Nanomaterials

In the last decades, optimizing implant properties in terms of materials and biointerface characteristics represents one of the main quests in biomedical research. Modifying and engineering polyvinylidene fluoride (PVDF) as scaffolds becomes more and more attractive to multiples areas of bio-applications (e.g., bone or cochlear implants). Nevertheless, the acceptance of an implant is affected by its inflammatory potency caused by surface-induced modification. Therefore, in this work, three types of nano-micro squared wells like PVDF structures (i.e., reversed pyramidal shape with depths from 0.8 to 2.5 microns) were obtained by replication, and the influence of their characteristics on the inflammatory response of human macrophages was investigated in vitro. FTIR and X-ray photoelectron spectroscopy analysis confirmed the maintaining chemical structures of the replicated surfaces, while the topographical surface characteristics were evaluated by AFM and SEM analysis. Contact angle and surface energy analysis indicated a modification from superhydrophobicity of casted materials to moderate hydrophobicity based on the structure’s depth change. The effects induced by PVDF casted and micron-sized reversed pyramidal replicas on macrophages behavior were evaluated in normal and inflammatory conditions (lipopolysaccharide treatment) using colorimetric, microscopy, and ELISA methods. Our results demonstrate that the depth of the microstructured surface affects the activity of macrophages and that the modification of topography could influence both the hydrophobicity of the surface and the inflammatory response. Full article

The effectiveness of nanoscale zero-valent iron(nZVI) immobilized on activated carbon (nZVI/AC) in removing antimonite (Sb(III)) from simulated contaminated water was investigated with and without a magnetic fix-bed column reactor. The experiments were all conducted in fixed-bed columns. A weak magnetic field (WMF) was proposed to increase the exclusion of paramagnetic Sb(III) ions by nZVI/AC. The Sb(III) adsorption to the nZVI and AC surfaces, as well as the transformation of Sb(III) to Sb(V) by them, were both increased by using a WMF in nZVI/AC. The increased sequestration of Sb(III) by nZVI/AC in the presence of WMF was followed by faster nZVI corrosion and dissolution. Experiments were conducted as a function of the pH of the feed solution (pH 5.0–9.0), liquid flow rate (5–15 mL·min⁻¹), starting Sb(III) concentration (0.5–1.5 mg·L⁻¹), bed height nZVI/AC (10–40 cm), and starting Sb(III) concentration (0.5–1.5 mg·L⁻¹). By analyzing the breakthrough curves generated by different flow rates, different pH values, different inlet Sb(III) concentrations, and different bed heights, the adsorbed amounts, equilibrium nZVI uptakes, and total Sb(III) removal percentage were calculated in relation to effluent volumes. At pH 5.0, the longest nZVI breakthrough time and maximal Sb(III) adsorption were achieved. The findings revealed that the column performed effectively at the lowest flow rate. With increasing bed height, column bed capacity and exhaustion time increased as well. Increasing the Sb(III) initial concentration from 0.5 to 1.5 mg·L⁻¹ resulted in the rise of adsorption bed capacity from 3.45 to 6.33 mg·g⁻¹. Full article

Improved compounds of Ce(III) and Ce(IV)-doped hydroxyapatite (Ca_10-xCe_x(PO₄)₆(OH)₂) with different concentrations such as x = 0.5, 1, 2.5, 5, and 10%, obtained by the simple co-precipitation method were synthesized. The cerium (3⁺) and cerium (4⁺)-doped hydroxyapatite were evaluated for biocompatibility and fluorescence properties. It was found that the cerium-HAp powders were non-toxic, even at higher level of concentration. The synthesized powders were further characterized by FTIR spectrometry, UV-Vis spectroscopy, XRD diffraction, SEM and TEM analysis. Therefore, the present study proves that the developed cerium (3⁺) and cerium (4⁺)-doped hydroxyapatite, respectively can be widely used as luminescent labeling materials, with improved biological properties. Full article

