A High-Entropy Single-Atom Catalyst Toward Oxygen Reduction Reaction in Acidic and Alkaline Conditions.

The design of high-entropy single-atom catalysts (HESAC) with 5.2 times higher entropy compared to single-atom catalysts (SAC) is proposed, by using four different metals (FeCoNiRu-HESAC) for oxygen reduction reaction (ORR). Fe active sites with intermetallic distances of 6.1 Å exhibit a low ORR overpotential of 0.44 V, which originates from weakening the adsorption of OH intermediates. Based on density functional theory (DFT) findings, the FeCoNiRu-HESAC with a nitrogen-doped sample were synthesized. The atomic structures are confirmed with X-ray photoelectron spectroscopy (XPS), X-ray absorption (XAS), and scanning transmission electron microscopy (STEM). The predicted high catalytic activity is experimentally verified, finding that FeCoNiRu-HESAC has overpotentials of 0.41 and 0.37 V with Tafel slopes of 101 and 210 mVdec-1 at the current density of 1 mA cm-2 and the kinetic current densities of 8.2 and 5.3 mA cm-2, respectively, in acidic and alkaline electrolytes. These results are comparable with Pt/C. The FeCoNiRu-HESAC is used for Zinc-air battery applications with an open circuit potential of 1.39 V and power density of 0.16 W cm-2. Therefore, a strategy guided by DFT is provided for the rational design of HESAC which can be replaced with high-cost Pt catalysts toward ORR and beyond.

Confined In-Situ Encapsulation of Co/C Composites with Increased Heterogeneous Interface Polarization for Enhanced Electromagnetic Performance.

It is an urgent problem to realize reliable microwave absorption materials (MAMs) with low density. To address this issue, a series of controlled experiments w ere carried out, which indicated that the tubular structure enables excellent microwave absorption properties with a lower powder filling rate. This performance is attributable to the combined dielectric and magnetic loss mechanisms provided by Co/C and the interface polarization facilitated by multiple heterogeneous interfaces. Particularly, Co@C nanotubes, benefiting from the enhanced heterointerface polarization due to their abundant specific surface area and the reduced electron migration barrier induced by their 1D stacked structure, effectively achieved a dual enhancement of dielectric loss and polarization loss at lower powder filling ratios. Furthermore, the magnetic coupling effect of magnetic nanoparticle arrays in tubular structures is demonstrated by micromagnetic simulation, which have been few reported elsewhere. These propertied enable Co@C nanotubes to achieve minimum reflection loss and maximum effective absorption broadband values of 61.0 dB and 5.5 GHz, respectively, with a powder filling ratio of 20 wt% and a thickness of 1.94 mm. This study reveals the significance of designing 1D structures in reducing powder filling ratio and matching thickness, providing valuable insights for developing MAMs with different microstructures.

Low-Temperature Vapor-Phase Growth of 2D Metal Chalcogenides.

2D metal chalcogenides (MCs) have garnered significant attention from both scientific and industrial communities due to their potential in developing next-generation functional devices. Vapor-phase deposition methods have proven highly effective in fabricating high-quality 2D MCs. Nevertheless, the conventionally high thermal budgets required for synthesizing 2D MCs pose limitations, particularly in the integration of multiple components and in specialized applications (such as flexible electronics). To overcome these challenges, it is desirable to reduce the thermal energy requirements, thus facilitating the growth of various 2D MCs at lower temperatures. Numerous endeavors have been undertaken to develop low-temperature vapor-phase growth techniques for 2D MCs, and this review aims to provide an overview of the latest advances in low-temperature vapor-phase growth of 2D MCs. Initially, the review highlights the latest progress in achieving high-quality 2D MCs through various low-temperature vapor-phase techniques, including chemical vapor deposition (CVD), metal-organic CVD, plasma-enhanced CVD, atomic layer deposition (ALD), etc. The strengths and current limitations of these methods are also evaluated. Subsequently, the review consolidates the diverse applications of 2D MCs grown at low temperatures, covering fields such as electronics, optoelectronics, flexible devices, and catalysis. Finally, current challenges and future research directions are briefly discussed, considering the most recent progress in the field.

