Showing papers on "Nickel published in 2006"

Hydrogen oxidation and production using nickel-based molecular catalysts with positioned proton relays

Abstract: Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [Ni(PPh2NPh2)2(CH3CN)](BF4)2, 6a, (where PPh2NPh2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 A. The cation of [Ni(PCy2NBz2)2](BF4)2, 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six-membered rings formed upon coordination of the diphosphine ligands to th...

Iron nanoparticles: the core-shell structure and unique properties for Ni(II) sequestration.

Abstract: It is demonstrated that iron nanoparticles function as a sorbent and a reductant for the sequestration of Ni(II) in water. A relatively high capacity of nickel removal is observed (0.13 g Ni/g Fe, or 4.43 mequiv Ni(II)/g), which is over 100% higher than the best inorganic sorbents available. High-resolution X-ray photoelectron spectroscopy (HR-XPS) confirms that the zerovalent iron nanoparticles have a core-shell structure and exhibit characteristics of both hydrous iron oxides (i.e., as a sorbent) and metallic iron (i.e., as a reductant). Ni(II) quickly forms a surface complex and is then reduced to metallic nickel on the nanoparticle surface. The dual properties of iron nanoparticles may offer efficient and unique solutions for the separation and transformation of metal ions and other environmental contaminants.

Non-metal Catalysts for Dioxygen Reduction in an Acidic Electrolyte

Abstract: Active non-metal catalysts for the Oxygen Reduction Reaction (ORR) were prepared by decomposition of acetonitrile vapor at 900°C over a pure alumina support, and supports containing 2 wt% Fe or 2 wt% Ni on alumina. The exposed alumina and metal in the samples were subsequently washed away with HF acid to purify the solid carbon material. The sample prepared with iron was the most active sample for the ORR, with only 100 mV greater overpotential than a commercial 20 wt% Pt / Vulcan Carbon catalyst. However, nitrogen-containing carbon deposited on pure alumina (which contained less than 1 ppm metal contamination) was also quite active, demonstrating that platinum or iron is not required for ORR activity. Characterization by XPS and TEM revealed that the more active samples had nanostructured carbon with more edge plane exposure than the less active tube structures formed from the nickel sample.

Effect of Pressure on the Behavior of Copper-, Iron-, and Nickel-Based Oxygen Carriers for Chemical-Looping Combustion

Abstract: The combustion process integrated by coal gasification and chemical-looping combustion (CLC) could be used in power plants with a low energy penalty for CO2 capture. This work analyzes the main characteristics related to the CLC process necessary to use the syngas obtained in an integrated gasification combined cycle (IGCC) power plant. The kinetics of reduction with H2 and CO and oxidation with O2 of three high-reactivity oxygen carriers used in the CLC system have been determined in a thermogravimetric analyzer at atmospheric pressure. The iron- and nickel-based oxygen carriers were prepared by freeze-granulation, and the copper-based oxygen carrier was prepared by impregnation. The changing grain size model (CGSM) was used for the kinetic determination, assuming spherical grains for the freeze-granulated particles containing iron and nickel and a platelike geometry for the reacting surface of the copper-based impregnated particles. The dependence of the reaction rates on temperature was low, with the a...

Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations

Abstract: Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported from the deposition site at the free nickel surface to the perimeter of the growing graphene layer via surface or subsurface diffusion. Three different processes are identified to govern the growth of graphene layers, depending on the termination of the graphene perimeter at the nickel surface, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings.

CO2 reforming of CH4 over La–Ni based perovskite precursors

Abstract: LaNiO3 and La2NiO4 type perovskites were prepared by the “self-combustion” method and were used as catalyst precursors for the CO2 reforming of CH4 reaction at 700 °C. The catalysts were tested in reduced and non-reduced form. High CH4 and CO2 conversion were obtained without carbon deposition. This result was explained by the occurrence of the RWGS (reverse water gas shift) reaction. The La2NiO4 perovskite used as precursor presents the smallest nickel particles after the reduction treatment. Consequently the catalytic activity is higher than that obtained with Ni/La2O3 or LaNiO3. When La2NiO4 is used without treatment prior to the reaction high methane and carbon dioxide conversions are reached but a carbon deposition is observed. The perovskite structure is not completely transformed and the presence of metallic nickel particles at the surface of La2NiO4 would be responsible for the carbon deposition. It is assumed that the role of the support is to allow the activation of carbon dioxide, which is favoured over La2O3 whereas it is limited over La2NiO4. Consequently the reaction between the complex C–Ni species (resulting from methane activation at the surface of the nickel particle) and gaseous CO2 is inhibited over Ni/La2NiO4 leading to a carbon accumulation at the surface of the catalyst. As soon as the perovskite structure is completely transformed, after reductive treatment or during the reaction, a high activity is reached and no carbon deposition was further observed, the catalytic performances being optimal when the average nickel particles size is the smallest.

