Two-dimensional (2D) transition metal carbides (MXenes) exhibit outstanding performances in many applications, such as energy storage, optoelectronics, and electrocatalysts. However, colloidal ...solutions of Ti3C2Tx MXene flakes deteriorate rapidly under ambient conditions due to the conversion of the titanium carbide to titanium dioxide. Here, we discuss the dominant factors influencing the rate of oxidation of Ti3C2Tx MXene flakes, and present guidelines for their storage with the aim of maintaining the intrinsic properties of the as-prepared material. The oxidation stability of the Ti3C2Tx flakes is dramatically improved in a system where water molecules and temperature were well-controlled. It was found that aqueous solutions of Ti3C2Tx MXene can be chemically stable for more than 39 weeks when the storage temperature (−80 °C) is sufficiently low to cease the oxidation processes. It was also found that if the Ti3C2Tx flakes are dispersed in ethanol, the degradation process can be significantly delayed even at 5 °C. Moreover, the oxidation stability of the Ti3C2Tx flakes is dramatically improved in both cases, even in the presence of oxygen-containing atmosphere. We demonstrate practical applications of our approach by employing Ti3C2Tx in a gas sensor showing that when oxidation is inhibited, the device can retain the original electrical properties after 5 weeks of storage.
Oxidation-resistant titanium carbide MXene films Lee, Yonghee; Kim, Seon Joon; Kim, Yong-Jae ...
Journal of materials chemistry. A, Materials for energy and sustainability,
2020, Letnik:
8, Številka:
2
Journal Article
Recenzirano
Two-dimensional transition metal carbides (MXenes) have attracted much attention due to their excellent electrical conductivity and outstanding performances in energy storage, telecommunication, and ...sensing applications. It is known that MXene flakes are readily oxidized in either humid air or aqueous environments. While the chemical instability of MXenes may limit their use in applications involving ambient environments and long-term operation, oxidation behaviour of MXene films has not been addressed. In this work, we demonstrate a hydrogen annealing method to increase the oxidation stability of Ti
3
C
2
MXene in two different aspects: (1) dramatic improvement in the oxidation stability of pristine MXene films against harsh conditions (100% relative humidity, 70 °C), and (2) large recovery in the electrical conductivity of previously oxidized Ti
3
C
2
MXene films. We also demonstrate an electric-field-induced heater capable of stable operation under highly oxidizing conditions, based on the oxidation-resistant MXene film. A total loss of heat generation ability was observed for the as-prepared MXene film, while the hydrogen-annealed one maintained its bright infrared radiation, under the highly oxidizing conditions. This work offers a solution to industrial applications of unprotected MXene films, securing their stable and long-term operation in humid conditions.
We have demonstrated a highly stable electric heater made of oxidation-resistant MXene film, which was capable of stable operation in air under highly oxidizing conditions (70 °C, 100% RH).
Understanding the etching mechanisms of MXene and obtaining direct insights into the influence of etchants on structural features and defects are of critical importance for improving MXene ...properties, optimization of etching protocols, and exploring new MXene compositions. Despite their importance, such studies have been challenging because of the monoatomic thickness of the A-element layers being etched and aggressive etchants that hinder in situ studies. Here, we visualize the etching behavior of the Ti3AlC2 MAX phase in different etchants at the atomic scale using focused ion beam and electron microscopy. We also report on the structural changes in the Ti3AlC2 phase as a function of etching time and etchant type (LiF/HCl, HF, or NH4HF2) to reveal the etching mechanism for the first time. Interestingly, direct visualization reveals an unexpected stepwise etching where the edge Al atoms at the middle layers of the MAX particle are not etched despite contact with the acidic etchant counterintuitively. Also, while the propagation of the etching front occurs in the direction normal to the inner basal plane for all etchants, we reveal that HF and NH4HF2 etch the grain boundaries of polycrystal MAX particles to expose more edge sites to the etchant, which is not observed for LiF/HCl.
