Synthesis of Nanosized γ-Cyclodextrin Metal-Organic Frameworks as Carriers of Limonene for Fresh-Cut Fruit Preservation Based on Polycaprolactone Nanofibers.

To address the issue of bacterial growth on fresh-cut fruits, this paper reports the synthesis of nanosized γ-cyclodextrin metal-organic frameworks (CD-MOFs) using an ultrasound-assisted method and their application as carriers of limonene for antibacterial active packaging. The effects of the processing parameters on the morphology and crystallinity of the CD-MOFs are investigated, and the results prove that the addition of methanol is the key to producing nanosized CD-MOFs. The limonene loading content of the nanosized CD-MOFs can reach approximately 170 mg g-1. The sustained-release behaviors of limonene in the CD-MOFs are evaluated. Molecular docking simulations reveal the distribution and binding sites of limonene in the CD-MOFs. CD-MOFs are deposited on the surfaces of polycaprolactone (PCL) nanofibers via an immersion method, and limonene-loaded CD-MOF@PCL nanofibers are prepared. The morphology, crystallinity, thermal stability, mechanical properties, and antibacterial activity of the nanofibers are also studied. The nanofiber film effectively inhibits bacterial growth and prolongs the shelf life of fresh-cut apples. This study provides a novel strategy for developing antibacterial active packaging materials based on CD-MOFs and PCL nanofibers.

Quantum dots as advanced nanomaterials for food quality and safety applications: A comprehensive review and future perspectives.

The importance of food quality and safety lies in ensuring the best product quality to meet consumer demands and public health. Advanced technologies play a crucial role in minimizing the risk of foodborne illnesses, contamination, drug residue, and other potential hazards in food. Significant materials and technological advancements have been made throughout the food supply chain. Among them, quantum dots (QDs), as a class of advanced nanomaterials with unique physicochemical properties, are progressively demonstrating their value in the field of food quality and safety. This review aims to explore cutting-edge research on the different applications of QDs in food quality and safety, including encapsulation of bioactive compounds, detection of food analytes, food preservation and packaging, and intelligent food freshness indicators. Moreover, the modification strategies and potential toxicities of diverse QDs are outlined, which can affect performance and hinder applications in the food industry. The findings suggested that QDs are mainly used in analyte detection and active/intelligent food packaging. Various food analytes can be detected using QD-based sensors, including heavy metal ions, pesticides, antibiotics, microorganisms, additives, and functional components. Moreover, QD incorporation aided in improving the antibacterial and antioxidant activities of film/coatings, resulting in extended shelf life for packaged food. Finally, the perspectives and critical challenges for the productivity, toxicity, and practical application of QDs are also summarized. By consolidating these essential aspects into this review, the way for developing high-performance QD-based nanomaterials is presented for researchers and food technologists to better capitalize upon this technology in food applications.

Bio-aerogels: Fabrication, properties and food applications.

Traditional inorganic aerogels sustainability, biodegradability, and environmental safety concerns have driven researchers to find their safe green alternatives. Recently, interest in the application of bio-aerogels has rapidly increased in the food industry due to their unique characteristics such as high specific surface area and porosity, ultralow density, tunable pore size and morphology, and superior properties (physicochemical, mechanical, and functional). Bio-aerogels, a special category of highly porous unique materials, fabricated by the sol-gel method followed by drying processes, comprising three-dimensional networks of interconnected biopolymers (e.g., polysaccharides and proteins) with numerous air-filled pores. The production of bio-aerogels begins with the formation of a homogeneously dispersed precursor solution, followed by gelation and wet gel drying procedures by employing special drying techniques including atmospheric-, freeze-, and supercritical drying. Due to their special properties, bio-aerogels have emerged as sustainable biomaterial for many industrial applications, i.e., encapsulation and controlled delivery, active packaging, heavy metals separation, water and air filtration, oleogels, and biosensors. Bio-aerogels are low-cost, biocompatible, and biodegradable sustainable material that can be used in improving the processing, storage, transportation, and bioavailability of food additives, functional ingredients, and bioactive substances for their health benefits with enhanced shelf-life.

Revealing the Intrinsic Atomic Structure and Chemistry of Amorphous LiO2-Containing Products in Li-O2 Batteries Using Cryogenic Electron Microscopy.

