Noble-Nanoparticle-Decorated Ti3C2T x MXenes for Highly Sensitive Volatile Organic Compound Detection.

Two-dimensional transition-metal carbides and nitrides (MXenes) have been regarded as promising sensing materials because of their high surface-to-volume ratios and outstanding electronic, optical, and mechanical properties with versatile transition-metal and surface chemistries. However, weak gas-molecule adsorption of MXenes poses a serious limitation to their sensitivity and selectivity, particularly for trace amounts of volatile organic compounds (VOCs) at room temperature. To deal with these issues, Au-decorated MXenes are synthesized by a facile solution mixing method for room-temperature sensing of a wide variety of oxygen-based and hydrocarbon-based VOCs. Dynamic sensing experiments reveal that optimal decoration of Au nanoparticles (NPs) on Ti3C2T x MXene significantly elevates the response and selectivity of the flexible sensors, especially in detecting formaldehyde. Au-Ti3C2T x gas sensors exhibited an extremely low limit of detection of 92 ppb for formaldehyde at room temperature. Au-Ti3C2T x provides reliable gas response, low noise level, ultrahigh signal-to-noise ratio, high selectivity, as well as parts per billion level of formaldehyde detection. The prominent mechanism for Au-Ti3C2T x in sensing formaldehyde is elucidated theoretically from density functional theory simulations. The results presented here strongly suggest that decorating noble-metal NPs on MXenes is a feasible strategy for the development of next-generation ultrasensitive sensors for Internet of Things.

DNA-Functionalized Ti3C2Tx MXenes for Selective and Rapid Detection of SARS-CoV-2 Nucleocapsid Gene.

Coronavirus disease 2019 (COVID-19) is an emerging human infectious disease caused by severe acute respiratory syndrome 2 (SARS-CoV-2, initially called novel coronavirus 2019-nCoV) virus. Thus, an accurate and specific diagnosis of COVID-19 is urgently needed for effective point-of-care detection and disease management. The reported promise of two-dimensional (2D) transition-metal carbides (Ti3C2Tx MXene) for biosensing owing to a very high surface area, high electrical conductivity, and hydrophilicity informed their selection for inclusion in functional electrodes for SARS-CoV-2 detection. Here, we demonstrate a new and facile functionalization strategy for Ti3C2Tx with probe DNA molecules through noncovalent adsorption, which eliminates expensive labeling steps and achieves sequence-specific recognition. The 2D Ti3C2Tx functionalized with complementary DNA probes shows a sensitive and selective detection of nucleocapsid (N) gene from SARS-CoV-2 through nucleic acid hybridization and chemoresistive transduction. The fabricated sensors are able to detect the SARS-CoV-2 N gene with sensitive and rapid response, a detection limit below 105 copies/mL in saliva, and high specificity when tested against SARS-CoV-1 and MERS. We hypothesize that the MXenes' interlayer spacing can serve as molecular sieving channels for hosting organic molecules and ions, which is a key advantage to their use in biomolecular sensing.

Surface Functionalization of Ti3C2Tx MXene with Highly Reliable Superhydrophobic Protection for Volatile Organic Compounds Sensing.

Two-dimensional (2D) transition-metal carbides (Ti3C2Tx MXene) have received a great deal of attention for potential use in gas sensing showing the highest sensitivity among 2D materials and good gas selectivity. However, one of the long-standing challenges of the MXenes is their poor stability against hydration and oxidation in a humid environment, limiting their long-term storage and applications. Integration of an effective protection layer with MXenes shows promise for overcoming this major drawback. Herein, we demonstrate a surface functionalization strategy for Ti3C2Tx with fluoroalkylsilane (FOTS) molecules through surface treatment, providing not only a superhydrophobic surface, mechanical/environmental stability but also enhanced sensing performance. The experimental results show that high sensitivity, good repeatability, long-term stability, and selectivity and faster response/recovery property were achieved by the FOTS-functionalized when Ti3C2Tx was integrated into chemoresistive sensors sensitive to oxygen-containing volatile organic compounds (ethanol, acetone). FOTS functionalization provided protection to sensing response when the dynamic response of the Ti3C2Tx-F sensor to 30 ppm of ethanol was measured over in the 5 to 80% relative humidity range. Density functional theory simulations suggested that the strong adsorption energy of ethanol on Ti3C2Tx-F and the local structure deformation induced by ethanol adsorption, contributing to the gas-sensing enhancement. This study offers a facile and practical solution for developing highly reliable MXene based gas-sensing devices with response that is stable in air and in the presence of water.

Sulfur-Doped Titanium Carbide MXenes for Room-Temperature Gas Sensing.

