International Iberian Nanotechnology Laboratory
Recent publications
A simple and effective preparation of solution-processed chalcogenide thermoelectric materials is described. First, PbTe, PbSe, and SnSe were prepared by gram-scale colloidal synthesis relying on the reaction between metal acetates and diphenyl dichalcogenides in hexadecylamine solvent. The resultant phase-pure chalcogenides consist of highly crystalline and defect-free particles with distinct cubic-, tetrapod-, and rod-like morphologies. The powdered PbTe, PbSe, and SnSe products were subjected to densification by spark plasma sintering (SPS), affording dense pellets of the respective chalcogenides. Scanning electron microscopy shows that the SPS-derived pellets exhibit fine nano-/micro-structures dictated by the original morphology of the key constituting particles, while the powder X-ray diffraction and electron microscopy analyses confirm that the SPS-derived pellets are phase-pure materials, preserving the structure of the colloidal synthesis products. The resultant solution-processed PbTe, PbSe, and SnSe exhibit low thermal conductivity, which might be due to the enhanced phonon scattering developed over fine microstructures. For undoped n-type PbTe and p-type SnSe samples, an expected moderate thermoelectric performance is achieved. In contrast, an outstanding figure-of-merit of 0.73 at 673 K was achieved for undoped n-type PbSe outperforming, the majority of the optimized PbSe-based thermoelectric materials. Overall, our findings facilitate the design of efficient solution-processed chalcogenide thermoelectrics.
In this work, we present a comparative study on the influence of the geometric shape of plastic optical fiber (POF) sensors in their response to refractive index (RI) of external media. Three different geometric shapes were simulated using the finite element-method (FEM), one being a simple U-shaped POF sensor (FU), and the other two based on the same U shape but with one and two additional small curves in the fiber, FO1 and FO2, respectively, allowing for an increased exposure of the evanescent field. The results of simulations showed that the shapes of sensors FO1 and FO2 would allow for higher sensitivities compared to that of the simple U-shaped sensor FU, and that FO2 would show an even higher sensitivity due to an increased evanescent field exposure enabled by the additional curves on its shape. A set of POF sensors were fabricated according to the designs simulated, and then tested in several sucrose solutions corresponding to RI from 1.3330 to 1.4242. The POF sensors manufactured showed sensitivities (optical power loss) of 36, 102, and 217%/RIU for FU, FO1, and FO2, respectively, from air to pure water (RI 1.000 to 1.333), and 330, 656, and 904%/RIU for FU, FO1, and FO2, respectively, from pure water to sucrose solution (RI 1.333 to 1.381). The correlation between the results from simulations and experiments shows that POF sensors based on RI sensing, such as chemical sensors, gas sensors, and biosensors, can be significantly improved with small modifications in their shape design.
The oxygen evolution reaction (OER) is crucial to future energy systems based on water electrolysis. Iridium oxides are promising catalysts due to their resistance to corrosion under acidic and oxidizing conditions. Highly active iridium (oxy)hydroxides prepared using alkali metal bases transform into low activity rutile IrO2 at elevated temperatures (>350 °C) during catalyst/electrode preparation. Depending on the residual amount of alkali metals, we now show that this transformation can result in either rutile IrO2 or nano-crystalline Li-intercalated IrOx. While the transition to rutile results in poor activity, the Li-intercalated IrOx has comparative activity and improved stability when compared to the highly active amorphous material despite being treated at 500 °C. This highly active nanocrystalline form of lithium iridate could be more resistant to industrial procedures to produce PEM membranes and provide a route to stabilize the high populations of redox active sites of amorphous iridium (oxy)hydroxides.
Carbon-based materials, such as graphene oxide and reduced graphene oxide membranes have been recently used to fabricate ultrathin, high-flux, and energy-efficient membranes for ionic and molecular sieving in aqueous solution. However, these membranes appeared rather unstable during long-term operation in water with a tendency to swell over time. Membranes produced from pristine, stable, layered graphene materials may overcome these limitations while providing high-level performance. In this paper, an efficient and “green” strategy is proposed to fabricate μm-thick, graphene-based laminates by liquid phase exfoliation in Cyrene and vacuum filtration on a PVDF support. The membranes appear structurally robust and mechanically stable, even after 90 days of operation in water. In ion transport studies, the membranes show size selection (>3.3 Å) and anion-selectivity via the positively charged nanochannels forming the graphene laminate. In antibiotic (tetracycline) diffusion studies under dynamic conditions, the membrane achieve rejection rates higher than 95%. Sizable antibacterial properties are demonstrated in contact method tests with Staphylococcus aureus and Escherichia coli bacteria. Overall, these “green” graphene-based membranes represent a viable option for future water management applications.
