Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution.

Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3-8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6-8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T' phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T' phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T'-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T'-MoS2 a mass activity of 85 ± 23 A [Formula: see text] at the overpotential of -50 mV and a mass-normalized exchange current density of 127 A [Formula: see text] and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T'-TMDs will also be effective supports for other catalysts targeting other important reactions.

1T'-transition metal dichalcogenide monolayers stabilized on 4H-Au nanowires for ultrasensitive SERS detection.

Unconventional 1T'-phase transition metal dichalcogenides (TMDs) have aroused tremendous research interest due to their unique phase-dependent physicochemical properties and applications. However, due to the metastable nature of 1T'-TMDs, the controlled synthesis of 1T'-TMD monolayers (MLs) with high phase purity and stability still remains a challenge. Here we report that 4H-Au nanowires (NWs), when used as templates, can induce the quasi-epitaxial growth of high-phase-purity and stable 1T'-TMD MLs, including WS2, WSe2, MoS2 and MoSe2, via a facile and rapid wet-chemical method. The as-synthesized 4H-Au@1T'-TMD core-shell NWs can be used for ultrasensitive surface-enhanced Raman scattering (SERS) detection. For instance, the 4H-Au@1T'-WS2 NWs have achieved attomole-level SERS detections of Rhodamine 6G and a variety of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spike proteins. This work provides insights into the preparation of high-phase-purity and stable 1T'-TMD MLs on metal substrates or templates, showing great potential in various promising applications.

Boosting the reaction kinetics in aprotic lithium-carbon dioxide batteries with unconventional phase metal nanomaterials.

Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO2) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO2 batteries with unconventional phase 4H/face-centered cubic (fcc) iridium (Ir) nanostructures grown on gold template. Significantly, 4H/fcc Ir exhibits superior electrochemical performance over fcc Ir in facilitating the round-trip reaction kinetics of Li+-mediated CO2 reduction and evolution, achieving a low charge plateau below 3.61 V and high energy efficiency of 83.8%. Ex situ/in situ studies and theoretical calculations reveal that the boosted reaction kinetics arises from the highly reversible generation of amorphous/low-crystalline discharge products on 4H/fcc Ir via the Ir-O coupling. The demonstration of flexible Li-CO2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

Identification of kukoamine a as an anti-osteoporosis drug target using network pharmacology and experiment verification.

BACKGROUND: Osteoporosis (OP) is a major and growing public health problem characterized by decreased bone mineral density and destroyed bone microarchitecture. Previous studies found that Lycium Chinense Mill (LC) has a potent role in inhibiting bone loss. Kukoamine A (KuA), a bioactive compound extract from LC was responsible for the anti-osteoporosis effect. This study aimed to investigate the anti-osteoporosis effect of KuA isolated from LC in treating OP and its potential molecular mechanism. METHOD: In this study, network pharmacology and molecular docking were investigated firstly to find the active ingredients of LC such as KuA, and the target genes of OP by the TCMSP platform. The LC-OP-potential Target gene network was constructed by the STRING database and network maps were built by Cytoscape software. And then, the anti-osteoporotic effect of KuA in OVX-induced osteoporosis mice and MC3T3-E1 cell lines were investigated and the potential molecular mechanism including inflammation level, cell apoptosis, and oxidative stress was analyzed by dual-energy X-ray absorptiometry (DXA), micro-CT, ELISA, RT-PCR, and Western Blotting. RESULT: A total of 22 active compounds were screened, and we found KuA was identified as the highest active ingredient. Glycogen Phosphorylase (PYGM) was the target gene associated with a maximum number of active ingredients of LC and regulated KuA. In vivo, KuA treatment significantly increased the bone mineral density and improve bone microarchitecture for example increased BV/TV, Tb.N and Tb.Th but reduced Tb.Sp in tibia and lumber 4. Furthermore, KuA increased mRNA expression of osteoblastic differentiation-related genes in OVX mice and protects against OVX-induced cell apoptosis, oxidative stress level and inflammation level. In vitro, KuA significantly improves osteogenic differentiation and mineralization in cells experiment. In addition, KuA also attenuated inflammation levels, cell apoptosis, and oxidative stress level. CONCLUSION: The results suggest that KuA could protect against the development of OP in osteoblast cells and ovariectomized OP model mice and these found to provide a better understanding of the pharmacological activities of KuA again bone loss.

Phase-assisted Bessel-metasurface: a single-sized approach for simultaneous printing and holography.

