Structural characterization and surface heterogeneity of bimodal mesoporous silicas functionalized with aminopropyl groups and loaded aspirin

Bimodal mesoporous materials were modified with different amount of 3-aminopropyltriethoxysilane and employed as aspirin carriers. The modified and drug loaded bimodal mesoporous materials were characterized with XRD, FT-IR, TEM and elemental analysis methods to explore the influence of amino groups and drug molecules on the mesoporous surface. Meanwhile, the mesoporous surface energy states was calculated by the density functional theory based on the N₂ sorption analysis. According to the surface energy distributions of samples including before and after modification and drug loading, it can be deduced that through superficial modification with amino groups, the surface energy moves to high state, implying the introduction of amino moieties could provide the mesoporous surface with much active sites. Besides, the interaction between the amino groups and drug molecules is weak, and hence the controlled drug delivery would be possible.     

Synthesis and enhanced photocatalytic activity of tin oxide nanoparticles coated on multi-walled carbon nanotube

A nanocomposite of SnO₂ nanoparticles coated on multi-walled carbon nanotube (MWNT@SnO₂) was synthesized and characterized by thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, nitrogen physisorption measurements, photoluminescence. The results show that the SnO₂ nanoparticles with a narrow size of 4 nm are uniformly deposited on MWNT. The photocatalytic activity of the nanocomposite was studied using methyl orange as a model organic pollutant. MWNT@SnO₂ exhibits much higher photocatalytic activity than that of commercial TiO₂ (P-25). The promotion is mainly contributed from electron transfer between SnO₂ and MWNT.     

CuO-CeO2 binary oxide nanoplates: Synthesis, characterization, and catalytic performance for benzene oxidation

This work reports the first synthesis of CuO-CeO₂ binary oxides with a plate-like morphology by a solvothermal method. The as-prepared CuO-CeO₂ nanoplates calcined at 400 °C were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectrum, and tested for catalytic oxidation of dilute benzene in air. Various structural characterizations showed that large amounts of copper species were exposed on the CuO-CeO₂ nanoplate surface. The effect of the synthesis conditions on the structure of the product, as well as the growth process of the nanoplates, has been studied and discussed. The CuO-CeO₂ nanoplates exhibited an excellent catalytic activity for benzene oxidation despite its relatively low surface area and could catalyze the complete oxidation of benzene at a temperature as low as 240 °C.     

Synthesis,characterization and catalytic activity studies of Pd-based supported nanoparticle catalyst anchoring on poly(N-vinyl-2-pyrrolidone) modified CMK-3

Pd nanoparticle-poly(N-vinyl-2-pyrrolidone)/CMK-3 (Pd-PVP/CMK-3) composite was prepared by in situ polymerization method which was effectively employed as a novel heterogeneous catalyst for the Suzuki–Miyaura cross-coupling reaction. The physical and chemical properties of Pd nanoparticle-PVP/CMK-3 were investigated using FT-IR, XRD, BET, UV–vis, TEM and TGA techniques. The reaction was carried out between aryl halides and phenylboronic acid in the presence of water at room temperature. The stability of the catalyst was good and could be reused 10 times without much loss of activity in Suzuki–Miyaura reaction.     

Pd-porphyrin functionalized ionic liquid-modified mesoporous SBA-15: An efficient and recyclable catalyst for solvent-free Heck reaction

The Pd-porphyrin functionalized ionic liquid could be covalently anchored in the channels of mesoporous SBA-15 through ion-pair electrostatic interaction between imidazolium-cationic and Pd-porphyrin-anionic moieties. Such modified SBA-15 materials were prepared successfully via a post-synthesis (surface sol-gel polymerization) or a one-pot sol-gel procedure, which were characterized by powder X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, N₂ sorption, elemental analysis, and transmission electron microscopy. The modified SBA-15 materials are efficient and recyclable catalysts for cross-coupling of aryl iodides or activated aryl bromides with ethyl acrylate without activity loss and Pd leaching even after 9 runs.     

Synthesis of mesoporous Co/Ce-SBA-15 materials and their catalytic performance in the catalytic oxidation of benzene

Cerium-containing SBA-15 mesoporous materials, with different Ce/Si molar ratios, were synthesized by a direct hydrothermal synthesis method and further modified by impregnation with 10, 15 and 20 wt.% Co. Characterizations by powder X-ray diffraction (XRD), N₂ sorption, inductively coupled plasma (ICP) and UV-vis spectroscopy were carried out. The small-angle XRD and N₂ sorption characterizations showed that these Co supported materials have less-ordered mesoporous structures with partial blockage of pores, and their specific surface area, pore volume and pore size were relatively lower than those of unsupported cerium-containing SBA-15. Spinel Co₃O₄ constituted the predominant cobalt phase in the prepared catalysts, and CeO₂ was also detected. All the Co supported catalysts exhibited high catalytic activity in the oxidation of benzene.     

Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO₃H-MCM-41-NH₂. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state ¹³C CP/MAS NMR and solid-state ²⁹Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO₃H-MCM-41-NH₂) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.     

Quasi-cube ZnFe2O4 nanocrystals: Hydrothermal synthesis and photocatalytic activity with TiO2 (Degussa P25) as nanocomposite

The fabrication and photocatalytic application of zinc ferrite nanocrystals were reported. Quasi-cube ZnFe₂O₄ nanocrystals with typical small sizes of 5-15 nm were successfully synthesized by a facile hydrothermal approach. ZnFe₂O₄/P25 nanocomposite was prepared by physically grinding the ZnFe₂O₄ nanocrystals with TiO₂ (commercial Degussa P25) at ambient temperature, and it exhibited excellent photocatalytic activity for the mineralization of Rhodamine B. UV-vis measurement and photocatalytic test results showed that ZnFe₂O₄ nanocrystals exhibited effective band-gap coupling to P25 nanopowders by simply physical grinding without any surface modification or high-energy balling, which is usually adopted in conventional mixture process. This phenomenon can be attributed to the high surface activities of the as-obtained tiny ZnFe₂O₄ nanocrystals and commercial P25 nanoparticles. It may imply that the mixing process of composite materials would be simplified by further lowering the grain sizes of their component particles.     

Synthesis of ordered large-pore mesoporous carbon for Cr(VI) adsorption

Highly ordered mesoporous carbon with large accessible pores (OMC-P) was prepared by using laboratory-made poly(ethylene oxide)-b-polystyrene diblock copolymer as template via the evaporation-induced self-assembly method. The OMC-P was first used as adsorbent for removal of Cr(VI) ion from aqueous solution. Adsorption behavior was studied as a function of time, concentration of adsorbate, temperature, and pH. The kinetics of adsorption of Cr(VI) ion onto OMC-P is well fit to the pseudo-second order model. The Cr(VI) ion adsorption is favored at lower temperatures and at initial acid pH values in the equilibrium. The Freundlich and the Langmuir isotherm fit the equilibrium data satisfactorily. The influence of porosity on equilibrium adsorption capacity was investigated on three types of carbon materials, namely, OMC-P, ordered mesoporous carbon templated from amphiphilic triblock copolymer F127 (OMC-F) and commercial activated carbon (AC). The prepared OMC-P exhibits much higher adsorption performance than the other two carbons.     

CuO microflowers composed of nanosheets: Synthesis, characterization, and formation mechanism

CuO microflowers composed of nanosheets with tunable size have been fabricated through a simple reaction in ammonia solution at 90-180 °C, in which the nanosheets with zigzag edges were 20-40 nm in thickness and 500-800 nm in width. The high ammonia concentration, high ratio of CNH₃ to CCu2+ (R_ac) and elevated temperature were necessary for the formation of microflowers, and the ammonia concentration was critical for the morphology evolution of the particles. The fabrication mechanism of CuO microflowers based on the assembly of Cu(OH)₂ nanobelts was discussed. In addition, the CuO microflowers showed effective catalytic activity on the decomposition of ammonium perchlorate.     

Controlled synthesis of anatase TiO2 octahedra with enhanced photocatalytic activity

Titanium dioxide (TiO₂) nanocrystals with specific exposed crystal facet have attracted considerable interest due to their promising applications in the fields of energy and environment. In this paper, we report on a simple solvothermal approach for the synthesis of anatase TiO₂ octahedra with high yield, using titanium(IV) sulfate and hydrazine hydrate as the starting materials. The formation mechanism of anatase TiO₂ octahedra is suggested. The samples were characterized with XRD, Raman, SEM, TEM, FTIR, XPS, and UV/vis techniques, and further tested as a candidate in photocatalysis to decompose methyl orange in aqueous solution at room temperature. The results show that SO₄²⁻ ions not only benefit the formation of octahedral nanocrystals, but also inhibit nitrogen doping into TiO₂ matrix. More importantly, it is found that the octahedral TiO₂ nanocrystals show enhanced photocatalytic activity compared to TiO₂ P25 and anatase TiO₂ counterparts.     

