Zn(OAc)2/AC催化固定床上CO2与1,2-丙二醇合成碳酸丙烯酯及其反应机理

以负载型乙酸锌为催化剂,在固定床上实现了CO₂和1,2-丙二醇(PG)合成碳酸丙烯酯(PC)反应。考察了不同载体和负载量对负载型乙酸锌催化性能的影响以及反应条件对PC合成反应的影响。结果表明:负载量为40% (质量分数)的Zn(OAc)₂/AC催化性能最好。CO₂与PG合成PC适宜的反应条件为:PG、乙腈和CO₂的摩尔比为1:1.8:11,CO₂ 压力 4.0 MPa,反应温度160 ℃和液空速0.9 h^-1。在此条件下,PC收率和选择性分别为6.3%和49.0%。采用原位红外结合设计实验研究了无水乙酸锌分别与CO₂和PG之间的相互作用,发现CO₂与乙酸锌之间的化学吸附比较弱,而PG与乙酸锌之间的化学吸附较强,能够活化PG。据此推测了乙酸锌催化CO₂与PG合成PC的反应机理。     

Selective synthesis of mixed alcohols from syngas over catalyst Fe2O3/Al2O3 in slurry reactor

The Fe₂O₃/Al₂O₃ catalyst was studied to selectively synthesize mixed alcohols from syngas in a continuously stirred slurry reactor with the oxygenated solvent Polyethylene Glycol-400 (PEG-400). The selectivity of mixed alcohols in the products reached as high as 95 wt.% and the C₂₊ alcohols (mainly ethanol) was more than 40 wt.% in the total alcohol products at the reaction conditions of 250 °C, 3.0 MPa, H₂/CO = 2 and space velocity = 360 ml/g_cat h. The hydrogen temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) measurements of the catalyst confirmed that the FeO phase was responsible for the high selectivity to mixed alcohols in the process. And the oxygenated solvent PEG-400 was also necessary for the selective synthesis of mixed alcohols in the reaction system.     

Functionalized magnetic core-shell Fe3O4@SiO2 nanoparticles as selectivity-enhanced chemosensor for Hg(II)

A colorimetric and ‘‘turn-on” fluorescent chemosensor Rho-Fe₃O₄@SiO₂ for Hg²⁺ in which N-(rhodamine-6G)lactam-ethylenediamine (Rho-en) is conjugated with the magnetic core-shell Fe₃O₄@SiO₂ NPs has been strategically designed and synthesized. The final product was characterized by X-ray power diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR) and UV-visible absorption and fluorescence emission. Fluorescence and UV-visible spectra results showed that the resultant multifunctional nanoparticles Rho-Fe₃O₄@SiO₂ exhibited selective ‘turn-on’ type fluorescent enhancements and distinct color changes with Hg²⁺. The selectivity of the Rho-Fe₃O₄@SiO₂ for Hg(II) ion is better than that of the Rho-en in the same conditions. In addition, the presence of magnetic Fe₃O₄ nanoparticles in the sensor Rho-Fe₃O₄@SiO₂ NPs would also facilitate the magnetic separation of the Hg(II)-Rho-Fe₃O₄@SiO₂ from the solution.     

Synthesis of Fe2O3 nanoparticles for nitrogen dioxide gas sensing applications

Iron (III) oxide, Fe₂O₃, nanoparticles of approximately 40 nm diameter were synthesized by sol–gel method and their nitrogen dioxide adsorption and desorption kinetics were investigated by custom fabricated gas sensor unit. The morphology and crystal structure of Fe₂O₃ nanoparticles were studied by scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) respectively. The roughness of film surface was investigated by atomic force microscopy (AFM). Relative sensitivity of Fe₂O₃ nanoparticles for NO₂ sensor was determined by electrical resistance measurements. Our reproducible experimental results show that Fe₂O₃ nanoparticles have a great potential for nitrogen dioxide sensing applications operating at a temperature of 200 °C.     

