Extraordinary Structural Reconstruction of Nanolaminated Ta2FeC MAX Phase for Enhanced Oxygen Evolution Performance.

Renewable energy technologies, such as water splitting, heavily depend on the oxygen evolution reaction (OER). Nanolaminated ternary compounds, referred to as MAX phases, show great promise for creating efficient electrocatalysts for OER. However, their limited intrinsic oxidative resistance hinders the utilization of conductivity in Mn+1Xn layers, leading to reduced activity. In this study, a method is proposed to improve the poor inoxidizability of MAX phases by carefully adjusting the elemental composition between Mn+1Xn layers and single-atom-thick A layers. The resulting Ta2FeC catalyst demonstrates superior performance compared to conventional Fe/C-based catalysts with a remarkable record-low overpotential of 247 mV (@10 mA cm-2) and sustained activity for over 240 h. Notably, during OER processing, the single-atom-thick Fe layer undergoes self-reconstruction and enrichment from the interior of the Ta2FeC MAX phase toward its surface, forming a Ta2FeC@Ta2C@FeOOH heterostructure. Through density functional theory (DFT) calculations, this study has found that the incorporation of Ta2FeC@Ta2C not only enhances the conductivity of FeOOH but also reduces the covalency of Fe─O bonds, thus alleviating the oxidation of Fe3+ and O2-. This implies that the Ta2FeC@Ta2C@FeOOH heterostructure experiences less lattice oxygen loss during the OER process compared to pure FeOOH, leading to significantly improved stability. These results highlight promising avenues for further exploration of MAX phases by strategically engineering M- and A-site engineering through multi-metal substitution, to develop M2AX@M2X@AOOH-based catalysts for oxygen evolution.

Dual-Phase Structure through Selective Etching of the Double A-Element MAX Phase in Lewis Acidic Molten Salts.

Two-dimensional (2D) MXene materials with innovative properties and versatile applications have gained immense popularity among scientists. The green and environmentally friendly Lewis acid salt etching route has opened up immense possibilities for the advancement of 2D MXene materials. In this study, we precisely etched the Al element from the double A-element MAX phases Ti2(SnyAl1-y)C by employing Lewis molten salt guided by redox potentials. This approach led to the discovery of a novel Ti2SnyCClx dual-phase structure consisting of Ti2SnC and Ti2CClx. We then established that the etching of the MAX phase via Lewis acid salt is facilitated by the oxidation of M-site elements, with the MX sublayer acting as an electron transmission conduit to enable the oxidation of A-site elements. This work is dedicated to unraveling the underlying mechanisms governing the etching processes using Lewis molten salt, thereby contributing to a more profound comprehension of these innovative etching routes.

Regulating the Electronic Structure of MAX Phases Based on Rare Earth Element Sc to Enhance Electromagnetic Wave Absorption.

MAX phases are highly promising materials for electromagnetic (EM) wave absorption because of their specific combination of metal and ceramic properties, making them particularly suitable for harsh environments. However, their higher matching thickness and impedance mismatching can limit their ability to attenuate EM waves. To address this issue, researchers have focused on regulating the electronic structure of MAX phases through structural engineering. In this study, we successfully synthesized a ternary MAX phase known as Sc2GaC MAX with the rare earth element Sc incorporated into the M-site sublayer, resulting in exceptional conductivity and impressive stability at high temperatures. The Sc2GaC demonstrates a strong reflection loss (RL) of -47.7 dB (1.3 mm) and an effective absorption bandwidth (EAB) of 5.28 GHz. It also achieves effective absorption of EM wave energy across a wide frequency range, encompassing the X and Ku bands. This exceptional performance is observed within a thickness range of 1.3 to 2.1 mm, making it significantly superior to other Ga-MAX phases. Furthermore, Sc2GaC exhibited excellent absorption performance even at elevated temperatures. After undergoing oxidation at 800 °C, it achieves a minimum RL of -28.3 dB. Conversely, when treated at 1400 °C under an argon atmosphere, Sc2GaC demonstrates even higher performance, with a minimum RL of -46.1 dB. This study highlights the potential of structural engineering to modify the EM wave absorption performance of the MAX phase by controlling its intrinsic electronic structure.

