TEMPO氧化修饰的天然多糖纳米纤维增强复合材料及其功能化研究进展

纤维素和几丁质具有相似的结构，是自然界中储量丰富的两类天然多糖。经2, 2, 6, 6-四甲基哌啶氮氧化物(TEMPO)氧化修饰制备的纤维素和几丁质纳米纤维，不仅具有多糖类物质的良好亲水性、生物可降解性、生物相容性及丰富的官能团(羟基、羧基、乙酰氨基和氨基等)所带来的特定化学性质，而且还具有纳米纤维的纳米尺寸效应、大比表面积、高表面活性、高结晶度和手性液晶相结构等特点，已成为生物质纳米材料领域的研究重点之一。本文对TEMPO氧化修饰制备天然多糖纳米纤维的方法及剥离机制进行了总结，同时重点综述了TEMPO氧化修饰的天然多糖纳米纤维在薄膜、凝胶、导电、医用、电磁屏蔽及环境等复合材料的增强和功能升级等方面的研究进展，强调了纤维素和几丁质纳米纤维的官能团及纳米尺寸在复合材料中的增效机制。最后，对天然多糖纳米纤维的发展方向及其在各领域应用的机遇与挑战进行了展望。     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.     

Eco-friendly and degradable red phosphorus nanoparticles for rapid microbial sterilization under visible light

Pathogens pose a serious challenge to environmental sanitation and a threat to public health.The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs,which further threatens public health.To address this issue,the use of non-chemical antibacterial means has become a new trend for environmental disinfection.In this study,we developed red phosphorus nanoparticles(RPNPs),a safe and degradable photosensitive material with good photocatalytic and photothermal properties.The red phosphorus nanoparticles were prepared using a template method and ultrasonication.Under the irradiation of simulated sunlight for 20 min,the RPNPs exhibited an efficiency of 99.98%in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities.Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks.Both the RPNPs and their degradation products were nontoxic to fibroblast cells.Therefore,such RPNPs are expected to be used as a new type of low-cost,efficient,degradable,biocompatible,and eco-friendly photosensitive material for environmental disinfection.     

Fabrication of oxide-based near infrared-shielding coatings for a smart window to prevent infrared-induced photoaging in human skin

Oxide-based near infrared (IR)-shielding coatings consisting of quarter‐wave stacks of oxygen-deficient tantalum oxide (Ta₂O_5?x) and silicon oxide (SiO₂) multilayers and tin-doped indium oxide (In₂O₃) (ITO) films with the thicknesses of 200–600 nm can block the passage of IR-A (wavelength: 760–1400 nm) and IR-B (wavelength: 1400–3000 nm) radiation, respectively. In this study, the optical properties and microstructure of these oxide-based IR-shielding coatings were investigated. Transmission electron microscopy images indicated that amorphous Ta₂O_5?x/amorphous SiO₂ multilayers were uniform and dense. ITO films were found to be highly crystalline and show carrier concentrations of up to 7.1 × 10²⁰ cm^?3, resulting in the strong IR-B optical absorption due to the plasma excitation of the free carriers. Oxide-based IR-shielding coatings with an ITO thickness of 420 nm were found to have near-IR shielding rates of >90% and an average visible light transmittance of >70%. The effects of IR on human keratinocytes were studied to evaluate the IR-induced photoaging in human skin. It was found that the downregulation of cellular proliferation and the enhancement of senescence-associated β-galactosidase activity induced by IR irradiation were significantly inhibited by oxide-based IR-shielding coatings. Thus, this study provides a facile method for the development of coatings for smart windows with high IR-shielding ability and high visible light transmittance.     

Recent advances during CH4 dry reforming for syngas production: A mini review

Given the continuing issues of environment and energy, methane dry reforming for syngas production have sparked interest among researchers, but struggled with the process immaturity owing to catalyst deactivation. This review summarizes the recent advances in the development of efficient and stable catalysts with strong resistance to coking and metal sintering, including the application of novel materials, the assessment of advanced characterizations and the compatibility to improved reaction system. One feasible option is the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a fine metal dispersion and surface confinement effect via a metal exsolution strategy and exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also extend the option because of their unique morphology and microstructure. It also is elaborated that progresses were achieved in advanced characterizations application, leading to success in the establishment of reaction mechanisms and attributions to the formed robust catalysts. In addition, the perspective described the upgrade of reaction system to a higher reaction efficiency and milder reaction conditions. The combination of efficient reaction systems and robust catalysts paves a way for a scaling-up application of the process.     

