有序介孔碳CMK-3微波负载NiO及其电容性能研究

微波法负载具有简便、快速、均匀的优点. 本文尝试以乙二醇为还原剂, Ni(Ac)₂为Ni源, 通过微波辐射负载及低温空气煅烧在CMK-3上形成NiO. 对样品进行X射线衍射(XRD)、透射电子显微镜(TEM)、N₂吸脱附等结构表征及循环伏安(CV)等电化学性能测试. 结果显示, 微波法并经低温空气煅烧后有序介孔碳CMK-3的小角XRD峰强度变弱、比表面积下降、孔容减小, 但却使其比电容从229.3 F/g提高到295.9 F/g, 大于文献报导中介孔碳负载MnO₂, RuO₂•xH₂O后的比电容值. 由此说明微波法是有效的负载方法, 具有较好的应用前景.     

Formation of graphitic structures in cobalt- and nickel-doped carbon aerogels

We have prepared carbon aerogels (CAs) doped with cobalt or nickel through sol-gel polymerization of formaldehyde with the potassium salt of 2,4-dihydroxybenzoic acid, followed by ion exchange with M(NO3)2 (where M = Co2+ or Ni2+), supercritical drying with liquid CO2, and carbonization at temperatures between 400 and 1050 degrees C under a N2 atmosphere. The nanostructures of these metal-doped carbon aerogels were characterized by elemental analysis, nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Metallic nickel and cobalt nanoparticles are generated during the carbonization process at about 400 and 450 degrees C, respectively, forming nanoparticles that are approximately 4 nm in diameter. The sizes and size dispersion of the metal particles increase with increasing carbonization temperatures for both materials. The carbon frameworks of the Ni- and Co-doped aerogels carbonized below 600 degrees C mainly consist of interconnected carbon particles with a size of 15-30 nm. When the samples are pyrolyzed at 1050 degrees C, the growth of graphitic nanoribbons with different curvatures is observed in the Ni- and Co-doped carbon aerogel materials. The distance of graphite layers in the nanoribbons is approximately 0.38 nm. These metal-doped CAs retain the overall open cell structure of metal-free CAs, exhibiting high surface areas and pore diameters in the micro- and mesoporic region.     

ZrMn Oxides for Aqueous‐Phase Ketonization of Acetic Acid: Effect of Crystal and Porosity

Aqueous‐phase ketonization of bio‐based acetic acid is important to improve the conversion efficiency of biomass resources. In this study, ZrMn mixed oxides (ZrMnO_x) with high aqueous‐phase ketonization activity are synthetized through a carbonization/oxidation method (COM) and solvothermal method (STM). The results show that ZrMnO_x prepared by COM possesses tetragonal ZrO₂, and hausmannite Mn₃O₄ is observed only at a high oxidation temperature of 750 °C. Low‐temperature and long oxidation results in decreased crystallinity and crystallite size, which is related to highly dispersed Mnⁿ⁺ species. The catalysts with improved acid sites possess high ketonization activity. Surface areas and pore size of ZrMnO_x synthetized by STM are controlled by the solvents for thermal treatment. Compared with water as solvent, ethanol increases the surface area and pore size, resulting in high ketonization activity.     

Removal of sulfur from commercial kerosene using nanocrystalline NiFe2O4 based sorbents

This paper deals with the simultaneous removal of sulfur from commercial kerosene at room temperature using sorbents containing NiFe₂O₄ nanoparticles. The nanocrystalline NiFe₂O₄ based sorbents were prepared using the combustion route. The effect of fuel content on the surface properties and desulferization activity of Ni/Fe mixed oxide sorbents has been studied.It was observed that incorporation of metal cations (Ni²⁺) into the hematite (α-Fe₂O₃) crystal structure alters the surface properties and desulferization activity of the investigated oxides, which in turn depends on the nature and concentration of the incorporated metal cation and the released heat during the combustion process. The effect of fuel content in modifying the resultant surface area could be directly related to the variations in the rate of crystal growth of the solids studied depending upon preparation temperature. Interestingly, all the prepared ferrites exhibit a narrow pore size distribution in the range of 0.9–2 nm. The capacity of NiFe₂O₄ to adsorb sulfur from commercial kerosene was evaluated in terms of their textural and chemical characteristics.     

