Organic-Inorganic Hybrid Glasses of Atomically Precise Nanoclusters.

Organic-inorganic atomically precise nanoclusters provide indispensable building blocks for establishing structure-property links in hybrid condensed matter. However, robust glasses of ligand-protected nanocluster solids have yet to be demonstrated. Herein, we show [Cu4I4(PR3)4] cubane nanoclusters coordinated by phosphine ligands (PR3) form robust melt-quenched glasses in air with reversible crystal-liquid-glass transitions. Protective phosphine ligands critically influence the glass formation mechanism, modulating the glasses' physical properties. A hybrid glass utilizing ethyldiphenylphosphine-based nanoclusters, [Cu4I4(PPh2Et)4], exhibits superb optical properties, including >90% transmission in both visible and near-infrared wavelengths, negligible self-absorption, near-unity quantum yield, and high light yield. Experimental and theoretical analyses demonstrate the structural integrity of the [Cu4I4(PPh2Et)4] nanocluster, i.e., iodine-bridged tetranuclear cubane, has been fully preserved in the glass state. The strong internanocluster CH-π interactions found in the [Cu4I4(PPh2Et)4] glass and subsequently reduced structural vibration account for its enhanced luminescence properties. Moreover, this highly transparent glass enables performant X-ray imaging and low-loss waveguiding in fibers drawn above the glass transition. The discovery of "nanocluster glass" opens avenues for unraveling glass formation mechanisms and designing novel luminescent glasses of well-defined building blocks for advanced photonics.

High-Efficiency Circularly Polarized Light-Emitting Diodes Based on Chiral Metal Nanoclusters.

Circularly polarized light-emitting diodes (CP-LEDs) are critical for next-generation optical technologies, ranging from holography to quantum information processing. Currently deployed chiral luminescent materials, with their intricate synthesis and processing and limited efficiency, are the main bottleneck for CP-LEDs. Chiral metal nanoclusters (MNCs) are potential CP-LED materials, given their ease of synthesis and processability as well as diverse structures and excited states. However, their films are usually plagued by inferior electronic quality and aggregation-caused photoluminescence quenching, necessitating their incorporation into host materials; without such a scheme, MNC-based LEDs exhibit external quantum efficiencies (EQEs) < 10%. Herein, we achieve an efficiency leap for both CP-LEDs and cluster-based LEDs by using novel chiral MNCs with aggregation-induced emission enhancement. CP-LEDs using enantiopure MNC films attain EQEs of up to 23.5%. Furthermore, by incorporating host materials, the devices yield record EQEs of up to 36.5% for both CP-LEDs and cluster-based LEDs, along with electroluminescence dissymmetry factors (|gEL|) of around 1.0 × 10-3. These findings open a new avenue for advancing chiral light sources for next-generation optoelectronics.

Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C-C Multiple Bond.

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.

Radioluminescent Cu-Au Metal Nanoclusters: Synthesis and Self-Assembly for Efficient X-ray Scintillation and Imaging.

Zero-dimensional (0D) scintillation materials have drawn tremendous attention due to their inherent advantages in the fabrication of flexible high-energy radiation scintillation screens by solution processes. Although considerable progress has been made in the development of 0D scintillators, such as the current leading lead-halide perovskite nanocrystals and quantum dots, challenges still persist, including potential issues with self-absorption, air stability, and eco-friendliness. Here, we present a strategy to overcome those limitations by synthesis and self-assembly of a new class of scintillators based on metal nanoclusters. We demonstrate the gram-scale synthesis of an atomically precise nanocluster with a Cu-Au alloy core exhibiting high phosphorescence quantum yield, aggregation-induced emission enhancement (AIEE) behavior, and intense radioluminescence. By controlling solvent interactions, the AIEE-active nanoclusters were self-assembled into submicron spherical superparticles in solution, which we exploited as a novel building block for flexible particle-deposited scintillation films with high-resolution X-ray imaging performance. This work reveals metal nanoclusters and their self-assembled superstructures as a promising class of scintillators for practical applications in high-energy radiation detection and imaging.

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry.

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58 H20 PET36 (PPh3 )4 ]2+ (Cu58 ; PET: phenylethanethiolate; PPh3 : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into the surface-defective analog [Cu57 H20 PET36 (PPh3 )4 ]+ (Cu57 ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57 . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58 , Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts.

Atomically Precise Defective Copper Nanocluster Catalysts for Highly Selective C-C Cross-Coupling Reactions.

