磁性TiO2/CoFe2O4纳米复合光催化材料的制备

以磁性CoFe2O4为核,采用改进的溶胶-凝胶法,制备了磁性TiO2/CoFe2O4纳米复合光催化材料.利用VSM(振动样品磁强计)技术对其磁性能进行了研究,结果表明:由该法所得的TiO2/CoFe2O4纳米复合光催化材料的饱和磁化强度虽稍弱于纯CoFe2O4纳米材料,但其矫顽力则优于CoFe2O4.TEM、XRD、UV-Vis等的结果表明,该纳米复合材料中的TiO2为锐钛矿结构;与TiO2相比,纳米复合材料对光的吸收拓展到了整个紫外-可见区,且吸收强度大大增强.对染料废水光催化降解的模拟研究表明,该复合材料在紫外光下,6 h可以使亚甲基蓝染料溶液的脱色率达95%,且重复使用3次时染料溶液的脱色率仍能保持在90%,明显优于纯TiO2.     

Hierarchical Fe3O4@TiO2 Yolk–Shell Microspheres with Enhanced Microwave‐Absorption Properties

A facile and efficient strategy for the synthesis of hierarchical yolk–shell microspheres with magnetic Fe₃O₄ cores and dielectric TiO₂ shells has been developed. Various Fe₃O₄@TiO₂ yolk–shell microspheres with different core sizes, interstitial void volumes, and shell thicknesses have been successfully synthesized by controlling the synthetic parameters. Moreover, the microwave absorption properties of these yolk–shell microspheres, such as the complex permittivity and permeability, were investigated. The electromagnetic data demonstrate that the as‐synthesized Fe₃O₄@TiO₂ yolk–shell microspheres exhibit significantly enhanced microwave absorption properties compared with pure Fe₃O₄ and our previously reported Fe₃O₄@TiO₂ core–shell microspheres, which may result from the unique yolk–shell structure with a large surface area and high porosity, as well as synergistic effects between the functional Fe₃O₄ cores and TiO₂ shells.     

等离子体修饰磁载TiO2光催化剂性能研究

以化学共沉法制备的CoFe₂O₄纳米粒子为磁核,采用TiCl₄水解包覆技术制备磁载二氧化钛纳米复合粒子CoFe₂O₄ /TiO_x(TCF),利用低温等离子体技术修饰TCF制备了CoFe₂O₄/TiO₂(PTCF)纳米复合光催化剂。运用VSM(振动样品磁强计)技术对样品磁性能进行研究,结果表明：等离子体修饰后的复合材料仍具有较高的饱和磁化强度,可在外加磁场作用下实现催化剂在水中的分离与回收;样品的XRD、TEM和UV-Vis分析测试结果表明：等离子体修饰后的复合材料有锐钛矿型TiO₂存在;TEM谱图显示磁核CoFe₂O₄的平均粒径约为20 nm,TCF复合粒子的粒径约为30~40 nm,TiO₂包覆层的厚度为10~20 nm。与纯TiO₂相比PTCF样品对光的吸收拓展到整个紫外-可见区,扩大了光谱响应范围;对甲基橙溶液降解的光催化活性评价研究表明：TCF复合粒子等离子体修饰后的PTCF纳米复合光催剂的光催化活性明显提高。     

Synthesis of Bi<Subscript>2</Subscript>O<Subscript>4</Subscript>@TiO<Subscript>2</Subscript> Heterojunction with Enhanced Visible Light Photocatalytic Activity

A novel Bi₂O₄@TiO₂ heterojunction was constructed by a simple two-step method. The charges migration between Bi₂O₄ and TiO₂ via the heterojunction improves the electron/hole separation efficiency. Furthermore, Bi₂O₄@TiO₂ heterostructures exhibit better adsorption capability for methyl orange molecular due to their higher specific surface area than pure Bi₂O₄. As a result, Bi₂O₄@TiO₂ hybrids show an improved visible light photocatalytic activity and photostability for the degradation of methyl orange.     