Graphitic carbon fiber felt (GCFF) with a crystalline graphitic carbon structure was facilely prepared by a combination of electrospinning and graphitization (2800 °C heat treatment) and was used as ...an interlayer between the cathode and separator in Li-S batteries. This GCFF interlayer trapped the polysulfides on the cathode side and increased the utilization of sulfur by suppressing the shuttle phenomenon. Also, the GCFF was shown to be able to act as an upper current collector to reduce the charge-transfer resistance owing to the high crystallinity of the graphitic carbon fibers. The sulfur cathode with the GCFF interlayer showed a high specific initial discharge capacity of 1280.14 mAh g−1 and excellent cycling stability (1004.62 mAh g−1 after 100 cycles) at 0.2 C. Also, an image of the glass fiber (GF) separator on the anode side confirmed the presence of an SEI after 200 cycles, which apparently resulted from stable Li deposition on the Li metal because of the low or medium concentration of sulfur in the electrolyte solution. Our observations should contribute to elucidating the key features of complex three-dimensional carbon fabrics with crystalline graphitic structures that allow them, when inserted as interlayers, to markedly improve the performance of rechargeable batteries.
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•3D web-structured graphitic carbon fiber felt (GCFF) as an efficient interlayer.•The superior electrical resistivity owing to graphitic carbon-carbon bonds.•The GCFF interlayer suppressed the shuttle phenomenon by trapping the polysulfides.•High-performance Li-S batteries (1004.62 mAh g−1 after 100 cycles).
MXenes are a prominent family of two-dimensional materials because of their metallic conductivity and abundant surface functionalities. Although MXenes have been extensively studied as bulk particles ...or free-standing films, thin and transparent films are needed for optical, optoelectronic, sensing, and other applications. In this study, we demonstrate a facile method to fabricate ultrathin (∼10 nm), Ti3C2T x MXene films by an interfacial assembly technique. The self-assembling behavior of MXene flakes resulted in films with a high stacking order and strong plane-to-plane adherence, where optimal films of 10 nm thickness displayed a low sheet resistance of 310 Ω/□. By using surface tension, films were transferred onto various types of planar and curved substrates. Moreover, multiple films were consecutively transferred onto substrates from a single batch of solution, showing the efficient use of the material. When the films were utilized as gas sensing channels, a high signal-to-noise ratio, up to 320, was observed, where the gas response of films assembled from small MXene flakes was 10 times larger than that from large flakes. This work provides a facile and efficient method to allow MXenes to be further exploited for thin-film applications.
Layered structures of transition metal dichalcogenides stacked by van der Waals interactions are now attracting the attention of many researchers because they have fascinating electronic, optical, ...thermoelectric, and catalytic properties emerging at the monolayer limit. However, the commonly used methods for preparing monolayers have limitations of low yield and poor extendibility into large-area applications. Herein, we demonstrate the synthesis of large-area MoSe2 with high quality and uniformity by selenization of MoO3 via chemical vapor deposition on arbitrary substrates such as SiO2 and sapphire. The resultant monolayer was intrinsically doped, as evidenced by the formation of charged excitons under low-temperature photoluminescence analysis. A van der Waals heterostructure of MoSe2 on graphene was also demonstrated. Interestingly, the MoSe2/graphene heterostructures show strong quenching of the characteristic photoluminescence from MoSe2, indicating the rapid transfer of photogenerated charge carriers between MoSe2 and graphene. The development of highly controlled heterostructures of two-dimensional materials will further promote advances in the physics and chemistry of reduced dimensional systems and will provide novel applications in electronics and optoelectronics.
This paper describes a general approach for transferring clean single-layer graphene onto silicon nitride nanopore devices and the use of the electron beam of a transmission electron microscope (TEM) ...to drill size-controlled nanopores in freely suspended graphene. Besides nanopore drilling, we also used the TEM to heal and completely close the unwanted secondary holes formed by electron beam damage during the drilling process. We demonstrate electron beam assisted shrinking of irregularly shaped 40-60 nm pores down to 2 nm, exhibiting an exquisite control of graphene nanopore diameter. Our fabrication workflow also rendered graphene nanopores hydrophilic, allowing easy wetting and use of the pores for studying protein translocation and protein-protein interaction with a high signal to noise ratio.
