ALBERT

Description: In recent years, the field of nanoporous metals has undergone accelerated developments as these materials possess high specific surface areas, well-defined pore sizes, functional sites, and a wide range of functional properties. Nanoporous gold (NPG) is, surely, the most attractive system in the class of nanoporous metals: it combines several desired characteristics as occurrence of surface plasmon resonances, enormous surface area, electrochemical activity, biocompatibility, in addition to feasibility in preparation. All these properties concur in the exploitatiton of NPG as an efficient and versatile sensong platform. In this regard, NPG-based sensors have shown exceptional sensitivity and selectivity to a wide range of analytes ranging from molecules to biomolecules (and until the single molecule detection) and the enormous surface/volume ratio was shown to be crucial in determining these performances. Thanks to these characteristics, NPG-based sensors are finding applications in medical, biological, and safety fields so as in medical diagnostics and monitoring processes. So, a rapidly growing literature is currently investigating the properties of NPG systems toward the detection of a multitude of classes of analytes highlighting strengths and limits. Due to the extension, complexity, and importance of this research field, in the present review we attempt, starting from the discussion of specific cases, to focus our attention on the basic properties of NPG in connection to the main sensing applications, i.e., surface enhanced Raman spectroscopy-based and electrochemical-based sensing. Owing to the nano-sized pore channels and Au ligaments, which are much smaller than the wavelength of visible light (400–700 nm), surface plasmon resonances of NPG can be effectively excited by visible light and presents unique features compared with other nanostructured metals, such as nanoparticles, nanorods, and nanowires. This characteristics leads to optical sensors exploiting NPG through unique surface plasmon resonance properties that can be monitored by UV-Vis, Raman, or fluorescence spectroscopy. On the other hand, the catalytic properties of NPG are exploited electrochemical sensors are on the electrical signal produced by a specific analyte adsorbed of the NPG surface. In this regard, the enourmous NPG surface area is crucial in determining the sensitivity enhancement. Due to the extension, complexity, and importance of the NPG-based sensing field, in the present review we attempt, starting from the discussion of specific cases, to focus our attention on the basic properties of NPG in connection to the main sensing applications, i.e., surface enhanced Raman spectroscopy-based and electrochemical-based sensing. Starting from the discussion of the basic morphological/structural characteristics of NPG as obtained during the fabrication step and post-fabrication processes, the review aims to a comprehensive schematization of the main classes of sensing applications highlighting the basic involved physico-chemical properties and mechanisms. In each discussed specific example, the main involved parameters and processes governing the sensing mechanism are elucidated. In this way, the review aims at establishing a general framework connecting the processes parameters to the characteristics (pore size, etc.) of the NPG. Some examples are discussed concerning surface plasmon enhanced Uv-Vis, Raman, fluorescence spectroscopy in order to realize efficient NPG-based optical sesnors: in this regard, the underlaying connections between NPG structural/morphological properties and the optical response and, hence, the optical-based sensing performances are described and analyzed. Some other examples are discussed concerning the exploitation of the electrochemical characteristics of NPG for ultra-high sensitivity detection of analytes: in this regard, the key parameters determing the NPG activity and selectivity selectivity toward a variety of reactants are discussed, as high surface-to-volume ratio and the low coordination of surface atoms. In addition to the use of standard NPG films and leafs as sensing platforms, also the role of hybrid NPG-based nanocomposites and of nanoporous Au nanostructures is discussed due to the additional increase of the electrocatalytic acticvity and of exposed surface area resulting in the possible further sensitivity increase.

Description: There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5–100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

Description: Non-enzymatic electrochemical glucose sensing was obtained by gold nanostructures on graphene paper, produced by laser or thermal dewetting of 1.6 and 8 nm-thick Au layers, respectively. Nanosecond laser annealing produces spherical nanoparticles (AuNPs) through the molten-phase dewetting of the gold layer and simultaneous exfoliation of the graphene paper. The resulting composite electrodes were characterized by X-ray photoelectron spectroscopy, cyclic voltammetry, scanning electron microscopy, micro Raman spectroscopy and Rutherford back-scattering spectrometry. Laser dewetted electrode presents graphene nanoplatelets covered by spherical AuNPs. The sizes of AuNPs are in the range of 10–150 nm. A chemical shift in the XPS Au4f core-level of 0.25–0.3 eV suggests the occurrence of AuNPs oxidation, which are characterized by high stability under the electrochemical test. Thermal dewetting leads to electrodes characterized by faceted not oxidized gold structures. Glucose was detected in alkali media at potential of 0.15–0.17 V vs. saturated calomel electrode (SCE), in the concentration range of 2.5μM−30 mM, exploiting the peak corresponding to the oxidation of two electrons. Sensitivity of 1240 µA mM−1 cm−2, detection limit of 2.5 μM and quantifications limit of 20 μM were obtained with 8 nm gold equivalent thickness. The analytical performances are very promising and comparable to the actual state of art concerning gold based electrodes.

Description: Metal nanostructures are, nowadays, extensively used in applications such as catalysis, electronics, sensing, optoelectronics and others. These applications require the possibility to design and fabricate metal nanostructures directly on functional substrates, with specifically controlled shapes, sizes, structures and reduced costs. A promising route towards the controlled fabrication of surface-supported metal nanostructures is the processing of substrate-deposited thin metal films by fast and ultrafast pulsed lasers. In fact, the processes occurring for laser-irradiated metal films (melting, ablation, deformation) can be exploited and controlled on the nanoscale to produce metal nanostructures with the desired shape, size, and surface order. The present paper aims to overview the results concerning the use of fast and ultrafast laser-based fabrication methodologies to obtain metal nanostructures on surfaces from the processing of deposited metal films. The paper aims to focus on the correlation between the process parameter, physical parameters and the morphological/structural properties of the obtained nanostructures. We begin with a review of the basic concepts on the laser-metal films interaction to clarify the main laser, metal film, and substrate parameters governing the metal film evolution under the laser irradiation. The review then aims to provide a comprehensive schematization of some notable classes of metal nanostructures which can be fabricated and establishes general frameworks connecting the processes parameters to the characteristics of the nanostructures. To simplify the discussion, the laser types under considerations are classified into three classes on the basis of the range of the pulse duration: nanosecond-, picosecond-, femtosecond-pulsed lasers. These lasers induce different structuring mechanisms for an irradiated metal film. By discussing these mechanisms, the basic formation processes of micro- and nano-structures is illustrated and justified. A short discussion on the notable applications for the produced metal nanostructures is carried out so as to outline the strengths of the laser-based fabrication processes. Finally, the review shows the innovative contributions that can be proposed in this research field by illustrating the challenges and perspectives.

Description: Bimetallic Au/Pd nanoscale-thick films were sputter-deposited at room temperature on a silicon carbide (SiC) surface, and the surface-morphology evolution of the films versus thickness was studied with scanning electron microscopy. This study allowed to elucidate the Au/Pd growth mechanism by identifying characteristic growth regimes, and to quantify the characteristic parameters of the growth process. In particular, we observed that the Au/Pd film initially grew as three-dimensional clusters; then, increasing Au/Pd film thickness, film morphology evolved from isolated clusters to partially coalesced wormlike structures, followed by percolation morphology, and, finally, into a continuous rough film. The application of the interrupted coalescence model allowed us to evaluate a critical mean cluster diameter for partial coalescence, and the application of Vincent’s model allowed us to quantify the critical Au/Pd coverage for percolation transition.