The Microstructure of Cobalt Silica Gel Catalyst in the Presence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Additive

The physico-chemical characteristics and microstructure of cobalt silica gel catalysts with an Al₂O₃ additive (up to 10%) for the synthesis of hydrocarbons by the Fischer–Tropsch method are studied using a set of methods including X-ray diffraction, BET, IR spectroscopy, and temperature-programmed reduction of H₂, as well as scanning and transmission electron microscopy. Phases with a spinel structure, Со₃О₄, CoAl₂O₄, and solid solutions on their basis are identified in the samples. The addition of Al₂O₃ changes the degree of heterogeneity and the orientation of the cobalt crystallites in the oxide and reduced forms of the catalysts. Addition of 1% Al₂O₃ stabilizes Со₃О₄ in the spinel form with a structure close to the normal one and promotes the formation of cobalt with a unimodal distribution of particles with an average size of 8 nm. The catalyst is characterized by maximum activity and selectivity with respect to C⁵⁺ carbons.     

Characterization of the microstructures of copper-based aerogels on the sol–gel process

In this thesis, we will elaborate on the sol–gel process during the preparation of monolithic copper-based aerogel. The microstructure of the copper-based aerogel appears to be various due to the different amounts of raw materials, such as polyacrylic acid, propene oxide, deionized water (H₂O) and copper(II) chloride (CuCl₂) in the sol–gel process. The proper molar ratios between these reactants play a crucial factor in mediating the morphology of the aerogel. The aerogels are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy and Brunauer–Emmett–Teller methods. The combined results indicate that the copper-based aerogel shows a typical three-dimensional porous structure with a large surface areas about 568 m²/g, and the skeleton structure of the aerogel is composed of a large number of primary particles with the size about a few nanometers.     

Preparation and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>composite particles

Using Fe₃O₄ nano-particles as seeds, a new type of Fe₃O₄/Au composite particles with core/shell structure and diameter of about 170 nm was prepared by reduction of Au³⁺ with hydroxylamine in an aqueous solution. Particle size analyzer and transmission electron microscope were used to analyze the size distribution and microstructure of the particles in different conditions. The result showed that the magnetically responsive property and suspension stability of Fe₃O₄ seeds as well as reduction conditions of Au³⁺to Au⁰are the main factors which are crucial for obtaining a colloid of the Fe₃O₄/Au composite particles with uniform particle dispersion, excellent stability, homogeneity in particle sizes, and effective response to an external magnet in aqueous suspension solutions. UV-Vis analysis revealed that there is a characteristic peak of Fe₃O₄/Au fluid. For particles with d(0.5)=168 nm, the λmax is 625 nm.     

Facile synthesis of TiO<Subscript>2</Subscript>/Ag composite aerogel with excellent antibacterial properties

In this study, the effective TiO₂/Ag composite antibacterial aerogel powder is prepared by facile sol–gel method and ethanol supercritical technology. The surface morphology, structural properties, and chemical components are monitored by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and energy disperse?spectroscopy (EDS). Meanwhile, absorbance spectra and specific surface area of TiO₂/Ag composite aerogel are characterized by UV-Vis spectra and Brunauer–Emmett–Teller. The TiO₂/Ag composite aerogel with Ti/Ag molar ratios of 10:1, 30:1, 50:1 are measured for its antibacterial property by using Escherichia coliform (E.coli) and Staphylococcus aureus (S. aureus). The results show that the size of TiO₂ and Ag nanoparticles are 40?nm and 25?nm, respectively. Simultaneously, the obtained composite aerogel with a porous structure possessed a surface area of 148?m²/g, an average pore size 11.5?nm, and a pore volume 0.39?cm³/g. With the increase of Ag content, the antibacterial properties of composite aerogel are greatly improved compared with pure TiO₂ aerogel. When Ag/Ti molar ratios was 1:10, the highest antibacterial rate can up to 99%, and the inhibition bands of E. coli and S. aureus are 23?mm and 19?mm, respectively.

