Nanoporous Au Behavior in Methyl Orange Solutions.

Nanoporous (NP) gold, the most extensively studied and efficient NP metal, possesses exceptional properties that make it highly attractive for advanced technological applications. Notably, its remarkable catalytic properties in various significant reactions hold enormous potential. However, the exploration of its catalytic activity in the degradation of water pollutants remains limited. Nevertheless, previous research has reported the catalytic activity of NP Au in the degradation of methyl orange (MO), a toxic azo dye commonly found in water. This study aims to investigate the behavior of nanoporous gold in MO solutions using UV-Vis absorption spectroscopy and high-performance liquid chromatography. The NP Au was prepared by chemical removal of silver atoms of an AuAg precursor alloy prepared by ball milling. Immersion tests were conducted on both pellets and powders of NP Au, followed by examination of the residual solutions. Additionally, X-ray photoelectron spectroscopy and electrochemical impedance measurements were employed to analyze NP Au after the tests. The findings reveal that the predominant and faster process involves the partially reversible adsorption of MO onto NP Au, while the catalytic degradation of the dye plays a secondary and slower role in this system.

Ru-Cu Nanoheterostructures for Efficient Hydrogen Evolution Reaction in Alkaline Water Electrolyzers.

Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode for the HER composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru-Cu nanoheterostructures (Ru mass loading = 52 µg/cm2). Such an electrode exhibits a stable, over 250 h, low overpotential of 74 mV at -200 mA/cm2 for the HER in 1 M NaOH. The high activity of the electrode is attributed, by structural analysis, operando X-ray absorption spectroscopy, and first-principles simulations, to synergistic functionalities: (1) mechanically robust, vertically aligned Cu NRs with high electrical conductivity and porosity provide fast charge and gas transfer channels; (2) the Ru electronic structure, regulated by the size of Cu clusters at the surface, facilitates the water dissociation (Volmer step); (3) the Cu clusters grown atop Ru exhibit a close-to-zero Gibbs free energy of the hydrogen adsorption, promoting fast Heyrovsky/Tafel steps. An alkaline electrolyzer (AEL) coupling the proposed cathode and a stainless-steel anode can stably operate in both continuous (1 A/cm2 for over 200 h) and intermittent modes (accelerated stress tests). A techno-economic analysis predicts the minimal overall hydrogen production cost of US$2.12/kg in a 1 MW AEL plant of 30 year lifetime based on our AEL single cell, hitting the worldwide targets (US$2-2.5/kgH2).

Alloying Bi-Doped Cs2Ag1-xNaxInCl6 Nanocrystals with K+ Cations Modulates Surface Ligands Density and Photoluminescence Efficiency.

We show how, in the synthesis of yellow-emissive Bi-doped Cs2Ag1-xNaxInCl6 double perovskite nanocrystals (NCs), preventing the transient formation of Ag0 particles increases the photoluminescence quantum yield (PLQY) of the NCs from ∼30% to ∼60%. Calculations indicate that the presence of even a single Ag0 species on the surface of a NC introduces deep trap states. The PL efficiency of these NCs is further increased to ∼70% by partial replacement of Na+ with K+ ions, up to a 7% K content, due to a lattice expansion that promotes a more favorable ligands packing on the NC surface, hence better surface passivation. A further increase in K+ lowers the PLQY, due to both the activation of nonradiative quenching channels and a lower oscillator strength of the BiCl6→AgCl6 transition (through which PL emission occurs). The work indicates how a deeper understanding of parameters influencing carrier trapping/relaxation can boost the PLQY of double perovskites NCs.

From Rice Husk Ash to Silica-Supported Carbon Nanomaterials: Characterization and Analytical Application for Pre-Concentration of Steroid Hormones from Environmental Waters.

Rice husk (RH) in the rice industry is often air-burnt to obtain energy in the form of heat and RH ash (RHA) residue. In this work, RHA was applied as a starting material to obtain silica-supported carbon nanomaterials, resulting in a new reuse of a globally produced industrial waste product, in a circular economy approach. The preparation involves ultrasound-assisted one-pot oxidation with a sulfonitric mixture followed by wet oven treatment in a closed vessel. A study of oxidation times and RHA amount/acid volume ratio led to a solid material (nC-RHA@SiO2) and a solution containing silica-supported carbon quantum dots (CQD-RHA@SiO2). TEM analyses evidenced that nC-RHA@SiO2 consists of nanoparticle aggregates, while CQD-RHA@SiO2 are carbon-coated spherical silica nanoparticles. The presence of oxygenated carbon functional groups, highlighted by XPS analyses, makes these materials suitable for a wide range of analytical applications. As the main product, nC-RHA@SiO2 was tested for its affinity towards steroid hormones. Solid-phase extractions were carried out on environmental waters for the determination of target analytes at different concentrations (10, 50, and 200 ng L−1), achieving quantitative adsorption and recoveries (RSD < 20%, n = 3). The method was successfully employed for monitoring lake, river, and wastewater treatment plant water samples collected in Northern Italy.

