Shape-controlled synthesis of highly monodisperse and small size gold nanoparticles

We describe here that fine control of nanoparticle shape and size can be achieved by systematic varia-tion of experimental parameters in the seeded growth procedure in aqueous solution. Cubic and spherical gold nanoparticles are obtained respectively. In particularly, the Au cubes are highly mono-disperse in 33±2 nm diameter. The experimental methods involve the preparation of Au seed particles and the subsequent addition of an appropriate quantity of Au seed solution to the aqueous growth solutions containing desired quantities of CTAB and ascorbic acid (AA). Here, AA is a weak reducing agent and CTAB is not only a stable agent for nanoparticles but also an inductive agent for leading increase in the face of nanoparticle. Ultraviolet visible spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM) are used to characterize the nanoparticles. The results show that the different size gold nanoparticles displayed high size homogenous distribution and formed mono-membrane at the air/solid interface.     

稳定分散的纳米银溶胶的制备及其表征

Stable aqueous dispersive colloidal Ag nanoparticles were prepared by reducing silver nitrate with sodium borohydride in the presence of 3-mercaptopropionic acid. The formation process of the Ag nanoparticles was investigated by UV-Visible spectroscopy and transmission electron microscopy. The results show that the spherical and rodlike particles and aggregates are formed in the initial stage of the reaction， then the rodlike particles and aggregates are gradually decomposed into small spherical particles， and the final obtained Ag nanoparticles with an average size of 8 nm are in uniform shapes and narrow size distribution， and the colloid remains stable for more than one month， which makes it convenient for use in practice. The presence of capping agent plays an extra role over nanoparticles stabilization and morphology. The presence of capping agent on the surface of Ag nanoparticle is confirmed by the X-ray photoelectron spectroscopy. It is found that Ag nanoparticles are negatively charged in alkaline condition， whereas they are positively charged in acid condition. Electrosteric effect is responsible for their long-term stability.     

Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming

The deactivation behavior by crystallite growth of nickel nanoparticles on various supports(carbon nanofibers, zirconia, Si C, α-Al_2O_3 and γ-Al_2O_3) was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers(CNF),Zr O_2, SiC, γ-Al_2O_3 and α-Al_2O_3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO_2 SiC γ-Al_2O_3 α-Al_2O_3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles(~12 nm) supported on α-Al_2O_3 were found to outgrow Ni particles with initially larger size(~20 nm). It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.     

Chemical preparation and investigation of Fe-P-B ultrafine amorphous alloy particles

A series of Fe-P-B ultrafine amorphous alloy particles has been prepared by the chemical reduction method The composition and size of the particles have been effectively adjusted.Mossbauer spectroscopy in addition to sonic other techniques has been used to investigate the reaction process,the factors that influence the preparation,the crystallization of the particles,and the interactions between the components within them.The results indicate that the co-deposition of iron,phosphorus and boron atoms in the solution at room temperature forms Fe-P-B amorphous alloy particles,and a preferential bonding of Fe-P bond to Fe-B one exists in the particles.     

Hydrogenation of phenylpyruvic acid to phenylalanine catalyzed by Ni-B/SiO2

Phenylalanine （Phe） is a significant amino acid that cannot be synthesized by human themselves but must be taken from environment. It was initially found that the nanosized amorphous Ni-B/SiO2 alloy prepared by the chemical reduction method was an effective catalyst for the preparation of Phe from phenylpyruvic acid （PPA） by amination and hydrogenation. It has been found that the amorphous Ni-B/SiO2 alloy catalyst exhibits superior activity and selectivity to the traditional catalysts Raney Ni and Urushibara nickel. The effects of reaction time, amounts of catalysts and ammonia solution, reaction temperature, and H2 pressure on the reaction have been investigated systematically. The results indicated that the yield of Phe was 97.9%, and the selectivity for Phe reached 98.9% when the reaction was carried out for 3 h at 333 K and 2.0 MPa of H2 with m（Cat.） ： m（PPA） = 0.6 ： 1.0 and n（NH3） ： n（PPA） = 3 ： 1. The catalysts were characterized by XRD, AAS, XPS, BET, and TEM, and the relationship between the catalyst structure and the catalytic activity was discussed in detail. It was found that the reason why Ni-B/SiO2 amorphous alloy catalyst was much more active for the preparation of Phe could be accounted for by the presence of electron-rich Ni due to electron donation from alloying B; the smaller size of Ni-B particles, the larger specific surface area of Ni-B/SiO2.     

