Titanium (IV) Oxide Nanotubes in Design of Active SERS Substrates for High Sensitivity Analytical Applications: Effect of Geometrical Factors in Nanotubes and in Ag-n Deposits

In this chapter, we summarize the results of recent investigations into TiO2 nanotubular oxide layers on Ti metal loaded with Ag nanoparticles, which act as efficient surface plasmon resonators. These Ag-n/TiO2 NT/Ti composite layers appear to be useful as platforms for precise surface analytical investigations of minute amounts of numerous types of organic molecules: pyridine (Py), mercaptobenzoic acid (MBA), 5-(4-dimethylaminobenzylidene) rhodamine (DBRh) and rhodamine (R6G); such investigations are known as surface enhanced Raman Spectroscopy (SERS). Geometrical factors related to the nanotubes and the silver deposit affect the SERS activity of the resulting composite layers. The results presented here show that, for a carefully controlled amount of Ag-n deposit located mainly on the tops of titania nanotubes, it is possible to obtain high-quality, reproducible SERS spectra for probe molecules at an enhancement factor of 105–106. This achievement makes it possible to detect organic molecules at concentrations as low as, e.g., 10−9 M for R6G molecules. SEM investigations suggest that the size of the nanotubes, and both the lateral and perpendicular distribution of Ag-n (on the tube tops and walls), are responsible for the SERS activity. These features of the Ag-n/TiO2 NT/Ti composite layer provide a variety of cavities and slits which function as suitable resonators for the adsorbed molecules

Nanofunctionalization of Additively Manufactured Titanium Substrates for Surface-Enhanced Raman Spectroscopy Measurements

Powder bed fusion using a laser beam (PBF-LB) is a commonly used additive manufacturing (3D printing) process for the fabrication of various parts from pure metals and their alloys. This work shows for the first time the possibility of using PBF-LB technology for the production of 3D titanium substrates (Ti 3D) for surface-enhanced Raman scattering (SERS) measurements. Thanks to the specific development of the 3D titanium surface and its nanoscale modification by the formation of TiO2 nanotubes with a diameter of ~80 nm by the anodic oxidation process, very efficient SERS substrates were obtained after deposition of silver nanoparticles (0.02 mg/cm2, magnetron sputtering). The average SERS enhancement factor equal to 1.26 × 106 was determined for pyridine (0.05 M + 0.1 M KCl), as a model adsorbate. The estimated enhancement factor is comparable with the data in the literature, and the substrate produced in this way is characterized by the high stability and repeatability of SERS measurements. The combination of the use of a printed metal substrate with nanofunctionalization opens a new path in the design of SERS substrates for applications in analytical chemistry. Methods such as SEM scanning microscopy, photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD) were used to determine the morphology, structure and chemical composition of the fabricated materials

Ag/ZrO2Ag/ZrO_2-NT/Zr hybrid material : a new platform for SERS measurements

In this paper, we present recent results of our attempts to produce nanoporous zirconia, as well as our investigations of a hybrid material consisting of nanoporous zirconia loaded with Ag-nanoparticles, Ag- n/ZrO 2 -NT/Zr, which could be used as an active SERS substrate. The Zr-based hybrid material, as our investigations have shown, is an active and stable substrate in SERS investigations aimed at detecting various organic molecules: mercaptobenzoic acid, pyridine and two different dyes – rodhanine deriva- tives. The SERS spectra for the probe molecules adsorbed on silver nanoparticles on a ZrO 2 -NT/Zr platform display characteristic intensity ratios different from those measured on previously studied nanoporous substrates based on Ti and Al, which ensure a different (alternative) interaction between the investi- gated adsorbate and adsorbent. In order to characterize our new substrate we used high-resolution SEM and surface analytical techniques: XPS (X-ray photoelectron spectroscopy) and SERS (surface enhanced Raman spectroscopy)

Materials characterization of TiO2TiO_2 nanotubes decorated by Au nanoparticles for photoelectrochemical applications

The structural and chemical modification of TiO(2) nanotubes (NTs) by the deposition of a well-controlled Au deposit was investigated using a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), Raman measurements, UV-Vis spectroscopy and photoelectrochemical investigations. The fabrication of the materials focused on two important factors: the deposition of Au nanoparticles (NPs) in UHV (ultra high vacuum) conditions (1–2 × 10(−8) mbar) on TiO(2) nanotubes (NTs) having a diameter of ∼110 nm, and modifying the electronic interaction between the TiO(2) NTs and Au nanoparticles (NPs) with an average diameter of about 5 nm through the synergistic effects of SMSI (Strong Metal Support Interaction) and LSPR (Local Surface Plasmon Resonance). Due to the formation of unique places in the form of “hot spots”, the proposed nanostructures proved to be photoactive in the UV-Vis range, where a characteristic gold plasmonic peak was observed at a wavelength of 580 nm. The photocurrent density of Au deposited TiO(2) NTs annealed at 650 °C was found to be much greater (14.7 μA cm(−2)) than the corresponding value (∼0.2 μA cm(−2)) for nanotubes in the as-received state. The IPCE (incident photon current efficiency) spectral evidence also indicates an enhancement of the photoconversion of TiO(2) NTs due to Au NP deposition without any significant change in the band gap energy of the titanium dioxide (E(g) ∼3.0 eV). This suggests that a plasmon-induced resonant energy transfer (PRET) was the dominant effect responsible for the photoactivity of the obtained materials

Diffusion controlled electrochemical analysis of MoS2 and MOF derived metal oxide–carbon hybrids for high performance supercapacitors

Abstract In the context of emerging electric devices, the demand for advanced energy storage materials has intensified. These materials must encompass both surface and diffusion-driven charge storage mechanisms. While diffusion-driven reactions offer high capacitance by utilizing the bulk of the material, their effectiveness diminishes at higher discharge rates. Conversely, surface-controlled reactions provide rapid charge/discharge rates and high power density. To strike a balance between these attributes, we devised a tri-composite material, TiO2/Carbon/MoS2 (T10/MoS2). This innovative design features a highly porous carbon core for efficient diffusion and redox-active MoS2 nanosheets on the surface. Leveraging these characteristics, the T10/MoS2 composite exhibited impressive specific capacitance (436 F/g at 5 mV/s), with a significant contribution from the diffusion-controlled process (82%). Furthermore, our symmetrical device achieved a notable energy density of ~ 50 Wh/kg at a power density of 1.3 kW/kg. This concept holds promise for extending the approach to other Metal–Organic Framework (MOF) structures, enabling enhanced diffusion-controlled processes in energy storage applications