Preparation of magnetic Fe3O4/TiO2/Ag composite microspheres with enhanced photocatalytic activity

The novel three-component Fe₃O₄/TiO₂/Ag composite mircospheres were prepared via a facile chemical deposition route. The Fe₃O₄/TiO₂ mircospheres were first prepared by the solvothermal method, and then Ag nanoparticles were anchored onto the out-layer of TiO₂ by the tyrosine-reduced method. The as-prepared magnetic Fe₃O₄/TiO₂/Ag composite mircospheres were applied as photocatalysis for the photocatalytic degradation of methylene blue. The results indicate that the photocatalytic activity of Fe₃O₄/TiO₂/Ag composite microspheres is superior to that of Fe₃O₄/TiO₂ due to the dual effects of the enhanced light absorption and reduction of photoelectron–hole pair recombination in TiO₂ with the introduction of Ag NPs. Moreover, these magnetic Fe₃O₄/TiO₂/Ag composite microspheres can be completely removed from the dispersion with the help of magnetic separation and reused with little or no loss of catalytic activity.     

具有分级多孔结构和光催化性质的核-壳纳米球(HP-Fe2O3@TiO2)

通过溶剂热和溶胶-凝胶涂层法, 设计并制备了具有分级多孔结构和光催化性质的核-壳纳米球(HP-Fe₂O₃@TiO₂). 透射电子显微镜(TEM)照片证明所得HP-Fe₂O₃@TiO₂样品具备分级多孔结构, 这是因为HP-Fe₂O₃@TiO₂的内核-Fe₂O₃具有大孔空隙, 同时外壳-TiO₂具有介孔空隙. 此外, 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)以及氮气吸附-脱附曲线深入研究了HP-Fe₂O₃@TiO₂的结构及其性质. 分别在可见及紫外光照下, 研究了样品在H₂O₂体系下的光催化降解亚甲基蓝(MB)的性质. 所观察到的HP-Fe₂O₃@TiO₂纳米球的光催化性能, 可归因于核-壳结构的协同作用, 这进一步表明, TiO₂外壳对α-Fe₂O₃的光催化活性有重要影响作用. 在可见光照射下, HP-Fe₂O₃@TiO₂ (1 mL Ti(OC₄H₉)₄ (TBT))具有较优异的光催化活性. 同时, HP-Fe₂O₃@TiO₂ (4mL TBT)具备优异的单分散形貌, 并在紫外光照射下, 表现出最优的光催化活性.     

Fabrication and characterization of Fe_3O_4@SiO_2@TiO_2@Ho nanostructures as a novel and highly efficient photocatalyst for degradation of organic pollution

In this work we synthesize a novel and highly efficient photocatalyst for degradation of methyl orange and rhodamine B. In addition, a new method for synthesis of Fe_3O_4@SiO_2@TiO_2@Ho magnetic core-shell nanoparticles with spherical morphology is proposed. The crystal structures, morphology and chemical properties of the as-synthesized nanoparticles were characterized using Fourier transform infrared spectroscopy(FT-IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM), energy dispersive X-ray(EDS), X-ray diffraction(XRD), UV–vis diffuse reflectance spectroscopy(DRS) and vibrating sample magnetometer(VSM) techniques. The photocatalytic activity of Fe_3O_4@SiO_2@TiO_2@Ho was investigated by degradation of methyl orange(MO) as cationic dye and rhodamine B(Rh B) as anionic dye in aqueous solution under UV/vis irradiation. The results indicate that about 92.1% of Rh B and78.4% of MO were degraded after 120 and 150 min, respectively. These degradation results show that Fe_3O_4@SiO_2@TiO_2@Ho nanoparticles are better photocatalyst than Fe3O4@Si O2@TiO 2@Ho for degradation of MO and Rh B. As well as, the catalyst shows high recovery and stability even after several separation cycles.     