Aprotic lithium-oxygen batteries (LOBs) are promising energy storage systems characterized by ultrahigh theoretical energy density. Extensive research has been devoted to this battery technology, yet the detailed operational mechanisms involved, particularly unambiguous identification of various discharge products and their specific distributions, are still unknown or are subjects of controversy. This is partly because of the intrinsic complexity of the battery chemistry but also because of the lack of atomic-level insight into the oxygen electrodes acquired via reliable techniques. In the current study, it is demonstrated that electron beam irradiation could induce crystallization of amorphous discharge products. Cryogenic conditions and a low beam dosage have to be used for reliable transmission electron microscopy (TEM) characterization. High-resolution cryo-TEM and electron energy loss spectroscopy (EELS) analysis of toroidal discharge particles unambiguously identified the discharge products as a dominating amorphous LiO2 phase with only a small amount of nanocrystalline Li2O2 islands dispersed in it. In addition, uniform mixing of carbon-containing byproducts is identified in the discharge particles with cryo-EELS, which leads to a slightly higher charging potential. The discharge products can be reversibly cycled, with no visible residue after full recharge. We believe that the amorphous superoxide dominating discharge particles can lead researchers to reconsider the chemistry of LOBs and pay special attention to exclude beam-induced artifacts in traditional TEM characterizations.

Self-Regulated Phenomenon of Inorganic Artificial Solid Electrolyte Interphase for Lithium Metal Batteries.

Solid electrolyte interphase (SEI) is crucial for suppressing Li dendrite growth in high-energy lithium metal (LiM) batteries. Unfortunately, the naturally formed SEI on the LiM anode surface in carbonate electrolytes cannot suppress Li dendrites, resulting in a continuous consumption of electrolytes and LiM during cycling. Artificial SEI normally lacks self-healing and self-regulating capability, gradually losing the effectiveness during cycling. In this work, we report the self-regulating phenomenon of LiRAP-ASEI that can effectively suppress Li dendrites and is investigated using in situ optical microscopy and COMSOL multiphysics simulation. The effectiveness of self-regulated LiRAP-ASEI is further evaluated in the most aggressive Li/sulfur cells with a lean electrolyte (10 µL mAh-1) and LiRAP-ASEI/LiM (2.5-fold excess of LiM). The LiRAP@Cu∥sulfur@C cells show a stable 3000 cycle life at a current density of 11.5 mA cm-2. The self-regulated phenomenon holds great promise for the development of high-energy-density LMBs.

Effect of static-state fermentation on volatile composition in rapeseed meal.

BACKGROUND: Fermented rapeseed meal has been used as an alternative protein source for animal feed, but the volatile compounds and how their contents change during fermentation have not been reported. To clarify the effect of static-state fermentation on its aroma, the volatile compounds of rapeseed meal during different stages of fermentation were analyzed using an electronic nose system and headspace solid-phase microextraction-gas chromatography-mass spectrometry. RESULTS: The results suggested that the volatile compounds in the raw rapeseed meal, mostly hydrocarbons and some aldehydes, were lost. The levels of the volatile compounds resulting from microbial metabolism, especially pyrazines, greatly increased during fermentation. Nonanal was the dominant volatile measured in the headspace of raw rapeseed meal. However, the volatile compounds found at high concentrations in rapeseed meal after 5 days of fermentation were tetramethylpyrazine, followed by butanoic acid, benzenepropanenitrile, 2-methylbutanoic acid, trimethylamine, 2,3,5-trimethyl-6-ethylpyrazine, and 2,3,5-trimethylpyrazine. CONCLUSION: The fermentation process could significantly change the composition and content of volatile compounds in rapeseed meal. The results may provide reference data for studies on the choice of fermentation period and formation mechanism of flavor substances in fermented rapeseed meal. © 2020 Society of Chemical Industry.

Storage characteristics of infrared radiation stabilized rice bran and its shelf-life evaluation by prediction modeling.

