Loading of Single Atoms of Iron, Cobalt, or Nickel to Enhance the Electrocatalytic Hydrogen Evolution Reaction of Two-Dimensional Titanium Carbide.

The rational design of advanced electrocatalysts at the molecular or atomic level is important for improving the performance of hydrogen evolution reactions (HERs) and replacing precious metal catalysts. In this study, we describe the fabrication of electrocatalysts based on Fe, Co, or Ni single atoms supported on titanium carbide (TiC) using the molten salt method, i.e., TiC-FeSA, TiC-CoSA, or TiC-NiSA, to enhance HER performance. The introduction of uniformly distributed transition-metal single atoms successfully reduces the overpotential of HERs. Overpotentials of TiC-FeSA at 10 mA cm-2 are 123.4 mV with 61.1 mV dec-1 Tafel slope under acidic conditions and 184.2 mV with 85.1 mV dec-1 Tafel slope under alkaline conditions, which are superior to TiC-NiSA and TiC-CoSA. TiC samples loaded with transition-metal single atoms exhibit high catalytic activity and long stability under acidic and basic conditions. Density functional theory calculations indicate that the introduction of transition-metal single atoms effectively reduces the HER barrier of TiC-based electrocatalysts.

A Laser-Processed Carbon-Titanium Carbide Heterostructure Electrode for High-Frequency Micro-Supercapacitors.

Micro-supercapacitors (MSCs) are an important energy storage component for future miniaturized electronic systems, yet their key performance indexes such as high-frequency response, energy density, and cycle life still have a large room to be improved. Herein, a laser-processed carbon-titanium carbide heterostructure (LCTH) electrode is demonstrated, which can excellently address the above key challenges by employing a unique one-step laser-processing fabrication method. Different from the other reported electrode structures, this LCTH electrode shows a heterogeneous structure, featuring the carbon nanofoam layer which provides extremely short ion transport channels and abundant electrochemical active sites, and the underlying titanium carbide layer which can provide excellent electron conductivity and contribute to the pseudo-capacitance. The assembled symmetric supercapacitor can stably work at the voltage window of 3.5 V at an ultra-high frequency of approximately 1121.3 Hz, exhibiting an ultra-high areal specific energy density of 721 µFV2 cm-2 at 120 Hz and a cycle life of 140 000 cycles with capacitance retention of 100.95%, which is superior to most reported MSCs. The as-fabricated MSC is compatible with the contemporary embedded electronic component fabrication processes, which shows significant advantages in large-scale fabrication and system integration, demonstrating a broad prospect for future system-in-package applications.

Simple and sensitive fluorescence sensing of methyl parathion based on the inner filter effect of p-nitrophenol on nitrogen-doped titanium carbide quantum dots.

It is of great significance to develop an effective method for methyl parathion (MP) detection. Herein, a novel nitrogen-doped titanium carbide quantum dots (N-Ti3 C2 QDs) was prepared and used to construct a simple and sensitive fluorescence sensing platform of MP by making use of inner filter effect (IFE). The prepared N-Ti3 C2 QDs can exhibit strong blue fluorescence at 434 nm. Meanwhile, MP could hydrolyze to produce p-nitrophenol (p-NP) under alkaline conditions, which showed a characteristic ultraviolet-visible (UV-visible) absorption peak at 405 nm, resulting in the fluorescence of N-Ti3 C2 QDs is effectively quenched by p-NP. In addition, the investigation of time-resolved fluorescence decays indicated that the corresponding quenching mechanism of p-NP on N-Ti3 C2 QDs is due to the IFE. After optimizing the conditions, the as-developed fluorescence sensing platform displayed wide detection range (0.1-30 µg mL-1 ) and low detection limit (0.036 µg mL-1 ) for MP, and it was also successfully applied for MP analysis in real water samples, thus it is expected that this simple, sensitive and enzyme-free sensing platform shows great applications.