Synthesis and characterization of magnetic nanoparticles

Magnetic nanoparticles with average diameter in the range of 6.4-8.3 nni have been synthesized by a chemical co-precipitation of Fe(Ⅱ)and Fe(Ⅲ)salts in 1.5 M NH4OH solution.The size of the magnetic particles is dependent on both temperature and the ionic strength of the iron ion solutions.The magnetic particles formed at higher temperature or lower ionic strength were slightly larger than those formed at lower temperature or higher ionic strength respectively.In spite of the different reaction conditions,all the resultant nanoparticles are nearly spherical and have a similar crystalline structure.At 300 K,such prepared nanoparticles are superparam-agnetic.The saturation magnetizations for 7.8 and 6.4 nm particles are 71 and 63 emu/g respectively,which are only ~ 20-30% less than the saturation magnetization(90 emu/g)of bulk Fe3O4 Our results indicated that a control of the reaction conditions could be used to tailor the size of magnetic nanoparticles in free precipitation.     

Preparation and evaluation of Fe3O4-core@Ag-shell nanoeggs for the development of fingerprints

The surface of individual, relatively dispersed Fe3O4 nanospheres is coated with a thiol-terminated silane, then the thiol on the Fe3O4 particles’ surfaces treats with nano-Ag colloidal solution to form Ag-modified Fe3O4 nanoparticles. Eventually, a solid shell of Ag is capped onto the Ag-modified Fe3O4 nanoparticles by reducing aliquots of AgNO3 solution using NaBH4 as a reducing agent. The as-prepared Fe3O4 -core@Ag-shell nanoeggs, which are uniform in size, highly monodisperse, stable against aggregation and have high magnetization, were depended on thin shell of the attached nano-Ag, the size of Fe3O4 nanoparticles, the volume of thiol-terminated silane as well as the ultrasonication. The Fe3O4 -core@Ag-shell nanoeggs are proposed to detect fingermarks on different surface, with which the fingermarks can be viewed directly, due to the clear ridge detail.     

Immobilized silver nanoparticles on silica gel as an efficient catalyst in nitroarene reduction

<正>Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed aggregates.This letter describes a way of synthesising silver nanoparticles and their protection to aggregate by silica gel.The combination of catalytic quantities of immobilized silver nanoparticles with reductive ability of NaBH_4 efficiently reduces aromatic nitroarenes to the corresponding amines in aqueous medium.Noteworthy is that highly chemoselective reactions were achieved in the presence of other functional groups such as halogen and carboxylic acid groups.The silver particles immobilized on silica gel are stable in the presence of oxygen for several months.     

Role of size and pretreatment of Pd particles on their behaviour in the direct synthesis of H_2O_2

Two families of catalysts, based on Pd nanoparticles supported on ceramic asymmetric tubular alumina membranes, are studies in the direct synthesis of H_2O_2. They are prepared by depositing Pd in two ways:(i) reduction with N_2H_4 in an ultrasonic bath and(ii) by impregnation-deposition. The first preparation leads to larger particles, with average size of around 11 nm, while the second preparation leads to smaller particles, with average size around 4 nm. The catalytic membranes were tested as prepared, after thermal treatment in air and after further pre-reduction with H_2 in mild(100 ℃) conditions. Samples were characterized by TEM, CO-chemisorption monitored by DRIFTS method and TPR, while catalytic tests have been performed in a semi-batch recirculation membrane reactor. Experimental catalytic results were analysed using two kinetics models to derive the reaction constants for the parallel and consecutive reactions of the kinetic network. Smaller particles of Pd show lower selectivity due to the higher rate of parallel combustion, even if the better dispersion of Pd and thus higher metal surface area in the sample lead to a productivity in H_2O_2 similar or even higher than the sample with the larger Pd particles. Independently on the presence of smaller or larger Pd nanoparticles, an oxidation treatment leads to a significant enhancement in the productivity, although the catalyst progressively reduces during the catalytic process. The inhibition of the parallel combustion reaction(to water) induced from the calcination treatment remains after the in-situ reduction of the oxidized Pd species formed during the pre-treatment.This is likely due to the elimination of defect sites which dissociatively activate oxygen, and tentatively attributed to Pd sites able to give three- and four-fold coordination of CO.     

