Search Results (157)

Nanoparticle superlattices—periodic assemblies of uniformly spaced nanocrystals—bridge the nanoscale precision of individual particles with emergent collective properties akin to those of bulk materials. Recent advances demonstrate that multivalent ions and charged polymers can guide the co-assembly of nanoparticles, imparting electrostatic gating and enabling semiconductor-like behavior. However, the specific roles of anion geometry, valency, and charge density in mediating ion transport remain unclear. Here, we employ coarse-grained molecular dynamics simulations to investigate how applied electric fields (0–0.40 V/nm) modulate ionic conductivity and spatial distribution in trimethylammonium-functionalized gold nanoparticle superlattices assembled with four phosphate anions of distinct geometries and charges. Our results reveal that linear anions outperform ring-shaped analogues in conductivity due to higher charge densities and weaker interfacial binding. Notably, charge density exerts a greater influence on ion mobility than size alone. Under strong fields, anions accumulate at nanoparticle interfaces, where interfacial adsorption and steric constraints suppress transport. In contrast, local migration is governed by geometrical confinement and field strength. Analyses of transition probability and residence time further indicate that the rigidity and delocalized charge of cyclic anions act as mobility barriers. These findings provide mechanistic insights into the structure–function relationship governing ion transport in superlattices, offering guidance for designing next-generation ion conductors, electrochemical sensors, and energy storage materials through anion engineering. Full article

Biomass reforming under mild conditions for synergistic hydrogen production, driven by renewable solar energy, has rapidly emerged as a promising strategy that not only enables the efficient reutilization of biomass but also facilitates the generation of high-purity hydrogen. In this work, ZnCdS (ZCS) nanoparticles and CoWO₄ (CW) nanocrystals were assembled via a solvothermal method to construct a ZCS/CW S-type heterojunction composite. The resultant materials’ physicochemical characteristics were methodically described. With lignin model compounds (PP-ol) and sodium lignosulfonate as substrates, the ZnCdS/CoWO₄-10% catalyst demonstrated a significant generation of hydrogen activity, producing hydrogen at rates of 223.30 μmol·g⁻¹·h⁻¹ and 140.28 μmol·g⁻¹·h⁻¹, respectively, according to experimental results. The formation of heterojunctions endows composite photocatalysts with higher hydrogen evolution rates compared to single-component catalysts. This is attributed to energy band bending at the interface of the heterojunction, which facilitates efficient charge separation while maintaining strong redox capabilities. High-value compounds like phenol and acetophenone were formed when the oxidation products in the post-reaction lignin model compound solution were subsequently analyzed using high-performance liquid chromatography. Additionally, a convincing mechanism for the catalytic reaction was suggested. It is expected that this study will offer a viable route for the creation of effective photocatalytic materials, high-value organic waste transformation, and sustainable hydrogen production. Full article

We report the observation of a linear electro-optic (EO) response in CsPbX₃ (X = Cl, Br, I) perovskite nanocrystal (NC) films fabricated via electrophoretic deposition (EPD). Under an alternating electric field, the EPD films exhibit clear linear EO modulation of transmitted light intensity, indicating the formation of an anisotropic medium through field-induced NC alignment. In contrast, spin-coated NC films show no measurable linear EO response, underscoring the critical role of structural anisotropy introduced by EPD. All EPD samples exhibit a decreasing EO response with increasing modulation frequency, consistent with the involvement of slow ion migration dynamics. The halide composition influences EO behavior, with Br/Cl mixed-composition films maintaining the highest EO response at elevated frequencies, and Br-based NCs showing stronger EO signals than their Cl counterparts, while Bi-doped CsPbBr₃ films exhibit quenched photoluminescence yet retain a measurable but weaker EO response, underscoring the trade-off between defect-induced nonradiative recombination and EO activity. These results highlight the potential of EPD-assembled perovskite NCs for reconfigurable EO applications by tailoring composition and microstructure. Full article