Aggregates and hydrogels prepared by self-assembly of amphiphilic copolymers with surfactants

Mesoporous carbons containing cobalt nanoparticles are synthesized by tri-or quad-constituent self assembly of Pluronic F127, phenol-formaldehyde oligomer (resol), cobalt acetylacetonate (acac), and optionally tetraethyl orthosilicate (TEOS, optional). Upon pyrolysis in N₂ atmosphere, the resol provides sufficient carbon yield to maintain the ordered structure, while decomposition of the Co(acac) yields cobalt nanoparticles. To provide increased surface area, the dispersed silicate from condensation of TEOS can be etched after carbonization to yield micropores, Without silica templated micropores, the surface area decreases as the cobalt content increases, but there is a concurrent increase in the volume-average pore diameter (BHJ) and a dramatic increase in the adsorption capacity of methylene green with the equilibrium adsorption capacity from 2 to 90 mg/g with increasing Co content. Moreover, the surface area and pore size of mesoporous composites can be dramatically increased by addition of TEOS and subsequent etching. These composites exhibit extremely high adsorption capacity up to 1151 mg/g, which also increases with increases in the Co content. Additionally, the inclusion of cobalt nanoparticles provides magnetic separation from aqueous suspension. The in situ synthesis of the Co nanoparticles yields to a carbon shell that can partially protect the Co from leaching in acidic media; after 96 h in 2 M HCl, the powders remain magnetic.     

由微孔棒状羟基磷灰石为模板合成的新型层次孔炭材料的电化学电容性能

电化学电容器已经成为极具潜力的可满足高功率需求的储能系统器件. 多孔炭具有大比表面积、高导电性、化学惰性、廉价及可调孔结构等优势, 因此成为电化学电容器最为常用的电极材料. 本文报道由微孔棒状羟基磷灰石为模板及蔗糖为碳源合成的新型具有层次孔道结构的孔炭材料的电化学电容器的性能. 采用X射线衍射分析仪、扫描电子显微镜、透射电子显微镜、X射线光电子能谱及BET表面分析仪表征了合成的多孔炭的形貌及表面特性. 采用循环伏安法、交流阻抗图谱分析及恒流充放电评价多孔炭材料在1 mol·L^-1硫酸中的电化学电容性能. 多孔炭具有高的比表面积(719.7 m²·g^-1)和大的孔容(1.32 cm³·g^-1), 其无序的孔道由任意分布的微孔、坍塌的中孔及类模板形状的相互交织的棒状中孔组成. 随着炭化温度的增加, 微孔及棒状中孔的密度随之降低, 在炭化温度高达900℃时, 孔径分布图上出现了三个峰. 正是由于这些特殊的结构特征, 由900℃炭化得到的多孔炭制成的电极展示出很好的电化学电容性能.     

Strong cellulose nanofibre–nanosilica composites with controllable pore structure

Flexible nanocellulose composites with silica nanoparticle loading from 5 to 77 wt% and tunable pore size were made and characterised. The pore structure of the new composites can be controlled (100–1000 nm to 10–60 nm) by adjusting the silica nanoparticle content. Composites were prepared by first complexing nanoparticles with a cationic dimethylaminoethyl methacrylate polyacrylamide, followed by retaining this complex in a nanocellulose fibre network. High retention of nanoparticles resulted. The structural changes and pore size distribution of the composites were characterised through scanning electron microscopy (SEM) and mercury porosimetry analysis, respectively. The heavily loaded composites formed packed bed structures of nanoparticles. Film thickness was approximately constant for composites with low loading, indicating that nanoparticles filled gaps created by nanocellulose fibres without altering their structure. Film thickness increased drastically for high loading because of the new packed bed structure. Unexpectedly, within the investigated loading range, the level of the tensile index on nanocellulose mass basis remained constant, showing that the silica nanoparticles did not significantly interfere with the bonding between the cellulose nanofibres. This hierarchically engineered material remains flexible at all loadings, and its unique packing enables use in applications requiring nanocellulose composites with controlled pore structure and high surface area.     

