RESUMO
Extending applications of Ti3C2Tx MXene in nanocomposites and across fields of electronics, energy storage, energy conversion, and sensor technologies necessitates simple and efficient analytical methods. Raman spectroscopy is a critical tool for assessing MXene composites; however, high laser powers and temperatures can lead to the materials' deterioration during the analysis. Therefore, an in-depth understanding of MXene photothermal degradation and changes in its oxidation state is required, but no systematic studies have been reported. The primary aim of this study was to investigate the degradation of the MXene lattice through Raman spectroscopic analysis. Distinct spectral markers were related to structural alterations within the Ti3C2Tx material after subjecting it to thermal- and laser-induced degradation. During the degradation processes, spectral markers were revealed for several specific steps: a decrease in the number of interlayer water molecules, a decrease in the number of -OH groups, formation of C-C bonds, oxidation of the lattice, and formation of TiO2 nanoparticles (first anatase, followed by rutile). By tracking of position shifts and intensity changes for Ti3C2Tx, the spectral markers that signify the initiation of each step were found. This spectroscopic approach enhances our understanding of the degradation pathways of MXene, and facilitating enhanced and dependable integration of these materials into devices for diverse applications, from energy storage to sensors.
RESUMO
Layered MAX phases and two-dimensional (2D) MXenes derived from them are among the most studied materials due to their attractive properties and numerous potential applications. The tunability of their structure and composition allows for every property to be modulated over a wide range. Particularly, elemental replacement and formation of a solid solution without changing the structure allow fine-tuning of material properties. While solid solutions on the M (metal) site have received attention, the partial replacement of carbon with nitrogen (carbonitrides) has received little attention. By applying this concept, herein we report the synthesis of three families of titanium carbonitride Tin+1Al(C1-yNy)n MAX phases and Tin+1(C1-yNy)nTx MXenes with one, two, and three C/N layers. This greatly expands the variety of known MAX phases and MXenes to encompass 16 titanium carbonitrides with tunable X-site chemistries and different 2D layer thicknesses, including MXenes in the Ti4(C1-yNy)3Tx system, which have not been previously reported. We further investigated the relationship among the composition, structure, stability, and synthesis conditions of the MXenes and their respective Al-based MAX phases. This range of materials will enable fundamental studies of the N/C ratio effect on optoelectronic, electromagnetic, and mechanical properties of MXenes, as well as tuning those properties for specific applications.
RESUMO
Ti3C2Tx MXene is emerging as the enabling material in a broad range of wearable and implantable medical technologies, thanks to its outstanding electrical, electrochemical, and optoelectronic properties, and its compatibility with high-throughput solution-based processing. While the prevalence of Ti3C2Tx MXene in biomedical research, and in particular bioelectronics, has steadily increased, the long-term stability and degradation of Ti3C2Tx MXene films have not yet been thoroughly investigated, limiting its use for chronic applications. Here, we investigate the stability of Ti3C2Tx films and electrodes under environmental conditions that are relevant to medical and bioelectronic technologies: storage in ambient atmosphere (shelf-life), submersion in saline (akin to the in vivo environment), and storage in a desiccator (low-humidity). Furthermore, to evaluate the effect of the MXene deposition method and thickness on the film stability in the different conditions, we compare thin (25 nm), and thick (1.0 µm) films and electrodes fabricated via spray-coating and blade-coating. Our findings indicate that film processing method and thickness play a significant role in determining the long-term performance of Ti3C2Tx films and electrodes, with highly aligned, thick films from blade coating remarkably retaining their conductivity, electrochemical impedance, and morphological integrity even after 30 days in saline. Our extensive spectroscopic analysis reveals that the degradation of Ti3C2Tx films in high-humidity environments is primarily driven by moisture intercalation, ingress, and film delamination, with evidence of only minimal to moderate oxidation.
RESUMO
MXenes are being heavily investigated in biomedical research, with applications ranging from regenerative medicine to bioelectronics. To enable the adoption and integration of MXenes into therapeutic platforms and devices, however, their stability under standard sterilization procedures must be established. Here, we present a comprehensive investigation of the electrical, chemical, structural, and mechanical effects of common thermal (autoclave) and chemical (ethylene oxide (EtO) and H2O2 gas plasma) sterilization protocols on both thin-film Ti3C2Tx MXene microelectrodes and mesoscale arrays made from Ti3C2Tx-infused cellulose-elastomer composites. We also evaluate the effectiveness of the sterilization processes in eliminating all pathogens from the Ti3C2Tx films and composites. Post-sterilization analysis revealed that autoclave and EtO did not alter the DC conductivity, electrochemical impedance, surface morphology, or crystallographic structure of Ti3C2Tx and were both effective at eliminating E. coli from both types of Ti3C2Tx-based devices. On the other end, exposure to H2O2 gas plasma sterilization for 45 min induced severe degradation of the structure and properties of Ti3C2Tx films and composites. The stability of the Ti3C2Tx after EtO and autoclave sterilization and the complete removal of pathogens establish the viability of both sterilization processes for Ti3C2Tx-based technologies.
Assuntos
Escherichia coli , Peróxido de Hidrogênio , Titânio/farmacologia , EsterilizaçãoRESUMO
Dynamic control of electromagnetic wave jamming is a notable technological challenge for protecting electronic devices working at gigahertz frequencies. Foam materials can adjust the reflection and absorption of microwaves, enabling a tunable electromagnetic interference shielding capability, but their thickness of several millimetres hinders their application in integrated electronics. Here we show a method for modulating the reflection and absorption of incident electromagnetic waves using various submicrometre-thick MXene thin films. The reversible tunability of electromagnetic interference shielding effectiveness is realized by electrochemically driven ion intercalation and de-intercalation; this results in charge transfer efficiency with different electrolytes, accompanied by expansion and shrinkage of the MXene layer spacing. We finally demonstrate an irreversible electromagnetic interference shielding alertor through electrochemical oxidation of MXene films. In contrast with static electromagnetic interference shielding, our method offers opportunities to achieve active modulation that can adapt to demanding environments.
RESUMO
It is highly important to implement various semiconducting, such as n- or p-type, or conducting types of sensing behaviors to maximize the selectivity of gas sensors. To achieve this, researchers so far have utilized the n-p (or p-n) two-phase transition using doping techniques, where the addition of an extra transition phase provides the potential to greatly increase the sensing performance. Here, we report for the first time on an n-p-conductor three-phase transition of gas sensing behavior using Mo2CTx MXene, where the presence of organic intercalants and film thickness play a critical role. We found that 5-nm-thick Mo2CTx films with a tetramethylammonium hydroxide (TMAOH) intercalant displayed a p-type gas sensing response, while the films without the intercalant displayed a clear n-type response. Additionally, Mo2CTx films with thicknesses over 700 nm exhibited a conductor-type response, unlike the thinner films. It is expected that the three-phase transition was possible due to the unique and simultaneous presence of the intrinsic metallic conductivity and the high-density of surface functional groups of the MXene. We demonstrate that the gas response of Mo2CTx films containing tetramethylammonium (TMA) ions toward volatile organic compounds (VOCs), NH3, and NO2 is â¼30 times higher than that of deintercalated films, further showing the influence of intercalants on sensing performance. Also, DFT calculations show that the adsorption energy of NH3 and NO2 on Mo2CTx shifts from -0.973, -1.838 eV to -1.305, -2.750 eV, respectively, after TMA adsorption, demonstrating the influence of TMA in enhancing sensing performance.