skip to main content

Title: Chemical modification in and on single phase [NiO] 0.5 [Al 2 O 3 ] 0.5 nanopowders produces “chocolate chip‐like” Ni x @[NiO] 0.5‐x [Al 2 O 3 ] 0.5 nanocomposite nanopowders

Phase‐pure [NiO]0.5[Al2O3]0.5spinel nanoparticles (NPs) with limited aggregation were obtained via liquid‐feed flame spray pyrolysis (LF‐FSP) by combusting metalloorganic precursor solutions. Thereafter “chocolate chip‐like” Nix[NiO0.5‐x][Al2O3]0.5nanoparticles consisting of primary [NiO0.5‐x][Al2O3]0.5particles with average particle sizes of 40‐60 nm decorated with Ni metal particles (<10 nm in diameter) dispersed on the surface were synthesized by heat treating the spinel NPs at 800°C/7 h in flowing 5% H2:N2100 mL/min in a fluidized bed reactor. The synthesized materials were characterized using TEM, XRD, FTIR, and TGA/DTA. The Ni depleted areas consist primarily of γ‐Al2O3. The Ni content (800°C) was determined by TGA to be ≈11.3 wt.% based on TGA oxidation behavior. The successful synthesis of such nanocomposites with limited aggregation on a high temperature support provides a facile route to synthesize well‐defined NP catalysts. This work serves as a baseline study for an accompanying paper, wherein thin, flexible, dense films made from these same NPs are used as regenerable catalysts for carbon nanotube syntheses.

more » « less
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Date Published:
Journal Name:
Journal of the American Ceramic Society
Page Range / eLocation ID:
p. 7145-7153
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. NiO/β-(Al x Ga 1− x ) 2 O 3 /Ga 2 O 3 heterojunction lateral geometry rectifiers with diameter 50–100  μm exhibited maximum reverse breakdown voltages >7 kV, showing the advantage of increasing the bandgap using the β-(Al x Ga 1− x ) 2 O 3 alloy. This Si-doped alloy layer was grown by metal organic chemical vapor deposition with an Al composition of ∼21%. On-state resistances were in the range of 50–2180 Ω cm 2 , leading to power figures-of-merit up to 0.72 MW cm −2 . The forward turn-on voltage was in the range of 2.3–2.5 V, with maximum on/off ratios >700 when switching from 5 V forward to reverse biases up to −100 V. Transmission line measurements showed the specific contact resistance was 0.12 Ω cm 2 . The breakdown voltage is among the highest reported for any lateral geometry Ga 2 O 3 -based rectifier. 
    more » « less
  2. This Review highlights basic and transition metal conducting and semiconducting oxides. We discuss their material and electronic properties with an emphasis on the crystal, electronic, and band structures. The goal of this Review is to present a current compilation of material properties and to summarize possible uses and advantages in device applications. We discuss Ga 2 O 3 , Al 2 O 3 , In 2 O 3 , SnO 2 , ZnO, CdO, NiO, CuO, and Sc 2 O 3 . We outline the crystal structure of the oxides, and we present lattice parameters of the stable phases and a discussion of the metastable polymorphs. We highlight electrical properties such as bandgap energy, carrier mobility, effective carrier masses, dielectric constants, and electrical breakdown field. Based on literature availability, we review the temperature dependence of properties such as bandgap energy and carrier mobility among the oxides. Infrared and Raman modes are presented and discussed for each oxide providing insight into the phonon properties. The phonon properties also provide an explanation as to why some of the oxide parameters experience limitations due to phonon scattering such as carrier mobility. Thermal properties of interest include the coefficient of thermal expansion, Debye temperature, thermal diffusivity, specific heat, and thermal conductivity. Anisotropy is evident in the non-cubic oxides, and its impact on bandgap energy, carrier mobility, thermal conductivity, coefficient of thermal expansion, phonon modes, and carrier effective mass is discussed. Alloys, such as AlGaO, InGaO, (Al x In y Ga 1− x− y ) 2 O 3 , ZnGa 2 O 4 , ITO, and ScGaO, were included where relevant as they have the potential to allow for the improvement and alteration of certain properties. This Review provides a fundamental material perspective on the application space of semiconducting oxide-based devices in a variety of electronic and optoelectronic applications. 
    more » « less
  3. 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 transmission 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. 
    more » « less
  4. Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 
    more » « less
  5. La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF), having thermochemical stability, superior ionic and electronic conductivity, and structural flexibility, was investigated as a cathode in SOECs. Exsolution of nanoparticles by reduction of LSNF at elevated temperatures can modulate the characteristics of adsorption, electron transfer, and oxidation states of catalytically active atoms, consequently improving the electrocatalytic activity. The exsolution of NiFe and La 2 NiO 4 nanoparticles to the surface of LSNF under reducing atmosphere (5% H 2 /N 2 ) was verified at various temperatures (500–800 °C) by IFFT from ETEM, TPR and in situ XRD. The exsolved nanoparticles obtained uniform size distribution (4.2–9.2 nm) and dispersion (1.31 to 0.61 × 10 4 particle per μm 2 ) depending on the reduction temperature (700–800 °C) and time (0–10 h). The reoxidation of the reduced LSNF (Red-LSNF) was verified by the XRD patterns, indicative of its redox ability, which allows for redistribution of the nanoparticles between the surface and the bulk. TPD-DRIFTS analysis demonstrated that Red-LSNF had superior H 2 O and CO 2 adsorption behavior as compared to unreduced LSNF, which we attributed to the abundance of oxygen vacancy sites and the exsolved NiFe and La 2 NiO 4 nanoparticles. After the reduction of LSNF, the decreases in the oxidation states of the catalytically active ions, Fe and Ni, were characterized on the surface by XPS as well as in the bulk by XANES. The electrochemical performance of the Red-LSNF cell was superior to that of the LSNF cell for electrolysis of H 2 O, CO 2 , and H 2 O/CO 2 . 
    more » « less