Hydrogen production in fluidized bed by chemical-looping cycle

To investigate the feasibility of a chemical-looping hydrogen generation system, we investigated the reduction and water splitting reaction characteristics for three mediators and two reducing gas in a bubbling fluidized bed reactor (0.02 m I.D.). For three oxygen carrier particles (NiO/bentonite, Fe₂O₃/bentonite, (NiO:Fe₂O₃)/bentonite), hydrogen was used as a reduction gas and water was used as an oxidation gas. For (NiO: Fe₂O₃)/bentonite particle, carbon monoxide, which is the main component in the syngas from coal or heavy residue, was used as a reducing gas to check reactivity for the carbon containing fuels and carbon deposition characteristics. Based on the reactivity tests, (NiO: Fe₂O₃)/bentonite particle was selected as the best mediator for the chemical-looping hydrogen generation system to achieve stable continuous operation. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Porous Fe3O4/C microspheres for efficient broadband electromagnetic wave absorption

Porous Fe₃O₄/C microspheres, which were Fe₃O₄ nanocrystals (～8?nm) embedded in an open nanostructured carbon network, were successfully synthesized via a facile hydrothermal process. The porous Fe₃O₄/C microspheres possessed many distinct attributes that facilitate efficient broadband electromagnetic wave absorption (EMWA). EMWs were attenuated through multiple reflections and absorption in the 3D interconnected porous structure of the microspheres; these processes collectively improved the interaction between the EMWs and the absorber. Additionally, the carbon network and embedded Fe₃O₄ nanoparticles caused significant dielectric losses and magnetic losses, respectively, which also enhanced EMWA. The EMWA characteristics of the microspheres could be precisely tuned via changing the carbon content to achieve optimized impedance matching. Porous Fe₃O₄/C microspheres with a 71.5?wt% carbon content displayed particularly impressive EMWA properties: a maximum reflection loss (RL) value of ??31.75 across broad band frequencies in the range of 7.76–12.88?GHz (RL < ?10?dB) at an absorber thickness of 3.0?mm. These excellent EMWA properties may be attributed to both dielectric loss (carbon) and magnetic loss (Fe₃O₄). Additionally, the 3D interconnected porous structure of the Fe₃O₄/C microspheres is especially favorable for impedance matching.     

Magnetic-field-induced Fe3O4@CNTs/PES/SPSf composite membrane for efficient removal of methylene blue by adsorption and catalytic degradation

Novel composite membranes are successfully developed for adsorption and catalytic degradation of methylene blue (MB) by blending Fe₃O₄-coated CNTs (Fe₃O₄@CNTs) nanoparticles in polyethersulfone (PES) and sulfonated polysulfone (SPSf) matrix via nonsolvent-induced phase separation (NIPS) method assisted by magnetic field. Fe₃O₄@CNTs nanoparticles migrate to the separation layer under the induction of magnetic field, thus Fe₃O₄@CNTs/PES/SPSf composite membranes prepared under magnetic field exhibit a better dye removal ability compared with that without magnetic field. The MB removal ratio by Fe₃O₄@CNTs/PES/SPSf composite membrane containing 8 wt% Fe₃O₄@CNTs (M2−M) can reach up to 99% in 30 min under the conditions of 0.25 g composite membrane, 20 mg/L MB, 0.1 mol/L H₂O₂, pH = 3 and 80°C. Furthermore, the composite membranes show excellent recycling performance, as the MB removal capacity remains at 99% even after four cycles.     

Desulphurization of diesel fuels using intermediate Lewis acids loaded on activated charcoal and alumina

According to Pearson’s hard/soft (Lewis) acids/bases concept, sulfur compounds in diesel will prefer to interact with intermediate or soft Lewis acid sites since they are soft to intermediate bases. In this work, intermediate Lewis metal oxides (MO) acids were loaded on activated carbon (AC) and alumina (Al₂O₃) to desulfurize diesel using adsorption. For carbon-loaded MO, NiO showed the highest desulfurization activity of 89% and 50% when using both model diesel and conventional diesel, respectively. The activity of Al₂O₃ and Al₂O₃ supported MO was approximately four times less than that of AC for model diesel desulphurization. It is suggested that the low activity of Al₂O₃ is due to lower surface area, pore distribution, and the strong acidity nature of Al₂O₃ since the adsorbates are soft to intermediate Lewis bases. Lower activity, 2–4 times, was observed when treating conventional diesel compared to model diesel. This lower activity is due to competitive adsorption with compounds such as naphthalene and indole. Despite this difference, the activity trends were generally maintained suggesting that the use of model diesel is not a bad technique for screening adsorbents. Selectivity on AC was observed to decrease in this order: 4-MDBT?>?1,4,6-TMDBT?>?4,6-DMDBTZ?～?4E,6-MDBT?～?2,4,6-TMDBT. This suggests that steric hindrances dominate selectivity for these high-molecular weight molecules. Finally, it was observed that the challenge with regeneration of adsorbent (AC) that treated conventional diesel using solvent extraction is competitive desorption of hydrocarbons and sulfur compounds.     