In Situ Defect Engineering of Controllable Carrier Types in WSe2 for Homomaterial Inverters and Self-Powered Photodetectors.

WSe2 has a high mobility of electrons and holes, which is an ideal choice as active channels of electronics in extensive fields. However, carrier-type tunability of WSe2 still has enormous challenges, which are essential to overcome for practical applications. In this work, the direct growth of n-doped few-layer WSe2 is realized via in situ defect engineering. The n-doping of WSe2 is attributed to Se vacancies induced by the H2 flow purged in the cooling process. The electrical measurements based on field effect transistors demonstrate that the carrier type of WSe2 synthesized is successfully transferred from the conventional p-type to the rarely reported n-type. The electron carrier concentration is efficiently modulated by the concentration of H2 during the cooling process. Furthermore, homomaterial inverters and self-powered photodetectors are fabricated based on the doping-type-tunable WSe2. This work reveals a significant way to realize the controllable carrier type of two-dimensional (2D) materials, exhibiting great potential in future 2D electronics engineering.

Two-dimensional materials for high density, safe and robust metal anodes batteries.

With a high specific capacity and low electrochemical potentials, metal anode batteries that use lithium, sodium and zinc metal anodes, have gained great research interest in recent years, as a potential candidate for high-energy-density storage systems. However, the uncontainable dendrite growth during the repeated charging process, deteriorates the battery performance, reduces the battery life and more importantly, raises safety concerns. With their unique properties, two-dimensional (2D) materials, can be used to modify various components in metal batteries, eventually mitigating the dendrite growth, enhancing the cycling stability and rate capability, thus leading to safe and robust metal anodes. In this paper, we review the recent advances of 2D materials and summarize current research progress of using 2D materials in the applications of (i) anode design, (ii) separator engineering, and (iii) electrolyte modifications by guiding metal ion nucleation, increasing ion conductivity, homogenizing the electric field and ion flux, and enhancing the mechanical strength for safe metal anodes. The 2D material modifications provide the ultimate solution for obtaining dendrite-free metal anodes, realizes the high energy storage application, and indicates the importance of 2D materials development. Finally, in-depth understandings of subsequent metal growth are lacking due to research limitations, while more advanced characterizations are welcome for investigating the metal deposition mechanism. The more facile and simplified preparation of 2D materials possess great prospects in high energy density metal anode batteries, and thus fulfils the development of EVs.

Electrochemical Detection of Dopamine Release from Living Neurons Using Graphene Oxide-Incorporated Polypyrrole/Gold Nanocluster Hybrid Nanopattern Arrays.

Stem-cell-based therapeutics have shown immense potential in treating various diseases that are currently incurable. In particular, partial recovery of Parkinson's disease, which occurs due to massive loss or abnormal functionality of dopaminergic (DAnergic) neurons, through the engraftment of stem-cell-derived neurons ex vivo is reported. However, precise assessment of the functionality and maturity of DAnergic neurons is still challenging for their enhanced clinical efficacy. Here, a novel conductive cell cultivation platform, a graphene oxide (GO)-incorporated metallic polymer nanopillar array (GOMPON), that can electrochemically detect dopamine (DA) exocytosis from living DAnergic neurons, is reported. In the cell-free configuration, the linear range is 0.5-100 µm, with a limit of detection of 33.4 nm. Owing to its excellent biocompatibility, a model DAnergic neuron (SH-SY5Y cell) can be cultivated and differentiated on the platform while their DA release can be quantitatively measured in a real-time and nondestructive manner. Finally, it is showed that the functionality of the DAnergic neurons derived from stem cells can be precisely assessed via electrochemical detection of their DA exocytosis. The developed GOMPON is highly promising for a wide range of applications, including real-time monitoring of stem cell differentiation into neuronal lineages, evaluating differentiation protocols, and finding practical stem cell therapies.

Revealing Variable Dependences in Hexagonal Boron Nitride Synthesis via Machine Learning.

