Two-dimensional Transition Metal Carbides Research Articles

2D MXene Biomaterials for Catalytic Medical Applications.

In recent years, two-dimensional transition metal carbides, nitrides, and carbonitrides, termed as MXenes, have been widely applied in energy storage, photocatalysis and biomedicine owing to their unique physicochemical properties of large specific surface area, high electrical conductivity, excellent optical performance, good stability, etc. Moreover, due to their strong light absorption capacity in the first and second near-infrared bio-window, and their ability of being simply functionalized with multiple organic/inorganic materials, MXene biomaterials have shown great potential in the field of catalytic therapy. This review will summarize the common catalytic mechanism of MXene biomaterials and their latest applications in catalytic medicine such as tumor therapy, antibacterial and anti-inflammatory, and present the current challenges and opportunities in clinical translation for future development to promote the advancement of MXene biomaterials in the field of catalytic medicine.

Catalyst breakthroughs in methane dry reforming: Employing machine learning for future advancements

Rising levels of atmospheric carbon dioxide (CO2) and methane (CH4) have sparked the interest of researchers in resolving this issue. Various technologies have been utilized such as dry reformation of methane (DRM), that turns these greenhouse gases (GHGs) into syngas. Numerous studies have been done in recent years to produce efficient and competitive catalysts for DRM. However, a “state of the art” review is still required due to a lack of literature on improvements and scalability of robust catalytic systems. This study aims to evaluate recent advancements in catalyst formulations, their activities, stability, and selectivity. We have discussed a variety of materials, including Metal-Organic Frameworks (MOF), a type of two-dimensional transition metal carbides and nitrides (MXene), reducible and irreducible metal oxides, transition metal oxides, zeolites, carbon, and biochar-based catalysts, which are responsible for improving the effectiveness of the DRM process. Furthermore, machine learning (ML) approaches are highlighted for their potential in catalyst design and optimization, providing increased accuracy and efficiency. This review highlights major enhancements to the DRM method, which result in higher hydrogen yield and catalyst stability. Novel catalysts have been created to tackle crucial problems including coking and sintering, which are necessary to progress commercialization. To ensure successful commercial application, future research should concentrate on finding catalysts with excellent features that are also economically viable. This study provides a significant resource for future catalyst development and promotes greater cooperation between academic and commercial communities.

Nitrogen-doping engineering in two-dimensional transition-metal carbides for electrochemical hydrogen evolution

Developing electrocatalysts with the trade-off between overall electrocatalytic performance and economic cost towards hydrogen evolution reaction (HER) is crucial for producing green hydrogen fuels. Although theoretical studies have reported the potential of two-dimensional (2D) MXenes for the HER, their electrocatalytic performance is still unsatisfactory for the particular application due to their low intrinsic active and MXene stacking. To address this problem, we herein modify the electronic structure and increase the interlayer spacing between 2D Ti3C2Tx MXenes through ammonia (NH3)-assisted hydrothermal approach. The effect of synthesis temperature on the nitrogen doping mechanism and electrochemical behaviors for the HER is systemically explored. As a result, the nitrogen (N)-doped Ti3C2Tx MXene fabricated at 160 °C exhibits the highest HER activity among all 2D N-doped Ti3C2Tx nanosheets with the overpotential/Tafel slope of 186.91 mVRHE/115.94 mVRHE dec−1 in an acidic solution. Due to the synergistic contribution of nitrogen, the N-doped Ti3C2Tx-160 °C has mass activity of 337.95 mA mg−1 at 0.3 VRHE, being 27.50-fold higher than that of pristine Ti3C2Tx. This work indicated that heteroatom doping is a facile but efficient approach for modulating the electronic structure and intrinsic activity of MXene-based materials for electrochemical reactions.

