Fluorinating All Interfaces Enables Super-Stable Solid-State Lithium Batteries by In Situ Conversion of Detrimental Surface Li2CO3.

Li-stuffed battery materials intrinsically have surface impurities, typically Li2CO3, which introduce severe kinetic barriers and electrochemical decay for a cycling battery. For energy-dense solid-state lithium batteries (SSLBs), mitigating detrimental Li2CO3 from both cathode and electrolyte materials is required, while the direct removal approaches hardly avoid Li2CO3 regeneration. Here, a decarbonization-fluorination strategy to construct ultrastable LiF-rich interphases throughout the SSLBs by in situ reacting Li2CO3 with LiPF6 at 60 °C is reported. The fluorination of all interfaces effectively suppresses parasitic reactions while substantially reducing the interface resistance, producing a dendrite-free Li anode with an impressive cycling stability of up to 7000 h. Particularly, transition metal dissolution associated with gas evolution in the cathodes is remarkably reduced, leading to notable improvements in battery rate capability and cyclability at a high voltage of 4.5 V. This all-in-one approach propels the development of SSLBs by overcoming the limitations associated with surface impurities and interfacial challenges.

Transmission Electron Microscopy Peeled Surface Defect of Perovskite Quantum Dots to Improve Crystal Structure.

Transmission electron microscopy (TEM) is an excellent characterization method to analyze the size, morphology, crystalline state, and microstructure of perovskite quantum dots (PeQDs). Nevertheless, the electron beam of TEM as an illumination source provides high energy, which causes morphological variation (fusion and melting) and recession of the crystalline structure in low radiolysis tolerance specimens. Hence, a novel and facile strategy is proposed: electron beam peel [PbBr6]4- octahedron defects from the surface of QDs to optimize the crystal structure. TEM and high-angle annular dark-field scanning TEM (HAADF) tests indicate that the [PbBr6]4- octahedron would be peeled from the surface of QDs when QDs samples were irradiated under high-power irradiation, and then a clear image would be obtained. To avoid interference from a protective film of "carbon deposits" on the surface of the sample when using high resolution TEM, amorphous carbon film (15-20 nm) was deposited on the surface of QDs film and then characterized by TEM and HAADF. The detection consequences showed that the defection of PbBr2 on the surface of QDs will gradually disappear with the extension of radiation time, which further verifies the conjecture.

Reconstructing 1D Fe Single-atom Catalytic Structure on 2D Graphene Film for High-Efficiency Oxygen Reduction Reaction.

The ordinary intrinsic activity and disordered distribution of metal sites in zero/one-dimensional (0D/1D) single-atom catalysts (SACs) lead to inferior catalytic efficiency and short-term endurance in the oxygen reduction reaction (ORR), which restricts the large-scale application of hydrogen-oxygen fuel cells and metal-air batteries. To improve the activity of SACs, a mild synthesis method was chosen to conjugate 1D Fe SACs with 2D graphene film (Fe SAC@G) that realized a composite structure with well-ordered atomic-Fe coordination configuration. The product exhibits outstanding ORR electrocatalytic efficiency and stability in 0.1 M KOH aqueous solution. DFT-D computational results manifest the intrinsic ORR activity of Fe SAC@G originated from the newly-formed FeN4 -O-FeN4 bridge structure with moderate adsorption ability towards ORR intermediates. These findings provide new ways for designing SACs with high activity and long-term stability.

Systematic exploration of N, C configurational effects on the ORR performance of Fe-N doped graphene catalysts based on DFT calculations.

Metal single-atom catalysts (MSATs), such as Fe-N coordination doped sp2-carbon matrices, have emerged as a promising oxygen reduction reaction (ORR) catalyst to replace their costly platinum (Pt) based counterparts in fuel cells. In this work, we employ density functional theory (DFT) to systematically discuss the electronic-structure and surface-stress effects of N, C configurations on Fe-N doped graphene in single and double vacancy. The formation energy (E f) of Fe-N-gra dropped off with the increase of N atoms incorporated for both single and double vacancy groups. The theoretical overpotentials on Fe-N-C sites were calculated and revealed that moderate N-doping levels and doping configuration could enhance the ORR activity of Fe-N coordination structures in the double vacancy and that doping N atoms is not effective for ORR activity in single vacancy. By exploring the d-band centers, we found that ligand effects and surface tension effects contribute to the modification of the d-band centers of metal Fe atoms. An optimum Fe-N-C ORR catalyst should exhibit moderate surface stress properties and an ideal N, C ligand configuration. This study provides new insight into the effects of N atom doping in Fe-N-gra catalysts and could help guide the rational design of high-performance carbon-based ORR electrocatalysts.