Ecotoxicological Effects of Titanium Aluminum Carbide Composites on Biochemical and Metabolic Parameters of Galleria mellonella.

Metal composites have been extensively used in various fields such as automotive industry, medicine and pharmacy. However, the high exposure of these chemicals may have an adverse effect on the living organisms. In this study, the effect of titanium aluminum carbide (Ti3AlC2) on the model organism Galleria mellonella was investigated. The change in the metabolic enzymes such as alanine transferase, aspartate transferase, gamma-glutamyl transferase, lactate dehydrogenase, amylase, creatine kinase, alkaline phosphatase in the hemolymph of G. mellonella which was exposed to Ti3AlC2 was determined. The contents of the bilirubin, albumin, uric acid and the total protein were also measured after the Ti3AlC2 exposure on the model organism. The results of our study clearly indicate that Ti3AlC2 has adverse effects on the model organism G. mellonella.

In-situ TiO2-x decoration of titanium carbide MXene for photo/sono-responsive antitumor theranostics.

BACKGROUND: Sonodynamic therapy (SDT) has emerged as a noninvasive therapeutic modality that involves sonosensitizers and low-intensity ultrasound. However, owing to the rapid recombination of charge carriers, most of the sonosensitizers triggered poor reactive oxygen species (ROS) generation, resulting in unsatisfactory sonodynamic therapeutic effects. RESULTS: Herein, a photo/sono-responsive nanoplatform was developed through the in-situ systhesis of TiO2-x on the surface of two-dimensional MXene (titanium carbide, Ti3C2) for photoacoustic/photothermal bimodal imaging-guided near-infrared II (NIR-II) photothermal enhanced SDT of tumor. Because of several oxygen vacancies and smaller size (~ 10 nm), the in-situ formed TiO2-x nanoparticles possessed narrow band gap (2.65 eV) and high surface area, and thus served as a charge trap to restrict charge recombination under ultrasound (US) activation, resulting in enhanced sonodynamic ROS generation. Moreover, Ti3C2 nanosheets induced extensive localized hyperthermia relieves tumor hypoxia by accelerating intratumoral blood flow and tumor oxygenation, and thus further strengthened the efficacy of SDT. Upon US/NIR-II laser dual-stimuli, Ti3C2@TiO2-x nanoplatform triggered substantial cellular killing in vitro and complete tumor eradication in vivo, without any tumor recurrence and systemic toxicity. CONCLUSION: Our work presents the promising design of photo/sono-responsive nanoplatform for cancer nanotheranostics.

Molecularly imprinted ratiometric electrochemical sensor based on carbon nanotubes/cuprous oxide nanoparticles/titanium carbide MXene composite for diethylstilbestrol detection.

Conventional molecularly imprinted polymers (MIP)-based electrochemical sensors are generally susceptible to the changes of personal operation, electrode surface, and solution conditions. Herein, a ratiometric strategy was employed through introducing Cu2O nanoparticles (NPs) as inner reference probe to realize the reliable detection of diethylstilbestrol (DES). MIP film was prepared by electropolymerization of 1H-pyrrole-3-carboxylicacid in the presence of DES on carbon nanotubes/cuprous oxide/titanium carbide (CNT/Cu2O NPs/Ti3C2Tx) modified electrodes. The Ti3C2Tx with accordion-like structure not only possessed good electrical conductivity, but also facilitated the immobilization of Cu2O NPs, which contributed to stabilizing the signal. CNT was introduced to further improve the sensitivity of the sensor. Under optimum conditions, the MIP/CNT/Cu2O NPs/Ti3C2Tx electrochemical sensors showed a broad linear response range of 0.01 to 70 µM, and a low detection limit of 6 nM (S/N = 3). Moreover, the sensor was applied to detect DES in real samples including lake water, milk, and pork, and the recoveries for spiked standard were 88-112%. Thus, this work provides a new way for reliable DES detection.

Wrinkled Titanium Carbide (MXene) with Surface Charge Polarizations through Chemical Etching for Superior Electromagnetic Interference Shielding.