Multi-material structures make it possible to obtain effective solutions to engineering problems by combining the benefits of different materials to meet the requirements of different working conditions. The aim of this multifunctional 420 stainless steel-copper structure is to create a hybrid solution in which copper acts as heat-transfer enhancer (through cooling channels) while maintaining the required mechanical properties of the steel matrix. This work focuses on a combined engineering process consisting of CNC machining through holes on a 420 stainless steel surface substrate and subsequent filling with copper by hot pressing. The influence of the copper filling on the physical, chemical, microstructural, mechanical, and thermal properties of this multi-material solution was analysed. The machined area (5% of the total surface area) consisted of nine holes with a diameter of approximately 1 mm. The multi-material samples showed high densification, homogeneous microstructures, and a well-defined and sharp interface between the two materials. The microhardness values measured for the 420 stainless steel and copper were 759 and 57 HV, respectively, and the thermal conductivity of the multi-material was ≅ 59% higher than the 420 stainless steel (39.74 and 16.40 W/m K, respectively).
High‐performance platinum group metal‐free (PGM‐free) electrocatalysts were prepared from porous organic polymers (POPs) precursors with highly‐porous structures and adjustable surface area. A resin phenol‐melamine‐based POP and an iron salt were used to synthesize Fe−N−C catalysts with different iron contents (0.2–1.3 wt.%). Electrochemical and spectroscopical characterization allowed us to elucidate the effect of Fe content on the material's structure, surface chemistry, and electrocatalytic activity toward the oxygen reduction reaction (ORR). The increase of iron content led to a specific surface area decrease, preserving the morphological structure, with the formation of highly‐active catalytic sites, as indicated by X‐ray photoelectron spectroscopy (XPS) analysis. The rotating ring disk electrode experiments, performed at pH=13, confirmed the high ORR activity of both 0.5 Fe (E1/2=0.84 V) and 1.3 Fe (E1/2=0.83 V) catalysts, which were assembled at the cathode of a H2‐fed anion exchange membrane fuel cells (AEMFC) equipped with a FAA‐3‐50 membrane, evidencing promising performance (0.5 Fe, maximum power density, Max PD=69 mA cm−2 and 1.3 Fe, Max PD=87 mA cm−2) with further advancement prospects. More or less: A sustainable soft templating strategy allowed preparing highly porous Fe−N−C catalysts with different Fe contents. The effect of Fe content on the material's structure and electrocatalytic activity toward the oxygen reduction reaction (ORR) was elucidated. The formation of high‐active nitrogen‐ and iron‐based functional groups endowed electrocatalysts with excellent ORR activity.
Unmanned aerial vehicles (UAVs) with high-resolution optical and infrared ( IR ) imaging have been introduced in recent years to perform inexpensive and fast inspections in operation and maintenance activities of solar power plants, reducing the labor needed, while lowering the on-site inspection time. Even though UAVs can acquire images extremely quickly, the analysis of those images is still a time-consuming procedure that should be performed by a trained professional. Therefore, a computer vision approach may be used to accelerate image analysis. In this work, a dataset of IR images was created from a 10-MW solar power plant and a comparative analysis between mask R- convolutional neural network (CNN) and U-Net was performed for two experiments. Concerning the defective module segmentation, the mask R-CNN algorithm achieved a mean average precision at intersection over union (IoU) = 0.50 of 0.96, using augmentation data. Regarding the segmentation and classification of failure type, the algorithm reached a value of 0.88 considering the same evaluation metric and data augmentation. When compared to the U-Net in terms of IoU, the mask R-CNN outperformed it with 0.87 and 0.83 for the first and second experiments, respectively.
