Stabilizing and Activating Active Sites: 1T-MoS2 Supported Pd Single Atoms for Efficient Hydrogen Evolution Reaction.

Metallic 1T-MoS2 with high intrinsic electronic conductivity performs Pt-like catalytic activity for hydrogen evolution reaction (HER). However, obtaining pure 1T-MoS2 is challenging due to its high formation energy and metastable properties. Herein, an in situ SO4 2--anchoring strategy is reported to synthesize a thin layer of 1T-MoS2 loaded on commercial carbon. Single Pd atoms, constituting a substantial loading of 7.2 wt%, are then immobilized on the 1T-phase MoS2 via Pd─S bonds to modulate the electronic structure and ensure a stable active phase. The resulting Pd1/1T-MoS2/C catalyst exhibits superior HER performance, featuring a low overpotential of 53 mV at the current density of 10 mA cm-2, a small Tafel slope of 37 mV dec-1, and minimal charge transfer resistance in alkaline electrolyte. Moreover, the catalyst also demonstrates efficacy in acid and neutral electrolytes. Atomic structural characterization and theoretical calculations reveal that the high activity of Pd1/1T-MoS2/C is attributed to the near-zero hydrogen adsorption energy of the activated sulfur sites on the two adjacent shells of atomic Pd.

Metabolite Profiling and Biological Activity Assessment of Paeonia ostii Anthers and Pollen Using UPLC-QTOF-MS.

Paeonia ostii is an important economic oil and medicinal crop. Its anthers are often used to make tea in China with beneficial effects on human health. However, the metabolite profiles, as well as potential biological activities of P. ostii anthers and the pollen within anthers have not been systematically analyzed, which hinders the improvement of P. ostii utilization. With comprehensive untargeted metabolomic analysis using UPLC-QTOF-MS, we identified a total of 105 metabolites in anthers and pollen, mainly including phenylpropanoids, polyketides, organic acids, benzenoids, lipids, and organic oxygen compounds. Multivariate statistical analysis revealed the metabolite differences between anthers and pollen, with higher carbohydrates and flavonoids content in pollen and higher phenolic content in anthers. Meanwhile, both anthers and pollen extracts exhibited antioxidant activity, antibacterial activity, α-glucosidase and α-amylase inhibitory activity. In general, the anther stage of S4 showed the highest biological activity among all samples. This study illuminated the metabolites and biological activities of anthers and pollen of P. ostii, which supports the further utilization of them.

Cooperative Shielding of Bi-Electrodes via In Situ Amorphous Electrode-Electrolyte Interphases for Practical High-Energy Lithium-Metal Batteries.

Solid-state Li-metal batteries offer a great opportunity for high-security and high-energy-density energy storage systems. However, redundant interfacial modification layers, intended to lead to an overall satisfactory interfacial stability, dramatically debase the actual energy density. Herein, a dual-interface amorphous cathode electrolyte interphase/solid electrolyte interphase CEI/SEI protection (DACP) strategy is proposed to conquer the main challenges of electrochemical side reactions and Li dendrites in hybrid solid-liquid batteries without sacrificing energy density via LiDFOB and LiBF4 in situ synergistic conversion. The amorphous CEI/SEI products have an ultralow mass proportion and act as a dynamic shield to cooperatively enforce dual electrodes with a well-preserved structure. Thus, this in situ DACP layer subtly reconciles multiple interfacial compatibilities and a high energy density, endowing the hybrid solid-liquid Li-metal battery with a sustainably brilliant cycling stability even at practical conditions, including high cathode loading, high voltage (4.5 V), and high temperature (45 °C) conditions, and enables a high-energy-density (456 Wh kg-1) pouch cell (11.2 Ah, 5 mA h cm-2) with a lean electrolyte (0.92 g Ah-1, containing solid and liquid phases). The compatible modification strategy points out a promising approach for the design of practical interfaces in future solid-state battery systems.

P3/O3 Integrated Layered Oxide as High-Power and Long-Life Cathode toward Na-Ion Batteries.