Biomass-Based Shape-Stabilized Composite Phase-Change Materials with High Solar-Thermal Conversion Efficiency for Thermal Energy Storage.

To alleviate the increasing energy crisis and achieve energy saving and consumption reduction in building materials, preparing shape-stabilized phase-change materials using bio-porous carbon materials from renewable organic waste to building envelope materials is an effective strategy. In this work, pine cone porous biomass carbon (PCC) was prepared via a chemical activation method using renewable biomaterial pine cone as a precursor and potassium hydroxide (KOH) as an activator. Polyethylene glycol (PEG) and octadecane (OD) were loaded into PCC using the vacuum impregnation method to prepare polyethylene glycol/pine cone porous biomass carbon (PEG/PCC) and octadecane/pine cone porous biomass carbon (OD/PCC) shape-stabilized phase-change materials. PCCs with a high specific surface area and pore volume were obtained by adjusting the calcination temperature and amount of KOH, which was shown as a caterpillar-like and block morphology. The shape-stabilized PEG/PCC and OD/PCC composites showed high phase-change enthalpies of 144.3 J/g and 162.3 J/g, and the solar-thermal energy conversion efficiencies of the PEG/PCC and OD/PCC reached 79.9% and 84.8%, respectively. The effects of the contents of PEG/PCC and OD/PCC on the temperature-controlling capability of rigid polyurethane foam composites were further investigated. The results showed that the temperature-regulating and temperature-controlling capabilities of the energy-storing rigid polyurethane foam composites were gradually enhanced with an increase in the phase-change material content, and there was a significant thermostatic plateau in energy absorption at 25 °C and energy release at 10 °C, which decreased the energy consumption.

Two-Dimensional MXenes Derived from Medium/High-Entropy MAX Phases M2 GaC (M = Ti/V/Nb/Ta/Mo) and their Electrochemical Performance.

Two-dimensional (2D) transition metal carbides and/or nitrides, MXenes, are prepared by selective etching of the A-site atomically thin metal layers from their MAX phase precursors. High entropy MXenes, the most recent subfamily of MXenes, are in their infancy and have attracted great interest recently. They are currently synthesized mainly through wet chemical etching of Al-containing MAX phases, while various MAX phases with A-sites elements other than Al have not been explored. It is important to embody non-Al MAX phases as precursors for the high entropy MXenes synthesis to allow for new compositions. In this work, it is reported on the design and synthesis of Ga-containing medium/high entropy MAX phases and then their corresponding medium/high entropy MXenes. Gallium atomic layer etching is carried out using a Lewis acid molten salt (CuCl2). The as-prepared (Ti1/4 V1/4 Nb1/4 Ta1/4 )2 CTx exhibits a Li+ specific capacity of ≈400 mAh g-1 . For (Ti1/5 V1/5 Nb1/5 Ta1/5 Mo1/5 )2 CTx a specific capacity of 302 mAh g-1 is achieved after 300 cycles, and high cycling stability is observed at high current densities. This work is of great significance for expanding the family members of MXenes with tunable chemistries and structures.

Chemical scissor-mediated structural editing of layered transition metal carbides.

Intercalated layered materials offer distinctive properties and serve as precursors for important two-dimensional (2D) materials. However, intercalation of non-van der Waals structures, which can expand the family of 2D materials, is difficult. We report a structural editing protocol for layered carbides (MAX phases) and their 2D derivatives (MXenes). Gap-opening and species-intercalating stages were respectively mediated by chemical scissors and intercalants, which created a large family of MAX phases with unconventional elements and structures, as well as MXenes with versatile terminals. The removal of terminals in MXenes with metal scissors and then the stitching of 2D carbide nanosheets with atom intercalation leads to the reconstruction of MAX phases and a family of metal-intercalated 2D carbides, both of which may drive advances in fields ranging from energy to printed electronics.

