Photocatalytic Conversion of Methane to Ethanol at a Three-Phase Interface with Concentration-Matched Hydroxyl and Methyl Radicals.

The direct oxidation of CH4 to C2H5OH is attractive but challenging owing to the intricate processes involving carbon-chain growth and hydroxylation simultaneously. The inherent difficulty arises from the strong tendency of CH4 to overoxidize in the commonly used pressurized powder suspension systems rich in reactive oxygen radicals (ROR), which are specifically designed for CH4 concentration and activation. Meanwhile, the strong tendency of nucleophilic attack of potent ROR on the C-C bond of the resulting product C2H5OH ultimately leads to a higher selectivity for C1 oxygenates. This study addresses this multifaceted issue by designing a three-phase interface based on a hydrophilic floating Fe(III)-cross-linked macroporous alginate hydrogel film encapsulated with C3N4 [Fe(III)@ACN] to simultaneously enhance the accessibility of H2O and CH4 molecules to the active sites and species within the macroporous channel. The hydrophilic properties of Fe(III)@ACN allow the in situ production of H2O2 from C3N4 through the water oxidation reaction under irradiation. The concurrent photoinduced Fe(II) triggers Fenton reaction with H2O2 to produce •OH. The enhanced mass transfer of CH4 at the three-phase interface ensures the efficient formation of •CH3 by reacting with •OH, ultimately facilitating carbon-chain growth in the conversion pathway from CH4 to CH3OH and finally to C2H5OH with •CH3 and •OH present in comparable concentrations. Thus, the Fe(III)@ACN catalyst exhibits a remarkable 96% selectivity for alcohol, achieving a 90% selectivity for C2H5OH in the alcohol products. The C2H5OH production rate reaches 171.7 µmol g-1 h-1 without the need for precious-metal additive.

Impact of the uniaxial strain on terahertz modulation characteristics in flexible epitaxial VO2 film across the phase transition.

Exploring flexible electronics is on the verge of innovative breakthroughs in terahertz (THz) communication technology. Vanadium dioxide (VO2) with insulator-metal transition (IMT) has excellent application potential in various THz smart devices, but the associated THz modulation properties in the flexible state have rarely been reported. Herein, we deposited an epitaxial VO2 film on a flexible mica substrate via pulsed-laser deposition and investigated its THz modulation properties under different uniaxial strains across the phase transition. It was observed that the THz modulation depth increases under compressive strain and decreases under tensile strain. Moreover, the phase-transition threshold depends on the uniaxial strain. Particularly, the rate of the phase transition temperature depends on the uniaxial strain and reaches approximately 6 °C/% in the temperature-induced phase transition. The optical trigger threshold in laser-induced phase transition decreased by 38.9% under compressive strain but increased by 36.7% under tensile strain, compared to the initial state without uniaxial strain. These findings demonstrate the uniaxial strain-induced low-power triggered THz modulation and provide new insights for applying phase transition oxide films in THz flexible electronics.

Regulating the interface defect of TiO2/Ag2O nanoheterojunction and its effect on photogenerated carrier dynamics.

In this paper, the defects of TiO2/Ag2O nanoheterojunctions are regulated to evaluate the effect of the interface defects on carrier trapping and recombination dynamics by time-resolved photoluminescence spectroscopy (TRPL) and time-resolved terahertz (THZ) spectroscopy. TRPL spectra reveal that interface defects can act as a recombination center and have an accelerative effect on the recombination process of photogenerated carriers under ultraviolet light. Moreover, THZ spectroscopy results demonstrate that interface defects can effectively trap electrons and expedite the Auger recombination. Furthermore, the influence of interface defects on the photocarrier dynamics of TiO2/Ag2O nanoheterojunctions was comprehensively analyzed, providing a valuable experimental reference for the regulation and application of interface defect-fabricated nanoheterojunctions.

A terahertz meta-sensor array for 2D strain mapping.

Large-scale stretchable strain sensor arrays capable of mapping two-dimensional strain distributions have gained interest for applications as wearable devices and relating to the Internet of Things. However, existing strain sensor arrays are usually unable to achieve accurate directional recognition and experience a trade-off between high sensing resolution and large area detection. Here, based on classical Mie resonance, we report a flexible meta-sensor array that can detect the in-plane direction and magnitude of preloaded strains by referencing a dynamically transmitted terahertz (THz) signal. By building a one-to-one correspondence between the intrinsic electrical/magnetic dipole resonance frequency and the horizontal/perpendicular tension level, arbitrary strain information across the meta-sensor array is accurately detected and quantified using a THz scanning setup. Particularly, with a simple preparation process of micro template-assisted assembly, this meta-sensor array offers ultrahigh sensor density (~11.1 cm-2) and has been seamlessly extended to a record-breaking size (110 × 130 mm2), demonstrating its promise in real-life applications.