Photocatalysis enhancement of CaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>@TiO<Subscript>2</Subscript> composite powders

CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were synthesized by a sol–gel method under mild conditions (i.e. low temperature and ambient pressure). The as-prepared powders were characterized by transmission electron microscopy (TEM) and analyzed by X-ray diffraction (XRD). The photocatalytic behavior of the TiO₂-base surfaces was evaluated by the degradation of nitrogen monoxide gas. It suggested that CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were composed of anatase titania and that CaAl₂O₄:Eu²⁺, Nd³⁺. TiO₂ particles were deposited on the surface of CaAl₂O₄:Eu²⁺, Nd³⁺ to form uniform film. CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders exhibited higher photocatalytic activity compared with pure TiO₂ under visible light. And the result also clearly indicated that the long afterglow phosphor absorbed and stored lights for the TiO₂ to remain photocatalytic activity in the dark.     

Electrochemical performance of spindle-like Fe2Co-MOF and derived magnetic yolk-shell CoFe2O4 microspheres for supercapacitor applications

Nanostructured cobalt ferrite (CoFe₂O₄) has been synthesized by a two-step process, a facile ultrasonic-assisted solvothermal technique for Fe₂Co-MOF preparation and subsequent calcination. X-ray diffraction (XRD) patterns confirm the formation of MIL-88A(Fe) structure of Fe₂Co-MOF and the cubic spinel structure of CoFe₂O₄. Field emission scanning electron microscope (FESEM) images reveal that calcination process converts the spindle-like morphology of Fe₂Co-MOF to yolk-shell CoFe₂O₄ microspheres. From Brunauer–Emmett–Teller (BET) analysis, the specific surface areas of 36.0 and 29.2 m² g^?1 are measured for Fe₂Co-MOF and CoFe₂O₄, respectively. Vibrating sample magnetometer (VSM) analysis of CoFe₂O₄ displays high coercivity of 2500 Oe due to surface anisotropy. Conversion of Fe₂Co-MOF to CoFe₂O₄ reduces the optical band gap from 1.92 to 1.77 eV. Electrochemical performance of Fe₂Co-MOF and CoFe₂O₄ deposited on Ni foams (NFs) is examined by cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) tests. Specific capacitances of 489.9 and 192.6 F g^?1 have been achieved from GCD curves at a current density of 1 A g^?1 for Fe₂Co-MOF/NF and CoFe₂O₄/NF electrodes, respectively. Fe₂Co-MOF/NF electrode exhibits more cyclic stability than CoFe₂O₄/NF electrode after 3000 cycles.

     

Constructing a Visible-Active CoFe2O4@Bi2O3/NiO Nanoheterojunction as Magnetically Recoverable Photocatalyst with Boosted Ofloxacin Degradation Efficiency

Constructing visible-light-active Z-scheme heterojunctions has proven fruitful in enhancing the photocatalytic activity of photocatalysts for superior water clean-up. Herein, we report the fabrication of a CoFe₂O₄@Bi₂O₃/NiO (CBN) Z-scheme nanoheterojunction. The obtained CBN heterojunction was used for visible-light-assisted degradation of ofloxacin (OFL) in water. The OFL degradation efficiency achieved by the CBN heterojunction was 95.2% in 90 min with a rate constant of k_app = 0.03316 min⁻¹, which was about eight times that of NiO and thirty times that of CoFe₂O₄. The photocatalytic activity of a Bi₂O₃/NiO Z-scheme heterojunction was greatly enhanced by the visible activity and redox mediator effect of the cobalt ferrite co-catalyst. Higher charge-carrier separation, more visible-light capture, and the Z-scheme mechanism in the Z-scheme system were the important reasons for the high performance of CBN. The scavenging experiments suggested ^●O₂⁻ as an active species for superior OFL degradation. The possible OFL degradation pathway was predicted based on LC-MS findings of degradation intermediate products. The magnetic nature of the CBN helped in the recovery of the catalyst after reuse for six cycles. This work provides new insights into designing oxide-based heterojunctions with high visible-light activity, magnetic character, and high redox capabilities for potential practical applications in environmental treatment.     