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Schematic representation of growth mechanism of TiO₂/Ag composite aerogel (a) and antibacterial performance test (b, c)

     

Understanding the accumulated cycle capacity fade caused by the secondary particle fracture of LiNi<Subscript>1-x-y</Subscript>Co<Subscript>x</Subscript>Mn<Subscript>y</Subscript>O<Subscript>2</Subscript> cathode for lithium ion batteries

Effect of secondary particle fracture on the accumulated cycle capacity fade of LiNi_1-x-yCo_xMn_yO₂ cathode is difficult to evaluate since performance degradation of electrode material is always caused by several factors simultaneously. Herein, LiNi_0.5Co_0.2Mn_0.3O₂ single particles (Sin-P) are prepared and introduced as a reference to understand the accumulated cycle capacity fade caused by the secondary particle fracture of LiNi_0.5Co_0.2Mn_0.3O₂ secondary particles (Sec-P). Sec-P exhibited accumulated cycle capacity fade compared to Sin-P when cycled at high rate, high voltage, and high temperature. The accumulated cycle capacity fade was mainly caused by the secondary particle fracture of Sec-P, which was confirmed by the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM) analysis. Further, XPS and electrochemical impedance spectroscopy (EIS) analysis indicated that the surface property changes and resistance rise were responsible for the accumulated cycle capacity fade. The study provides a novel way to analyze the accumulated cycle capacity fade caused by the secondary particle fracture and is helpful for understanding the performance degradation mechanism of electrode material.     

Improvement of the electrochemical properties of a LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode material formed by a new solid-state synthesis method

In order to avoid the shortcomings of large particle size and poor uniformity of material synthesized by the traditional solid-state method, this paper utilizes a simple improvement of calcination process (i.e., calcination–milling–recalcination) based on the traditional solid-state synthesis to successfully prepare a large number of well-distributed, micrometer-sized, spherical secondary LiNi_0.5Mn_1.5O₄ particles. Each particle is composed of nano- and/or sub-micrometer-sized grains. Results of the electrochemical performance tests show that the material exhibits a remarkable cycle performance and rate capability compared with that obtained from traditional synthesis method; the spherical LiNi_0.5Mn_1.5O₄ particles can deliver a large capacity of 135.8 mAh g^?1 at a 1 C discharge rate with a high retention of 77 % after 741 cycles and a good capacity of 105.9 mAh g^?1 at 10 C. Cyclic voltammetry measurements confirm that the significantly improved electrochemical properties are due to enhanced electronic conductivity and lithium-ion diffusion coefficient resulting from the optimized morphology and particle size. This improved method is more suitable for mass production.     

Structural evolution and magnetic properties of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers by electrospinning

The SrFe₁₂O₁₉/poly (vinyl pyrrolidone) (PVP) composite fiber precursors were prepared by the sol-gel assisted electrospinning with ferric nitrate, strontium nitrate and PVP as starting reagents. Subsequently, the M-type strontium ferrite (SrFe₁₂O₁₉) nanofibers were derived from calcination of these precursors at 750–1,000 °C.The composite precursors and strontium ferrite nanofibers were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer. The structural evolution process of strontium ferrite consists of the thermal decomposition and M-type strontium ferrite formation. After calcined at 750 °C for 2 h the single M-type strontium ferrite phase is formed by reactions of iron oxide and strontium oxide produced during the precursor decomposition process. The nanofiber morphology, diameter, crystallite size and grain morphology are mainly influenced by the calcination temperature and holding time. The SrFe₁₂O₁₉ nanofibers characterized with diameters of around 100 nm and a necklace-like structure obtained at 900 °C for 2 h, which is fabricated by nanosized particles about 60 nm with the plate-like morphology elongated in the preferred direction perpendicular to the c-axis, show the optimized magnetic property with saturation magnetization 59 A m² kg⁻¹ and coercivity 521 kA m⁻¹. It is found that the single domain critical size for these M-type strontium ferrite nanofibers is around 60 nm.     

Effects of KIO<Subscript>3</Subscript> additive on the direct electrosynthesis of K<Subscript>2</Subscript>FeO<Subscript>4</Subscript>

An electrosynthesis in 14.5 M KOH electrolyte using KIO₃ additive is presented for the direct synthesis of solid K₂FeO₄, with a highest efficiency of 77.6%, purities of 95.3–97.8% and a yield of 68 g l⁻¹ K₂FeO₄ at 65°C. The results show that using the additive during synthesis of ferrate(VI) can increase the current efficiency by 26% than the blank in degree. Its function is similar to the results of using ultrasonic. The techniques of CV, EDX, IR, SEM and XRD are used to feature the Fe electrode or K₂FeO₄ samples. It is found that addition of KIO₃ can increase the potential of oxygen evolution on the CV of Fe anode in KOH significantly. The EDX measurement displays that K₂FeO₄ sample obtained using KIO₃ additive contains no iodine. The sample exhibits similar IR feature absorption spectra and XRD patterns but some dissimilar crystal morphologies to the one with blank.     

