Magnetic Nanoparticle Composites: Synergistic Effects and Applications

Composite materials are made from two or more constituent materials with distinct physical or chemical properties that, when combined, produce a material with characteristics which are at least to some degree different from its individual components. Nanocomposite materials are composed of different materials of which at least one has nanoscale dimensions. Common types of nanocomposites consist of a combination of two different elements, with a nanoparticle that is linked to, or surrounded by, another organic or inorganic material, for example in a core-shell or heterostructure configuration. A general family of nanoparticle composites concerns the coating of a nanoscale material by a polymer, SiO2 or carbon. Other materials, such as graphene or graphene oxide (GO), are used as supports forming composites when nanoscale materials are deposited onto them. In this Review we focus on magnetic nanocomposites, describing their synthetic methods, physical properties and applications. Several types of nanocomposites are presented, according to their composition, morphology or surface functionalization. Their applications are largely due to the synergistic effects that appear thanks to the co-existence of two different materials and to their interface, resulting in properties often better than those of their single-phase components. Applications discussed concern magnetically separable catalysts, water treatment, diagnostics-sensing and biomedicine

Stable Iron Oxide Nanoflowers with Exceptional Magnetic Heating Efficiency: Simple and Fast Polyol Synthesis

Magnetically induced hyperthermia has reached a milestone in medical nanoscience and in phase III clinical trials for cancer treatment. As it relies on the heat generated by magnetic nanoparticles (NPs) when exposed to an external alternating magnetic field, the heating ability of these NPs is of paramount importance, so is their synthesis. We present a simple and fast method to produce iron oxide nanostructures with excellent heating ability that are colloidally stable in water. A polyol process yielded biocompatible single core nanoparticles and nanoflowers. The effect of parameters such as the precursor concentration, polyol molecular weight as well as reaction time was studied, aiming to produce NPs with the highest possible heating rates. Polyacrylic acid facilitated the formation of excellent nanoheating agents iron oxide nanoflowers (IONFs) within 30 min. The progressive increase of the size of the NFs through applying a seeded growth approach resulted in outstanding enhancement of their heating efficiency with intrinsic loss parameter up to 8.49 nH m2 kgFe-1. The colloidal stability of the NFs was maintained when transferring to an aqueous solution via a simple ligand exchange protocol, replacing polyol ligands with biocompatible sodium tripolyphosphate to secure the IONPs long-term colloidal stabilization

Synthesis of Fine-Tuning Highly Magnetic Fe@FexOy Nanoparticles through Continuous Injection and a Study of Magnetic Hyperthermia

Core@shell Fe@FexOy nanoparticles (NPs) have the potential to be promising tools for many applications, thanks to their combination of an iron core, with a high magnetic moment and an iron oxide shell which could protect the core from oxidation. However, the deterioration of NPs structure can lead to the shrinking of the core and the hollowing of the structure, diminishing the magnetic properties. The ability to retain the iron core under biomedically compatible conditions is desirable for many applications. In this paper, we have developed a synthetic method to produce core@shell α-Fe@FexOy NPs with tunable sizes and evaluated the retention of the stable magnetic α-Fe core upon exposure to air and after ligand exchange and its resulting effect on the magnetic hyperthermia. In particular, using a continuous injection of the precursor, we were able to finely tune the final size of the core@shell NPs producing four samples with average sizes of 12, 15, 18, and 20 nm. The structural properties of the particles were studied, and while the size increases, the chemical stability of the iron core is enhanced, and the magnetic properties improved accordingly. Particles larger than 20 nm were shown to be prone to aggregation, resulting in an abrupt increase of the particle size distribution. Two samples with high magnetization saturation value and low polydispersity, 15 and 18 nm, were transferred in water using a dopamine-functionalized poly(isobutylene-alt-maleic anhydride) polymer, resulting in colloidal stability over a wide range of pH and ionic strength comparable to physiological conditions. We found that the 18 nm particles retain their chemical properties over 2 months, with less oxidation of the Fe core; this results in a specific absorption rate (SAR) value of 660 W g−1 and intrinsic loss power (ILP) of 3.6 nHm2 kg−1 , while the 15 nm NPs resulted in the reduction of their properties due to oxidation of the core

Small iron oxide nanoparticles as MRI T1 contrast agent: scalable inexpensive water-based synthesis using a flow reactor