BACKGROUND: Rice bran is a nutrient-dense and resource-rich byproduct produced from the rice milling. The limitation of rice bran utilization is mainly caused by oxidative deterioration. Improvement of stability to prolong rice bran shelf-life has thus become an urgent requirement. RESULTS: The present study aimed to determine the characteristics of infrared radiation heat treatment of rice bran (IRRB) and raw rice bran stored under different temperatures. The effects of heating and storage time on physicochemical, microbial, storage stability and structural properties were investigated. Additionally, the prediction model for the shelf-life of rice bran was established based on free fatty acids and the peroxide value by fitting the curve of bran lipid oxidation. The results obtained demonstrated that infrared radiation heating at 300 °C for 210 s resulted in decreased lipase activity and peroxidase activity of 73.05% and 81.50%, respectively. The free fatty acids and peroxide value of IRRB stored at 4 and 25 °C for 8 weeks were only reached at 2.35% and 3.17% and 2.53 and 3.64 meq kg-1 , respectively. The shelf-life prediction model showed the the shelf-life of infrared radiation-treated samples increased to 71.6 and 25.8 weeks under storage at 4 and 25 °C, respectively. CONCLUSION: The stabilizing process could effectively suppress microbial growth and had no prominent effect on the physicochemical and microstructure properties of rice bran and, simultaneously, storage life was greatly extended. © 2020 Society of Chemical Industry.

Fabrication, characterization, and in vitro digestion of gelatin/gluten oleogels from thermally crosslinked electrospun short fiber aerogel templates.

In this work, the electrospun short fiber-based oleogels (ESFO) were formed by thermal crosslinking. Gelatin and gluten nanofibers were obtained via electrospinning, then homogenized and transformed into short fiber dispersions. Through freeze-drying, electrospun short fiber-based aerogel (ESF-A) templates were obtained for oil adsorption. All ESF-A exhibited the micromorphology of loose fibrous pore structure and prominent changes of characteristic peaks in the thermal and infrared analyses. Moreover, the highly crosslinked templates owned excellent hydrophobicity and mechanical performances (elastic modulus: 0.25 kPa, yield strength: 14.56 kPa, compressive strength: 52.54 kPa, and the final compression recovery: 91.27%). Meanwhile, the oil adsorption/oil holding capacity could reach 76.56 g/g and 80.04%, respectively. Through thermal crosslinking, ESF-O presented good and controllable rheological/in vitro digestion properties, which were further confirmed by PCA analysis. According to different application conditions, ESF-O properties could be adjusted by different degrees of fiber addition or thermal crosslinking.

Novel f-CaO soft sensor for cement clinker based on integrated model of dual-parallel structure.

Aiming at the problem that the cement production process is inherently affected by uncertainty, time delay, and strong coupling among variables, this paper proposed a novel soft sensor of free calcium oxide in a cement clinker. The model utilizes a dual-parallel integrated structure with an optimized integration of one-dimensional convolutional neural networks, long and short-term memory networks, graphical neural networks, and extreme gradient boosting. The proposed model can mitigate the risks associated with overfitting while incorporating the strengths of each individual model and excels in extracting both local and global features as well as temporal and spatial characteristics from the original time series data, ensuring its stability. The experimental results demonstrate that this dual-parallel integrated model exhibits superior robustness, predictive accuracy, and generalization capabilities when compared to single models or enhancements made to other deep learning algorithms.

Energy difference-driven ROS reduction for electrochemical tracking crop growth sensitized with electron-migration nanostructures.

Aiming for sustainable crop productivity under changing climate conditions, it is essential to develop handy models for in-situ monitoring of reactive oxygen species (ROS). Herein, this work reports a simple electrochemical sensing toward hydrogen peroxide (H2O2) for tracking crop growth status sensitized with electron-migration nanostructure. To be specific, Cu-based metal-organic frameworks (MOFs) with high HOMO energy level are designed for H2O2 reduction on account of Cu(I)/Cu(II) redox switchability. Importantly, the sensing performance is improved by electrochemically reduced graphene oxide (GO) with ready to use feature. To overcome the shortcomings of traditional liquid electrolytes, conductive hydrogel as semi-solid electrolyte exhibits the adhesive property to the cut plant petiole surface. Benefitting from the preferred composite models and conductive hydrogel, the electrochemical sensing toward H2O2 with high sensitivity and good anti-interference against the coexistent molecules, well qualified for acquiring plant growth status.

Stable encapsulation of camellia oil in core-shell zein nanofibers fabricated by emulsion electrospinning.