Wafer-scale monolayer two-dimensional (2D) materials have been realized by epitaxial chemical vapor deposition (CVD) in recent years. To scale up the synthesis of 2D materials, a systematic analysis of how the growth dynamics depend on the growth parameters is essential to unravel its mechanisms. However, the studies of CVD-grown 2D materials mostly adopted the control variate method and considered each parameter as an independent variable, which is not comprehensive for 2D materials growth optimization. Herein, we synthesized a representative 2D material, monolayer hexagonal boron nitride (hBN), on single-crystalline Cu (111) by epitaxial chemical vapor deposition and varied the growth parameters to regulate the hBN domain sizes. Furthermore, we explored the correlation between two growth parameters and provided the growth windows for large flake sizes by the Gaussian process. This new analysis approach based on machine learning provides a more comprehensive understanding of the growth mechanism for 2D materials.

Constructing Spatially Separated Cage-Like Z-scheme Heterojunction Photocatalyst for Enhancing Photocatalytic H2 Evolution.

Heterojunctions coupled into micro-mesoscopic structures is an attractive strategy to optimize the light harvesting and carrier separation of semiconductor photocatalysts. A self-templating method of ion exchange is reported to synthesize an exquisite hollow cage-structured Ag2 S@CdS/ZnS that direct Z-scheme heterojunction photocatalyst. On the ultrathin shell of the cage, Ag2 S, CdS, and ZnS with Zn-vacancies (VZn ) are arranged sequentially from outside to inside. Among them, the photogenerated electrons are excited by ZnS to the VZn energy level and then recombine with the photogenerated holes that are generated by CdS, while the electrons remained in the CdS conduction band are further transferred to Ag2 S. The ingenious cooperation of the Z-scheme heterojunction with the hollow structure optimizes the photogenerated charges transport channel, spatially separated the oxidation and reduction half-reactions, decreases the charge recombination probability, and simultaneously improves the light harvesting efficiency. As a result, the photocatalytic hydrogen evolution activity of the optimal sample is 136.6 and 17.3 times higher than that of cage-like ZnS with VZn and CdS by, respectively. This unique strategy demonstrates the tremendous potential of the incorporation of heterojunction construction to morphology design of photocatalytic materials, and also provided a reasonable route for designing other efficient synergistic photocatalytic reactions.

Hollow mesoporous organosilica nanoparticles reduced graphene oxide based nanosystem for multimodal image-guided photothermal/photodynamic/chemo combinational therapy triggered by near-infrared.

Developing a nanosystem that can perform multimodal imaging-guided combination therapy is highly desirable but challenging. In this study, we introduced multifunctional nanoparticles (NPs) consisting of graphene oxide-grafted hollow mesoporous organosilica loaded with the drug doxorubicin (DOX) and photosensitizers tetraphenylporphyrin (TPP). These NPs were encapsulated by thermosensitive liposomes that release their contents once the temperature exceeds a certain threshold. Metal oxide NPs grown on the graphene oxide (GO) surface served multiple roles, including enhancing photothermal efficiency, acting as contrast agents to improve magnetic resonance imaging, increasing the sensitivity and specificity of photoacoustic imaging, and catalysing hydrogen peroxide for the generation of reactive oxygen species (ROS). When locally injected, the HMONs-rNGO@Fe3 O4 /MnOx@FA/DOX/TPP NPs effectively enriched in subcutaneous Hela cell tumour of mice. The photothermal/photodynamic/chemo combination therapy triggered by near-infrared (NIR) successfully suppressed the tumour without noticeable side effects. This study presented a unique approach to develop multimodal imaging-guided combination therapy for cancer.

Epitaxial substitution of metal iodides for low-temperature growth of two-dimensional metal chalcogenides.

