ACS Nanoscience Au最新文献

Materials referred to as “high entropy” contain a large number of elements randomly distributed on the lattice sites of a crystalline solid, such that a high configurational entropy is presumed to contribute significantly to their formation and stability. High temperatures are typically required to achieve entropy stabilization, which can make it challenging to synthesize colloidal nanoparticles of high entropy materials. Nonetheless, strategies are emerging for the synthesis of colloidal high entropy nanoparticles, which are of interest for their synergistic properties and unique catalytic functions that arise from the large number of constituent elements and their interactions. In this Perspective, we highlight the classes of materials that have been made as colloidal high entropy nanoparticles as well as insights into the synthetic methods and the pathways by which they form. We then discuss the concept of “high entropy” within the context of colloidal materials synthesized at much lower temperatures than are typically required for entropy to drive their formation. Next, we identify and address challenges and opportunities in the field of high entropy nanoparticle synthesis. We emphasize aspects of materials characterization that are especially important to consider for nanoparticles of high entropy materials, including powder X-ray diffraction and elemental mapping with scanning transmission electron microscopy, which are among the most commonly used techniques in laboratory settings. Finally, we share perspectives on emerging opportunities and future directions involving colloidal nanoparticles of high entropy materials, with an emphasis on synthesis, characterization, and fundamental knowledge that is needed for anticipated advances in key application areas.

The nanopore sensing method holds the promise of delivering a single molecule technology for identification of biological proteins, direct detection of post-translational modifications, and perhaps de novo determination of a protein’s amino acid sequence. The key quantity measured in such nanopore sensing experiments is the magnitude of the ionic current passing through a nanopore blocked by a polypeptide chain. Establishing a relationship between the amino acid sequence of a peptide fragment confined within a nanopore and the blockade current flowing through the nanopore remains a major challenge for realizing the nanopore protein sequencing. Using the results of all-atom molecular dynamics simulations, here we compare nanopore sequencing of DNA with nanopore sequencing of proteins. We then delineate the factors affecting the blockade current modulation by the peptide sequence, showing that the current can be determined by (i) the steric footprint of an amino acid, (ii) its interactions with the pore wall, (iii) the local stretching of a polypeptide chain, and (iv) the local enhancement of the ion concentration at the nanopore constriction. We conclude with a brief discussion of the prospects for purely computational prediction of the blockade currents.

Ligand dynamics plays a critical role in the chemical and biological properties of gold nanoparticles (AuNPs). In this study, ligands featuring hydrophobic alkanethiol interiors and hydrophilic shells were used to systematically examine the effects of ligand headgroups on the ligand dynamics. Solution nuclear magnetic resonance (NMR) spectroscopy provided quantitative insight into the monolayer ligand dynamics. Notably, the introduction of hydrophobic moieties to the cationic headgroups significantly decreased ligand conformational mobility; however, variations in hydrophobicity among these moieties had a limited effect on this reduction. Further examination of ligand dynamics under various physiological conditions, including ionic strength and temperature, showed that ligands bound to the AuNP surface become less conformationally mobile with an increase in ionic strength or decreasing temperature. This exploration of ligand dynamics provides insight into designing nanoparticles tailored to specific biological applications.

Iron phosphide (FeP) nanoparticles have excellent properties such as fast charge transfer kinetics, high electrical conductivity, and high stability, making them a promising catalyst for hydrogen evolution reaction (HER). A challenge to the wide use of iron phosphide nanomaterials for this application is the available synthesis protocols that limit control over the resulting crystalline phase of the product. In this study, we report a method for synthesizing FeP through a solution-based process. Here, we use iron oxyhydroxide (β-FeOOH) as a cost-effective, environmentally friendly, and air-stable source of iron, along with tri-n-octylphosphine (TOP) as the phosphorus source and solvent. FeP is formed in a nanobundle morphology in the solution phase reaction at a temperature of 320 °C. The materials were characterized by pXRD and transmission electron microscopy (TEM). The optimization parameters evaluated to produce the phosphorus-rich FeP phase included the reaction rate, time, amount of TOP, and reaction temperature. Mixtures of Fe₂P and FeP phases were obtained at shorter reaction times and slow heating rates (4.5 °C /min), while longer reaction times and faster heating rates (18.8 °C/min) favored the formation of phosphorus-rich FeP. Overall, the reaction lever that consistently yielded FeP as the predominant crystalline phase was a fast heat rate.

