Effect of core-shell reversal on the structural,magnetic and adsorptive properties of Fe2O3-GO nanocomposites

Effect of core-shell reversal on the nanocomposites of graphene oxide (GO) and ferric oxide (Fe₂O₃) was studied. Fe₂O₃@GO core-shell nanosheets were synthesized by sonication method, while the GO@Fe₂O₃ core-shell nanospheres by employing N,N′-dicyclohexylcarbodimide as the binding agent for the wrapping of GO sheets on pre-formed Fe₂O₃ nanoparticles (NPs). The phase composition, crystallinity and morphology of the nanocomposites were characterized by FT-IR, TEM, SEM-EDS, VSM, BET surface area study and XRD techniques. The saturation magnetization (M_s) was 1.25 and 0.51 emu g⁻¹ for GO@Fe₂O₃ and Fe₂O₃@GO respectively owing to the dependence of magnetic properties on the reversal of core-shell. BET analysis revealed the surface area of 100.32 m² g⁻¹ and 45.69 m² g⁻¹ for GO@Fe₂O₃ and Fe₂O₃@GO nanocomposites respectively. The fabricated nanocomposites were analyzed as adsorbents for the uptake of Pb (II) ions. The impact of various factors affecting adsorption process such as pH, adsorbent dose, contact time, temperature and metal ion concentration was also investigated. GO@Fe₂O₃ core-shell nanospheres showed a higher adsorption capacity for Pb (II) ions as compared to Fe₂O₃@GO core-shell nanosheet with the maximum adsorption capacities (q_m) of 303.0 and 125.0 mg g⁻¹ respectively. The equilibrium data was estimated by Freundlich, Langmuir, D-R and Temkin isotherm models. Thermodynamic analysis confirmed the spontaneous and exothermic nature of the adsorption process. The adsorption kinetics was significantly fitted to pseudo-second order model. The results confirmed that core-shell reversal can significantly alter the adsorptive properties of Fe₂O₃-GO nanocomposite     

Fabrication of magnetic polybenzoxazine-based carbon nanofibers with Fe3O4 inclusions with a hierarchical porous structure for water treatment

Hierarchical porous, magnetic Fe₃O₄@carbon nanofibers (Fe₃O₄@CNFs) based on polybenzoxazine precursors have been synthesized by a combination of electrospinning and in situ polymerization. The benzoxazine monomers could easily form thermosetting nanofibers by in situ ring-opening polymerization and subsequently be converted into CNFs by carbonization. The resultant fibers with an average diameter of 130 nm are comprised of carbon fibers with embedded Fe₃O₄ nanocrystals, and could have a high surface area of 1885 m² g^?1 and a porosity of 2.3 cm³ g^?1. Quantitative pore size distribution and fractal analysis were used to investigate the hierarchical porous structure using N₂ adsorption and synchrotron radiation small-angle X-ray scattering measurements. The role of precursor composition and activation process for the effects of the porous structure is discussed, and a plausible correlation between surface fractal dimension and porous parameter is proposed. The Fe₃O₄@CNFs exhibit efficient adsorption for organic dyes in water and excellent magnetic separation performance, suggesting their use as a promising adsorbent for water treatment, and also provided new insight into the design and development of a carbon nanomaterial based on a polybenzoxazine precursor.     

Continuous preparation of Fe3O4 nanoparticles combined with surface modification by L-cysteine and their application in heavy metal adsorption

