Continuous Flow Synthesis of a Zr Magnetic Framework Composite for Post-Combustion CO2 Capture.

Metal-organic frameworks (MOFs) have an unprecedented ability to store gas molecules, however energy efficient regeneration remains challenging. Use of magnetic induction to aid this shows promise, but economical synthesis of the requisite composites is unresolved. Continuous flow chemistry has been reported as a rapid and reliable method of MOF synthesis, delivering step-change improvements in space time yields (STY). Here the scalable production of nanomaterials suitable for regeneration by magnetic induction is demonstrated. The zirconium MOF composite, MgFe2 O4 @UiO-66-NH2 is prepared using continuous flow chemistry resulting in a material of comparable performance to its batch counterpart. Upscaling using flow chemistry gave STY >25 times that of batch synthesis. Magnetic induced regeneration using this mass produced MFC for carbon capture is then demonstrated.

A Gallium-Based Magnetocaloric Liquid Metal Ferrofluid.

We demonstrate a magnetocaloric ferrofluid based on a gadolinium saturated liquid metal matrix, using a gallium-based liquid metal alloy as the solvent and suspension medium. The material is liquid at room temperature, while exhibiting spontaneous magnetization and a large magnetocaloric effect. The magnetic properties were attributed to the formation of gadolinium nanoparticles suspended within the liquid gallium alloy, which acts as a reaction solvent during the nanoparticle synthesis. High nanoparticle weight fractions exceeding 2% could be suspended within the liquid metal matrix. The liquid metal ferrofluid shows promise for magnetocaloric cooling due to its high thermal conductivity and its liquid nature. Magnetic and thermoanalytic characterizations reveal that the developed material remains liquid within the temperature window required for domestic refrigeration purposes, which enables future fluidic magnetocaloric devices. Additionally, the observed formation of nanometer-sized metallic particles within the supersaturated liquid metal solution has general implications for chemical synthesis and provides a new synthetic pathway toward metallic nanoparticles based on highly reactive rare earth metals.

Fast deswelling of nanocomposite polymer hydrogels via magnetic field-induced heating for emerging FO desalination.

Freshwater shortage is one of the most pressing global issues. Forward osmosis (FO) desalination technology is emerging for freshwater production from saline water, which is potentially more energy-efficient than the current reverse osmosis process. However, the lack of a suitable draw solute is the major hurdle for commercial implementation of the FO desalination technology. We have previously reported that thermoresponsive hydrogels can be used as the draw agent for a FO process, and this new hydrogel-driven FO process holds promise for further development for practical application. In the present work, magnetic field-induced heating is explored for the purpose of developing a more effective way to recover water from swollen hydrogel draw agents. The composite hydrogel particles are prepared by copolymerization of sodium acrylate and N-isopropylacrylamide in the presence of magnetic nanoparticles (γ-Fe2O3, <50 nm). The results indicate that the magnetic heating is an effective and rapid method for dewatering of hydrogels by generating the heat more uniformly throughout the draw agent particles, and thus, a dense skin layer commonly formed via conventional heating from the outside of the particle is minimized. The FO dewatering performance is affected by the loading of magnetic nanoparticles and magnetic field intensity. Significantly enhanced liquid water recovery (53%) is achieved under magnetic heating, as opposed to only around 7% liquid water recovery obtained via convection heating. Our study shows that the magnetic heating is an attractive alternative stimulus for the extraction of highly desirable liquid water from the draw agent in the polymer hydrogel-driven forward osmosis process.

Uniaxial polarization analysis of bulk ferromagnets: theory and first experimental results.

On the basis of Brown's static equations of micromagnetics, the uniaxial polarization of the scattered neutron beam of a bulk magnetic material is computed. The approach considers a Hamiltonian that takes into account the isotropic exchange interaction, the antisymmetric Dzyaloshinskii-Moriya interaction, magnetic anisotropy, the dipole-dipole interaction and the effect of an applied magnetic field. In the high-field limit, the solutions for the magnetization Fourier components are used to obtain closed-form results for the spin-polarized small-angle neutron scattering (SANS) cross sections and the ensuing polarization. The theoretical expressions are compared with experimental data on a soft magnetic nanocrystalline alloy. The micromagnetic SANS theory provides a general framework for polarized real-space neutron methods, and it may open up a new avenue for magnetic neutron data analysis on magnetic microstructures.

