Phosphonic acid-functionalized hollow silica spheres by nitroxide mediated polymerization

A new strategy to prepare phosphonic acid-functionalized hollow silica spheres is proposed via nitroxide mediated polymerization of diisopropyl p-vinylbenzyl phosphonate on the surface of hollow silica spheres (HSSs) and hydrolysis thereafter. The thickness of the organic layer of PVBPA can be controlled by the quantity of the monomers. The structure and morphology of poly(vinylbenzyl phosphonic acid) (PVBPA) grafted HSSs (HPSSs) are confirmed by FTIR and TEM. The addition of HPSS in PVBPA membranes can improve the water retentivity of the composite membranes. The composite membranes with HPSSs exhibit higher water uptake and proton conductivity than the pure PVBPA membranes.     

Sustainable porous hollow carbon spheres with high specific surface area derived from Kraft lignin

Hollow carbon spheres (HCSs) have attracted tremendous interest in recent years due to their intriguing structure-induced physicochemical properties and significant potential for numerous applications. However, the preparation of HCSs with precise structural control using a simple and scalable strategy remains challenging. In this work, hollow carbon particles having a well-defined spherical morphology were successfully produced using a green, economical, and facile spray drying method together with a carbonization process. Kraft lignin was employed as the carbon precursor in place of lignosulfonate with potassium hydroxide (KOH) as an activation agent. The high specific surface area (1536.5–2424.8 m² g^?1) with micro-mesoporous structure of HCSs can be easily tuned by controlling the mass ratio of KOH to carbon precursor. The KOH-to-lignin mass ratios were utilized below 1.5, lower than those in previous studies typically used higher than 3, which was in accordance with green chemistry principles. In addition, these HCSs have applications as electrode materials in supercapacitors for energy storage devices. With the great achievements and continuous efforts in this important field, these results suggest that our approach will open a new path for the development of advanced carbon materials and high value-added utilization of Kraft lignin as a promising material for potential applications.     

Synthesis and characterization of amorphous hollow carbon spheres

Nanostructured carbon materials have attracted enormous attention in last two decades due to their unique chemical, electrical, and mechanical properties. In this work, amorphous hollow carbon spheres (AHCSs) with diameters in the range of 100–750 nm, which are dispersed among bent graphitized carbon nanotubes, are synthesized by using radio frequency plasma enhanced chemical vapor deposition in mixed CH₄/H₂ gases. The carbon spheres were characterized with scanning electron microscope, energy-dispersive X-ray spectroscopy, Raman spectroscopy, and transmission electron microscopy. It is found that MgO and Co/Ni nanoparticles as well as hydrogen play crucial roles in the formation of AHCSs. Moreover, a possible growth mechanism of AHCSs was proposed. The results of this study provide new insights into the fundamental understanding of nonstructural carbon materials toward applications in nanodevices.     

Simple synthesis of hollow carbon spheres from glucose

Hollow carbon spheres were prepared by the reaction between glucose and Zn particles at 550 °C. Scanning and transmission electron microscopies reveal that most of the spheres are about 1-2 µm in diameter, similar to the sizes of the Zn particle. The shells of the spheres are comprised of numerous hollow nanospheres with the diameter of 10-100 nm. The specific surface area of the spheres is 207 m²/g. The Zn particles act as both the reactant and the template for the micron-scale spheres, and the H₂ bubbles generated during the reaction as the template for the hollow nanospheres.     

Fabrication of hollow silver spheres by MPTMS-functionalized hollow silica spheres as templates

In this study, we provide a strategy to prepare the hollow silver spheres by accumulating the silver nanoparticles on the surface of 3-mercaptopropyltrimethoxysilane (MPTMS)-functionalized silica as templates, which was accomplished by the chemisorption between silver nanoparticles and thiol groups. Then, the resulting hollow silver spheres were obtained through the chemical wet etching process with 10 M HF solution. In conventional method, the fabrication of hollow silver spheres from core-shell spheres was not easy due to the difficulties in retaining the shell structures during core removal. The method in this paper could overcome this limitation. The major focus of study is on understanding the mechanism of formation of the hollow silver spheres through the self-assembly behavior by chemisorption between silver nanoparticles and thiol groups. The silver-coated silica and hollow silver spheres were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), and X-ray photoelectron spectroscopy (XPS).     

Nitrogen-doped hollow carbon spheres with enhanced electrochemical capacitive properties

Nitrogen-doped hollow carbon spheres (N-HCS) with uniform size have been synthesized via the hydrothermal method using pyrrole as the precursor. After carbonization at 850 °C, the average diameter of N-HCS is ca. 370 nm with shell thickness of ～15 nm. The electrochemical capacitive behavior of N-HCS was investigated by cyclic voltammetry and galvanostatic charge–discharge method in 1.0 M H₂SO₄ aqueous solution. Results show that N-HCS have high specific capacitance (345.2 F g^?1 at 0.2 A g^?1) and high-rate capability with the increase of the scan rate from 10 to 1000 mV s^?1 due to the synergetic effects of the unique hollow nanostructure and the N-doped thin carbon shell. In addition, the capacitance retains 98.1% after 1500 cycles even at a high loading current density of 10 A g^?1.     