Small iron oxide nanoparticles (IONPs) were synthesised in water via co-precipitation by quenching particle growth after the desired magnetic iron oxide phase formed. This was achieved in a millifluidic multistage flow reactor by precisely timed addition of an acidic solution. IONPs (≤5 nm), a suitable size for positive T1 magnetic resonance imaging (MRI) contrast agents, were obtained and stabilised continuously. This novel flow chemistry approach facilitates a reproducible and scalable production, which is a crucial paradigm shift to utilise IONPs as contrast agents and replace currently used Gd complexes. Acid addition had to be timed carefully, as the inverse spinel structure formed within seconds after initiating the co-precipitation. Late quenching allowed IONPs to grow larger than 5 nm, whereas premature acid addition yielded undesired oxide phases. Use of a flow reactor was not only essential for scalability, but also to synthesise monodisperse and non-agglomerated small IONPs as (i) co-precipitation and acid addition occurred at homogenous environment due to accurate temperature control and rapid mixing and (ii) quenching of particle growth was possible at the optimum time, i.e., a few seconds after initiating co-precipitation. In addition to the timing of growth quenching, the effect of temperature and dextran present during co-precipitation on the final particle size was investigated. This approach differs from small IONP syntheses in batch utilising either growth inhibitors (which likely leads to impurities) or high temperature methods in organic solvents. Furthermore, this continuous synthesis enables the low-cost (<£10 per g) and large-scale production of highly stable small IONPs without the use of toxic reagents. The flow-synthesised small IONPs showed high T1 contrast enhancement, with transversal relaxivity (r2) reduced to 20.5 mM−1 s−1 and longitudinal relaxivity (r1) higher than 10 mM−1 s−1, which is among the highest values reported for water-based IONP synthesis

Environmental STEM Study of the Oxidation Mechanism for Iron and Iron Carbide Nanoparticles

The oxidation of solution-synthesized iron (Fe) and iron carbide (Fe2C) nanoparticles was studied in an environmental scanning transmission electron microscope (ESTEM) at elevated temperatures under oxygen gas. The nanoparticles studied had a native oxide shell present, that formed after synthesis, an ~3 nm iron oxide (FexOy) shell for the Fe nanoparticles and ~2 nm for the Fe2C nanoparticles, with small void areas seen in several places between the core and shell for the Fe and an ~0.8 nm space between the core and shell for the Fe2C. The iron nanoparticles oxidized asymmetrically, with voids on the borders between the Fe core and FexOy shell increasing in size until the void coalesced, and finally the Fe core disappeared. In comparison, the oxidation of the Fe2C progressed symmetrically, with the core shrinking in the center and the outer oxide shell growing until the iron carbide had fully disappeared. Small bridges of iron oxide formed during oxidation, indicating that the Fe transitioned to the oxide shell surface across the channels, while leaving the carbon behind in the hollow core. The carbon in the carbide is hypothesized to suppress the formation of larger crystallites of iron oxide during oxidation, and alter the diffusion rates of the Fe and O during the reaction, which explains the lower sensitivity to oxidation of the Fe2C nanoparticles

Shape controlled iron oxide nanoparticles: inducing branching and controlling particle crystallinity

Anisotropic nanoparticles (NPs) have garnered a great deal of attention for their applications in catalysis, magnetism and biomedicine. However, synthetic strategies to grow such NPs are still limited as their growth mechanisms are poorly understood. This work presents the synthesis of iron oxide nanoparticles (IONPs) based on the decomposition of iron(III) acetylacetonate in organic solvents to form anisotropic IONPs that are branched or multiply branched. We fully explore their growth parameters to understand the effect of varying amounts of oleylamine (OAm), as well as a nitrogen purge on particle morphology. We show here the synthetic relationship between a wide range of sizes and shapes of IONPs that are both isotropic and anisotropic. Of all the parameters, the amount of oleylamine in the reaction is the key to tune the particle size while the effect of a nitrogen gas purge during synthesis was shown to be crucial for the formation of the branched and multiply branched NPs. Two multiply branched NP systems with only a small difference in the synthetic conditions were shown to have radically different magnetic properties, such as heating in an alternating magnetic field. This was attributed to the defects found in the structure of one and not in the other. By following their development during growth, crystal defects were observed in both systems during the early stages of the reaction. However, for the multiply branched structure that became single crystalline, the aggregation of the nuclei occurred earlier in the reaction, allowing more time for growth and crystallite rearrangement to occur. These results have wide ranging implications for controlling the properties of anisotropic nanomaterials with similar structures, including their magnetic behavior

Unravelling the growth mechanism of the co-precipitation of iron oxide nanoparticles with the aid of synchrotron X-Ray diffraction in solution