VO2 Films Decorated with an MXene Interface for Decreased-Power-Triggered Terahertz Modulation.

VO2, which exhibits semiconductor-metal phase transition characteristics occurring on a picosecond time scale, holds great promise for ultrafast terahertz modulation in next-generation communication. However, as of now, there is no reported prototype for an ultrafast device. The temperature effect has been proposed as one of the major obstacles. Consequently, reducing the excitation threshold for the phase transition would be highly significant. The traditional strategy typically involves chemical doping, but this approach often leads to a decrease in phase transition amplitude and a slower transition speed. In this work, we proposed a design featuring a highly conductive MXene interfacial layer between the VO2 film and the substrate. We demonstrate a significant reduction in the phase transition threshold for both temperature and laser-induced phase transition by adjusting the conductivity of the MXene layers with varying thicknesses. Our observations show that the phase transition temperature can be decreased by 9 °C, while the pump fluence for laser excitation can be reduced by as high as 36%. The ultrafast phase transition process on a picosecond scale, as revealed by the optical-pump terahertz-probe method, suggests that the MXene layers have minimal impact on the phase transition speed. Moreover, the reduced phase transition threshold can remarkably alleviate the photothermal effect and inhibit temperature rise and diffusion in VO2 triggered by laser. This study offers a blueprint for designing VO2/MXene hybrid films with reduced phase transition thresholds. It holds significant potential for the development of low-power, intelligent optical and electrical devices including, but not limited to, terahertz modulators based on phase transition phenomena.

Highly Flexible Ti3C2Tx MXene/Waterborne Polyurethane Membranes for High-Efficiency Terahertz Modulation with Low Insertion Loss.

The dynamic control of terahertz (THz) wave transmission on flexible functional materials is a fundamental building block for wearable electronics and sensors in the THz range. However, achieving high-efficiency THz modulation and low insertion loss is a great challenge while maintaining the excellent flexibility and stretchability of the materials. Herein, we report a Ti3C2Tx MXene/waterborne polyurethane (WPU) membrane prepared by a vacuum-assisted filtration method, which exhibits excellent THz modulation properties across stretching. The hydrophilic Ti3C2Tx MXene and WPU enable the uniform 3D distribution of Ti3C2Tx MXene in the WPU matrix. Particularly, the stretchability with the maximum strain of the membranes can reach 200%, accompanied by dynamic tuning of THz transmittance for more than 90% and an insertion loss as low as -4.87 dB. The giant THz modulation continuously decreases with MXene content per unit area, accompanied by a lower density of the MXene interface and diminished THz absorption during stretching. Such a design opens a pathway for achieving flexible THz modulators with a high modulation depth and low insertion loss, which would be used for THz flexible and wearable devices.

Photothermal conversion of Ti2O3 film for tuning terahertz waves.

Dynamic tuning of terahertz (THz) wave is vital for the development of next generation THz devices. Utilization of solar energy for tuning THz waves is a promising, eco-friendly, and sustainable way to expand THz application scenarios. Ti2O3 with an ultranarrow bandgap of 0.1eV exhibits intriguing thermal-induced metal-insulator transition (MIT), and possesses excellent photothermal conversion efficiency. Herein, Ti2O3 film was fabricated by a two-step magnetron sputtering method, and exhibited an excellent photothermal conversion efficiency of 90.45% and demonstrated temperature-dependent THz transmission characteristics with a wideband at 0.1-1 THz. We supposed to combine photothermal conversion characteristics with temperature-dependent THz transmission properties of Ti2O3 film, which could introduce solar light as the energy source for tuning THz waves. Our work will provide new sight for investigating MIT characteristics of Ti2O3 at THz regime and exhibit huge potential in the application of tuning terahertz waves in outdoor scenarios in the future.

Microbial Community, Fermentation Quality, and in vitro Degradability of Ensiling Caragana With Lactic Acid Bacteria and Rice Bran.