Two-dimensional titanium carbide MXenes, Ti3C2Tx, possess high surface area coupled with metallic conductivity and potential for functionalization. These properties make them especially attractive for the highly sensitive room-temperature electrochemical detection of gas analytes. However, these extraordinary materials have not been thoroughly investigated for the detection of volatile organic compounds (VOCs), many of which hold high relevance for disease diagnostics and environmental protection. Furthermore, the insufficient interlayer spacing between MXene nanoflakes could limit their applicability and the use of heteroatoms as dopants could help overcome this challenge. Here, we report that S-doping of Ti3C2Tx MXene leads to a greater gas-sensing performance to VOCs compared to their undoped counterparts, with unique selectivity to toluene. After S-doped and pristine materials were synthesized, characterized, and used as electrode materials, the as-fabricated sensors were subjected to room-temperature dynamic impedimetric testing in the presence of VOCs with different functional groups (ethanol, hexane, toluene, and hexyl-acetate). Unique selectivity to toluene was obtained by both undoped and doped Ti3C2Tx MXenes, but an enhancement of response in the range of ∼214% at 1 ppm to ∼312% at 50 ppm (3-4 folds increase) was obtained for the sulfur-doped sensing material. A clear notable response to 500 ppb toluene was also obtained with sulfur-doped Ti3C2Tx MXene sensors along with excellent long-term stability. Our experimental measurements and density functional theory analysis offer insight into the mechanisms through which S-doping influences VOC analyte sensing capabilities of Ti3C2Tx MXenes, thus opening up future investigations on the development of high-performance room-temperature gas sensors.

Selective Detection of Ethylene by MoS2-Carbon Nanotube Networks Coated with Cu(I)-Pincer Complexes.

The plant hormone ethylene (C2) can induce premature fruit ripening and flower senescence at levels below 1 ppm, which has motivated efforts to develop cost-effective methods for C2 monitoring during the transport and storage of climacteric fruits. Here, we describe a nanocomposite film composed of exfoliated MoS2, single-walled carbon nanotubes (SCNTs), and Cu(I)-tris(mercaptoimidazolyl)borate complexes (Cu-Tm) for real-time detection of C2 at levels down to 100 ppb. A copercolation network of MoS2 and SCNTs was deposited onto interdigitated Ag electrodes printed on plastic substrates and then coated with Cu-Tm with a final conductance in the 0.5 mS range. Reversible changes in relative conductance (-ΔG/G0) were measured upon C2 exposure with a linear response at sub-ppm levels. The thin-film sensors were highly selective toward C2, and they responded weakly to other volatile organic compounds or water at similar partial pressures. A mechanism is proposed in which Cu-Tm behaves as a chemically sensitive n-type dopant for MoS2, based on spectroscopic characterization and density functional theory modeling. Cu-Tm-coated MoS2/SCNT sensors were also connected to a battery-powered wireless transmitter and used to monitor C2 production from various fruit samples, validating their utility as practical, field-deployable sensors.

Nanohybrids of a MXene and transition metal dichalcogenide for selective detection of volatile organic compounds.

Two-dimensional transition metal carbides/nitrides, known as MXenes, have been recently receiving attention for gas sensing. However, studies on hybridization of MXenes and 2D transition metal dichalcogenides as gas-sensing materials are relatively rare at this time. Herein, Ti3C2Tx and WSe2 are selected as model materials for hybridization and implemented toward detection of various volatile organic compounds. The Ti3C2Tx/WSe2 hybrid sensor exhibits low noise level, ultrafast response/recovery times, and good flexibility for various volatile organic compounds. The sensitivity of the hybrid sensor to ethanol is improved by over 12-fold in comparison with pristine Ti3C2Tx. Moreover, the hybridization process provides an effective strategy against MXene oxidation by restricting the interaction of water molecules from the edges of Ti3C2Tx. An enhancement mechanism for Ti3C2Tx/WSe2 heterostructured materials is proposed for highly sensitive and selective detection of oxygen-containing volatile organic compounds. The scientific findings of this work could guide future exploration of next-generation field-deployable sensors.

Surface Functionalization of Layered Molybdenum Disulfide for the Selective Detection of Volatile Organic Compounds at Room Temperature.

Semiconducting two-dimensional (2D) transition-metal dichalcogenides (TMDCs) are considered promising sensing materials due to the high surface-to-volume ratio and active sensing sites. However, the reported strategies for 2D TMDCs toward sensing of volatile organic compounds (VOCs) present with some drawbacks. These include high operation temperatures, low gas response, and complex fabrication, limiting the development of room-temperature gas sensors. In this study, 2D MoS2 nanoflakes were prepared by liquid-phase exfoliation, and their surface was functionalized with Au nanoparticles (NPs) through a facile solution mixing method. MoS2 decorated with Au NPs with an average size of 10 nm was used as a material platform for an electrochemical sensor to detect a wide variety of VOCs at room temperature. Through dynamic sensing tests, the enhancement of gas-sensing performance in terms of response and selectivity, especially in detecting oxygen-based VOCs (acetone, ethanol, and 2-propanol), was demonstrated. After Au functionalization, the response of the gas sensor to acetone improved by 131% (changing from 13.7% for pristine MoS2 to 31.6% for MoS2-Au(0.5)). Sensing tests under various relative humidity values (10-80%), bending or long-term conditions, indicated the sound robustness and flexibility of the sensor. Density functional theory simulations suggested that the adsorption energy of VOC molecules on MoS2-Au is significantly higher than that on pristine MoS2, contributing to the gas-sensing enhancement; a VOC-sensing mechanism for Au-decorated MoS2 nanoflakes was proposed for the first time for the highly sensitive and selective detection of oxygen-based VOCs.