Despite the fact that the high conductivity of two-dimensional laminated transition metal carbides/nitrides (MXenes) contributes to the outstanding electromagnetic interference (EMI) shielding by the reflection of electromagnetic waves (EWs), it is difficulty to improve EMI shielding by pursuing higher conductivity due to the limitation of intrinsic properties. Here, we achieve superior EMI shielding by introducing the absorption of EWs in MXenes with micro-sized wrinkles which are induced by abundant Ti vacancies under chemical etching. The shielding effectiveness is up to 107 dB at a thickness of 20 µm. Combining with atomic-scale structure observation and the first-principles calculations, it is concluded that the promotion of EMI shielding originates from the resonant absorption of formed electric dipoles induced by the asymmetrical distribution of charge densities near Ti vacancies. Our results could open a new vista for developing two-dimensional EMI shielding materials.

Ex vivo and in vivo fluorescence detection and imaging of adenosine triphosphate.

BACKGROUND: Ex vivo and in vivo detection and imaging of adenosine triphosphate (ATP) is critically important for the diagnosis and treatment of diseases, which still remains challenges up to present. RESULTS: We herein demonstrate that ATP could be fluorescently detected and imaged ex vivo and in vivo. In particular, we fabricate a kind of fluorescent ATP probes, which are made of titanium carbide (TC) nanosheets modified with the ROX-tagged ATP-aptamer (TC/Apt). In the constructed TC/Apt, TC shows superior quenching efficiency against ROX (e.g., ~ 97%). While in the presence of ATP, ROX-tagged aptamer is released from TC surface, leading to the recovery of fluorescence of ROX under the 545-nm excitation. Consequently, a wide dynamic range from 1 µM to 1.5 mM ATP and a high sensitivity with a limit of detection (LOD) down to 0.2 µM ATP can be readily achieved by the prepared TC/Apt. We further demonstrate that the as-prepared TC/Apt probe is feasible for accurate discrimination of ATP in different samples including living cells, body fluids (e.g., mouse serum, mouse urine and human serum) and mouse tumor models. CONCLUSIONS: Fluorescence detection and imaging of ATP could be readily achieved in living cells, body fluids (e.g., urine and serum), as well as mouse tumor model through a new kind of fluorescent ATP nanoprobes, offering new powerful tools for the treatment of diseases related to abnormal fluctuation of ATP concentration.

Growth of Single-Walled Carbon Nanotubes with Controlled Structure: Floating Carbide Solid Catalysts.

Single-walled carbon nanotube (SWNT) horizontal arrays with specific chirality can be enriched using solid carbide catalysts on substrates. However, scale-up production by continuous loading of the solid catalysts onto the substrates is challenging. Described here is the preparation of a floating carbide solid catalyst (FSC) for the controlled growth of SWNTs. The FSC, titanium carbide (TiC) nanoparticle, was directly obtained in the carrier gas phase by decomposition and carbonization of the titanocene dichloride precursor at high temperature. By using the TiC nanoparticle FSC, both SWNT horizontal arrays and randomly distributed networks can be obtained. The chirality of the as-grown SWNTs were thermodynamically controlled to have fourfold symmetry. Further optimization of growth condition resulted in an abundance of (16,8) tubes with about a 74 % content. This FSC chemical vapor deposition (FSCCVD) method has potential for realizing mass growth of SWNTs with controlled structures.

Ti3 C2 MXene Paper for the Effective Adsorption and Controllable Release of Aroma Molecules.