ZnCl2 Mediated Synthesis of InAs Nanocrystals with Aminoarsine.

The most developed approaches for the synthesis of InAs nanocrystals (NCs) rely on pyrophoric, toxic, and not readily available tris-trimethylsilyl (or tris-trimethylgermil) arsine precursors. Less toxic and commercially available chemicals, such as tris(dimethylamino)arsine, have recently emerged as alternative As precursors. Nevertheless, InAs NCs made with such compounds need to be further optimized in terms of size distribution and optical properties in order to meet the standard reached with tris-trimethylsilyl arsine. To this aim, in this work we investigated the role of ZnCl2 used as an additive in the synthesis of InAs NCs with tris(dimethylamino)arsine and alane N,N-dimethylethylamine as the reducing agent. We discovered that ZnCl2 helps not only to improve the size distribution of InAs NCs but also to passivate their surface acting as a Z-type ligand. The presence of ZnCl2 on the surface of the NCs and the excess of Zn precursor used in the synthesis enable the subsequent in situ growth of a ZnSe shell, which is realized by simply adding the Se precursor to the crude reaction mixture. The resulting InAs@ZnSe core@shell NCs exhibit photoluminescence emission at ∼860 nm with a quantum yield as high as 42±4%, which is a record for such heterostructures, given the relatively high mismatch (6%) between InAs and ZnSe. Such bright emission was ascribed to the formation, under our peculiar reaction conditions, of an In-Zn-Se intermediate layer between the core and the shell, as indicated by X-ray photoelectron spectroscopy and elemental analyses, which helps to release the strain between the two materials.

One-step functionalization of mildly and strongly reduced graphene oxide with maleimide: an experimental and theoretical investigation of the Diels-Alder [4+2] cycloaddition reaction.

For large-scale graphene applications, such as the production of polymer-graphene nanocomposites, exfoliated graphene oxide (GO) and its reduced form (rGO) are presently considered to be very suitable starting materials, showing enhanced chemical reactivity with respect to pristine graphene, in addition to suitable electronic properties (i.e., tunable band gap). Among other chemical processes, a suitable way to obtain surface decoration of graphene is through a direct one-step Diels-Alder (DA) reaction, e.g. through the use of dienophile or diene moieties. However, the feasibility and extent of decoration largely depends on the specific graphene microstructure that in the case of rGO sheets is not easy to control and generally presents a high degree of inhomogeneity owing to various on-plane functionalization (e.g., epoxide and hydroxyl groups) or in-plane lattice defects. In an effort to gain some insights into the covalent functionalization of variably reduced GO samples, we present a combined experimental and theoretical study on the DA cycloaddition reaction of maleimide, a dienophile functional unit well-suited for chemical conjugation of polymers and macromolecules. In particular, we considered both mildly and strongly reduced GOs. Using thermogravimetry, Raman and X-Ray photoelectron spectroscopy, and elemental analysis we show evidence of variable chemical reactivity of rGO as a function of the residual oxygen content. Moreover, from quantum mechanical calculations carried out at the DFT level on different graphene reaction sites, we provide a more detailed molecular view to interpret experimental findings and to assess the reactivity series of different graphene modifications.

Colloidal Bismuth Chalcohalide Nanocrystals.

Here we present a colloidal approach to synthesize bismuth chalcohalide nanocrystals (BiEX NCs, in which E=S, Se and X=Cl, Br, I). Our method yields orthorhombic elongated BiEX NCs, with BiSCl crystallizing in a previously unknown polymorph. The BiEX NCs display a composition-dependent band gap spanning the visible spectral range and absorption coefficients exceeding 105  cm-1 . The BiEX NCs show chemical stability at standard laboratory conditions and form colloidal inks in different solvents. These features enable the solution processing of the NCs into robust solid films yielding stable photoelectrochemical current densities under solar-simulated irradiation. Overall, our versatile synthetic protocol may prove valuable in accessing colloidal metal chalcohalide nanomaterials at large and contributes to establish metal chalcohalides as a promising complement to metal chalcogenides and halides for applied nanotechnology.

Nanocrystals of Lead Chalcohalides: A Series of Kinetically Trapped Metastable Nanostructures.