Multiprincipal Element M2 FeC (M = Ti,V,Nb,Ta,Zr) MAX Phases with Synergistic Effect of Dielectric and Magnetic Loss.

Electromagnetic (EM) wave pollution is harmful to human health and environment, thus it is absolutely important to develop new electromagnetic wave absorbing materials. MAX phases have been attracted more attention as a potential candidate for electromagnetic wave absorbing materials due to their high conductivity and nanolaminated structure. Herein, two new magnetic MAX phases with multiprincipal elements ((Ti1/3 Nb1/3 Ta1/3 )2 FeC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 FeC) in which Fe atoms replace Al atoms in the A sites are successfully synthesized by an isomorphous replacement reaction of multiprincipal (Ti1/3 Nb1/3 Ta1/3 )2 AlC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 AlC MAX phases with Lewis acid salt (FeCl2 ). (Ti1/3 Nb1/3 Ta1/3 )2 FeC and (Ti0.2 V0.2 Nb0.2 Ta0.2 Zr0.2 )2 FeC exhibit ferromagnetic behavior, and the Curie temperature (Tc ) are 302 and 235 K, respectively. The dual electromagnetic absorption mechanisms that include dielectric and magnetic loss, which is realized in these multiprincipal MAX phases. The minimum reflection loss (RL) of (Ti1/3 Nb1/3 Ta1/3 )2 FeC is -44.4 dB at 6.56 GHz with 3 mm thickness, and the effective bandwidth is 2.48 GHz. Additionally, the electromagnetic wave absorption properties of the magnetic MAX phases indicate that magnetic loss also plays an important role besides dielectric loss. This work shows a promising composition-design strategy to develop MAX phases with good EM wave absorption performance via simultaneously regulating dielectric and magnetic loss together.

Nanolaminated Ternary Transition Metal Carbide (MAX Phase)-Derived Core-Shell Structure Electrocatalysts for Hydrogen Evolution and Oxygen Evolution Reactions in Alkaline Electrolytes.

The development of abundant, cheap, and highly active catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is important for hydrogen production. Nanolaminate ternary transition metal carbides (MAX phases) and their derived two-dimensional transition metal carbides (MXenes) have attracted considerable interest for electrocatalyst applications. Herein, four new MAX@MXene core-shell structures (Ta2CoC@Ta2CTx, Ta2NiC@Ta2CTx, Nb2CoC@Nb2CTx, and Nb2NiC@Nb2CTx), in which the core region is Co/Ni-MAX phases while the edge region is MXenes, have been prepared. Under alkaline electrolyte conditions, the Ta2CoC@Ta2CTx core-shell structure showed an overpotential of 239 mV and excellent stability during the HER with MXenes as the active sites. For the OER, the Ta2CoC@Ta2CTx core-shell structure showed an overpotential of 373 mV and a small Tafel plot (56 mV dec-1), which maintained a bulk crystalline structure and generated Co-based oxyhydroxides that formed by surface reconstruction as active sites. Considering rich chemical compositions and structures of MAX phases, this work provides a new strategy for designing multifunctional electrocatalysts and also paves the way for further development of MAX phase-based materials for clean energy applications.

Four-in-One Stimulus-Responsive Long-Lived Luminescent Systems Based on Pyrene-Doped Amorphous Polymers.

Materials exhibiting ultralong luminescent lifetime show promising applications in the fields of information encryption, sensing, and bioimaging. Herein, we present a low-cost and general strategy to achieve stimulus-responsive ultralong organic phosphorescence (UOP) based on pyrene chromophores doped into polymer matrices. The UOP of the resulted systems presents radiation-, concentration-, time-, and excitation-dependent characteristics. The UOP color can be turned from blue to red by changing the excitation wavelength or the concentration of chromophores. Experimental results prove that these characteristics are attributed to the consumption of triplet oxygen and the different aggregation states of chromophores in the polymer matrices. Finally, we demonstrate that these systems could be applied for multilevel information encryption. This work would promote further development of multi-responsive long-lived luminescent materials.

Cross-Linked Polyphosphazene Nanospheres Boosting Long-Lived Organic Room-Temperature Phosphorescence.