Olfactory sensing and perception play an important role in people's daily lives and greatly affects senses, emotions, and behavior. In particular, the development of the controlled release of aroma enhances human's well-being and strengthens interactions with surroundings through olfactory display, especial when combined with visual and audial cues. Here, Ti3 C2 MXene plays a dual-function role as the adsorption site of aroma molecules and the heating source for the controlled release of aroma molecules. Due to abundant termination groups on the surface and the metallic nature, Ti3 C2 MXene provides abundant active sites for the interaction with aroma molecules; simultaneously, MXene can be electrically heated to thermally desorb the aroma molecules from the interaction sites. This approach eliminates the interface incompatibility issues between the heating source and the molecular encapsulation layer in conventional olfactory display system. This work presents the controlled release of the aroma molecule phenethyl alcohol (PA) using Ti3 C2 MXene paper. Ti3 C2 MXene paper serves as the adsorption material and a heating source that achieves 100 °C within 1 s. The relative amount of PA released reaches nearly 100% after 1 min of heating.

Intertwined Titanium Carbide MXene within a 3 D Tangled Polypyrrole Nanowires Matrix for Enhanced Supercapacitor Performances.

The exploration of the rational design and synthesis of unique and robust architectured electrodes for the high capacitance, rate capability, and stability of supercapacitors is crucial to the future of energy storage technology. Herein, an in situ synthesis of multilayered titanium carbide MXene tightly caging within a 3 D conducting tangled polypyrrole (PPy) nanowire (NW) network is proposed as an effective strategy to prevent the aggregation of MXene, profoundly enhancing the electrochemical performance of the supercapacitor. Owing to the beneficial effects of an ideal 3 D interconnected porous structure and high electrical conductivity, the obtained electrode exhibits fast charge and ion transport kinetics as well as full usage of active material. As expected, the 3 D Ti3 C2 Tx @PPY NW exhibits a specific capacitance five times higher than that of pristine MXene (610 F g-1 ), a good rate capability up to a current density of 25 A g-1 , and excellent stability with 100 % retention after 14 000 cycles at 4 A g-1 , outperforming the known state-of-the-art MXene-based supercapacitor. Our work provides a facile method for enhancing the performance of MXene-based energy storage devices.

A composite film prepared from titanium carbide Ti3C2Tx (MXene) and gold nanoparticles for voltammetric determination of uric acid and folic acid.

In this study, a solution-processing based galvanic deposition approach is described for in-situ deposition of gold nanoparticles (AuNP) on delaminated titanium Ti3C2Tx nanosheets under ultrasonication. The nanocomposite (AuNP@Ti3C2Tx) was placed on a glassy carbon electrode (GCE) and then applied to electrochemically with label-free, and simultaneously sense uric acid (UA), and folic acid (FA) at physiological pH. The modified GCE has attractive figures of merit: (i) The working potentials for UA and AA are well separated (+0.35 V and 0.70 V vs. Ag|AgCl); (ii) wide linear responses (from 0.03-1520 µM for UA and from 0.02-3580 µM for FA; (iii) good electrochemical sensitivities for both UA and FA (0.53 and 0.494 µAµM-1.cm-2, respectively), and (iv) detection limits of 11.5 nM (UA) and 6.20 nM (FA). The electrode exhibited good repeatability (RSD = 4.4%), acceptable reproducibility (RSD = 4.1%), and excellent stability (91.8% over one-month storage). The method was applied to analyze spiked serum samples, and modified GCE is shown appreciable recoveries (97.1-98.8% and 96.8-98.0% for UA, and FA, respectively). Graphical abstractA photograph (top left) of colloidal suspension of gold nanoparticles (AuNPs). They were grown on the delaminated titanium carbide Ti3C2Tx MXene nanosheet via galvanic displacement deposition method, and their corresponding a low-resolution transmission electron microscopy micrograph (top right) of AuNP@Ti3C2Tx. The graphical representation of AuNP@Ti3C2Tx drop-casted on glassy carbon electrode (GCE) (bottom left), and their voltammetric measurement were applied in the presence of both uric acid and folic acid with increasing the concentration of both analytes (bottom right).

Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance.