We developed dye-sensitized solar cells based on anatase–titanium dioxide (A-TiO₂) nanotubes (TiNTs) and nanocubes (TiNcs) with {001} crystal facets generated using simple and facile electrochemical anodization. We also demonstrated a simple way of developing one-dimensional, two-dimensional, and three-dimensional self-assembled TiO₂ nanostructures via electrochemical anodization, using them as an electron-transporting layer in DSSCs. TiNTs maintain tubular arrays for a limited time before becoming nanocrystals with {001} facets. Using FESEM and TEM, we observed that the TiO₂ nanobundles were transformed into nanocubes with {001} facets and lower fluorine concentrations. Optimizing the reaction approach resulted in better-ordered, crystalline anatase TiNTs/Ncs being formed on the Ti metal foil. The anatase phase of as-grown TiO₂ was confirmed by XRD, with (101) being the predominant intensity and preferred orientation. The nanostructured TiO₂ had lattice values of a = 3.77–3.82 and c = 9.42–9.58. The structure and morphology of these as-grown materials were studied to understand the growth process. The photoconversion efficiency and impedance spectra were explored to analyze the performance of the designed DSSCs, employing N719 dye as a sensitizer and the I⁻/I³⁻ redox pair as electrolytes, sandwiched with a Pt counter-electrode. As a result, we found that self-assembled TiNTs/Ncs presented a more effective photoanode in DSSCs than standard TiO₂ (P25). TiNcs (0.5 and 0.25 NH₄F) and P25 achieved the highest power conversion efficiencies of 3.47, 3.41, and 3.25%, respectively. TiNcs photoanodes have lower charge recombination capability and longer electron lifetimes, leading to higher voltage, photocurrent, and photovoltaic performance. These findings show that electrochemical anodization is an effective method for preparing TiNTs/Ncs and developing low-cost, highly efficient DSSCs by fine-tuning photoanode structures and components. Full article

Lead halide perovskite quantum dots, also known as perovskite nanocrystals, are considered one of the most promising photovoltaic materials for solar cells due to their outstanding optoelectronic properties and simple preparation techniques. The key factors restricting the photoelectric conversion efficiency of solar cell systems are the separation and transmission performances of charge carriers. Here, femtosecond time-resolved ultrafast spectroscopy was used to measure the interfacial charge transfer dynamics of different sizes of CsPbBr₃ assembled with TiO₂. The effect of perovskite size on the charge transfer is discussed. According to our experimental data analysis, the time constants of the interfacial electron transfer and charge recombination of the assembled systems of CsPbBr₃ and titanium dioxide become larger when the size of the CsPbBr₃ nanocrystals increases. We discuss the physical mechanism by which the size of perovskites affects the rate of charge transfer in detail. We expect that our experimental results provide experimental support for the application of novel quantum dots for solar cell materials. Full article

Metal halide perovskite (MHP) nanocrystals (NCs) offer great potential for high-efficiency optoelectronic devices; however, they suffer from structural softness and chemical instability. Doping MHP NCs can overcome this issue. In this work, we synthesize Mn-doped methylammonium lead bromide (MAPbBr₃) NCs using the ligand-assisted reprecipitation method and investigate their structural and optical stability. X-ray diffraction confirms Mn²⁺ substitution at Pb²⁺ sites and lattice contraction. Photoluminescence (PL) measurements show a blue shift, significant PL quantum yield enhancement, reaching 72% at 17% Mn²⁺ doping, and a 34% increase compared to undoped samples, attributed to effective defect passivation and reduced non-radiative recombination, supported by time-resolved PL data. Mn²⁺ doping also improves long-term stability under ambient conditions. Low-temperature PL reveals the crystal-phase transitions of perovskite NCs and Mn-doped NCs to be somewhat different than those of pure MAPbBr₃. Mn²⁺ incorporation into perovskite promotes self-assembly into superlattices with larger crystal sizes, better structural order, and stronger inter-NC coupling. These results demonstrate that Mn²⁺ doping enhances both optical performance and structural robustness, advancing the potential of MAPbBr₃ NCs for stable optoelectronic applications. Full article

Ordered mesoporous carbon materials (OMCMs) are widely used as high-performance electrode materials due to their uniform pore structure, excellent electrical conductivity, and good stability. In this paper, three OMCMs with controllable N content were prepared by a nanocasting method using Fe₃O₄ nanocrystals as the template and organic ligands as the carbon source. By adopting a ligand exchange strategy, oleic acid, oleic amine, and octyl amine were successfully capped onto the Fe₃O₄ nanocrystals, respectively, which allowed the rational control of the elemental composition of OMCMs at the molecular level. Further characterizations revealed that the nitrogen content of the resulting OMCMs increased as the proportion of nitrogen atoms in the ligand increased, while the order of the porous structure decreased as the hydrocarbon chain length decreased. This study demonstrates that both the N-doping content and the order of the OMCMs are influenced by the N-containing ligand. This finding will provide a fundamental aspect for their further applications as high-performance electrode and catalytic materials in the field of electrochemistry. Full article

