Magnetic Hybrids Research Articles

High-entropy TiVNbMoC3Tx MXene hybrid with balanced dielectric-magnetic loss for high-efficient electromagnetic wave absorption with environmental stability

With the advent of the 5G era, there is a growing demand for electromagnetic wave (EMW) absorbers that offer both efficient absorption and improved environmental stability. Transition metal carbides/carbonitrides (MXene), with their atomic-layered structures and high electrical conductivity, offer substantial potential for crafting efficient electromagnetic functional materials. Yet, enhancing the antioxidant capabilities and addressing the poor loss mechanisms of traditional MXene absorbers remain challenging tasks. In this context, a TiVNbMoC3Tx high-entropy MXene (HE-MXene) and its magnetic hybrids were synthesized for the first time. The unique multicomponent structure of high-entropy MXene reduces grain boundary formation, thereby slowing the progression of oxidation reactions. The incorporation of magnetic nanoparticles induces interface polarization loss or strong magnetic coupling, thereby enhancing EMW attenuation. These magnetic HE-MXene hybrids demonstrated a minimum reflection loss of −57.59 dB at a matching thickness of 1.46 mm and an effective absorption bandwidth (EAB) of 4.72 GHz at a thickness of 1.53 mm. Furthermore, the magnetic hybrids also exhibited outstanding oxidation and electrochemical corrosion resistance. This research provides valuable theoretical insights for the development of electromagnetic composites within high entropy (HE) systems, showcasing significant potential for long-term applications.

Trametes versicolor Laccase-Based Magnetic Inorganic-Protein Hybrid Nanobiocatalyst for Efficient Decolorization of Dyes in the Presence of Inhibitors.

In the present investigation, an ecofriendly magnetic inorganic-protein hybrid system-based enzyme immobilization was developed using partially purified laccase from Trametes versicolor (TvLac), Fe3O4 nanoparticles, and manganese (Mn), and was successfully applied for synthetic dye decolorization in the presence of enzyme inhibitors. After the partial purification of crude TvLac, the specific enzyme activity reached 212 U∙mg total protein-1. The synthesized Fe3O4/Mn3(PO4)2-laccase (Fe3O4/Mn-TvLac) and Mn3(PO4)2-laccase (Mn-TvLac) nanoflowers (NFs) exhibited encapsulation yields of 85.5% and 90.3%, respectively, with relative activities of 245% and 260%, respectively, compared with those of free TvLac. One-pot synthesized Fe3O4/Mn-TvLac exhibited significant improvements in catalytic properties and stability compared to those of the free enzyme. Fe3O4/Mn-TvLac retained a significantly higher residual activity of 96.8% over that of Mn-TvLac (47.1%) after 10 reuse cycles. The NFs showed potential for the efficient decolorization of synthetic dyes in the presence of enzyme inhibitors. For up to five reuse cycles, Fe3O4/Mn-TvLac retained a decolorization potential of 81.1% and 86.3% for Coomassie Brilliant Blue R-250 and xylene cyanol, respectively. The synthesized Fe3O4/Mn-TvLac showed a lower acute toxicity towards Vibrio fischeri than pure Fe3O4 nanoparticles did. This is the first report of the one-pot synthesis of biofriendly magnetic protein-inorganic hybrids using partially purified TvLac and Mn.

Highly efficient Cu(II) capture by salicylaldoxime functionalized magnetic polydopamine core-shell hybrids: Behavior and mechanism

Functionalized magnetic nanocomposites were considered as promising adsorbents owing to their abundant functional groups and ease of separation properties. Herein, we combined the solvothermal method with molecular copolymerization to synthesize a salicylaldoxime-grafted magnetic polydopamine (SMP) core-shell hybrid and exploited it for Cu(II) adsorption. The physicochemical properties of SMP were comprehensively studied by SEM, TEM, XRD, FT-IR, TGA, XPS, and VSM measurements. The results manifested that polydopamine acts as a bridge connecting magnetic iron oxide and salicylaldoxime to fabricated core-shell hybrids with rich functional groups. The batch experimental results showed that the Cu(II) adsorption was consumingly pH-reliant behavior, while adsorption data fitted the pseudo-second-order kinetic model and Langmuir isothermal model well, and the adsorption process achieved equilibrium within 60 min. Moreover, SMP exhibited remarkable anti-interference and can be recycled for 5 times with an inconspicuous decrease in adsorption performance. Importantly, salicylaldoxime functionalization endowed SMP with maximum Cu(II) adsorption capacity of 141.24 mg/g at pH 6.0 and 25 °C as compared with pure MP. Based on FT-IR and XPS study, the main adsorption mechanisms were proposed with a synergistic effect including a strong chemical chelation and partial Cu(II) reduction. Importantly, this strategy can be extended to multifunctional magnetic composites for Cu-contaminated wastewater cleanup.