We report the effects of screening capacity, surface roughness, and interfacial epitaxy of the bottom electrodes on the polarization switching, domain wall (DW) roughness, and ferroelectric Curie temperature (T_C) of PbZr_0.2Ti_0.8O₃ (PZT)-based free-standing membranes. Singe crystalline 10–50 nm (001) PZT and PZT/La_0.67Sr_0.33MnO₃ (LSMO) membranes are prepared on Au, correlated oxide LSMO, and two-dimensional (2D) semiconductor MoS₂ base layers. Switching the polarization of PZT yields nonvolatile current modulation in the MoS₂ channel at room temperature, with an on/off ratio of up to 2 × 10⁵ and no apparent decay for more than 3 days. Piezoresponse force microscopy studies show that the coercive field E_c for the PZT membranes varies from 0.75 to 3.0 MV cm^–1 on different base layers and exhibits strong polarization asymmetry. The PZT/LSMO membranes exhibit significantly smaller E_c, with the samples transferred on LSMO showing symmetric E_c of about −0.26/+0.28 MV cm^–1, smaller than that of epitaxial PZT films. The DW roughness exponent ζ points to 2D random bond disorder dominated DW roughening (ζ = 0.31) at room temperature. Upon thermal quench at progressively higher temperatures, ζ values for PZT membranes on Au and LSMO approach the theoretical value for 1D random bond disorder (ζ = 2/3), while samples on MoS₂ exhibits thermal roughening (ζ = 1/2). The PZT membranes on Au, LSMO, and MoS₂ show T_C of about 763 ± 12, 725 ± 25, and 588 ± 12 °C, respectively, well exceeding the bulk value. Our study reveals the complex interplay between the electrostatic and mechanical boundary conditions in determining ferroelectricity in free-standing PZT membranes, providing important material parameters for the functional design of PZT-based flexible nanoelectronics.

Micro- and nanoscopic particles that swim autonomously and self-assemble under the influence of chemical fuels and external fields show promise for realizing systems capable of carrying out large-scale, predetermined tasks. Different behaviors can be realized by tuning swimmer interactions at the individual level in a manner analogous to the emergent collective behavior of bacteria and mammalian cells. However, the limited toolbox of weak forces with which to drive these systems has made it difficult to achieve useful collective functions. Here, we review recent research on driving swimming and particle self-organization using acoustic fields, which offers capabilities complementary to those of the other methods used to power microswimmers. With either chemical or acoustic propulsion (or a combination of the two), understanding individual swimming mechanisms and the forces that arise between individual particles is a prerequisite to harnessing their interactions to realize collective phenomena and macroscopic functionality. We discuss here the ingredients necessary to drive the motion of microscopic particles using ultrasound, the theory that describes that behavior, and the gaps in our understanding. We then cover the combination of acoustically powered systems with other cross-compatible driving forces and the use of ultrasound in generating collective behavior. Finally, we highlight the demonstrated applications of acoustically powered microswimmers, and we offer a perspective on the state of the field, open questions, and opportunities. We hope that this review will serve as a guide to students beginning their work in this area and motivate others to consider research in microswimmers and acoustic fields.

Altering the physical and chemical properties of a layered material through intercalation has emerged as a unique strategy toward tunable applications. In this work, we demonstrate a wet chemical method to intercalate titanium, hafnium, and zirconium into 2D layered nanomaterials. The metals are intercalated using bis-tetrahydrofuran metal halide complexes. Metal intercalation is demonstrated in nanomaterials of Bi₂Se₃, Si₂Te₃, MoO₃, and GeS. This strategy intercalates, on average, 3 atm % or less of Hf, Ti, and Zr that share charge with the host nanomaterial. This methodology is used to chemochromically alter MoO₃ from transparent white to dark blue.