The delamination of titanium carbide sheets, an intriguing class of two-dimensional materials, has been critically dependent on the extraction of interlayer Al in acidic media, such as concentrated hydrofluoric acid (HF) or a mixture of hydrochloric acid (HCl) and a fluoride salt. Herein, we report an organic-base-driven intercalation and delamination of titanium carbide that takes advantage of the amphoteric nature of interlayer Al. The resulting aluminum-oxoanion-functionalized titanium carbide sheets manifested unusually strong optical absorption in the near-infrared (NIR) region with a mass extinction coefficient as high as 29.1 L g-1 cm-1 at 808 nm. Thus, the performance of this material is comparable or even superior to that of state-of-the-art photoabsorption materials, including gold-based nanostructures, carbon-based materials, and transition-metal dichalcogenides. Preliminary studies show that the titanium carbide sheets serve as efficient photothermal agents against tumor cells.

Interacting Carbon Nitride and Titanium Carbide Nanosheets for High-Performance Oxygen Evolution.

Free-standing flexible films, constructed from two-dimensional graphitic carbon nitride and titanium carbide (with MXene phase) nanosheets, display outstanding activity and stability in catalyzing the oxygen-evolution reaction in alkaline aqueous system, which originates from the Ti-N(x) motifs acting as electroactive sites, and the hierarchically porous structure with highly hydrophilic surface. With this excellent electrocatalytic ability, comparable to that of the state-of-the-art precious-/transition-metal catalysts and superior to that of most free-standing films reported to date, they are directly used as efficient cathodes in rechargeable zinc-air batteries. Our findings reveal that the rational interaction between different two-dimensional materials can remarkably promote the oxygen electrochemistry, thus boosting the entire clean energy system.

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been recognized as promising substitutes for current energy-storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long-life Li-S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid-liquid polysulfide interconversion and liquid-solid precipitation of lithium sulfides more than non-polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm-2 , the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance.

Charge polarization at a Au-TiC interface and the generation of highly active and selective catalysts for the low-temperature water-gas shift reaction.

Au atoms in contact with TiC(001) undergo significant charge polarization. Strong metal-support interactions make Au/TiC(001) an excellent catalyst for the low-temperature water-gas shift (WGS), with turnover frequencies orders of magnitude larger than those observed for conventional metal/oxide catalysts. DFT calculations indicate that the WGS reaction follows an associative mechanism with HOCO as a key intermediate.

Temperature Evolution of Composition, Thermal, Electrical and Magnetic Properties of Ti3C2Tx-MXene.

MXenes are a family of two-dimensional nanomaterials. Titanium carbide MXene (Ti3C2Tx-MXene), reported in 2011, is the first inorganic compound reported among the MXene family. In the present work, we report on the study of the composition and various physical properties of Ti3C2Tx-MXene nanomaterial, as well as their temperature evolution, to consider MXenes for space applications. X-ray diffraction, thermal analysis and mass spectroscopy measurements confirmed the structure and terminating groups of the MXene surface, revealing a predominant single OH layer character. The temperature dependence of the specific heat shows a Debye-like character in the measured range of 2 K-300 K with a linear part below 10 K, characteristic of conduction electrons of metallic materials. The electron density of states (DOS) calculations for Ti3C2OH-MXene reveal a significant DOS value at the Fermi level, with a large slope, confirming its metallic character, which is consistent with the experimental findings. The temperature dependence of electrical resistivity of the MXene samples was tested for a wide temperature range (3 K-350 K) and shows a decrease on lowering temperature with an upturn at low temperatures, where negative magnetoresistance is observed. The magnetoresistance versus field is approximately linear and increases its magnitude with decreasing temperature. The magnetization curves are straight lines with temperature-independent positive slopes, indicating Pauli paramagnetism due to conduction electrons.

Surface Decoration of TiC Nanocrystals onto the Graphite Anode Enables Fast-Charging Lithium-Ion Batteries.