Low-cost and stable sodium-layered oxides (such as P2- and O3-phases) are suggested as highly promising cathode materials for Na-ion batteries (NIBs). Biphasic hybridization, mainly involving P2/O3 and P2/P3 biphases, is typically used to boost their electrochemical performances. Herein, a P3/O3 intergrown layered oxide (Na2/3 Ni1/3 Mn1/3 Ti1/3 O2 ) as high-rate and long-life cathode for NIBs via tuning the amounts of Ti substitution in Na2/3 Ni1/3 Mn2/3- x Tix O2 (x = 0, 1/6, 1/3, 2/3) is demonstrated. The X-ray diffraction (XRD) Rietveld refinement and aberration-corrected scanning transmission electron microscopy show the co-existence of P3 and O3 phases, and density functional theory calculation corroborates the appearance of the anomalous O3 phase at the Ti substitution amount of 1/3. The P3/O3 biphasic cathode delivers an unexpected rate capability (≈88.7% of the initial capacity at a high rate of 5 C) and cycling stability (≈68.7% capacity retention after 2000 cycles at 1 C), superior to those of the sing phases P3-Na2/3 Ni1/3 Mn2/3 O2 , P3-Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 , and O3-Na2/3 Ni1/3 Ti2/3 O2 . The highly reversible structural evolution of the P3/O3 integrated cathode observed by ex situ XRD, ex situ X-ray absorption spectra, and the rapid Na+ diffusion kinetics, underpin the enhancement. These results show the important role of P3/O3 biphasic hybridization in designing and engineering layered oxide cathodes for NIBs.

Uniform Nucleation of Lithium in 3D Current Collectors via Bromide Intermediates for Stable Cycling Lithium Metal Batteries.

The conductive framework is generating considerable interest for lithium metal anodes to accommodate Li+ deposition, due to its ability to reduce electrode current density by increasing the deposition area. However, in most cases, the electroactive surface area is not fully utilized for the nucleation of Li in 3D current collectors, especially under high current densities. Herein, uniform nucleation of Li in the conductive skeleton is achieved by a two-step synergetic process arising from CuBr- and Br-doped graphene-like film. The modified electrode regulates Li nucleating in uniform pancake-like seeds and growing into a granular Li metal ascribed to the excellent lithiophilicity of CuBr- and Br-doping sites and the low Li diffusion barrier on the surface of generated LiBr, as confirmed by the experimental and computational results. Therefore, the modified anode endows small nucleation overpotential, a high-reversibility Li plating/stripping process, and excellent performance in full batteries with industrially significant cathode loading. This work suggests that a two-step cooperative strategy opens a viable route to the development of a Li anode with high reversibility for stable cycling Li metal batteries.

Microbial-Phosphorus-Enabled Synthesis of Phosphide Nanocomposites for Efficient Electrocatalysts.

Transition-metal phosphides have recently been identified as low-cost and efficient electrocatalysts that are highly active for the hydrogen evolution reaction. Unfortunately, to achieve a controlled phosphidation of nonprecious metals toward a desired nanostructure of metal phosphides, the synthetic processes usually turned complicated, high-cost, and even dangerous due to the reaction chemistry related to different phosphorus sources. It becomes even more challenging when considering the integration of those active metal phosphides with the structural engineering of their conductive matrix toward a favorable architecture for optimized catalytic performance. Herein, we identified that the biomass itself could act as an effective synthetic platform for the construction of supported metal phosphides by recovering its inner phosphorus upon reacting with transition-metals ions, forming well-dispersed, highly active nanoparticles of metal phosphides incorporated in the nanoporous carbon matrix, which promised high catalytic activity in the hydrogen evolution reaction. Our synthetic protocol not only provides a simple and effective strategy for the construction of a large variety of highly active nanoparticles of metal phosphides but also envisions new perspectives on an integrated utilization of the essential ingredients, particularly phosphorus, together with the innate architecture of the existing biomass for the creation of functional nanomaterials toward sustainable energy development.

Simultaneous phase-shifting dual-wavelength interferometry based on independent component analysis.

An independent component analysis-based simultaneous phase-shifting dual-wavelength interferometry approach is proposed. By using a one-time phase-shifting procedure, the simultaneous phase-shifting operation of two illumination wavelengths can be implemented, and then the background intensity and two orthogonal independent components of each single wavelength can be separated from a sequence of simultaneous phase-shifting dual-wavelength interferograms with random phase shifts. Subsequently, the wrapped phases of single wavelength can be calculated by above two orthogonal independent components; thus the unambiguous phase of synthetic wavelength can be achieved. Both the simulation and experimental results show that the proposed approach reveals the advantages of high accuracy, rapid speed, high stability, and good adaptability for arbitrary phase shifts.

Dynamic phase measurement based on spatial carrier-frequency phase-shifting method.

Combining spatial carrier-frequency phase-shifting (SCPS) technique and Fourier transform method, from one-frame spatial carrier-frequency interferogram (SCFI), a novel phase retrieval method is proposed and applied to dynamic phase measurement. First, using the SCPS technique, four-frame phase-shifting sub-interferograms can be constructed from one-frame SCFI. Second, using Fourier transform method, the accurate phase-shifts of four sub-interferograms can be extracted rapidly, so there is no requirement of calibration for the carrier-frequency in advance compared to most existing SCPS methods. Third, the wrapped phase can be retrieved with the least-squares algorithm through using the above phase-shifts. Finally, the phase variations of a water droplet evaporation and a Jurkat cell apoptosis induced by a drug are presented with the proposed method. Both the simulation and experimental results demonstrate that in addition to maintaining high accuracy of the SCPS method, the proposed method reveals more rapid processing speed of phase retrieval, and this will greatly facilitate its application in dynamic phase measurement.

