Nanomaterials

Adsorption of toxic compounds from water using zeolites and magnetite was developed due to the various advantages of their applicability. In the last twenty years, the use of zeolite-based compositions in the form of zeolite/inorganic or zeolite/polymer and magnetite has been accelerated for the adsorption of emergent compounds from water sources. The main adsorption mechanisms using zeolite and magnetite nanomaterials are high surface adsorption, ion exchange capacity and electrostatic interaction. This paper shows the capacity of Fe₃O₄ and ZSM-5 nanomaterials of adsorbing the emerging pollutant acetaminophen (paracetamol) during the treatment of wastewater. The efficiencies of the Fe₃O₄ and ZSM-5 in the wastewater process were systematically investigated using adsorption kinetics. During the study, the concentration of acetaminophen in the wastewater was varied from 50 to 280 mg/L, and the maximum Fe₃O₄ adsorption capacity increased from 25.3 to 68.9 mg/g. The adsorption capacity of each studied material was performed for three pH values (4, 6, 8) of the wastewater. Langmuir and Freundlich isotherm models were used to characterize acetaminophen adsorption on Fe₃O₄ and ZSM-5 materials. The highest efficiencies in the treatment of wastewater were obtained at a pH value of 6. Fe₃O₄ nanomaterial presented a higher removal efficiency (84.6%) compared to ZSM-5 nanomaterial (75.4%). The results of the experiments show that both materials have a potential to be used as an effective adsorbents for the removal of acetaminophen from wastewater. Full article

Porous carbon materials have demonstrated exceptional performance in various energy and environment-related applications. Recently, research on supercapacitors has been steadily increasing, and porous carbon materials have emerged as the most significant electrode material for supercapacitors. Nonetheless, the high cost and potential for environmental pollution associated with the preparation process of porous carbon materials remain significant issues. This paper presents an overview of common methods for preparing porous carbon materials, including the carbon-activation method, hard-templating method, soft-templating method, sacrificial-templating method, and self-templating method. Additionally, we also review several emerging methods for the preparation of porous carbon materials, such as copolymer pyrolysis, carbohydrate self-activation, and laser scribing. We then categorise porous carbons based on their pore sizes and the presence or absence of heteroatom doping. Finally, we provide an overview of recent applications of porous carbon materials as electrodes for supercapacitors. Full article

In this work, a facile synthesis method was adopted to synthesize MOF-14 with mesoporous structure. The physical properties of the samples were characterized by PXRD, FESEM, TEM and FT-IR spectrometry. By coating the mesoporous-structure MOF-14 on the surface of a quartz crystal microbalance (QCM), the fabricated gravimetric sensor exhibits high sensitivity to p-toluene vapor even at trace levels. Additionally, the limit of detection (LOD) of the sensor obtained experimentally is lower than 100 ppb, and the theoretical detection limit is 57 ppb. Furthermore, good gas selectivity and fast response (15 s) and recovery (20 s) abilities are also illustrated along with high sensitivity. These sensing data indicate the excellent performance of the fabricated mesoporous-structure MOF-14-based p-xylene QCM sensor. On the basis of temperature-varying experiments, an adsorption enthalpy of −59.88 kJ/mol was obtained, implying the existence of moderate and reversible chemisorption between MOF-14 and p-xylene molecules. This is the crucial factor that endows MOF-14 with exceptional p-xylene-sensing abilities. This work has proved that MOF materials such as MOF-14 are promising in gravimetric-type gas-sensing applications and worthy of future study. Full article

Metal–organic frameworks (MOFs), composed of metal nodes and inorganic linkers, are promising for a wide range of applications due to their unique periodic frameworks. Understanding structure–activity relationships can facilitate the development of new MOFs. Transmission electron microscopy (TEM) is a powerful technique to characterize the microstructures of MOFs at the atomic scale. In addition, it is possible to directly visualize the microstructural evolution of MOFs in real time under working conditions via in situ TEM setups. Although MOFs are sensitive to high-energy electron beams, much progress has been made due to the development of advanced TEM. In this review, we first introduce the main damage mechanisms for MOFs under electron-beam irradiation and two strategies to minimize these damages: low-dose TEM and cryo-TEM. Then we discuss three typical techniques to analyze the microstructure of MOFs, including three-dimensional electron diffraction, imaging using direct-detection electron-counting cameras, and iDPC-STEM. Groundbreaking milestones and research advances of MOFs structures obtained with these techniques are highlighted. In situ TEM studies are reviewed to provide insights into the dynamics of MOFs induced by various stimuli. Additionally, perspectives are analyzed for promising TEM techniques in the research of MOFs’ structures. Full article