This study aimed to assess the effects of microbial inoculants and growth stage on fermentation quality, microbial community, and in vitro degradability of Caragana silage from different varieties. Caragana intermedia (CI) and Caragana korshinskii (CK) harvested at the budding (BU) and blooming (BL) stages were used as raw materials to prepare silage, respectively. The silages at each growth stage were treated for ensiling alone (control), with 5% rice bran (RB), a combination of RB with commercial Lactobacillus plantarum (RB + LP), and a combination of RB with a selected strain Lactobacillus plantarum L694 (RB + L694). The results showed that the crude protein (CP) content of CI was higher than that of CK, and delay in harvest resulted in greater CP content in Caragana at BL stage. After 60 days of fermentation, the concentrations of lactic acid (LA) in the RB + L694 treatments were higher than those in control treatments (p < 0.05), while the pH, concentrations of NH3-N, neutral detergent fiber with the addition of α-amylase (aNDF) were lower than those in control treatments (p < 0.05). RB + L694 treatments could decrease acid detergent fiber (ADF) content except in CIBL. In CK silages, adding RB + L694 could reduce bacterial diversity and richness (p < 0.05). Compared with the control, RB + L694 treatment contained higher Lactobacillus and Enterobacter (p < 0.05). In vitro NDF and DM degradability (IVNDFD and IVDMD) was mostly affected by growth period, and additive RB + l694 treatment had higher IVDMD and lower IVNDFD than other treatments (p < 0.05). Consequently, the varieties, growth stages, and additives could influence the fermentation process, while the blooming stage should be selected in both Caragana. Furthermore, the results showed that RB and L. plantarum could exert a positive effect on fermentation quality of Caragana silage by shifting bacterial community composition, and RB + L694 treatments outperformed other additives.

Volatile and Nonvolatile Switching of Phase Change Material Ge2Sb2Te5 Revealed by Time-Resolved Terahertz Spectroscopy.

Phase change materials exhibit unique advantages in reconfigurable photonic devices due to drastic tunability of photoelectric properties. Here, we systematically investigate the thermal equilibrium process and the ultrafast dynamics of Ge2Sb2Te5 (GST) driven by femtosecond (fs) pulses, using time-resolved terahertz spectroscopy. Both fs-pulse-driven crystallization and amorphization are demonstrated, and the threshold of photoinduced crystallization (amorphization) is determined to be 8.4 mJ/cm2 (10.1 mJ/cm2). The ultrafast carrier dynamics reveal that the cumulative photothermal effect plays a crucial role in the ultrafast crystallization, and modulation depth of volatile (nonvolatile) THz has switching limits up to 30% (15%). A distinctive phonon absorption at 1.1 THz is observed, providing fingerprint spectrum evidence of crystalline lattice formation driven by intense fs pulses. Finally, multistate volatile (nonvolatile) THz switching is implemented by tuning optical pump fluence. These results provide insight into the photoinduced phase change of GST and offer benefits for all optical THz functional devices.

Intratumoral synthesis of transformable metal-phenolic nanoaggregates with enhanced tumor penetration and retention for photothermal immunotherapy.

Rationale: Effective photothermal therapy (PTT) remains a great challenge due to the difficulties of delivering photothermal agents with both deep penetration and prolonged retention at tumor lesion spatiotemporally. Methods: Here, we report an intratumoral self-assembled nanostructured aggregate named FerH, composed of a natural polyphenol and a commercial iron supplement. FerH assemblies possess size-increasing dynamic kinetics as a pseudo-stepwise polymerization from discrete nanocomplexes to microscale aggregates. Results: The nanocomplex can penetrate deeply into solid tumors, followed by prolonged retention (> 6 days) due to the in vivo growth into nanoaggregates in the tumor microenvironment. FerH performs a targeting ablation of tumors with a high photothermal conversion efficiency (60.2%). Importantly, an enhanced immunotherapeutic effect on the distant tumor can be triggered when co-administrated with checkpoint-blockade PD-L1 antibody. Conclusions: Such a therapeutic approach by intratumoral synthesis of metal-phenolic nanoaggregates can be instructive to address the challenges associated with malignant tumors.

Optical-Transparent Self-Assembled MXene Film with High-Efficiency Terahertz Reflection Modulation.

The modulation of the terahertz (THz) wave is fundamental for its applications in next-generation communications, biological imaging, sensing, and so forth. Searching for higher efficient modulation is still in progress, although plenty of materials have been explored for tuning THz wave. In this work, optical-transparent self-assembled MXene films are used to modulate the THz reflection at the SiO2/MXene/air interface based on the impedance matching mechanism. By adjusting the number of stacked MXene layers/concentrations of MXene dispersions, the sheet conductivity of the MXene films will be changed so that the impedance at the SiO2/MXene/air interface can be tuned and lead to a giant modulation of THz reflection. Particularly, we demonstrate that the MXene films have highly efficient THz modulation from antireflection to reflection-enhancing with a relative reflection of 27% and 406%, respectively. This work provides a new pathway for developing the MXene films with the combination of optical-transparency and high smart THz reflection characteristics, and the films can be applied for THz antireflection or reflection-enhancing.

