Nickel

About: Nickel is a research topic. Over the lifetime, 79308 publications have been published within this topic receiving 1210058 citations. The topic is also known as: Ni & element 28.

Catalyst and binder effects in the use of filamentous graphite for AMS

Abstract: Filamentous graphite produced by the reduction of carbon dioxide over a transition metal catalyst has been used as a sample material in the AMS counting of 14C for several years. While iron has been the most common catalyst used, cobalt and nickel have also been investigated. We have compared the reaction's total isotopic fractionation using these three metals in various powder forms. The graphites produced over these catalysts have been compared with respect to ion beam intensity and measured isotope ratio in our AMS system. The use of the reduction catalysts as graphite binders improved the very poor thermal conductivity of pure filamentous graphite. The relative advantages of the elements for modern contamination of the sample material were also determined.

Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases

Abstract: Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2PhN2Ph)2(CH3CN)](BF4)2, 3a (where P2PhN2Ph is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s−1 establishes that the rate of H2 production for the mononuclear nickel catalyst 3a is comparable to those observed for Ni-Fe hydrogenase enzymes. In the electrochemical oxidation of hydrogen catalyzed by [Ni(P2CyN2Bz)2](BF4)2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm−1 at 25°C). The hydrogen addition product exists as three nearly isoenergetic isomers 4A–4C, which have been identified by a combination of one- and two-dimensional 1H, 31P, and 15N NMR spectroscopies as Ni(0) complexes with a protonated amine in each cyclic ligand. The nature of the isomers, together with calculations, suggests a mode of hydrogen activation that involves a symmetrical interaction of a nickel dihydrogen ligand with two amine bases in the diphosphine ligands. Single deprotonation of 4 by an external base results in a rearrangement to [HNi(P2CyN2Bz)2](BF4), 5, and this reaction is reversed by the addition of a proton to the nickel hydride complex. The small energy differences associated with significantly different distributions in electron density and protons within these molecules may contribute to their high catalytic activity.