Heterogeneous Fenton degradation of Orange II by immobilization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles onto Al-Fe pillared bentonite

A novel catalyst, Fe₃O₄ nanoparticle decorated Al-Fe pillared bentonite (Fe₃O₄/Al-Fe-P-B), was prepared by in situ precipitation oxidization method. The catalyst was characterized by SEM, XRD and Raman spectroscopy. The Fe₃O₄ nanoparticles mainly exist on the surface or enter into the pore of bentonite, with better dispersing and less coaggregation. The catalytic activity of Fe₃O₄/Al-Fe-P-B was investigated in the degradation of Orange II (OII) by heterogeneous Fenton-like process. The effects of initial concentration of hydrogen peroxide, catalyst loading, temperature and initial pH on the degradation of OII were investigated. The Fe₃O₄/Al-Fe-P-B showed higher degradation efficiency of OII than bare Fe₃O₄ or Al-Fe-P-B in the degradation experiment. The enhanced catalytic activity of Fe₃O₄/Al-Fe-P-B in heterogeneous Fenton system was due to the synergistic effect between Al-Fe-P-B and Fe₃O₄. The novel catalyst can achieve solid-liquid separation easily by sample magnetic separation and has a good reusability and stability.     

Ultra‐deep desulfurization adsorbents for hydrotreated diesel with magnetic mesoporous aluminosilicates

Magnetic mesoporous aluminosilicates (MMAS) were synthesized by hydrothermal method and applied as ultra‐deep desulfurization adsorbents for hydrotreated diesel. The size of oleic‐coated magnetic Fe₃O₄ nanoparticles prepared by coprecipitation method was about 20 nm. MMAS shows better desulfurization properties for removal of sulfur compounds than NaY and MCM‐41. The amount of Fe₃O₄ nanoparticles has significant effects on specific surface area/pore volume and acidic properties, thus, can affect the desulfurization properties of MMAS. Desulfurization properties of MMAS can be improved with the increase of temperature from 30–70°C and decrease the oil to adsorbent ratio. With the increase of Fe₃O₄ content, adsorption capacity first increased and then decreased. The sulfur adsorption of MMAS was due to the synergetic effect of strong molecular affinity of the magnetite to the sulfur compound and large surface area/pore volume of the mesoporous aluminosilicates. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Magnetoresistive polyaniline-magnetite nanocomposites with negative dielectrical properties

Magnetic polyaniline (PANI) polymer nanocomposites (PNCs) reinforced with magnetite (Fe₃O₄) nanoparticles (NPs) have been successfully synthesized using a facile surface initiated polymerization (SIP) method. The chemical structures of the PANI/Fe₃O₄ PNCs are characterized by Fourier transform infrared (FT-IR) spectroscopy. The thermal stability of the PANI/Fe₃O₄ PNCs is performed by thermogravimetric analysis (TGA). Both transmission electron microscopy (TEM) and scanning electron microscopy (SEM) are used to characterize the morphologies of the PANI, Fe₃O₄ nanoparticles (NPs) and the PNCs. X-ray diffraction (XRD) shows a significant effect of the Fe₃O₄ NPs on the crystallization structure of the formed PANI. The dielectrical properties of these PNCs are strongly related to the Fe₃O₄ nanoparticle loadings and unique negative permittivity is observed in all the samples. Temperature dependent resistivity analysis from 50 to 290 K reveals a quasi 3-dimension variable range hopping (VRH) electron conduction mechanism for the nanocomposite samples. The PNCs do not show hysteresis loop with zero coercivity, indicating the superparamagnetic behavior at room temperature. The PNCs with 30 wt% Fe₃O₄ NP loading exhibit a larger positive magnetoresistance (MR = 95%) than 53% of the pure PANI.     

