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At least 73 records · Page 4

Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

We describe several related studies where simple iron, nickel, and cobalt complexes were prepared, decomposed, and characterized for aeronautics (Fischer-Tropsch catalysts) and space (high-fidelity lunar regolith simulant additives) applications. We describe the synthesis and decomposition of several new nickel dithiocarbamate complexes. Decomposition resulted in a somewhat complicated product mix with NiS predominating. The thermogravimetric analysis of fifteen tris(diorganodithiocarbamato)iron(III) has been investigated. Each undergoes substantial mass loss upon pyrolysis in a nitrogen atmosphere between 195 and 370 C, with major mass losses occurring between 279 and 324 C. Steric repulsion between organic substituents generally decreased the decomposition temperature. The product of the pyrolysis was not well defined, but usually consistent with being either FeS or Fe2S3 or a combination of these. Iron nanoparticles were grown in a silica matrix with a long-term goal of introducing native iron into a commercial lunar dust simulant in order to more closely simulate actual lunar regolith. This was also one goal of the iron and nickel sulfide studies. Finally, cobalt nanoparticle synthesis is being studied in order to develop alternatives to crude processing of cobalt salts with ceramic supports for Fischer-Tropsch synthesis.

Cowen, Jonathan E.↗

Method for producing nanoparticles and the nanoparticles produced therefrom

Disclosed herein is a method comprising disposing a container containing a metal and/or ferromagnetic solid and abrasive particles in a static magnetic field; where the container is surrounded by an induction coil; activating the induction coil with an electrical current, to heat up the metallic or ferromagnetic solid to form a fluid; generating sonic energy to produce acoustic cavitation and abrasion between the abrasive particles and the container; and producing nanoparticles that comprise elements from the container, the metal and/or the ferromagnetic solid and the abrasive particles. Disclosed herein too is a composition comprising first metal or a first ceramic; and particles comprising carbides and/or nitrides dispersed therein. Disclosed herein too is a composition comprising nanoparticles comprising chromium carbide, iron carbide, nickel carbide, γ-Fe and magnesium nickel.

36 MATERIALS SCIENCE↗

Method for producing nanoparticles and the nanoparticles produced therefrom

Disclosed herein is a method comprising disposing a container containing a metal and/or ferromagnetic solid and abrasive particles in a static magnetic field; where the container is surrounded by an induction coil; activating the induction coil with an electrical current, to heat up the metallic or ferromagnetic solid to form a fluid; generating sonic energy to produce acoustic cavitation and abrasion between the abrasive particles and the container; and producing nanoparticles that comprise elements from the container, the metal and/or the ferromagnetic solid and the abrasive particles. Disclosed herein too is a composition comprising first metal or a first ceramic; and particles comprising carbides and/or nitrides dispersed therein. Disclosed herein too is a composition comprising nanoparticles comprising chromium carbide, iron carbide, nickel carbide, γ-Fe and magnesium nitride.

Manuel, Michele Viola↗

Method for producing nanoparticles and the nanoparticles produced therefrom

Disclosed herein is a method comprising disposing a container containing a metal and/or ferromagnetic solid and abrasive particles in a static magnetic field; where the container is surrounded by an induction coil; activating the induction coil with an electrical current, to heat up the metallic or ferromagnetic solid to form a fluid; generating sonic energy to produce acoustic cavitation and abrasion between the abrasive particles and the container; and producing nanoparticles that comprise elements from the container, the metal and/or the ferromagnetic solid and the abrasive particles. Disclosed herein too is a composition comprising first metal or a first ceramic; and particles comprising carbides and/or nitrides dispersed therein. Disclosed herein too is a composition comprising nanoparticles comprising chromium carbide, iron carbide, nickel carbide, γ-Fe and magnesium nitride.

Manuel, Michele Viola↗

Method for producing nanoparticles and the nanoparticles produced therefrom

Disclosed herein is a method comprising disposing a container containing a metal and/or ferromagnetic solid and abrasive particles in a static magnetic field; where the container is surrounded by an induction coil; activating the induction coil with an electrical current, to heat up the metallic or ferromagnetic solid to form a fluid; generating sonic energy to produce acoustic cavitation and abrasion between the abrasive particles and the container; and producing nanoparticles that comprise elements from the container, the metal and/or the ferromagnetic solid and the abrasive particles. Disclosed herein too is a composition comprising first metal or a first ceramic; and particles comprising carbides and/or nitrides dispersed therein. Disclosed herein too is a composition comprising nanoparticles comprising chromium carbide, iron carbide, nickel carbide, γ-Fe and magnesium nitride.