A critical review on the removal of toxic pollutants from contaminated water using magnetic hybrids.

The persistence of organic/inorganic pollutants in the water has become a serious environmental issue. Among the different pollutants, dyes and heavy metal pollution in waterways are viewed as a global ecological problem that can have an impact on humans, plants, and animals. The necessity to develop a sustainable and environmentally acceptable approach to remove these toxic contaminants from the ecosystem has been raised. In the past two decades, rapid industrialization and anthropogenic activities in developed countries have aggravated environmental pollution. Industrial effluents that are discharged directly into the natural environment taint the water, which has a consequence for the water resources. Magnetic nanohybrids are broadly investigated materials used in the adsorption and photocatalytic degradation of poisonous pollutants present across water effluents. In the present review, the toxic health effects of heavy metals and dyes from the water environment have been discussed. This paper reviews the role of magnetic nanohybrids in the removal of pollutants from the water environment, providing an adequate point of view on their new advances regarding their qualities, connection methodologies, execution, and their scale-up difficulties.

Magneto-optics in a van der Waals magnet tuned by self-hybridized polaritons.

Controlling quantum materials with light is of fundamental and technological importance. By utilizing the strong coupling of light and matter in optical cavities1-3, recent studies were able to modify some of their most defining features4-6. Here we study the magneto-optical properties of a van der Waals magnet that supports strong coupling of photons and excitons even in the absence of external cavity mirrors. In this material-the layered magnetic semiconductor CrSBr-emergent light-matter hybrids called polaritons are shown to substantially increase the spectral bandwidth of correlations between the magnetic, electronic and optical properties, enabling largely tunable optical responses to applied magnetic fields and magnons. Our results highlight the importance of exciton-photon self-hybridization in van der Waals magnets and motivate novel directions for the manipulation of quantum material properties by strong light-matter coupling.

Separation and purification of target flavonoids using covalently connected MOFs@boronic acid-functionalized-COFs magnetic hybrids: Precise identification and enhanced stability

The magnetic boronate based sorbents have been widely used to separation of cis-diol containing flavonoids. However, It's still challenging due to its chemical structural fragility and low grafting efficiency. The major obstacles are low concentration, the hydrophobicity of flavoniods, and complexity of crude extract solutions. For solving these problems, a new kind of covalently connect MOF@boronic acid-functionalized-COFs core–shell hybrid composites based on magnetic colloidal nanocrystal clusters (MCNCs), MCNCs@NH2-UiO-66@BTCA-BA-COFs, with high surface area, abundant binding sites and excellent chemical and structurally stability were synthesized for enhancing the structure stability and selective recognition efficiency. The alkynylation COFs were not only to be facilely grated on the surface of magnetic microsphere@NH2-UiO-66 via Schiff-based reaction but also beneficial to the further modification of azide phenylboronic acid group via click reaction. Such mentioned advantages and covalently connect click strategy could generate highly structure stable and strong binding sites for the template flavonoids (Naringin, NRG). Adsorption equilibrium experiments were reached rapidly within 120 min, and the maximum equilibrium binding capacities of MCNCs@PDA@NH2-UiO-66@BTCA-BA-COFs were 31.20 µmol g−1 for NRG. Moreover, MCNCs@PDA@NH2-UiO-66@BTCA-BA-COFs exhibited a stronger selectivity towards NRG than other competitive targets (i.e rutin, catechol, hesperetin, o-nitrophenol). The MCNCs@PDA@NH2-UiO-66@BTCA-BA-COFs have shown outstanding reusability of 91.99 % loss in enrichment performance towards NRG after seven times repeatedly. The obtained MCNCs@PDA@NH2-UiO-66@BTCA-BA-COFs-based mass spectrum (MS) methods were applied to analyze the purity of NRG products. As excepted, a commercially available NRG with purity (approximately 60 %) could be effectively extracted and concentrated to 93.15 % purity. More interestingly, the separation performance of the sorbents was influenced by hydrophilic and hydrophobic performance. This approach provided an idea for constructing a new kind of hybrid sorbents with both enhanced functionality, suitable hydrophobic performance and fast magnetic-response behavior, which is of great significance to the field of separation and purification of hydrophobic flavonoids.