Corrosion mechanisms of Al2O3/MgAl2O4 by V2O5, NiO, Fe2O3 and vanadium slag

The effects of V₂O₅, NiO, Fe₂O₃ and vanadium slag on the corrosion of Al₂O₃ and MgAl₂O₄ have been investigated. The specimens of Al₂O₃ and MgAl₂O₄ with the respective oxides above mentioned were heated at 10 °C/min from room temperature up to three different temperatures: 1400, 1450 and 1500 °C. The corrosion mechanisms of each system were followed by XRD and SEM analyses. The results obtained showed that Al₂O₃ was less affected by the studied oxides than MgAl₂O₄. Alumina was only attacked by NiO forming NiAl₂O₄ spinel, while the MgAl₂O₄ spinel was attacked by V₂O₅ forming MgV₂O₆. It was also observed that Fe₂O₃ and Mg, Ni, V and Fe present in the vanadium slag diffused into Al₂O₃. On the other hand, the Fe₂O₃ and Ca, S, Si, Na, Mg, V and Fe diffused into the MgAl₂O₄ structure. Finally, the results obtained were compared with those predicted by the FactSage software.     

纳米Fe3O4稳定的Pickering型ASA乳液

利用纳米Fe₃O₄作为稳定剂和乳化剂来制备Pickering型ASA（alkenyl succinic anhydride） 施胶乳液,并研究了固体颗粒浓度、油水比、水分散相pH对乳液类型、稳定性、形态及施胶性能的影响。结果表明,纳米Fe₃O₄能够乳化制备均一稳定的Pickering型ASA乳液。乳液在室温下静置稳定,析出油相体积分数随固体颗粒用量的增加而增大,随油水比的增大而减小。油水比为2：1,水分散相浓度为0.1%（质量分数）时制备的ASA乳液稳定性最佳。固体颗粒部分吸附在油/水界面处,部分分散在分散相中,随分散相中固体颗粒浓度的增加,乳液稳定性变差。乳液静置分层之前,ASA发生部分水解。在放置1 h后用于纸页浆内施胶,随ASA乳液用量的增加,纸页表面接触角逐渐增大,且纸页表面粗糙度下降。在ASA的添加量为1.0%（质量分数）时,纸页表面接触角达到93.5°,纸页表面粗糙度为15.924 μm。     

Synthesis of spherical spinel LiMn2O4 with commercial manganese carbonate

Spherical spinel LiMn₂O₄ particles were successfully synthesized from a mixture of manganese compounds containing commercial manganese carbonate by sintering of the spray-dried precursor. Different preparation routes were investigated to improve the tap density and to enhance the electrochemical performance of LiMn₂O₄. The structure and morphology of the LiMn₂O₄ particles were confirmed by X-ray diffraction (XRD) and scanning electron microscopy. The results showed that hollow spherical LiMn₂O₄ particles could be obtained when only commercial MnCO₃ was used as the manganese source. These particles had a low tap density (ca.0.8 g/cm³). Perfect micron-sized spherical LiMn₂O₄ particles with good electrochemical performance were obtained by spray-drying a slurry composed of MnCO₃, Mn(CH₃CHOO)₂ and LiOH, followed by a dynamic sintering process and a stationary sintering process. The as-prepared spherical LiMn₂O₄ particles comprised hundreds of nanosize crystal grains and had a high tap density(ca. 1.4 g/cm³). The galvanostatic charge-discharge measurements indicated that the spherical LiMn₂O₄ particles had an initial capacity of 121 mAh/g between 3.0 and 4.2 V at 0.2 C rate and still delivered a reversible capacity of 112 mAh/g at 2 C rate. The retention of capacity after 50 cycles was still 96% of its initial capacity at 0.2 C. All the results showed that the as-prepared spherical LiMn₂O₄ particles had an excellent electrochemical performances. The methods we used for preparing spherical LiMn₂O₄ are energy-saving and suitable for industrial application.     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

Study of intrinsic sulfidation behavior of Fe2O3 for high temperature H2S removal

Iron-based sorbent was preferable for desulfurization from coal-derived gas due to economic consideration and favorable dynamic property. The intrinsic behavior of Fe-based sorbent should be primarily understood in the sulfidation process for improving its performance. A series of tests were carried out with Fe₂O₃, Fe and other compounds containing-Fe (FO) made from the same precursor FeC₂O₄·2H₂O in H₂S-N₂ mixture in this study. The formation of H₂ was observed with Fe and FO as sorbents. While SO₂ was detected with FO and Fe₂O₃ as sorbents, its concentration in outlet was gradually decreased. The crystal phase and surface chemical state of fresh and sulfided Fe₂O₃ with different reaction times were characterized by XRD and XPS measurements. The result suggested that the intrinsic H₂S removal by Fe₂O₃ would produce multi-phase of sulfides. The possible mechanism of sulfidation reaction was discussed.     

