Tuning fermi level and band gap in Li4Ti5O12 by doping and vacancy for ultrafast Li+ insertion/extraction

Li₄T_i5O₁₂ (LTO) attracts great interest due to the “zero strain” during cycles but the poor electronic and ionic conductivity critically impede the practical application. Herein, we report a synergy strategy of tuning localized electrons to shift Fermi level and band gap by Mg/Zr co-doping and oxygen vacancy incorporation, which significantly improves Li⁺ and electronic transport. More importantly, the intrinsic synergistic mechanism has been revealed by neutron diffraction, X-ray absorption spectra, and first-principles calculations. The “elastic effect” of lattice induced by Mg/Zr co-doping allows LTO to accommodate more oxygen vacancies to a certain degree without a severe lattice distortion, which largely improves the electronic conductivity. Mg/Zr co-doping and oxygen vacancy incorporation effectively enhanced the dynamic characteristics of LTO electrode, achieving the excellent rate performance (90 mAh/g at 20C) and cycle stability (96.9% after 500 cycles at 10C). First-principles calculations confirm Fermi level shifts to the conduction band, and the band gap becomes narrowed due to the synergistic modulation, and the intrinsic mechanism of the enhanced electronic and Li-ion conductivity is clarified. This study offers some insights into achieving the fast Li⁺ insertion/extraction by tuning the crystal and electronic structure with lattice doping and oxygen vacancy engineering.     

Improving the cold flow properties of biodiesel from waste cooking oil by ternary blending with bio-based alcohols and diesel from direct coal liquefaction

The utilization and popularization of biodiesel are always limited by its poor cold flow properties. Both bio-based alcohol and diesel from direct coal liquefaction (DDCL) has potential to enhance the cold flow properties of biodiesel. In this study, ternary blends of waste cooking oil biodiesel (BWCO) with DDCL and bio-based ethanol (ET) or 1-butanol (BT) were conducted to improve the cold flow properties of biodiesel. The pour point (PP), cold filter plugging point (CFPP), and cloud point (CP) of BWCO-ET, BWCO-BT, and BWCO-DDCL binary blends, and BWCO-ET-DDCL and BWCO-BT-DDCL ternary blends were comparatively assessed. Ternary phase diagrams were also applied to analyze the blending effect of the three components on the cold flow properties of biodiesel. Results showed that both DDCL, ET, and BT can remarkably enhance the cold flow properties of BWCO. When the ternary blends contain 20 vol.% BWCO and less than 40 vol.% ET or BT, DDCL together with ET or BT exerted positive effects on enhancing the low-temperature flow properties of BWCO, especially on the CP and CFPP. For ternary blends in 20:10:70 blending ratio, BWCO-BT-DDCL exhibited the lowest PP, CFPP, and CP of −23, −19, and −17°C, respectively. The crystallization behavior and crystal morphology of blended fuels are also observed via a polarizing optical microscope, and find that DDCL together with BT in biodiesel can effectively retard the aggregation of large crystals and inhibit crystals growth.     

Degradability and biocompatibility of bioglass/poly(amino acid) composites with different surface bioactivity as bone repair materials

Bioglass (BG) possesses excellent bioactivity and has been widely used in the manufacture of biomaterials. In this study, a composite with different surface bioactivity was fabricated via in situ melting polymerization by incorporating BG and poly(amino acid) (PAA) at a suitable ratio. The structure of the composite was characterized by Fourier transform infrared spectroscopy and XRD. The compressive strength of the BG/PAA composites was 139 MPa (BG:PAA = 30:70). The BG/PAA composites were degradable, and higher BG in composite showed higher weight loss after 4 weeks of incubation in simulated body fluid. In addition, the BG/PAA composite maintained adequate residual compressive strength during the degradation period. The SEM results showed the differences in surface bioactivities of the composites directly, and 30BG/PAA composite showed thicker apatite layer and higher Ca/p than 15BG/PAA. in vitro MG-63 cell culture experiments showed that the composite was noncytotoxic and thus allows cells to adhere, proliferate, and differentiate. This indicates that the composite has good biocompatibility. The implantations in the bone defects of rabbits for 4 and 12 weeks were studied. The composites had good biocompatibility and were capable of guiding new bone formation without causing any inflammation. The composite may be successfully used in the development of bone implants.     

