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.     

Ni2V2O7 dandelion microsphere for a high-performance electrocatalyst in water splitting

Water splitting is an effective way to produce hydrogen to solve the energy crisis problem, and inorganic metal compounds are widely used in electrocatalysis field due to efficient hydrogen evolution reaction (HER). Herein, we synthesize Ni₂V₂O₇ dandelion microsphere from nickel nitrate and vanadium pentoxide by “one-step hydrothermal” way, which exhibits large specific surface area of 102.74 m² g⁻¹. The as-prepared Ni₂V₂O₇ microsphere shows good electrocatalysis performances including OER overpotential of 358 mV and good stability, as well as HER overpotential of 195 mV. Furthermore, the Ni₂V₂O₇ microsphere electrode is assembled to Ni₂V₂O₇ microsphere//Ni₂V₂O₇ microsphere system, showing the water splitting voltage of 1.50 V at 10 mA cm⁻² by two-electrode method, which is much lower than those of commercial RuO₂//Pt/C system and most of spinel oxides electrocatalysts. Our work opens up a new and facile avenue for fabricating inorganic microsphere electrocatalyst in hydrogen production field.     

pH-sensitive self-assembling property of poly(ethyleneimine)/cinnamic acid mixture and its effect on pH-dependent release of monoolein cubic phase

Poly(ethyleneimine) (PEI)/cinnamic acid (CA) mixture was self-assembled into microsphere in aqueous phase. As the pH value increased, the self-assembly became hardly formed. As the molar ratio of the amino group of PEI to the carboxyl group of CA increased, the pH window for the formation of self-assembly became broader. The phase transition temperature of cubic phase was 58.5–67.5°C, depending on the PEI/CA content. The release of dye loaded in cubic phase containing PEI/CA increased in a first-order fashion. The release degree was higher at a lower pH value.     

纳米级过硫酸铵微胶囊的制备及性能

通过原位聚合法成功制备了以过硫酸铵为芯材、聚吡咯为壳材的微胶囊，并通过扫描电镜、激光粒度仪、红外光谱和拉曼光谱分析微胶囊的形貌和结构。结果表明：微胶囊的粒径分布集中在100~300 nm，且聚吡咯成功包覆过硫酸铵。微胶囊在水中分散时的电导率的变化过程说明微胶囊的释放过程为渗透释放；且随着甘油量的增加，微胶囊吸水速率加快，内部固体过硫酸铵溶解速率提高，对应过硫酸铵的释放速率提高。将过硫酸铵与等质量的微胶囊分别加入聚合物压裂液中，通过高温降黏实验，发现该微胶囊能延迟破胶7 h以上。     

Enhanced photoelectrochemical water splitting using gadolinium doped titanium dioxide nanorod array photoanodes

In this study highly oriented, rutile phase one dimensional Titania nanorod array (TiO₂ NRA) modified by gadolinium doping were synthesized on the conductive glass substrate (FTO) by the hydrothermal method. The effect of Gd doping on the photoelectrochemical performance of TiO₂ NRA was investigated. Crystal phase, structural, morphological and composition characteristics of these synthesized photoelectrodes were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). FE-SEM images clearly show that some of the Gd dopant is uniformly distributed on the surface of TiO₂ NRA in the form Gadolinia (Gd₂O₃) microsphere. These gadolinia microsphere play an important role in reducing the surface recombination of electron and hole supported by photoluminescence's studies. Linear sweep voltammetry results show that Gd doping results in a two-fold increase in photocurrent density as compared to pristine TiO₂ NRA. UV–visible spectra, and Mott-Schotty measurements show that Gd doping shift the flat-band potential of TiO₂ NRA more toward negative potential that results in effective charge separation and transportation in the Gd doped TiO₂ NRA (Gd@TiO₂ NRA). Applied biased photon to current efficiency (ABPE) equation was used to find solar to hydrogen efficiency (STH). Gd@TiO₂ NRA show optimum conversion efficiency of ~0.64% at 0.03 V vs Ag/AgCl, while pristine TiO₂ NRA display ~0.33% at −0.21 V vs Ag/AgCl.     