Two-dimensional (2D) MXenes sheet-like micro-structures have attracted attention as an effective electrochemical energy storage material due to their efficient electrolyte/cation interfacial charge transports inside the 2D sheets which results in ultrahigh rate capability and high volumetric capacitance. In this article, Ti₃C₂T_x MXene is prepared by a combination of ball milling and chemical etching from Ti₃AlC₂ powder. The effects of ball milling and etching duration on the physiochemical properties are also explored, as well as the electrochemical performance of as-prepared Ti₃C₂ MXene. The electrochemical performances of 6 h mechanochemically treated and 12 h chemically etched MXene (BM-12H) exhibit an electric double layer capacitance behavior with an enhanced specific capacitance of 146.3 F g⁻¹ compared to 24 and 48 h treated samples. Moreover, 5000-cycle stability tested sample’s (BM-12H) charge/discharge show increased specific capacitance due to the termination of the -OH group, intercalation of K⁺ ion and transformation to TiO₂/Ti₃C₂ hybrid structure in a 3 M KOH electrolyte. Interestingly, a symmetric supercapacitor (SSC) device fabricated in a 1 M LiPF₆ electrolyte in order to extend the voltage window up to 3 V shows a pseudocapacitance behavior due to Li on interaction/de-intercalation. In addition, the SSC shows an excellent energy and power density of 138.33 W h kg⁻¹ and 1500 W kg⁻¹, respectively. The ball milling pre-treated MXene exhibited an excellent performance and stability due to the increased interlayer distance between the MXene sheets and intercalation and deintercalation of Li⁺ ions. Full article

In this paper, the effect of atomic layer deposition (ALD)-derived Al₂O₃ passivation layers and annealing temperatures on the interfacial chemistry and transport properties of sputtering-deposited Er₂O₃ high-k gate dielectrics on Si substrate has been investigated. X-ray photoelectron spectroscopy (XPS) analyses have showed that the ALD-derived Al₂O₃ passivation layer remarkably prevents the formation of the low-k hydroxides generated by moisture absorption of the gate oxide and greatly optimizes the gate dielectric properties. Electrical performance measurements of metal oxide semiconductor (MOS) capacitors with different gate stack order have revealed that the lowest leakage current density of 4.57 × 10⁻⁹ A/cm² and the smallest interfacial density of states (Dit) of 2.38 × 10¹² cm⁻² eV⁻¹ have been achieved in the Al₂O_3/Er₂O₃/Si MOS capacitor, which can be attributed to the optimized interface chemistry. Further electrical measurements of annealed Al₂O_3/Er₂O₃/Si gate stacks at 450 °C have demonstrated superior dielectric properties with a leakage current density of 1.38 × 10⁻⁹ A/cm². At the same, the leakage current conduction mechanism of MOS devices under various stack structures is systematically investigated. Full article

In this work, we present a comprehensive theoretical and computational investigation of exciton fine structures of WSe${}_2$-monolayers, one of the best-known two-dimensional (2D) transition-metal dichalcogenides (TMDs), in various dielectric-layered environments by solving the first-principles-based Bethe–Salpeter equation. While the physical and electronic properties of atomically thin nanomaterials are normally sensitive to the variation of the surrounding environment, our studies reveal that the influence of the dielectric environment on the exciton fine structures of TMD-MLs is surprisingly limited. We point out that the non-locality of Coulomb screening plays a key role in suppressing the dielectric environment factor and drastically shrinking the fine structure splittings between bright exciton (BX) states and various dark-exciton (DX) states of TMD-MLs. The intriguing non-locality of screening in 2D materials can be manifested by the measurable non-linear correlation between the BX-DX splittings and exciton-binding energies by varying the surrounding dielectric environments. The revealed environment-insensitive exciton fine structures of TMD-ML suggest the robustness of prospective dark-exciton-based optoelectronics against the inevitable variation of the inhomogeneous dielectric environment. Full article