Manuel, Michele Viola↗

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗

Characterizing Performance of Electrocatalyst Nanoparticles Infiltrated into Ni-YSZ Cermet Anodes for Solid Oxide Fuel Cells

The infiltration of nanoparticle electrocatalysts into solid oxide fuel cell (SOFC) electrodes has been proven to produce a high density of electrochemically active sites, and reduce charge transfer polarization losses for SOFC electrodes. This is crucial for intermediate temperature operation, as these losses increase greatly at lower temperatures. Nickel-yttria stabilized zirconia (NiYSZ) cermets are low-cost, and exhibit excellent stability, but their main disadvantage stems from nickel coarsening and performance loss over their operational lifetimes. Infiltration of electrocatalyst nanoparticles has been shown to mitigate nickel coarsening and the consequent anode degradation. In this study, the effects of these infiltrants are observed in a standard Ni-YSZ electrode. In addition to nickel, mixed ionic and electronic conducting (MIEC) phases were infiltrated into Ni-YSZ scaffolds and their performances were characterized using electrochemical impedance spectroscopy (EIS). Cross-sectional microscopy of fractured cells was used to compare electrode microstructure and particle statistics. A model is proposed for how the nanoparticle electrocatalysts improve the anode performance.

25 ENERGY STORAGE↗

SYNTHESIS AND MODIFICATION OF HIGH-NICKEL CATHODE MATERIALS FOR NEXT GENERATION LITHIUM-ION BATTERIES

The limited worldwide Cobalt resource has spurred demand for new cathode materials with reduced Cobalt reliance. Substituting Cobalt with Nickel giving high-Nickel cathode material is a promising solution due to its high energy density and cheaper price. However, the poor cycling stability of high-nickel cathode materials is the major challenge that hinders their widespread adoption in electric vehicles and other energy storage applications. This work reports a significant advance in the development of high-nickel cathode materials with improved cycling stability. Firstly, a scalable synthesis route is developed to produce high-nickel cathodes with favorable morphology and high nickel content of 92%. Various low-cost doping elements including Mg, Al and Ti are screened to improve the structure of high-nickel cathodes during cycling. A Dual Protective strategy with AlPO4 nanoparticles as a representative is introduced as a low cost and effective approach to prolong the cycle stability of high-nickel cathodes. Finally, single-crystalline high-nickel cathodes are synthesized, and their electrochemical performance is compared with polycrystalline cathodes. The synthesized high-nickel cathode materials exhibit excellent electrochemical performance and significantly improved cycling stability. This work demonstrates promising pathways towards the commercialization of high-nickel cathode materials for Lithium Ion Batteries.

25 ENERGY STORAGE↗

DOE-BU-26096-4

The infiltration of nanoparticle electrocatalysts into solid oxide fuel cell (SOFC) electrodes has been proven to produce a high density of electrochemically active sites, and reduce charge transfer polarization losses in SOFC electrodes. This is crucial for intermediate temperature operation, as these losses increase greatly at lower temperatures. Nickel-yttria stabilized zirconia (Ni-YSZ) cermets are low-cost, and exhibit excellent stability, but their main disadvantage stems from nickel coarsening and performance loss over their operational lifetimes. Infiltration of electrocatalyst nanoparticles has been shown to mitigate nickel coarsening and the consequent anode degradation. In this work, the effects of these infiltrants have been observed in a standard Ni-YSZ electrode. In addition to nickel, mixed ionic and electronic conducting (MIEC) phases have been infiltrated into Ni-YSZ scaffolds and their performance characterized using electrochemical impedance spectroscopy (EIS). Cross-sectional microscopy of fractured cells has been used to compare electrode microstructure and particle statistics. A model has been proposed to explain the origin of anode performance enhancement from nanoscale electrocatalysts.