Photocatalytic debromination enhancement of Ph-C≡C-Cu by Fe3O4 modification

A series of Fe3O4/Ph-C≡C-Cu magnetic hybrids were synthesized by a repeatable photothermal method in this work. The structure and morphology studies proved that Ph-C≡C-Cu grow on the surface of Fe3O4 in a different way, which significantly affected its physical properties and photocatalytic performance. With 4% Fe3O4 modification, the photocatalytic degradation rate of high concentration of pentabromophenol (PBP, 3 ×10−4 M) achieved the highest, which is 6 times higher than those of pure Ph-C≡C-Cu and Fe3O4. The degradation of hexabromobenzene (HBB) over Ph-C≡C-Cu was also improved to be twice higher. The excellent photocatalytic activity of Fe3O4/Ph-C≡C-Cu can be attributed to the big surface area, high carrier generation, transfer and separation efficiency. The TONs exceed 1 of both PBP and HBB degradation demonstrates real photocatalytic processes.

Rational design of stimuli‐responsive magnetic polymer hybrid (nano)materials

AbstractCombining organic and inorganic materials is a fascinating strategy to produce hybrid materials that combine the advantages of both polymeric and inorganic materials. Among the various types of organic–inorganic hybrids, stimuli‐responsive magnetic polymer hybrids (RMPHs) are particularly promising materials for a wide variety of applications. While the magnetic properties are generally provided by the presence of magnetic nanoparticles, such as iron oxide nanoparticles, the polymeric compound brings the stimuli‐responsiveness, e.g. responsiveness to pH, temperature, redox reaction or irradiation. Furthermore, as the chemical structure and architecture of the polymeric materials are diverse and easily tunable, stimuli‐RMPHs have found applications in various domains, including catalysis, biotechnology, (bio)imaging and cancer therapy. Given the importance of the hybrids' shape and morphology for the targeted application, this review presents the possible synthetic strategies to rationally design stimuli‐RMPHs of various morphologies ranging from nanometric core–shell structures to nanogels, microgels and membranes. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Enzyme assisted magnetic hybrids as self-activated cascade reagent with synergistic activity for antimicrobial application

The abuse of antibiotics seriously threatens the public health, which leads to the urgent need to develop novel antimicrobial strategies. Reactive oxygen species (ROS) have been considered as an alternative approach for bacterial inactivation. At present, magnetic materials, especially iron oxide (Fe3O4) nanoparticles have gained widely application in biomedical field. Owing to the intrinsic peroxidase-like activity, Fe3O4 can catalyze the decomposition of hydrogen peroxide (H2O2) to generate hydroxyl radical (⋅OH) under acidic conditions. Recently, Fe3O4-based peroxidase mimics have been developed for wound infection therapy. However, the direct introduction of H2O2 with relative high concentration may induce undesired effect to normal tissues, and the infection site with near neutral pH still limits the antibacterial efficiency. Herein, carboxyl modified Fe3O4 immobilized silver nanoparticles (Ag NPs) and glucose oxidase (GOx) were synthesized as a self-activated cascade regent. GOx endowed the hybrids with catalytic activity, which could convert glucose into gluconic acid, which activated the peroxidase-like activity of Fe3O4 by decreasing the pH value. Moreover, the self-supplied H2O2 was subsequently catalyzed by Fe3O4 to generate ⋅OH. By combining the excellent antimicrobial performance of Ag NPs, the enzyme assisted magnetic hybrids exhibited robust antibacterial activity, which exhibited a great potential in bacteria-infected wound therapy.