Multifuctional Fe3O4@C/YVO4:Dy nanopowers: Preparation,luminescence and magnetic properties

As-synthesized Fe₃O₄ nanoparticles were encapsulated with carbon layers through a simple hydrothermal process. Fe₃O₄/C nanoparticles were coated with YVO₄:Dy³⁺ phosphors to form bifunctional Fe₃O₄@C@YVO₄:Dy³⁺ composites. Their structure, luminescence and magnetic properties were characterized by XRD, SEM, TEM, HRTEM, PL spectra and VSM. The experimental results indicated that the as-prepared bifunctional composites displayed well-defined core–shell structures. The ∼12 nm diameter YVO₄:Dy³⁺ shell exhibited tetragonal structure. Additionally, the composites exhibited a high saturation magnetization (13 emu/g) and excellent luminescence properties, indicating their promising potential as multifunctional biosensors for biomedical applications.     

Using a bifunctional polymer for the functionalization of Fe3O4 nanoparticles

A bifunctional maleimido-tetra(ethylene glycol)-poly(glycerol monoacrylate) (MAL-TEG-PGA) polymer was synthesized and used as a linker to couple functional biomolecules to iron oxide nanoparticles. The cell-penetrating peptide Tat was chosen as a model ligand and successfully conjugated to the surface of Fe₃O₄ nanoparticles using MAL-TEG-PGA. The Tat-conjugated Fe₃O₄ nanoparticles can be prepared simply by applying the linker to the iron oxide nanoparticles and then coupling the Tat peptide to the maleimide terminus or by coating the nanoparticles with a pre-coupled linker. Cell-uptake studies demonstrated that the Tat peptide was an efficient functional biomolecule to translocate iron oxide nanoparticles into the cell nucleus. Tat-conjugated nanoparticles thus prepared may be useful for drug or gene delivery.     

Sonochemical synthesis of magnetic core–shell Fe3O4@ZrO2 nanoparticles and their application to the highly effective immobilization of myoglobin for direct electrochemistry

In this study, bifunctional Fe₃O₄@ZrO₂ magnetic core–shell nanoparticles (NPs), synthesized by a simple and effective sonochemical approach, were attached to the surface of a magnetic glassy carbon electrode (MGCE) and successfully applied to the immobilization/adsorption of myoglobin (Mb) for constructing a novel biosensor platform. With the advantages of the magnetism and the excellent biocompatibility of the Fe₃O₄@ZrO₂ NPs, Mb could be easily immobilized on the surface of the electrode in the present of external magnetic field and well retained its bioactivity, hence dramatically facilitated direct electron transfer of Mb was demonstrated. The proposed Mb/Fe₃O₄@ZrO₂ biofilm electrode exhibited excellent electrocatalytic behaviors towards the reduction of H₂O₂ with a linear range from 0.64 μM to 148 μM. This presented system avoids the complex synthesis for protecting Fe₃O₄ NPs, supplies a simple, effective and inexpensive way to immobilize protein, and is promising for construction of third-generation biosensors and other bio-magnetic induction devices.     

Low-temperature synthesis of Bi2Fe4O9 nanoparticles via a hydrothermal method

Bi₂Fe₄O₉ (BFO) nanoparticles were successfully synthesized by a hydrothermal method at a temperature as low as 100 °C. The as-prepared powders, characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), transmission electron microscope (TEM) and physical property measurement system (PPMS), exhibited a pure BFO phase about 100 nm size with uniform sheet-like shape and exhibited an AF order at room temperature. It was found that high alkali concentration and alkali ion Na⁺ played a key role in the formation of BFO nanoparticles at a low temperature of 100 °C.     

Reduction and oxidation properties of Fe2O3/ZrO2 oxygen carrier for hydrogen production

Fe₂O₃ is a promising oxygen carrier for hydrogen production in the chemical-looping process. A set of kinetic studies on reduction with CH₄, CO and H₂ respectively, oxidation with water and oxygen containing Ar for chemical-looping hydrogen production was conducted. Fe₂O₃ (20 wt.%)/ZrO₂ was prepared by a co-precipitation method. The main variables in the TGA (thermogravimetric analyzer) experiment were temperatures and gas concentrations. The reaction kinetics parameters were estimated based on the experimental data. In the reduction by CH₄, CO and H₂, the reaction rate changed near FeO. Changes in the reaction rate due to phase transformation were observed at low temperature and low gas concentration during the reduction by CH₄, but the phenomenon was not remarkable for the reduction by CO and H₂. The reduction rate achieved using CO and H₂ was relatively faster than achieved using CH₄. The Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions was applied. A phase boundary controlled model (contacting sphere) was applied to the reduction of Fe₂O₃ to FeO by CH₄, and a different phase boundary controlled model (contacting infinite slab) was fit well to the reduction of FeO to Fe by CH₄. The reduction of Fe₂O₃ to Fe by CO and H₂ can be described by the former phase boundary controlled model (contacting sphere). This phase boundary controlled model (contacting sphere) also fit well for the oxidation of Fe to Fe₃O₄ by water and FeO to Fe₂O₃ by oxygen containing Ar. These kinetics data could be used to design chemical-looping hydrogen production systems.     