Strain-tunable electronic and optical absorption in the MXenes nanolayers: A DFT approach

Computational simulations using density functional theory (DFT) were performed to show that biaxial strain engineering within the range of −8% to +8% is an effective method for modifying the fundamental properties of two-dimensional (2D) transition metal carbides (MXenes). In this work, we computationally explored the effect of both compressive (0 to −8%) and tensile (0 to +8%) strain on the structural, electronic, and optical properties of M2CO2 MXenes (M = Ti, Zr, Sc and Hf) nanolayers. When compressive strains are applied, the charge transfer between layers increases because of decreased interlayer coupling. Conversely, tensile strains result in the opposite behavior. The strain-tunable band gap effect in Mo2CO2 nanolayers is revealed by investigating the valence band maximum (VBM) and conduction band minimum (CBM) in the band structure under biaxial strain. It is observed that the indirect-to-direct band gap transition occurs when the tensile strain is applied to Sc2CO2 and Ti2CO2 nanolayers. In most samples, the energy gap increases with an increase in tensile strain and decreases with an increase in compressive strain. The optical absorption coefficient indicates considerable absorption in the visible to ultraviolet (UV) region. Additionally, the absorption can be influenced by biaxial strains. In particular, under compressive strains (−8%) and Z-polarized light, the UV absorption peak in Hf2CO2, Ti2CO2, and Zr2CO2 reaches 68 %, 78 %, and 113 % respectively. The results indicate that these M2CO2 MXenes nanolayers will have significant potential for applications in tunable optoelectronic devices.

Advancements in Ti3C2Tx MXene Stability: Synergistic Antioxidant Strategies and Their Impact on Long-Lasting Flexible Sensors.

Two-dimensional (2D) transition metal carbides (Ti3C2Tx MXene) have demonstrated substantial application potential across various fields, owing to their excellent metallic conductivity and solution processability. However, the rapid oxidation of Ti3C2Tx in aqueous environments, leading to a loss of stability within mere days, poses a significant obstacle for its practical applications. Herein, we introduce an antioxidant strategy that combines free radical scavenging with surface passivation, culminating in the design and synthesis of imidazolium-based ionic liquids (ILs) incorporating siloxane groups. By deploying a straightforward hydrolysis-addition reaction, we successfully fabricated IL-modified Ti3C2Tx materials (Ti3C2Tx-IL). The Ti3C2Tx -IL not only displayed exceptional conductivity exceeding 3.85 × 104 S/m and hydrophilic contact angles below 45° but also showcased its superior chemical stability and antioxidation mechanisms through various analyses, including visual color change experiments, spectroscopic and energy spectrum characterization, free radical scavenging tests, and density-functional-theory-based molecular simulations. Furthermore, when utilized as a conductive filler in the fabrication of a poly(vinyl alcohol)/nanocellulose fiber (PVA/CNF) composite hydrogel (PCMIL), the resultant sensors exhibited remarkable mechanical performance with up to 535% strain, 1.59 MPa strength, 4.35 MJ/m3 toughness, and a conductivity of 3.40 mS/cm, as well as a high sensitivity gauge factor of 3.3. Importantly, even after 45 days of storage, the PCMIL retained most of its functionalities, demonstrating superior performance in human-machine interaction applications compared to hydrogels made from unmodified Ti3C2Tx. This research establishes a robust antioxidant protection strategy for Ti3C2Tx, offering substantial technical reinforcement for its prospective applications in the realm of flexible electronics and sensing technologies.

Highly sensitive MXene-based voltammetric sensor for nanomolar clozapine detection