The evolution of Pt nanoparticles in proton-exchanged membrane fuel cells is monitored before and after electrochemical potential cycling, using 2D and 3D identical location aberration-corrected transmission electron microscopy. This work demonstrates that 2D images might be a challenge to interpret due to the 3D nature of the carbon support. Thus, it is critical to combine both 2D and 3D observations to be able to fully understand the mechanisms associated with the durability of Pt catalyst nanoparticles. In particular, this investigation reveals that the mechanism of particle migration followed by coalescence is operative mainly across short distances (<0.5 nm). This work also shows that new Pt particles appear on the carbon support, as the result of Pt dissolution, followed by the formation of clusters, which grow by Ostwald ripening. This mechanism of Ostwald ripening is also responsible for changes in shape and particle growth, which later may result in coalescence.
This study aimed to evaluate a clothing prototype that incorporates sensors for the evaluation of pressure, temperature, and humidity for the prevention of pressure injuries, namely regarding physical and comfort requirements. A mixed-method approach was used with concurrent quantitative and qualitative data triangulation. A structured questionnaire was applied before a focus group of experts to evaluate the sensor prototypes. Data were analyzed using descriptive and inferential statistics and the discourse of the collective subject, followed by method integration and meta-inferences. Nine nurses, experts in this topic, aged 32.66 ± 6.28 years and with a time of profession of 10.88 ± 6.19 years, participated in the study. Prototype A presented low evaluation in stiffness (1.56 ± 1.01) and roughness (2.11 ± 1.17). Prototype B showed smaller values in dimension (2.77 ± 0.83) and stiffness (3.00 ± 1.22). Embroidery was assessed as inadequate in terms of stiffness (1.88 ± 1.05) and roughness (2.44 ± 1.01). The results from the questionnaires and focus groups’ show low adequacy as to stiffness, roughness, and comfort. The participants highlighted the need for improvements regarding stiffness and comfort, suggesting new proposals for the development of sensors for clothing. The main conclusions are that Prototype A presented the lowest average scores relative to rigidity (1.56 ± 1.01), considered inadequate. This dimension of Prototype B was evaluated as slightly adequate (2.77 ± 0.83). The rigidity (1.88 ± 1.05) of Prototype A + B + embroidery was evaluated as inadequate. The prototype revealed clothing sensors with low adequacy regarding the physical requirements, such as stiffness or roughness. Improvements are needed regarding the stiffness and roughness for the safety and comfort characteristics of the device evaluated.
Crystallization plays a critical role in determining crystal size, purity and morphology. Therefore, uncovering the growth dynamics of nanoparticles (NPs) atomically is important for the controllable fabrication of nanocrystals with desired geometry and properties. Herein, we conducted in situ atomic-scale observations on the growth of Au nanorods (NRs) by particle attachment within an aberration-corrected transmission electron microscope (AC-TEM). The results show that the attachment of spherical colloidal Au NPs with a size of about 10 nm involves the formation and growth of neck-like (NL) structures, followed by five-fold twin intermediate states and total atomic rearrangement. The statistical analyses show that the length and diameter of Au NRs can be well regulated by the number of tip-to-tip Au NPs and the size of colloidal Au NPs, respectively. The results highlight five-fold twin-involved particle attachment in spherical Au NPs with a size of 3–14 nm, and provide insights into the fabrication of Au NRs using irradiation chemistry.
Acute myeloid leukemia (AML) comprises a group of hematologic neoplasms characterized by abnormal differentiation and proliferation of myeloid progenitor cells. AML is associated with poor outcome due to the lack of efficient therapies and early diagnostic tools. The current gold standard diagnostic tools are based on bone marrow biopsy. These biopsies, apart from being very invasive, painful, and costly, have low sensitivity. Despite the progress uncovering the molecular pathogenesis of AML, the development of novel detection strategies is still poorly explored. This is particularly important for patients that check the criteria for complete remission after treatment, since they can relapse through the persistence of some leukemic stem cells. This condition, recently named as measurable residual disease (MRD), has severe consequences for disease progression. Hence, an early and accurate diagnosis of MRD would allow an appropriate therapy to be tailored, improving a patient’s prognosis. Many novel techniques with high potential in disease prevention and early detection are being explored. Among them, microfluidics has flourished in recent years due to its ability at processing complex samples as well as its demonstrated capacity to isolate rare cells from biological fluids. In parallel, surface-enhanced Raman scattering (SERS) spectroscopy has shown outstanding sensitivity and capability for multiplex quantitative detection of disease biomarkers. Together, these technologies can allow early and cost-effective disease detection as well as contribute to monitoring the efficiency of treatments. In this review, we aim to provide a comprehensive overview of AML disease, the conventional techniques currently used for its diagnosis, classification (recently updated in September 2022), and treatment selection, and we also aim to present how novel technologies can be applied to improve the detection and monitoring of MRD.