Chiral three-dimensional microporous nickel aspartate with extended Ni-O-Ni bonding.

Abstract: In the course of our investigation aimed at the preparation of homochiral coordination polymers using readily available in optically pure form ligands and building blocks of condensed metal polyhedra, we recently reported a one-dimensional nickel aspartate compound [Ni2O(l-Asp)(H2O)2]·4H2O (1) based on helical chains with extended Ni−O−Ni bonding. Here we report a new nickel aspartate [Ni2.5(OH)(l-Asp)2]·6.55H2O (2) with a three-dimensional Ni−O−Ni connectivity that forms at a higher pH and is based on the same helices as in 1 which are connected by additional nickel octahedra to generate a chiral open framework with one-dimensional channels with minimum van der Waals dimensions of 8 × 5 A. The crystal structure of 2 was determined by synchrotron single-crystal X-ray diffraction on a 10 × 10 × 240 μm crystal.

Hardening effect induced by incorporation of SiC particles in nickel electrodeposits

Abstract: Pure Ni and nickel matrix composite electrocoatings containing micron- and nano-SiC particles (1 μm and 20 nm respectively) were produced under direct and pulse current conditions from an additive-free Watts type bath. The effect of the particle size, codeposition percentage of SiC and type of imposed current on the microhardness as well as on the microstructure of the electrodeposits were investigated. Ni/SiC composite deposits prepared under either direct or pulse current conditions exhibited a considerable strengthening effect with respect to pure Ni coatings. The improved hardness of composite coatings was associated to specific structural modifications of Ni crystallites provoked by the adsorption of H+ on the surface of SiC particles, thus leading to a (211) texture mode of Ni crystal growth. Pulse electrodeposition significantly improved the hardness of the Ni/SiC composite coatings, especially at low duty cycles, in which grain refinement and higher SiC incorporation (vol. %) was achieved. The enhanced hardness of Ni/nano-SiC deposits, as compared to Ni/micron-SiC composites, was attributed to the increasing values of the number density of embedded SiC particles in the nickel matrix with decreasing particle size. In addition, the observed hardening effects of the SiC particles might be associated to the different embedding mechanisms of the particles, which could be characterized as inter-crystalline for micron-SiC and partially intra-crystalline for nano-SiC particles.

Corrosion resistance and Microstructure of electrodeposited nickel-cobalt alloy coatings

Abstract: Ni–Co alloys with varying cobalt content were electrodeposited employing sulphamate electrolyte. The changes in microstructure and corrosion behavior of electrodeposited nickel with respect to cobalt addition were studied. Scanning electron microscope, optical microscope and energy dispersive X-ray analysis were used to characterize the alloy coatings. The alloy co-deposition was observed to be anomalous type. The cross-section microhardness measurement indicated that the hardness reached the maxima for a cobalt content of 50 wt.% and then dropped with the increase in cobalt content. A correlation between microhardness and microstructure has been attempted. The optical micrographs indicated a change in microstructure from mixed columnar-fibrous to lamellar and finally to fibrous with increase in cobalt content. The X-ray diffraction (XRD) studies indicated the crystal structure to be cubic for cobalt content in the range of 0–50 wt.%. A transition to hexagonal structure was observed for a cobalt content of 70 wt.% and beyond. A change in preferred orientation was also observed with respect to cobalt addition. Potentiodynamic polarization and electrochemical impedance studies were used to study the corrosion behavior of Ni–Co alloys. The physical behavior was quantified with equivalent circuit. These studies indicated that the Ni–20% Co alloy exhibited better corrosion resistance in comparison to other Ni–Co alloys, plain nickel and plain cobalt coatings irrespective of the substrate (mild steel, brass) employed for deposition.

Recent developments in the electrodeposition of nickel and some nickel-based alloys

Abstract: The numerous theoretical and practical studies of the electrodeposition of nickel and its binary and selected ternary alloys with copper and cobalt over the last 10–15 years are reviewed. The reported mechanisms of the electrodeposition processes and accompanying evolution of hydrogen are considered. The complex influence of different bath compositions, pHs, current densities or potential ranges and temperature on the formation of single or multiple deposition layers are compared. The determination of the structure and morphology of the deposits on different substrates, including solid surfaces and particulate materials, using a range of analytical techniques are reported.