Due to the unprecedented wavefront shaping capability, the metasurface has demonstrated state-of-the-art performances in various applications, especially in printing and holography. Recently, these two functions have been combined into a single metasurface chip to achieve a capability expansion. Despite the progress, current dual-mode metasurfaces are realized at the expense of an increase in the difficulty of the fabrication, reduction of the pixel resolution, or strict limitation in the illumination conditions. Inspired by the Jacobi-Anger expansion, a phase-assisted paradigm, called Bessel metasurface, has been proposed for simultaneous printing and holography. By elaborately arranging the orientations of the single-sized nanostructures with geometric phase modulation, the Bessel metasurface can not only encode a greyscale printing image in real space but can reconstruct a holographic image in k-space. With the merits of compactness, easy fabrication, convenient observation, and liberation of the illumination conditions, the design paradigm of the Bessel metasurface would have promising prospects in practical applications, including optical information storage, 3D stereoscopic displays, multifunctional optical devices, etc.

Preparation of Au@Pd Core-Shell Nanorods with fcc-2H-fcc Heterophase for Highly Efficient Electrocatalytic Alcohol Oxidation.

Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and investigating the structure-dependent catalytic performance. Here, a wet-chemical synthesis method is used to prepare Au@Pd core-shell nanorods with a unique fcc-2H-fcc heterophase (fcc: face-centered cubic; 2H: hexagonal close-packed with a stacking sequence of "AB"). The obtained fcc-2H-fcc heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic ethanol oxidation performance with a mass activity as high as 6.82 A mgPd-1, which is 2.44, 6.96, and 6.43 times those of 2H-Pd nanoparticles, fcc-Pd nanoparticles, and commercial Pd/C, respectively. The operando infrared reflection absorption spectroscopy reveals a C2 pathway with fast reaction kinetics for the ethanol oxidation on the prepared heterophase Au@Pd nanorods. Our experimental results together with density functional theory calculations indicate that the enhanced performance of heterophase Au@Pd nanorods can be attributed to the unconventional 2H phase, the 2H/fcc phase boundary, and the lattice expansion of the Pd shell. Moreover, the heterophase Au@Pd nanorods can also serve as an efficient catalyst for the electrochemical oxidation of methanol, ethylene glycol, and glycerol. Our work in the area of phase engineering of nanomaterials (PENs) opens the way for developing high-performance electrocatalysts toward future practical applications.

Multifold Integration of Printed and Holographic Meta-Image Displays Enabled by Dual-Degeneracy.

By virtue of the unprecedented ability of manipulating the optical parameters, metasurfaces open up a new avenue for realizing ultra-compact image displays, e.g., nanoprinting on the surface and holographic displaying in the far-field. The multifold integration of these two functions into a single metasurface can undoubtedly expand the functionality and increase the information capacity. In this study, a minimalist tri-channel metasurface is proposed and experimentally demonstrated with multifold integration of printed and holographic displaying, which can generate two N-bit grayscale images and a four-step holographic image simultaneously. Benefiting from exploiting the degeneracy of energy allocation and the degeneracy of nanostructure orientations, the functionalities of nanoprinting and holography are combined without the need of a large amount of nanostructures with varied dimensions, which would facilitate both the metasurface design and fabrication. The proposed scheme provides a new idea in enhancing the functionality and capacity of metasurfaces without complicating their design, which has promising prospects for applications in ultra-compact image displays, high-density optical storage, optical anti-counterfeiting and many other related fields.

Correlations between incident and emission polarization in nanowire-particle coupled junctions.

Plasmonic nanostructures with subwavelength confinement are of great importance for the development of integrated nanophotonic circuits and devices. Here, we experimentally investigate how the polarization of the emitted light from nanowire-particle junction relies on the incident polarization. We demonstrate that the correlations can be effectively modulated by the particle position relative to the wire. By varying the wire-particle gap with only several nanometers, the nanowire-particle junction can be changed from polarization maintainer to rotator. Then, by moving the particle along the wire within half of the surface plasmon polariton (SPP) beat, the polarization behaviors can be tuned from positive to negative correlation. The mechanism can be well understood by the hybridization of wire-particle coupled mode and propagating SPP modes, which is verified by finite-difference time-domain simulations. These findings would provide a new degree of freedom for manipulating light polarization at the nanometer scale and additional flexibility for constructing nanophotonic devices.

Dual-channel anticounterfeiting color-nanoprinting with a single-size nanostructured metasurface.

Metasurface-based structural-colors are usually implemented by changing the dimensions of nanostructures to produce different spectral responses. Therefore, a single-size nanostructured metasurface usually cannot display structural-colors since it has only one design degree of freedom (DOF), i.e., the orientation angles of nanostructures. Here, we show structural-color nanoprinting images can be generated with a single-size nanostructured metasurface, enabled by designing the anisotropic nanostructure with different spectral responses along its long- and short-axis directions, respectively. More interestingly, the concept of orientation degeneracy of nanostructures can be applied in the metasurface design, which shows two spectral modulations can be implemented under different polarization directions of output light, thus extending the color-nanoprinting from single-channel to dual-channel. The proposed dual-channel metasurface used for anticounterfeiting color-nanoprinting has presented the advantages of ultra-compactness, high information capacity, and vivid colors, which can develop broad applications in fields such as high-end anticounterfeiting, high-density information storage, optical encryption, etc.