Synthesis and electrochemical properties of Li-rich Li[Ni<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>]O<Subscript>2</Subscript> for pouch-typed cell

Layered transition metal oxide LiNi _x Co _y MnzO₂ cathode materials with different Li amount were successfully synthesized via co-precipitation method. Monodispersed Li[Ni_0.5Co_0.2Mn_0.3]O₂ and Li-rich Li_1.1[Ni_0.5Co_0.2Mn_0.3]O₂ spherical agglomeration consisted of secondary particles, which is favorable for the higher tap-density of materials, can be easily obtained. The pouch-typed cells with obtained materials were assembled to investigate electrochemical performance at level of full-cell. The results show that the assembled pouch-typed full-cells with Li-rich sample present higher capacity, better rate capability and cycle life.     

X-ray photoelectron study of the interaction of H<Subscript>2</Subscript> and H<Subscript>2</Subscript>+O<Subscript>2</Subscript> mixtures on the Pt/MoO<Subscript>3</Subscript> model catalyst

The effects of H₂ and H₂ + O₂ gas mixtures of varying composition on the state of the surface of the Pt/MoO₃ model catalyst prepared by vacuum deposition of platinum on oxidized molybdenum foil were investigated by X-ray photoelectron spectroscopy (XPS) at room temperature and a pressure of 5–150 Torr. For samples with a large Pt/Mo ratio, the XP spectrum of large platinum particles showed that the effect of hydrogen-containing mixtures on the catalyst was accompanied by the reduction of molybdenum oxide. This effect results from the activation of molecular hydrogen due to the dissociation on platinum particles and subsequent spill-over of hydrogen atoms on the support. The effect was not observed at low platinum contents in the model catalyst (i.e., for small Pt particles). It is assumed for the catalyst that the loss of its hydrogen-activating ability is a consequence of the formation of platinum hydride. Possible participation of platinum hydride as intermediate in hydrogen oxidation to H₂O₂ is discussed.     

Synthesis of electrospun BaSrTiO<Subscript>3</Subscript>/PVP nanofibers

Ba_1−x Sr _x TiO₃(x = 0–0.5, BST) nanofibers with diameters of 150–210 nm were prepared by using electrospun BST/polyvinylpyrrolidone (PVP) composite fibers by calcination for 2 h at temperatures in the range of 650–800 °C in air. The morphology and crystal structure of calcined BST/PVP nanofibers were characterized as functions of calcination temperature and Sr content with an aid of XRD, FT-IR, and TEM. Although several unknown XRD peaks were detected when the fibers were calcined at temperatures less than 750 °C, they disappeared with increasing the temperature (above 750 °C) due to its thermal decomposition and complete reaction in the formation of BST. In addition, the FT-IR studies of BST/PVP fibers revealed that the intensities of the O–H stretching vibration bands (at 3430 and 1425 cm⁻¹) became weaker with increasing the calcination temperature and a broad band at 540 cm⁻¹, Ti–O vibration, appeared sharper and narrower after calcination above 750 °C due to the formation of metal oxide bonds. However, no effect of Sr content on the crystal structure of the composites was detected.     

Hydrothermal synthesis of core-shell structured PS@GdPO<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript>/Ce<Superscript>3+</Superscript> spherical particles and their luminescence properties

Non-aggregated spherical polystyrene (PS) particles were coated with GdPO₄:Tb³⁺/Ce³⁺ phosphor layers by a conventional hydrothermal synthesis using poly(vinylpyrrolidone) (PVP) as an additive without further annealing treatment. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), as well as luminescence decay experiments were used to characterise the resulting core-shell structured PS@GdPO₄:Tb³⁺/Ce³⁺ samples. The results of XRD indicated that the PS particles were successfully coated with the GdPO₄:Tb³⁺/Ce³⁺ phosphor layers, which could be further verified by the images of FESEM. Under ultraviolet excitation, the PS@GdPO₄:Tb³⁺/Ce³⁺ phosphors show Tb³⁺ characteristic emission, i.e. ⁵D₄-⁷F_J (J = {6, 5, 4, 3}) emission lines with green emission ⁵D₄-⁷F₅ (543 nm) as the most prominent group. The core-shell phosphors so obtained have potential applications in field emission display (FED) and plasma display panels (PDP).     