Composite of sulfur impregnated in porous hollow carbon spheres as the cathode of Li-S batteries with high performance

Carbon-sulfur composites as the cathode of rechargeable Li-S batteries have shown outstanding electrochemical performance for high power devices. Here, we report the promising electrochemical charge-discharge properties of a carbon-sulfur composite, in which sulfur is impregnated in porous hollow carbon spheres (PHCSs) via a melt-diffusion method. Instrumental analysis shows that the PHCSs, which were prepared by a facile template strategy, are characterized by high specific surface area (1520 m²·g^?1), large pore volume (2.61 cm³·g^?1), broad pore size distribution from micropores to mesopores, and high electronic conductivity (2.22 S·cm^?1). The carbon-sulfur composite with a sulfur content of 50.2 wt.% displays an initial discharge capacity of 1450 mA·h·g^?1 (which is 86.6% of the theoretical specific capacity) and a reversible discharge capacity of 1357 mA·h·g^?1 after 50 cycles at 0.05 C charge-discharge rate. At a higher rate of 0.5C, the capacity stabilized at around 800 mA·h·g^?1 after 30 cycles. The results illustrate that the porous carbon-sulfur composites with hierarchically porous structure have potential application as the cathode of Li-S batteries because of their effective improvement of the electronic conductivity, the repression of the volume expansion, and the reduction of the shuttling loss.      

Sculpturing solid polymer spheres into internal gridded hollow carbon spheres under controlled pyrolysis micro-environment

Porous carbon spheres with an internal gridded hollow structure and microporous shell have always been attractive as carbon hosts for electrochemical energy storage. Such carbon hosts can limit active species loss and enhance electronic conductivity throughout the entire framework. Herein, a synthesis approach of internal gridded hollow carbon spheres is developed from solid polymer spheres rather than originally gridded polymer spheres under a controlled pyrolysis micro-environment. The crucial point of this approach is the fabrication of a silica fence around solid polymer spheres, under which the free escaping of the pyrolysis gas will be partly impeded, thus offering a reconstitution opportunity for an internal structure of solid polymer spheres. As a result, the interior of carbon spheres is sculptured into a gridded hollow structure with microporous skin. Furthermore, the size and density of carbon-bridge grids can be modulated by altering the crosslinking degree of polymer spheres and varying pyrolysis conditions. Such gridded hollow carbon spheres show good performance as sulfur hosts for Li-S battery.     

磷掺杂中空碳球的制备及其电容性能EI北大核心CSCD

以酚醛预聚体和苯乙烯为原料通过水热法一步合成中空聚合物球(HPS),再以三氯化磷为反应剂通过傅-克反应对HPS处理得到含磷交联聚合物,经高温炭化和KOH活化制备磷掺杂中空碳球(AP-HCS)。采用FT-IR,TG,SEM,TEM,Raman,BET,XPS等手段对含磷聚合物和碳材料的组成、结构与形貌进行表征,测试碳材料在1 mol/L H2SO4介质中的电容性能。结果表明:AP-HCS的比表面积可达2177 m2/g,在1 A/g电流密度下,比电容为288 F/g,5 A/g电流密度下经循环充放电5000次后比电容值仍能保持88.9%,具备良好的电容性能。     

Synthesis and release of trace elements from hollow and porous hydroxyapatite spheres

It is known that organic species regulate fabrication of hierarchical biological forms via solution methods. However, in this study, we observed that the presence of inorganic ions plays an important role in the formation and regulation of biological spherical hydroxyapatite formation. We present a mineralization method to prepare ion-doped hydroxyapatite spheres with a hierarchical structure that is free of organic surfactants and biological additives. Porous and hollow strontium-doped hydroxyapatite spheres were synthesized via controlling the concentration of strontium ions in a calcium and phosphate buffer solution. Similarly, fluoride and silicon-doped hydroxyapatite spheres were synthesized. While spherical particle formation was attainable at low and high temperature for Sr-doped hydroxyapatite, it was only possible at high temperature in the F/Si-doped system. The presence of inorganic ions not only plays an important role in the formation and regulation of biological spherical hydroxyapatite, but also could introduce pharmaceutical effects as a result of trace element release. Such ion release results showed a sustained release with pH responsive behavior, and significantly influenced the hydroxyapatite re-precipitation. These ion-doped hydroxyapatite spheres with hollow and porous structure could have promising applications as bone/tooth materials, drug delivery systems, and chromatography supports.     

炭化聚苯乙烯/聚苯胺核-壳聚合物颗粒制备中空炭球

以磺化聚苯乙烯球为模板,苯胺为碳源,利用模板法制备了中空炭球结构.采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、傅立叶-红外光谱(FT-IR)和热重分析(TGA)对所制的样品进行了表征.结果表明:所制中空炭球的壁厚为35nm且粒径均匀,中空炭球的形貌和壳层厚度受聚苯乙烯模板磺化度的影响....     