Lithium-sulfur (Li-S) batteries have nice prospects because of their excellent energy density and theoretical specific capacity. However, the dissolution of lithium polysulfides and shuttle effects lead to a low coulombic efficiency and cycle performance of Li-S batteries. Therefore, designing electrode materials that can suppress the shuttle effect and adsorb polysulfides is of great significance. In this work, a Co and N-codoped carbon composite via heating a type of Co-etched zeolitic imidazolate framework-67 (ZIF-67), nanocube precursor, in inert gas is reported as a cathode sulfur carrier material for Li-S batteries. The experimental results show that high-temperature carbonization results in mesoporous structures inside the material which not only provide ion channels for the reaction but also improve the adsorption capacity of polysulfides. Furthermore, the exposed metal Co sites and N atoms can also inhibit the shuttle effect. When the annealing temperature is 600 °C, the sulfur composite exhibits a good cycling stability and rate performance. The cathode showed an improved initial specific capability of 1042 and still maintained 477 mAh g⁻¹ at the rate of 1 C (1 C = 1672 mA g⁻¹). Furthermore, at 5 C, a stable specific discharge capacity of 608 mAh g⁻¹ was obtained. Full article

We demonstrate a simple method to fabricate all solid state, thermally reduced Graphene Oxide (TRGO) microsupercapacitors (µ-SCs) prepared using the atmospheric pressure chemical vapor deposition (APCVD) and a mask-free axiDraw sketching apparatus. The Fourier transform infrared spectroscopy (FTIR) shows the extermination of oxygen functional groups as the reducing temperature (RT) increases, while the Raman shows the presence of the defect and graphitic peaks. The electrochemical performance of the µ-SCs showed cyclic voltammetry (CV) potential window of 0–0.8 V at various scan rates of 5–1000 mVs⁻¹ with a rectangular shape, depicting characteristics of electric double layer capacitor (EDLC) behavior. The µ-SC with 14 cm⁻² (number of digits per unit area) showed a 46% increment in capacitance from that of 6 cm⁻², which is also higher than the µ-SCs with 22 and 26 cm⁻². The TRGO-500 exhibits volumetric energy and power density of 14.61 mW h cm⁻³ and 142.67 mW cm⁻³, respectively. The electrochemical impedance spectroscopy (EIS) showed the decrease in the equivalent series resistance (ESR) as a function of RT due to reduction of the resistive functional groups present in the sample. Bode plot showed a phase angel of −85° for the TRGO-500 µ-SC device. The electrochemical performance of the µ-SC devices can be tuned by varying the RT, number of digits per unity area, and connection configuration (parallel or series). Full article

Self-polarized piezoelectric devices have attracted significant interest owing to their fabrication processes with low energy consumption. Herein, novel poling-free piezoelectric nanogenerators (PENGs) based on self-polarized polyvinylidene difluoride (PVDF) induced by the incorporation of different surface-modified barium titanate nanoparticles (BTO NPs) were prepared via a fully printing process. To reveal the effect of intermolecular interactions between PVDF and NP surface groups, BTO NPs were modified with hydrophilic polydopamine (PDA) and hydrophobic 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) to yield PDA-BTO and PFD-BTO, respectively. This study demonstrates that the stronger hydrogen bonding interactions existed in PFD-BTO/PVDF composite film comparative to the PDA-BTO/PVDF composite film induced the higher β-phase formation (90%), which was evidenced by the XRD, FTIR and DSC results, as well as led to a better dispersion of NPs and improved mechanical properties of composite films. Consequently, PFD-BTO/PVDF-based PENGs without electric poling exhibited a significantly improved output voltage of 5.9 V and power density of 102 μW cm⁻³, which was 1.8 and 2.9 times higher than that of PDA-BTO/PVDF-based PENGs, respectively. This study provides a promising approach for advancing the search for high-performance, self-polarized PENGs in next-generation electric and electronic industries. Full article