Unraveling the magnetic softness in Fe-Ni-B-based nanocrystalline material by magnetic small-angle neutron scattering.

Magnetic small-angle neutron scattering is employed to investigate the magnetic interactions in (Fe0.7Ni0.3)86B14 alloy, a HiB-NANOPERM-type soft magnetic nanocrystalline material, which exhibits an ultrafine microstructure with an average grain size below 10 nm. The neutron data reveal a significant spin-misalignment scattering which is mainly related to the jump of the longitudinal magnetization at internal particle-matrix interfaces. The field dependence of the neutron data can be well described by micromagnetic small-angle neutron scattering theory. In particular, the theory explains the 'clover-leaf-type' angular anisotropy observed in the purely magnetic neutron scattering cross section. The presented neutron data analysis also provides access to the magnetic interaction parameters, such as the exchange-stiffness constant, which plays a crucial role towards the optimization of the magnetic softness of Fe-based nanocrystalline materials.

Performance evaluation of CuBTC composites for room temperature oxygen storage.

Oxygen is commonly separated from air using cryogenic liquefaction. The inherent energy penalties of phase change inspire the search for energy-efficient separation processes. Here, an alternative approach is presented, where we determine whether it is possible to utilise simpler, stable materials in the right process to achieve overall energy efficiency. Adsorption and release by Metal-Organic Frameworks (MOFs) are an attractive alternative due to their high adsorption and storage capacity at ambient conditions. Cu-BTC/MgFe2O4 composites were prepared, and magnetic induction swing adsorption (MISA) used to release adsorbed oxygen quickly and efficiently. The 3 wt% MgFe2O4 composites exhibited an oxygen uptake capacity of 0.34 mmol g-1 at 298 K and when exposed to a magnetic field of 31 mT, attained a temperature rise of 86 °C and released 100% of adsorbed oxygen. This water vapor stable pelletized system, can be filled and emptied within 10 minutes requiring around 5.6 MJ kg-1 of energy.

Magnetic Guinier law.

Small-angle scattering of X-rays and neutrons is a routine method for the determination of nanoparticle sizes. The so-called Guinier law represents the low-q approximation for the small-angle scattering curve from an assembly of particles. The Guinier law has originally been derived for nonmagnetic particle-matrix-type systems and it is successfully employed for the estimation of particle sizes in various scientific domains (e.g. soft-matter physics, biology, colloidal chemistry, materials science). An important prerequisite for it to apply is the presence of a discontinuous interface separating particles and matrix. Here, the Guinier law is introduced for the case of magnetic small-angle neutron scattering and its applicability is experimentally demonstrated for the example of nanocrystalline cobalt. It is well known that the magnetic microstructure of nanocrystalline ferromagnets is highly nonuniform on the nanometre length scale and characterized by a spectrum of continuously varying long-wavelength magnetization fluctuations, i.e. these systems do not manifest sharp interfaces in their magnetization profile. The magnetic Guinier radius depends on the applied magnetic field, on the magnetic interactions (exchange, magnetostatics) and on the magnetic anisotropy-field radius, which characterizes the size over which the magnetic anisotropy field is coherently aligned into the same direction. In contrast to the nonmagnetic conventional Guinier law, the magnetic version can be applied to fully dense random-anisotropy-type ferromagnets.

Colossal Magnetization and Giant Coercivity in Ion-Implanted (Nb and Co) MoS2 Crystals.

Colossal saturation magnetization and giant coercivity are realized in MoS2 single crystals doped with Nb and/or Co using an ion implantation method. Magnetic measurements have demonstrated that codoping with 2 at % Nb and 4 at % Co invoked a "giant" coercivity, as high as 9 kOe at 100 K. Doping solely with 5 at % Nb induces a "colossal" magnetization of 1800 emu/cm3 at 5 K, which is higher than that of metallic Co. The high magnetization is due to the formation of Nb-rich defect complexes, as confirmed by first-principles calculations. It is proposed that the high coercivity is due to the combined effects of strong directional exchange coupling induced by the Nb and Co doping and pinning effects from defects within the layered structure. This high magnetization mechanism is also applicable to 2D materials with bilayers or few layers of thickness, as indicated by first-principles calculations. Hence, this work opens a potential pathway for the development of 2D high-performance magnetic materials.

Confinement-Induced Giant Spin-Orbit-Coupled Magnetic Moment of Co Nanoclusters in TiO2 Films.