L-cysteine functionalized Fe₃O₄ magnetic nanoparticles (Cys–Fe₃O₄ MNPs) were continuously fabricated by a simple high-gravity reactive precipitation method combined with surface modification through a novel impinging stream-rotating packed bed with the assistance of sonication. The obtained Cys–Fe₃O₄ MNPs was characterized by XRD, TEM, FTIR, TGA and VSM, and further used for the removal of heavy metal ions from aqueous solution. The influence of pH values, contact time and initial metal concentration on the adsorption efficiency were investigated. The results revealed that the adsorption of Pb(II) and Cd(II) were pH dependent process, and the pH 6.0 was found to be optimum condition. Moreover, the adsorption kinetic for Cys–Fe₃O₄ MNPs followed the mechanism of the pseudo-second order kinetic model, and their equilibrium data were fitted with the Langmuir isothermal model well. The maximum adsorption capacities calculated from Langmuir equation were 183.5 and 64.35 mg g⁻¹ for Pb(II) and Cd(II) at pH 6.0, respectively. Furthermore, the adsorption and regeneration experiment showed there was about 10% loss in the adsorption capacity of the as-prepared Cys–Fe₃O₄ MNPs for heavy metal ions after 5 times reuse. All the above results provided a potential method for continuously preparing recyclable adsorbent applied in removing toxic metal ions from wastewater through the technology of process intensification.     

Synthesis,structure and magnetic properties of spinel ferrite (Ni,Cu, Co)Fe2O4 from low nickel matte

Spinel ferrite (Ni, Cu, Co)Fe₂O₄ was synthesized from the low nickel matte by using a co-precipitation-calcination method for the first time. The influences of the added amount of NiCl₂·6H₂O, calcination temperature and time on the structure and magnetic properties of the as-prepared ferrites were studied in detail by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy, and Vibrating sample magnetometer (VSM). It is indicated that pure (Ni, Cu, Co)Fe₂O₄ with cubic phase could be obtained under the experimental conditions (NiCl₂·6H₂O added amount of 3.0: 100 g mL⁻¹, calcination temperature from 800 to 1000 °C and calcination time from 1 to 3 h). With increasing calcination temperature and time, saturation magnetization (M_S) of the synthesized (Ni, Cu, Co)Fe₂O₄ increased and the coercivity (H_C) decreased. Under the optimum conditions (i.e. NiCl₂·6H₂O added amount of 3.0: 100 g mL⁻¹, 1000 °C, 3 h), the M_S and H_C values of the product were approximately 46.1 emu g⁻¹ and 51.0 Oe, respectively, which were competitive to those of other nickel ferrites synthesized from pure chemical reagents. This method explores a novel pathway for efficient and comprehensive utilization of the low nickel matte.     

Activated carbon/CoFe2O4 composites: Facile synthesis,magnetic performance and their potential application for the removal of malachite green from water

Activated carbon/CoFe₂O₄ composite (AC/CFO) was synthesized by a simple one-step refluxing route and was used as adsorbent for the removal of malachite green (MG) dye from water. The structure, morphology and magnetic properties of as-prepared composite were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). The results indicated that CoFe₂O₄ particles deposited on the surface of activated carbon in the composite were uniform with the particle size in the range of 14–20 nm. The composite adsorbents exhibited a clearly hysteretic behavior under applied magnetic field, which allowed their magnetic separation from water. Batch experiments were carried out to investigate adsorption isotherms and kinetics of MG onto the composite. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity of 89.29 mg g^?1. The adsorption kinetics was found to follow pseudo-second-order kinetic model. It was indicated that the as-prepared composite could be used as a promising and effective adsorbent for the removal of MG from water.     

Immobilization of Aspergillus niger xylanase A on Fe3O4-coated chitosan magnetic nanoparticles for xylooligosaccharide preparation

Aspergillus niger xylanase A (XylA) was immobilized onto Fe₃O₄-coated chitosan magnetic nanoparticles prepared by the layer-by-layer self-assembly approach. The Fe₃O₄-coated chitosan magnetic nanoparticles showed a high binding capacity of 162.2 mg ∙ g^− 1-particles and a recovery activity of 56.5% for XylA. The immobilized XylA showed improved thermostability and storage stability compared with free XylA. The immobilized XylA retained 87.5% activity after seven successive reactions by magnetic separation. Xylotriose and xylohexaose were the main products released from birchwood xylan and wheat bran insoluble xylan by immobilized XylA, respectively.     