Optimizing the physicochemical properties of the chitosan-based activated carbon (Ch-ACs) can greatly enhance its performance toward heavy metal removal from contaminated water. Herein, Ch was converted into a high surface area (1556 m²/g) and porous (0.69 cm³/g) ACs with large content of nitrogen (~16 wt%) using K₂CO₃ activator and urea as nitrogen-enrichment agents. The prepared Ch-ACs were tested for the removal of Cr(VI) and Pb(II) at different pH, initial metal ions concentration, time, activated carbon dosage, and temperature. For Cr(VI), the best removal was at pH = 2, while for Pb(II) the best pH for its removal was in the range of 4–6. At 25 °C, the Temkin model gives the best fit for the adsorption of Cr(VI), while the Langmuir model was found to be better for Pb(II) ions. The kinetics of adsorption of both heavy metal ions were found to be well-fitted by a pseudo-second-order model. The findings show that the efficiency and the green properties (availability, recyclability, and cost effectiveness) of the developed adsorbent made it a good candidate for wastewaters treatment. As preliminary work, the prepared sorbent was also tested regarding the removal of heavy metals and other contaminations from real wastewater and the obtained results were found to be promising. Full article

Nanoparticles (NPs) functionalized with antibodies (Abs) on their surface are used in a wide range of bioapplications. Whereas the attachment of antibodies to single NPs to trigger the internalization in cells via receptor-mediated endocytosis has been widely studied, the conjugation of antibodies to larger NP assemblies has been much less explored. Taking into account that NP assemblies may be advantageous for some specific applications, the possibility of incorporating targeting ligands is quite important. Herein, we performed the effective conjugation of antibodies onto a fluorescent NP assembly, which consisted of fluorinated Quantum Dots (QD) self-assembled through fluorine–fluorine hydrophobic interactions. Cellular uptake studies by confocal microscopy and flow cytometry revealed that the NP assembly underwent the same uptake procedure as individual NPs; that is, the antibodies retained their targeting ability once attached to the nanoassembly, and the NP assembly preserved its intrinsic properties (i.e., fluorescence in the case of QD nanoassembly). Full article

Aqueous rechargeable zinc ion batteries (ARZIBs) have gained wide interest in recent years as prospective high power and high energy devices to meet the ever-rising commercial needs for large-scale eco-friendly energy storage applications. The advancement in the development of electrodes, especially cathodes for ARZIB, is faced with hurdles related to the shortage of host materials that support divalent zinc storage. Even the existing materials, mostly based on transition metal compounds, have limitations of poor electrochemical stability, low specific capacity, and hence apparently low specific energies. Herein, NH₄V₄O₁₀ (NHVO), a layered oxide electrode material with a uniquely mixed morphology of plate and belt-like particles is synthesized by a microwave method utilizing a short reaction time (~ 0.5 h) for use as a high energy cathode for ARZIB applications. The remarkable electrochemical reversibility of Zn²⁺/H⁺ intercalation in this layered electrode contributes to impressive specific capacity (417 mAh g⁻¹ at 0.25 A g⁻¹) and high rate performance (170 mAh g⁻¹ at 6.4 A g⁻¹) with almost 100% Coulombic efficiencies. Further, a very high specific energy of 306 Wh Kg⁻¹ at a specific power of 72 W Kg⁻¹ was achieved by the ARZIB using the present NHVO cathode. The present study thus facilitates the opportunity for developing high energy ARZIB electrodes even under short reaction time to explore potential materials for safe and sustainable green energy storage devices. Full article