We report the colloidal synthesis of a series of surfactant-stabilized lead chalcohalide nanocrystals. Our work is mainly focused on Pb4S3Br2, a chalcohalide phase unknown to date that does not belong to the ambient-pressure PbS-PbBr2 phase diagram. The Pb4S3Br2 nanocrystals herein feature a remarkably narrow size distribution (with a size dispersion as low as 5%), a good size tunability (from 7 to ∼30 nm), an indirect bandgap, photoconductivity (responsivity = 4 ± 1 mA/W), and stability for months in air. A crystal structure is proposed for this new material by combining the information from 3D electron diffraction and electron tomography of a single nanocrystal, X-ray powder diffraction, and density functional theory calculations. Such a structure is closely related to that of the recently discovered high-pressure chalcohalide Pb4S3I2 phase, and indeed we were able to extend our synthesis scheme to Pb4S3I2 colloidal nanocrystals, whose structure matches the one that has been published for the bulk. Finally, we could also prepare nanocrystals of Pb3S2Cl2, which proved to be a structural analogue of the recently reported bulk Pb3Se2Br2 phase. It is remarkable that one high-pressure structure (for Pb4S3I2) and two metastable structures that had not yet been reported (for Pb4S3Br2 and Pb3S2Cl2) can be prepared on the nanoscale by wet-chemical approaches. This highlights the important role of colloidal chemistry in the discovery of new materials and motivates further exploration into metal chalcohalide nanocrystals.

Microwave-Induced Structural Engineering and Pt Trapping in 6R-TaS2 for the Hydrogen Evolution Reaction.

The nanoengineering of the structure of transition metal dichalcogenides (TMDs) is widely pursued to develop viable catalysts for the hydrogen evolution reaction (HER) alternative to the precious metallic ones. Metallic group-5 TMDs have been demonstrated to be effective catalysts for the HER in acidic media, making affordable real proton exchange membrane water electrolysers. Their key-plus relies on the fact that both their basal planes and edges are catalytically active for the HER. In this work, the 6R phase of TaS2 is "rediscovered" and engineered. A liquid-phase microwave treatment is used to modify the structural properties of the 6R-TaS2 nanoflakes produced by liquid-phase exfoliation. The fragmentation of the nanoflakes and their evolution from monocrystalline to partly polycrystalline structures improve the HER-activity, lowering the overpotential at cathodic current of 10 mA cm-2 from 0.377 to 0.119 V. Furthermore, 6R-TaS2 nanoflakes act as ideal support to firmly trap Pt species, which achieve a mass activity (MA) up 10 000 A gPt -1 at overpotential of 50 mV (20 000 A gPt -1 at overpotentials of 72 mV), representing a 20-fold increase of the MA of Pt measured for the Pt/C reference, and approaching the state-of-the-art of the Pt mass activity.

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst.

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. The physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec-1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm-2. This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

Effect of the Counteranion on the Formation Pathway of Cu2ZnSnS4 (CZTS) Nanoparticles under Solvothermal Conditions.

Cu2ZnSnS4 and Cu2ZnSnSe4 (CZTS and CZTSe, respectively) and their mixed chalcogenide phase Cu2ZnSnSxSe4-x (CZTSS(e)) are benign and cheap photovoltaic absorber materials that represent a valuable alternative to the more expensive chalcogenide systems: i.e., Cu(In,Ga)SS(e)2 (CIGSS(e)). One of the main challenges related to the fabrication of CZTS(e) layers is the control over both the crystalline phase (tetragonal, cubic, or hexagonal) and the formation of binary (MS, M = Cu(II), Zn(II), Sn(II); M'2-xS, M'= Cu(I), x = 0, 0.2; M″S2, M″ = Sn(IV)) and ternary products (CTS phases, Cu2SnS3, Cu3SnS4) that hinder the performance of the corresponding devices. In the present work, we rationalize the formation pathway of the CZTS phase through binary and ternary products when salt precursors with chloride and acetate as counteranions, respectively, are employed. The results show that the counteranions have a remarkable influence on the formation pathway of CZTS nanoparticles. The use of chloride precursors leads to the predominant formation of CTSs ternary phases (Cu2SnS3, Cu3SnS4), whereas the formation of the CZTS phase is not observed even for higher temperature and longer reaction time (250 °C, 24 h). In the case of acetates the copresence of CZTS as the main product, together with binary and ternary phases, is observed in the early stages of the reaction even at lower temperature and shorter reaction time (200 °C, 2 h), while when the reaction time and temperature are increased, only the CZTS phase is observed. In addition to a careful microstructural characterization of the as-synthesized materials by Raman spectroscopy, X-ray diffraction (XRD), Energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM), we shed light on the reactivity among the metal precursors, the organic ligand oleylamine, and the sulfur precursor carbon disulfide (CS2) by 13C nuclear magnetic resonance (13C NMR) and investigate in depth the effect on particle surfaces by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and XPS. A rationale for the formation pathway of CZTS nanoparticles is proposed and supported by experimental evidence.