Surface Plasmon Resonance Biosensors with Magnetic Sandwich Hybrids for Signal Amplification.

The conventional signal amplification strategies for surface plasmon resonance (SPR) biosensors involve the immobilization of receptors, the capture of target analytes and their recognition by signal reporters. Such strategies work at the expense of simplicity, rapidity and real-time measurement of SPR biosensors. Herein, we proposed a one-step, real-time method for the design of SPR biosensors by integrating magnetic preconcentration and separation. The target analytes were captured by the receptor-modified magnetic nanoparticles (MNPs), and then the biotinylated recognition elements were attached to the analyte-bound MNPs to form a sandwich structure. The sandwich hybrids were directly delivered to the neutravidin-modified SPR fluidic channel. The MNPs hybrids were captured by the chip through the neutravidin–biotin interaction, resulting in an enhanced SPR signal. Two SPR biosensors have been constructed for the detection of target DNA and beta-amyloid peptides with high sensitivity and selectivity. This work, integrating the advantages of one-step, real-time detection, multiple signal amplification and magnetic preconcentration, should be valuable for the detection of small molecules and ultra-low concentrations of analytes.

Progress in graphene-based magnetic hybrids towards highly efficiency for microwave absorption

• Graphene-based magnetic microwave absorption materials (MAMs) is classified according to their components including magnetic metal, multiple alloy and metal-free hybrids. • Special structural features and regulation strategies of graphene-based magnetic MAMs are introduced. • Challenges and prospects based on graphene-based magnetic MAMs are prospected. Nowadays, the yearning for microwave absorption materials (MAMs) are more and more urgent for dealing with the increasingly serious electromagnetic pollution and the demand of modern military security. Among potential candidates, the graphene (GE) based magnetic hybrids have advantages in structural controllable and designing flexibility, providing opportunities for achieving highly efficiency of microwave absorption (MA). Thus, the structural regulation and MA performances of GE-based magnetic hybrids arouse great attention in related fields. In this review, we summarize the recently progress in MA performance of GE-based magnetic hybrids. Typical absorption process and corresponding mechanism are firstly introduced, for guiding the design of GE-based magnetic MAMs. Then, the magnetic components, synthesis methods, structural features and regulation strategies of these GE-related magnetic materials are reviewed, and their influences on MA performances have also been discussed. Challenges, and prospects of the GE-based magnetic MAMs are suggested. This review provides a brief but systematic introduction to GE-based magnetic MAMs, which may pave the way for the design of MAMs with highly efficient MA performances.

Recent Advances of Magnetic Gold Hybrids and Nanocomposites, and Their Potential Biological Applications

Magnetic gold nanoparticles (mGNP) have become a great interest of research for nanomaterial scientists because of their significant magnetic and plasmonic properties applicable in biomedical applications. Various synthetic approaches and surface modification techniques have been used for mGNP including the most common being the coprecipitation, thermal decomposition, and microemulsion methods in addition to the Brust Schiffrin technique, which involves the reduction of metal precursors in a two-phase system (water and toluene) in the presence of alkanethiol. The hybrid magnetic–plasmonic nanoparticles based on iron core and gold shell are being considered as potential theranostic agents. In this critical review, in addition to future works, we have summarized recent developments for synthesis and surface modification of mGNP with their applications in modern biomedical science such as drug and gene delivery, bioimaging, biosensing, and neuro-regeneration, neuro-degenerative and arthritic disorders. This review includes techniques and biological applications of mGNP majorly based on research from the previous six years.

Enhanced phosphate remediation of contaminated natural water by magnetic zeolitic imidazolate framework-8@engineering nanomaterials (ZIF8@ENMs)