To significantly reduce the charging time of commercial lithium-ion batteries (LIBs), it is essential to control the surface properties of graphite anodes because the charging process involves sluggish interfacial kinetics between graphite and the electrolyte. For the effective surface modification of graphite, herein we demonstrate the surface decoration with titanium carbide (TiC) nanocrystals onto graphite particles via a simple wet-coating process. The high electrical conductivity, low Li+ adsorption energy, and small surface diffusion barrier of the TiC nanocrystals facilitate fast Li+ adsorption and migration in the graphite surface by reducing the overpotential upon the charging process. The feasibility of the TiC nanocrystal-decorated graphite (TiC@AG) anode is thoroughly examined with an in-depth understanding of the interfacial reaction mechanism. Furthermore, the full-cell with a commercial cathode (LiNi0.8Co0.1Mn0.1O2) and TiC@AG anode demonstrates an impressive capacity retention (94.5%) after 300 cycles under fast-charging condition (3 C-charging and 1 C-discharging) without any sign of Li plating. The charging time of the TiC@AG full-cell was estimated at 16.2 min (80% of state of charge), which is substantially shorter than that of the artificial graphite full-cell. Our findings offer practical insights into the design principles of advanced graphite anodes, contributing to the realization of fast-charging LIBs.

Electrochemical Performance of Biocompatible TiC Films Deposited through Nonreactive RF Magnetron Sputtering for Neural Interfacing.

The efficacy of neural electrode stimulation and recording hinges significantly on the choice of a neural electrode interface material. Transition metal carbides (TMCs), particularly titanium carbide (TiC), have demonstrated exceptional chemical stability and high electrical conductivity. Yet, the fabrication of TiC thin films and their potential application as neural electrode interfaces remains relatively unexplored. Herein, we present a systematic examination of TiC thin films synthesized through nonreactive radio frequency (RF) magnetron sputtering. TiC films were optimized toward high areal capacitance, low impedance, and stable electrochemical cyclability. We varied the RF power and deposition pressure to pinpoint the optimal properties, focusing on the deposition rate, surface roughness, crystallinity, and elemental composition to achieve high areal capacitance and low impedance. The best-performing TiC film showed an areal capacitance of 475 µF/cm2 with a capacitance retention of 93% after 5000 cycles. In addition, the electrochemical performance of the optimum film under varying scanning rates demonstrated a stable electrochemical performance even under dynamic and fast-changing stimulation conditions. Furthermore, the in vitro cell culture for 3 weeks revealed excellent biocompatibility, promoting cell growth compared with a control substrate. This work presents a novel contribution, highlighting the potential of sputtered TiC thin films as robust neural electrode interface materials.

Multifunctional Aspects of Mechanical and Electromechanical Properties of Composites Based on Silicone Rubber for Piezoelectric Energy Harvesting Systems.

Energy harvesting systems fabricated from rubber composite materials are promising due to their ability to produce green energy with no environmental pollution. Thus, the present work investigated energy harvesting through piezoelectricity using rubber composites. These composites were fabricated by mixing titanium carbide (TiC) and molybdenum disulfide (MoS2) as reinforcing and electrically conductive fillers into a silicone rubber matrix. Excellent mechanical and electromechanical properties were produced by these composites. For example, the compressive modulus was 1.55 ± 0.08 MPa (control) and increased to 1.95 ± 0.07 MPa (6 phr or per hundred parts of rubber of TiC) and 2.02 ± 0.09 MPa (6 phr of MoS2). Similarly, the stretchability was 133 ± 7% (control) and increased to 153 ± 9% (6 phr of TiC) and 165 ± 12% (6 phr of MoS2). The reinforcing efficiency (R.E.) and reinforcing factor (R.F.) were also determined theoretically. These results agree well with those of the mechanical property tests and thus validate the experimental work. Finally, the electromechanical tests showed that at 30% strain, the output voltage was 3.5 mV (6 phr of TiC) and 6.7 mV (6 phr of MoS2). Overall, the results show that TiC and MoS2 added to silicone rubber lead to robust and versatile composite materials. These composite materials can be useful in achieving higher energy generation, high stretchability, and optimum stiffness and are in line with existing theoretical models.