We report the successful synthesis of monodispersed Cu₂S nanocrystals and the subsequent formation of highly ordered nanocrystal superlattices. The synthesis is performed under ambient air conditions using simple experimental setups, making the process both accessible and scalable. By systematically tuning the reaction temperature and duration, we demonstrate precise control over the nanocrystal size, which is crucial in achieving uniformity and monodispersity. Furthermore, we uncover a previously unidentified nanocrystal growth mechanism that plays a key role in producing highly monodisperse Cu₂S nanocrystals. This insight into the growth process enhances our fundamental understanding of nanocrystal formation and could be extended to the synthesis of other semiconductor nanomaterials. The self-assembly of these nanocrystals into superlattices is carefully examined using electron diffraction techniques, revealing the presence of pseudo-crystalline structures. The ordered arrangement of nanocrystals within these superlattices suggests strong interparticle interactions and opens up new possibilities to tailor their collective optical, electronic, and mechanical properties for potential applications in optoelectronics, nanomedicine, and energy storage. Full article

In this paper, a composite separator for lithium-ion batteries was successfully prepared by electrostatic spinning, based on polyacrylonitrile (PAN) and 5% cellulose nanocrystals (CNCs) derived from sisal fiber. Its physical and electrochemical properties as well as the enhanced mechanism were investigated. The obtained 5%CNCs/PAN separator offers an excellent thermal stability, ultra-high electrolyte uptake (486 ± 30%), high ionic conductivity (2.82 mS cm⁻¹ at 25 °C) and a wide electrochemical window (5.3 V). In addition, a lithium-ion battery assembled with the 5%CNCs/PAN separator can work stably for 1000 h at 5 mA cm⁻². The CNCs in the electrolyte enable the immobilization of PF₆⁻, thereby inhibiting the migration of anions and increasing its Li⁺ transfer number (t_Li⁺) to 0.75, which is 65.3% higher than that of a pure PAN separator. The battery with the 5%CNCs/PAN separator retains 97.4% of its initial reversible capacity after 100 cycles, which is much higher than that of a pure PAN separator, with a value of 62.9%. These results suggest the potential utility of 5%CNCs/PAN separators as high-performance separators required in lithium-ion batteries. Full article

The spray pyrolysis deposition of nanostructured Pb_1−xSn_xSe alloy films, x = 0.0 to 1.0, from as-prepared Pb_1−xSn_xSe alloy colloids as the starting solution is reported. The colloidal dispersions were prepared by dissolving selenium in an amine–thiol mixture, reacted with the Sn and Pb precursors in propylene glycol, and subsequently sprayed onto glass substrates at 300 °C. Structural characterization indicated the formation of the alloyed rock-salt cubic phase for 0.0 ≤ x ≤ 0.75, oxidized Pb and Se phases produced during the deposition, and only orthorhombic SnSe for x = 1.0 with Se and SnSe₂ as impurities. Nanocrystalline films ranging from 16 to 16.5 nm in size were obtained. The films displayed a shift in their optical structure and a non-monotonic variation in the band gap energy, first a decrease, reaching the minimum at x = 0.30 and a further increase in the Sn content. The decrease in the optical band gap resembles that of a topological insulator behavior. The morphology of the alloyed films confirmed the large nanocrystal formation by self-assembly processes in both the PbSe and SnSe phases and segregated PbSnSe platelets for x ≥ 0.30. Seebeck coefficient revealed that a typical semiconductor behavior dominated by bipolar transport, and p-type conductivity, but only for x = 0.0 n-type conductivity was exhibited. The maximal Seebeck coefficient magnitude behaved similarly to the band gap energy, evidencing the influence of energy band structure and the topological character. Full article

Numerous strategies have been demonstrated to enhance the mechanical stretchability of electromechanical sensors for widespread applications in wearable electronics. However, ranging from composite to microstructural materials, their electromechanical sensing performances are usually vulnerable to large stretching deformations due to the low-ductility of the infilled conductive components and the modulus mismatch between the flexible polymer substrate and conductive fillers. Here, a novel design strategy is proposed to fabricate ultra-stretchable electromechanical composites constructed by a triple-level interaction conductive network (Tri-LICN) in buckled-TPU microfibers for strain sensors. The Tri-LICN is established by bridging one-dimensional cellulose nanocrystals (CNC) with zero-dimensional gold-nanoparticles (AuNPs) and two-dimensional MXene sheets using interface self-assembly and ultrasound-assisted anchoring to eliminate the modulus mismatching between the conductive material and polymer substrate. The buckled-TPU microfibers are introduced to improve the mechanical stretchability of composites by the external-stimuli-induced imbalance of the stretching conformation of TPU macromolecules. The Tri-LICN MXene/CNC/AuNPs@TPU composite sensor displays an enhanced strain sensitivity (GF~2514) with a fast response time (~150 ms) over a wide operational strain up to 200% and excellent durability over 1000 tensile cycles. Our finding offers a promising approach to enhancing the performance of stretchable sensors based on polymer materials, providing new opportunities for the development of next-generation electronics. Full article