Preparation and characterization of polyvinyl chloride based nanocomposite nanofiltration-membrane modified by iron oxide nanoparticles for lead removal from water

In this research (polyvinyl chloride-blend-cellulose acetate/iron oxide nanoparticles) nanocomposite membranes were prepared by casting technique to lead removal from wastewaters. The effect of blend ratio of polymer binder (PVC to CA) and Fe₃O₄ nanoparticles concentration on physico-chemical characteristics of membranes were studied. Water permeability and ionic rejection tests, water content and mechanical properties measurements and SEM analysis were carried out in membranes characterizations. Obviously, modified membrane containing 10 wt% CA and 0.1 wt% Fe₃O₄ nanoparticles showed better performance in lead removal compared to other modified membranes and also pristine ones.     

Magnetic properties of PAN-based carbon fibres modified with magnetite nanoparticles

The magnetic properties of PAN-based carbon fibres modified with magnetite nanoparticles are presented and analyzed. PAN fibres and PAN-based carbon fibres modified with different amounts of magnetite are characterized by the use of magnetization measurements and Mössbauer spectroscopy techniques. The investigations revealed that magnetite (Fe₃O₄) decomposed into Fe_α, Fe_γ and cementite (Fe₃C). Precise analysis of the phase’s contents for different carbon fibres has been carried out in relation to the initial magnetite compound. Analysis of the Mössbauer spectra allowed the determination of the phase contents in fibres with different initial magnetite concentrations. Partial transformation of magnetite into γ-Fe induces catalytic carbonization and formation of a highly crystalline carbon matrix at 1000 °C. The apparent crystallite size in carbon fibres containing 30% magnetite was almost seven times higher than that found in the pure carbon fibres.     

Nickel Oxide Based Supported Catalysts for the In-situ Reactions of Methanation and Desulfurization in the Removal of Sour Gases from Simulated Natural Gas

Supported nickel oxide based catalysts were prepared by wetness impregnation method for the in-situ reactions of H₂S desulfurization and CO₂ methanation from ambient temperature up to 300 °C. Fe/Co/Ni (10:30:60)–Al₂O₃ and Pr/Co/Ni (5:35:60)–Al₂O₃ catalysts were revealed as the most potential catalysts, which yielded 2.9% and 6.1% of CH₄ at reaction temperature of 300 °C, respectively. From XPS, Ni₂O₃ and Fe₃O₄ were suggested as the surface active components on the Fe/Co/Ni (10:30:60)–Al₂O₃ catalyst, while Ni₂O₃ and Co₃O₄ on the Pr/Co/Ni (5:35:60)–Al₂O₃ catalyst.     

Effect of surface modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles on the preparation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/polystyrene composite particles via miniemulsion polymerization

Fe₃O₄ nanoparticles were modified by n-octadecyltrimethoxysilane (C18TMS) and 3-trimethoxysilylpropylmethacrylate (MPS). The modified Fe₃O₄ nanoparticles were used to prepare Fe₃O₄/polystyrene composite particles by miniemulsion polymerization. The effect of surface modification of Fe₃O₄ on the preparation of Fe₃O₄/polystyrene composite particles was investigated by transmission electron microscopy, Fourier transform infrared spectrophotometer (FT-IR), contact angle, and vibrating sample magnetometer (VSM). It was found that C18TMS modified Fe₃O₄ nanoparticles with high hydrophobic property lead to the negative effect on the preparation of the Fe₃O₄/polystyrene composite particles. The obtained composite particles exhibited asymmetric phase-separated structure and wide size distribution. Furthermore, un-encapsulated Fe₃O₄ were found in composite particles solution. MPS modified Fe₃O₄ nanoparticles showed poor hydrophobic properties and resulted in the obtained Fe₃O₄/polystyrene composite particles with regular morphology and narrow size distribution because the ended C=C of MPS on the surface of Fe₃O₄ nanoparticles could copolymerize with styrene which weakened the phase separation distinctly.     

Preparation of Pt nanoparticle-loaded three-dimensional Fe3O4/carbon with high electro-oxidation activity

A three-dimensional (3D) Fe₃O₄/carbon material functionalized with amino and hydroxyl groups was synthesized by decomposing 2,4,5-trichlorophenol/ferrocene mixture in the presence of ammonia and polyethylene glycol in solvothermal conditions at 250 °C for 30 h by a one-step process. The 3D Fe₃O₄/carbon materials can be loaded with Pt nanoparticles without adding any reducing agent; Pt-loaded 3D Fe₃O₄/carbon hybrid materials have superior electrochemical catalytic activity toward methanol oxidation and the oxidation current density on them is nearly triple that on a commercial Pt/C catalyst.     

