Cd‐rich interior with 46 % Cu^I being randomly distributed within 84 % of the NC volume creating additional transition states for PL. Color‐tunable solid‐state luminescence remains stable in air enabling fabrication of light‐emitting diodes (LEDs).     

Adding magnetic ionic liquid monomers to the emulsion polymerization tool‐box: Towards polymer latexes and coatings with new properties

Magnetic ionic liquid monomers were synthesized and then polymerized to get magnetic polymer latexes and films. First, a series of 1‐vinyl‐3‐dodecyl‐imidazolium monomers having metal halides counter‐anions such as FeCl₃Br^?, CoCl₂Br^?, and MnCl₂Br^? were synthesized. These ionic liquid monomers were first homopolymerized to lead to magnetic poly(ionic liquids) and characterized. Secondly, magnetic latexes were synthesized by using the magnetic ionic liquids as surfmers (surfactant + monomer) in the emulsion polymerization of methyl methacrylate/n‐butyl acrylate. It was found that the powders obtained by freeze‐drying the latexes presented a paramagnetic behavior with weak antiferromagnetic interactions between the adjacent metal ions. Although the ratio of magnetic ionic liquid/monomer was only 2% these poly(methyl methacrylate‐co‐butyl acrylate) powders and latexes responded to a magnetic field due to the surfmer paramagnetic nature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1145–1152     

Lead‐Free Sodium–Indium Double Perovskite Nanocrystals through Doping Silver Cations for Bright Yellow Emission

Lead‐free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Herein, we synthesize the direct band gap double perovskites undoped and Ag‐doped Cs₂NaInCl₆ NCs by variable temperature hot injection. The Cs₂NaInCl₆ NCs have little photoluminescence because of dark self‐trapped excitons (STEs). The dark STEs can be converted into bright STEs by doping with Ag⁺ to produce a bright yellow emission, with the highest photoluminescence quantum efficiency of 31.1 %. The dark STEs has been directly detected experimentally by ultrafast transient absorption (TA) techniques. The dynamics mechanism is further studied. In addition, the Ag‐doped NCs show better stability than the undoped ones. This result provides a new way to enhance the optical properties of lead‐free perovskites NCs for high‐performance light emitters.     

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu₂S) NCs through a redox reaction with iodine molecules (I₂), which formed vacancies accompanied by a localized surface plasmon response. X‐ray spectroscopy and diffraction reveal transformation from Cu₂S to Cu‐depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well‐defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.     

Incorporating Rare‐Earth Terbium(III) Ions into Cs2AgInCl6:Bi Nanocrystals toward Tunable Photoluminescence

The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs₂AgInCl₆ NCs to impart and tune the optical performances in the visible light region. Tb³⁺ ions were incorporated into Cs₂AgInCl₆ NCs and occupied In³⁺ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (⁵D₄→⁷F_6‐3) of Tb³⁺ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb³⁺. By controlling Tb³⁺ ions concentration, the emission colors of Bi‐doped Cs₂Ag(In_1?xTb_x)Cl₆ NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb³⁺ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.     

Composition‐Dependent Hot Carrier Relaxation Dynamics in Cesium Lead Halide (CsPbX3, X=Br and I) Perovskite Nanocrystals

Cesium‐based perovskite nanocrystals (NCs) have outstanding photophysical properties improving the performances of lighting devices. Fundamental studies on excitonic properties and hot‐carrier dynamics in perovskite NCs further suggest that these materials show higher efficiencies compared to the bulk form of perovskites. However, the relaxation rates and pathways of hot‐carriers are still being elucidated. By using ultrafast transient spectroscopy and calculating electronic band structures, we investigated the dependence of halide in Cs‐based perovskite (CsPbX₃ with X=Br, I, or their mixtures) NCs on the hot‐carrier relaxation processes. All samples exhibit ultrafast (<0.6 ps) hot‐carrier relaxation dynamics with following order: CsPbBr₃ (310 fs)>CsPbBr_1.5I_1.5 (380 fs)>CsPbI₃ NC (580 fs). These result accounts for a reduced light emission efficiency of CsPbI₃ NC compared to CsPbBr₃ NC.