Structural influence of graft and block polycations on the adsorption of BSA.

Protein adsorption is considered as an important factor for the low transfection efficiency of polycations in vivo. In this study, two typical polycations of equal molecular weight with different structures were chosen to investigate their adsorption on bovine serum albumin (BSA), including the block copolymer named poly (N-vinylpyrrolidone)-b-poly (2-dimethylaminoethyl methacrylate) (PVP-b-PDMAEMA, i.e. PbP) and graft copolymer named PVP-g-PDMAEMA (PgP), respectively. Fluorescence spectroscopy was used to confirm the binding constants and binding sites between polycations and BSA in static state. The binding constants were 4.1×10(4)M(-1) vs 8.3×10(4)M(-1) and binding sites were 0.3 vs 1.1 for PbP and PgP, respectively, indicating PgP had stronger binding affinity with BSA. Surface plasmon resonance (SPR) was used to study the dynamical non-specific interaction between BSA and polycations as well as the polyplexes. The numbers of both PbP and PgP adsorbed on BSA increased with concentration of polycations increasing, and the number of PgP adsorbed on BSA is higher compared with PbP when their concentration is low. When their concentration is high, the number of PbP adsorbed on BSA is more than that of PgP. However, PgP/DNA polyplexes showed higher adsorption amount compared with PbP/DNA polyplexes at different N/P ratios.

Shape evolution and thermal stability of lysozyme crystals: effect of pH and temperature.

The properties of crystalline protein materials are closely linked to crystal shape. However, the effective strategies for the shape control of protein crystals are lacking. The conventional sitting-drop vapor-diffusion method was employed to investigate the influence of pH and temperature on the crystal nucleation behavior of hen egg white lysozyme. Moreover, the size distributions of protein crystals grown at different conditions were analyzed. Differential scanning calorimetry was employed to evaluate the thermal stability of lysozyme crystals. The results indicated that pH and temperature will affect the supersaturation and electrostatic interactions among protein molecules in the nucleation process. In particular, the crystals with different aspect ratios can be selectively nucleated, depending upon the choice of pH and temperature. Therefore, this study provided a simple method for obtaining shape-controlled lysozyme crystals and supplied some information on thermal behaviors of lysozyme crystals grown at different pH values.

Ultrathin carbon nanotube-DNA hybrid membrane formation by simple physical adsorption onto a thin alumina substrate.

Ultrathin carbon nanotube membranes can be prepared on alumina substrates by a facile immersion-adsorption approach, which involves two steps, the first step DNA wrapping and the second step uniform adsorption of the DNA-wrapped nanotubes onto porous alumina. In this approach, DNA wrapping imparts a hydrophilic nature to the carbon nanotubes, which enhances the interaction between the nanotubes and hydrophilic porous alumina and results in the self-assembly formation of ultrathin nanotube membranes with well-controlled thickness, biocompatibility, conductivity and optical properties.

The new insight on ultrastructure of C-type starch granules revealed by acid hydrolysis.

C-type starch granule could be considered as the mixture of A- and B-polymorphs. The ultrastructure of C-type starch granules has not been elucidated detailedly by comparison with that of A- or B-type starch. To better understand the ultrastructure of C-type starch granules, Environment Scanning Electron Microscope (ESEM) and Field Emission Gun Transmission Electron Microscope (FEG-TEM) have been used to analyze the conformation and ultrastructure of C-type starch granule from Rhizoma Dioscorea during acid hydrolysis. SEM results showed that the amorphous areas were mainly located interior part of C-type starch granules whereas the crystalline regions were found mostly in the peripheral region of the granules. The grain size can be confirmed to be about 4.5-9 nm from the HR-TEM micrographs. The nanocrystals from acid-thinned starch displayed the typical face-centered cubic structure. This selected area electron diffraction patterns showed that individual C-type starch granule consisted of A- and B-type polymorphs.