Transition tungsten nitrides

Figure 8.8 Structure of FeWN2. An example of a ternary transition metal nitride containing octahedral iron and trigonal prismatic tungsten. Small white = Iron, Black = Tungsten, Large...

Figure 8.9 Structure of MnMoN2 and j3-MnWN2. Examples of ternary transition metal nitrides containing octahedral manganese and trigonal prismatic molybenum/tungsten. Small white = Manganese, Black = Molybenum/Tungsten, Large white = Nitrogen.

The early transition metal nitrides of titanium, zirconium, hafnium, tantalum, and tungsten as well as titanium and tantalum carbide are effective diffusion... 

Transition metal carbides, such as tungsten carbide and its alloys, tantalum carbide, titanium carbide, and molybdenum carbide (Cowling et al, 1970,1971 Voorhies et al., 1972 Scholl et ah, 1992,1994 Borup et al., 2007), have been studied as catalysts for electrochemical reactions. However, it has been found that these transition metal carbides are unstable under high potentials and in acid solution, and this limits their application as PEM fuel cell catalysts (Borup et al., 2007). Transition metal nitrides have been studied as electrochemical catalysts in PEM fuel cell environments, and Zhong et al. (2006) showed that molybdenum nitride supported on carbon powder resulted in a cell performance of about 0.3 V at 0.2 A cm, and the catalyst was stable for 60 h of cell operation. However, the long-term performance durability is still questionable. 

Leclercq, L., Almazouari, A., Dufour, M., and Leclercq, G. 1996. Carbide-oxide interactions in bulk and supported tungsten carbide catalysts for alcohol synthesis. In Chemistry of transition metal carbides and nitrides, ed. S. T. Oyama, 345-61. Glasgow Blackie. 

There have been significant advances during the last decade in the synthesis of high specific surface area (Sg) carbides and nitrides of transition metals.1 2 This has naturally prompted interest in the application of these materials as catalysts. Carbides of molybdenum and tungsten received the most attention because they catalyze many reactions that typically occur on noble metals. In several reactions, molybdenum carbides show catalytic activity similar to that of ruthenium and surface reactivity of tungsten carbides resembles that of platinum.3-7... 

The carbides and nitrides of the early transition metals have attracted considerable attention. Much of this can be attributed to the catalytic properties of these materials. Levy and Boudart1 were the first to note the Pt-like catalytic behavior of WC, which for many reactions is more catalytically active than metallic tungsten.2 Others have noted that the early transition metal carbides and nitrides, in general, are excellent catalysts for reactions characteristic of the more expensive noble metals.3,4 For example, WC has been found to catalyze the isomerization of neopentane to isopentane,1 a reaction that previously had been known to be catalyzed only by iridium and platinum.5... 

The crystal structures adopted by the binary carbides and nitrides are similar to those found in noble metals. The resemblance is not coincidental, and has been explained using Engel-Brewer valence bond theory [5]. Briefly, the main group elements C and N increase the metal s effective s-p electron count, so that structures and chemical properties of the early transition metals resemble those of the Group 8 metals. This idea was first introduced by Levy and Boudart [6] who noted that tungsten carbide had platinum-like properties. 

Tungsten carbide — WC, belongs to a class of Group IV B-VIB transition metal carbides and nitrides, often referred to as interstitial alloys, in which the carbon and nitrogen atoms occupy the interstitial lattice positions of the metal [i]. These compounds possess properties known from group VIII B precious metals like platinum and palladium [ii]. Thus, they show remarkable catalytic activities, attributed to a distinct electronic structure induced by the presence of carbon or nitrogen in the metal lattice. Tungsten carbide resembles platinum in its electrocatalytic oxidation activity (- electrocatalysis) and is therefore often considered as an inexpensive anode electrocatalyst for fuel cell [iii] and -> biofuel cell [iv] application. 

The metal nitrides of the transition metals of the subgroups of the IVth, Vth and Vlth groups are very similar to the corresponding carbides in their. structures (interstitial compounds of the MN type) and their properties such as hardness, melting point and electrical conductivity (see Table 5.6-3). Tungsten and molybdenum nitrides are exceptions with different structures and decompose with nitrogen loss above 800°C. 

Carbides and nitrides of transition metals are usually hard and some of them are used as hard materials. Tungsten carbide, which was briefly described above, is a major component of cutting tools and wear-resistant materials. Titanium carbide. Tie, and nitride, TiN, are two other major hard materials that are widely used in tools. They also find application as hard coatings (in particular, TiN [177]) and components of ceramic matrix composites [178]. Both TiC and TiN show a very... 

The utility of carbide and nitride catalysts has prompted numerous studies of their reactivity that use carbide and nitride overlayers as the catalyst rather than bulk carbides or nitrides. This approach permits careful manipulation of the surface metal/nonmetal stoichiometry, which is crucial to probing reactivity. These studies consistently reveal the catalytic activity of carbide and nitride overlayers and, in several cases, the similarities between their behavior and that of noble metal catalysts. For example, the same benzene yield and reaction pathway for the dehydrogenation of cyclohexane was observed for both p(4x4)-C/Mo(110) and Pt(l 11) surfaces. Furthermore, carbon-modified tungsten may be a more desirable catalyst for direct methanol fuel cells than Pt or Ru surfaces because the transition metal carbide exhibits higher activity toward methanol and water dissociation and is more CO-tolerant. ... 

The metals of the nine early-transition elements, i.e., titanium, zirconium, and hafiiium of Group IV, vanadium, niobium, and tantalum of Group V, and chromium, molybdenum, and tungsten of Group VI, fit the criteria of size and site availability, and form interstitial nitrides.1 1... 

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