The development of functional materials and the use of nanotechnology are ongoing projects. These fields are closely linked, but there is a need to combine them more actively. Nanoarchitectonics, a concept that comes after nanotechnology, is ready to do this. Among the related research efforts, research into creating functional materials through the formation of thin layers on surfaces, molecular membranes, and multilayer structures of these materials have a lot of implications. Layered structures are especially important as a key part of nanoarchitectonics. The diversity of the components and materials used in layer-by-layer (LbL) assemblies is a notable feature. Examples of LbL assemblies introduced in this review article include quantum dots, nanoparticles, nanocrystals, nanowires, nanotubes, g-C₃N₄, graphene oxide, MXene, nanosheets, zeolites, nanoporous materials, sol–gel materials, layered double hydroxides, metal–organic frameworks, covalent organic frameworks, conducting polymers, dyes, DNAs, polysaccharides, nanocelluloses, peptides, proteins, lipid bilayers, photosystems, viruses, living cells, and tissues. These examples of LbL assembly show how useful and versatile it is. Finally, this review will consider future challenges in layer-by-layer nanoarchitectonics. Full article

Transition metal oxides are considered promising anode materials for high performance flexible electrodes due to their abundant reserves and excellent specific capacity. However, their inherent low conductivity, large volume effect, and poor cycling performance limit their applications. Herein, we report a novel “spontaneous complexation and exfoliation” strategy for the fabrication of flexible MnO NCs@rGO thin-film electrodes, which overcomes the aforementioned drawbacks and pushes the mechanical flexibility and lithium-ion (Li⁺) storage performance to a higher level. The combination of large-area few-layer reduced graphene oxide (rGO) films and ultrafine MnO nanocrystals (MnO NCs) provides a high density of electrochemical active sites. Notably, the layer-by-layer embedded structure not only enables the MnO NCs@rGO electrodes to withstand various mechanical deformations but also produces a strong synergistic effect of enhanced reaction kinetics by providing an enlarged electrode/electrolyte contact area and reduced electron/ion transport resistance. The elaborately designed flexible MnO NCs@rGO anode provides a specific capacity of about 1220 mAh g⁻¹ over 1000 cycles, remarkable high-rate capacity (50.0 A g⁻¹), and exceptional cycling stability. Finally, the assembled flexible lithium-ion full cells achieve zero capacity loss during repeated large-angle bending, demonstrating immense potential as a high-performance flexible energy storage device. This work provides valuable insights into unique structural designs for durable and ultra-fast lithium ion batteries. Full article

In this study, epoxy-based composites were fabricated using a layer-by-layer assembly technique, and their mechanical properties were systematically evaluated. The inclusion of cellulose nanocrystals led to variations in the mechanical properties of the composites. These modified properties were assessed through tensile and flexural tests, with each layer cast to enhance strength. Due to the inherent characteristics of epoxy, a single specimen was fabricated through chemical bonding, even post-curing. This approach demonstrated that a three-layer structure, developed using the layer-by-layer method, exhibited improved elastic and flexural moduli compared to a single-layer composite. This improvement aligns with theoretical predictions, which suggest that stiffness increases when stiffer materials are positioned farther from the neutral axis in a layered structure. Furthermore, numerical analysis validated changes in stress distribution across each layer. Consequently, this method enables the production of composites with superior mechanical properties while minimizing the quantity of cellulose nanocrystals required. Full article

Bio-based eco-friendly cellulose nanocrystals (CNCs) gain an increasing interest for diverse applications. We report the results of an investigation of hydrogels spontaneously formed by the self-assembly of carboxylated CNCs in the presence of CaCl₂ using several complementary techniques: rheometry, isothermal titration calorimetry, FTIR-spectroscopy, cryo-electron microscopy, cryo-electron tomography, and polarized optical microscopy. Increasing CaCl₂ concentration was shown to induce a strong increase in the storage modulus of CNC hydrogels accompanied by the growth of CNC aggregates included in the network. Comparison of the rheological data at the same ionic strength provided by NaCl and CaCl₂ shows much higher dynamic moduli in the presence of CaCl₂, which implies that calcium cations not only screen the repulsion between similarly charged nanocrystals favoring their self-assembly, but also crosslink the polyanionic nanocrystals. Crosslinking is endothermic and driven by increasing entropy, which is most likely due to the release of water molecules surrounding the interacting COO⁻ and Ca²⁺ ions. The hydrogels can be easily destroyed by increasing the shear rate because of the alignment of rodlike nanocrystals along the direction of flow and then quickly recover up to 90% of their viscosity in 15 s, when the shear rate is decreased. Full article