Mo, Boshan↗

Multimaterial Aerosol Jet Printed Magnetic Nanocomposites for Microwave Circuits

Here this article demonstrates the process and characterization of additively manufactured polymer-matrix magnetic nanocomposites. These nanocomposites are composed of nickel-zinc ferrite (Ni 0.5 Zn 0.5 Fe 2 O 4 ) nanoparticles in a polyimide matrix. These materials are printed using multimaterial aerosol jet printing where aerosols of nickel-zinc ferrite and polyimide inks are mixed in place to fabricate structures with nonunity relative permeability. To characterize these materials, we use energy-dispersive X-ray spectroscopy to estimate the content of ferrite in the composite, fitted simulation models, and ring resonator measurements to estimate the permeability. In fully aerosol jet printed 1-mm 2 inductors, we demonstrate an increase in inductance density of 40% in a 4.5-turn microstrip spiral inductor using this printed composite. These fully printed inductors demonstrate an inductance density of 4.2-nH/mm 2 . EDS analysis shows films with 18 wt.% Ni 0.5 Zn 0.5 Fe 2 O 4 . Finally, we show microstrip transmission lines on printed composite compared to the same on polyimide subjected to a dc magnetic bias, displaying a magnetic resonance behavior.

42 ENGINEERING↗

Precursor-mediated in situ growth of hierarchical N-doped graphene nanofibers confining nickel single atoms for CO 2 electroreduction

Despite the various strategies for achieving metal–nitrogen–carbon (M–N–C) single-atom catalysts (SACs) with different microenvironments for electrochemical carbon dioxide reduction reaction (CO 2 RR), the synthesis–structure–performance correlation remains elusive due to the lack of well-controlled synthetic approaches. Here, we employed Ni nanoparticles as starting materials for the direct synthesis of nickel (Ni) SACs in one spot through harvesting the interaction between metallic Ni and N atoms in the precursor during the chemical vapor deposition growth of hierarchical N-doped graphene fibers. By combining with first-principle calculations, we found that the Ni-N configuration is closely correlated to the N contents in the precursor, in which the acetonitrile with a high N/C ratio favors the formation of Ni-N 3 , while the pyridine with a low N/C ratio is more likely to promote the evolution of Ni-N 2 . Moreover, we revealed that the presence of N favors the formation of H-terminated edge of sp 2 carbon and consequently leads to the formation of graphene fibers consisting of vertically stacked graphene flakes, instead of the traditional growth of carbon nanotubes on Ni nanoparticles. With a high capability in balancing the *COOH formation and *CO desorption, the as-prepared hierarchical N-doped graphene nanofibers with Ni-N 3 sites exhibit a superior CO2RR performance compared to that with Ni-N 2 and Ni-N 4 ones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual Protective Mechanism of AlPO 4 Coating on High-Nickel Cathode Material for High Energy Density and Long Cycle Life Lithium-Ion Batteries

Cathode material with high nickel content is a promising candidate for the future generation of Li-ion batteries (LIBs). However, severe structural degradation during cycling limits its practical use, especially for electric vehicles. Herein, AlPO 4 nanoparticles were synthesized and then coated onto the surface of a high-nickel layer-structured cathode via a dry coating method. The AlPO 4 nanoparticles coating significantly improved the cycling stability from 69.2% to over 80% capacity retention after 140 cycles. Furthermore, the structure and chemical composition of the AlPO 4 -coated cathode was investigated by XRD, SEM, XPS, and STEM. Compared with the non-coated cathode, we revealed a dual protective mechanism for enhanced cycling stability, where Al doping and Li 3 PO 4 coating play synergistic roles in protecting cathode material through long-term cycling. This work demonstrates a facile and environmentally friendly approach toward improving the performance of high-nickel LIB cathodes, which can be easily scaled up for industrial applications.