Prestructured MXene fillers with uniform channels to enhance CO2 selective permeation in mixed matrix membranes

The packing pattern of two-dimensional (2D) sheet-like fillers in membranes is relatively random, leading to the unfavorable permeability from tortuous diffusion pathway. A new strategy that using prestructured materials with uniform channels as fillers was proposed. In this work, Ti₃AlC₂ is etched to prepare multilayered MXene (m-MXene), the channels aggregate as a whole unit, ensure the impossibility of ineffective packing compared with traditional individual sheets, largely facilitating the selective permeation. Then, the m-MXene/Poly (amide-6-b-ethylene oxide) (Pebax) MMMs are synthesized. SEM images demonstrate the accordion shaped structure of filler, which is the multi-channels laminates. Furthermore, the results of gas permeation test exhibit enhanced performance of m-MXene/Pebax MMMs. MMM with 0.5 wt.% m-MXene behaved best, CO₂ permeability of 86.22 Barrer as well as CO₂/N₂ selectivity of 104.85, transcending the Robeson upper bound (2008). Having distinct enhancement for CO₂ separation, the m-MXene/Pebax MMMs in this work offer prospective practical applications.     

Thin-film composite forward osmosis membrane prepared from polyvinyl chloride/cellulose carbamate substrate and its potential application in brackish water desalination

Synthesized by the reaction between α-cellulose and m-tolyl isocyanate (MTI), cellulose carbamate (CC) was blended with polyvinyl chloride (PVC) to fabricate substrates for thin-film composite (TFC) forward osmosis (FO) membranes. The introduction of CC into substrates improved both membrane structure and performance. The substrates exhibited higher porosity and hydrophilicity, and better connective pore structure; while rejection layer exhibited better morphology but limited cross-linked degree decrease after the introduction of CC. According to the results, the CC blend ratio of 10% was the optimal ratio. With this blend ratio, the TFC-10 membrane presented favorable water permeability (1.86 LMH/bar) and structure parameter (337 μm), which resulted in excellent FO performance (water flux with a value of 40.40 LMH and specific salt flux with a value of 0.099 g/L under rejection layer faces draw solution [DS] mode when 1 M NaCl and deionized water were utilized as DS and feed solution). In addition, the TFC-10 membrane showed good water flux and low-sulfate ion leakage in the potential application of brackish water desalination.     

An improved strategy to synthesize graphite oxide with controllable interlayer spacing as coatings for anticorrosion application

A facile method to synthesize nanoscale graphene oxide (GO) with controllable interlayer spacing was carried out using two-step oxidation process and much less acid to improve the efficiency of the oxidation. The X-ray diffraction results demonstrated that GO had been successfully prepared from graphite because of disappearance of characteristic peaks of pristine graphite at about 2θ = 26.5° along with appearance of a sharp major peak of GO at about 2θ = 9.4°. The increased basal spacing d₀₀₁ of as-prepared GO could reach as high as 9.39 Å, suggesting higher degree of oxidation than that prepared by the classical Hummers' synthesis, and characterization results from Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy further confirmed this conclusion. The influence of GO on anti-corrosion performance of nanocomposite coatings composited with the 2,5-dimethoxyaniline (DMA) conductive polymer was examined via potentiodynamic polarization curve tests in 3.5 wt% NaCl aqueous solution. The results demonstrated that the incorporation of GO significantly decreased the corrosion current density (i_corr = 2.62 μA/cm²) in the case of GO-PDMA coating, reflecting excellent physical isolation of GO and its synergistic effect with PDMA against the infiltration of water and corrosive electrolyte.     