Clozapine is vital for managing schizophrenia and other psychiatric disorders. As a potent medication with risks of severe side effects, accurate detection ensures effective treatment monitoring, patient safety, and optimization of therapeutic outcomes. Herein, niobium carbide two-dimensional transition metal carbides (Nb2CTx MXene) was prepared by etching niobium aluminum carbide (Nb2AlC), which was next partially oxidized by a hydrothermal method to niobium oxide (Nb2O5)/Nb2CTx and ultrasonically bound to carboxylated multi-walled carbon nanotubes (MWCNTs-COOH). It was modified onto a glassy carbon electrode for the detection of the antipsychotic drug clozapine ingested by humans. The morphology and electrochemical properties of MXene-based nanocomposite electrode were verified by scanning electron microscopy, X-ray diffractometry, Raman, cyclic voltammetry and electrochemical impedance characterization methods. The results showed that electrode responded well to clozapine solutions, with good linearity (R2 = 0.9979 and 0.9995) of the peak currents with clozapine concentrations (0.01–1.0 μM and 1.0–10.0 μM) and that this sensor had good immunity, repeatability, reproducibility and stability. The limit of detection was 8.38 nM and the recovery was 92.5 % ~ 106.5 % in real serum and urine samples. The MXene-based sensors offer excellent analytical performance and hold promise for cost-effective generalisation to the detection of nanomolar clozapine in a variety of clinical applications.

MXene Synthesis and Carbon Capture Applications: Mini-Review.

MXenes, a class of two-dimensional transition metal carbides, nitrides, and carbonitrides, have garnered significant attention due to their remarkable potential for energy storage, electrocatalysis, and gas separation applications. The fabrication processes of MXene involve building up the MXene structure from constituent elements and the selective elimination of M-A bonds from the precursor MAX. However, considerable efforts are still required to design and develop efficient MXene-based technologies. This review article aims to briefly analyse the synthesis methods employed for MXene production, ranging from direct synthesis and conventional chemical wet etching approach to the more recent molten salt etching technique. The review highlights the advancements made in achieving precise control over the terminal groups, which is paramount for tailoring the properties of MXenes for specific applications. Furthermore, the potential of MXene-based materials for carbon capture applications, particularly in developing advanced adsorbents, is emphasized. The in-depth examination of MXene synthesis techniques and their implications for carbon capture applications provides a solid foundation for developing and optimizing these promising materials.

Effects of Concentration and Surface Termination on the Workfunction of Ti3C2X2 MXene (X=F,Cl,O,OH)

Titanium carbide (Ti3C2), belonging to the MXene family, has become a focal point of research due to its exceptional electronic and structural properties. As a two-dimensional transition metal carbide, Ti3C2 exhibits promising potential in a variety of applications, ranging from electronic devices to energy storage. Among the key parameters influencing its electronic behavior, the work function plays a pivotal role. This study aims to elucidate the intricate relationship between concentration, surface termination, and the work function of Ti3C2X2 through first-principles density functional theory (DFT) calculations. First-principles DFT calculations were employed to investigate the electronic structure of Ti3C2X2, focusing on the influence of varying concentrations of surface functional groups. Hydroxyl (-OH), oxygen (-O), chlorine (-Cl), and fluoride (-F) terminations were specifically chosen as representative functional groups for their prevalence in experimental studies and potential technological applications. These calculations provide a quantum-level understanding of the electronic properties and behaviors of Ti3C2 under different surface conditions. Our results indicate a notable sensitivity of the work function of Ti3C2 to changes in both concentration and the type of surface termination. The presence of functional groups induces charge redistribution within the MXene layers, significantly impacting the overall electronic landscape. The variation in charge distribution directly correlates with changes in the work function, illustrating the dynamic nature of Ti3C2 in response to surface modifications. Furthermore, an in-depth analysis of the correlation between concentration, surface termination, and the energetics of charge transfer at the Ti3C2 surface provides valuable insights. The interplay between these factors reveals intricate mechanisms that govern the observed variations in the work function. The concentration-dependent charge transfer at the surface serves as a key determinant, emphasizing the importance of carefully tailoring the composition to achieve desired electronic properties. The understanding gained from this study has significant implications for the tailored design and utilization of Ti3C2 in various technological applications. By manipulating concentration and surface termination, researchers and engineers can fine-tune the work function to meet specific requirements in electronic devices, sensors, and energy storage systems. This level of control over electronic properties enhances the versatility and applicability of Ti3C2 in emerging technologies. In conclusion, our investigation highlights the critical roles of concentration and surface termination in modulating the work function of Ti3C2. The pronounced sensitivity of this parameter to surface modifications underscores the need for a comprehensive understanding of the underlying electronic mechanisms. By elucidating the interplay between concentration, surface termination, and charge transfer, this study provides valuable insights that pave the way for the strategic design and implementation of Ti3C2 in advanced technological applications. The ability to fine-tune electronic properties opens new avenues for exploiting the full potential of Ti3C2 in diverse fields, driving innovation and progress in materials science and technology.