Core-shell-type Fe3O4@carbon nanoparticles and their fabrication using silanic/polymeric amino functionalization

A facile strategy for the fabrication of a carbon shell on Fe₃O₄ nanoparticles with a cluster structure has been proposed. Unlike the conventional solvothermal process using an autoclave, the proposed synthesis method could yield core-shell structured Fe₃O₄@C nanoparticles at low temperature and atmospheric pressure. This synthesis method was based on the chemical bonding among the terminal amine groups, introduced on the Fe₃O₄ surface, and carbonization by the catalytic reaction of glucose (carbon source) with sulfuric acid. The properties of the Fe₃O₄@C nanoparticles so obtained depended on the terminal amine groups that modified the iron oxide surface. The effects of the silane- and polymer-based amination on the fabrication of the carbon shell were investigated.     

Studies on Properties of Rice Straw/Polymer Nanocomposites Based on Polycaprolactone and Fe3O4 Nanoparticles and Evaluation of Antibacterial Activity

Modified rice straw/Fe₃O₄/polycaprolactone nanocomposites (ORS/Fe₃O₄/PCL-NCs) have been prepared for the first time using a solution casting method. The RS/Fe₃O₄-NCs were modified with octadecylamine (ODA) as an organic modifier. The prepared NCs were characterized by using X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The XRD results showed that as the intensity of the peaks decreased with the increase of ORS/Fe₃O₄-NCs content in comparison with PCL peaks, the Fe₃O₄-NPs peaks increased from 1.0 to 60.0 wt. %. The TEM and SEM results showed a good dispersion of ORS/Fe₃O₄-NCs in the PCL matrix and the spherical shape of the NPs. The TGA analysis indicated thermal stability of ORS/Fe₃O₄-NCs increased after incorporation with PCL but the thermal stability of ORS/Fe₃O₄/PCL-NCs decreased with the increase of ORS/Fe₃O₄-NCs content. Tensile strength was improved with the addition of 5.0 wt. % of ORS/Fe₃O₄-NCs. The antibacterial activities of the ORS/Fe₃O₄/PCL-NC films were examined against Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus) by diffusion method using nutrient agar. The results indicated that ORS/Fe₃O₄/PCL-NC films possessed a strong antibacterial activity with the increase in the percentage of ORS/Fe₃O₄-NCs in the PCL.     

Anchoring mesoporous Fe3O4 nanospheres onto N-doped carbon nanotubes toward high-performance composite electrodes for supercapacitors

Fe-based oxide electrodes for practical applications in supercapacitors (SCs) suffer from low conductivity and poor structural stability. To settle these issues, we report on the design and synthesis of Fe₃O₄/carbon nanocomposites via firmly anchoring mesoporous Fe₃O₄ nanospheres onto N-doped carbon nanotubes (N-CNTs) via C–O–Fe bonds. Mesoporous Fe₃O₄ nanospheres are featured by rich electroactive sites and short ion diffusion pathways. The N-CNTs, on the other hand, serve as the scaffolds, which not only provide conductive networks but also suppress the accumulation between mesoporous Fe₃O₄ nanospheres as well as alleviate volume changes during charge/discharge cycles. Accordingly, the constructed Fe₃O₄/N-CNTs nanocomposite electrode demonstrates improved specific capacity values of up to 314 C g⁻¹ at 1 A g⁻¹, with 92% retention of the initial capacity after 5000 cycles at 10 A g⁻¹. In addition, the assembled Fe₃O₄/N-CNTs//active carbon (AC) asymmetric supercapacitor (ASC) device possesses an energy density of 25.3 Wh kg⁻¹, suggesting that the prepared Fe₃O₄/N-CNTs nanocomposites are promising electrode materials for use in SCs.     

Electromagnetic interference shielding effectiveness of hybrid multifunctional Fe3O4/carbon nanofiber composite

Electromagnetic interference shielding effectiveness (EMI SE) of multifunctional Fe₃O₄/carbon nanofiber composites in the X-band region (8.2–12.4 GHz) is studied. Here, we examine the contributing effects of various parameters such as Fe₃O₄ content, carbonization temperature and thickness on total shielding efficiency (SE_total) of different samples. The maximum EMI SE of 67.9 dB is obtained for composite of 5 wt.% Fe₃O₄ (0.7 mm thick) with the dominant shielding by absorption (SE_A) of electromagnetic radiation. The enhanced electromagnetic shielding performance of Fe₃O₄/carbon nanofiber composites is attributed to the increment of both magnetic and dielectric losses due to the incorporation of magnetite nanofiller (Fe₃O₄) in electrically conducting carbon nanofiber matrix as well as the specific nanofibrous structure of carbon nanofiber mats, which forms a higher aspect ratio structure with randomly aligned nanofibers. Furthermore, we prove that the addition of elastomeric polydimethylsiloxane (PDMS) as a coating for carbon nanofiber composite strengthens the composite structure without interfering with its electromagnetic shielding efficiency.     