Three-dimensionally ordered macroporous cross-linked polystyrene incorporating functional group via hydrophilic spacer arm

<正>A versatile and effective method for incorporating functional groups on the pore wall of three-dimensionally ordered macroporous cross-linked polystyrene(3DOM CLPS) by hydrophilic spacer arm has been investigated.The 3DOM CLPS with pore size 865 nm was prepared by sacrifice template method.The hydrophilic spacer arm(polyethylene glycol,molecular weight is 600) was grafted to the 3DOM CLPS via nucleophilic substitution reaction.The other side of active hydroxyl can be further converted into a lot of other functional groups.In this report,the chelating ligand 2-mercaptobenzothiazole(MBZ) group was introduced on the end of the PGE chain to evidence the versatile functionalization approach.The functionalized ordered macroporous materials were characterized by FT-IR,element analyzer,SEM.The results reveal that the pores were successfully bonded with 2-mercaptobenzothiazole groups via hydrophilic spacer arms and the original morphology of ordered macroporous materials were remained after functionalization.The MBZ group density is 0.052 mmol/m~2.The functionalized 3DOM CLPS are expected to application as heavy metal ions adsorbent.     

Immobilization of Glucose Oxidase on Ordered Macroporous Silicas Functionalized with Amino Group

A novel glucose oxidase immobilized on three‐dimensionally ordered macroporous (3DOM) material has been prepared by firstly preparation of hybrid 3DOM SiO₂‐NH₂ materials using colloidal crystal method, and following covalent immobilization of glucose oxidase on the pore walls of the 3DOM materials. The materials were characterized by SEM, FTIR, DSC and BET techniques. SEM observation shows that the macropores are highly ordered and are interconnected by small windows. FTIR measurement shows that there are amino and organic groups in the pore walls. The surface area of the 3DOM SiO₂‐NH₂ material is about 10.2 m²/g. The loaded amount of enzyme is increased with amino content in the materials. The immobilized enzyme has high activity, thermal stability and can be reused.     

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.     

三维有序大孔杂化SiO2的制备、表征及应用

本研究将有机-无机杂化功能材料与有序大孔材料独特的有序开孔结构相结合,在制备的三维有序大孔二氧化硅（3DOM SiO₂）孔壁上可控接枝带有功能基团的聚合物链段,制备3DOM杂化材料。采用表面引发原子转移自由基（SI-ATRP）接枝技术在3DOM SiO₂孔壁上可控接枝聚甲基丙烯酸缩水甘油酯（PGMA）链段,讨论了接枝条件对接枝量及接枝链段分子量的影响,并利用FT-IR、SEM、TGA、GPC等对接枝过程进行了表征。PGMA接枝链段上环氧基团可进一步与亲核试剂（二乙醇胺,浓硫酸和二乙烯三胺）发生开环反应,得到一系列带有不同官能团的具有较高接枝密度的功能杂化多孔材料,同时,利用该种材料对水中的水杨酸进行了吸附实验,吸附结果表明经二乙烯三胺开环后得到的功能化多孔材料对水杨酸具有很高的吸附量。本研究对于发展新型杂化多孔材料提供了新的方法。     

三维有序大孔杂化SiO2的制备、表征及应用

将有机-无机杂化功能材料与有序大孔材料独特的有序开孔结构相结合,在制备的三维有序大孔二氧化硅(3DOM Si O2)孔壁上可控接枝带有功能基团的聚合物链段,制备3DOM杂化材料。采用表面引发原子转移自由基(SI-ATRP)接枝技术在3DOM Si O2孔壁上可控接枝聚甲基丙烯酸缩水甘油酯(PGMA)链段,讨论了接枝条件对接枝量及接枝链段分子量的影响,并利用FTIR、SEM、TGA、GPC等对接枝过程进行了表征。PGMA接枝链段上环氧基团可进一步与亲核试剂(二乙醇胺,浓硫酸和二乙烯三胺)发生开环反应,得到一系列带有不同官能团的具有较高接枝密度的功能杂化多孔材料,同时,利用该种材料对水中的水杨酸进行了吸附实验,吸附结果表明经二乙烯三胺开环后得到的功能化多孔材料对水杨酸具有很高的吸附量。     

Synthesis of Three‐dimensionally Ordered Macroporous TiO2 and TiO2/WO3 Composites and Their Photocatalytic Performance

This work presents the characterization and preparation of three‐dimensionally ordered macroporous TiO₂ and TiO₂/WO₃ composite nanoparticles with enhanced visible‐light‐responsive properties for rhodamine B (Rh B) photodegradation. The 3DOM TiO₂ and TiO₂/WO₃ composites were prepared through a dip‐infiltrating sol‐gel process using a polystyrene (PS) colloidal crystal template. The materials were characterized by SEM, TEM, XRD, BET, XPS and UV/Vis. The 3DOM TiO₂/WO₃ composite structures ranged from well‐defined 3DOM structures, which are highly ordered and interconnected via small pore windows, to collapsed three‐dimensional structures as the WO₃ content increased. The photoresponse range and specific surface area of the composite increased with less than 0.025 g of WCl₆. The 3DOM TiO₂/WO₃ composite with less than 0.025 g of WCl₆ exhibited a higher catalytic activity than 3DOM TiO₂ for the photocatalytic degradation of Rh B under simulated sunlight illumination.     