Preparation and balanced mechanical properties of solid and foamed isotactic polypropylene/SEBS composites

This study presents a self-designed foaming apparatus and routes to manufacture foamed isotactic polypropylene (iPP) blends with uniform and dense cells, using styrene-ethylene-butadiene-styrene (SEBS) block copolymer as toughening additive. The addition of SEBS can clearly enhance the impact strength of solid iPP, iPP blends with a 20 wt% SEBS has obtained high notched impact strength of 75 kJ/m², which is ca. 16 times larger than that of neat iPP. Relatively fine microcellular iPP-SEBS foams with the average cell size of several micrometers, and the cell density of 10⁹ cells/cm³ were fabricated using a batch foaming procedure. Moreover, using our self-designed mold and compression foaming method, iPP-SEBS foams with balanced mechanical properties were produced. With the increasing of SEBS, tensile strength and flexural strength were slightly decreased, but the impact strength was increased clearly. The balanced mechanical properties between stiffness and toughness were achieved after compression foaming.     

Sodium citrate-assisted synthesis of nano-manganese oxide on carbon fiber for enhancing the mechanical and frictional performances of carbon fiber-reinforced resin matrix composites

Aiming to enhance the carbon fiber (CF)/resin interfacial adhesion, this report describes the novel application of sodium citrate (SC) as an auxiliary reducing agent and surface regulator to control the morphology of nano-manganese dioxide (MnO₂) on the CF surface. The composites were fabricated by means of controlling the molar concentration ratio of SC to Mn source (0:1, 1:3, 1:2, and 1:1) in hydrothermal synthesis. The results reveal that MnO₂ nanosheets on the CF surface become denser as the concentration of SC is 1/3 of Mn source, which makes advance to the surface roughness and surface energy of CF. Simultaneously, the tensile strength of as-prepared composite is increased by 52.8%. The homologous friction coefficient tends to be high and stable and the wear volume is significantly reduced by 63.8 and 26.5% under the applied loads of 3 and 5 N in contrast with the original composites prepared without SC. As a result, it can be inferred that SC plays a crucial role in enhancing the interfacial bonding strength between the CF and matrix, providing insights into the interface control of CF-reinforced resin matrix composites.     

Fabrication of Pebax/SAPO mixed matrix membranes for CO2/N2 separation

Mixed matrix membranes (MMMs) were prepared by solvent evaporation method using Pebax-1074 polymer as matrix and inorganic zeolite SAPO-23 as dopant. The morphology, surface functional groups, microstructure, thermal stability, and separation performance of MMMs were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and gas permeation, respectively. The effects of dopant loading amount, permeation temperature, and permeation pressure on the structure and properties of MMMs were investigated. The results showed that the introduction of SAPO zeolite reduced the crystallinity of the MMMs and improved the CO₂/N₂ selectivity. Under the conditions of 30°C and 0.15 MPa, the MMMs prepared by incorporating with 5% SAPO zeolite in content exhibited the highest CO₂/N₂ selectivity of 72.0 together with the CO₂ permeability of 98.2 Barrer.     

Supercritical carbon dioxide assisted fabrication of biomimetic sodium alginate/silk fibroin nanofibrous scaffolds

In this study, biomimetic sodium alginate (SA)/silk fibroin (SF) scaffolds were successfully fabricated by supercritical CO₂ technology. The SA/SF scaffolds exhibited an interconnected porous and extracellular matrix (ECM)-like nanofibrous structures. Moreover, the SA microparticles were embedded in the SF scaffolds. Increasing the content of SA microparticles could improve tensile strength and compressive strength of the SF scaffolds and reduce the porosity of the SF scaffolds. The addition of the SA microparticles could also regulate the degradation rate of the SA/SF scaffolds. Furthermore, the results of in vitro biocompatibility evaluation, indicated that the SA/SF scaffolds exhibited no obvious cytotoxicity and higher cell adhesion ability and were more favorable for L929 fibroblasts proliferation than pure SF scaffolds. Therefore, the SA/SF scaffolds with ECM-like nanofibrous and interconnected porous structure have potential application in skin tissue engineering.