Optically transparent polymer composites: A study on the influence of filler/dopant on electromagnetic interference shielding mechanism

Composite materials made of polymers and carbon-based ferromagnetic filler are attractive for electromagnetic interference shielding through a combination of reflection and microwave absorption. It is possible to enhance their shielding properties by controlling electrical conductivity, dielectric, and magnetic properties. In this work, the aforementioned properties are tailored to achieve optically transparent films with microwave absorbing properties. Nanocarbon materials, namely carbon nanotubes, graphene nanoribbons (GNR) and their ferromagnetic nanocomposites with Fe₃O₄ and cobalt in PVA-PEDOT:PSS matrix were made and tested in X-band. The highest shielding effectiveness for PVA films with nanocarbon filler was observed for 0.5 wt% GNR − Fe₃O₄ at 16.36 dB (9.7 GHz) with 79.8% transmittance.     

Modification of Magnetite Cellulose Nanoparticles via Click Reaction for use in Controlled Drug Delivery

Superparamagnetic Fe₃O₄ nanoparticles (MNPs) were functionalized by modified cellulose. The modified cellulose was synthesized through bromoacetylation of cellulose (BACell) followed by the substitution of sodium azide to form BACell-N₃. The remaining methylene bromide groups on BACell-N₃ was further reacted with the MNPs to form Fe₃O₄/Cell-N₃. Then propargyl alcohol (PA) was immobilized on the azide-terminated Fe₃O₄ nanoparticles through copper (I)-catalyzed azide-alkyne cycloaddition (click reaction) to form Fe₃O₄/Cell/TAA nanoparticles. Doxorubicin (DOX) was loaded on prepared nanoparticles and release profiles of the DOX as a model drug from the Fe₃O₄/Cell/TAA nanoparticles and its loading capacity were determined by UV–Vis absorption at λ_max 483?nm.     

Desulfurization characteristics of CuO-Fe2O3 sorbents

A series of CuO-Fe₂O₃ sorbents with 25 wt% SiO₂ as a support were prepared based on a simple mixing method in order to evaluate the effects of Fe₂O₃ on their desulfurization reactivities. The initial reactivities of sorbents were tested by using a TGA and their cyclic performance was investigated in a GC/microreactor system. The activation energy calculated by the Chatterjee-Conrad method based on the TGA experiment decreased as the content of Fe₂O₃ increased. Sulfur loading in the cyclic reactions increased with increase of Fe₂O₃ content, and its maximum value was 8.9 g sulfur per 100 g sorbent. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Fe3O4 nanoparticles encapsulated in electrospun porous carbon fibers with a compact shell as high-performance anode for lithium ion batteries

Fe₃O₄ nanoparticles encapsulated in porous carbon fibers (Fe₃O₄@PCFs) as anode materials in lithium ion batteries are fabricated by a facile single-nozzle electrospinning technique followed by heat treatment. A mixed solution of polyacrylonitrile (PAN) and polystyrene (PS) containing Fe₃O₄ nanoparticles is utilized to prepare hybrid precursor fibers of Fe₃O₄@PS/PAN. The resulted porous Fe₃O₄/carbon hybrid fibers composed of compact carbon shell and Fe₃O₄-embeded honeycomb-like carbon core are formed due to the thermal decomposition of PS and PAN. The Fe₃O₄@PCF composite demonstrates an initial reversible capacity of 1015 mAh g⁻¹ with 84.4% capacity retention after 80 cycles at a current density of 0.2 A g⁻¹. This electrode also exhibits superior rate capability with current density increasing from 0.1 to 2.0 A g⁻¹, and capacity retention of 91% after 200 cycles at 2.0 A g⁻¹. The exceptionally high performances are attributed to the high electric conductivity and structural stability of the porous carbon fibers with unique structure, which not only buffers the volume change of Fe₃O₄ with the internal space, but also acts as high-efficient transport pathways for ions and electrons. Furthermore, the compact carbon shell can promote the formation of stable solid electrolyte interphase on the fiber surface.