Mesoporous silica engineered nanomaterials are of interest to the industry due to their drug-carrier ability. Advances in coating technology include using mesoporous silica nanocontainers (SiNC) loaded with organic molecules as additives in protective coatings. The SiNC loaded with the biocide 4,5-dichloro-2-octyl-4-isothiazolin-3-one (DCOIT), i.e., SiNC-DCOIT, is proposed as an additive for antifouling marine paints. As the instability of nanomaterials in ionic-rich media has been reported and related to shifting key properties and its environmental fate, this study aims at understanding the behaviour of SiNC and SiNC-DCOIT in aqueous media with distinct ionic strengths. Both nanomaterials were dispersed in (i) low- (ultrapure water—UP) and (ii) high- ionic strength media—artificial seawater (ASW) and f/2 medium enriched in ASW (f/2 medium). The morphology, size and zeta potential (ζP) of both engineering nanomaterials were evaluated at different timepoints and concentrations. Results showed that both nanomaterials were unstable in aqueous suspensions, with the initial ζP values in UP below −30 mV and the particle size varying from 148 to 235 nm and 153 to 173 nm for SiNC and SiNC-DCOIT, respectively. In UP, aggregation occurs over time, regardless of the concentration. Additionally, the formation of larger complexes was associated with modifications in the ζP values towards the threshold of stable nanoparticles. In ASW, SiNC and SiNC-DCOIT formed aggregates (<300 nm) independently of the time or concentration, while larger and heterogeneous nanostructures (>300 nm) were detected in the f/2 medium. The pattern of aggregation detected may increase engineering nanomaterial sedimentation rates and enhance the risks towards dwelling organisms. Full article

We present a study with a numerical model based on $\overrightarrow{k}·\overrightarrow{p}$, including electromechanical fields, to evaluate the electromechanical and optoelectronic properties of single GaAs quantum dots embedded in direct band gap AlGaAs nanowires. The geometry and the dimensions of the quantum dots, in particular the thickness, are obtained from experimental data measured by our group. We also present a comparison between the experimental and numerically calculated spectra to support the validity of our model. Full article

In the context of the widespread distribution of zero valent iron nanoparticles (nZVI) in the environment and its possible exposure to many aquatic and terrestrial organisms, this study investigates the effects, uptake, bioaccumulation, localisation and possible transformations of nZVI in two different forms (aqueous dispersion—Nanofer 25S and air-stable powder—Nanofer STAR) in a model plant—Arabidopsis thaliana. Seedlings exposed to Nanofer STAR displayed symptoms of toxicity, including chlorosis and reduced growth. At the tissue and cellular level, the exposure to Nanofer STAR induced a strong accumulation of Fe in the root intercellular spaces and in Fe-rich granules in pollen grains. Nanofer STAR did not undergo any transformations during 7 days of incubation, while in Nanofer 25S, three different behaviours were observed: (i) stability, (ii) partial dissolution and (iii) the agglomeration process. The size distributions obtained by SP-ICP-MS/MS demonstrated that regardless of the type of nZVI used, iron was taken up and accumulated in the plant, mainly in the form of intact nanoparticles. The agglomerates created in the growth medium in the case of Nanofer 25S were not taken up by the plant. Taken together, the results indicate that Arabidopsis plants do take up, transport and accumulate nZVI in all parts of the plants, including the seeds, which will provide a better understanding of the behaviour and transformations of nZVI once released into the environment, a critical issue from the point of view of food safety. Full article

Thermoelectric energy conversion based on flexible materials has great potential for applications in the fields of low-power heat harvesting and solid-state cooling. Here, we show that three-dimensional networks of interconnected ferromagnetic metal nanowires embedded in a polymer film are effective flexible materials as active Peltier coolers. Thermocouples based on Co-Fe nanowires exhibit much higher power factors and thermal conductivities near room temperature than other existing flexible thermoelectric systems, with a power factor for Co-Fe nanowire-based thermocouples of about 4.7 mW/K${}^2$m at room temperature. The effective thermal conductance of our device can be strongly and rapidly increased by active Peltier-induced heat flow, especially for small temperature differences. Our investigation represents a significant advance in the fabrication of lightweight flexible thermoelectric devices, and it offers great potential for the dynamic thermal management of hot spots on complex surfaces. Full article