Long-lived organic room-temperature phosphorescence (RTP) has sparked intense explorations, owing to the outstanding optical performance and exceptional applications. Because triplet excitons in organic RTP experience multifarious relaxation processes resulting from their high sensitivity, spin multiplicity, inevitable nonradiative decay, and external quenchers, boosting RTP performance by the modulated triplet-exciton behavior is challenging. Herein, we report that cross-linked polyphosphazene nanospheres can effectively promote long-lived organic RTP. Through molecular engineering, multiple carbonyl groups (C═O), heteroatoms (N and P), and heavy atoms (Cl) are introduced into the polyphosphazene nanospheres, largely strengthening the spin-orbit coupling constant by recalibrating the electronic configurations between singlet (Sn) and triplet (Tn) excitons. In order to further suppress nonradiative decay and avoid quenching under ambient conditions, polyphosphazene nanospheres are encapsulated with poly(vinyl alcohol) matrix, thus synchronously prompting phosphorescence lifetime (173 ms longer), phosphorescence efficiency (∼12-fold higher), afterglow duration time (more than 20 s), and afterglow absolute luminance (∼19-fold higher) as compared with the 2,3,6,7,10,11-hexahydroxytriphenylene precursor. By measuring the emission intensity of the phosphorescence, an effective probe based on the nanospheres is developed for visible, quantitative, and expeditious detection of volatile organic compounds. More significantly, the obtained films show high selectivity and robustness for anisole detection (7.1 × 10-4 mol L-1). This work not only demonstrates a way toward boosting the efficiency of RTP materials but also provides a new avenue to apply RTP materials in feasible detection applications.

Long-Lived Room Temperature Phosphorescence Crystals with Green Light Excitation.

Long-lived room temperature phosphorescence (RTP) materials are promising for applications in various fields including security information, medical diagnostics, and molecular imaging because of their unique optical properties. Previous RTP materials are mainly excited by ultraviolet light, while synthesizing long-lived RTP materials with visible-light-excitation remains a challenge. In particular, long-lived RTP materials that can be excited by green light are rare. Herein, a feasible and concise chemical strategy for constructing hydrogen-bonded frameworks in an aqueous environment is developed to fabricate large-size, green-light-excited, and excitation-dependent long-lived RTP carbon dot crystals (m,p/CDs-ME). The RTP performance of the crystals exhibits strong excitation wavelength dependence, leading to a full range of visible-light tuning from blue to red. Importantly, the maximum excitation wavelength of the RTP crystals is around 500 nm, thus successfully realizing green light excitation. m,p/CDs-ME presents long-lived phosphorescence (130 ms) under 500 nm excitation in aqueous solution, making it highly suitable for dopamine detection. This work not only provides a general guideline for the development of large size long-lived RTP crystals but also extends the operation scope of long-lived RTP materials in the detection of biomarkers by visible light excitation.

Electrochemical Lithium Storage Performance of Molten Salt Derived V2SnC MAX Phase.

MAX phases are gaining attention as precursors of two-dimensional MXenes that are intensively pursued in applications for electrochemical energy storage. Here, we report the preparation of V2SnC MAX phase by the molten salt method. V2SnC is investigated as a lithium storage anode, showing a high gravimetric capacity of 490 mAh g-1 and volumetric capacity of 570 mAh cm-3 as well as superior rate performance of 95 mAh g-1 (110 mAh cm-3) at 50 C, surpassing the ever-reported performance of MAX phase anodes. Supported by operando X-ray diffraction and density functional theory, a charge storage mechanism with dual redox reaction is proposed with a Sn-Li (de)alloying reaction that occurs at the edge sites of V2SnC particles where Sn atoms are exposed to the electrolyte followed by a redox reaction that occurs at V2C layers with Li. This study offers promise of using MAX phases with M-site and A-site elements that are redox active as high-rate lithium storage materials.

Ultrastable Tb-Organic Framework as a Selective Sensor of Phenylglyoxylic Acid in Urine.