Magneto-optical investigation and hyperfine interactions of copper substituted Fe3O4 nanoparticles

Copper substituted Fe₃O₄ nanoparticles (NPs) (Cu_xFe_1−xFe₂O₄ (0.0≤x≤1.0)) were synthesized by polyol method and the effect of Cu²⁺ substitution on structural, magnetic and optical properties of Fe₃O₄ was investigated. X-ray diffraction (XRD), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), UV–Visible spectroscopy and Vibrating sample magnetometer (VSM) were used to study the physical properties of the products. The room temperature (RT) magnetization (σ–H) curves revealed the superparamagnetic nature of the products. The extrapolated specific saturation magnetization (σ_s) decreases from 42.69 emu/g to 14.14 emu/g with increasing Cu content (x). The particle size dependent Langevin fit studies were applied to determine the magnetic particle dimensions (D_mag). The average magnetic particle diameter is about 9.89 nm. The observed magnetic moments of NPs are in range of (0.61–1.77) µ_B and rather less than 4 µ_B of bulk Fe₃O₄ and 1 µ_B of bulk CuFe₂O₄. Magnetic anisotropy was assigned as uniaxial and calculated effective anisotropy constants (K_eff) are between 10.89×10⁴ Erg/g and 26.95×10⁴ Erg/g. The average value of magnetically inactive layer for Cu_xFe_1−xFe₂O₄ NPs was calculated as 1.23 nm. The percent diffuse reflectance spectroscopy (DR%) and Kubelka–Munk theory were applied to determine the energy band gap (E_g) of NPs. The extrapolated optical E_g values from Tauc plots are between minimum 1.98 eV to 2.31 eV. From 57Fe Mössbauer spectroscopy data, the variation in line width, isomer splitting, quadrupole splitting and hyperfine magnetic field values on Cu⁺² ion substitution have been determined. Although, the Mössbauer spectra for the sample x=0.2 and 0.8 are composed of paramagnetic doublets, ferromagnetic sextets were also formed for other products.     

Synthesis,characterization of Fe3O4@glycine doped polypyrrole magnetic nanocomposites and their potential performance to remove toxic Cr(VI)

Fe₃O₄ coated glycine doped polypyrrole magnetic nanocomposite (Fe₃O₄@gly-PPy NC) was prepared via coating of suspended Fe₃O₄ nanoparticles with gly-PPy. FE-SEM and HR-TEM images indicated that Fe₃O₄ nanoparticles were encapsulated by precipitating gly-PPy moieties. Chromium(VI) adsorption followed a Langmuir isotherm with maximum capacity of 238–303 mg/g for a temperature range of 25–45 °C at pH 2. The adsorption process was governed by the ionic interaction and the reduction of Cr(VI) to Cr(III) by the PPy moiety. Results showed that NCs are effective adsorbents for the removal of Cr(VI) from wastewater and can be separated by external magnetic field from the reactor.     

Magnetic porous carbons with high adsorption capacity synthesized by a microwave-enhanced high temperature ionothermal method from a Fe-based metal-organic framework

Magnetic porous carbons with high surface areas were easily synthesized from a Fe-based metal-organic framework (MOF) by a novel microwave-enhanced high temperature ionothermal method. By choosing a Fe-based MOF called MIL-100(Fe) as both a Fe and C precursor and a porous template, and furfuryl alcohol as a second precursor, a series of γ-Fe₂O₃/C composites with strong magnetism were prepared in 3 min by a microwave-enhanced high temperature ionothermal method. Structure, morphology and magnetic property, as well as porosity of the products, were carefully studied by powder X-ray diffraction, X-ray photoelectron spectroscopy, the BET surface area method, thermogravimetry, vibrating sample magnetometry, scanning electron microscopy, and high resolution transmission electron microscopy. The obtained γ-Fe₂O₃/C composites possess both high surface areas and magnetic characteristics. Their adsorption properties were preliminarily tested by the adsorptive removal of methylene blue from aqueous solution. The results suggest that such magnetic carbon composite exhibited high adsorption capacity (303.95 mg g⁻¹) and fast adsorption kinetics, as well as a perfect magnetic separation performance (M_s = 4.12–19.54 emu g⁻¹), for the MB removal from aqueous solution.     

