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More, Karren Leslie

Publications and source records attributed to More, Karren Leslie.

At least 19 records

Helium irradiated cavity formation and defect energetics in Ni-based binary single-phase concentrated solid solution alloys

In this study, binary single-phase concentrated solid solution alloys (SPCSAs), including Ni 80 Co 20 , Ni 80 Fe 20 , Ni 80 Cr 20 , Ni 80 Pd 20 , and Ni 80 Mn 20 (in atomic percentage), were irradiated with 200 keV He + ions at 500 °C. He cavity size and density distribution were systematically investigated using transmission electron microscope. Here we show that alloying elements have a clear impact on He cavity formation. Cavity size is the smallest in Ni 80 Mn 20 but the largest in Ni 80 Co 20 . Alloying elements could also substantially affect cavity density profile. In-depth examination of cavities at peak damage region (~500 nm) and at low damage region (~300 nm) demonstrates that cavity size is depth (damage) dependent. Competition between consumption and production of vacancies and He atoms could lead to varied cavity size. Density functional theory (DFT) calculations were performed to obtain the formation and migration energies of interstitials and vacancies. Combined experimental and simulation results show that smaller energy gap between interstitial and vacancy migration energies may lead to smaller cavity size and narrower size distribution observed in Ni 80 Mn 20 , comparing with Ni 80 Co 20 . Finally, the results of this study call attention to alloying effects of specific element on cavity formation and defect energetics in SPCSAs, and could provide fundamental understanding to predict radiation effects in more complexed SPCSAs, such as high entropy alloys.

36 MATERIALS SCIENCE↗

Unraveling the Effects of Strontium Incorporation on Barite Growth—In Situ and Ex Situ Observations Using Multiscale Chemical Imaging

Impurity ions influence mineral growth rates through a variety of kinetic and thermodynamic processes that also affect partitioning of the impurity ion between the solid and solution. Here in this paper, the effect of an impurity ion, strontium, on Barite (BaSO 4 ) (001) growth rates was studied using a combination of high-resolution in situ microscopy with ex situ chemical imaging techniques. In the presence of strontium, $\langle$120$\rangle$ steps roughened and bifurcated. The overall Barite growth rate also decreased with increasing aqueous strontium-to-barium ratio ([Sr]/[Ba]aq) < 1. Analysis of the reacted solids using chemical imaging techniques indicated strontium incorporated uniformly across all step orientations into the Barite growth hillock for [Sr]/[Ba] aq < 1. However, at [Sr]/[Ba] aq > 5, steps with an apparent [010] orientation were expressed and growth in the [010] step direction led to an increase in the overall growth rate of the surface. Strontium became preferentially incorporated into the [010] step direction, rather than being homogeneously distributed. The [Sr]/[Ba] s in the newly grown solid was found to correlate directly with that of solutions at [Sr]/[Ba] aq < 5, but not for higher [Sr]/[Ba] aq . Solid composition analyses indicate that thermodynamic equilibrium was not achieved. However, kinetic transport modeling successfully reproduces the shift in growth mechanism.

36 MATERIALS SCIENCE↗

Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2 O in alkaline electrolytes