C<Subscript>18</Subscript>-Free Organic–Inorganic Hybrid Silica Particles Derived from Sole Silsesquioxane for Reversed-Phase HPLC

Ethyl-bridged organic–inorganic hybrid silica particles were prepared via a sol–gel and hydrothermal synthesis approach using 1,2-bis(triethoxysilyl)ethane (BTESE) as the sole precursor, and triblock copolymer poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (P123) and dodecyltrimethylammonium bromide (DTAB) as combined templates. The morphology, pore structure, chemical composition and liquid chromatographic performance of the obtained materials were investigated in detail. The particles exhibit a high surface area of 1136.40 m²/g, together with a pore volume of 0.39 cm³/g and an average pore size of 2.30 nm. Used as stationary phase for high-performance liquid chromatography (HPLC), the particles without extra bonding either C₁₈ or C₈ can successfully separate a mixture of uracil, phenol, pyridine, methylbenzene, ethylbenzene and tert-butylbenzene. The obtained materials also show practical application in the separation of phthalate acid esters (PAEs), which are harmful to environment and human health. Although the columns packed with ethyl-bridged organic–inorganic hybrid silica show lower column efficiency and peak symmetry compared to commercial column, they have considerably higher chemical stability in alkaline mobile phase. The HSS column also possesses high mechanical stability which is similar to that of the commercial column.     

Al-doped La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> as oxide anode for solid oxide fuel cells using dry C<Subscript>3</Subscript>H<Subscript>8</Subscript> fuel

Direct hydrocarbon type solid oxide fuel cells are attractive from simple gas feed process and also high energy conversion efficiency. In this study, La_0.5Sr_0.5MnO₃ (LSM55) perovskite oxide was studied as oxide anode for direct hydrocarbon type solid oxide fuel cell (SOFC). Although reasonable power density like 1 W/cm² and open circuit voltage (OCV) (1.1 V) at 1273 K was exhibited when H₂ was used as fuel, the power density as well as OCV of the cell using LSM55 for anode was significantly decreased when dry C₃H₈ was used for fuel. After power generation measurement, LSM55 phase was decomposed to MnO and La₂MnO₄. Effects of various dopants to Mn site in LSM55 were studied and it was found that partial substitution of Mn in LSM55 with other cation, especially transition metal, is effective for increasing maximum power density. In particular, reasonable high power density can be achieved on the cell using Ni-doped LSM55 for anode. On the other hand, Al substitution is effective for increasing stability against reduction and so, dopant effects of Al were studied in more details for dry C₃H₈ fuel. The power density as well as OCV increased with increasing Al content and the highest power density was achieved at x = 0.4 in La_0.5Sr_0.5Mn_1 ? x Al _x O₃. Among the examined composition, it was found that the cell using La_0.5Sr_0.5Mn_0.6Al_0.4O₃ anode shows the largest power density (0.2 W/cm²) at 1173 K and high OCV (1.01 V) against dry C₃H₈ fuel.     

FT-IR study on CO<Subscript>2</Subscript> adsorbed species of CO<Subscript>2</Subscript> sorbents

The stability of amine-functionalized silica sorbents prepared through the incipient wetness technique with primary, secondary, and tertiary amino organosilanes was investigated. The prepared sorbents were exposed to different gaseous streams including CO₂/N₂, dry CO₂/air with varying concentration, and humid CO₂/air mixtures to demonstrate the effect of the gas conditions on the CO₂ adsorption capacity and the stability of the different amine structures. The primary and secondary amine-functionalized adsorbents exhibited CO₂ sorption capacity, while tertiary amine adsorbent hardly adsorbed any CO₂. The secondary amine adsorbent showed better stability than the primary amine sorbent in all the gas conditions, especially dry conditions. Deactivation species were evaluated using FT-IR spectra, and the presence of urea was confirmed to be the main deactivation product of the primary amine adsorbent under dry condition. Furthermore, it was found that the CO₂ concentration can affect the CO₂ sorption capacity as well as the extent of degradation of sorbents.     