(Invited) Insights into the Electrocatalytic Behavior of Mxenes

The continued rise in global energy consumption, along with the associated environmental hazards, pose a significant risk to our society’s infrastructure unless the main source is changed. Electrocatalysis involving hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), and oxygen reduction reaction (ORR), provide a pathway for energy storage and conversion due to their enhanced environmental friendliness and efficient energy input compared to their thermocatalytic counterparts. Currently, the state-of-the-art electrocatalysts suffer from scarcity and high cost. MXenes, a novel family of two-dimensional (2D) transition metal carbide and nitride materials, show potential as cost-efficient and highly abundant electrocatalysts with limited knowledge on their electrocatalytic mechanisms. This is especially true when considering the often-overlooked nitride family of MXenes. Herein, we investigate the electrocatalytic performance of a Ti2N nitride MXene under different electrocatalytic conditions. The effect of surface phenomena is investigated through manipulation of the surface passivation layer, as evidenced by Raman and Fourier-transform infrared (FTIR) spectroscopies, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Successful decoupling of the bulk and surface phenomena is achieved through Raman laser power attenuation. Under acidic medium, the surface reactivity towards HER is poor but the bulk reactivity for NRR is favored, making it an optimal NRR catalyst. Under alkaline medium, the surface reactivity of the pristine Ti2N MXene for ORR is high, but also leads to surface passivation and thus hinders the electrocatalytic activity. Overall, these results provide fundamental insights into future optimization strategies of the Ti2N nitride MXene, along with other MXene electrocatalysts, towards electrocatalytic applications.

(Invited) Tunable Chemistry of 2D Carbide Mxenes for Hydrogen Evolution Reaction

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) are a large family of earth-abundant materials with more than forty compositions synthesized since 2011, such as Ti2CT x , Mo2CT x , Nb2CT x , Ti3C2T x , Mo2TiC2Tx, and Mo2Ti2C3T x . MXenes have emerged as promising candidates for catalytic energy storage and conversion because their 2D surfaces are electrochemically active combined with MXenes’ hydrophilicity, high electrical conductivity, and affinity to bond to molecules and nanomaterials to form hybrid structures. MXenes electrochemical properties can be tuned by the control of multiple variables: in the MXene formula of M n +1X n T x , the transition metals (M) can be any of the groups 4, 5, 6 of the periodic table or their combination, X can be carbon, nitrogen, or a solid solution of both, surface terminations (T x ) can be any of the group 16 and 17, and the ‘n’ (MXene 2D flake thicknesses) can be 1 to 4. In this talk, we will discuss the control of MXene transition metals, their thicknesses, and surfaces to tune their electrocatalytic behavior. Specifically, we present a systematic study of 20 different MXenes, including novel compositions such as W2TiC2T x and Mo2Nb2C3T x and high-entropy MXenes, and discuss how we achieve low overpotential for hydron evolution reaction (as low as ~160 mV).