We report the air-sensitivity, atomic structure, and magnetic anisotropy of VI3 single crystals. We find that VI3 nanocrystals exhibit a large MR/MS ratio of around 0.75 and a uniaxial anisotropic constant of an order of 105 erg cc-1 below the Curie temperature. Furthermore, density functional theory calculations reveal that both the monolayer and bulk VI3 are ferromagnetic insulators, and the magnetic moment of the system arises mainly from the d orbital of the V atom. These findings open a feasible avenue to fabricating TEM specimens of air-sensitive layered materials, providing an in-depth comprehensive understanding of a layered ferromagnetic VI3.
In recent years, printed electronics reached enormous popularity as a result of their huge potential to offer unique features that are not attainable through traditional fabrication, namely low‐cost production, multifunctionality, stretchability, sustainability, and flexibility. Being expected a galloping increase in the use of printed technologies in the near future, due to the digitalization efforts associated with the Internet of Things and the 4.0 revolution, it is timely and desirable to discuss the joint features, the interrelations, the complementarities, the interdependency, and the most demanding challenges linked to the relation between printed technologies and electronic materials. In this context, this study offers a broad review of the numerous printing technologies used in the processing of electronics, commonly used substrates, the most effective printed electronic materials, and the key post‐printing treatments such as sintering. Disruptive challenges in various printing techniques, (un)expected future research directions of printed electronics, and imminent application trends are also highlighted, following a critical and subjective perspective.
Titanium (Ti) and its alloys are the most widely used metallic biomaterials in total joint replacement; however, increasing evidence supports the degradation of its surface due to corrosion and wear processes releasing debris (ions, and micro and nanoparticles) and contribute to particle-induced osteolysis and implant loosening. Cell-to-cell communication involving several cell types is one of the major biological processes occurring during bone healing and regeneration at the implant-bone interface. In addition to the internal response of cells to the uptake and intracellular localization of wear debris, a red flag is the ability of titanium dioxide nanoparticles (mimicking wear debris) to alter cellular communication with the tissue background, disturbing the balance between osseous tissue integrity and bone regenerative processes. This study aims to understand whether titanium dioxide nanoparticles (TiO2 NPs) alter osteoblast-derived exosome (Exo) biogenesis and whether exosomal protein cargos affect the communication of osteoblasts with human mesenchymal stem/stromal cells (HMSCs). Osteoblasts are derived from mesenchymal stem cells coexisting in the bone microenvironment during development and remodelling. We observed that TiO2 NPs stimulate immature osteoblast- and mature osteoblast-derived Exo secretion that present a distinct proteomic cargo. Functional tests confirmed that Exos derived from both osteoblasts decrease the osteogenic differentiation of HMSCs. These findings are clinically relevant since wear debris alter extracellular communication in the bone periprosthetic niche, contributing to particle-induced osteolysis and consequent prosthetic joint failure.
Large-scale production of graphene nanosheets (GNSs) has led to the availability of solution-processable GNSs on the commercial scale. The controlled vacuum filtration method is a scalable process for the preparation of wafer-scale films of GNSs, which can be used for gas sensing applications. Here, we demonstrate the use of this deposition method to produce functional gas sensors, using a chemiresistor structure from GNS solution-based techniques. The GNS suspension was prepared by liquid-phase exfoliation (LPE) and transferred to a polyvinylidene fluoride (PVDF) membrane. The effect of non-covalent functionalization with Co-porphyrin and Fe-phthalocyanines on the sensor properties was studied. The pristine and functionalized GNS films were characterized using different techniques such as Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and electrical characterizations. The morphological and spectroscopic analyses both confirm that the molecules (Co-porphyrin and Fe-phthalocyanine) were successfully adsorbed onto the GNSs surface through π-π interactions. The chemiresistive sensor response of functionalized GNSs toward the low concentrations of nitrogen dioxide (NO2) (0.5–2 ppm) was studied and compared with those of the film of pristine GNSs. The tests on the sensing performance clearly showed sensitivity to a low concentration of NO2 (5 ppm). Furthermore, the chemical modification of GNSs significantly improves NO2 sensing performance compared to the pristine GNSs. The sensor response can be modulated by the type of adsorbed molecules. Indeed, Co-Por exhibited negative responsiveness (the response of Co-Por-GNS sensors and pristine GNS devices was 13.1% and 15.6%, respectively, after exposure to 0.5 ppm of NO2). Meanwhile, Fe-Phc-GNSs induced the opposite behavior resulting in an increase in the sensor response (the sensitivity was 8.3% and 7.8% of Fe-Phc-GNSs and pristine GNSs, respectively, at 0.5 ppm NO2 gas).