Point defects in nanoparticles have long been hypothesized to play an important role in governing the particle's electronic structure and physicochemical properties. However, single point defects in material systems usually exist with other heterogeneities, obscuring the chemical role of the effects. Herein, we report the synthesis of novel atomically precise, copper hydride nanoclusters (NCs), [Cu28 H10 (C7 H7 S)18 (TPP)3 ] (Cu28 ; TPP: triphenylphosphine; C7 H7 S: o-thiocresol) with a defined defect in the gram scale via a one-pot reduction method. The Cu28 acts as a highly selective catalyst for C-C cross-couplings. The work highlights the potential of defective NCs as model systems for investigating individual defects, correlating defects with physiochemical properties, and rationally designing new nanoparticle catalysts.

[Cu36H10(PET)24(PPh3)6Cl2] Reveals Surface Vacancy Defects in Ligand-Stabilized Metal Nanoclusters.

Precise identification and in-depth understanding of defects in nanomaterials can aid in rationally modulating defect-induced functionalities. However, few studies have explored vacancy defects in ligand-stabilized metal nanoclusters with well-defined structures, owing to the substantial challenge of synthesizing and isolating such defective metal nanoclusters. Herein, a novel defective copper hydride nanocluster, [Cu36H10(PET)24(PPh3)6Cl2] (Cu36; PET: phenylethanethiolate; PPh3: triphenylphosphine), is successfully synthesized at the gram scale via a simple one-pot reduction method. Structural analysis reveals that Cu36 is a distorted half cubic nanocluster, evolved from the perfect Nichol's half cube. The two surface copper vacancies in Cu36 are found to be the principal imperfections, which result in some structural adjustments, including copper atom reconstruction near the vacancies as well as ligand modifications (e.g., substitution, migration, and exfoliation). Density functional theory calculations imply that the above-mentioned defects have a considerable influence on the electronic structure and properties. The modeling suggests that the formation of defective Cu36 rather than the perfect half cube is driven by the enlargement of the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the nanocluster. The structural evolution induced by the surface copper atom vacancies provides atomically precise insights into the defect-induced readjustment of the local structure and introduces new avenues for understanding the chemistry of defects in nanomaterials.

[Cu15 (PPh3 )6 (PET)13 ]2+ : a Copper Nanocluster with Crystallization Enhanced Photoluminescence.

Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio-imaging, cell labeling, phototherapy, and photo-activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu15 (PPh3 )6 (PET)13 ]2+ , which exhibits bright emission in the near-infrared (NIR) region (≈720 nm) and crystallization-induced emission enhancement (CIEE) phenomenon. Single crystal X-ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu6 core and a, unique among metal clusters, "tri-blade fan"-like structure. An in-depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π-π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.

[Cu81(PhS)46(tBuNH2)10(H)32]3+ Reveals the Coexistence of Large Planar Cores and Hemispherical Shells in High-Nuclearity Copper Nanoclusters.

Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu81(PhS)46(tBuNH2)10(H)32]3+ (Cu81), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu81 exhibits extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.

3D porous ZnO-SnS p-n heterojunction for visible light driven photocatalysis.

A novel two-step solution approach is put forward to design a unique three dimensional (3D) porous ZnO-SnS p-n heterojunction under mild conditions. This special 3D structure is induced via flower-like ZnO in which SnS serves as an efficient photosensitizer to improve the light harvesting across the whole visible range. A profound investigation of the mechanism shows that this 3D porous ZnO-SnS material effectively integrates the large surface area and high redox potential of ZnO, and wide visible-light harvesting of SnS, which largely promotes the transfer and separation rate of carriers. The systematic study on the active species generated during the photocatalysis illustrates that it is the photoelectrons, ˙OH and O2˙- that play the crucial role in the degradation of dyes. As a result, the noble-metal free photocatalyst degrades nearly 100% of rhodamine B (RhB) within 80 min and methylene blue (MB) in 40 min under visible light. The photocatalytic activity is 10 times higher than that of the pure flower-like ZnO and two times higher than that of the SnS material. Moreover, the photocatalyst is easily separated and reused at least four times without obvious change in efficiency and properties. This work provides an effective strategy for the synthesis of 3D porous p-n heterojunction semiconductor-based photocatalysts with low cost and low toxicity, which present promising applications in the field of solar energy storage and conversion.

Self-assembly of Au15 into single-cluster-thick sheets at the interface of two miscible high-boiling solvents.