Ammonia (NH 3 ) is considered an important chemical for both agriculture fertilizer and renewable energy. The conventional Haber-Bosh process to produce NH 3 is energy intensive and leads to significant CO 2 emission. Alternatively, electrochemical synthesis of ammonia (ESA) through the nitrogen reduction reaction (NRR) by using renewable electricity has recently attracted significant attention. Herein, we report a metal-organic framework-derived nitrogen-doped nanoporous carbon as an electrocatalyst for the NRR. It exhibits a remarkable production rate of NH 3 up to 3.4 ×10 –6 mol cm –2 h –1 with a Faradaic efficiency (FE) of 10.2% at –0.3 V vs . RHE under room temperature and ambient pressure using aqueous 0.1 M KOH electrolyte. Increasing the temperature to 60 °C further improves production rates to 7.3 × 10 –6 mol cm –2 h –1 . The stability of the nitrogen-doped carbon electrocatalyst was demonstrated during an 18-h continuous test with constant production rates. First principles calculations were used to elucidate the possible active sites and reaction pathway. The moiety, which consists of three pyridinic N atoms (N 3 ) adjacent with one carbon vacancy embedded in a carbon layer, is able to strongly adsorb N 2 and further realize N≡N triple bond dissociation for the subsequent protonation process. The rate-determining step of the NRR is predicted to be the adsorption and bond activation of N 2 molecule. Increasing overpotentials is favorable for the protonation process during NH 3 generation. Further doping Fe into the nitrogen-doped carbon likely blocks the N 3 active sites and facilitates the hydrogen evolution reaction, a strong competitor to the NRR, thus yielding negative effect on ammonia production. Furthermore, this work provides a new insight into the rational design and synthesis of nitrogen-doped and defect-rich carbon as efficient NRR catalysts for NH 3 synthesis at ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potentiostatic and Potential Cycling Dissolution of Polycrystalline Platinum and Platinum Nano-Particle Fuel Cell Catalysts

The dissolution of Pt in aqueous electrolytes has been studied for over forty years, most recently in the context of understanding the observed loss in electrochemically-active surface area (ECA) of cathode electrocatalysts in polymer electrolyte fuel cells. Despite extensive research, there are many unresolved issues regarding the dissolution of nano-particle Pt, such as the source of the observed potential dependence of potentiostatic and potential cycling dissolution rates. To help resolve these issues, in this paper we present results of measurements of the concentration of dissolved Pt and Pt dissolution rates for carbon-supported platinum nano-particles (Pt/C) in dilute perchloric acid, as a mimic of the PEFC cathode environment, as a function of potential and upper potential limit of potential cycling. Also presented, for comparison, are results of similar studies on polycrystalline platinum. In situ Pt L III X-ray absorption spectroscopy was used to determine the extent of oxidation, the coordination environment, and loss of Pt from the Pt nano-particles to elucidate the mechanism of Pt dissolution. Finally, based on the correlation of these studies with those presented in the literature, mechanisms for Pt dissolution under potentiostatic and potential cycling conditions are proposed.

36 MATERIALS SCIENCE↗

Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

We report that hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO 2 and todorokite-MnO 2 . The other two phases have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl 2 solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g -1 , 44.4 mg g -1 , and 43.1 mg g -1 in NaCl, KCl, and MgCl 2 solutions, respectively) and high ion removal rates (as large as 0.112 mg g -1 s -1 , 0.165 mg g -1 s -1 , and 0.164 mg g -1 s -1 in NaCl, KCl, and MgCl 2 solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. In conclusion, this work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions.

36 MATERIALS SCIENCE↗

Low temperature stabilization process for production of carbon fiber having structural order

A method for producing a carbon fiber, the method comprising: (i) subjecting a continuous carbon fiber precursor having a polymeric matrix in which strength-enhancing particles are incorporated to a stabilization process during which the carbon fiber precursor is heated to within a temperature range ranging from the glass transition temperature to no less than 20.degree. C. below the glass transition temperature of the polymeric matrix, wherein the maximum temperature employed in the stabilization process is below 400.degree. C., for a processing time within said temperature range of at least 1 hour in the presence of oxygen and in the presence of a magnetic field of at least 1 Tesla, while said carbon fiber precursor is held under an applied axial tension; and (ii) subjecting the stabilized carbon fiber precursor, following step (i), to a carbonization process. The stabilized carbon fiber precursor, resulting carbon fiber, and articles made thereof are also described.