The different features of the impact of nanoparticles on cells, such as the structure of the core, presence/absence of doping, quality of surface, diameter, and dose, were used to define quasi-SMILES, a line of symbols encoded the above physicochemical features of the impact of nanoparticles. The correlation weight for each code in the quasi-SMILES has been calculated by the Monte Carlo method. The descriptor, which is the sum of the correlation weights, is the basis for a one-variable model of the biological activity of nano-inhibitors of human lung carcinoma cell line A549. The system of models obtained by the above scheme was checked on the self-consistence, i.e., reproducing the statistical quality of these models observed for different distributions of available nanomaterials into the training and validation sets. The computational experiments confirm the excellent potential of the approach as a tool to predict the impact of nanomaterials under different experimental conditions. In conclusion, our model is a self-consistent model system that provides a user to assess the reliability of the statistical quality of the used approach.
We describe a user-friendly, open source software for single-particle detection/counting in a continuous-flow. The tool automatically processes video images of particles, including pre-conditioning, followed by size-based discrimination for independent detection of fluorescent and non-fluorescent particles of different sizes. This is done by interactive tuning of a reduced set of parameters that can be checked with a robust, real-time quality control of the original video files. The software provides a concentration distribution of the particles in the transverse direction of the fluid flow. The software is a versatile tool for many microfluidic applications and does not require expertise in image analysis.
Zn:ZnO nanostructures have been studied extensively due to their potential use in many applications, such as oxygen scavengers for food packaging applications. Under atmospheric conditions, ZnO grows on the surface of Zn via an oxidation process. The mechanisms governing Zn oxidation are still not fully understood, with classical oxidation models, such as the Cabrera Mott, underestimating the oxide thickness of Zn:ZnO core–shell structures. In this work, Ab initio DFT calculations were performed to assess the adsorption properties of oxygen molecules on Zn:ZnO heterostructures to help elucidate the mechanisms involved in the growth of a ZnO film on a Zn substrate. Results suggest that the charge transfer mechanism from the Zn:ZnO heterostructures to the adsorbed oxygen layer can be promoted by two different processes: the electronic doping of ZnO due to the formation of the Zn:ZnO interface and the excess surface charge due to the presence of dangling bonds on the as cleaved ZnO.
The incorporation of interface passivation structures in ultrathin Cu(In,Ga)Se 2 based solar cells is shown. The fabrication used an industry scalable lithography technique—nanoimprint lithography (NIL)—for a 15 × 15 cm ² dielectric layer patterning. Devices with a NIL nanopatterned dielectric layer are benchmarked against electron-beam lithography (EBL) patterning, using rigid substrates. The NIL patterned device shows similar performance to the EBL patterned device.The impact of the lithographic processes in the rigid solar cells’ performance were evaluated via X-ray Photoelectron Spectroscopy and through a Solar Cell Capacitance Simulator. The device on stainless-steel showed a slightly lower performance than the rigid approach, due to additional challenges of processing steel substrates, even though scanning transmission electron microscopy did not show clear evidence of impurity diffusion. Notwithstanding, time-resolved photoluminescence results strongly suggested elemental diffusion from the flexible substrate. Nevertheless, bending tests on the stainless-steel device demonstrated the mechanical stability of the CIGS-based device.
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224 members
K B Vinayakumar
  • Micro and Nano Engineering
N. Vasimalai
  • Environmental Monitoring
Ana R L Ribeiro
  • Nanosafety group
Av. Mestre José Veiga, 4715-330, Braga, Braga, Portugal
Head of institution
Lars Montelius