The efficient enrichment and reutilization of phosphate from natural water still remains a daunting challenge to satisfy the increasingly stringent phosphate discharge criteria. In response to this problem, the presented study successfully synthesizes a series of magnetic zeolitic imidazolate framework-8@engineering nanomaterials (ZIF8@ENMs) via a two-step hydrothermal and coprecipitation method by facilely growing ZIF8 and/or Fe3O4 on various functional ENMs. Structure morphology, chemical composition and hysteresis curve characterizations demonstrate the successful formation of magnetic Fe3O4-ZIF8@ENM. Amongst the prepared magnetic ZIF8@ENMs hybrids, the Fe3O4-ZIF8@ENMs possessing massive hydroxyl groups is demonstrated to harvest the maximum adsorption capacity of 441.7 mg g−1 under neutral condition. Such-acquired adsorption capacity evidently surpass state-of-the-art adsorbents. Systematic assessment of the chemical condition effects on phosphate removal, revealing its conspicuous merits of robust pH independence (94.63–98.20%), high selectivity pinpointing phosphate within complex cations, ease-of-separation and satisfactory recycle. The outstanding performance of magnetic ZIF8@ENMs are mainly derived from the formed strong ZnOP, FeOP and electrostatic interactions between phosphate and adsorbents. Along this line, designing magnetic MOFs-based hybrids towards phosphate are anticipated to be promising avenues for advanced treatment of phosphate-like contaminants and efficient recycle in practical applications.

Recycling of mining waste in the synthesis of magnetic nanomaterials for removal of nitrophenol and polycyclic aromatic hydrocarbons

Iron mining residues were successfully used in the fast and inexpensive sol-gel synthesis of magnetic hybrids (CoFe2O4/NOM), with water rich in natural organic matter (NOM) as solvent. XRD analyses revealed formation of the cobalt ferrite phase, while SEM and TEM images showed the formation of nanostructures. The hybrids obtained (HbSF and HbLM) providedexcellent rates of conversion (99%) of nitrophenol in short times of 50 and 120 s, respectively. The hybrids also showed high performance in the adsorption of PAHs,achieving removals of 75–88% (HbSF)and 72–81% (HbLM).This work contributes to the conversion of industrial operations from linear to cyclic processes.

Fabrication of graphitic carbon nitride functionalized P–CoFe2O4 for the removal of tetracycline under visible light: Optimization, degradation pathways and mechanism evaluation

In this study, nano-sized CoFe2O4 composites were prepared through co-precipitation process. Then the phosphorus-doped strong magnetic graphitic carbon nitride hybrids composites (P–CoFe2O4@GCN) was stemmed from the CoFe2O4 composites via the thermal polymerization method. The TEM results show that the CoFe2O4 nanoparticles have been successfully embedded into the graphitic carbon nitride (GCN). The BET specific surface area of P–CoFe2O4@GCN-1 could reach 36.91 m2/g, which was 5.38 times higher than that of GCN. Thus, it provided sufficient reaction active sites to enhance the photocatalytic activity for tetracycline (TC) decomposition. The results from the photocatalytic experiments showed that the degradation efficiency of TC by P–CoFe2O4@GCN-1 could reach 96.2% within 60 min, which is 3.19 times higher than that of GCN. The h+, O2•- and •OH radicals detected by the electron spin resonance (ESR) were responsible for the TC decomposition in the photocatalytic reaction system. Persulfate (PS) can further activate the hybrid mixture system, and the fitting model predicted by the response surface methodology (RSM) indicated that the maximum tetracycline removal could reach 99.6% within 30 min. In addition, the degradation intermediates of TC were detected by HPLC-MS and the photodegradation mechanism was discussed.

Preparation and characterization of PAni(CA)/Magnetic iron oxide hybrids and evaluation in adsorption/photodegradation of blue methylene dye

In this work hybrids of citric acid doped polyaniline and magnetic iron oxide (MOM) were prepared by in situ chemical polymerization and evaluated in blue methylene dye (MB) adsorption/photodegradation in aqueous medium. The samples were characterized by vibration absorption spectroscopy in the infrared region, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, Mössbauer spectroscopy, vibration sample magnetometry and electrical conductivity measurements using the four-point method. The characterization results showed that magnetic iron oxide consists of magnetite and maghemite phases with superparamagnetic behavior at room temperature. The hybrids materials present magnetic iron oxide particles dispersed in the polymer phase and electrical conductivity of the order of 10−2S cm−1 and showed adsorbent properties. The adsorption process prevails in relation to the photodegradation, but in the hybrids with higher content of MOM an increase in MB removal was observed under UV irradiation, with reduction of 99% of the dye concentration, indicating synergism between the MOM -polymer phases in the photocatalytic action. These results are related to the hybrids morphology.

