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1. Effect of manganese substitution of ferrite nanoparticles on particle grain structure

   https://doi.org/10.1039/D2NA00200K  

   Yan, Zichun ; Chaluvadi, Anish ; FitzGerald, Sara ; Spence, Sarah ; Bleyer, Christopher ; Zhu, Jiazhou ; Crawford, Thomas M. ; Getman, Rachel B. ; Watt, John ; Huber, Dale L. ; et al ( August 2022 , Nanoscale Advances)

   To investigate the influence of manganese substitution on the saturation magnetization of manganese ferrite nanoparticles, samples with various compositions (MnxFe3−xO4,x = 0, 0.25, 0.5, 0.75, and 1) were synthesized and characterized. The saturation magnetization of such materials was both calculated using density functional theory and measured via vibrating sample magnetometry. A discrepancy was found; the computational data demonstrated a positive correlation between manganese content and saturation magnetization, while the experimental data exhibited an inverse correlation. X-ray diffraction (XRD) and magnetometry results indicated that the crystallite diameter and the magnetic diameter decrease when adding more manganese, which could explain the loss of magnetization of the particles. For 20 nm nanoparticles, with increasing manganese substitution level, the crystallite size decreases from 10.9 nm to 6.3 nm and the magnetic diameter decreases from 15.1 nm to 3.5 nm. Further high resolution transmission electron microscopy (HRTEM) analysis confirmed the manganese substitution induced defects in the crystal lattice, which encourages us to find ways of eliminating crystalline defects to make more reliable ferrite nanoparticles.
2. On the synthesis and characterization of bimagnetic CoO/NiFe ₂ O ₄ heterostructured nanoparticles

   https://doi.org/10.1063/9.0000561  

   Uddin, Muhammad S. ; Mayanovic, Robert A. ; Benamara, Mourad ( February 2023 , AIP Advances)

   Bimagnetic nanoparticles show promise for applications in energy efficient magnetic storage media and magnetic device applications. The magnetic properties, including the exchange bias of nanostructured materials can be tuned by variation of the size, composition, and morphology of the core vs overlayer of the nanoparticles (NPs). The purpose of this study is to investigate the optimal synthesis routes, structure and magnetic properties of novel CoO/NiFe 2 O 4 heterostructured nanocrystals (HNCs). In this work, we aim to examine how the size impacts the exchange bias, coercivity and other magnetic properties of the CoO/NiFe 2 O 4 HNCs. The nanoparticles with sizes ranging from 10 nm to 24 nm were formed by synthesis of an antiferromagnetic (AFM) CoO core and deposition of a ferrimagnetic (FiM) NiFe 2 O 4 overlayer. A highly crystalline magnetic phase is more likely to occur when the morphology of the core-overgrowth is present, which enhances the coupling at the AFM-FiM interface. The CoO core NPs are prepared using thermal decomposition of Co(OH) 2 at 600 °C for 2 hours in a pure argon atmosphere, whereas the HNCs are obtained first using thermal evaporation followed by hydrothermal synthesis. The structural and morphological characterization made using X-ray diffraction (XRD), high-resolution transmissionmore »electron microscopy (HR-TEM), and scanning electron microscopy (SEM) techniques verifies that the HNCs are comprised of a CoO core and a NiFe 2 O 4 overgrowth phase. Rietveld refinement of the XRD data shows that the CoO core has the rocksalt (Fd3 m) crystal structure and the NiFe 2 O 4 overgrowth has the spinel (C12/m1) crystal structure. SEM-EDS data indicates the presence and uniform distribution of Co, Ni and Fe in the HNCs. The results from PPMS magnetization measurements of the CoO/NiFe 2 O 4 HNCs are discussed herein.« less
3. Highly porous, low band-gap Ni _x Mn _3−x O ₄ (0.55 ≤ x ≤ 1.2) spinel nanoparticles with in situ coated carbon as advanced cathode materials for zinc-ion batteries

   https://doi.org/10.1039/c9ta05101e  

   Long, Jun ; Gu, Jinxing ; Yang, Zhanhong ; Mao, Jianfeng ; Hao, Junnan ; Chen, Zhongfang ; Guo, Zaiping ( July 2019 , Journal of Materials Chemistry A)