Structure and photocatalytic activity studies of TiO2-supported over Ce-modified Al-MCM-41

Ce-Al-MCM-41, TiO₂/Al-MCM-41 and TiO₂/Ce-Al-MCM-41 materials with varying contents of Ce (by impregnation) and TiO₂ loaded (by solid-state dispersion) on Al-MCM-41 support are prepared. The Ce modified and TiO₂ loaded composite systems are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (DRS) and X-ray photoelectron spectroscopy (XPS) techniques. The DRS and XPS of low Ce content (0.2-0.5 wt.%) modified Al-MCM-41 samples are showing more characteristic of Ce³⁺ species wherein cerium in interaction with Al-MCM-41 and that of high Ce (0.8, 3.0 wt.%) content modified samples are showing the characteristic of both Ce⁴⁺and Ce³⁺species. A series of Ce-modified Al-MCM-41 and TiO₂ loaded composite catalysts are evaluated for photocatalytic degradation of phenol under UV irradiation. Low Ce content in Ce³⁺ state on Al-MCM-41 is showing good photoactivity in comparison with high Ce content samples and pure ceria. The composite TiO₂/Ce-Al-MCM-41 is showing enhanced degradation activity due decreased rate of electron-hole recombination on TiO₂ surface by the redox properties of cerium. The photocatalyst TiO₂/Ce-Al-MCM-41 with an optimum of 10 wt.% TiO₂ and 0.3 wt.% Ce is showing maximum phenol degradation activity. The possible mechanism of phenol degradation on the composite photocatalyst is proposed.     

One step synthesis of Bi@Bi2O3@carboxylate-rich carbon spheres with enhanced photocatalytic performance

Bi@Bi₂O₃@carboxylate-rich carbon core-shell nanosturctures (Bi@Bi₂O₃@CRCSs) have been synthesized via a one-step method. The core–shell nanosturctures of the as-prepared samples were confirmed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and Raman spectroscopy. The formation of Bi@Bi₂O₃@CRCSs core–shell nanosturctures should attribute to the synergetic roles of different functional groups of sodium gluconate. Bi@Bi₂O₃@CRCSs exhibits significant enhanced photocatalytic activity under visible light irradiation (λ > 420 nm) and shows an O₂-dependent feature. According to trapping experiments of radicals and holes, hydroxyl radicals were not the main active oxidative species in the photocatalytic degradation of MB, but O₂⁻ are the main active oxidative species.     

Synthesis and characterization of nickel ferrite magnetic nanoparticles

Nickel ferrite (NiFe₂O₄) nanoparticles are prepared by a polyvinyl alcohol (PVA) assisted sol-gel auto-combustion method. The structure, composition, morphology and magnetic properties of the gel precursor are characterized by powder XRD, FT-IR, TGA, HR-SEM, TEM, HR-TEM and VSM. XRD confirms the formation of single-phase nickel ferrite with space group of Fd3m and inverse spinel structure. The vibration properties of nanoparticles are analysed by FT-IR spectrum. The thermal decomposition of the gel precursors is investigated by TGA. HR-SEM and TEM images show that the particles have spherical shape with particle size in the range of ∼30 nm and consistent with XRD result. The magnetic properties of these nanoparticles are studied for confirming the ferromagnetic behaviour at room temperature.     

Preparation and characterization of ZnO-TiO2 nanocomposite for photocatalytic disinfection of bacteria and detoxification of cyanide under visible light

ZnO-TiO₂ nanocomposite was prepared by modified ammonia-evaporation-induced synthetic method. It was characterized by powder X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray, UV-visible diffuse reflectance, photoluminescence and electrochemical impedance spectroscopies. Incorporation of ZnO leads to visible light absorption, larger charge transfer resistance and lower capacitance. The nanocomposite effectively catalyzes the inactivation of E. coli under visible light. Further, the prepared nanocomposite displays selective photocatalysis. While its photocatalytic efficiency to detoxify cyanide with visible light is higher than that of TiO₂ P25, its efficiency to degrade methylene blue, sunset yellow and rhodamine B dyes under UV-A light is less than that of TiO₂ P25.     