Two-Channel VO2 Memory Meta-Device for Terahertz Waves.

Vanadium oxide (VO2), as one of the classical strongly correlated oxides with a reversible and sharp insulator-metal transition (IMT), enables many applications in dynamic terahertz (THz) wave control. Recently, due to the inherent phase transition hysteresis feature, VO2 has shown favorable application prospects in memory-related devices once combined with metamaterials or metasurfaces. However, to date, VO2-based memory meta-devices are usually in a single-channel read/write mode, which limits their storage capacity and speed. In this paper, we propose a reconfigurable meta-memory based on VO2, which favors a two-channel read/write mode. Our design consists of a pair of large and small split-ring resonators, and the corresponding VO2 patterns are embedded in the gap locations. By controlling the external power supply, the two operation bands can be controlled independently to achieve at least four amplitude states, including "00", "01", "10", and "11", which results in a two-channel storage function. In addition, our research may provide prospective applications in fields such as THz switching, photon storage, and THz communication systems in the future.

Interfacial Embedding of Laser-Manufactured Fluorinated Gold Clusters Enabling Stable Perovskite Solar Cells with Efficiency Over 24.

Tackling the interfacial loss in emerged perovskite-based solar cells (PSCs) to address synchronously the carrier dynamics and the environmental stability, has been of fundamental and viable importance, while technological hurdles remain in not only creating such interfacial mediator, but the subsequent interfacial embedding in the active layer. This article reports a strategy of interfacial embedding of hydrophobic fluorinated-gold-clusters (FGCs) for highly efficient and stable PSCs. The p-type semiconducting feature enables the FGC efficient interfacial mediator to improve the carrier dynamics by reducing the interfacial carrier transfer barrier and boosting the charge extraction at grain boundaries. The hydrophobic tails of the gold clusters and the hydrogen bonding between fluorine groups and perovskite favor the enhancement of environmental stability. Benefiting from these merits, highly efficient formamidinium lead iodide PSCs (champion efficiency up to 24.02%) with enhanced phase stability under varied relative humidity (RH) from 40% to 95%, as well as highly efficient mixed-cation PSCs with moisture stability (RH of 75%) over 10 000 h are achieved. It is thus inspiring to advance the development of highly efficient and stable PSCs via interfacial embedding laser-generated additives for improved charge transfer/extraction and environmental stability.

Flexible and Giant Terahertz Modulation Based on Ultra-Strain-Sensitive Conductive Polymer Composites.

Dynamic tuning of terahertz (THz) wave has a great potential application as smart THz devices, such as switches, modulators, sensors, and so on. However, the realization of flexible THz modulation with high efficiency is rarely observed, which is nearly absent from the booming development and demands on flexible electronics. Here, we report a flexible THz modulation based on conductive polymer composites composed of thermoplastic polyurethane (TPU) and conductive particles (Ni). By designing the additive content of Ni particles, such a flexible layer exhibits resistivity change of 6-7 orders under tensile strain due to the formation of an electron-transport channel provided by the in situ evolution of the Ni network. It could be used to dynamically control the THz transmission with a giant modulation depth of around 96%, at a high strain operation (up to around 58.5%). Moreover, these characteristics are demonstrated to be available for highly tension sensitive THz spectroscopy and imaging. This work opens up a connection between flexible polymer-based composites and THz dynamic devices. It proposes an unprecedented flexible THz modulation with giant tuning efficiency and provides a scheme for contactless and passive tension sensors.

Comparative investigation on thermal decomposition of powdered and pelletized biomasses: Thermal conversion characteristics and apparent kinetics.

In this work, the thermal degradation behaviors of two kinds of biomasses (pinewood and rice husk) with powder and pellet under three oxygen concentrations were investigated by a self-designed macro-thermogravimetric analyzer. An obvious hysteresis of thermal degradation of biomass pellets was observed under three conditions. The maximum activation energy of biomass pellets was significantly greater than that of biomass powders, while their average activation energies were almost equal based on distributed activation energy model. For the oxygen-rich combustion, the comprehensive combustion character index of powdered and pelletized biomasses ranged from 3.92 × 10-7 to 5.16 × 10-7%2·min-2·°C-3 and from 1.82 × 10-7 to 1.91 × 10-7%2·min-2·°C-3, respectively. Furthermore, the derived biochar of powdered biomass has a higher caloricity than that of pelletized biomass during combustion by TG-DSC analysis. The performances of thermal degradation observed by macro-thermogravimetric analyzer could factually reveal the influence of mass and heat transfer on the thermochemical conversion of powdered and pelletized biomasses.