This study aimed to develop core-shell nanofibers by emulsion electrospinning using zein-stabilized emulsions to encapsulate camellia oil effectively. The increasing oil volume fraction (φ from 10% to 60%) increased the apparent viscosity and average droplet size of emulsions, resulting in the average diameter of electrospun fibers increasing from 124.5 nm to 286.2 nm. The oil droplets as the core were randomly distributed in fibers in the form of beads, and the core-shell structure of fibers was observed in TEM images. FTIR indicated that hydrogen bond interactions occurred between zein and camellia oil molecules. The increasing oil volume fraction enhanced the thermal stability, hydrophobicity, and water stability of electrospun nanofiber films. The core-shell nanofibers with 10%, 20%, 40%, and 60% camellia oil showed encapsulation efficiency of 78.53%, 80.25%, 84.52%, and 84.39%, respectively, and had good storage stability. These findings contribute to developing zein-based core-shell electrospun fibers to encapsulate bioactive substances.

Novel Ag-coated nanofibers prepared by electrospraying as a SERS platform for ultrasensitive and selective detection of nitrite in food.

Nitrite is commonly used as a preservative and color fixative in the meat industry. However, the risk of it transforming into N-nitrosamine restricts its intake. Herein, a novel sensitive Ag-coated nanofiber surface-enhanced Raman scattering (SERS) platform was developed for rapid nitrite detection. The electrospraying technique was firstly used to assemble Ag nanoparticles (NPs) on the nanofibers to obtaine SERS platform. The homogeneity and long-term stability of the SERS platform were evaluated. The limit of detection (LOD) of the SERS platform was estimated to be 2.216 × 10-12 mol/L, corresponding to 15.29 ng·L-1 and good linearity was shown between the relative SERS intensity and nitrite concentration range of 10-1 to 10-4 mol/L. The Ag-coated nanofiber SERS platform was utilized to assay-five common nitrite foods, and the results provided valid evidence for the compatibility of SERS platform in quantitative nitrite detection.

Dual-functional shikonin-loaded quaternized chitosan/polycaprolactone nanofibrous film with pH-sensing for active and intelligent food packaging.

Recently, intelligent packaging has emerged for monitoring food quality in food industry. This study aimed to develop the electrospun HACC/PCL/SKN nanofibrous films with improved antimicrobial and antioxidant activity as intelligent packaging to monitor food freshness. The SKN loading resulted in nanoscale uniform fibers (approximately 55.0 nm), and the HACC/PCL/SKN nanofibrous films presented improved hydrophobicity, barrier properties and mechanical properties. Release kinetics study demonstrated that the loading effect led to a sustained release of SKN from fibers. The HACC/PCL film containing 2 wt% SKN showed good antibacterial effect during 24 h, suggesting enhanced antimicrobial activity. Moreover, the SKN-based solutions and films exhibited pH-responsive color changes from red (pH 2) to blue-purple (pH 12). Finally, the HACC/PCL/SKN film effectively provided a spoilage indication for shrimp stored at different temperatures for 3 days by color changes. This work provides a promising strategy for developing multi-functional film as an intelligent packaging in food industry.

Schiff base cross-linked dialdehyde cellulose/gelatin composite aerogels as porous structure templates for oleogels preparation.

Recently, biopolymer-based structured oil has emerged to substitute saturated and trans-fats. Herein, the porous biopolymeric networks with the cellular structure were developed with cross-linked dialdehyde cellulose (DAC) and gelatin to prepare oleogels. The determination of aldehyde content in the DAC molecular chain revealed a high degree of oxidation of cellulose. The FTIR data showed the covalent cross-linking bond between the DAC and gelatin. The covalent cross-linking between DAC and gelatin promoted the composite aerogel (DG) to form a porous three-dimensional network structure with enhanced thermal stability, mechanical properties, and water stability. The DAC/gelatin composite aerogel with 5 wt% DAC (DG-5) exhibited the highest porosity (91.27 %) and lowest pore diameter (10.52 µm) with greater capillary force, resulting in a high oil absorption capacity of 11.24 g/g and oil holding capacity of 55.57 %. The DG oleogels containing 6 % thymol in the oil phase showed good antibacterial activities against Escherichia coli and Staphylococcus aureus for 24 h. This work provides a facile and promising strategy for developing oleogels by DAC/gelatin cross-linked conjugates as aerogel templates for oil structuring.

Nudging Strategies for Arable Land Protection Behavior in China.