ZIF-derivatized catalysts have shown high potential in catalysis. Herein, bean sprout-like Co-TiO₂/Ti nanostructures were first synthesized by thermal treatment at 800 °C under Ar-flow conditions using sacrificial ZIF-67 templated on Ti sheets. It was observed that ZIF-67 on Ti sheets started to thermally decompose at around 350 °C and was converted to the cubic phase Co₃O₄. The head of the bean sprout structure was observed to be Co₃O₄, while the stem showed a crystal structure of rutile TiO₂ grown from the metallic Ti support. Cu sputter-deposited Co-TiO₂/Ti nanostructures were also prepared for photocatalytic and electrocatalytic CO₂ reduction performances, as well as electrochemical oxygen reaction (OER). Gas chromatography results after photocatalytic CO₂ reduction showed that CH₃OH, CO and CH₄ were produced as major products with the highest MeOH selectivity of 64% and minor C₂ compounds of C₂H₂, C₂H₄ and C₂H₆. For electrocatalytic CO₂ reduction, CO, CH₄ and C₂H₄ were meaningfully detected, but H₂ was dominantly produced. The amounts were observed to be dependent on the Cu deposition amount. Electrochemical OER performances in 0.1 M KOH electrolyte exhibited onset overpotentials of 330–430 mV (vs. RHE) and Tafel slopes of 117–134 mV/dec that were dependent on Cu-loading thickness. The present unique results provide useful information for synthesis of bean sprout-like Co-TiO₂/Ti hybrid nanostructures and their applications to CO₂ reduction and electrochemical water splitting in energy and environmental fields. Full article

Marine nano-ecotoxicology has emerged with the purpose to assess the environmental risks associated with engineered nanomaterials (ENMs) among contaminants of emerging concerns entering the marine environment. ENMs’ massive production and integration in everyday life applications, associated with their peculiar physical chemical features, including high biological reactivity, have imposed a pressing need to shed light on risk for humans and the environment. Environmental safety assessment, known as ecosafety, has thus become mandatory with the perspective to develop a more holistic exposure scenario and understand biological effects. Here, we review the current knowledge on behavior and impact of ENMs which end up in the marine environment. A focus on titanium dioxide (n-TiO₂) and silver nanoparticles (AgNPs), among metal-based ENMs massively used in commercial products, and polymeric NPs as polystyrene (PS), largely adopted as proxy for nanoplastics, is made. ENMs eco-interactions with chemical molecules including (bio)natural ones and anthropogenic pollutants, forming eco- and bio-coronas and link with their uptake and toxicity in marine organisms are discussed. An ecologically based design strategy (eco-design) is proposed to support the development of new ENMs, including those for environmental applications (e.g., nanoremediation), by balancing their effectiveness with no associated risk for marine organisms and humans. Full article

To improve the heat dissipation efficiency of batteries, the eutectic mass ratios of each component in the ternary low-melting phase change material (PCM), consisting of stearic acid (SA), palmitic acid (PA), and lauric acid (LA), was explored in this study. Subsequently, based on the principle of high thermal conductivity and low leakage, SA–PA–LA/expanded graphite (EG)/carbon fiber (CF) composite phase change material (CPCM) was prepared. A novel double-layer CPCM, with different melting points, was designed for the battery-temperature control test. Lastly, the thermal management performance of non-CPCM, single-layer CPCM, and double-layer CPCM was compared via multi-condition charge and discharge experiments. When the mass ratio of SA to PA is close to 8:2, better eutectic state is achieved, whereas the eutectic mass ratio of the components of SA–PA–LA in ternary PCM is 29.6:7.4:63. SA–PA–LA/EG/CF CPCM formed by physical adsorption has better mechanical properties, thermal stability, and faster heat storage and heat release rate than PCM. When the CF content in SA–PA–LA/EG/CF CPCM is 5%, and the mass ratio of SA–PA–LA to EG is 91:9, the resulting SA–PA–LA/EG/CF CPCM has lower leakage rate and better thermal conductivity. The temperature control effect of single-layer paraffin wax (PW)/EG/CF CPCM is evident when compared to the no-CPCM condition. However, the double-layer CPCM (PW/EG/CF and SA–PA–LA/EG/CF CPCM) can further reduce the temperature rise of the battery, effectively control the temperature and temperature difference, and primarily maintain the battery in a lower temperature range during usage. After adding an aluminum honeycomb to the double-layer CPCM, the double-layer CPCM exhibited better thermal conductivity and mechanical properties. Moreover, the structure showed better battery temperature control performance, while meeting the temperature control requirements during the charging and discharging cycles of the battery. Full article