The integration of various two-dimensional (2D) materials on wafers enables a more-than-Moore approach for enriching the functionalities of devices1-3. On the other hand, the additive growth of 2D materials to form heterostructures allows construction of materials with unconventional properties. Both may be achieved by materials transfer, but often suffer from mechanical damage or chemical contamination during the transfer. The direct growth of high-quality 2D materials generally requires high temperatures, hampering the additive growth or monolithic incorporation of different 2D materials. Here we report a general approach of growing crystalline 2D layers and their heterostructures at a temperature below 400 °C. Metal iodide (MI, where M = In, Cd, Cu, Co, Fe, Pb, Sn and Bi) layers are epitaxially grown on mica, MoS2 or WS2 at a low temperature, and the subsequent low-barrier-energy substitution of iodine with chalcogens enables the conversion to at least 17 different 2D crystalline metal chalcogenides. As an example, the 2D In2S3 grown on MoS2 at 280 °C exhibits high photoresponsivity comparable with that of the materials grown by conventional high-temperature vapour deposition (~700-1,000 °C). Multiple 2D materials have also been sequentially grown on the same wafer, showing a promising solution for the monolithic integration of different high-quality 2D materials.

Salt-Assisted Selective Growth of H-phase Monolayer VSe2 with Apparent Hole Transport Behavior.

Vanadium diselenide (VSe2) exhibits versatile electronic and magnetic properties in the trigonal prismatic (H-) and octahedral (T-) phases. Compared to the metallic T-phase, the H-phase with a tunable semiconductor property is predicted to be a ferrovalley material with spontaneous valley polarization. Herein we report an epitaxial growth of the monolayer 2D VSe2 on a mica substrate via the chemical vapor deposition (CVD) method by introducing salt in the precursor. Our first-principles calculations suggest that the monolayer H-phase VSe2 with a large lateral size is thermodynamically favorable. The honeycomb-like structure and the broken symmetry are directly observed by spherical aberration-corrected scanning transmission electron microscopy (STEM) and confirmed by giant second harmonic generation (SHG) intensity. The p-type transport behavior is further evidenced by the temperature-dependent resistance and field-effect device study. The present work introduces a new phase-stable 2D transition metal dichalcogenide, opening the prospect of novel electronic and spintronics device design.

Machine Learning-Aided Design of Gold Core-Shell Nanocatalysts toward Enhanced and Selective Photooxygenation.

We demonstrate the use of the machine learning (ML) tools to rapidly and accurately predict the electric field as a guide for designing core-shell Au-silica nanoparticles to enhance 1O2 sensitization and selectivity of organic synthesis. Based on the feature importance analysis, obtained from a deep neural network algorithm, we found a general and linear dependent descriptor (θ ∝ aD0.25t-1, where a, D, and t are the shape constant, size of metal nanoparticles, and distance from the metal surface) for the electric field around the core-shell plasmonic nanoparticle. Directed by the new descriptor, we synthesized gold-silica nanoparticles and validated their plasmonic intensity using scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) mapping. The nanoparticles with θ = 0.40 demonstrate an ∼3-fold increase in the reaction rate of photooxygenation of anthracene and 4% increase in the selectivity of photooxygenation of dihydroartemisinic acid (DHAA), a long-standing goal in organic synthesis. In addition, the combination of ML and experimental investigations shows the synergetic effect of plasmonic enhancement and fluorescence quenching, leading to enhancement for 1O2 generation. Our results from time-dependent density functional theory (TD-DFT) calculations suggest that the presence of an electric field can favor intersystem crossing (ISC) of methylene blue to enhance 1O2 generation. The strategy reported here provides a data-driven catalyst preparation method that can significantly reduce experimental cost while paving the way for designing photocatalysts for organic drug synthesis.

Electrically controlled mRNA delivery using a polypyrrole-graphene oxide hybrid film to promote osteogenic differentiation of human mesenchymal stem cells.

Direct messenger ribonucleic acid (mRNA) delivery to target cells or tissues has revolutionized the field of biotechnology. However, the applicability of regenerative medicine is limited by the technical difficulties of various mRNA-loaded nanocarriers. Herein, we report a new conductive hybrid film that could guide osteogenic differentiation of human adipose-derived mesenchymal stem cells (hADMSCs) via electrically controlled mRNA delivery. To find optimal electrical conductivity and mRNA-loading capacity, the polypyrrole-graphene oxide (PPy-GO) hybrid film was electropolymerized on indium tin oxide substrates. We found that the fluorescein sodium salt, a molecule partially mimicking the physical and chemical properties of mRNAs, can be effectively absorbed and released by electrical stimulation (ES). The hADMSCs cultivated on the PPy-GO hybrid film loaded with pre-osteogenic mRNAs showed the highest osteogenic differentiation under electrical stimulation. This platform can load various types of RNAs thus highly promising as a new nucleic acid delivery tool for the development of stem cell-based therapeutics. Electronic Supplementary Material: Supplementary material (electrochemical and FT-IR analysis on the film, additional SEM, AFM and C-AFM images of the film, optical and fluorescence images of cells, and the primers used for RT-qPCR analysis) is available in the online version of this article at 10.1007/s12274-022-4613-y.