In this paper, we have fabricated non-volatile memory resistive switching (RS) devices and analyzed analog memristive characteristics using lateral electrodes with mesoporous silica–titania (meso-ST) and mesoporous titania (meso-T) layers. For the planar-type device having two parallel electrodes, current–voltage (I–V) curves and pulse-driven current changes could reveal successful long-term potentiation (LTP) along with long-term depression (LTD), respectively, by the RS active mesoporous two layers for 20~100 μm length. Through mechanism characterization using chemical analysis, non-filamental memristive behavior unlike the conventional metal electroforming was identified. Additionally, high performance of the synaptic operations could be also accomplished such that a high current of 10⁻⁶ Amp level could occur despite a wide electrode spacing and short pulse spike biases under ambient condition with moderate humidity (RH 30~50%). Moreover, it was confirmed that rectifying characteristics were observed during the I–V measurement, which was a representative feature of dual functionality of selection diode and the analog RS device for both meso-ST and meso-T devices. The memristive and synaptic functions along with the rectification property could facilitate a chance of potential implementation of the meso-ST and meso-T devices to neuromorphic electronics platform. Full article

Seeking sensitive, large-scale, and low-cost substrates is highly important for practical applications of surface-enhanced Raman scattering (SERS) technology. Noble metallic plasmonic nanostructures with dense hot spots are considered an effective construction to enable sensitive, uniform, and stable SERS performance and thus have attracted wide attention in recent years. In this work, we reported a simple fabrication method to achieve wafer-scale ultradense tilted and staggered plasmonic metallic nanopillars filled with numerous nanogaps (hot spots). By adjusting the etching time of the PMMA (polymethyl methacrylate) layer, the optimal SERS substrate with the densest metallic nanopillars was obtained, which possessed a detection limit down to 10⁻¹³ M by using crystal violet as the detected molecules and exhibited excellent reproducibility and long-term stability. Furthermore, the proposed fabrication approach was further used to prepare flexible substrates; for example, a SERS flexible substrate was proven to be an ideal platform for analyzing low-concentration pesticide residues on curved fruit surfaces with significantly enhanced sensitivity. This type of SERS substrate possesses potential in real-life applications as low-cost and high-performance sensors. Full article

A core–shell nanowire heterostructure is an important building block for nanowire-based optoelectronic devices. In this paper, the shape and composition evolution induced by adatom diffusion is investigated by constructing a growth model for alloy core–shell nanowire heterostructures, taking diffusion, adsorption, desorption and incorporation of adatoms into consideration. With moving boundaries accounting for sidewall growth, the transient diffusion equations are numerically solved by the finite element method. The adatom diffusions introduce the position-dependent and time-dependent adatom concentrations of components A and B. The newly grown alloy nanowire shell depends on the incorporation rates, resulting in both shape and composition evolution during growth. The results show that the morphology of nanowire shell strongly depends on the flux impingement angle. With the increase in this impingement angle, the position of the largest shell thickness on sidewall moves down to the bottom of nanowire and meanwhile, the contact angle between shell and substrate increases to an obtuse angle. Coupled with the shell shapes, the composition profiles are shown as non-uniform along both the nanowire and the shell growth directions, which can be attributed to the adatom diffusion of components A and B. The impacts of parameters on the shape and composition evolution are systematically investigated, including diffusion length, adatom lifetime and corresponding ratios between components. This kinetic model is expected to interpret the contribution of adatom diffusion in growing alloy group-IV and group III-V core–shell nanowire heterostructures. Full article

A hydrothermal method was successfully employed to synthesize kesterite Cu₂ZnSnS₄ (CZTS) nanoparticles. X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and optical ultraviolet-visible (UV-vis) spectroscopy were used for characterization of structural, chemical, morphological, and optical properties. XRD results confirmed that a nanocrystalline CZTS phase corresponding to the kesterite structure was formed. Raman analysis confirmed the existence of single pure phase CZTS. XPS results revealed the oxidation states as Cu⁺, Zn²⁺, Sn⁴⁺, and S²⁻. FESEM and TEM micrograph images revealed the presence of nanoparticles with average sizes between 7 nm to 60 nm. The synthesized CZTS nanoparticles bandgap was found to be 1.5 eV which is optimal for solar photocatalytic degradation applications. The properties as a semiconductor material were evaluated through the Mott–Schottky analysis. The photocatalytic activity of CZTS has been investigated through photodegradation of Congo red azo dye solution under solar simulation light irradiation, proving to be an excellent photo-catalyst for CR where 90.2% degradation could be achieved in just 60 min. Furthermore, the prepared CZTS was reusable and can be repeatedly used to remove Congo red dye from aqueous solutions. Full article