The potential of an innovation for establishing a simultaneous mechanical, thermal, and electrical connection between two metallic surfaces without requiring a prior time-consuming and expensive surface nanoscopic planarization and without requiring any intermediate conductive material has been explored. The method takes advantage of the intrinsic nanoscopic surface roughness on the interconnecting surfaces: the two surfaces are locked together for electrical interconnection and bonding with a conventional die bonder, and the connection is stabilized by a dielectric adhesive filled into nanoscale valleys on the interconnecting surfaces. This “nano-locking” (NL) method for chip interconnection and bonding is demonstrated by its application for the attachment of high-power GaN-based semiconductor dies to its device substrate. The bond-line thickness of the present NL method achieved is under 100 nm and several hundred times thinner than those achieved using mainstream bonding methods, resulting in a lower overall device thermal resistance and reduced electrical resistance, and thus an improved overall device performance and reliability. Different bond-line thickness strongly influences the overall contact area between the bonding surfaces, and in turn results in different contact resistance of the packaged devices enabled by the NL method and therefore changes the device performance and reliability. The present work opens a new direction for scalable, reliable, and simple nanoscale off-chip electrical interconnection and bonding for nano- and micro-electrical devices. Besides, the present method applies to the bonding of any surfaces with intrinsic or engineered surface nanoscopic structures as well. Full article

Potassium ion batteries (KIBs) are considered as promising alternatives to lithium ion batteries (LIBs), following the rapid increase of demand for portable devices, and the development of electric vehicles and smart grids. Though there has been a promising breakthrough in KIB tech niques, exploring the promising anode materials for KIBs is still a challenge. Rational design with first-principle methods can help to speed up the discovery of potential anodes for KIBs. With density functional calculations, GeC with graphene-like 2D structure (g-GeC) is shown to be a desired anode material for applications in KIBs. The results show that the 2D g-GeC with a high concentration of K ions is thermodynamically stable, due to the strong interaction between C and Ge in GeC layer with the proper interaction between K and GeC. The storage capacity can be about 320 mAh/g, higher than that (279 mAh/g) in graphite. The low energy barrier (0.13 eV) of K ions diffusion on the honeycomb structure with proper voltage profile indicates the fast charge transfer. These theoretical finds are expected to stimulate the future experimental works in KIBs. Full article

Molecular Doping (MD) involves the deposition of molecules, containing the dopant atoms and dissolved in liquid solutions, over the surface of a semiconductor before the drive-in step. The control on the characteristics of the final doped samples resides on the in-depth study of the molecule behaviour once deposited. It is already known that the molecules form a self-assembled monolayer over the surface of the sample, but little is known about the role and behaviour of possible multiple layers that could be deposited on it after extended deposition times. In this work, we investigate the molecular surface coverage over time of diethyl-propyl phosphonate on silicon, by employing high-resolution morphological and electrical characterization, and examine the effects of the post-deposition surface treatments on it. We present these data together with density functional theory simulations of the molecules–substrate system and electrical measurements of the doped samples. The results allow us to recognise a difference in the bonding types involved in the formation of the molecular layers and how these influence the final doping profile of the samples. This will improve the control on the electrical properties of MD-based devices, allowing for a finer tuning of their performance. Full article

Polymer-based composites with high thermal conductivity and dielectric breakdown strength have gained increasing attention due to their significant application potential in both power electronic devices and power equipment. In this study, we successfully prepared novel sandwich AlN/epoxy composites with various layer thicknesses, showing simultaneously and remarkably enhanced dielectric breakdown strength and thermal conductivity. The most optimized sandwich composite, with an outer layer thickness of 120 μm and an inner layer thickness of 60 μm (abbreviated as 120-60) exhibits a high through-plane thermal conductivity of 0.754 W/(m·K) (4.1 times of epoxy) and has a dielectric breakdown strength of 69.7 kV/mm, 8.1% higher compared to that of epoxy. The sandwich composites also have higher in-plane thermal conductivity (1.88 W/(m·K) for 120-60) based on the novel parallel models. The sandwich composites with desirable thermal and electrical properties are very promising for application in power electronic devices and power equipment. Full article