Arable land protection is critical to the sustainable development of agriculture in China and acceleration of the realization of the trinity protection goal of the quantity, quality, and ecology of arable land. As a new program of behavioral science to promote social development, nudge has gradually gained the favor of researchers and policy makers due to its unique advantages of small cost and substantial effect. However, current research and practical exploration of arable land protection behavior intervention based on the idea of nudging are still lacking. Implicit nudging strategies directly target the heuristic and analytic systems of arable land protection behavior of each stakeholder and possess more advantages than traditional intervention strategies. Therefore, this article designs six arable land protection behavior nudging strategies from the perspectives of cognition and motivation to realize the theoretical discussion of "generating medium-scale returns with nano-level investment". The nudging strategies of the cognitive perspective include default options, framing effects, and descriptive norms, while those of the motivation perspective aim to stimulate home and country, and heritage and benefit motives to promote arable land protection behavior of various stakeholders. The utility of nudge to arable land protection behavior may be controversial in practice. Therefore, the implementation in China should be based on the division of farmers, the number of options should be appropriate, and the external environment of arable land protection behavior should be fully considered.

Electrospun pullulan nanofiber loading zanthoxylum bungeanum essential oil/ß-cyclodextrin inclusion complexes for active packaging.

In this study, zanthoxylum bungeanum essential oil/ß-cyclodextrin inclusion complexes (ZBEO/ß-CD-ICs) were first prepared by precipitation method. When the addition of ZBEO was 1 g, the reaction time was 4 h and the reaction temperature was 55 °C, the recovery (73.88%) and loading content (9.53%) reached the highest value. The characterization results showed inclusion complexation changed the crystalline structure, enhanced interaction among molecules and increased the thermal stability. Then, nanofiber films containing ZBEO/ß-CD-ICs were prepared by electrospinning. When the total polymer concentration was constant at 20%, with the increase of ZBEO/ß-CD-IC content, the diameter of nanofiber and mechanical strength decreased, but the temperature corresponding to the maximum rate of weight loss increased. X-ray diffraction analysis proved that the addition of ZBEO/ß-CD-IC increased the crystallinity degree of film. The Fourier transform infrared spectra indicated hydrogen bond interactions among molecules. Releasing behavior of ZBEO indicated that increase of temperature and relative humidity accelerated the releasing speed. Antibacterial and antioxidant activity results demonstrated the increase of ZBEO content enhanced antibacterial and antioxidant efficiency, Z40P10 nanofibers had the maximum antibacterial rate of 62.02% against S. aureus and the maximum antioxidant activity of 60.18%.

Covalent Organic Framework-Incorporated Nanofibrous Membrane as an Intelligent Platform for Wound Dressing.

Covalent organic frameworks (COFs) possess fascinating features that have sparked increasing interest as drug carriers in biomedical applications. However, the promising properties of COFs in wound healing have rarely been reported. Herein, a facile one-pot method is reported to prepare a curcumin-loaded COF (CUR@COF) by the condensation reaction and the Schiff base reaction and to further incorporate CUR@COF into polycaprolactone (PCL) nanofibrous membranes (CUR@COF/PCL NFMs) through electrospinning to develop a pH-triggered drug release platform for wound dressing. CUR@COF has a high CUR loading capacity of 27.68%, and CUR@COF/PCL NFMs exhibit increased thermal stability, improved mechanical properties, good biocompatibility, and enhanced antibacterial and antioxidant activities. More importantly, CUR@COF-based membranes show a pH-responsive CUR release profile by protonation under acidic conditions, suggesting the promotion of CUR release from membranes under an acidic extracellular microenvironment. The histopathological analysis and immunofluorescence staining of an in vivo skin defect model indicate that CUR@COF/PCL NFMs can accelerate wound healing and skin regeneration by reducing the expression of inflammatory factors (TNF-α) and enhancing the expression of angiogenesis (VEGF). This work provides a new strategy by employing COF-based drug-encapsulated nanocomposites for wound dressing applications.

Recent advances in the extraction, chemical composition, therapeutic potential, and delivery of cardamom phytochemicals.

