The surface oxidation and reduction chemistry of zirconium-nickel compounds examined by XPS

doi:10.1016/0169-4332(88)90098-0

Applied Surface Science

Volume 31, Issue 3, April 1988, Pages 341-369

https://doi.org/10.1016/0169-4332(88)90098-0 Get rights and content

Abstract

Zirconium-nickel intermetallic compounds, Zr₂Ni, ZrNi, ZrNi₃, Zr₂Ni₇ and ZrNi₅ have been investigated by X-ray photoelectron spectroscopy (XPS) for their response to oxidation and reduction. Chemical and structural changes were found to be composition dependent. Results indicate that preferential reaction, segregation and oxide ordering of one metal component or the other under specific treatment conditions explain the observed catalytic activity of these materials for ethylene hydrogenation.

References (54)

C.A. Luengo et al.
J. Catalysis
(1977)
T. Takeshita et al.
J. Catalysis
(1976)
G.B. Atkinson et al.
J. Catalysis
(1977)
K. Soga et al.
J. Catalysis
(1979)
H. Imamura et al.
J. Catalysis
(1980)
B.Yu. Rakhamimov et al.
Petrol. Chem. USSR
(1980)
V.I. Nefedov et al.
Surface Interface Anal.
(1980)
G.B. Atkinson et al.
V.V. Lunin et al.
Khim. Tverd. Topl.
(1984)
R. Szymanski et al.
J. Catalysis
(1986)
A.G. Moldovan et al.
J. Solid State Chem.
(1978)

R.L. Chin et al.

J. Phys. Chem.

(1980)

T.A. Dang et al.

J. Phys. Chem.

(1984)

C. Yoon et al.

J. Electrochem. Soc.

(1987)

C. Ping Li et al.

Appl. Spectrosc.

(1984)

J. McCarty et al.

J. Catalysis

(1975)

M.A. Smith et al.

J. Vacuum Sci. Technol.

(1979)

J. Kleefeld et al.

Thin Solid Films

(1979)

R.F. Voitovich et al.

Soviet J. Powder Met. Ceram.

Poroshkovaya Metallurgiya

(1978)

V.T. Coon et al.

J. Phys. Chem.

(1977)

K. Soga et al.

J. Phys. Chem.

(1976)

A. Elattar et al.

Science

(1977)

V.V. Lunin et al.

Dokl. Akad. Nauk SSSR

(1978)

A. Elattar et al.

Advan. Chem. Ser.

(1979)

H. Imamura et al.

J. Phys. Chem.

(1979)

H. Imamura et al.

J. Phys. Chem.

(1979)

J.H. Sinfelt

Bimetallic Catalysts: Discoveries, Concepts and Applications

E.G. Baglin et al.

Ind. Eng. Chem. Prod. Res. Develop.

(1981)

Cited by (41)