Magnetic cellulose nanocrystals hybrids reinforced phase change fiber composites with highly thermal energy storage efficiencies

The intrinsic intermittence of solar energy raises the necessity for thermal energy storage (TES) systems to balance the contradiction between energy supply and demand energy. This work experimentally provides solid-liquid phase change materials (PCMs) with sufficient storage capacity and discharging rate to offer heating for agriculture products by enhancing heat transfer in phase change fiber composites (PCF). To achieve this, we prepared dipole responsive magnetic/solar-driven PCF composites reinforced with magnetic cellulose nanocrystals hybrids (MCNC). The obtained PCF/MCNC-5% showed excellent magnetic property with a saturation magnetization (MS) value of 1.3 emu/g and effective latent heat phase change enthalpies of 69.2 ± 3.5 J/g – 83.1 ± 4.2 J/g. More importantly, PCF/MCNC-5% showed robust high magnetic to thermal energy storage efficiency of 32.5 % and solar light accelerated energy storage efficiency of 58.5 %. These advantages make the PCF composites promising and more desirable for drying and preservation of the fruits and other agriculture products.

Facile synthesis of uniformly loaded Fe3O4–TiO2/RGO ternary hybrids for enhanced photocatalytic activities

Abstract Different from reported core-shell magnetic hybrids, Fe3O4–TiO2/RGO recyclable photocatalysts were synthesized by depositing both TiO2 and Fe3O4 nanoparticles homogeneously onto the graphene sheet through a facile one-pot hydrothermal approach. The unique structure can not only utilize the superior magnetism of Fe3O4 but also allow the photocatalytic property of Fe3O4 to full play, which can offer a synergistic effect with TiO2 and RGO. The characterization results of SEM and TEM demonstrated that Fe3O4 grains without the shell, as well as TiO2 particles, densely anchored onto RGO layers. According to the VSM analysis and cycle experiments, the as-prepared Fe3O4–TiO2/RGO catalyst maintained superior magnetism, stability and recycling performance. In particular, the photo-degradation ability of phenol was significantly affected by the molar ratio of iron to titanium and the optimized composites exhibited 96.6 mg g−1 total removal capacity under UV-light. The ESR spectra revealed that the uniform loaded Fe3O4 nanoparticles may further accelerate the transfer of photo-induced electrons, the designed structure of the ternary components in close contact with each other promotes the synergistic effect and the generation of hydroxyl radicals (·OH) and superoxide anion (O2·-). This work provides a novel facile fabrication of magnetic photocatalyst with uniformly loaded structure and outstanding photocatalytic performance, which has great application prospects in remediating organic contaminated water.

Controlling the Superconducting Transition by Rotation of an Inversion Symmetry-Breaking Axis

We consider a hybrid structure where a material with Rashba-like spin-orbit coupling is proximity coupled to a conventional superconductor. We find that the superconducting critical temperature T_{c} can be tuned by rotating the vector n characterizing the axis of broken inversion symmetry. This is explained by a leakage of s-wave singlet Cooper pairs out of the superconducting region, and by conversion of s-wave singlets into other types of correlations, among these s-wave odd-frequency pairs robust to impurity scattering. These results demonstrate a conceptually different way of tuning T_{c} compared to the previously studied variation of T_{c} in magnetic hybrids.

Magnetic bead-enzyme assemble for triple-parameter telomerase detection at single-cell level.

In this work, we developed a triple-parameter strategy for the detection of telomerase activity from cancer cells and urine samples. This strategy was developed based on magnetic bead-enzyme hybrids combined with fluorescence analysis, colorimetric assay, or adenosine triphosphate (ATP) meter as readout. The application of magnetic bead-enzyme hybrids has the advantages of magnetic separation and signal amplification. These detection methods can be used individually or in combination to achieve the optimal sensing performance and make the results more convincing. Among them, the ATP meter with portable size had easy operation and low cost, and this response strategy provided a higher sensitivity at the single-cell level. The designed strategy was suitable as naked-eye sensor and point-of-care testing (POCT) for rapid assaying of telomerase activity. Graphical abstract Magnetic bead-enzyme assemble for triple-parameter telomerase detection.