Hierarchical Nanocages Assembled by NiCo-Layered Double Hydroxide Nanosheets for a High-Performance Hybrid Supercapacitor.

Layered double hydroxides (LDHs) have attracted broad attention as cathode materials for hybrid supercapacitors (HSCs) because of their ultrahigh theoretical specific capacitance, high compositional flexibility, and adjustable interlayer spacing. However, as reported, specific capacitance of LDHs is still far below the theoretical value, inspiring countless efforts to these ongoing challenges. Herein, a hierarchical nanocage structure assembled by NiCo-LDH nanosheet arrays was rationally designed and fabricated via a facile solvothermal method assisted by the ZIF-67 template. The transformation from the ZIF-67 template to this hollow structure is achieved by a synergistic effect involving the Kirkendall effect and the Ostwald ripening process. The enlarged specific surface area co-occurred with broadened interlayer spacing of LDH nanosheets by finely increasing the Ni concentration, leading to synchronous improvement of electron/ion transfer kinetics. The optimized NiCo-LDH-210 electrode displays a maximum specific capacitance of 2203.6 F g-1 at 2 A g-1, excellent rate capability, and satisfactory cycling stability because of the highly exposed active sites and shortened ion transport paths provided by vertically aligned LDH nanosheets together with the cavity. Furthermore, the assembled HSC device achieves a superior energy density of 57.3 Wh kg-1 with prominent cycling stability. Impressively, the design concept of complex construction derived from metal-organic frameworks (MOF) derivatives shows tremendous potential for use in energy storage systems.

Band Alignment Engineering by Twist Angle and Composition Modulation for Heterobilayer.

Atomically thin monolayer semiconducting transition metal dichalcogenides (TMDs), exhibiting direct band gap and strong light-matter interaction, are promising for optoelectronic devices. However, an efficient band alignment engineering method is required to further broaden their practical applications as versatile optoelectronics. In this work, the band alignment of two vertically stacked monolayer TMDs using the chemical vapor deposition (CVD) method is effectively tuned by two strategies: 1) formulating the compositions of MoS2(1-x) Se2x alloys, and 2) varying the twist angles of the stacked heterobilayer structures. Photoluminescence (PL) results combined with density functional theory (DFT) calculation show that by changing the alloy composition, a continuously tunable band alignment and a transition of type II-type I-type II band alignment of TMD heterobilayer is achieved. Moreover, only at moderate (10°-50°) twist angles, a PL enhancement of 28%-110% caused by the type I alignment is observed, indicating that the twist angle is coupled with the global band structure of heterobilayer. A heterojunction device made with MoS0.76 Se1.24 /WS2 of 14° displays a significantly high photoresponsivity (55.9 A W-1 ), large detectivity (1.07 × 1010 Jones), and high external quantum efficiency (135%). These findings provide engineering tools for heterostructure design for their application in optoelectronic devices.

Conductive Hydrogel Conduits with Growth Factor Gradients for Peripheral Nerve Repair in Diabetics with Non-Suture Tape.

Diabetic patients suffer from peripheral nerve injury with slow and incomplete regeneration owing to hyperglycemia and microvascular complications. This study develops a graphene-based nerve guidance conduit by incorporating natural double network hydrogel and a neurotrophic concentration gradient with non-invasive treatment for diabetics. GelMA/silk fibroin double network hydrogel plays quadruple roles for rapid setting/curing, suitable mechanical supporting, good biocompatibility, and sustainable growth factor delivery. Meanwhile, graphene mesh can improve the toughness of conduit and enhance conductivity of conduit for regeneration. Here, novel silk tapes show quick and tough adhesion of wet tissue by dual mechanism to replace suture step. The in vivo results demonstrate that gradient concentration of netrin-1 in conduit have better performance than uniform concentration caused by chemotaxis phenomenon for axon extension, remyelination, and angiogenesis. Altogether, GelMA/silk graphene conduit with gradient netrin-1 and dry double-sided adhesive tape can significantly promote repairing of peripheral nerve injury and inhibit the atrophy of muscles for diabetics.