Quantized Electronic Doping towards Atomically Controlled "Charge-Engineered" Semiconductor Nanocrystals.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au+ species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au+ to paramagnetic Au2+ (5d9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

PbS Quantum Dots Decorating TiO2 Nanocrystals: Synthesis, Topology, and Optical Properties of the Colloidal Hybrid Architecture.

Fabrication of heterostructures by merging two or more materials in a single object. The domains at the nanoscale represent a viable strategy to purposely address materials' properties for applications in several fields such as catalysis, biomedicine, and energy conversion. In this case, solution-phase seeded growth and the hot-injection method are ingeniously combined to fabricate TiO2/PbS heterostructures. The interest in such hybrid nanostructures arises from their absorption properties that make them advantageous candidates as solar cell materials for more efficient solar light harvesting and improved light conversion. Due to the strong lattice mismatch between TiO2 and PbS, the yield of the hybrid structure and the control over its properties are challenging. In this study, a systematic investigation of the heterostructure synthesis as a function of the experimental conditions (such as seeds' surface chemistry, reaction temperature, and precursor concentration), its topology, structural properties, and optical properties are carried out. The morphological and chemical characterizations confirm the formation of small dots of PbS by decorating the oleylamine surface capped TiO2 nanocrystals under temperature control. Remarkably, structural characterization points out that the formation of heterostructures is accompanied by modification of the crystallinity of the TiO2 domain, which is mainly ascribed to lattice distortion. This result is also confirmed by photoluminescence spectroscopy, which shows intense emission in the visible range. This originated from self-trapped excitons, defects, and trap emissive states.

Homotypic targeting and drug delivery in glioblastoma cells through cell membrane-coated boron nitride nanotubes.

Glioblastoma multiforme (GBM) is one of the most aggressive types of brain cancer, characterized by rapid progression, resistance to treatments, and low survival rates; the development of a targeted treatment for this disease is still today an unattained objective. Among the different strategies developed in the latest few years for the targeted delivery of nanotherapeutics, homotypic membrane-membrane recognition is one of the most promising and efficient. In this work, we present an innovative drug-loaded nanocarrier with improved targeting properties based on the homotypic recognition of GBM cells. The developed nanoplatform consists of boron nitride nanotubes (BNNTs) loaded with doxorubicin (Dox) and coated with cell membranes (CM) extracted from GBM cells (Dox-CM-BNNTs). We demonstrated as Dox-CM-BNNTs are able to specifically target and kill GBM cells in vitro, leaving unaffected healthy brain cells, upon successful crossing an in vitro blood-brain barrier model. The excellent targeting performances of the nanoplatform can be ascribed to the protein component of the membrane coating, and proteomic analysis of differently expressed membrane proteins present on the CM of GBM cells and of healthy astrocytes allowed the identification of potential candidates involved in the process of homotypic cancer cell recognition.

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis.

Among the large family of transition metal dichalcogenides, recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in-plane anisotropy, and the presence of active sites at its surface makes ReS2 interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time-consuming and complex, therefore limiting its large-scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS2 at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution-based synthesis with surface functionalization strategies, the feasibility of colloidal ReS2 nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2 . In addition, the integration of the ReS2 nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential competitive with devices based on ReS2 produced by CVD, and even with MoS2 , WS2 , and MoSe2 electrocatalysts.

A New Drug Delivery System Based on Tauroursodeoxycholic Acid and PEDOT.

Localized drug delivery represents one of the most challenging uses of systems based on conductive polymer films. Typically, anionic drugs are incorporated within conductive polymers through electrostatic interaction with the positively charged polymer. Following this approach, the synthetic glucocorticoid dexamethasone phosphate is often delivered from neural probes to reduce the inflammation of the surrounding tissue. In light of the recent literature on the neuroprotective and anti-inflammatory properties of tauroursodeoxycholic acid (TUDCA), for the first time, this natural bile acid was incorporated within poly(3,4-ethylenedioxythiophene) (PEDOT). The new material, PEDOT-TUDCA, efficiently promoted an electrochemically controlled delivery of the drug, while preserving optimal electrochemical properties. Moreover, the low cytotoxicity observed with viability assays, makes PEDOT-TUDCA a good candidate for prolonging the time span of chronic neural recording brain implants.

Increasing responsivity and air stability of PbS colloidal quantum dot photoconductors with iodine surface ligands.