Elucidating the Interactions between Different Transition Metal Cations and Ti3C2Tx MXene through Intercalation Method for Electrochemical Applications

MXenes, are a family of two-dimensional (2D) transition metal carbides, nitrides and/ or carbonitrides.[1] The intercalation of different metal cations and organic molecules into MXene for tuning MXenes’ electronic and electrochemical properties have been widely reported.[2] [3] [4] However, transition metals (TMs) which have distinct electrochemical behaviors[5] [6] have not been explored in the literature of MXenes’ intercalation. Therefore, we herein compared the intercalation effects of different TM cations on Ti3C2Tx, for offering a general insight on the influences of multi-valent, redox-active TMs on MXenes. In particular, the changes on the physiochemical and electrochemical properties of MXenes were investigated using different in-situ and ex-situ methods, for a better understanding on the interfacial interactions of TM cations and MXenes in the confined environment of MXenes’ multilayer structures. This work serves as a foundation for the fine-tuning of MXenes’ properties by utilizing a variety of TM cations intercalation for different electrochemical systems.[1] B. Anasori, M. R. Lukatskaya, Y. Gogotsi, Nature Reviews Materials 2017, 2, 16098.[2] M. R. Lukatskaya, O. Mashtalir, E. Ren Chang, Y. Dall’Agnese, P. Rozier, L. Taberna Pierre, M. Naguib, P. Simon, M.W. Barsoum, Y. Gogotsi, Science 2013, 341, 1502-1505.[3] J. Li, H. Wang, X. Xiao, Energy & Environmental Materials 2020, 3, 306-322[4] M. Ghidiu, S. Kota, J. Halim, A. W. Sherwood, N. Nedfors, J. Rosen, V. N. Mochalin, M. W. Barsoum, Chemistry of Materials 2017, 29, 1099-1106.[5] D. Göhl, H. Rueß, M. Pander, A. R. Zeradjanin, K. J. J. Mayrhofer, J. M. Schneider, A. Erbe, M. Ledendecker, Journal of The Electrochemical Society 2020, 167, 021501.[6] M. Esmaeilirad, A. Baskin, A. Kondori, A. Sanz-Matias, J. Qian, B. Song, M. Tamadoni Saray, K. Kucuk, A. R. Belmonte, P. N. M. Delgado, J. Park, R. Azari, C. U. Segre, R. Shahbazian-Yassar, D. Prendergast, M. Asadi, Nature Communications 2021, 12, 5067.

Shrinking Lithium-Ion Batteries by Replacing Metal Current Collectors with MXene Films

The demand for high-performance energy storage devices has been rapidly increasing due to the growing need for renewable energy integration and portable electronics. Traditional lithium-ion batteries have become the preferred choice for numerous applications due to their impressive energy density, but they are reaching limitations of capacity. At the cell level, around 25 w% consists of passive components like current collectors, conductive additives, binders, and separators. Especially, copper (Cu) and aluminum (Al) foils have been commonly used as current collectors for the anode and cathode in lithium-ion batteries (LIBs), contributing around 7 wt% and 8 wt%, respectively, to the overall weight. Despite constituting a considerable portion of the battery, these passive components often receive less attention in the development of high-power batteries. In recent years, the focus has been on decreasing the thickness of these metal current collectors and developing lightweight alternative materials to enhance energy efficiency to potentially boost the performance metrics of a Li-ion battery cell to boost the performance metrics of a Li-ion battery cell. MXenes, a family of two-dimensional transition metal carbides, nitrides, and carbonitrides emerge as a promising solution to address this limitation. In particular, Ti3C2T x MXene possesses a 2D morphology with excellent electrical conductivity (up to 20,000 S/cm), high surface area, good mechanical properties, and hydrophilicity. These attributes, coupled with ease of processing, make it very suitable for battery passive components. In this study, we focus on replacing the conventional copper current collector with thinner MXene film current collectors for high-mass loading graphite anode electrodes. Our results show improved capacities and rate performances of electrode materials using Ti3C2T x MXene current collectors while also reducing electrode weight and thickness. The electrode-level gravimetric capacity significantly increased by 98.5 mAh g-1 (from 140 mAh g-1 for Cu@graphite to 238.5 mAh g-1 for MXene@graphite). The areal and volumetric capacities increased as well. This study highlights the potential of MXene current collectors in improving the performance of lithium-ion batteries, paving the way for more efficient and lightweight energy storage solutions.