25 ENERGY STORAGE↗

Zirconium Carbide Mediates Coke‐Resistant Methane Dry Reforming on Nickel‐Zirconium Catalysts

Abstract Graphitic deposits anti‐segregate into Ni 0 nanoparticles to provide restored CH 4 adsorption sites and near‐surface/dissolved C atoms, which migrate to the Ni 0 /ZrO 2 interface and induce local Zr x C y formation. The resulting oxygen‐deficient carbidic phase boundary sites assist in the kinetically enhanced CO 2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO 2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni‐CeZr x O y catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of aluminum incorporation and aqueous conditions on metal ion release of high-Ni transition metal oxide nanomaterials

Developing a materials perspective of how to control the degradation and negative impact of complex metal oxides requires an integrated understanding of how these nanomaterials transform in the environment and interact with biological systems. Doping with aluminum is known to stabilize oxide materials, but has not been assessed cohesively from synthesis to environmental fate and biological impact. In the present study, the influence of aluminum doping on metal ion release from transition metal oxides was investigated by comparing aqueous transformations of lithium nickel cobalt aluminum oxide (LiNi 0.82 Co 0.15 Al 0.03 O 2 ; NCA) and lithium nickel cobalt oxide (LiNi 0.80 Co 0.20 O 2 ; NC) nanoparticles and by calculating the energetics of metal release using a density functional theory (DFT) and thermodynamics method. Two model environmental organisms were used to assess biological impact, and metal ion release was compared for NCA and NC nanoparticles incubated in their respective growth media: moderately hard reconstituted water (MHRW) for the freshwater invertebrate Daphnia magna (D. magna) and minimal growth medium for the Gram-negative bacterium Shewanella oneidensis MR-1 (S. oneidensis). Further, the amount of metal ions released was reduced for NCA compared to NC in MHRW, which correlated to changes in the modeled energetics of release upon Al substitution in the lattice. In minimal medium, metal ion release was approximately an order of magnitude higher compared to MHRW and was similar to the stoichiometry of the bulk nanoparticles for both NCA and NC. Interpretation of the release profiles and modeling indicated that the increase in total metal ion release and the reduced influence of Al doping arises from lactate complexation of metal ions in solution. The relative biological impacts of NC and NCA exposure for both S. oneidensis and D. magna were consistent with the metal release trends observed for minimal medium and MHRW, respectively. Together, these results demonstrate how a combined experimental and computational approach provides valuable insight into the aqueous transformations and biological impacts of complex metal oxide nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanowire-Based Materials as Coke-Resistant Catalyst Supports for Dry Methane Reforming

In this paper, nanowire-supported catalysts loaded with nickel are shown to be coke resistant compared to nanoparticle-supported catalysts. Specifically, Ni-loaded titania-based nanowire catalysts were tested with the dry methane reforming process in a laboratory-scale continuous packed-bed atmospheric reactor. The CO 2 conversion rate stayed above 90% for over 30 h on stream under coke-promoting conditions, such as high flow rates, low temperatures, and a high ratio of CH 4 to CO 2 . The coke (C x H y , x>>y) on the spent catalyst surface for both nanowire- and nanoparticle-supported catalysts was characterized by TGA, temperature-programmed reduction (TPR), and electron microscopy (SEM/TEM/EDS), and it was revealed that the types of carbon species present and their distribution over the morphology-enhanced materials played a major role in the deactivation. The CO 2 conversion activity of Ni supported on titania nanoparticles was reduced from ~80% to less than 72% in 30 h due to the formation of a graphitic coke formation. On the other hand, Ni particles supported on nanowires exhibited cube-octahedral morphologies, with a high density of non- (111) surface sites responsible for the increased activity and reduced graphitic coke deposition, giving a sustained and stable catalytic activity during a long time-on-stream experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Integrated Electrochemical Approach to the Precision Synthesis of Sustainable Catalyst Materials

There is a pressing need to replace critical materials such as platinum group elements (PGE) in applications related to energy. This work responds to the need for fundamental principles of materials design to replace these metals by addressing a gap in the understanding of how to precisely control the surface structure of nanoscale materials. Electrochemical nanomaterials synthesis, such as techniques developed in the PI’s research group, expands the toolbox of available synthetic handles to include both electrochemical and chemical parameters, providing access to control over synthetic conditions in ways that are not possible in purely chemical nanoparticle growth. However, electrochemical materials synthesis (electrodeposition) is inherently serial, limiting throughput and preventing widespread implementation. Initial efforts in the short period of this award resulted in an innovative, high throughput, parallel approach to synthetic discovery for the electrodeposition of shaped metal nanoparticles that overcomes this limitation. Looking ahead, this work establishes an important capability that will enable researchers to push boundaries in the shape control of nanoparticles composed of non-PGE such as copper, iron, nickel, or cobalt.

36 MATERIALS SCIENCE↗