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.     

Sorption of phenol from aqueous solution by novel magnetic polysulfone microcapsules containing Cyanex 923

This paper describes the sorption of phenol from aqueous solution by using novel magnetic polysulfone (PSF) microcapsules containing Fe₃O₄ nanoparticles and mixture of trialkyl-phosphine oxides (Cyanex 923) (Cyanex 923/Fe₃O₄@PSF microcapsules). The preparation of the Cyanex 923/Fe₃O₄@PSF microcapsules was based on the phase-inversion technique. The prepared microcapsules were characterized by using Fourier Transform Infrared Spectroscopy (FT-IR), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and Vibrating Sample Magnetometer (VSM). Fe₃O₄ nanoparticles in the microcapsules provided easier separation via application of external magnetic field. The experiments indicated that phenol could be removed from aqueous solution at a pH range between 3 and 9. The Cyanex 923/Fe₃O₄@PSF microcapsules prepared with dispersed phase containing 3.35% of Cyanex 923 (by wt.) provided the highest removal. The sorption reached an equilibrium in 120 min and it obeyed the pseudo-second order kinetic model. The non-linear Chi-square (χ²) statistical test showed that Langmuir isotherm model better represented the sorption data in comparison to Freundlich and Redlich–Peterson models. The Langmuir sorption capacity (Q_o) and sorption constant (b) were 0.664 mmol/g and 0.855 L/mmol, respectively. The regenerated microcapsules could be used five times with no change in their sorption capacity and magnetic separability.     

New LiNi0.5PrxFe2−xO4 nanocrystallites: Synthesis via low cost route for fabrication of smart advanced technological devices

Praseodymium substituted nano-crystalline Li-Ni spinel ferrites with different Pr³⁺ contents were synthesized by micro-emulsion method. X-ray diffraction (XRD), scanning electron spectroscopy (SEM) and vibrating sample magnetometery (VSM) techniques were employed to study the impact of substitution of the Pr³⁺ on the structure, surface morphology and magnetic parameters. XRD confirmed the formation of the single phase spinel ferrites of all compositions of LiNi_0.5Pr_xFe_2−xO₄ nanocrystallites. The crystallite size determined from XRD data by Scherrer formula was calculated in range from 40 nm to 70 nm. However the nanoparticles size estimated by SEM was found 35–115 nm. The room temperature VSM measurements were carried out in the applied field range from “−10,000 Oe” to “10000” Oe. Saturation magnetization (M_S) (41 emu/g) and coercivity (H_C) values (156.9 Oe) of LiNi_0.5Fe₂O₄ were improved by the addition of rare earth Pr³⁺ cations. The value of Hc is low, which is a strong indication of soft ferrites. The synthesized LiNi_0.5Pr_xFe_2−xO₄ ferrites may be utilized for low core losses on transformers.     

Heat generation properties in AC magnetic field for Y3Fe5O12 powder material synthesized by a reverse coprecipitation method

Ferrimagnetic Y₃Fe₅O₁₂ powder was synthesized by a reverse coprecipitation method in order to study its heat generation property in an AC magnetic field. An orthorhombic YFeO₃ phase having a small particle size (<100 nm) was obtained for the samples calcined at a low temperature. The maximum heat generation ability in an AC magnetic field was obtained for the Y₃Fe₅O₁₂ ferrite powder by calcination at 1100 °C. The heat generation ability was reduced for the samples calcined at a higher temperature. The particle growth with the formation of the cubic single phase might influence the heat generation ability. The heat generation ability and the hysteresis loss value were proportional to the cube of the magnetic field (H³), because the coercivity value of the B–H curve was proportional to the square of the amplitude of the AC magnetic field (H²). The heat generation ability (W g⁻¹) of the Y₃Fe₅O₁₂ sample sintered at 1100 °C can be expressed by the equation 2.2×10⁻⁴∙f∙H³ using the frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which has the highest heat generation ability of the reported magnetic materials. The hysteresis loss value for the B–H curve agreed with the heat generation ability of the samples calcined at 1100 °C and lower temperatures.     