Theoretical Investigation of a Novel Two-Dimensional Non-MXene Mo3C2 as a Prospective Anode Material for Li- and Na-Ion Batteries.

A new two-dimensional (2D) non-MXene transition metal carbide, Mo3C2, was found using the USPEX code. Comprehensive first-principles calculations show that the Mo3C2 monolayer exhibits thermal, dynamic, and mechanical stability, which can ensure excellent durability in practical applications. The optimized structures of Lix@(3×3)-Mo3C2 (x = 1-36) and Nax@(3×3)-Mo3C2 (x = 1-32) were identified as prospective anode materials. The metallic Mo3C2 sheet exhibits low diffusion barriers of 0.190 eV for Li and 0.118 eV for Na and low average open circuit voltages of 0.31-0.55 V for Li and 0.18-0.48 V for Na. When adsorbing two layers of adatoms, the theoretical energy capacities are 344 and 306 mA h g-1 for Li and Na, respectively, which are comparable to that of commercial graphite. Moreover, the Mo3C2 substrate can maintain structural integrity during the lithiation or sodiation process at high temperature. Considering these features, our proposed Mo3C2 slab is a potential candidate as an anode material for future Li- and Na-ion batteries.

Hierarchical porous microrod In2O3@C@Ti3C2TX composite anode for high-performance lithium-ion batteries

In2O3, employed as an anode, demonstrates exceptional capacity in lithium-ion batteries (LIBs). Nonetheless, its propensity for significant volume expansion results in internal fracturing and reorganization. Two-dimensional double transition metal carbides and nitrides (MXenes), characterized by unique out-of-plane metal atom ordering, exhibit promising electrical properties due to their chemical versatility and intricate structure. However, MXenes' tendency to aggregate or stack into lamellar structures impedes their practical energy storage application. To address these issues, a hierarchical porous microrods In2O3@C@Ti3C2TX (HPMR-In2O3@C@Ti3C2TX) composite anode material was synthesized through electrostatic self-assembly of MIL-68 (In) and Ti3C2TX, followed by carbonization. This synthesis produced continuous one-dimensional microrods with hierarchical porous channels in HPMR-In2O3@C, offering a substantial specific surface area, numerous Li+ storage sites, and enhanced charge transfer rates. Moreover, the interlayer space within Ti3C2TX acts as an electrolyte reservoir, facilitating comprehensive electrochemical reactions and accommodating volume changes during charge-discharge cycles. Consequently, the HPMR-In2O3@C@Ti3C2TX anode exhibited remarkable properties, including a high initial discharge specific capacity of 1406 mAh g-1 at 0.1 C, outstanding cycling performance, and superior rate performance. This research presents a promising direction for the advancement of high-performance anode materials for lithium-ion batteries.

Mechanism of the Terahertz Wave-MXene Interaction and Surface/Interface Chemistry of MXene for Terahertz Absorption and Shielding.