In the current work, we followed a green chemistry route to prepare and characterize the silver nanoparticles (AgNPs) using Syzygium aromaticum (clove) extract at room temperature. Suitably, the ...clove extract acted as a reducing agent as well as a capping agent, and these reactions occurred rapidly. The formation of the AgNPs was confirmed by the observation of the distinct absorption peak at a wavelength of 418 nm using ultraviolet–visible (UV–Vis) spectroscopy, and a morphological study confirmed the uniform distribution of the optimally spherical nanoparticles. Fourier transform infrared spectroscopy (FTIR) results indicated the methoxy and allyl functional groups of eugenol of the clove extract to be responsible for the bioreduction of silver ions and for the stabilization of the resulting nanoparticles (flavonoids). We also found the AgNPs to be effective catalysts of the degradation of three pollutant organic dyes viz., 4‐nitrophenol, methylene blue and rhodamine B, in the presence of excess NaBH4. The antibacterial and antifungal activities of the bio‐synthesized AgNPs were also explored. Overall, the results suggested the potential use of clove extract as a resource for the synthesis of AgNPs having a broad range of possible commercial and biomedical applications.
An illustration of the AgNP‐catalyzed reduction of 4‐Nitrophenol as well as of the other tested compounds, i.e., the organic dyes of Methylene blue and Rhodamine B.
The influence of capping agents on silver nanoparticles (AgNPs) was investigated through a rapid and single-pot chemical reduction method. Four capping agents were tested: polyethylene glycol (PEG), ...ethylenediaminetetraacetic acid (EDTA), polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA). FTIR studies demonstrated that the formed AgNPs were properly encapsulated by their respective capping agents. Structural and morphological studies confirmed the following relative average particle sizes: PEG-AgNPs > EDTA-AgNPs > PVP-AgNPs > PVA-AgNPs. Optical absorption and photoluminescence studies showed, respectively, a greater absorption blue shift and greater emission intensity for the smaller capped particles. Zeta potential analysis of the PVA-AgNPs showed a value of -46.6 mV, indicating their high stability. The PVA-AgNPs were thus not only observed to be the smallest, most blue-shifted and most stable of the tested AgNPs, but also they displayed the highest antibacterial activity. The PVA-AgNPs were therefore applied as a localized surface plasmon resonance (LSPR)-based H sub(2)O sub(2) sensor, which is important because the detection of reactive oxygen species such as H sub(2)O sub(2) is of significance in the medical and environmental fields. The sensor based on the PVA-AgNPs successfully detected H sub(2)O sub(2) at concentrations as low as 10 super(-7) M. New biosensors using these NPs should thus find promising opportunities in a variety of fields.
Gas molecules are known to interact with two-dimensional (2D) materials through surface adsorption where the adsorption-induced charge transfer governs the chemiresistive sensing of various gases. ...Recently, titanium carbide (Ti3C2T x ) MXene emerged as a promising sensing channel showing the highest sensitivity among 2D materials and unique gas selectivity. However, unlike conventional 2D materials, MXenes show metallic conductivity and contain interlayer water, implying that gas molecules will likely interact in a more complex way than the typical charge transfer model. Therefore, it is important to understand the role of all factors that may influence gas sensing. Here, we studied the gas-induced interlayer swelling of Ti3C2T x MXene thin films and its influence on gas sensing performance. In situ X-ray diffraction was employed to simultaneously measure dynamic swelling behavior where Ti3C2T x MXene films displayed selective swelling toward ethanol vapor over CO2 gas. Results show that the controlling sodium ion concentration in the interlayers is highly important in tuning the swelling behavior and gas sensing performance. The degree of swelling matched well with the gas response intensity, and the highest gas selectivity toward ethanol vapor was achieved for Ti3C2T x sensing channels treated with 0.3 mM NaOH, which also displayed the largest amount of swelling. Our results demonstrate that controlling the interlayer transport of Ti3C2T x MXene is essential for enhancing the selective sensing of gas molecules.
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