Wet (nano)blanket: The self-assembly of Au nanoclusters into single-cluster-thick nanosheets is performed in two miscible high-boiling solvents with a slight polarity difference, which generates microphase separation and acts as a soft template to direct the self-assembly in a two-dimensional orientation.

Preparation of textured and transparent BiVO4 photoelectrodes based on Mo-doped BiVO4 nanoparticles for constructing a stand-alone tandem water splitting device.

Crystallographic orientation control is an effective method to improve the photoelectrochemical water splitting efficiency of BiVO4 photoanodes. Herein, textured and transparent Mo-BiVO4 photoanodes are fabricated by spin-coating Mo-doped BiVO4 nanoparticles on FTO. The photoelectrodes exhibit a current density of 4.15 mA cm-2 and 2.50 mA cm-2 for sulfite and water oxidation, respectively. By connecting the photoelectrode with a CsPbBrI2 perovskite solar cell, a stand-alone tandem water splitting device with a current density of 2.13 mA cm-2 and an STH of 2.43% can be achieved.

Facile Synthesis of Flower-Like MnCo2 O4 @PANi-rGO: A High-Performance Anode Material for Lithium-Ion Batteries.

Flower-like MnCo2 O4 was prepared in a self-assembly process and used in the formation of MnCo2 O4 @polyaniline (MnCo2 O4 @PANi) that proceeds by a simple in situ polymerization. The MnCo2 O4 @PANi-reduced graphite oxide (MnCo2 O4 @PANi-rGO) composite was then synthesized by introducing rGO into MnCo2 O4 @PANi. This modification improves the overall electronic conductivity of the MnCo2 O4 @PANi-rGO because of the dual conductive functions of rGO and PANi; it also provides a buffer for the changes in electrode volume during cycling, thus improving the lithium-storage performance of MnCo2 O4 @PANi-rGO. The electrochemical performance of the samples was evaluated by charge/discharge cycling testing, cyclic voltammetry, and electrochemical impedance spectroscopy. MnCo2 O4 @PANi-rGO delivers a discharge capacity of 745 mAh g-1 and a Coulombic efficiency of 100 % after 1050 cycles at a current density of 500 mA g-1 , and is a promising anode material for lithium-ion batteries.

Oxygen-Defective Ultrathin BiVO4 Nanosheets for Enhanced Gas Sensing.

BiVO4 nanomaterials are potentially applicable in gas sensing, but the sensing performance is limited by the less active sites on the BiVO4 surface. In this work, we propose a strategy to improve the gas-sensing performance of BiVO4 by forming ultrathin nanosheets and introducing oxygen vacancies, which increase the surface active sites. Two-dimensional (2D) BiVO4 nanosheets with oxygen vacancies are prepared through a colloidal method with the assistance of nitric acid. Gas sensors based on the oxygen-defective 2D ultrathin BiVO4 nanosheets exhibit an enhanced sensing response, which is 3.4 times higher than those of the sensors based on oxygen-abundant BiVO4 nanosheets. The density functional theory calculation is employed to uncover the promoting effects of oxygen vacancies on enhancing the O2 adsorption capability of BiVO4 nanosheets. This work is not only expected to build a wide range of 2D metal oxide semiconductors with a high gas-sensing performance but also gives an insight into the mechanism of the enhanced response induced by the oxygen vacancies, which will be a guideline for further designing high-performance sensing materials.

Advances in Cathode Materials for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) represent a promising energy storage technology, and they show potential for next-generation high-energy systems due to their high specific capacity, abundant constitutive resources, non-toxicity, low cost, and environment friendliness. Unlike their ubiquitous lithium-ion battery counterparts, the application of LSBs is challenged by several obstacles, including short cycling life, limited sulfur loading, and severe shuttling effect of polysulfides. To make LSBs a viable technology, it is very important to design and synthesize outstanding cathode materials with novel structures and properties. In this review, we summarize recent progress in designs, preparations, structures, and properties of cathode materials for LSBs, emphasizing binary, ternary, and quaternary sulfur-based composite materials. We especially highlight the utilization of carbons to construct sulfur-based composite materials in this exciting field. An extensive discussion of the emerging challenges and possible future research directions for cathode materials for LSBs is provided.

Phosphine-Free Synthesis of Metal Chalcogenide Quantum Dots by Directly Dissolving Chalcogen Dioxides in Alkylthiol as the Precursor.