PbS colloidal quantum dots (QDs) are a promising material for the realization of low-cost, high-responsivity near-infrared photodetectors. Previously reported attempts showed high responsivity but a fast performance decay in air-exposed devices, demanding encapsulation of the photodetectors. Conversely, devices with very high air stability have been demonstrated but the low trap-state density hinders photoconductive gain and reduces overall responsivity. In this paper, photoconductive devices prepared with partially tetrabutylammonium iodide exchanged PbS QDs are presented with enhanced air stability and high responsivity at low voltage, low optical power.

Chloride-Induced Thickness Control in CdSe Nanoplatelets.

Current colloidal synthesis methods for CdSe nanoplatelets (NPLs) routinely yield samples that emit, in discrete steps, from 460 to 550 nm. A significant challenge lies with obtaining thicker NPLs, to further widen the emission range. This is at present typically achieved via colloidal atomic layer deposition onto CdSe cores, or by synthesizing NPL core/shell structures. Here, we demonstrate a novel reaction scheme, where we start from 4.5 monolayer (ML) NPLs and increase the thickness in a two-step reaction that switches from 2D to 3D growth. The key feature is the enhancement of the growth rate of basal facets by the addition of CdCl2, resulting in a series of nearly monodisperse CdSe NPLs with thicknesses between 5.5 and 8.5 ML. Optical characterization yielded emission peaks from 554 nm up to 625 nm with a line width (fwhm) of 9-13 nm, making them one of the narrowest colloidal nanocrystal emitters currently available in this spectral range. The NPLs maintained a short emission lifetime of 5-11 ns. Finally, due to the increased red shift of the NPL band edge photoluminescence excitation spectra revealed several high-energy peaks. Calculation of the NPL band structure allowed us to identify these excited-state transitions, and spectral shifts are consistent with a significant mixing of light and split-off hole states. Clearly, chloride ions can add a new degree of freedom to the growth of 2D colloidal nanocrystals, yielding new insights into both the NPL synthesis as well as their optoelectronic properties.

WS2-Graphite Dual-Ion Batteries.

A novel WS2-graphite dual-ion battery (DIB) is developed by combining a conventional graphite cathode and a high-capacity few-layer WS2-flake anode. The WS2 flakes are produced by exploiting wet-jet milling (WJM) exfoliation, which allows large-scale and free-material loss production (i.e., volume up to 8 L h-1 at concentration of 10 g L-1 and exfoliation yield of 100%) of few-layer WS2 flakes in dispersion. The WS2 anodes enable DIBs, based on hexafluorophosphate (PF6-) and lithium (Li+) ions, to achieve charge-specific capacities of 457, 438, 421, 403, 295, and 169 mAh g-1 at current rates of 0.1, 0.2, 0.3, 0.4, 0.8, and 1.0 A g-1, respectively, outperforming conventional DIBs. The WS2-based DIBs operate in the 0 to 4 V cell voltage range, thus extending the operating voltage window of conventional WS2-based Li-ion batteries (LIBs). These results demonstrate a new route toward the exploitation of WS2, and possibly other transition-metal dichalcogenides, for the development of next-generation energy-storage devices.

Shape-Pure, Nearly Monodispersed CsPbBr3 Nanocubes Prepared Using Secondary Aliphatic Amines.

Fully inorganic cesium lead halide perovskite (CsPbX3) nanocrystals (NCs) have been extensively studied due to their excellent optical properties, especially their high photoluminescence quantum yield (PLQY) and the ease with which the PL can be tuned across the visible spectrum. So far, most strategies for synthesizing CsPbX3 NCs are highly sensitive to the processing conditions and ligand combinations. For example, in the synthesis of nanocubes of different sizes, it is not uncommon to have samples that contain various other shapes, such as nanoplatelets and nanosheets. Here, we report a new colloidal synthesis method for preparing shape-pure and nearly monodispersed CsPbBr3 nanocubes using secondary amines. Regardless of the length of the alkyl chains, the oleic acid concentration, and the reaction temperature, only cube-shaped NCs were obtained. The shape purity and narrow size distribution of the nanocubes are evident from their sharp excitonic features and their ease of self-assembly in superlattices, reaching lateral dimensions of up to 50 µm. We attribute this excellent shape and phase purity to the inability of secondary amines to find the right steric conditions at the surface of the NCs, which consequently limits the formation of low-dimensional structures. Furthermore, no contamination from other phases was observed, not even from Cs4PbBr6, presumably due to the poor ability of secondary aliphatic amines to coordinate to PbBr2 and, hence, to provide a reaction environment that is depleted in Pb.