Surface chemistry of materials that host quantum bits such as diamond is an important avenue of exploration as quantum computation and quantum sensing platforms mature. Interfacing diamond in general and nanoscale diamond (ND) in particular with silica is a potential route to integrate room temperature quantum bits into photonic devices, fiber optics, cells, or tissues with flexible functionalization chemistry. While silica growth on ND cores has been used successfully for quantum sensing and biolabeling, the surface mechanism to initiate growth was unknown. This report describes the surface chemistry responsible for silica bond formation on diamond and uses X-ray absorption spectroscopy (XAS) to probe the diamond surface chemistry and its electronic structure with increasing silica thickness. A modified Stöber (Cigler) method was used to synthesize 2–35 nm thick shells of SiO₂ onto carboxylic acid-rich ND cores. The diamond morphology, surface, and electronic structure were characterized by overlapping techniques including electron microscopy. Importantly, we discovered that SiO₂ growth on carboxylated NDs eliminates the presence of carboxylic acids and that basic ethanolic solutions convert the ND surface to an alcohol-rich surface prior to silica growth. The data supports a mechanism that alcohols on the ND surface generate silyl–ether (ND–O–Si–(OH)₃) bonds due to rehydroxylation by ammonium hydroxide in ethanol. The suppression of the diamond electronic structure as a function of SiO₂ thickness was observed for the first time, and a maximum probing depth of ∼14 nm was calculated. XAS spectra based on the Auger electron escape depth was modeled using the NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to support our experimental results. Additionally, resonant inelastic X-ray scattering (RIXS) maps produced by the transition edge sensor reinforces the chemical analysis provided by XAS. Researchers using diamond or high-pressure high temperature (HPHT) NDs and other exotic materials (e.g., silicon carbide or cubic-boron nitride) for quantum sensing applications may exploit these results to design new layered or core–shell quantum sensors by forming covalent bonds via surface alcohol groups.

In this work, we demonstrate a photoluminescence-based method to monitor the kinetics of an organohalide reaction by way of detecting released bromide ions at cesium lead halide nanoparticles. Small aliquots of the reaction are added to an assay with known concentrations of CsPbI₃, and the resulting Br-to-I halide exchange (HE) results in rapid and sensitive wavelength blueshifts (Δλ) due to CsPbBr_xI_3–x intermediate concentrations, the wavelengths of which are proportional to concentrations. An assay response factor, C, relates Δλ to Br^– concentration as a function of CsPbI₃ concentration. The observed kinetics, as well as calculated rate constants, equilibrium, and activation energy of the solvolysis reaction tested correspond closely to synthetic literature values, validating the assay. Factors that influence the sensitivity and performance of the assay, such as CsPbI₃ size, morphology, and concentration, are discussed.

This paper describes coinage-metal-doped InP quantum dots (QDs) as a platform for enhanced electron transfer to molecular acceptors relative to undoped QDs. A synthetic strategy is developed to prepare doped InP/ZnSe QDs. First-principles DFT calculations show that Ag⁺ and Cu⁺ dopants localize photoexcited holes while leaving electrons delocalized. This charge carrier wave function modulation is leveraged to enhance electron transfer to molecular acceptors by up to an order of magnitude. Examination of photoluminescence quenching data suggests that larger electron acceptors, such as anthraquinone and methyl viologen, bind to the QD surface in two ways: by direct adsorption to the surface and by adsorption following displacement of a weakly bound surface cation-ligand complex. Reactions with larger acceptors show the greatest increases in electron transfer between doped and undoped quantum dots, while smaller acceptors show smaller enhancements. Specifically, benzoquinone shows the smallest, followed by naphthoquinone and then methyl viologen and anthraquinone. These results demonstrate the benefits of dopant-induced excited-state carrier localization on photoinduced charge transfer and highlight design principles for improved implementation of quantum dots in photoredox catalysis.