Semiconductor quantum dots (QDs) are competitive emitting materials in developing new-generation light-emitting diodes (LEDs) with high color rendering and broad color gamut. However, the use of highly toxic alkylphosphines cannot be fully avoided in the synthesis of metal selenide and telluride QDs because they are requisite reducing agents and solvents for preparing chalcogen precursors. In this work, we demonstrate the phosphine-free preparation of selenium (Se) and tellurium (Te) precursors by directly dissolving chalcogen dioxides in the alkylthiol under the mild condition. The chalcogen dioxides are reduced to elemental chalcogen clusters, while the alkylthiol is oxidized to disulfides. The chalcogen clusters further combine with the disulfides, generating dispersible chalcogen precursors. The resulting chalcogen precursors are suitable for synthesizing various metal chalcogenide QDs, including CdSe, CdTe, Cu2Te, Ag2Te, PbTe, HgTe, and so forth. In addition, the precursors are of high reactivity, which permits a shorter QD synthesis process at lower temperature. Owing to the high quantum yield (QYs) and easy tunability of the photoluminescence (PL), the as-synthesized QDs are further employed as down-conversion materials to fabricate monochrome and white LEDs.

Aqueous-Processed Insulating Polymer/Nanocrystal Hybrid Solar Cells.

A novel kind of hybrid solar cell (HSC) was developed by introducing water-soluble insulating polymer poly(vinyl alcohol) (PVA) into nanocrystals (NCs), which revealed that the most frequently used conjugated polymer could be replaced by an insulating one. It was realized by strategically taking advantage of the characteristic of decomposition for the polymer at annealing temperature, and it was interesting to discover that partial decomposition of PVA left behind plenty of pits on the surfaces of CdTe NC films, enlarging surface contact area between CdTe NCs and subsequently evaporated MoO3. Moreover, the residual annealed PVA filled in the voids among spherical CdTe NCs, which led to the decrease of leakage current. An improved shunt resistance (increased by ∼80%) was achieved, indicating the charge-carrier recombination was effectively overcome. As a result, the new HSCs were endowed with increased Voc, fill factor, and power conversion efficiency compared with the pure NC device. This approach can be applied to other insulating polymers (e.g., PVP) with advantages in synthesis, type, economy, stability, and so on, providing a novel universal cost-effective way to achieve higher photovoltaic performance.

Phosphine-free synthesis of Ag-In-Se alloy nanocrystals with visible emissions.

As promising heavy metal-free emitting materials, Ag-In-Se nanocrystals (NCs) are conventionally synthesized using organic phosphine agents and exhibit near-infrared emissions. In this work, we demonstrate a rapid phosphine-free approach for synthesizing Ag-In-Se alloy NCs with the emissions tunable to the visible region on the basis of the phosphine-free dissolution of Se powder. At room temperature, Se powder is reduced by dodecanethiol and dissolved in oleylamine to produce a Se precursor. The resultant Se precursor is highly active, which permits rapid synthesis at a relatively low temperature, such as at 90 °C for 150 s. By optimizing the size, structure, and composition, the photoluminescence quantum yield of the as-synthesized Ag-In-Se NCs is enhanced to up to 10%. The growth of the Ag-In-Se NCs involves composition and phase transition, which strongly depend on the reaction temperature. The Ag2Se nuclei form first, and the Ag-In-Se NCs are produced by doping In(3+) into the preformed Ag2Se nuclei. Tetragonal phase Ag-In-Se is obtained below 170 °C, while the orthorhombic phase appears over 190 °C. The potential of Ag-In-Se NCs as red emitting phosphors for lighting-emitting diodes is further demonstrated.

A totally phosphine-free synthesis of metal telluride nanocrystals by employing alkylamides to replace alkylphosphines for preparing highly reactive tellurium precursors.

Despite the developments in the wet chemical synthesis of high-quality semiconductor nanocrystals (NCs) with diverse elemental compositions, telluride NCs are still irreplaceable materials owing to their excellent photovoltaic and thermoelectric performances. Herein we demonstrate the dissolution of elemental tellurium (Te) in a series of alkylamides by sodium borohydride (NaBH4) reduction at relatively low temperature to produce highly reactive precursors for hot-injection synthesis of telluride NCs. The capability to tune the reactivity of Te precursors by selecting injection temperature permits control of NC size over a broad range. The current preparation of Te precursors is simple, economical, and totally phosphine-free, which will promote the commercial synthesis and applications of telluride NCs.