   Aqueous zinc ion batteries (ZIBs) are emerging as a highly promising alternative technology for grid-scale applications where high safety, environmental-friendliness, and high specific capacities are needed. It remains a significant challenge, however, to develop a cathode with a high rate capability and long-term cycling stability. Here, we demonstrate diffusion-controlled behavior in the intercalation of zinc ions into highly porous, Mn 4+ -rich, and low-band-gap Ni x Mn 3−x O 4 nano-particles with a carbon matrix formed in situ (with the composite denoted as Ni x Mn 3−x O 4 @C, x = 1), which exhibits superior rate capability (139.7 and 98.5 mA h g −1 at 50 and 1200 mA g −1 , respectively) and outstanding cycling stability (128.8 mA h g −1 remaining at 400 mA g −1 after 850 cycles). Based on the obtained experimental results and density functional theory (DFT) calculations, cation-site Ni substitution combined with a sufficient doping concentration can decrease the band gap and effectively improve the electronic conductivity in the crystal. Furthermore, the amorphous carbon shell and highly porous Mn 4+ -rich structure lead to fast electron transport and short Zn 2+ diffusion paths in a mild aqueous electrolyte. This study provides an examplemore »of a technique to optimize cathode materials for high-performance rechargeable ZIBs and design advanced intercalation-type materials for other energy storage devices.« less
4. Size-dependent magnetic properties of Mn-Co-NiO based heterostructured nanoparticles

   https://doi.org/10.1063/9.0000583  

   Ishrak, Farhan ; Mayanovic, Robert A. ; Benamara, Mourad ( February 2023 , AIP Advances)

   In this work, we investigate the synthesis, along with the structural and magnetic properties, of novel Mn-Co-NiO-based heterostructured nanocrystals (HNCs). The objective is to develop novel, well-structurally ordered inverted antiferromagnetic (AFM) NiO–ferrimagnetic (FiM) spinel phase overgrowth HNCs. Inverted HNCs are particularly promising for magnetic device applications because their magnetic properties are more easily controlled by having well-ordered AFM cores, which can result in magnetic structures having large coercivities, tunable blocking temperatures, and other enhanced magnetic effects. The synthesis of the HNCs is accomplished using a two-step process: In the first step, NiO nanoparticles are synthesized using a thermal decomposition method. Subsequently, Mn-Co overgrowth phases are grown on the NiO nanoparticles via hydrothermal nanophase epitaxy, using a fixed pH level (∼5.3) of the aqueous medium. This pH level was selected based on previous work in our laboratory showing that NiO/Mn 3 O 4 HNCs of constant size have optimal coercivity and exchange bias when synthesized at a pH of 5.0. The crystalline structure and gross morphology of the Mn-Co-NiO-based HNCs have been analyzed using X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) techniques, respectively. Analysis using these techniques shows that the HNCs are composed of a NiO core and a CoMnmore »2 O 4 overgrowth phase. Rietveld refinement of XRD data shows that the NiO core has the rocksalt (Fm[Formula: see text]m) cubic crystal structure and the CoMn 2 O 4 overgrowth has the spinel ( I4 1 / amd) crystal structure. Moreover, an increased relative amount of the CoMn 2 O 4 overgrowth phase is deposited with decreasing NiO core particle size during the synthesis of the HNCs. The results from PPMS magnetization and high-resolution transmission electron microscopy (HRTEM) characterization of the Mn-Co-NiO-based HNCs are discussed herein.« less
5. The impact of site selectivity and disorder on the thermoelectric properties of Yb ₂₁ Mn ₄ Sb ₁₈ solid solutions: Yb ₂₁ Mn _4−x Cd _x Sb ₁₈ and Yb _21−y Ca _y Mn ₄ Sb ₁₈

   https://doi.org/10.1039/d1ma00497b  

   He, Allan ; Cerretti, Giacomo ; Kauzlarich, Susan M. ( August 2021 , Materials Advances)

   Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca aremore »isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K.« less