Industrial pollution and harmful chemicals seriously affect environment and human health. Styrene is a common air toxicant with widespread exposure sources, including smoking, automobile exhaust, and plastic pollutants. Phenylglyoxylic acid (PGA) is a typical biomarker for exposed styrene. Therefore, it is crucial to quickly identify and quantitatively detect PGA. Herein, an ultrastable terbium metal-organic framework (Tb-MOF 1) was developed, and the luminescence film (1/PLA) consisting of polylactic acid (PLA) and 1 was fabricated as a sensor for rapid detection of PGA. The sensor possesses the advantages of efficient detection [limit of detection (LOD) is 1.05 × 10-4 mg/mL] and rapid response speed (less than 10 s) for PGA in urine. Furthermore, this sensor exhibits high stability, outstanding anti-interference ability, and excellent recyclability. Based on this film technology, a paper-based probe was then developed for portable and convenient detection. The probe could easily distinguish different concentrations of PGA under the naked eye toward practical sensing applications. Meanwhile, photoinduced electron transfer was demonstrated to be responsible for the luminescence sensing. Hence, this study indicates that Tb-MOF is a promising material to detect PGA for evaluating the effect of styrene on the body.

Ultraviolet irradiation-responsive dynamic ultralong organic phosphorescence in polymeric systems.

Room temperature phosphorescence (RTP) has drawn extensive attention in recent years. Efficient stimulus-responsive phosphorescent organic materials are attractive, but are extremely rare because of unclear design principles and intrinsically spin-forbidden intersystem crossing. Herein, we present a feasible and facile strategy to achieve ultraviolet irradiation-responsive ultralong RTP (IRRTP) of some simple organic phosphors by doping into amorphous poly(vinyl alcohol) matrix. In addition to the observed green and yellow afterglow emission with distinct irradiation-enhanced phosphorescence, the phosphorescence lifetime can be tuned by varying the irradiation period of 254 nm light. Significantly, the dynamic phosphorescence lifetime could be increased 14.3 folds from 58.03 ms to 828.81 ms in one of the obtained hybrid films after irradiation for 45 min under ambient conditions. As such, the application in polychromatic screen printing and multilevel information encryption is demonstrated. The extraordinary IRRTP in the amorphous state endows these systems with a highly promising potential for smart flexible luminescent materials and sensors with dynamically controlled phosphorescence.

Simple Vanilla Derivatives for Long-Lived Room-Temperature Polymer Phosphorescence as Invisible Security Inks.

Developing novel long-lived room-temperature polymer phosphorescence (RTPP) materials could significantly expand their application scope. Herein, a series of RTPP materials based on eight simple vanilla derivatives for security ink application are reported. Attributed to strong mutual hydrogen bonding with polyvinyl alcohol (PVA) matrix, vanilla-doped PVA films exhibit ultralong phosphorescence emission under ambient conditions observed by naked eyes, where methyl vanillate shows the longest emission time up to 7 s. Impressively, when vanilla-doped PVA materials are utilized as invisible security inks, and the inks not only present excellent luminescent emission stability under ambient conditions but also maintain perfect reversibility between room temperature and 65°C for multiple cycles. Owing to the unique RTPP performance, an advanced anticounterfeiting data encoding/reading strategy based on handwriting technology and complex pattern steganography is developed.

Clinic-pathological features of metabolic associated fatty liver disease with hepatitis B virus infection.