ConspectusOver the past two decades, terahertz (THz) technology has undergone rapid development, driven by advancements and the growing demand for THz applications across various scientific and technological domains. As the cornerstone of THz technology, strong THz-matter interactions, especially realized as high THz intrinsic absorption in nanometer-thick materials, play a highly important role in various applications including but not limited to THz absorption/shielding, detection, etc. The rigorous electromagnetic theory has posited a maximum intrinsic absorption of 50% for electromagnetic waves by thin films, and the succinct impedance matching condition has also been formulated to guide the design of highly intrinsically absorbing materials. However, these theories face challenges when applied to the THz spectrum with an ultrabroad bandwidth. Existing thin films typically achieve a maximum intrinsic absorption within a narrow frequency range, significantly limiting the performance of THz absorbers and detectors. To date, both theoretical frameworks and experimental solutions are lacking in overcoming the challenge of achieving broadband maximum intrinsic absorption in the THz regime.In this Account, we describe how two-dimensional (2D) transition-metal carbide and/or nitride (MXene) films with nanometer thickness can realize the maximum intrinsic absorption in the ultrabroad THz band, which successfully addresses the forementioned longstanding issue. Surprisingly, traditional DC impedance matching theory fails to explain this phenomenon, while we instead propose a novel theory of AC impedance matching to provide a satisfactory explanation. By delving into the microscopic transport behavior of free electrons in MXene, we discover that intraflake transport dominates terahertz conductivity under THz wave excitation, while interflake transport primarily dictates DC conductivity. This not only elucidates the significant disparities between DC and AC impedance in MXenes but also underscores the suitability of AC impedance matching for achieving broadband THz absorption limits. Furthermore, we identify a high electron concentration and short relaxation time as crucial factors for achieving broadband maximum absorption in the THz regime. Although approaching the THz intrinsic absorbing limits, it still faces hurdles to the use of MXene in practical applications. First, diverse and uncontrollable terminations exist on the surface of MXene stemming from the synthesis process, which largely influence the electron structure and THz absorbing property of MXene. Second, MXene suffers from poor stability in the presence of oxygen and water. To address the above issues, we have undertaken distinctive works to precisely control the terminations and suppress the oxidation of MXene even at high temperature through surface and interface chemistry, such as low-temperature Lewis basic halide treatment and building a Ti3C2Tx/extracted bentonite (EB) interface. For practical application consideration, we proposed a copolymer-polyacrylic latex (PAL)-based MXene waterborne paint (MWP) with a strong intermolecular polar interaction between MWP and the substrate provided by the cyano group in PAL. This not only has strong THz EMI shielding/absorption efficiency but also can easily adhere to various substrates that are commonly used in the THz band. These studies may have significant implications for future applications of MXene nanofilms in THz optoelectronic devices.

Rational design of MXene-based vacancy-confined single-atom catalyst for efficient oxygen evolution reaction

Two-dimensional transition metal carbides (MXenes) have been demonstrated to be promising supports for single-atom catalysts (SACs) to enable efficient oxygen evolution reaction (OER). However, the rational design of MXene-based SACs depends on an experimental trial-and-error approach. A theoretical guidance principle is highly expected for the efficient evaluation of MXene-based SACs. Herein, high-throughput screening was performed through first-principles calculations and machine learning techniques. Ti3C2(OH)x, V3C2(OH)x, Zr3C2(OH)x, Nb3C2(OH)x, Hf3C2(OH)x, Ta3C2(OH)x, and W3C2(OH)x were screened out based on their excellent stability. Zn, Pd, Ag, Cd, Au, and Hg were proposed to be promising single atoms anchored in MXenes based on cohesive energy analysis. Hf3C2(OH)x with a Pd single atom delivers a theoretical overpotential of 81 mV. Both moderate electron-deficient state and high covalency of metal–carbon bonds were critical features for the high OER reactivity. This principle is expected to be a promising approach to the rational design of OER catalysts for metal-air batteries, fuel cells, and other OER-based energy storage devices.

Identifying the presence of subsurface oxygen on the Ti3C2 MXene using H2O as a probe molecule: A DFT study

Oxycarbide MXenes are two-dimensional transition metal carbides with subsurface oxygen content within their carbon layers. Substitutional oxygen atoms are thermodynamically very stable, impose virtually no lattice strain on their surroundings, and do not change the metallic behaviour of Ti3C2, making them very difficult to detect experimentally. Here, water is suggested as a probe to identify subsurface oxygen atoms on the H2-exposed and heat pre-treated Ti3C2 MXene. Independently of the oxygen concentration, density functional theory calculations show that water can adsorb near subsurface oxygen atoms as well as on stoichiometric Ti3C2 regions of the material and is deemed appropriate for identifying substitutional oxygen defects on Ti3C2 through frequency analysis. The calculated stretching mode of water increases by at least 67 cm−1 in the presence of subsurface oxygen, allowing the experimental detection of this defect, even at the lowest concentration considered, i.e., a replacement of 3 % of carbon by oxygen atoms.