Inactivation of Escherichia coli on Immobilized CuO/CoFe2O4‐TiO2 Thin‐Film under Simulated Sunlight Irradiation

Composite photocatalysts of CuO/CoFe₂O₄‐TiO₂ were successfully synthesized by a sol‐gel method and fixed on ordinary tiles. The photosterilization of Escherichia coli was examined on CuO/CoFe₂O₄‐TiO₂ thin films under a xenon lamp irradiation. The film was characterized by XRD, and the morphology was observed by SEM. Disinfection data indicated that CuO/CoFe₂O₄‐TiO₂ composite photocatalysts have the much better photocatalytic activity than CuO/CoFe₂O₄ and TiO₂. The optimized composition of the nanocomposites has been found to be m_CuO/CoFe2O4:m_TiO2=3:7, with loadings ranging from 790 to 1400 mg/m². The photocatalytic inactivated rate of E. coli (10⁵ CFU/mL) reached 98.4% under the xenon lamp of 150 W within 30 min.     

Preparation and characterization of a novel DABCO-based ionic liquid supported on Fe3O4@TiO2 nanoparticles and investigation of its catalytic activity in the synthesis of quinazolinones

In this study, quinazolinone derivatives have been synthesized via a suitable and efficient procedure by one-potmulti-component reactions of 3-amino-1,2,4-triazole or 2-aminobenzimidazole, dimedone and aromatic aldehydes in the presence of Fe₃O₄@TiO₂-IL as nanocatalyst under solvent-free condition. The products were prepared in good to excellent yields using Fe₃O₄@TiO₂-IL magnetic nanocatalyst. The Fe₃O₄@TiO₂ magnetic nanoparticles (MNPs) were prepared using beet juice extract and functionalized with IL based on DABCO. Moreover, the core-shell structured magnetic Fe₃O₄@TiO₂-IL has been characterized by different techniques such as ¹H-NMR, FT-IR, VSM, XRD, SEM, TGA, TEM and EDX. To the best of our knowledge, the prepared ionic liquid displayed a good protective and activator agent for magnetic nanocatalyst.     

Ultrasound-assisted synthesis of CoFe2O4/Ce-UiO-66 nanocomposite for photocatalytic aerobic oxidation of aliphatic alcohols

During the past years, light-driven selective oxidation of various alcohols has attracted increasing attention as a green and eco-friendly manner to convert visible light energy into valuable compounds. In this work, magnetic CoFe₂O₄/Ce-UiO-66 embedded structure composites are elaborately designed for the photocatalytic oxidation of aliphatic alcohols under visible-light irradiation and aerobic condition at room temperature. The CoFe₂O₄/Ce-UiO-66 structure was prepared using a simple and fast ultrasound-assisted technique in 60 min at room temperature. As compared with the unmodified CoFe₂O₄, the embedded composite exhibited better visible-light sensitization performance. The catalyst showed high chemical stability in the reaction conditions and can be recovered quickly and reused for at least five reaction runs in the aerobic oxidation reaction condition.     

Nano‐Fe3O4@TiO2/Cu2O Core‐shell Composite: A Convenient Magnetic Separable Catalyst for A3 and KA2 Coupling

An eco‐efficient one‐pot three component reaction between different aldehydes or ketones with alkynes and amines for the synthesis of propargylamines was performed using Fe₃O₄@TiO₂/Cu₂O as a nano‐magnetic composite under solvent free condition. The catalyst showed remarkable catalytic activity by decreasing the time of the reaction in comparison of other reported magnetic catalysts. In addition, the Fe₃O₄@TiO₂/Cu₂O can be easily recycled and reutilized for five times without apparent loss of catalytic activity.     

