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author:

Tanaka, Ken-ichi (Tanaka, Ken-ichi.) [1] | Yuan, Youzhu (Yuan, Youzhu.) [2] | Xie, Zhaoxiong (Xie, Zhaoxiong.) [3] | Oyama, S. Ted (Oyama, S. Ted.) [4] | He, Hong (He, Hong.) [5]

Indexed by:

EI Scopus SCIE

Abstract:

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.

Keyword:

Adsorption and quasi-compounds Ammonia decomposition reaction Ammonia synthesis reaction Dynamic intermediates Hydrogen isotope effect Quasi-compounds in catalysis

Community:

  • [ 1 ] [Tanaka, Ken-ichi]Univ Tokyo, Kohoku Ku, 414-1 Mamedo Cho, Yokohama, Kanagawa 2220032, Japan
  • [ 2 ] [Yuan, Youzhu]Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
  • [ 3 ] [Xie, Zhaoxiong]Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
  • [ 4 ] [Yuan, Youzhu]Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, Xiamen 361005, Peoples R China
  • [ 5 ] [Oyama, S. Ted]Fuzhou Univ, Coll Chem Engn, Fuzhou 350116, Fujian, Peoples R China
  • [ 6 ] [Oyama, S. Ted]Univ Tokyo, Dept Chem Syst Engn, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1138656, Japan
  • [ 7 ] [He, Hong]Chinese Acad Sci, Res Ctr Ecoenvironm Sci, Beijing 100085, Peoples R China

Reprint 's Address:

  • [Yuan, Youzhu]Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China;;[Yuan, Youzhu]Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, Xiamen 361005, Peoples R China;;[He, Hong]Chinese Acad Sci, Res Ctr Ecoenvironm Sci, Beijing 100085, Peoples R China

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Source :

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

Cited Count:

WoS CC Cited Count:

SCOPUS Cited Count:

ESI Highly Cited Papers on the List: 0 Unfold All

WanFang Cited Count:

Chinese Cited Count:

30 Days PV: 0

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