High magnetization materials are in great demand for the fabrication of advanced multifunctional magnetic devices. Notwithstanding this demand, the development of new materials with these attributes has been relatively slow. In this work, we propose a new strategy to achieve high magnetic moments above room temperature. Our material engineering approach invoked the embedding of magnetic nanoclusters in an oxide matrix. By precisely controlling pulsed laser deposition parameters, Co nanoclusters are formed in a 5 at % Co-TiO2 film. The presence of these nanoclusters was confirmed using transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray absorption fine structure. The film exhibits a very high saturation magnetization of 99 emu/cm3. Detailed studies using X-ray magnetic circular dichroism confirm that Co has an enhanced magnetic moment of 3.5 µB/atom, while the Ti and O also contribute to the magnetic moments. First-principles calculations supported our hypothesis that the metallic Co nanoclusters surrounded by a TiO2 matrix can exhibit both large spin and orbital moments. Moreover, a quantum confinement effect results in a high Curie temperature for the embedded Co nanoclusters. These findings reveal that 1-2 nm nanoclusters that are quantum confined can exhibit very large magnetic moments above room temperature, representing a promising advance for the design of new high magnetization materials.

Towards energy efficient separations with metal organic frameworks.

The huge energy requirement for industrial separations of chemical mixtures has necessitated the need for the development of energy efficient and alternative separation techniques in order to mitigate the negative environmental impacts associated with greenhouse gas emissions from fossil fuel combustions for energy generation. A promising approach involves the use of magnetic framework composites (MFCs) for gas capture and release via localised magnetic induction heating in a process known as magnetic induction swing adsorption (MISA). This feature article presents an overview of the mechanism of induction heating of magnetic nanoparticles, incorporation of the nanoparticles into metal organic frameworks to form MFCs and the potential of deploying MFCs for the mitigation of greenhouse gas emissions using the MISA process. We also present an overview of the potential energy savings as a result of the efficiency of magnetic induction heating and we give a perspective on the future directions in material and process development that could lead to widespread deployment of the MISA process for industrial separation operations.

Intrinsic or Interface Clustering-Induced Ferromagnetism in Fe-Doped In2O3-Diluted Magnetic Semiconductors.

Five percent Fe-doped In2O3 films were deposited using a pulsed laser deposition system. X-ray diffraction and transmission electron microscopy analysis show that the films deposited under oxygen partial pressures of 10-3 and 10-5 Torr are uniform without clusters or secondary phases. However, the film deposited under 10-7 Torr has a Fe-rich phase at the interface. Magnetic measurements demonstrate that the magnetization of the films increases with decreasing oxygen partial pressure. Muon spin relaxation (µSR) analysis indicates that the volume fractions of the ferromagnetic phases in PO2 = 10-3, 10-5, and 10-7 Torr-deposited samples are 23, 49, and 68%, respectively, suggesting that clusters or secondary phases may not be the origin of the ferromagnetism and that the ferromagnetism is not carrier-mediated. We propose that the formation of magnetic bound polarons is the origin of the ferromagnetism. In addition, both µSR and polarized neutron scattering demonstrate that the Fe-rich phase at the interface has a lower magnetization compared to the uniformly distributed phases.

Magnetic Metal-Organic Frameworks for Efficient Carbon Dioxide Capture and Remote Trigger Release.

Magnetic metal-organic framework (MOF) composites show highly efficient CO2 desorption capacities upon their exposure to an alternating magnetic field, demonstrating a magnetic induction swing strategy for potentially low-energy regeneration of MOF adsorbents.

Chemically induced permanent magnetism in Au, Ag, and Cu nanoparticles: localization of the magnetism by element selective techniques.

We report a direct observation of the intrinsic magnetization behavior of Au in thiol-capped gold nanoparticles with permanent magnetism at room temperature. Two element specific techniques have been used for this purpose: X-ray magnetic circular dichroism on the L edges of the Au and 197Au Mössbauer spectroscopy. Besides, we show that silver and copper nanoparticles synthesized by the same chemical procedure also present room-temperature permanent magnetism. The observed permanent magnetism at room temperature in Ag and Cu dodecanethiol-capped nanoparticles proves that the physical mechanisms associated to this magnetization process can be extended to more elements, opening the way to new and still not-discovered applications and to new possibilities to research basic questions of magnetism.