Microemulsion-mediated hydrothermal growth of pagoda-like Fe3O4 microstructures and their application in a lithium–air battery

This paper reported the growth of novel pagoda-like Fe₃O₄ particles via a facile microemulsion-mediated hydrothermal procedure. The chemical compositions and morphologies of the as-grown Fe₃O₄ particles were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), and field emission scanning electron microscopy (FE-SEM). The morphologies of the as-prepared sample evolved from pagoda-like to pinwheel-like to flower-like shapes with increasing reaction time. In addition, the NaOH concentration and polyethylene glycol (PEG)-2000 had key effects on the formation of the final product. The electrocatalytic properties of the prepared pagoda-like micro-Fe₃O₄, as catalytic materials for a lithium–air battery, were further evaluated by galvanostatic charge/discharge cycling and electrochemical impedance spectrometry (EIS). Results showed that the cell displayed an initial discharge capacity of 1429 mA h g⁻¹ at a voltage of 1.5–4.5 V at 100 mA g⁻¹.     

Co-precipitation of a Ni–Zn ferrite precursor powder: Effects of heat treatment conditions and deagglomeration on the structure and magnetic properties

A Ni–Zn ferrite precursor powder was synthesized by co-precipitation upon adding ammonia to an aqueous solution of the precursor iron, nickel, and zinc nitrate salts. The powder was calcined at a range of temperatures (200–1200 °C) and the crystalline phase evolution was assessed by X-ray diffraction coupled with Rietveld refinement. Intermediate phases (NiFe₂O₄ and Fe₂O₃) with increasing crystallinity coexisted in the system up to 1000 °C. The required Ni_0.8Zn_0.2Fe₂O₄ phase could only be attained at 1200 °C. The magnetic properties measured using a vibrating sample magnetometer revealed high magnetization saturation level (～59 emu/gm) above 400 °C. The coercivity showed a steady decrease with increasing heat treatment temperature, leading to a change from a hard to soft magnetic state. The BET specific surface area and the SEM morphology were found to be dependent on calcination temperature, atmosphere (air or N₂) and on the milling procedure.     

Polymer-derived mesoporous Ni/SiOC(H) ceramic nanocomposites for efficient removal of acid fuchsin

In this paper, magnetic porous Ni-modified SiOC(H) ceramic nanocomposites (Ni/SiOC(H)) were successfully prepared via a template-free polymer-derived ceramic route, which involves pyrolysis at 600 °C of nickel-modified allylhydridopolycarbosilane (AHPCS-Ni) precursors synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with nickel(II)acetylacetonate (Ni(acac)₂). The resultant Ni/SiOC(H) nanocomposites are comprised of in-situ formed nanoscaled Ni socialized with small amounts of NiO and nickel silicides embedded in the amorphous SiOC(H) matrix. The materials show ferromagnetic behavior and excellent magnetic properties with the saturation magnetization in the range of 1.71–7.08 emu g⁻¹. Besides, the Ni/SiOC(H) nanocomposites are predominantly mesoporous with a high BET surface area and pore volume in the range of 253–344 and 0.134–0.185 cm³ g⁻¹, respectively. The measured porosity features cause an excellent adsorption capacity towards a template dye acid fuchsin with the adsorption capacity Q_t at 10 min of 80.7–85.8 mg g⁻¹ and the Q_e at equilibrium of 123.8–129.8 mg g⁻¹.     

A facile method for preparation of iron based catalysts for high temperature water gas shift reaction

Nanocrystalline Fe₃O₄ based catalysts with theoretical particle size of 31–78 nm were synthesized by a facile direct pyrolysis method and employed in high temperature water gas shift reaction. XRD analysis showed that this method led to obtaining the catalysts directly in the active phase with chromium and copper incorporated into magnetite lattice. The results showed that the addition of chromium significantly increases the BET surface area of the pure iron oxide from 14.87 to 35.42 m² g⁻¹. Among the catalysts evaluated, Fe–Cr–Cu catalyst revealed higher activity compared to commercial catalyst and showed high stability during 10 h time on stream.     