Olefins oxidation with molecular O2 in the presence of chiral Mn (III) salen complex supported on magnetic CoFe2O4@SiO2@CPTMS

In the present study, CoFe₂O₄@SiO₂@CPTMS nanocomposite was synthesized and the homogeneous chiral Mn‐salen complex was anchored covalently onto the surface of CoFe₂O₄@SiO₂@CPTMS nanocomposite. The heterogeneous Mn‐salen magnetic nanocatalyst (CoFe₂O₄@SiO₂@CPTMS@ chiral Mn (III) Complex) was characterized by different techniques including transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), powder X‐ray diffraction (XRD) and thermogravimetric analysis (TGA). Then, the aerobic enantioselective oxidation of olefins to the corresponding epoxide was investigated in the presence of magnetic chiral CoFe₂O₄@SiO₂@Mn (III) complex at ambient conditions within 90 min. The results showed the corresponding products were synthesized with excellent yields and selectivity. In addition, the heterogeneous CoFe₂O₄@SiO₂@ CPTMS@ chiral Mn (III) complex has benefits such as high selectivity and comparable catalytic reactivity with its homogeneous analog as well as mild reaction condition, facile recovery, and recycling of the heterogeneous catalyst.     

Removal of Chromium Ions by Fe3O4‐containing Polypyrrole Matrix and Environmental Applications

In this work, the PPy/Fe₃O₄@TiO₂ composite was synthesized and characterized by X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and magnetic measurements (using a vibrating sample magnetometer). The adsorption performance of PPy/Fe₃O₄@TiO₂ composite for Cr(VI) ions was evaluated by UV irradiation. The effects of pH, adsorbent dose, contact time, and the initial concentration on the adsorption performance of Cr(VI) onto PPy/Fe₃O₄@TiO₂ were investigated. The maximum adsorption capacity of Cr(VI) upon doped PPy/Fe₃O₄@TiO₂ is 85.30 mg/g at room temperature. The total adsorption process likely follows the Langmuir model and pseudo‐second‐order kinetics. Our study suggests that the PPy/Fe₃O₄@TiO₂ composite can be efficiently used for the adsorption of Cr(VI) ions.     

Facile Hydrogen‐Bond‐Assisted Polymerization and Immobilization Method to Synthesize Hierarchical Fe3O4@Poly(4‐vinylpyridine‐co‐divinylbenzene)@Au Nanostructures and Their Catalytic Applications

Hierarchical Fe₃O₄@poly(4‐vinylpyridine‐co‐divinylbenzene)@Au (Fe₃O₄@P(4‐VP–DVB)@Au) nanostructures were fabricated successfully by means of a facile two‐step synthesis process. In this study, well‐defined core–shell Fe₃O₄@P(4‐VP–DVB) microspheres were first prepared with a simple polymerization method, in which 4‐VP was easily polymerized on the surface of Fe₃O₄ nanoparticles by means of strong hydrogen‐bond interactions between ? COOH groups on poly(acrylic acid)‐modified Fe₃O₄ nanoparticles and a 4‐VP monomer. HAuCl₄ was adsorbed on the chains of a P(4‐VP) shell and then reduced to Au nanoparticles by NaBH₄, which were embedded into the P(4‐VP) shell of the composite microspheres to finally form the Fe₃O₄@P(4‐VP–DVB)@Au nanostructures. The obtained Fe₃O₄@P(4‐VP–DVB)@Au catalysts with different Au loadings were applied in the reduction of 4‐nitrophenol (4‐NP) and exhibited excellent catalytic activity (up to 3025 h^?1 of turnover frequency), facile magnetic separation (up to 31.9 emu g^?1 of specific saturation magnetization), and good durability (over 98 % of conversion of 4‐NP after ten runs of recyclable catalysis and almost negligible leaching of Au).     