Sintering of nickel catalysts: Effects of time, atmosphere, temperature, nickel-carrier interactions, and dopants

Abstract: Supported nickel catalysts are widely used in the steam-reforming process for industrial scale production of hydrogen and synthesis gas. This paper provides a study of sintering in nickel-based catalysts (Ni/Al 2 O 3 and Ni/MgAl 2 O 4 ). Specifically the influence of time, temperature, atmosphere, nickel-carrier interactions and dopants on the rate of sintering is considered. To probe the sintering kinetics, all catalysts were analyzed by sulfur chemisorption to determine the Ni surface area. Furthermore selected samples were further analyzed using X-ray diffraction (XRD), mercury porosimetry, BET area measurements, and electron microscopy (EM). The observed sintering rates as a function of time, temperature, and P H 2 O / P H 2 ratio were consistent with recent model predictions [J. Sehested, J.A.P. Gelten, I.N. Remediakis, H. Bengaard, J.K. Norskov, J. Catal. 223 (2004) 432] over a broad range of environmental conditions. However, exposing the catalysts to severe sintering conditions the loss of nickel surface area is faster than model predictions and the deviation is attributed to a change in the sintering mechanism and nickel removal by nickel-carrier interactions. Surprisingly, alumina-supported Ni particles grow to sizes larger than the particle size of the carrier indicating that the pore diameter does not represent an upper limit for Ni particle growth. The effects of potassium promotion and sulfur poisoning on the rates of sintering were also investigated. No significant effects of the dopants were observed after ageing at ambient pressure. However, at high pressures of steam and hydrogen (31 bar and H 2 O:H 2 = 10:1) potassium promotion increased the sintering rate relative to that of the unpromoted catalyst. Sulfur also enhances the rate of sintering at high pressures, but the effect of sulfur is less than for potassium.

XRD and XPS Study of Cu−Ni Interactions on Reduced Copper−Nickel−Aluminum Oxide Solid Solution Catalysts

Abstract: Copper−nickel−aluminum oxide solid solutions were reduced in hydrogen to produce alumina-supported copper−nickel alloy catalysts. XRD patterns of reduced oxides showed that the type of active metals which emerged upon reduction were sensitive to the reduction temperature and the copper content. Variations from +0.8 to +1 eV were found in the experimental Ni 2p3/2 binding energy (BE) of nickel in the solid solutions compared to the experimental Ni 2p3/2 BE of bulk nickel, attributed to the Ni−Ni arrangements in the solid solution. Also, when the curve-fitted BE values of Ni 2p3/2 and Cu 2p3/2 of different reduced solid solutions were compared, it was found that copper and nickel were in different chemical states depending on reduction temperature and the amount of the copper. Changes in Ni 2p3/2 BE in the reduced solid solutions were also discussed in terms of the filling of nickel d-hole bands due to nickel−copper d−d band interactions. At both high copper content and reduction temperature, copper had a t...

Phase Stability of Nickel Hydroxides and Oxyhydroxides

Abstract: In this paper, we investigate the phase stability of nickel hydroxides from first-principles. We predict that the previously uncharacterized crystal structure of III‐NiOOH is actually derived from the P3 host. Furthermore, we identify a plausible crystal structure for the -NiO2H2O0.67K0.33Hx phase that is consistent with available experimental observations. The proposed crystal structure has a P3 host and the K ions reside exactly between adjacent trigonal prismatic sites of the intercalation layer. We have also calculated the topotactic voltage curves for the and phases, and predict the existence of a large step in voltage at -NiOOH, which effectively limits the capacity of the Ni-hydroxide compound to one electron per Ni ion. Methodology We combine first-principles electronic structure calculations with a cluster expansion approach for the disorder of protons in the materials to calculate phase stability and thermodynamic properties of the nickel hydroxide system. The electronic structure calculations

Biomolecule-assisted synthesis and electrochemical hydrogen storage of porous spongelike Ni3S2 nanostructures grown directly on nickel foils.

Abstract: Nanothread-based porous spongelike Ni 3 S 2 nanostructures were synthesized directly on Ni foil by using a simple biomolecule-assisted method. By varying the experimental parameters, other novel Ni 3 S 2 nanostructures could also be fabricated on the nickel substrate. The electrochemical hydrogen-storage behavior of these novel porous Ni 3 S 2 nanostructures was investigated as an example of the potential properties of such porous materials. The thread-based porous spongelike Ni 3 S 2 could electrochemically charge and discharge with the high capacity of 380 mAhg -1 (corresponding to 1.4 wt % hydrogen in single-walled nanotubes (SWNT)). A novel two-charging-plateaux phenomenon was observed in the synthesized porous spongelike Ni 3 S 2 nanostructures, suggesting two independent steps in the charging process. We have demonstrated that the morphology of the synthesized Ni 3 S 2 nanostructures had a noticeable influence on their electrochemical hydrogen-storage capacity. This is probably due to the size and density of the pores as well as the microcosmic morphology of different nickel sulfide nanostructures. These novel porous Ni 3 S 2 nanostructures should find wide applications in hydrogen storage, high-energy batteries, luminescence, and catalytic fields. This facile, environmentally benign, and solution-phase biomolecule-assisted method can be potentially extended to ' the preparation of other metal sulfide nanostructures on metal substrates, such as Cu, Fe, Sn, and Pb foils.