ZnIn2S4/In(OH)3 hollow microspheres fabricated by one-step l-cysteine-mediated hydrothermal growth for enhanced hydrogen production and MB degradation

An intervening barrier for photocatalytic water decomposition and pollutant degradation is the frustratingly quick recombination of e⁻ - h⁺ pairs. Delicate design of heterojunction photocatalysts by coupling the semiconductors at nanoscale with well-matched geometrical and electronic alignments is an effective strategy to ameliorate the charge separation. Here a facile and environment-friendly l-cysteine-assisted hydrothermal process under weakly alkaline conditions is demonstrated for the first time to fabricate ZnIn₂S₄/In(OH)₃ hollow microspheres with intimate contact, which are verified by XRD, SEM, (HR)TEM, XPS, N₂ adsorption-desorption, UV–Vis DRS and photoluminescence spectra. ZnIn₂S₄/In(OH)₃ heterostructure (L-cys/Zn²⁺ = 4, molar ratio) with a band-gap of 2.50 eV, demonstrates the best photocatalytic performance for water reduction and MB degradation under visible light, outperforming its counterparts (In(OH)₃ and ZnIn₂S₄). The excellent activity of ZnIn₂S₄/In(OH)₃ heterostructure arises from the intercrossed band-edge positions as well as the unique hollow structure with large surface area and wide pore-size distribution, which are beneficial for the efficient charge migration from bulk to surface as well as at the interface between ZnIn₂S₄ and In(OH)₃. This work provides an efficient and eco-friendly strategy for one-pot synthesis of heterostructured composites with intimate contact for photocatalytic application.     

溶剂热合成多级ZnO微球及其光催化降解苯酚

以乙二醇为溶剂,KAc为助剂,采用溶剂热法合成多级ZnO微球。通过改变反应温度来调控ZnO微球形貌,并对合成的ZnO微球进行XRD、SEM、PL和UV-Vis DRS等表征分析。结果表明,合成的ZnO为六方纤锌矿晶体结构,由短纳米棒自组装成多级微球。在紫外-可见光照射下,ZnO表现出优异的光催化降解苯酚活性,180℃合成的ZnO样品光催化活性明显优于其他温度合成的样品。用0.1 g的ZnO降解100 mL浓度为5 mg·L~(-1)的苯酚溶液,光照150 min降解率达94.5%。多级ZnO微球光催化性能的提高可推测为较窄的禁带宽度(3.08 eV)有利于吸收光子,较小的晶粒尺寸(25.38 nm)、粗糙的表面以及中空结构有利于反应液与催化剂表面的充分接触。此外,由捕获实验证实光催化降解苯酚的机理是羟基(·OH)为主要的活性自由基,在苯酚降解过程中起主要作用。     

Application of chitosan–alginate microspheres for the sustained release of bacteriophage in simulated gastrointestinal conditions

This study was designed to evaluate the acid stability, release property and antimicrobial efficacy of Escherichia coli O157:H7 bacteriophages encapsulated in chitosan–alginate microspheres under the simulated gastrointestinal conditions. The bacteriophages belonging to Myoviridae family were stable at the pH above 4 in trypticase soy broth. The chitosan–alginate microspheres exhibited protective effect on the viability of bacteriophages in the simulated gastric conditions at pH 2.0 and pH 2.5, showing 4.8 and 5.6 log PFU mL^‐1, respectively, after 1 h of incubation at 37 °C. The release per cent of bacteriophages from microspheres gradually increased up to 65% in the simulated intestinal condition (pH 7.5) at 37 °C for 6 h. The lytic efficacy of chitosan‐ and alginate‐encapsulated bacteriophages against E. coli O157:H7 was significantly maintained in the simulated intestinal conditions to 10 h of incubation (1.3 log reduction). The results suggest that the chitosan–alginate microspheres can be used as a reliable delivery system for bacteriophages.     

Carbonaceous microsphere-based superabsorbent polymer as filler for coating of NPK fertilizer: Fabrication,properties, swelling,and nitrogen release characteristics

Recently, the use of controlled release fertilizers in agriculture has resulted in huge benefits in plant growth and cultivation. Superabsorbent polymer (SAP)-coated fertilizers have the added advantage in retaining water in soil after irrigation and also reduce the nutrient release rate from soil in a controlled manner. This study aimed to produce a nitrogen–phosphorus–potassium (NPK) fertilizer coated with superabsorbent carbonaceous microspheres polymer (SPC) by inverse suspension polymerization method with water-retention and controlled release properties. Two sets of experiments were conducted: (1) three different weight percentages and (2) different materials. NPK coated with SPC showed increasing water-retention ability with respect to carbon microsphere percentages and retains >80% water at the 30th day of experiment compared with pure NPK and NPK coated with SAP. The slow release behavior of all samples was investigated by induced coupled plasma mass spectrometry spectrometry and results showed that NPK coated with SAP and SPC has a low release rate with <50% nutrient release compared with uncoated NPK at the 30th day. The release mechanism kinetics of NPK coated with SAP and SPC were studied based on the Kosmeyer–Peppas model. The mechanisms approached Fickian diffusion-controlled release as the n value for both samples was less than 0.5. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48396.