Hydrothermal preparation of octadecahedron Fe3O4 thin film for use in an electrochemical supercapacitor

A Fe₃O₄ film with regularly edge-affected cubic (octadecahedron) morphology was successfully prepared on stainless steel foil by a simple and benign hydrothermal process. The potential for the use of the film in a supercapacitor was tested by investigating the electrochemical behavior of the Fe₃O₄ film using cyclic voltammetry (CV) and galvanostatic charge/discharge tests. The Fe₃O₄ film showed a CV indicative of a typical pseudocapactive behavior in 1 mol L⁻¹ Na₂SO₃ solution. Furthermore, this film exhibited a specific capacitance of 118.2 F g⁻¹ at the current of 6 mA between −1 and 0.1 V with a capacity retention of 88.75% after 500 cycles.     

Synthesis and magnetic properties of nanoporous Co3O4 nanoflowers

Nanoporous Co₃O₄ hierarchical nanoflowers have been prepared through sequential process of a hydrothermal reaction and heat treatment. These nanoflowers consisting of a great deal of Co₃O₄ nanofibers have bimodal pore structures and Brunauer–Emmett–Teller surface area of 34.61 m²/g. The temperature dependence curves of magnetization in zero-field-cooled and field-cooled exhibit main antiferromagnet and weak ferromagnet of Co₃O₄ nanoflowers at blocking temperature of 34 K, respectively. In addition, analysis of their optic properties obviously indicates red shift of absorption peaks, exhibiting quantum-confined effect and traits of semiconductor.     

Preparation of propylene carbonate by alcoholysis of urea from the perspective of homogeneous reaction: Influence of dissolution and precipitation of metal oxide catalysts

The dissolution process of metal oxide catalysts in the alcoholysis of urea by 1, 2-propylene glycol (PG) to the synthesis of propylene carbonate (PC) was investigated. It was found that the reaction was mainly catalyzed by homogeneous catalysts. The metal oxide reacted with ammonia and isocyanate acid, the decomposition products of urea, to form a complex and dissolved into the reaction system. The dissolved amount of catalyst was positively correlated with the PC yield by using different oxides and salts as catalysts. The Fourier-transform infrared spectroscopy (FTIR) result of the catalysts reacting with urea showed that the dissolution-precipitation process of the catalysts was related to the decomposition of urea. The results of catalytic test indicated that both the dissolved amount of catalysts and the structure of the complex affected PC yields. A reaction mechanism was proposed based on the results. From the mechanism, a complex catalyst with at least two ammonia ligands is better for this reaction.     

Accommodation of impurities in α-Al2O3, α-Cr2O3 and α-Fe2O3

Atomic scale computer simulation was used to predict the mechanisms and energies associated with the accommodation of aliovalent and isovalent dopants in three host oxides with the corundum structure. Here we consider a much more extensive range of dopant ions than has previously been the case. This enables a rigorous comparison of calculated mechanism energetics. From this we predict that divalent ions are charge compensated by oxygen vacancies and tetravalent ions by cation vacancies over the full range of dopant radii. When defect associations are included in the model these conclusions remain valid. At equilibrium, defects resulting from extrinsic dopant solution dominate intrinsic processes, except for the largest dopant cations. Solution reaction energies increase markedly with increasing dopant radius. The behaviour of cluster binding energies is more complex.     

Influence of CuO on the formation and coexistence of 3CaO·SiO2 and 3CaO·3Al2O3·CaSO4 minerals

The influence of CuO on the formation and coexistence of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals in Portland cement containing 3CaO·3Al₂O₃·CaSO₄ mineral is reported in this paper. The results show that a suitable amount of CuO can lower the clinkering temperature and improve the burn-ability of clinkers. It can also promote the formation of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals and facilitate the coexistence of the two minerals in the clinkers. But adding 1% CuO to the raw material can cause the decomposition of 3CaO·3Al₂O₃·CaSO₄.