BACKGROUND: Metabolic associated fatty liver disease (MAFLD) is a novel concept proposed in 2020. AIM: To compare the characteristics of MAFLD and MAFLD with hepatitis B virus (HBV) infection. METHODS: Patients with histopathologically proven MAFLD from a single medical center were included. Patients were divided into MAFLD group (without HBV infection) and HBV-MAFLD group (with HBV infection). Propensity score matching was utilized to balance the baseline characteristics between two groups. RESULTS: A total of 417 cases with MAFLD were included, 359 (86.1%) of whom were infected with HBV. There were significantly more males in the HBV-MAFLD group than in the MAFLD group (P < 0.05). After propensity score matching, 58 pairs were successfully matched with no significant differences found in gender, age, body mass index, lipid levels, liver enzymes, and the other metabolic associated comorbidities between the two groups (P > 0.05). The rank sum test results showed that the degree of liver steatosis in the MAFLD group was more severe than that in the HBV-MAFLD group, while the degree of inflammation and fibrosis in the liver was less severe (P < 0.05). In multivariate analysis, HBV infection was associated with significantly lower grade of hepatic steatosis [odds ratio (OR) = 0.088, 95% confidence interval (CI): 0.027-0.291] but higher inflammation level (OR = 4.059, 95%CI: 1.403-11.742) and fibrosis level (OR = 3.016, 95%CI: 1.087-8.370) after adjusting for age, gender, and other metabolic parameters. CONCLUSION: HBV infection is associated with similar metabolic risks, lower steatosis grade, higher inflammation, and fibrosis grade in MAFLD patients.

Halogenated Ti3C2 MXenes with Electrochemically Active Terminals for High-Performance Zinc Ion Batteries.

The class of two-dimensional metal carbides and nitrides known as MXenes offer a distinct manner of property tailoring for a wide range of applications. The ability to tune the surface chemistry for expanding the property space of MXenes is thus an important topic, although experimental exploration of surface terminals remains a challenge. Here, we synthesized Ti3C2 MXene with unitary, binary, and ternary halogen terminals, e.g., -Cl, -Br, -I, -BrI, and -ClBrI, to investigate the effect of surface chemistry on the properties of MXenes. The electrochemical activity of Br and I elements results in the extraordinary electrochemical performance of the MXenes as cathodes for aqueous zinc ion batteries. The -Br- and -I-containing MXenes, e.g., Ti3C2Br2 and Ti3C2I2, exhibit distinct discharge platforms with considerable capacities of 97.6 and 135 mAh·g-1. Ti3C2(BrI) and Ti3C2(ClBrI) exhibit dual discharge platforms with capacities of 117.2 and 106.7 mAh·g-1. In contrast, the previously discovered MXenes Ti3C2Cl2 and Ti3C2(OF) exhibit no discharge platforms and only ∼50% of capacities and energy densities of Ti3C2Br2. These results emphasize the effectiveness of the Lewis-acidic-melt etching route for tuning the surface chemistry of MXenes and also show promise for expanding the MXene family toward various applications.

A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte.

Two-dimensional carbides and nitrides of transition metals, known as MXenes, are a fast-growing family of materials that have attracted attention as energy storage materials. MXenes are mainly prepared from Al-containing MAX phases (where A = Al) by Al dissolution in F-containing solution; most other MAX phases have not been explored. Here a redox-controlled A-site etching of MAX phases in Lewis acidic melts is proposed and validated by the synthesis of various MXenes from unconventional MAX-phase precursors with A elements Si, Zn and Ga. A negative electrode of Ti3C2 MXene material obtained through this molten salt synthesis method delivers a Li+ storage capacity of up to 738 C g-1 (205 mAh g-1) with high charge-discharge rate and a pseudocapacitive-like electrochemical signature in 1 M LiPF6 carbonate-based electrolyte. MXenes prepared via this molten salt synthesis route may prove suitable for use as high-rate negative-electrode materials for electrochemical energy storage applications.

Preparation of Ti3C2Tx/NiZn Ferrite Hybrids with Improved Electromagnetic Properties.

Ti3C2Tx/NiZn ferrite composites were synthesized using a co-precipitation hydrothermal method, and further consolidated using electric current field-assisted sintering technology. Nano NiZn ferrites were inserted into the Ti3C2Tx interlayers with uniform coverage on their surfaces. The incorporation of MXenes promoted the sintering kinetics of the NiZn ferrite ceramics. The electrical conductivity increased by six orders of magnitude compared to pure NiZn ferrite ceramics at room temperature. The present work provides a potential way to develop a large family of dense MXenes/ferrite multiphase ceramics. The multiphase ceramics could be potentially used for the on-beam-line higher-order mode load in advanced particle accelerators.