Life cycle cost of conventional,battery electric,and fuel cell electric vehicles considering traffic and environmental policies in China

Electric vehicles (EVs) are considered a promising alternative to conventional vehicles (CVs) to alleviate the oil crisis and reduce urban air pollution and carbon emissions. Consumers usually focus on the tangible cost when choosing an EV or CV but overlook the time cost for restricting purchase or driving and the environmental cost from gas emissions, falling to have a comprehensive understanding of the economic competitiveness of CVs and EVs. In this study, a life cycle cost model for vehicles is conducted to express traffic and environmental policies in monetary terms, which are called intangible cost and external cost, respectively. Battery electric vehicles (BEVs), fuel cell electric vehicles (FCEVs), and CVs are compared in four first-tier, four new first-tier, and 4 s-tier and below cities in China. The comparison shows that BEVs and FCEVs in most cities are incomparable with CVs in terms of tangible cost. However, the prominent traffic and environmental policies in first-tier cities, especially in Beijing and Shanghai, greatly increase the intangible and external costs of CVs, making consumers more inclined to purchase BEVs and FCEVs. The main policy benefits of BEVs and FCEVs come from three aspects: government subsidies, purchase and driving restrictions, and environmental taxes. With the predictable reduction in government subsidies, traffic and environmental policies present important factors influencing the competitiveness of BEVs and FCEVs. In first-tier cities, BEVs and FCEVs already have a competitive foundation for large-scale promotion. In new first-tier and second-tier and below cities, stricter traffic and environmental policies need to be formulated to offset the negative impact of the reduction in government subsidies on the competitiveness of BEVs and FCEVs. Additionally, a sensitivity analysis reveals that increasing the mileage and reducing fuel prices can significantly improve the competitiveness of BEVs and FCEVs, respectively.     

Thermodynamic modeling of gas solubility in aqueous sodium chloride solution

An electrolyte Equation of State is presented by combining the Cubic Plus Association Equation of State,Mean Spherical Approximation and the Born equation.This new model uses experimental relative static permittivity,intend to predict well the activity coefficients of individual ions (ACI) and liquid densities of aqueous solutions.This new model is applied to model water + NaCl binary system and water + gas +NaCl ternary systems.The cation/anion-water interaction parameters of are obtained by fitting the exper-imental data of ACI,mean ionic activity coefficients (MIAC) and liquid densities of water + NaCl binary system.The cation/anion-gas interaction parameters are obtained by fitting the experimental data of gas solubilities in aqueous NaCl solutions.The modeling results show that this new model can correlate well with the phase equilibrium and volumetric properties.Without gas,predictions for ACI,MIAC,and liquid densities present relative average deviations of 1.3％,3.6％ and 1.4％ compared to experimental ref-erence values.For most gas-containing systems,predictions for gas solubilities present relative average deviations lower than 7.0％.Further,the contributions of ACI,and salting effects of NaCl on gases are ana-lyzed and discussed.     

Electrospun Zn-doped Ga2O3 nanofibers and their application in photodegrading rhodamine B dye

Ultrawide band gap semiconductor materials have attracted considerable attention in recent years owing to their great potential in the photocatalytic field. In this study, Zn-doped Ga₂O₃ nanofibers with various concentrations were synthesized via electrospinning; they exhibited a superior photocatalytic degradation performance of rhodamine B dye compared to that of undoped Ga₂O₃ nanofibers. The Zn dopant replaced Ga sites via replacement doping, which could increase the concentration of oxygen vacancies and lead to enhanced photocatalytic properties. When the Zn concentration increased, a Ga₂O₃/ZnGa₂O₄ hybrid structure formed, which could further enhance the photocatalytic performance. The separation of photogenerated carriers due to Zn doping and heterojunctions were the primary causes of the enhanced photocatalytic performance. This study provides experimental data for the fabrication of high-performance photocatalysts based on Ga₂O₃ nanomaterials.     

Nano-Al doped-MoO3 high-energy composite films with excellent hydrophobicity and thermal stability

Developing the thermal stability of metal-based ceramic composites or their films has always been challenging and bottlenecks for the utilization of energy. In this paper, the novel mesh-like functional Al doped-MoO₃ nanocomposite film with even distribution and high purity was firstly fabricated by the high-efficiency electrophoretic deposition and surface modification. The optimal suspension turned out to be the mixture of isopropanol and the additives of polyethyleneimine and benzoic acid. The microtopography, crystalline structure, environmental resistance and thermal stability were analyzed by field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), X-ray diffractometer (XRD), exposure and droplet-impacting test, DSC analysis and ignition test, respectively. The water contact angle and sliding angle of product can reach ~170° and <1°, indicating the excellent anti-wetting property. In addition, the high heat-release (~3180 J/g) of product all kept almost unchangeable after six months exposure experiments, demonstrating the outstanding thermostability. The exquisite design idea here can perfectly match microelectromechanical system (MEMS), providing the valuable reference for fabricating other metal-based high-energy composites with long lifespan for real industrial applications.     

Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.