One‐Pot Synthesis of Pomegranate‐Structured Fe3O4/Carbon Nanospheres‐Doped Graphene Aerogel for High‐Rate Lithium Ion Batteries

A unique hierarchically nanostructured composite of iron oxide/carbon (Fe₃O₄/C) nanospheres‐doped three‐dimensional (3D) graphene aerogel has been fabricated by a one‐pot hydrothermal strategy. In this novel nanostructured composite aerogel, uniform Fe₃O₄ nanocrystals (5–10 nm) are individually embedded in carbon nanospheres (ca. 50 nm) forming a pomegranate‐like structure. The carbon matrix suppresses the aggregation of Fe₃O₄ nanocrystals, avoids direct exposure of the encapsulated Fe₃O₄ to the electrolyte, and buffers the volume expansion. Meanwhile, the interconnected 3D graphene aerogel further serves to reinforce the structure of the Fe₃O₄/C nanospheres and enhances the electrical conductivity of the overall electrode. Therefore, the carbon matrix and the interconnected graphene network entrap the Fe₃O₄ nanocrystals such that their electrochemical function is retained even after fracture. This novel hierarchical aerogel structure delivers a long‐term stability of 634 mA h g^?1 over 1000 cycles at a high current density of 6 A g^?1 (7 C), and an excellent rate capability of 413 mA h g^?1 at 10 A g^?1 (11 C), thus exhibiting great potential as an anode composite structure for durable high‐rate lithium‐ion batteries.     

Enhanced electrochemical properties of Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript>/C nanocomposite synthesized with phenolic resin as carbon source

Li₂ZnTi₃O₈/C nanocomposite has been synthesized using phenolic resin as carbon source in this work. The structure, morphology, and electrochemical properties of the as-prepared Li₂ZnTi₃O₈ samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), Raman spectroscopy (RS), galvanostatic charge–discharge, and AC impedance spectroscopy. SEM images show that Li₂ZnTi₃O₈/C was agglomerated with a primary particle size of ca. 40 nm. TEM images reveal that a homogeneous carbon layer (ca. 5 nm) formed on the surface of Li₂ZnTi₃O₈ particles which is favorable to improve the electronic conductivity and inhibit the growth of Li₂ZnTi₃O₈ during annealing process. The as-prepared Li₂ZnTi₃O₈/C composite with 6.0 wt.% carbon exhibited a high initial discharge capacity of 425 and 159 mAh g^?1 at 0.05 and 5 A g^?1, respectively. At a high current density of 1 A g^?1, 95.5 % of its initial value is obtained after 100 cycles.     

Synthesis of BaSnO<Subscript>3</Subscript>/SnO<Subscript>2</Subscript> Nanocomposites as Heterogeneous Additive for Composite Solid Electrolytes

Method of differential thermal analysis was used to study the thermolysis of a mixture of barium oxalate hydrate and α-SnO₂·H₂O, produced by precipitation from hydrochloric solutions. The methods of X-ray diffraction analysis, electron microscopy, and low-temperature nitrogen adsorption were used to examine the reaction products formed at various heating temperatures and determine their phase composition. The nanocomposite BaSnO₃/SnO₂ is the final product of thermolysis and subsequent heating to 950°C. The nanocomposite was used as a heterogeneous oxide additive for obtaining a CsNO₂–BaSnO₃/SnO₂ composite solid electrolyte. The conductivity of the composite exceeds that of the starting salt by more than order of magnitude.     

Synthesis of CeO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> hydrosols via peptization at elevated temperature

A method for synthesizing aggregation-stable CeO₂-ZrO₂ hydrosols with different particle compositions is developed based on the peptization of hydrated oxide precipitates at elevated temperature. It is shown that, by varying heat treatment time, sols can be obtained with particles that have different degrees of crystallinity and sizes of no larger than 6 nm.     

Thermal behavior of cellulose fibers with enzymatic or Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> treatment

Summary New regenerated cellulose fibers were developed during the last decades as environmentally friendly systems. In this work, three fibers: lyocell, modal and viscose were subjected to an enzymatic treatment. Likewise, different lyocell fibers were washed in a Na₂CO₃ solution under severe conditions. Analysis was performed by means of differential scanning calorimetry, thermogravimetry and scanning electron microscopy. In all samples, at low temperature, water desorption was detected. Furthermore, thermal analysis shows wide exothermic processes that began between 250 and 300°C corresponding to the main thermal degradation and it is associated to a depolymerization and decomposition of the regenerated cellulose. It is accompanied with mass more than 60% mass loss. Kinetic analysis was performed and activation energy values 152-202 kJ mol^-1 of the main degradation process are in agreement with literature values of cellulose samples.