Palladium supported on functionalized mesoporous silica as an efficient catalyst for Heck reaction

Pd nanoparticles supported in functionalized mesoporous silica were prepared. Mesoporous silica support was modified with [3-(2-aminoethyl aminopropyl)] trimethoxysilane. Palladium ions were grafted onto the functionalized mesoporous silica and reduced with hydrazine hydrate to obtain the Pd nanoparticles supported on functionalized mesoporous silica. The Pd loading in the nanocomposite of Pd supported on the functionalized mesoporous silica is 4.30 wt%. CO chemisorption analysis on the nanocomposite shows a Pd dispersion as high as 35% and a Pd surface area of 156 m²/g. The surface area, pore size, and pore volume decrease slightly with the incorporation of the Pd nanoparticles into the functionalized mesoporous silica. Pd supported on the functionalized mesoporous silica with controlled molar ratio of amino groups to palladium exhibits an excellent catalytic activity and low Pd leaching for the Heck carbon-carbon coupling reaction. The catalyst can be reused for at least six recycles in air with only a minor loss of activity.     

Synthesis and characterization of carbon-coated Fe3O4 nanoflakes as anode material for lithium-ion batteries

The carbon-coated Fe₃O₄ nanoflakes were synthesized by partial reduction of monodispersed hematite (Fe₂O₃) nanoflakes with carbon coating. The carbon-coated Fe₃O₄ nanoflakes were characterized by X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and galvanostatic charge/discharge measurements. It has been demonstrated that Fe₂O₃ can be completely converted to Fe₃O₄ during the reduction process and carbon can be successfully coated on the surface of Fe₃O₄ nanoflakes, forming a conductive matrix. As anode material for lithium-ion batteries, the carbon-coated Fe₃O₄ nanoflakes exhibit a large reversible capacity up to 740 mAh g⁻¹ with significantly improved cycling stability and rate capability compared to the bare Fe₂O₃ nanoflakes. The superior electrochemical performance of the carbon-coated Fe₃O₄ nanoflakes can be attributed to the synthetic effects between small particle size and highly conductive carbon matrix.     

Synthesis and characterization of Co-Sn substituted barium ferrite particles by a reverse microemulsion technique

A series of Co-Sn substituted barium ferrite particles have been successfully synthesized by a reverse microemulsion technique. The effects of heteroatom contents and precipitating agents were investigated, respectively. It was found that the presence of heteroatoms could enhance lattice parameters, affect morphology evolution and modulate magnetic properties. Particularly, an unusual saturation magnetization (>70.0 emu/g) could be achieved under low heteroatoms concentration due to preferential occupation in specific sites. Precipitating agents played a critical role in forming barium ferrite phase, only sufficient precipitating agents could produce high-purity phase. Besides, this method is not limited in the synthesis of Co-Sn substituted barium ferrite, it can be extended to other heteroatoms, such as Ni-Zr and La, and resultant products also show well crystalline phase and unique magnetic properties.     

Facile fabrication of p–n heterojunctions for Cu2O submicroparticles deposited on anatase TiO2 nanobelts

In this paper, Cu₂O particle-deposited TiO₂ nanobelts with p–n semiconductor heterojunction structure were successfully prepared via a two-step preparation process to investigate electron-transfer performance between p-type Cu₂O and n-type TiO₂. Various measurement results confirm that the amount of pure Cu₂O submicroparticles, with diameters within the range of 200–400 nm and deposited on the surface of TiO₂ nanobelts, can be controlled, and that the purity of Cu₂O is heavily affected by reaction time. Visible-light photodegradation activities of Rhodamine B show that photocatalysts have little or no photocatalytic activities mainly due to their p–n heterojunction structure, indicating that there hardly appears any electron-transfer from Cu₂O to TiO₂.     

Characterization of LiF-doped TiO2 and its photocatalytic activity for decomposition of trichloromethane

LiF-doped TiO₂ was prepared by hydrolysis of tetrabutyl titanate in a mixed LiF-H₂O-alcohol solution. The prepared LiF-doped TiO₂ powders were characterized by X-ray diffraction (XRD), differential thermal analysis-thermogravimetry (DTA-TG), X-ray photoelectron spectroscopy (XPS), UV-vis absorption spectroscopy and photoluminescence spectra (PL). The photocatalytic activity was evaluated by the decomposition of trichloromethane (CHCl₃). The results showed that LiF-doping increased the amount of O_OH and oxygen vacancy (OV) on the surface of TiO₂, which were beneficial to photocatalytic activity. LiF-doping inducted the new isolated energy band located above the valence band of TiO₂, which extended the absorption region of TiO₂ to visible light. The results of photocatalytic reaction showed that the photocatalytic activity of LiF-doped TiO₂ was 2.5 times higher than that of pure TiO₂.