36 MATERIALS SCIENCE↗

Final CRADA Report for Small Business Voucher (SBV) Pilot Project with TreadStone Technologies, Inc. – Novel Coating for Fuel Cell Metal Bipolar Plates

Light-weight metal is the preferred material for bipolar plate in the automotive proton exchange membrane (PEM) fuel cell stack. The challenge using metal bipolar plates is the high surface electrical contact resistance and the poor corrosion resistance in PEM fuel cell operation conditions. This SBV project involved specialized capabilities and expertise at Los Alamos National Laboratory (LANL) and Oak Ridge National Laboratory (ORNL) supporting TreadStone Technologies, Inc. and included ex-situ and in-situ drive-cycle tests that incorporated coated metallic bipolar plates (LANL tasks) and analysis of the surface chemistry and microstructure of coatings on stainless steel substrates (ORNL tasks).

30 DIRECT ENERGY CONVERSION↗

Bottom up synthesis of boron-doped graphene for stable intermediate temperature fuel cell electrodes

The high surface area and electrical conductivity of few-layered graphene would make it an ideal catalyst support and electrode in fuel cells apart from its susceptibility to oxidative corrosion. Here we report the single-step, bottom-up synthesis of oxidation-resistant boron-doped graphene and show its increased stability in the aggressive electrochemical environment of intermediate temperature solid acid fuel cells (SAFCs). Boron was shown to alter the growth mode of single walled carbon nanohorns by laser vaporization to produce high yields of thin (<20 layer) boron-doped (2–3 at.%) crystalline flakes of turbostratic graphene (B-GLF). Alternatively, adding partial pressures of hydrogen less effectively shifted the growth mode of SWCNHs toward planar, turbostratic graphene-like flakes (GLFs). Thermogravimetric analysis indicates that boron-doping enhances the oxidation resistance of few-layer GLFs by >140 °C, with large fractions of multilayered B-GLFs surviving 10 °C/min ramps to 1000 °C. These B-GLFs provided a stable Pt catalyst support and electrode over 40 h operation in SAFCs with cesium dihydrogen phosphate electrolyte operating at 250 °C, as opposed to undoped GLFs or SWCNHs which were nearly completely consumed. Furthermore, the facile synthesis and oxidation-resistant properties of boron-doped GLF appear promising for graphene applications in oxidizing environments.

25 ENERGY STORAGE↗

Investigation of a microporous iron( III ) porphyrin framework derived cathode catalyst in PEM fuel cells

In Polymer Electrolyte Membrane Fuel Cells (PEMFCs) the thickness, structure and morphology of the electrode layer play an important role in the cell performance. This effect becomes particularly significant when the cathode catalyst is based on a non-precious metal due to the higher catalyst loadings required to compensate for the lower catalytic activity when compared to Pt based catalysts. In this study, an iron( III ) porphyrin framework material was synthesized and pyrolyzed and its catalytic activity towards the oxygen reduction reaction (ORR) was evaluated using rotating disk electrode (RDE) experiments and single cell testing. Single cell performance was evaluated as a function of the electrode catalyst loading (electrode thickness) and oxygen partial pressure. As expected, the ORR kinetic overpotential was the major contributor to the overall voltage loss. However, the mass transport contribution to the voltage loss became more prominent with small increases in the cathode catalyst loading. Finally, the observed performance is discussed in the context of structure and morphology of the catalyst layer (CL), analyzed through scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5–2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H 2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. In conclusion, the hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

36 MATERIALS SCIENCE↗

Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of well dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.

36 MATERIALS SCIENCE↗

Probing Battery Chemistry with Liquid Cell Electron Energy Loss Spectroscopy

We demonstrate the ability to apply electron energy loss spectroscopy (EELS) to follow the chemistry and oxidation states of LiMn 2 O 4 and Li 4 Ti 5 O1 2 battery electrodes within a battery solvent. The use and importance of in situ electrochemical cells coupled with a scanning/transmission electron microscope (S/TEM) has expanded and been applied to follow changes in battery chemistry during electrochemical cycling. Furthermore, we discuss experimental parameters that influence measurement sensitivity and provide a framework to apply this important analytical method to future in situ electrochemical studies.

25 ENERGY STORAGE↗