Nickel-hydride

Catalytic Reactivity of Hydrogen on Palladium and Nickel Hydride Phases... 

II. Formation, Structure, and Properties of Palladium and Nickel Hydrides. 247... 

This review aims to present an account of the catalytic properties of palladium and nickel hydrides as compared with the metals themselves (or their a-phase solid solutions with hydrogen). The palladium or nickel alloys with the group lb metals, known to form /8-phase hydrides, will be included. Any attempts at commenting on the conclusions derived from experimental work by invoking the electronic structure of the systems studied will of necessity be limited by our as yet inadequate knowledge concerning the electronic structure of the singular alloys, which the hydrides undoubtedly are. 

A short survey of information on formation, structure, and some properties of palladium and nickel hydrides (including the alloys with group IB metals) is necessary before proceeding to the discussion of the catalytic behavior of these hydrides in various reactions of hydrogen on their surface. Knowledge of these metal-hydrogen systems is certainly helpful in the appreciation, whether the effective catalyst studied is a hydride rather than a metal, and in consequence is to be treated in a different way in a discussion of its catalytic activity. 

The nickel-hydrogen system has not been studied in such detail. The isotherm at 25°C is presented in Fig. 3 on the basis of the results obtained by Baranowski and Bochenska (11a). The /3-phase of nickel hydride appears when H/Ni exceeds 0.04 at an equilibrium pressure of 3400 atm. The characteristic H/Ni ratio in the /3-phase then amounts to 0.6. 

Standard Free Energies, Enthalpies, and Entropies of Formation of Palladium and Nickel Hydrides ... 

As has been shown by the X-ray diffraction method the parent metals (i.e. Pd or Ni), the a-phase, and /3-phase all have the same type of crystal lattice, namely face centered cubic of the NaCl type. However, the /9-phase exhibits a significant expansion of the lattice in comparison with the metal itself. Extensive X-ray structural studies of the Pd-H system have been carried out by Owen and Williams (14), and on the Ni-H system by Janko (8), Majchrzak (15), and Janko and Pielaszek (16). The relevant details arc to be found in the references cited. It should be emphasized here, however, that at moderate temperatures palladium and nickel hydrides have lattices of the NaCl type with parameters respectively 3.6% and 6% larger than those of the parent metals. Within the limits of the solid solution the metal lattice expands also with increased hydrogen concentration, but the lattice parameter does not depart significantly from that of the pure metal (for palladium at least up to about 100°C). 

On the basis of information on the properties of the nickel-hydrogen and nickel-copper-hydrogen systems available in 1966 studies on the catalytic activity of nickel hydride as compared with nickel itself were undertaken. As test reactions the heterogeneous recombination of atomic hydrogen, the para-ortho conversion of hydrogen, and the hydrogenation of ethylene were chosen. 

The coefficient of recombination of atomic hydrogen on nickel was about one order of magnitude higher than on nickel hydride at the same temperature. Even a partially decomposed hydride was still as inactive as the original hydride sample. 

As far as hydride decomposition is concerned, the relations are reversed. The larger the metal crystals are the slower their hydride decomposes (62). Moreover some deposits situated on the exit points of dislocations, for example on the surface of a nickel hydride crystal, inhibit hydrogen desorption and result in prolonging the hydride existence in the crystal (87). 

Baranowski [680] concluded that the decomposition of nickel hydride was rate-limited by a volume diffusion process the first-order equation [eqn. (15)] was obeyed and E = 56 kJ mole-1. Later, Pielaszek [681], using volumetric and X-ray diffraction measurements, concluded from observations of the effect of copper deposited at dislocations that transportation was not restricted to imperfect zones of the crystal but also occurred by diffusion from non-defective regions. The role of nickel hydride in catalytic processes has been reviewed [663]. 

The Icw-tenperature 1x2 phase is thermally uistable and explodes exactly at T = 220 K accompanied ty a sudden release of hydrogen in a very narrow TD state (14). This surface e q>losion is epparently associated with the thermal (teocnposition of a H-oontaining surface cotipomd, possibly nickel hydride. 

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