Ni/Ce co-doping δ-MnO<inf>2</inf> nanosheets with oxygen vacancy for enhanced electrocatalytic oxygen evolution reaction
2023, International Journal of Hydrogen Energy
Citation Excerpt :
As regards NiCe/MnO2, the peaks of Ce4+ and Ce3+ at 904 eV and 908 eV were shifted to lower binding energies of 903 eV and 907 eV, which is due to the allocation of excess electrons to Ce after Ni entered the δ-MnO2 lattice [49]. Furthermore, it is shown in Fig. 3e that Ni undergoes mutual oxidation-reduction in the presence of Ni3+ and Ni2+ in the catalyst Ni/MnO2 and NiCe/MnO2 [50]. The molar ratios of the bulk phases of MnO2, Ni/MnO2, Ce/MnO2 and CeNi/MnO2 were detected by ICP-AES to be very close to the experimental design values (Table 1), indicating that Ni or Ce was almost completely doped.
The design and manufacture of strongly engaged, low-cost, and resilient oxygen evolution reaction (OER) electrocatalysts is the most challenging task in electrochemical hydrolysis. Herein, Ce and Ni co-doped MnO₂ (NiCe/MnO₂) nanosheets (NSs) with oxygen vacancy (V_O) and abundant active sites have been prepared in one step employing a defect strategy. The co-doping of Ce/Ni on the one hand reduced the catalyst particle size and increased the specific surface area, which promoted the exposure of more active sites. On the other hand, heteroatom doping altered the species the crystalline surface, stimulating the formation of Vo and thus activating the catalyst performance simultaneously. The OER performance of NiCe/MnO₂ NSs was significantly enhanced over the pure δ-MnO₂, with an overpotential of 170 mV (10 mA cm⁻²), which was verified by density functional theory. This work shows a straightforward and practical method for making non-precious metal electrocatalysts with high electrochemical hydrolysis performance.
Effect of heat treatments on the microhardness and tensile strength of Al-0.25 wt.% Zr alloy
2015, Journal of Alloys and Compounds
Citation Excerpt :
As a result, Zr with its higher electropositivity is preferentially oxidized by O2 in the gas phase. This is in agreement with previous studies in the literature [44,45]. Variations of the microhardness and tensile strength of the Al–0.25 Zr alloy for different aging temperatures and aging times are given in Figs. 4–8.
In the present work, the effect of heat treatments on the microhardness and tensile properties of the Al–0.25 Zr (wt.%) alloy have been investigated. The Al–0.25 Zr (wt.%) alloy was melted in a vacuum furnace, and the molten alloy was poured into crucibles held in a hot filing furnace. Then, the samples were directionally solidified from bottom to top and aged isothermally and isochronally in a muffle furnace. Aging was performed in two ways: using a wide range of temperatures (350–600 °C) with a constant aging time (100 h) and a wide range of aging times (3–240 h) with a constant temperature (400 °C). The dependence of the microhardness (HV) and ultimate tensile strength (σ_UTS) on the aging temperatures and aging times was determined. According to the experimental results, the HV and σ_UTS values of the aged samples increase at a certain aging temperature and aging time values, reaching peak values at specific temperatures and aging times. The microhardness and ultimate tensile strength decreased with further increase of aging temperatures and aging times. The microscopic fracture surfaces of the aged samples under different aging conditions were observed using scanning electron microscopy. Fractographic analysis of the tensile fracture surfaces shows that the type of fracture changed significantly from ductile to brittle depending on the aging times. Transmission electron microscopy was also used to characterize the precipitation processes in an Al–0.25 Zr (wt.%) alloy aged at 400 °C for 120 h.
Surface modification of Zircaloy-4 substrates with nickel zirconium intermetallics
2013, Journal of Nuclear Materials
Citation Excerpt :
In either regime, Zr-4 is highly resistant to oxidation by steam and water compared to other metals, which makes it desirable for many applications [2–4]. Since nickel–zirconium (NiZr) intermetallics are known to readily oxidize [5], the surface-modification approach selected for this study consisted of plating Zr-4 substrates with Ni and performing a thermal treatment to react Ni and Zr-4. Since the solubility between Ni and Zr is limited and there are eight intermetallics in the NiZr phase diagram, an intermetallic coating was expected to result on the surface of the substrate [6,7].
Surfaces of Zircaloy-4 (Zr-4) substrates were modified with nickel–zirconium (NiZr) intermetallics to tailor oxidation performance for specialized applications. Surface modification was achieved by electroplating Zr-4 substrates with nickel (Ni) and then performing thermal treatments to fully react the Ni plating with the substrates, which resulted in a coating of NiZr intermetallics on the substrate surfaces. Both plating thickness and thermal treatment were evaluated to determine the effects of these fabrication parameters on oxidation performance and to identify an optimal surface modification process. Isothermal oxidation tests were performed on surface-modified materials at 290°, 330°, and 370 °C under a constant partial pressure of oxidant (i.e., 1 kPa D₂O in dry Ar at 101 kPa) for 64 days. Test results revealed an enhanced, transient oxidation rate that decreased asymptotically toward the rate of the Zr-4 substrate. Oxidation kinetics were analyzed from isothermal weight gain data, which were correlated with microstructure, hydrogen pickup, strength, and hardness.