The β-cyclodextrin shell of synthesized silver nanoparticles (βCD-AgNPs) are found to enhance the detection of hydrogen peroxide in urine when compared to the Horse Radish Peroxidase assay kit. Nanoparticles are confirmed by the UV-Vis absorbance of their localized surface plasmonic resonance (LSPR) at 384 nm. The mean size of the βCD-AgNPs is 53 nm/diameter; XRD analysis shows a face-centered cubic structure. The crystalline structure of type 4H hexagonal nature of the AgNPs with 2.4 nm β-CD coating onto is confirmed using aberration corrected high-resolution transmission electron microscopy (HRTEM). A silver atomic lattice at 2.50 Å and 2.41 Å corresponding to (100) and (101) Miller indices is confirmed using the HRTEM. The scope of βCD-AgNPs to detect hydrogen peroxide (H₂O₂) in aqueous media and human urine is investigated. The test is optimized by examining the effect of volumes of nanoparticles, the pH of the medium, and the kinetic and temperature effect on H₂O₂ detection. The βCD-AgNPs test is used as a refined protocol, which demonstrated improved sensitivity towards H₂O₂ in urine compared to the values obtained by the Horse Radish Assay kit. Direct assessment of H₂O₂ by the βCD-AgNPs test presented always with a linear response in the nM, μM, and mM ranges with a limit of detection of 1.47 nM and a quantitation limit of 3.76 nM. While a linear response obtained from 1.3 to 37.3 nmoles of H₂O₂/mole creatinine with a slope of 0.0075 and regression coefficient of 0.9955 when the βCD-AgNPs is used as refined test of creatinine. Values ranging from 34.62 ± 0.23 nmoles of H₂O₂/mole of creatinine and 54.61 ± 1.04 nmoles of H₂O₂/mole of creatinine when the matrix is not diluted and between 32.16 ± 0.42 nmoles of H₂O₂/mole of creatinine and 49.66 ± 0.80 nmoles of H₂O₂/mole of creatinine when the matrix is twice diluted are found in freshly voided urine of seven apparent healthy men aged between 20 and 40 years old. Full article

Oxynitride glasses are not yet commercialised primarily due to the impurities present in the network of these glasses. In this work, we investigated the microstructure and instinctive defects in nitrogen rich La-Si-O-N glasses. Glasses were prepared by heating a powder mixture of pure La metal, Si₃N₄, and SiO₂ in a nitrogen atmosphere at 1650–1800 °C. The microstructure and impurities in the glasses were examined by optical microscopy, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy in conjunction with electron energy-loss spectroscopy. Analyses showed that the glasses contain a small amount of spherical metal silicide particles, mostly amorphous or poorly crystalline, and having sizes typically ranging from 1 µm and less. The amount of silicide was estimated to be less than 2 vol. %. There was no systematic relation between silicide formation and glass composition or preparation temperature. The microstructure examination revealed that the opacity of these nitrogen rich glasses is due to the elemental Si arise from the decomposition reaction of silicon nitride and silicon oxide, at a high temperature above ~1600 °C and from the metallic silicide particles formed by the reduction of silicon oxide and silicon nitride at an early stage of reaction to form a silicide intermetallic with the La metal. Full article

Metal nanostructured materials, with many excellent and unique physical and mechanical properties compared to macroscopic bulk materials, have been widely used in the fields of electronics, bioimaging, sensing, photonics, biomimetic biology, information, and energy storage. It is worthy of noting that most of these applications require the use of nanostructured metals with specific controlled properties, which are significantly dependent on a series of physical parameters of its characteristic size, geometry, composition, and structure. Therefore, research on low-cost preparation of metal nanostructures and controlling of their characteristic sizes and geometric shapes are the keys to their development in different application fields. The preparation methods, physical and chemical properties, and application progress of metallic nanostructures are reviewed, and the methods for characterizing metal nanostructures are summarized. Finally, the future development of metallic nanostructure materials is explored. Full article