Thermal preparation and stabilization of crystalline silver particles in SiO<Subscript>2</Subscript>-based coating solutions

Ag/SiO₂ coating solutions for antimicrobial functionalisation can be prepared by a thermal reaction (reflux or solvothermal conditions) of mixtures of tetraethoxysilane, alkylamine compounds and AgNO₃. These coating solutions are especially useful for antimicrobial refinement of temperature sensitive materials like textiles or wood. Moreover coating application onto substrates such as glass or metal, as well as preparation of micrometer sized bulk particles by using a spray-drying process is also feasible. The efficiencies of AgNO₃ reduction in the presence of different amine compounds like triethanolamine, triethylamine or diethanolamine are compared. SiO₂ nanoparticles are formed by basic hydrolysis of tetraethoxysilane and stabilize the crystalline silver particles in the solution. The antimicrobial effect of silver containing coatings on textile fabrics is investigated.     

吸附法制备CuO-Ag/SiO2纳米复合物

利用吸附法原位制备CuO/SiO2、CuO-Ag/SiO2纳米复合物,研究了不同吸附质体系中预负载的纳米Ag粒子对CuO的影响。结果表明:Ag粒子对CuO的影响因吸附质的不同而不同。以Cu(Ac)2为吸附质,纳米Ag几乎没有影响;以NaOH为吸附质,纳米Ag使得CuO的晶粒粒径增大。这一结果与铜物种对Ag晶粒粒径的影响规律完全不同。通过比较不同吸附质的吸附行为,Cu(OH)2与硅胶表面的相互作用被认为是导致这一现象的原因。     

Preparation of uniform Au@SiO2 particles by direct silica coating on citrate-capped Au nanoparticles

Preparation of Au@SiO₂ particles by direct silica coating on three different sized citrate-capped Au nanoparticles (17, 25 and 33 nm) with Stöber method was investigated in this work. It was found that the uniformity of the resulting Au@SiO₂ particles was related to both the sizes of the Au nanoparticles and the concentration of citrate during the particle synthesis. When the citrate concentration during the particle synthesis was low, the 25 and 33 nm Au nanoparticles could be well dispersed in the Stöber system, thus resulting the formation of uniform Au@SiO₂ particles containing single core. However, small Au nanoparticles (17 nm) were identified to show poor stability in the Stöber system even under low citrate concentration, the silica coating must be performed in a pre-hydrolyzed Stöber system to get the uniform Au@SiO₂ particles. This approach was also applicable to citrate capped Ag nanoparticles. After removal of the excess citrate in the Ag prepared by citrate reduction, uniform Ag/SiO₂ particles containing single core colloids could also be prepared by the direct silica coating.     

三维有序大孔Ag/ZrO2-TiO2：制备及紫外光催化降解染料和水杨酸性能

采用聚苯乙烯(PS)微球作为模板剂,经溶胶-凝胶及煅烧后处理的方法制备了三维有序大孔(3DOM)复合材料Ag/ZrO2-TiO2。通过FTIR、XRD、XPS、N2吸附-脱附和SEM-EDS等对其进行了表征。结果显示,经PS微球作用后的复合材料Ag/ZrO2-TiO2具有锐钛矿晶型结构,其Ag以单质形式存在。该复合材料的孔结构高度有序,属三维有序大孔,平均孔直径为120 nm,孔壁由紧密堆积的Ag/ZrO2-TiO2纳米晶粒组成,孔收缩率约为40%。该复合材料表现出较好的紫外光催化降解水杨酸和甲基橙等染料性能,其活性明显高于商用光催化剂(Degussa P-25)、Ag/ZrO2-TiO2和3DOM ZrO2-TiO2,在90 min内对甲基橙的降解率达80.1%。     

Synthesis of Macroporous PMMA/Silica Nanocomposite Monoliths in Supercritical Carbon Dioxide

Summary: Macroporous monoliths consisting of silica nanoparticles embedded in poly(methyl methacrylate) (PMMA) were synthesized in supercritical CO₂. Well‐dispersed silica particles, pretreated with functional 3‐(trimethoxysilyl)propyl methacrylate (MPS), were to form colloidal PMMA nanocomposites followed by a sol‐gel transition forming interconnected structures resulting in micron‐sized pores with specific areas between 1 and 7 m² · g⁻¹. SEM and TEM results revealed uniform morphological characteristics of the composite materials and good dispersions of the silica nanoparticles.

SEM micrograph of PMMA/Silica nanocomposites forming interconnected macroporous monolith. The average size of the silica particles is 50 nm.