Dual-wavelength interferometry based on the spatial carrier-frequency phase-shifting method.

From a single-frame dual-wavelength spatial carrier-frequency interferogram (SCFI), we propose a novel phase retrieval method of dual-wavelength interferometry (DWI). First, by continuously moving the intercepted area pixel-by-pixel in a single-frame SCFI along the horizontal and vertical directions, we construct a sequence of phase-shifting sub-interferograms. Second, the wrapped phases of each single wavelength can be retrieved from those phase-shifting sub-interferograms via the least-squares iteration algorithm. Third, the phase of synthetic wavelength can be obtained by subtraction between the wrapped phases of single wavelengths. Both the numerical simulation and the experimental result demonstrate that the proposed method reveals greater accuracy and convenience. Furthermore, because only single-frame SCFI can perform the phase retrieval of DWI, the proposed method offers better ability in resisting external vibration and disturbance, which will greatly facilitate the application of DWI in the dynamic phase measurement.

Optimization of In Vitro Germination, Viability Tests and Storage of Paeonia ostii Pollen.

Paeonia ostii is an important woody oil crop mainly cross-pollinated. However, the low yield has become an important factor restricting the industrial development of P. ostii. Cross-pollination has become one of the important measures to increase the seed yield. Therefore, conservation of pollen with high vitality is crucial to ensure successful pollination of P. ostii. In this study, we found an effective methodological system to assess the viability, ability to germinate, and optimal storage conditions of P. ostii pollen grains. The optimal medium in vitro was 50 g/L sucrose, 100 mg/L boric acid, 50 g/L PEG6000, 100 mg/L potassium nitrate, 300 mg/L calcium nitrate, and 200 mg/L magnesium sulfate at pH 5.4. Optimal germination condition in vitro was achieved at 25 °C for 120 min, allowing easy observation of the germination percentage and length of the pollen tubes. In addition, the viability of pollen grains was assessed by comparing nine staining methods. Among them, MTT, TTC, benzidine-H2O2, and FDA were effective to distinguish between viable and non-viable pollen, and the results of the FDA staining method were similar to the pollen germination percentage in vitro. After evaluation of pollen storage, thawing and rehydration experiments showed that thawing at 4 °C for 30 min and rehydration at 25 °C for 30 min increased the germination percentage of pollen grains stored at low temperatures. The low-temperature storage experiments showed that 4 °C was suitable for short-term storage of P. ostii pollen grains, while -80 °C was suitable for long-term storage. This is the first report on the in vitro germination, viability tests, and storage of P. ostii pollen grains, which will provide useful information for P. ostii germplasm conservation and artificial pollination.

trans-Difluoroethylene Carbonate as an Electrolyte Additive for Microsized SiOx@C Anodes.

Microsized SiOx has been vigorously investigated as an advanced anode material for next-generation lithium-ion batteries. However, its practical application is seriously hampered by its huge volume variation during the repeated (de)lithiation process, which destroys the microparticle structure and results in rapid capacity fading. Herein, we propose the usage of trans-difluoroethylene carbonate (DFEC) as an electrolyte additive to maintain the structural integrity of microsized SiOx with a uniform carbon layer (SiOx@C). Compared with ethylene carbonate and fluoroethylene carbonate, DFEC has lower lowest unoccupied molecular orbital energy and higher reduction potential, which is easily reduced and promotes the in situ formation of a more stable LiF-rich solid electrolyte interphase (SEI) on the surface of anode materials. The LiF-rich SEI exhibits enhanced mechanical rigidity and ionic conductivity, thus enabling the microsized SiOx@C anodes' excellent lithium storage stability and high average Coulombic efficiency.

Steering elementary steps towards efficient alkaline hydrogen evolution via size-dependent Ni/NiO nanoscale heterosurfaces.