The effect of whole-body vibration in osteopenic patients after total knee arthroplasty: a randomized controlled trial.

BACKGROUND: Total knee arthroplasty (TKA) is an important treatment for knee osteoarthritis, but the result of whole-body vibration (WBV) in knee function rehabilitation and bone loss with osteopenia was unknown. Therefore, the purpose of this study is to study whether low-frequency, low-amplitude WBV can improve the clinical outcome of knee osteoarthritis. METHODS: This study was randomized and included 67 osteopenic patients (55-90 years, 85% women) for TKA surgery (control group N = 32, WBV group N = 35). All selected patients after TKA surgery tested clinical results, such as knee function and bone mass in baseline, 3 months after surgery, and 6 months after surgery. RESULTS: Compared to the control group, the WBV group improved pain scores, thigh circumference, lower limb muscle strength, joint activity, and joint function in 6 months after surgery. WBV intervention also improves bone density in the spine, the microstructure of the radius and tibia, and the bone turnover marker. At 3 months after TKA surgery, the WBV group had no significant effect on knee function and bone loss. CONCLUSIONS: Whole-body vibration for osteopenic patients with knee arthroplasty showed good therapeutic results in 6 months after TKA surgery, but the long-term therapeutic effect still needs to be further observed.

Co-assembled Monolayers as Hole-Selective Contact for High-Performance Inverted Perovskite Solar Cells with Optimized Recombination Loss and Long-Term Stability.

Self-assembled monolayers (SAMs) have been widely employed as an effective way to modify interfaces of electronic/optoelectronic devices. To achieve a good control of the growth and molecular functionality of SAMs, we develop a co-assembled monolayer (co-SAM) for obtaining efficient hole selection and suppressed recombination at the hole-selective interface in inverted perovskite solar cells (PSCs). By engineering the position of methoxy substituents, an aligned energy level and favorable dipole moment can be obtained in our newly synthesized SAM, ((2,7-dimethoxy-9H-carbazol-9-yl) methyl) phosphonic acid (DC-PA). An alkyl ammonium containing SAM is co-assembled to further optimize the surface functionalization and interaction with perovskite layer on top. A champion device with an excellent power conversion efficiency (PCE) of 23.59 % and improved device stability are achieved. This work demonstrates the advantage of using co-SAM in improving performance and stability of PSCs.

In Situ Raman Probing of Hot-Electron Transfer at Gold-Graphene Interfaces with Atomic Layer Accuracy.

Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal-2D material interfaces remain unclear. Herein, hot-electron transfer at Au-graphene interfaces has been in situ studied using surface-enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot-electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene.

Single-celled multifunctional metasurfaces merging structural-color nanoprinting and holography.

Nanostructured metasurfaces applied in structural-color nanoprinting and holography have been extensively investigated in the past several years. Recently, merging them together is becoming an emerging approach to improve the information capacity and functionality of metasurfaces. However, current approaches, e.g., segmenting, interleaving and stacking schemes for function merging, suffer from crosstalk, low information density, design and fabrication difficulties. Herein, we employ a single-celled approach to design and experimentally demonstrate a high-density multifunctional metasurface merging nanoprinting and holography, i.e., each nanostructure in the metasurface can simultaneously manipulate the spectra (enabled with varied dimensions of nanostructures) and geometric phase (enabled with varied orientation angles of nanostructures) of incident light. Hence, with different decoding strategies, a structural-color nanoprinting image emerges right at the metasurface plane under white light illumination, while a holographic image is reconstructed in the Fraunhofer diffraction zone under circularly polarized laser light incidence. And the two images have no crosstalk since they are independently designed and presented at different distances. Our proposal suggests a space-multiplexing scheme to develop advanced metasurfaces and one can find their markets in high-density information storage, optical information encryption, multi-channel image display, etc.

Asymmetric hologram with a single-size nanostructured metasurface.

Geometric metasurfaces, governed by PB phase, have shown their strong polarization sensitivity and can generate opposite phase delay when the handedness of incident circularly-polarized (CP) light is opposite. Here, we show this interesting characteristic can be employed to generate asymmetric forward and backward propagation with the same incident left- or right-handed CP light, which is hard to achieve with conventional optical elements and devices. Specifically, with the modified holographic design algorithm to consider both forward and backward CP light, an asymmetric meta-hologram is designed, which can project two different holographic images in the forward and backward directions, respectively. We demonstrate this concept by fabricating an asymmetric hologram with a single-size nanostructured metasurface, and the experimentally obtained holographic images in both directions have shown their advantages of high fidelity, broadband response and low crosstalk. The proposed asymmetric metasurface can play an important role in data storages, anti-counterfeitings, optical communications, displays and many other related fields.