Preparation and characterization of NiO nanoparticles from thermal decomposition of the [Ni(en)3](NO3)2 complex: A facile and low-temperature route

NiO nanoparticles with an average size of 15 nm were easily prepared via the thermal decomposition of the tris(ethylenediamine)Ni(II) nitrate complex [Ni(en)₃](NO₃)₂ as a new precursor at low temperature, and the nanoparticles were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV-Vis spectroscopy, BET specific surface area measurement, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and magnetic measurements. The magnetic measurements confirm that the product shows a ferromagnetic behavior at room temperature, which may be ascribed to a size confinement effect. The NiO nanoparticles prepared by this method could be an appropriate photocatalytic material due to a strong absorption band at 325 nm. This method is simple, fast, safe, low-cost and also suitable for industrial production of high purity NiO nanoparticles for applied purposes.     

Silica–silver nanostructured spheres prepared by spray pyrolysis of sol containing silver precursor

Silver–silica nanostructured composites were prepared by spray pyrolysis of aqueous sols of silica nanoparticles containing silver nitrate. The physical and chemical characteristics of the composites prepared at different Ag/Si atomic ratio in the sols and temperatures of pyrolysis were examined by TEM, SEM, XRD, FT-IR and UV-visible spectra. For the low silver ratios up to 0.2, well-dispersed silver particles were produced in the pore of the silica agglomerates with their size and surface plasmon resonance depending on the pore size and silver mobility, in addition to the loading and temperature. The formation of silver silicate and new-phase silica as well as crystallinity of the silver prepared was discussed. There was also explained how the temperature of preparation affected the morphologies of the composites produced with higher Ag/Si ratios greater than 1. Mechanism on the formation of silver–silica composites was proposed for the wide range of the ratios from 0.01 to 3.     

Green synthesis of activated carbon doped tungsten trioxide photocatalysts using leaf of basil (Ocimum basilicum) for photocatalytic degradation of methylene blue under sunlight

Tungsten oxide (WO₃) nanoparticles were prepared hydrothermally by basil leaves extract, and Activated Carbon (AC) was prepared by the carbonization of date pits. Moreover, 1, 2 and 3% of AC doped WO₃ nanoparticles have been fabricated under hydrothermal conditions. The obtained samples have been characterized by using different techniques such as x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), simultaneous thermogravimetric analysis (TG-DTGA), fourier transform infrared (FT-IR), BET surface area, and Ultra-Violet spectroscopy (UV–Vis). It was observed that band-gap energy of the fabricated materials decreases by increasing AC amount. Similarly, BET surface area and porosity results showed increasing the content of AC, surface area, pore size and pore volume were decreased. The functional groups, determined by FT-IR, played a significant role in the photocatalytic performance. The photocatalytic performance of fabricated samples was used for the degradation of methylene blue (MB) at neutral pH under visible light radiations, and it is observed that WO₃/3%AC photocatalyst showed the highest degradation of MB. Both, capped phytochemicals of basil extract and the nanocomposites, were improved the photocatalytic performance, about 94% photodegradation was observed within 25 min under the reaction conditions. The photocatalyst was stable and about 85% and 81% photodegradation of MB were found under the two times of reusability tests.     

Soft-templating synthesis and adsorption properties of mesoporous carbons with embedded silver nanoparticles

Mesoporous carbons containing silver nanoparticles have been successfully synthesized under acidic conditions by employing resorcinol and formaldehyde as carbon precursors and triblock copolymer EO₁₀₁PO₅₆EO₁₀₁ (Lutrol F127) as a soft template. Silver nanoparticles of ∼90 nm were added to the synthesis mixture to achieve 10 wt% and 20 wt% of Ag loading in the carbon. Also, tetraethyl orthosilicate (TEOS) was introduced to the system in order to improve adsorption properties of the silver-carbon composites and to reinforce its structure. The resulting carbons with incorporated silver nanoparticles featured high surface areas, large total pore volumes and primary mesopores in the range between ∼6–7 nm.     