The facile synthesis of biografted 2D derivatives complemented by a nuanced understanding of their properties are keystones for advancements in biosensing technologies. Herein, we thoroughly examine the feasibility of aminated graphene as a platform for the covalent conjugation of monoclonal antibodies towards human IgG immunoglobulins. Applying core-level spectroscopy methods, namely X-ray photoelectron and absorption spectroscopies, we delve into the chemistry and its effect on the electronic structure of the aminated graphene prior to and after the immobilization of monoclonal antibodies. Furthermore, the alterations in the morphology of the graphene layers upon the applied derivatization protocols are assessed by electron microscopy techniques. Chemiresistive biosensors composed of the aerosol-deposited layers of the aminated graphene with the conjugated antibodies are fabricated and tested, demonstrating a selective response towards IgM immunoglobulins with a limit of detection as low as 10 pg/mL. Taken together, these findings advance and outline graphene derivatives’ application in biosensing as well as hint at the features of the alterations of graphene morphology and physics upon its functionalization and further covalent grafting by biomolecules. Full article

This study investigates the influence of temperature and loading rate on the Mode I and Mode II interlaminar fracture behavior of carbon-nanotubes-enhanced carbon-fiber-reinforced polymer (CNT-CFRP). CNT-induced toughening of the epoxy matrix is characterized by producing CFRP with varying loading of CNT areal density. CNT-CFRP samples were subjected to varying loading rates and testing temperatures. Fracture surfaces of CNT-CFRP were analyzed using scanning electron microscopy (SEM) imaging. Mode I and Mode II interlaminar fracture toughness increased with increasing amount of CNT to an optimum value of 1 g/m², then decreased at higher CNT amounts. Moreover, it was found that CNT-CFRP fracture toughness increased linearly with the loading rate in Mode I and Mode II. On the other hand, different responses to changing temperature were observed; Mode I fracture toughness increased when elevating the temperature, while Mode II fracture toughness increased with increasing up to room temperature and decreased at higher temperatures. Full article

One-dimensional (1D) novel pentagonal materials have gained significant attention as a new class of materials with unique properties that could influence future technologies. In this report, we studied the structural, electronic, and transport properties of 1D pentagonal PdSe₂ nanotubes (p-PdSe₂ NTs). The stability and electronic properties of p-PdSe₂ NTs with different tube sizes and under uniaxial strain were investigated using density functional theory (DFT). The studied structures showed an indirect-to-direct bandgap transition with slight variation in the bandgap as the tube diameter increased. Specifically, (5 × 5) p-PdSe₂ NT, (6 × 6) p-PdSe₂ NT, (7 × 7) p-PdSe₂ NT, and (8 × 8) p-PdSe₂ NT are indirect bandgap semiconductors, while (9 × 9) p-PdSe₂ NT exhibits a direct bandgap. In addition, under low uniaxial strain, the surveyed structures were stable and maintained the pentagonal ring structure. The structures were fragmented under tensile strain of 24%, and compression of −18% for sample (5 × 5) and −20% for sample (9 × 9). The electronic band structure and bandgap were strongly affected by uniaxial strain. The evolution of the bandgap vs. the strain was linear. The bandgap of p-PdSe₂ NT experienced an indirect–direct–indirect or a direct–indirect–direct transition when axial strain was applied. A deformability effect in the current modulation was observed when the bias voltage ranged from about 1.4 to 2.0 V or from −1.2 to −2.0 V. Calculation of the field effect I–V characteristic showed that the on/off ratio was large with bias potentials from 1.5 to 2.0 V. This ratio increased when the inside of the nanotube contained a dielectric. The results of this investigation provide a better understanding of p-PdSe₂ NTs, and open up potential applications in next-generation electronic devices and electromechanical sensors. Full article

Electrocatalytic water splitting, as a sustainable, pollution-free and convenient method of hydrogen production, has attracted the attention of researchers. However, due to the high reaction barrier and slow four-electron transfer process, it is necessary to develop and design efficient electrocatalysts to promote electron transfer and improve reaction kinetics. Tungsten oxide-based nanomaterials have received extensive attention due to their great potential in energy-related and environmental catalysis. To maximize the catalytic efficiency of catalysts in practical applications, it is essential to further understand the structure–property relationship of tungsten oxide-based nanomaterials by controlling the surface/interface structure. In this review, recent methods to enhance the catalytic activities of tungsten oxide-based nanomaterials are reviewed, which are classified into four strategies: morphology regulation, phase control, defect engineering, and heterostructure construction. The structure–property relationship of tungsten oxide-based nanomaterials affected by various strategies is discussed with examples. Finally, the development prospects and challenges in tungsten oxide-based nanomaterials are discussed in the conclusion. We believe that this review provides guidance for researchers to develop more promising electrocatalysts for water splitting. Full article