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Catalysis is generally explained by the reaction of adsorbed species, but in certain cases it can be also understood by the involvement of surface "quasi-compounds". A quasi-compound is a combination of elements that can exist only on a specific crystalline surface, but cannot be taken out from the surface. A prominent example is found in the ammonia synthesis reaction. Decomposition of NH3 occurs on most metals and its kinetics is governed by the rate-determining desorption of N-2, but the synthesis reaction occurs only on a limited number of clean metals. Precious metals in pure form are inactive for the ammonia synthesis reaction, however, the reaction of adsorbed N(a) with H-2 on precious metals gives NH3 via NH(a). Among base metals Ni is also inactive for the ammonia synthesis reaction. But N-atoms form a quasi-compound Ni3N on Ni(110) rather than adsorbed species, and the hydrogenation of Ni3N with H gives NH3 via the NH(a) intermediate. On the other hand, adsorption of NH3 gives only NH2(a) on these metals. Interestingly, Ni3N on Ni(110) becomes inactive for reaction with H-atoms at temperatures higher than approximately 500 K, because the quasi-compound Ni3NH undergoes decomposition to Ni3N at approximatelt 500 K; that is, no NH2(a) is formed at temperatures higher than 500 K. A large inverse hydrogen isotope effect (r(D)/r(H) = 2-3) has been reported for the ammonia synthesis reaction on a doubly promoted Fe-catalyst, and interpreted on thermodynamic grounds. Therefore, we propose an alternative explanation for this inverse isotope effect based on the fact that the reaction of N(a) on the precious metals with H-2 + D-2 (H-2/D-2 = 1) gives equal amounts of NH(a) and ND(a). As discussed in this review, the contribution of labile quasi-compounds, [FexN] and [FexNH], is useful in this regard, and accounts for the formation of NH3 by the hydrogenation of an NH2 intermediate formed from [FexNH]. According to this mechanism, the activity of the Fe-surface is given by the steady rate of formation of labile [FexRN] and [FexNH] to give adsorbed NH2(a) on the Fe-surface.
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SURFACE SCIENCE
ISSN: 0039-6028
Year: 2019
Volume: 679
Page: 264-272
1 . 4 6 6
JCR@2019
2 . 1 0 0
JCR@2023
ESI Discipline: PHYSICS;
ESI HC Threshold:138
JCR Journal Grade:3
CAS Journal Grade:4
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 0
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