Metallic nickel supported on mesoporous silica as catalyst for hydrodeoxygenation: effect of pore size and structure

Catalytic hydrodeoxygenation (HDO) of anisole, a methoxy-rich lignin-derived bio-oil model compound, was carried out over a series of Ni-containing (5, 10, 20, and 30 wt%) catalysts with commercial silica and ordered mesoporous silica SBA-15 as support. Both supports and catalysts were characterized by N₂ adsorption–desorption isotherms, X-ray diffraction, CO chemisorption, and transmission electron microscopy (TEM). Catalytic reaction was performed at 250 °C and 10 bar H₂ pressure. Depending on the catalyst support used and the content of active metal, the catalytic activity and product distribution changed drastically. Increase of the nickel loading resulted in increased anisole conversion and C₆ hydrocarbon (benzene and cyclohexane) yield. However, loading more Ni than 20 wt% resulted in a decrease of both conversion and C₆ yield due to agglomeration of Ni particles. In addition, Ni/SBA-15 samples exhibited much stronger catalytic activity and selectivity toward C₆ hydrocarbon products compared with Ni/silica catalysts. The differences in catalytic activity among these catalysts can be attributed to the effect of the pore size and pore structure of mesoporous SBA-15. SBA-15 can accommodate more Ni species inside channels than conventional silica due to its high pore volume with uniform pore structure, leading to high HDO catalytic activity.     

Preparation and characterization of high-specific-surface-area activated carbons from K2CO3-treated waste polyurethane

An activated carbon with high specific surface area was prepared from polyurethane foam by chemical activation with K2CO3 and the influences of carbonization temperature and impregnation ratio on the pore structure of the prepared activated carbon were investigated. It was found that the specific surface area of the activated carbon was at a maximum value (about 2800 m(2)/g) at a carbonization temperature of 1073 K and at an impregnation ratio of 1.0. It was concluded that the polyurethane foam structure was modified during impregnation by K2CO3, K2CO3 promoted charring during carbonization, and then the weight loss behavior was changed below 700 and above 1000 K, carbon in the char was consumed by K2CO3 reduction, and this led to the high specific surface area. The prepared activated carbon had a very sharp micropore size distribution, compared with the commercial activated carbon having high specific surface area. The amounts of three organic vapors (benzene, acetone, and octane) adsorbed on the prepared activated carbons was much larger than those on the traditional coconut shell AC and the same as those on the commercial activated carbon except for octane. We surmised that the high specific surface area was due to the modification of the carbonization behavior of polyurethane foam by K2CO3.     

Preparation of Au Nanoparticles on Surface of Two Supports by Adsorption Phase Synthesis

By utilizing adsorption phase synthesis (APS), Au nanoparticles were prepared on the surface of SiO₂ with or without modification by Ni(OH)₂. TEM, XRD, and UV‐vis were employed to characterize the morphology of Au particles on the surface of two kinds of supports. The results showed that the average size of Au particles on the SiO₂ surface modified by Ni(OH)₂ was less than 5 nm. Due to high surface isoelectric point, Au particles formed in the adsorption layer were prone to distribute on the surface of SiO₂ modified by Ni(OH)₂. With content of Ni(OH)₂ in samples increasing, more Au particles with small size appeared on the support surface.     

基于杨梅单宁制备Pt/SiO_2-C催化剂及其对肉桂醛选择性催化加氢性能

以天然植物多酚杨梅单宁(BT)改性的SiO2为载体,经吸附Pt4+、Na BH4还原和碳化处理制得Pt/SiO2-C催化剂.对所制备的催化剂进行了表征,并考察了催化剂对肉桂醛液相选择性催化加氢的性能.结果表明,由于杨梅单宁分子的分散稳定作用,使碳化过程中纳米Pt粒子粒径适度增长且保持高度分散.碳化温度影响杨梅单宁的脱除效果、纳米Pt粒子晶型与粒径,以及载体的比表面积与孔径,最终影响肉桂醛催化加氢性能.500℃碳化处理得到的Pt/SiO2-C-500催化剂的催化性能最佳,在乙醇为溶剂,323.25 K和2MPa氢压条件下,肉桂醛6 h转化率为82.98%,生成肉桂醇的选择性达到91.33%,表现出较高的催化活性和选择性.同时,该催化剂重复使用5次后其催化活性仍为第一次反应活性的81.18%,体现出优良的重复使用性.     