Co-precipitation is the most ubiquitous method for forming iron oxide nanoparticles. For a typical co-precipitation synthesis, the pH of a ferrous and/or ferric ion solution is increased via the addition of a base. The latter can be added either slowly (a steady addition over either minutes or hours) or fast (a one-time addition) resulting in an abrupt increase in the pH. However, understanding the mechanism of particle formation is still lacking, which limits the reproducibility of the co-precipitation reaction due to intermediate phases still being present in the final product. In this work, we study in detail a co-precipitation synthesis with an abrupt increase in pH via the addition of sodium carbonate. Fast and reproducible mixing at defined precursor and base solution temperatures was achieved utilising a flow reactor. Transmission electron microscopy, electron diffraction and room temperature 57Fe Mössbauer spectroscopy showed a distinct transition from an amorphous ferrihydrite phase to a mixture of magnetite-maghemite (Fe3O4/γ-Fe2O3). Synchrotron X-ray diffraction revealed the initial formation of crystalline iron hydroxide carbonate (green rust) plates occurring before the Fe3O4/γ-Fe2O3 appeared. The ferrihydrite particles increase in size over time as the proportion of iron hydroxide carbonate plates are re-dissolved into solution, until the ferrihydrite particles crystallise into Fe3O4/γ-Fe2O3

Co-precipitation synthesis of stable iron oxide nanoparticles with NaOH: New insights and continuous production via flow chemistry

Co-precipitation is by far the most common synthesis for magnetic iron oxide nanoparticles (IONPs), as cheap and environmentally friendly precursors and simple experimental procedures facilitate IONP production in many labs. Optimising co-precipitation syntheses remains challenging however, as particle formation mechanisms are not well understood. This is partly due to the rapid particle formation (within seconds) providing insufficient time to characterise initial precipitates. To overcome this limitation, a flow chemistry approach has been developed using steady-state operation to “freeze” transient reaction states locally. This allowed for the first time a comprehensive analysis of the early stages of co-precipitation syntheses via in-situ Small Angle X-ray Scattering and in-situ synchrotron X-Ray Diffraction. These studies revealed that after mixing the ferrous/ferric chloride precursor with the NaOH base solution, the most magnetic iron oxide phase forms within 5 s, the particle size changes only marginally afterwards, and co-precipitation and agglomeration occur simultaneously. As these agglomerates were too large to achieve colloidal stability via subsequent stabiliser addition, co-precipitated IONPs had to be de-agglomerated. This was achieved by adding the appropriate quantity of a citric acid solution which yielded within minutes colloidally stable IONP solutions around a neutral pH value. The new insights into the particle formation and the novel stabilisation procedure (not requiring any ultra-sonication or washing step) allowed to design a multistage flow reactor to synthesise and stabilise IONPs continuously with a residence time of less than 5 min. This reactor was robust against fouling and produced stable IONP solutions (of ~1.5 mg particles per ml) reproducibly via fast mixing ( 500 ml/h) for low materials cost

In situ observation of oscillatory redox dynamics of copper

How a catalyst behaves microscopically under reaction conditions, and what kinds of active sites transiently exist on its surface, is still very much a mystery to the scientific community. Here we present an in situ study on the red-ox behaviour of copper in the model reaction of hydrogen oxidation. Direct imaging combined with on-line mass spectroscopy shows that activity emerges near a phase boundary, where complex spatio-temporal dynamics are induced by the competing action of simultaneously present oxidizing and reducing agents. Using a combination of in situ imaging with in situ X-ray absorption spectroscopy and scanning photoemission microscopy, we reveal the relation between chemical and morphological dynamics and demonstrate that a static picture of active sites is insufficient to describe catalytic function of redox-active metal catalysts. The observed oscillatory redox dynamics provide a unique insight on phase-cooperation and a convenient and general mechanism for constant re-generation of transient active sites

Continuous production of iron oxide nanoparticles via fast and economical high temperature synthesis

From all of the iron oxide nanoparticle (IONP) syntheses, thermal decomposition methods are the most developed for controlling particle properties, but suffer from poor reproducibility at larger scale. An alternative solution for large scale production is continuous synthesis, where the production volume can be increased with longer operation times. However, continuous thermal decomposition synthesis is not trivial as it requires oxygen and water removal from the precursor solution, reaction temperatures above 230 °C, and the formation of particles is likely to cause reactor fouling. This work presents a continuous thermal decomposition synthesis of IONPs using a tubular flow reactor, which provides inert reaction conditions at temperatures of up to 290 °C, and heating/cooling at rates which cannot be achieved in standard batch systems. This makes it possible to define the start and endpoint accurately, hence, allowing for a well-controlled and scalable thermal decomposition synthesis. A simple synthetic protocol was chosen using only ferric acetylacetonate, oleylamine, and 1-octadecene as a solvent, but no additives to minimise costs. In this flow reactor residence times of less than 10 min were shown to be sufficient to synthesise monodisperse IONPs of 5–7 nm and achieve precursor conversion between 10–70% depending on the reaction temperature. For all synthesis conditions tested, there was no indication of reactor fouling. Since the precursor conversion correlated to the residence time and reaction temperature, but particle sizes were comparable for all reaction conditions studied, the particle formation is proposed to follow mechanisms other than classical nucleation and growth. To examine possible economic advantages of such a continuous thermal decomposition process as compared to a conventional batch synthesis, a cost analysis, comparing costs assigned to chemicals, reactor equipment, energy and labour, was performed