Synthesis of orientedly bioconjugated core/shell Fe3O4@Au magnetic nanoparticles for cell separation

Orientedly bioconjugated core/shell Fe₃O₄@Au magnetic nanoparticles were synthesized for cell separation. The Fe₃O₄@Au magnetic nanoparticles were synthesized by reducing HAuCl₄ on the surfaces of Fe₃O₄ nanoparticles, which were further characterized in detail by TEM, XRD and UV-vis spectra. Anti-CD3 monoclonal antibody was orientedly bioconjugated to the surface of Fe₃O₄@Au nanoparticles through affinity binding between the Fc portion of the antibody and protein A that covalently immobilized on the nanoparticles. The oriented immobilization method was performed to compare its efficiency for cell separation with the non-oriented one, in which the antibody was directly immobilized onto the carboxylated nanoparticle surface. Results showed that the orientedly bioconjugated Fe₃O₄@Au MNPs successfully pulled down CD3⁺ T cells from the whole splenocytes with high efficiency of up to 98.4%, showing a more effective cell-capture nanostructure than that obtained by non-oriented strategy. This developed strategy for the synthesis and oriented bioconjugation of Fe₃O₄@Au MNPs provides an efficient tool for cell separation, and may be further applied to various fields of bioanalytical chemistry for diagnosis, affinity extraction and biosensor.     

Adsorption characteristics of Titan yellow and Congo red on CoFe2O4 magnetic nanoparticles

This paper assesses the adsorption characteristics of Titan yellow and Congo red on CoFe₂O₄ magnetic nanoparticles. The adsorption behavior of Titan yellow and Congo red from aqueous solution onto CoFe₂O₄ magnetic nanoparticles has been determined by investigating the effects of pH, concentration of the dye, amount of adsorbent, contact time, ionic strength and temperature. Experimental results indicated that CoFe₂O₄ nanoparticles can remove more than 98 % of each dye under optimum operational conditions of a dosage of 15.0 mg CoFe₂O₄, pH 3.0, initial dye concentration of 22–140 mg L^?1, and contact times of 2.0 and 15.0 min for Congo red and Titan yellow, respectively. Langmuir and Freundlich isotherm models have been used to evaluate the ongoing adsorption kinetic equations. Regeneration of the saturated adsorbent was possible by NaCl/acetone solution as eluent. The maximum adsorption capacities were 200.0 and 212.8 mg dye per gram adsorbent for Congo red and Titan yellow, respectively. With the help of adsorption isotherm, thermodynamic parameters such as free energy, enthalpy and entropy have been calculated. On the basis of pseudo-first-order and pseudo-second-order kinetic equations, different kinetic parameters have been obtained.     

Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of organic pollutants in water

In previous years, cobalt ferrite has gained huge consideration in the field of semiconductor photocatalysis for waste water treatment. Cobalt ferrite and its derivatives own tunable magnetic properties which results in higher absorption capability in comparison with other photocatalyst semiconductors. In the current review, a brief overview of CoFe₂O₄ as a semiconductor photocatalyst is presented and ferromagnetic behaviour of CoFe₂O₄ is also discussed. Few drawbacks such as agglomeration, photocorrosion and recombination rate of electrons-holes are also discussed. For the enhancement of photocatalytic action of cobalt ferrite, the role of cobalt ferrite with type I, type II, direct Z-scheme, solid state Z-scheme heterojunctions, Schottky and p-n heterojunctions based on different heterostructures were also discussed. In conclusive outlook formation of cobalt ferrite based heterojunctions is best approach for the enhancement of photocatalytic performance. This is because heterojunction formation enhanced the rate of charge separation and thus reduced the electron–hole recombination. Herein, this review highlights the CoFe₂O₄ based heterojunctions for the photodegradation of noxious organic pollutants in water. Furthermore, the future expectations and challenges in exploiting CoFe₂O₄ nanocomposites for water treatment, also discussed in precise conclusion of this review.