Oxidation behaviour of binary zirconium alloys containing intermetallic precipitates
2011, Journal of Nuclear Materials
Citation Excerpt :
This question could not be answered here. As an example in the case of Ni containing alloys two different behaviours have been reported by Auger studies: two studies have reported a depletion of the outermost oxide layer in Ni [11,30] for samples oxidised in autoclave, and two others [31,32] have reported Ni to enrich above the stoichiometry of the intermetallic on the surface for exposures to oxygen and hydrogen. These observations do not clarify the oxidation behaviour of Ni containing SPPs and their behaviour in the oxide close to the surface.
To better understand the oxidation behaviour of Zr alloys, binary alloys containing 1 wt.% Fe, Ni, Cr or 0.6 wt.% Nb were oxidised in different oxidation environments at pressures ranging from 130 Pa to 10 MPa at 688 K and at different oxidation times. The surface of the oxidised alloys was analysed and the precipitate oxidation behaviour was found to be alloying element specific. Two different precipitate oxidation behaviours were observed in these alloys, precipitates with oxidation rates similar to the Zr-matrix (Fe and Ni) and others which show a delayed oxidation (Cr and Nb). In the case of Zr1%Fe pure iron oxide crystals of more than 1 μm size were observed at the surface of the material oxidised for longer oxidation times. In the oxide of Zr1%Cr and Zr0.6%Nb small crescent-shaped cracks were observed at the precipitate–oxide interface. In this study, materials oxidised for 110 days are examined in detail, and compared with those oxidised for lower pressures and/or shorter periods of time.
The low-temperature thermal oxidation of copper, Cu<inf>3</inf>O <inf>2</inf>, and its influence on past and future studies
2005, Vacuum
Due to its enormous technological importance there is a renewed interest in the oxidation of copper. However, due to the complex nature of oxidation of copper, the existence and importance of Cu₃O₂, which is a metastable defect structure of Cu₂O, have not gained enough attention from researchers working on the oxidation of copper or copper alloys. The evidence for the Cu₃O₂ phase has been utilized to reinterpret previous Pulse Field Desorption Mass Spectrometry (PFDMS) and X-ray Photoelectron Spectroscopy (XPS) data. With additional Linear Sweep Voltammetry (LSV) and Galvanostatic Reduction (GR) data, an attempt has been made to delineate the complex nature of the oxidation of copper based on the Modified Cabrera Mott (C–M) Model. It is also emphasized that surface scientists should recognize Cu₃O₂ in new studies on copper oxidation and in interpreting already existing copper oxidation data. Need for more vacuum and low-pressure-based studies is stressed to characterize the distinct overlayers that can be formed by temperature and pressure control. Surface studies of oxidation of metals and alloys need to be supported and complemented by other techniques such as chemical and electrochemical methods.
Surface segregation behaviors of amorphous Ni <inf>65</inf> Nb <inf>35</inf> alloy under oxidation in O <inf>2</inf> at various temperatures
1999, Applied Surface Science
Variations of surface morphology and chemical composition of amorphous Ni₆₅Nb₃₅ alloy after oxidation in 1 atm O₂ at temperatures from room temperature to 773 K have been investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) depth profile methods. Inverse segregation behaviors have been observed at two oxidation temperature ranges. At the lower temperature range (≤373 K), Nb segregates at the surface as Nb₂O₅; while at the higher temperature range (≥523 K), Ni segregates at the surface as metallic Ni and NiO. Different oxidation mechanisms have been suggested to operate in the two oxidation temperature ranges, which may be concerned with different oxidation rates of Nb and diffusion speeds of O and Ni ions in the Nb₂O₅ layer at different temperatures. The affinities of Ni and Nb to oxygen may act as the driving force of the segregation.

View all citing articles on Scopus

View full text

The surface oxidation and reduction chemistry of zirconium-nickel compounds examined by XPS

Abstract

J. Catalysis

J. Catalysis

J. Catalysis

J. Catalysis

J. Catalysis

Petrol. Chem. USSR

Surface Interface Anal.

Khim. Tverd. Topl.

J. Catalysis

J. Solid State Chem.

J. Phys. Chem.

J. Phys. Chem.

J. Electrochem. Soc.

Appl. Spectrosc.

J. Catalysis

J. Vacuum Sci. Technol.

Thin Solid Films

Poroshkovaya Metallurgiya

J. Phys. Chem.

J. Phys. Chem.

Science

Dokl. Akad. Nauk SSSR

Advan. Chem. Ser.

J. Phys. Chem.

J. Phys. Chem.

Bimetallic Catalysts: Discoveries, Concepts and Applications

Ind. Eng. Chem. Prod. Res. Develop.