Super-Resolution Photoacoustic Microscopy via Modified Phase Compounding.

Acoustic-resolution photoacoustic micro- scopy (AR-PAM) system can provide 3-D images of facial tissues. The lateral resolution of AR-PAM depends on the numerical aperture (NA) of the acoustic lens and the central frequency of the ultrasonic transducer. There is a trade-off between resolution enhancement and imaging depth. The acoustic beam is tight in the acoustic focal plane but expands in the out-of-focus regions, deteriorating the resolution. High-NA AR-PAM has depth-variant resolution. Synthetic aperture focusing technique (SAFT) based on a virtual detector (VD) concept can compensate for the beam shape and improve the lateral resolution via beamforming. Although, beamforming can enhance the resolution but the lateral resolution in the focal plane is still limited by acoustic diffraction. Structured-illumination can shift the spatial spectrum of an image to low frequencies hence high-frequency contents can be reserved to overcome the diffraction limit. Conventional structured-illumination via using a three-phase-shifting method can improve the resolution by two folds. Here, a modified phase-shifting method is used to generate the second harmonic of the fringes and double the spectral shift. In this idea, higher frequency information compared to the three-phase shifting method can fall into the band-limited system response. The modified phase-shifting method expands the spatial bandwidth and increases the lateral resolution by five folds. The mathematical relations and the theory are discussed in the context. Tungsten filament result shows resolution improvement from 44.6 [Formula: see text] to 11.3 [Formula: see text] by the modified structured illumination. In vivo and ex vivo experimental results validate the system performance.

Quasi-Continuous Network Structure Greatly Improved the Anti-Arc-Erosion Capability of Ag/Y2O3 Electrical Contacts.

Ag/Y2O3 has excellent potential to replace Ag/CdO as the environmentally friendly electrical contact material. Using spherical Y2O3 as the starting material, Ag/Y2O3 contacts with a quasi-continuous network structure were successfully fabricated by a low-energy ball milling treatment. The mean size of Y2O3 used ranged from 243 to 980 nm. Due to the differences in the size of Y2O3, Ag/Y2O3 contacts had different primitive microstructures, thereby exhibiting distinctive anti-arc-erosion capabilities. Ag/Y2O3 contact prepared using 243 nm Y2O3 showed the best anti-arc-erosion capability and the most outstanding electrical performance measures, such as low contact resistance, less mass transfer, and no failure up to 105 cycle times. The quasi-continuous network structure formed in the micro-scale was responsible for the excellent electrical performance. The short distance between Y2O3 particles in the network promoted the cathode arc motion, and thus alleviated the localized erosion. The results obtained herein may inspire further attempts to design electrical contacts rationally.

Rational Control on Quantum Emitter Formation in Carbon-Doped Monolayer Hexagonal Boron Nitride.

Single-photon emitters (SPEs) in hexagonal boron nitride (hBN) are promising candidates for quantum light generation. Despite this, techniques to control the formation of hBN SPEs down to the monolayer limit are yet to be demonstrated. Recent experimental and theoretical investigations have suggested that the visible wavelength single-photon emitters in hBN originate from carbon-related defects. Here, we demonstrate a simple strategy for controlling SPE creation during the chemical vapor deposition growth of monolayer hBN via regulating surface carbon concentration. By increasing the surface carbon concentration during hBN growth, we observe increases in carbon doping levels by 2.4-fold for B-C bonds and 1.6-fold for N-C bonds. For the same samples, we observe an increase in the SPE density from 0.13 to 0.30 emitters/µm2. Our simple method enables the reliable creation of hBN SPEs in monolayer samples for the first time, opening the door to advanced two-dimensional (2D) quantum state engineering.