Dietary phytochemicals including plant-derived alkaloids, carotenoids, organosulfur compounds, phenolics, and phytosterols, are health-promoting bioactive compounds that help in the prevention and mitigation of chronic diseases and microbial infections beyond basic nutrition supply. This article covers recent advances in the extraction, chemical composition, therapeutic potential (nutraceutical and antimicrobial), and delivery of black and green cardamom-derived phytochemicals. In recent years, advance extraction techniques (e.g., enzyme- assisted-, instant controlled pressure drop-, microwave- assisted-, pressurized liquid-, sub- critical-, supercritical fluid-, and ultrasound-assisted extractions) have been applied to obtain phytochemicals from cardamom. The bioactive constituents identification techniques, specifically GC-MS analysis revealed that 1,8-cineole and α-terpinyl acetate were the principle bioactive components in black and green cardamom. Regarding therapeutic potential, research findings have indicated desirable health properties of cardamom phytochemicals, including antioxidant-, anti-hypercholesterolemic, anti-platelet aggregation, anti-hypertensive, and gastro-protective effects. Moreover, antimicrobial investigations revealed that cardamom phytochemicals effectively inhibited growth of pathogenic microorganisms (bacteria and fungi), biofilm formation inhibition (Gram-negative and Gram-positive bacteria) and bacterial quorum sensing inhibition. Encapsulation and delivery vehicles, including microcapsules, nanoparticles, nanostructured lipid carriers, and nanoliposomes were effective strategies to enhance their stability, bioavailability and bioefficacy. In conclusion, cardamom phytochemicals had promising therapeutic potentials (antioxidant and antimicrobial) due to polyphenols, thus could be used as functional additive to increase shelf life, inhibit oxidative rancidity and confer pleasant aroma to commercial edibles as well as mitigate oxidative stress and lifestyle related chronic diseases (e.g., cardiovascular and gastrointestinal diseases). A future perspective concerning the fabrication of functional foods, nutraceuticals and antibiotics to promote cardamom phytochemicals applications as biotherapeutic agents at large-scale requires thorough investigations, e.g., optimum dose and physical form of supplementation to obtain maximum health benefits.

Impact of glycation on physical properties of composite gluten/zein nanofibrous films fabricated by blending electrospinning.

In this study, the gluten/zein nanofibrous films were fabricated by blending electrospinning and then glycated with xylose via Maillard reaction. The average fiber diameter of the gluten film decreased from 551 to 343 nm with the increasing ratio of zein, but increased significantly to a range of 717-521 nm after glycation, which induced a higher thermal stability of the nanofibers with an order to disorder transition. The glycated composite films showed the reduced water vapor permeability and improved water stability with a stiffer and more elastic network structure, due to the enhanced intermolecular entanglements and interactions between polymer chains. The results from this work suggested that the composite gluten/zein electrospun films may be glycated via Maillard reaction to obtain desirable physical properties for active food-packaging applications.

Cryo-Electron Tomography of Highly Deformable and Adherent Solid-Electrolyte Interphase Exoskeleton in Li-Metal Batteries with Ether-Based Electrolyte.

The 3D nanocomposite structure of plated lithium (LiMetal ) and solid electrolyte interphases (SEI), including a polymer-rich surficial passivation layer (SEI exoskeleton) and inorganic SEI "fossils" buried inside amorphous Li matrix, is resolved using cryogenic transmission electron microscopy. With ether-based DOLDME-LiTFSI electrolyte, LiF and Li2 O nanocrystals are formed and embedded in a thin but tough amorphous polymer in the SEI exoskeleton. The fast Li-stripping directions are along [ 1 ¯ 10 ] or [ 12 1 ¯ ] , which produces eight exposed {111} planes at halfway charging. Full Li stripping produces completely sagging, empty SEI husks that can sustain large bending and buckling, with the smallest bending radius of curvature observed approaching tens of nanometers without apparent damage. In the 2nd round of Li plating, a thin LiBCC sheet first nucleates at the current collector, extends to the top end of the deflated SEI husk, and then expands its thickness. The apparent zero wetting angle between LiBCC and the SEI interior means that the heterogeneous nucleation energy barrier is zero. Due to its complete-wetting property and chemo-mechanical stability, the SEI largely prevents further reactions between the Li metal and the electrolyte, which explains the superior performance of Li-metal batteries with ether-based electrolytes. However, uneven refilling of the SEI husks results in dendrite protrusions and some new SEI formation during the 2nd plating. A strategy to form bigger SEI capsules during the initial cycle with higher energy density than the following cycles enables further enhanced Coulombic efficiency to above 99%.