A first-principles study of the lithium storage properties of transition metal doped TM-Ti2CO2 (TM=Sc, V, Cr, Mn, Fe, Co, Ni and Cu)

Two-dimensional transition metal carbides, known as MXenes, have garnered significant interest for their potential applications in lithium-ion batteries anode materials, owing to their distinctive properties. Doping, a prevalent method for material modification, involves the substitution of metal atoms within MXenes with other elements to modulate material properties. Given that MXenes inherently contain transition metals, doping with additional transition metals presents an optimal approach for enhancing their performance. In this study, we investigated the effect of doping eight transition metals (Sc, V, Cr, Mn, Fe, Co, Ni, Cu) onto Ti2CO2, aiming to elucidate their impact on the lithium storage properties of the material. Our findings reveal that the introduction of different dopant atoms induces changes in the d-band center of the material, consequently influencing the adsorption energy of lithium ions on the MXene surface in a nearly linear fashion. What’s more, doping with Sc, Cr, and Mn atoms results in an elevation of the migration energy, while doping with Fe, Co, Ni, and Cu atoms leads to a notable increase in the open circuit voltage (OCV). Remarkably, only V atom doping demonstrates an optimal combination of suitable adsorption energy, OCV (0.66 V), and minimal diffusion energy (0.11 eV). These results underscore the significance of transition metal doping in tailoring the lithium storage properties of MXene-based anode materials, offering insights for the design and optimization of next-generation lithium-ion batteries.

Nb2C and Nb2CO2 MXenes as Anodes in Li-Ion Batteries: A Comparative Study by First-Principles Calculations.

The new generation of Li-ion batteries is based on integrating 2D materials into the electrodes to increase the energy density while reducing the charging time and size. The two-dimensional transition metal carbide or nitride (MXene) materials offer ideal electronic properties, such as metallic behavior, low energy barriers for Li-ion diffusion, and structural stability. This study focuses on Nb2C and Nb2CO2 MXenes, which have shown promising Li-storage capacity, especially the oxidized phase. By using density functional theory (DFT) and thermodynamic criteria, we studied the Li intercalation process in both MXenes. The results show that the Li intercalation process in the oxidized phase is more stable. Also, the Li diffusion barriers are 35 and 250 meV for the bare and oxidized phase, due to the strong interaction between Li ions and O functional groups. Nb2C and Nb2CO2 MXenes deliver a maximum gravimetric theoretical capacity of 275 and 233.26 mA h/g, respectively, with a stable performance.

Tailoring the ion storage of MXene by aramid nanofibers towards self-standing electrodes for flexible solid-state supercapacitors

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) are a class of 2D nanomaterials that can offer excellent properties for high-performance supercapacitors. Nevertheless, irreversible restacking of MXene sheets decreases the interlayer spacing, which inhibits the ion intercalation between the MXene nanosheets and finally deteriorates the electrochemical performance of supercapacitors. Herein, aramid nanofibers (ANFs) are mixed with Ti3C2T x MXene to prepare MXene/ANFs composite films. The restacking of MXene sheets is inhibited by the electrostatic repulsion between ANFs and MXene. The ANFs act as intercalation agents to increase the interlayer spacing of the composite films, which can improve the ion storage ability of supercapacitors. Furthermore, the ANFs enhance the mechanical strength of the composite films due to the strong hydrogen bonding interaction and nanomechanical interlocking between ANFs and MXene, endowing the composite films with self-standing property. The resultant composite films are used as electrodes for flexible solid-state supercapacitors to achieve high specific capacitance (996.5 mF cm−2 at 5 mV s−1) and outstanding cycling stability. Thus, this work provides a potential strategy to regulate the properties of 2D nanomaterials, which may expand the application of them in energy storage, ionic separation, osmotic energy conversion and beyond.