Structural,magnetic, and textural properties of iron oxide-reduced graphene oxide hybrids and their use for the electrochemical detection of chromium

Superparamagnetic Fe₃O₄ nanoparticles were anchored on reduced graphene oxide (RGO) nanosheets by co-precipitation of iron salts in the presence of different amounts of graphene oxide (GO). A pH dependent zeta potential and good aqueous dispersions were observed for the three hybrids of Fe₃O₄ and RGO. The structure, morphology and microstructure of the hybrids were examined by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, Raman and X-ray photoelectron spectroscopy. TEM images reveal lattice fringes (d₃₁₁ = 0.26 nm) of Fe₃O₄ nanoparticles with clear stacked layers of RGO nanosheets. The textural properties including the pore size distribution and loading of Fe₃O₄ nanoparticles to form Fe₃O₄–RGO hybrids have been controlled by changing the concentration of GO. An observed maximum (～10 nm) in pore size distribution for the sample with 0.25 mg ml^?1 of GO is different from that prepared using 1.0 mg ml^?1 GO. The superparamagnetic behavior is also lost in the latter and it exhibits a ferrimagnetic nature. The electrochemical behavior of the hybrids towards chromium ion was assessed and a novel electrode system using cyclic voltammetry for the preparation of an electrochemical sensor platform is proposed. The textural properties seem to influence the electrochemical and magnetic behavior of the hybrids.     

Structural,morphological and magnetic parameters investigation of multiferroic (1-x)Bi2Fe4O9- xCoFe2O4 nanocomposite ceramics

(1-x)Bi₂Fe₄O₉- xCoFe₂O₄ (0.0≤ x ≤1.0) multiferroic nanocomposites were prepared by wet chemical procedures combining reverse chemical co-precipitation and Pechini-type sol–gel techniques followed by mechanical blending process. The XRD and SAED results showed that the diffraction patterns are perfectly indexed to the constituent phases present in composite samples. The crystallite sizes of the constituent phases were 35.4 and 39.4 nm for cobalt and bismuth ferrites, respectively. The characteristic peaks in FT-IR spectra confirmed formation and purity of all specimens. FESEM micrographs revealed the uniform phase distribution with the mean grain size of approximately 40 and 230 nm for CoFe₂O₄ and Bi₂Fe₄O₉, respectively. TEM micrograph indicated suitable distribution in the as-prepared composite sample. The VSM results revealed that saturation and remnant magnetization increase by increasing CFO content in composites. Based on the results obtained from M-H curves, magnetic properties of composites did not originate only from linear combination of parent phases. The recorded coercivity values of all nanocomposites, for example 1443 Oe for x = 0.4 were higher than those of each parent phase i.e. 708 Oe for CoFe₂O₄ and 149 Oe for Bi₂Fe₄O_9, showing a noticeable improvement in magnetic properties.     

Preparation of mullite monoliths with well-defined macropores and mesostructured skeletons via the sol–gel process accompanied by phase separation

Mullite monoliths with well-defined macropores and mesostructured skeletons have been prepared via the sol–gel process accompanied by phase separation in the presence of poly(ethylene oxide) (PEO). Gelation of Al₂O₃–SiO₂ binary system with chloride salts as an additional precursor has been mediated by propylene oxide (PO) as an acid scavenger, while PEO worked as a phase-separation inducer. The dried gel and that heat-treated at 800 °C are amorphous, and γ-Al₂O₃ or Si–Al spinel phase nanocrystals are crystallized at 900–1000 °C. After heat-treated at and above 1100 °C for 5 h, the complete crystalline mullite is generated, and the macroporous monoliths in large dimensions of more than 15 mm × 15 mm × 10 mm are obtained. Heat-treatment at 200–1400 °C does not basically spoil the macroporous structure of monoliths, while decreases the macropore size and significantly alters the phase compositions and micro-mesoporous structure.