Alkaline hydrogen evolution reaction (HER), consisting of Volmer and Heyrovsky/Tafel steps, requires extra energy for water dissociation, leading to more sluggish kinetics than acidic HER. Despite the advances in electrocatalysts, how to combine active sites to synergistically promote both steps and understand the underlying mechanism remain largely unexplored. Here, Density Functional Theory (DFT) calculations predict that NiO accelerates the Volmer step while metallic Ni facilitates the Heyrovsky/Tafel step. A facile strategy is thus developed to control Ni/NiO heterosurfaces in uniform and well-dispersed Ni-based nanocrystals, targeting both reaction steps synergistically. By systematically modulating the surface composition, we find that steering the elementary steps through tuning the Ni/NiO ratio can significantly enhance alkaline HER activity, and Ni/NiO nanocrystals with a Ni/NiO ratio of 23.7% deliver the best activity, outperforming other state-of-the-art analogues. The results suggest that integrating bicomponent active sites for elementary steps is effective for promoting alkaline HER, but they have to be balanced.

Air-Stable and High-Voltage Layered P3-Type Cathode for Sodium-Ion Full Battery.

The development of highly efficient and stable cathodes for sodium-ion batteries (SIBs) is strategically critical to achieving large-scale electrical energy storage. Creating air-stable and high-voltage layered cathodes for sodium-ion full batteries still remains a challenge. Herein, we describe a rational design and preparation of a stable P3-Na2/3Ni1/4Mg1/12Mn2/3O2 cathode. The cathode displays a satisfactory working voltage of 3.6 V and excellent cyclic stability over 100 cycles at a 1 C rate without obvious capacity fading. The results of ex situ X-ray diffraction (XRD) demonstrate that the P3-type structure is well retained even when charged to 4.4 V. Furthermore, the structural characterization by XRD Rietveld refinement, scanning electron microscopy, and electrochemical testing certifies that the cathode maintains its structure commendably even when soaked in water for 12 h. In particular, the P3- Na2/3Ni1/4Mg1/12Mn2/3O2∥hard carbon full battery exhibits a desired competitively high voltage of 3.45 V and an attractive energy density of up to 412.2 W h kg-1 based on the cathode. The comprehensive results achieved by the specially designed strategy provide guidance toward the exploration of stable cathodes in the application of SIBs as modern energy-storage devices.

Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts.

Although single-atomically dispersed metal-Nx on carbon support (M-NC) has great potential in heterogeneous catalysis, the scalable synthesis of such single-atom catalysts (SACs) with high-loading metal-Nx is greatly challenging since the loading and single-atomic dispersion have to be balanced at high temperature for forming metal-Nx. Herein, we develop a general cascade anchoring strategy for the mass production of a series of M-NC SACs with a metal loading up to 12.1 wt%. Systematic investigation reveals that the chelation of metal ions, physical isolation of chelate complex upon high loading, and the binding with N-species at elevated temperature are essential to achieving high-loading M-NC SACs. As a demonstration, high-loading Fe-NC SAC shows superior electrocatalytic performance for O2 reduction and Ni-NC SAC exhibits high electrocatalytic activity for CO2 reduction. The strategy paves a universal way to produce stable M-NC SAC with high-density metal-Nx sites for diverse high-performance applications.

Scalable solid-state synthesis of coralline-like nanostructured Co@CoNC electrocatalyst for Zn-air batteries.

A facile and scalable solid-state synthesis strategy is developed to produce hierarchical coralline-like nanostructured electrocatalysts with cobalt nanoparticles and Co-NX sites for efficient oxygen reduction reaction, opening up an avenue for the mass production of non-precious metal catalysts for metal-air batteries and fuel cells, etc.

Encased Copper Boosts the Electrocatalytic Activity of N-Doped Carbon Nanotubes for Hydrogen Evolution.

Nitrogen (N)-doped carbons combined with transition-metal nanoparticles are attractive as alternatives to the state-of-the-art precious metal catalysts for hydrogen evolution reaction (HER). Herein, we demonstrate a strategy for fabricating three-dimensional (3D) Cu-encased N-doped carbon nanotube arrays which are directly grown on Cu foam (Cu@NC NT/CF) as a new efficient HER electrocatalyst. Cu nanoparticles are encased here instead of common transition metals (Fe, Co, or Ni) for pursuing a well-controllable morphology and an excellent activity by taking advantage of its more stable nature at high temperature and in acidic or alkaline electrolyte. It is discovered that metallic Cu exhibits strong electronic modulation on N-doped carbon to boost its electrocatalytic activity for HER. Such a nanostructure not only offers plenty of accessible highly active sites but also provides a 3D conductive open network for fast electron/mass transfer and facilitates gas escape for prompt mass exchange. As a result, the Cu@NC NT/CF electrode exhibits superior HER performance and durability, outperforming most of the reported M@NC materials. Furthermore, the etching experiments together with X-ray photoelectron spectroscopy (XPS) analysis reveal that the electronic modulation from encased Cu significantly enhances the HER activity of N-doped carbon. These findings open up opportunities for exploring other Cu-based nanomaterials as efficient electrocatalysts and understanding their catalytic processes.