A novel method for preparation of hollow and solid carbon spheres

Hollow and solid carbon spheres were prepared by the reaction of ferrocene and ammonium carbonate in a sealed quartz tube at 500°C. The morphology and microstructure of the product were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The carbon spheres are amorphous and their diameters range from 0·8–2·8 μm. The shell thickness of the hollow carbon spheres is not uniform and ranges from 100–180 nm. It is suggested that ammonium carbonate is crucial for the formation of carbon spheres and its amount also influences the morphology of the product. The method may be suitable for large scale preparation of carbon spheres.     

Photocatalytic performance of Gd ion modified titania porous hollow spheres under visible light

In this work, Gd-doped titania hollow spheres were prepared using hydrothermally prepared carbon spheres as template. The prepared samples were characterized by XRD, TEM, SEM, DRS and XPS. The photocatalytic activity of as-prepared hollow titania spheres was determined by degradation of Reactive Brilliant Red dye X-3B (C.I. reactive red 2) under visible light irradiation. The effect of Gd content on the physical structure and photocatalytic properties of doped titania hollow sphere samples was investigated. Results showed that there was an optimal Gd-doped content (4%) for the photocatalytic activity of X-3B degradation.     

Fabrication of calcined hierarchical porous hollow silicate micro-size spheres via double emulsion process

Silicate (7 to 12 μm) microspheres with porous shell were prepared via modified double emulsion (water₁/oil/water₂) method mediated with N₂ pressure filtration and calcination to completely remove the organic components. With the addition of sodium polymethacrylate (Na-PA) into the aqueous solution of water₁/oil/water₂ emulsion system then calcined, led to the formation of stable hierarchical macroporous (surface area: 42.94 m²/g) from mesoporous (surface area: 259.2 m²/g) shell wall of silicate hollow microspheres.     

Synthesis and TEM observation of fluffy hollow carbon spheres by FeCl3 catalyzed solvent-thermal reaction

Fluffy hollow carbon spheres with the diameter of 0.3–1.8 μm and shell thickness of 30–80 nm were successfully synthesized via FeCl₃ catalyzed solvent-thermal reaction in a sealed autoclave at 350 °C for 3 h, with CaC₂ and CCl₄ as carbon sources and reactants. XRD and TEM observations verify that the fluffy hollow carbon spheres are composed of curved and disordered carbon flakes with the interlayer instance of approximate 0.35 nm. Furthermore, MCNTs with Fe–Mn–Cr nanorods encapsulated are also observed. A possible growth mechanism for the fluffy hollow carbon sphere is proposed.     

The size modulation of hollow mesoporous carbon spheres synthesized by a simplified hard template route

Hollow mesoporous carbon spheres (HMCSs) have been prepared by a simplified replication route from a solid silica core/mesoporous silica shell aluminosilicate (SCMS-Al) template, which was synthesized by directly incorporating aluminum species into the mesoporous framework during template synthesis. The size of HMCSs can be tuned between 80 and 470 nm by simply changing the diameters of SCMS-Al. The HMCSs have uniform mesopores with a narrow pore size distribution (3.4-4.1 nm), and high surface area, (890-1150 m²/g) and total pore volumes (0.75-1.15 cm³/g). The techniques of N₂ sorption isotherms, TEM, EDX and SEM were used to characterize the as-synthesized spheres.     

Synthesis of submicron size hollow carbon spheres by a chemical reduction — solvothermal method using carbon tetrachloride as carbon source

A simple, rapid and energy efficient approach based on copper mediated chemical reduction — solvothermal method was employed to prepare submicron size hollow carbon spheres (SHCS) using carbon tetrachloride as carbon source. The obtained SHCS were characterized by means of various physico-chemical techniques like nitrogen adsorption-desorption measurements at 77 K, XRD, SEM, TEM, EDX and FT-Raman techniques. Thus characterized samples displayed macroporous nature of carbon with carbon and chloride contents of about 73% and 12% on atomic basis respectively. The presence of chloride content may open new avenues for surface modifications of SHCS in the area of catalysis and separation science.     

Submicrometer-sized hollow nickel spheres synthesized by autocatalytic reduction

A facile method to fabricate submicrometer-sized hollow nickel spheres by autocatalyzing the redox reaction around a sacrificial colloidal particle surface is presented in this paper. The size distribution of these spheres can be controlled by regulating the concentration of the alkali solution. The hollow nickel particles were characterized by field emission scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction. The hollow spheres produced by this process may have potential applications in many fields, including chemistry, biotechnology and materials science.     

One-step synthesis of hierarchically porous hybrid TiO2 hollow spheres with high photocatalytic activity

Hierarchically porous hybrid TiO₂ hollow spheres were solvothermally synthesized successfully by using tetrabutyl titanate as titanium precursor and hydrated metal sulfates as soft templates. The as-prepared TiO₂ spheres with hierarchically pore structures and high specific surface area and pore volume consisted of highly crystallized anatase TiO₂ nanocrystals hybridized with a small amount of metal oxide from the hydrated sulfate. The proposed hydrated-sulfate assisted solvothermal (HAS) synthesis strategy was demonstrated to be widely applicable to various systems. Evaluation of the hybrid TiO₂ hollow spheres for the photo-decomposition of methyl orange (MO) under visible-light irradiation revealed that they exhibited excellent photocatalytic activity and durability.