Formation metal nitrides

The only reactions of molecular nitrogen at ambient temperature are the formation of lithium nitride Li3N, reactions with certain transition metal complexes, and nitrogen fixation with nitrogenase in the bacteria of the root nodules of legumes and in blue algae (Sections 14.1.1 and 14.1.2). Above 500 °C nitrogen reacts with some elements, especially with metals (nitride formation). 

For pyrophoric materials, oxidation of the compound by oxygen or moisture in air proceeds so rapidly that ignition occurs. Many finely divided metals are pyrophoric, and their degree of reactivity depends on particle size, as well as factors such as the presence of moisture and the thermodynamics of metal oxide or metal nitride formation. Many other reducing agents, such as metal hydrides, alloys of reactive metals, low-valent metal salts, and iron sulfides, are also pyrophoric. 

Nitrogen interacts weakly with most of the Group Vlll/Ib metals. Dissociative adsorption is only possible on iron, ruthenium, and on metals toward the left of the Periodic Table. This behavior correlates well with the enthalpy of metal nitride formation which is positive for copper, nickel, and cobalt nitrides, but negative for... 

As a result of their reactivity, particular attention must be given to preparation and purification of the metals, the conditions under which the metals, alloys and compounds are handled and the choice of material for the containment vessel. Ultrapure group-IIB metals may be used without further purification, but it is advisable to purify the group-IIA metals by a multidistillation process, the final distillation preferably being carried out in situ. The reactants and products are best handled in an atmosphere of a purified inert gas, usually He or Ar (N2 cannot be used because of the ready formation of group-IIA metal nitrides) alternatively, they can be handled under vacuum or, in rare cases, under halide fluxes. The containment vessel is normally fabricated from a refractory. 

Fig. 9. The MoFe protein cycle of molybdenum nitrogenase. This cycle depicts a plausible sequence of events in the reduction of N2 to 2NH3 + H2. The scheme is based on well-characterized model chemistry (15, 105) and on the pre-steady-state kinetics of product formation by nitrogenase (102). The enzymic process has not been chsiracter-ized beyond M5 because the chemicals used to quench the reactions hydrolyze metal nitrides. As in Fig. 8, M represents an aji half of the MoFe protein. Subscripts 0-7 indicate the number of electrons trsmsferred to M from the Fe protein via the cycle of Fig. 8.

Li3(BN2) have already demonstrated the decomposition of (BN2) ions into boron nitride. The remaining nitride can lead to the formation of a binary metal nitride or reduce the transition metal ion under the formation of N2. Both mechanisms have been obtained experimentally, depending on the stability of the metal nitride. For instance niobium pentachloride forms NbN, titanium trichloride forms TiN, and nickel dichloride forms Ni, plus BN and nitrogen, respectively, in reactions with Li3(BN)2 (at 300-600°C) [24]. 

The preparation of similar precursors suitable for the deposition of metal nitrides is analogous to the preparations of phosphorus and arsenic compounds. The initial reaction of metal trialkyls MR3 (M = A1, Ga, In) with amines (NHR 2) results in the formation of oligomeric amido compounds [R2MNR 2] (n = 2 or 3) which eliminate alkanes on thermolysis. The incorporation of a proton as a substituent on the pnictide bridging ligand has been examined, and many compounds of the type [R2MNHR ]2 have been synthesized. The presence of this proton may facilitate /3-elimination, allowing lower deposition temperatures to be used. 

In February 1909, the results of the experiments on nitride formation had led to the outline of a patent application which covered the preparation of metal nitrides in the presence of auxiliary substances. Following a hypothetical concept of the action of these additions, they were defined as flux promoters." This draft of an application ended with the following sentence Finally, it is also advantageous to add a flux promoter to metals or alloys which serve as catalysts for the ammonia synthesis. This statement was made in view of the early catalytic experiments in which we had observed the synthesis of traces of ammonia in the presence of catalysts similar to those which acted favorably for the nitride formations. 

The main emphasis was laid, in this initial work, on Haber s catalysts, e.g., osmium and uranium compounds, as well as on a series of iron catalysts. Some other metals and their compounds which we tested are, as we know today, less accessibble to an activation by added substances than iron. Therefore, they showed no improvement or only small positive effects if used in the form of multicomponent catalysts. Finally, the substances which we added to the metal catalysts in this early stage of our work were mostly of the same type as those which had proved to favor the nitride formation, e.g., the flux promoting chlorides, sulfates, and fluorides of the alkali and alkaline earth metals. Again, we know today that just these compounds do not promote, but rather impair the activity of ammonia catalysts. 

In finely divided form, hafnium is pyrophoric, igniting in air spontaneously. However, bulk metal reacts slowly in oxygen or air above 400°C. The rate of oxidation increases with temperature. The product is hafnium dioxide, Hf02. It combines with nitrogen, carbon, boron, sulfur and silicon at very high temperatures to form hafnium nitride HfN, hafnium boride HfB, hafnium sulfide HfSi2, respectively. Nitride formation occurs at 900°C. 

Heating borazine in vacuo at 70°C yields poly(borazylene) polymers, which are soluble in solvents such as tetrahydrofuran or glyme and could be thermolyzed to boron nitride in good yields (120). Other soluble preceramic polymers were produced by transition-metal catalyzed formation of B-alkenylborazines (eq. 34) which were thermally polymerized under mild conditions to poly(alkenylborazines). The latter yielded boron nitride having low carbon contents when thermolyzed in an ammonia atmosphere (121). 

There are a limited number of techniques used for the synthesis of ternary and quaternary nitrides. In fact, the vast majority of these nitrides have been synthesized using only two methods (1) the reaction of a metal nitride with a metal or another metal nitride and (2) the reaction of two metal powders with nitrogen gas or ammonia. The first method has been the most common approach (Table 8.1, Reaction 1). Since these reactions usually require high temperatures (1073-2073 K), the inductive effect is Used to effect product formation. Li3N is a favored starting material due to its stability and relatively low melting temperature (mp = 1086 K), which... 

The very active metals are capable of combining directly with nitrogen to form nitrides. In the air the oxide is formed so much more readily, that nitride formation is likely to escape notice but if the metal is presented in powdered form in a thick mass the oxygen is all combined in the surface layer and only nitrogen penetrates to the interior where pure nitride is formed. 

Table 2. Heat and free energy of formation from the elements of transition metal nitrides (kJ mol-1) calculated from data in Ref. 22.

The Van Arkel process can also be used to make metal nitrides. Because of the tendency of NH3 to decompose at the temperatures needed for nitride formation (1300-1900 K), the gaseous reactant is a mixture of H2 and N2. The nitride forms as a layer around the tungsten wire. 

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