Synthesis of Ni/SiO<Subscript>2</Subscript> nanoparticles for catalytic benzene hydrogenation

Nickel nanoparticles supported on silica were prepared by hydrazine reduction in aqueous medium. The obtained solids were characterized by X-ray diffraction (XRD), Transmission Electronic Microscopy (TEM), Electron Diffraction (ED), hydrogen chemisorption, and Temperature Programmed Desorption of hydrogen (H₂-TPD). The catalytic properties were evaluated for benzene hydrogenation in the temperature range 75–230 °C. XRD patterns reveal presence of the metallic nickel particles with fcc structure. Metal dispersion and hydrogen storage increase with decreasing metal particle size. The H₂-TPD profiles exhibit two domains, one due to desorption of hydrogen from Ni metal and another due to spillover from metal to the support. The catalytic activity strongly depends on the metal loading. It increases with decreasing metal loading. This is attributed to metal surface area, which also increases with decreasing metal loading. Kinetic studies of benzene hydrogenation on the Ni catalysts showed that the benzene partial order is around −2. This significant negative value is ascribed to a strong adsorption of benzene on the catalyst surface.     

Synthesis of Supported Ultrafine Non‐noble Subnanometer‐Scale Metal Particles Derived from Metal–Organic Frameworks as Highly Efficient Heterogeneous Catalysts

The properties of supported non‐noble metal particles with a size of less than 1 nm are unknown because their synthesis is a challenge. A strategy has now been created to immobilize ultrafine non‐noble metal particles on supports using metal–organic frameworks (MOFs) as metal precursors. Ni/SiO₂ and Co/SiO₂ catalysts were synthesized with an average metal particle size of 0.9 nm. The metal nanoparticles were immobilized uniformly on the support with a metal loading of about 20 wt %. Interestingly, the ultrafine non‐noble metal particles exhibited very high activity for liquid‐phase hydrogenation of benzene to cyclohexane even at 80 °C, while Ni/SiO₂ with larger Ni particles fabricated by a conventional method was not active under the same conditions.     

Liquid-phase Reductive Deposition as Novel Preparation Method for Highly Dispersive Nickel Catalysts

We have been developing the selective deposition method onto TiO₂ nanoparticles, named as the liquid-phase selective-deposition method, where TiO₂ plays a role of formation center of Ni nanoparticles as well as protection from the aggregative growth of the particles. The concept of this method is to well disperse and stabilize Ni nanoparticles on TiO₂ surface by specific adsorption of Ni precursory complexes and then heterogeneous nucleation on the adsorption sites. The particle size was decreased with increasing the amount of Zn added, thus the catalytically active Ni surface area was increased. The selective deposition onto TiO₂ surface and addition of Zn to the nanoparticle promoted the catalytic activity of Ni–Zn nanoparticle, e.g. the catalytic activity of Ni–Zn/TiO₂ was ca. 10 times higher than that of the unsupported Ni nanoparticles. Ni in the nanocomposite was assigned as metallic, although their surface was oxidized under the atmospheric condition, but Zn and B were deposited as their oxide.     

Preparation and characterization of bimodal porous carbons derived from a styrene-divinylbenzene copolymer

A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO₂ clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N₂, followed by activation in CO₂ at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO₃ and H₂O₂ treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.     

Size-controlled synthesis of SnO2 nanoparticles using reverse microemulsion method

Tin oxide nanoparticles were prepared using an ionic surfactant (sodium dodecyl sulfate) and tin (IV) chloride as an inorganic precursor via the reverse microemulsion method. The size of the nanoparticles is controlled by variation of water-to-surfactant ratio. Eliminating of surfactant in prepared nanoparticles was confirmed by the infrared spectroscopy after sequential calcinations. Transmission electron microscopy, surface area, pore volume, average pore diameter, pore size distribution and X-ray diffraction results were used for evaluation of size distribution, shape and structure of prepared SnO₂ nanoparticles. Transmission electron micrographs confirmed that the obtained materials are spherical nanoparticles. The X-ray diffraction results show the crystalline phases of all samples are SnO₂ with tetragonal structured crystal. In addition, the X-ray diffraction and transmission electron microscopy data showed that the size of SnO₂ nanoparticles decreased with decreasing the water-to-surfactant ratio.