Silica-Coated Gold Nanorods with High Photothermal Efficiency and Biocompatibility as a Contrast Agent for In Vitro Terahertz Imaging.

The application of terahertz imaging in biomedical diagnostics is limited by the poor imaging contrast due to the strong absorption of terahertz waves by water molecules in the living body. To resolve this problem, gold nanorods (GNRs) have been considered as a possible contrast agent. However, the conventional preparation of GNRs requires using cetyltrimethylammonium bromide (CTAB) as a stabilizing surfactant, which is toxic to animals at high exposures. In this work, a modified seed-mediated growth method was proposed to synthesize silica-coated GNRs, which exhibited better stability and biocompatibility and the same cellular uptake efficiency as compared to those of uncoated GNRs. Moreover, silica-coated GNRs showed higher photothermal efficiency caused by the localized surface plasmon resonance that increased the terahertz reflection amplitude. In particular, the in vitro terahertz imaging of prostate cancer cells demonstrated noticeably higher contrast when silica-coated GNRs were used as a contrast agent. Hence, this study suggests a stable, biocompatible, and efficient contrast-enhancing agent for terahertz imaging, which can expand the scope of its clinical applications.

Metabolite analysis-aided diagnosis of papillary thyroid cancer.

Thyroid cancer is the most frequent endocrine tumor with a growing incidence worldwide. However, common diagnostic strategy for thyroid cancer classification is hardly to make a proper diagnosis in some cases. To assist classical approach, this study used metabolomics to screen and validate biomarkers from serum and urinary for papillary thyroid cancer (PTC). Overall, 124 untreated PTC, 76 untreated benign thyroid nodule (BTN), and 116 healthy control (HC) were collected in this study. Thirty-six differential metabolites were screened from non-targeted metabolomics with a discovery sample set in comparison with HC and BTN. Serum ß-hydroxybutyrate (BHB), docosahexaenoic acid (DHA), 1-methyladenosine (1-MedA), pregnanediol-3-glucuronide (PdG), urinary nicotinic acid mononucleotide (NAM) and xanthosine (Xan) were validated to be significantly differential by targeted metabolomics in validation set. The logistic regression model incorporating six biomarkers had excellent discrimination from receiver-operating characteristics (ROC) analysis, with area under the receiver-operating characteristic curve (AUC) of 0.943 (95% CI 0.902 to 0.983) and 0.952 (95% CI 0.921 to 0.983) for female alone and female + male samples, respectively. The prediction accuracy and false-negative rate in the real setting of one PTC to ten suspicious nodules were 84.7 and 17.7% with the threshold at probablity of 0.5. Results of a double-blind study for PTC and BTN had true positive value of 100% and true negative value of 91.7%. To conclude, BHB, DHA, 1-MedA, PdG, NAM and Xan are suitable biomarkers for PTC, and logistic regression models with the six biomarkers can be potentially used as clinical diagnosis.

One-Step Hydrothermal Synthesis of W-Doped VO2 (M) Nanorods with a Tunable Phase-Transition Temperature for Infrared Smart Windows.

Vanadium dioxide (VO2), with reversible metal-semiconductor transition near room temperature, is a compelling candidate for thermochromic windows. Nanocomposite coatings derived from VO2 nanoparticles are particularly superior to VO2 films due to their advantages in large-scale preparation, flexible shaping, and regulation of optical properties. In this work, we developed a novel method for one-step hydrothermal synthesis of W-doped VO2 (M) nanorods and studied their application in large-scale infrared smart windows. On introducing tartaric acid as a new reductant, VO2 underwent a two-stage phase evolution from the pure phase comprising VO2 (A) nanobelts to VO2 (M) nanorods, instead of the conventional three-stage B-A-M phase evolution during hydrothermal synthesis. This transition is very favorable for the large-scale hydrothermal synthesis of VO2 (M). The phase-transition temperature of VO2 (M) nanoparticles can be regulated systematically by W doping, with a reduction efficiency of about 24.52 °C/atom % W. Moreover, VO2 (M) composite films were fabricated using a convenient roller coating method, which exhibited significant midinfrared transmission switching up to 31%, with a phase-transition temperature of about 37.3 °C. This work demonstrates the significant progress in the one-step hydrothermal synthesis of VO2 (M) nanorods and provides significant insights into their applications in infrared smart windows.