Multiplexing meta-hologram with separate control of amplitude and phase.

Metasurfaces have shown their unique capabilities to manipulate the phase and/or amplitude properties of incident light at the subwavelength scale, which provides an effective approach for constructing amplitude-only, phase-only or even complexed amplitude meta-devices with high resolution. Most of meta-devices control the amplitude and/or phase of the incident light with the same polarization state; however, separately controlling of amplitude and phase of the incident light with different polarization states can provide a new degree of freedom for improving the information capacity of metasurfaces and designing multifunctional meta-devices. Herein, we combine the amplitude manipulation and geometric phase manipulation by only reconfiguring the orientation angle of the nanostructure and present a single-sized design strategy for a multiplexing meta-hologram which plays the dual roles: a continuous amplitude-only meta-device and a two-step phase-only meta-device. Two different modulation types can be readily switched merely by polarization controls. Our approach opens up the possibilities for separately and independently controlling of amplitude and phase of light to construct a multiplexing meta-hologram with a single-sized metasurface, which can contribute to the advanced research and applications in multi-folded optical anti-counterfeiting, optical information hiding and optical information encoding.

Multiplexed Anticounterfeiting Meta-image Displays with Single-Sized Nanostructures.

Metasurfaces have recently been used for multichannel image displays with pixel-size lower than a wavelength, which indicates the potential application in ultracompact anticounterfeiting with high-density and hidden information. However, current multichannel metasurfaces applied in anticounterfeiting are based on the sophisticated nanostructure design or at the cost of giving up some controls on the optical transmission matrix to encode multiple information channels. That is, the overall degrees of freedom offered by these metasurfaces are a "zero-sum game". Here, inspired by the orientation degeneracy indicated in Malus law, we propose a multiplexed anticounterfeiting metasurface consisting of single-sized nanostructures, which provide a new degree of freedom to increase the information capacity of anticounterfeiting without burdening the nanostructure design and fabrication. Specifically, the proposed metasurfaces can record a continuous grayscale image (channel 1) multiplexed with a totally/partially independent, interrelated, or watermarked anticounterfeiting pattern (channel 2). The two channels can be readily switched by polarization control. All experimental metasurface-images (meta-images) with high fidelity agree well with our design. With advantages such as ultracompactness, high-density information, multichannel displays, and strong concealment, the anticounterfeiting metasurfaces can empower advanced research and applications of metasurfaces in high-end optical anticounterfeiting and many other related fields.

In Situ Raman Monitoring and Manipulating of Interfacial Hydrogen Spillover by Precise Fabrication of Au/TiO2 /Pt Sandwich Structures.

The spillover of hydrogen species and its role in tuning the activity and selectivity in catalytic hydrogenation have been investigated in situ using surface-enhanced Raman spectroscopy (SERS) with 10 nm spatial resolution through the precise fabrication of Au/TiO2 /Pt sandwich nanostructures. In situ SERS study reveals that hydrogen species can efficiently spillover at Pt-TiO2 -Au interfaces, and the ultimate spillover distance on TiO2 is about 50 nm. Combining kinetic isotope experiments and density functional theory calculations, it is found that the hydrogen spillover proceeds via the water-assisted cleavage and formation of surface hydrogen-oxygen bond. More importantly, the selectivity in the hydrogenation of the nitro or isocyanide group is manipulated by controlling the hydrogen spillover. This work provides molecular insights to deepen the understanding of hydrogen activation and boosts the design of active and selective catalysts for hydrogenation.

Mechanism of resonant perfect optical absorption in dielectric film supporting metallic grating structures.

The mechanism of resonant perfect optical absorbers is quantitatively revealed by the coupled mode method for the air/grating/dielectric film/air four region system. The sufficient and necessary conditions of the perfect optical absorption are derived from the interface scattering coefficients analyses. The coupling of the Fabry-Perot modes in the grating slits and non-zero order quasi waveguide modes in the dielectric film play a key role for the perfect optical absorption when the light is incident from the grating side. The analytical sufficient and necessary conditions of the perfect optical absorption provide an efficient tool towards geometry design for the perfect optical absorption at the specific wavelengths. The advantages of a widely tunable perfect optical absorption wavelength, a high Q factor and the confined energy loss on metal surfaces make the air/grating/film/air structures promising for applications in sensing, modulation and detection.