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A R T I C L E I N F O
A B S T R A C T
Article history:
Received 19 March 2014
Accepted 23 April 2014
Published 20 October 2014
Keywords:
Ammonia synthesis catalyst
Discovery
Development
Challenge
Practice
Enlightenment
Ammonia synthesis catalyst found by HaberBosch achieves its history of 100 years. The current
understanding and enlightenment from foundation and development of ammonia synthesis catalyst
are reviewed, and its future and facing new challenge remained today are expected. Catalytic ammo
nia synthesis technology has played a central role in the development of the chemical industry dur
ing the 20th century. During 100 years, ammonia synthesis catalyst has come through diversified
seedtime such as Fe3O4based iron catalysts, Fe1xObased iron catalysts, rutheniumbased catalysts,
and discovery of a CoMoN system. Often new techniques, methods, and theories of catalysis have
initially been developed and applied in connection with studies of this system. Similarly, new discov
eries in the field of ammonia synthesis have been extended to other fields of catalysis. There is no
other practically relevant reaction that leads to such a close interconnection between theory, model
catalysis, and experiment as the highpressure synthesis of ammonia. Catalytic synthesis ammonia
reaction is yet a perfect model system for academic research in the field of heterogeneous catalysis.
Understanding the mechanism and the translation of the knowledge into technical perfection has
become a fundamental criterion for scientific development in catalysis research. The neverending
story has not ended yet. In addition to questions about the elementary steps of the reaction and the
importance of the real structure and subnitrides for the catalyst efficiency, as well as the wideopen
question about new catalyst materials, there are also different challenges thrown down by theory for
the experimentalist in the prediction of a biomimetic ammoniasynthesis path at room temperature
and atmospheric pressure including electrocatalysis, photocatalysis and biomimetic nitrogen fixa
tion.
2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
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Table 1
Development of ammonia synthesis catalysts.
Development stage
(1) Fe3O 4 based catalyst
(2) Fe1xObased catalyst
(3) Rubased catalyst
Year
1913
1986
1992
Inventor
BASF, Germany
Zhejiang Univ. of Technol., China
UKBP, Japan
Catalyst type
S610, KM
A301, ZA5
KAAP
Chemical composition
Fe3O 4+Al2 O3+K2 O+CaO+
Fe 1xO+Al2 O3 +K2 O+CaO+
RuBaK/AC
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Table 2
Comparison of iron catalysts and ruthenium catalysts.
Catalyst type
Resource
Fe
Ru/AC
abundant
scarce
Conditions
Manufacturing cost
T/C
P/MPa
(103* Yuan/m 3)
30
350525 (wide)
1030
1600
325450 (narrow)
10
H2 /N 2
23
2
Energy consumption
(GJ/t)
~ 27
~ 27
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(a)
Step
1
N2 + 2 *
i
2N *
NH * + *
N*+H*
NH * + H *
NH2 * + *
NH2 * + H *
NH3 + 2 *
H2 + 2 *
2H *
N2 + 3H2
2NH3
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(b)
Step
1
N2 + 2 *
N2 * + H2 *
i
N2 *
N 2H 2 *
N2H2 * + H2
N2H4*
N2H4 * + H2
2NH3 + *
N2 + 3H2
2NH3
Fig. 2. The mechanisms of N2 dissociative adsorption (a) and molecular adsorption (b) and their stoichiometric number.
Table 3
Theoretical energy consumption of ammonia synthesis [113].
Raw material
Water, air
H2 O + N 2 NH3 + O 2
Water, air, coal
C + H2 O + (N2+O2 ) NH3 + CO 2
Water, air, nature gas CH4 + H2O + (N2+O2) NH3 + CO 2
Water, air, light oil
C9 H2 O + H2 O + (N2+O 2) NH3 + CO2
Pure H2 and N2
H2 + N2 NH3
H = Hv
21.26
0.80
1.85
1.41
3.95
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[115118].
The main electrocatalysts which have been studied include
iron phthalocyanine catalystloaded gas diffusion electrodes,
the ceramic solid electrolyte and the molten salts
(LiCl/KCl/CsCl) and so on. Using solid electrolytes with high
proton conductivity at room temperature to improve the cur
rent efficiency and the stability of electrodes is an important
direction for future research on electrochemical ammonia syn
thesis [87,119,120].
Low current efficiency is the key to influence the efficiency
and product costs of electrochemical ammonia synthesis. With
the indepth study of the electrochemical ammonia synthesis, if
current efficiency and conversion rates can be significantly
improved so that the cost of the electrochemical ammonia syn
thesis can be focused on consumption of electric energy, the
electrochemical ammonia synthesis in the remote districts of
sufficient in electric energy, or effectively converting solar en
ergy, wind and water energy into electricity is expected to have
its place. Especially when the energy crisis in the future leads to
prices of oil, nature gas and coal etc. raise sharply which results
in costs of HaberBosch ammonia synthesis growing exponen
tially, the electrochemical ammonia synthesis will be regarded
as a useful alternative. Therefore, the study of electrochemical
ammonia synthesis still has potential application [115].
3.2.2. Research on photocatalytic ammonia synthesis catalysts
The most familiar photocatalytic reaction is natural photo
synthesis: CO2 + H2O CH2O + O2. Green plants absorb sunlight
by chlorophyll (photosensitizer), convert CO2 and H2O by plant
enzymes to carbohydrate and release O2. Photosynthesis is the
most important way to convert solar energy into chemical en
ergy. The most critical step in complex process of photosynthe
sis is the substances in photosynthetic reaction center absorb
photo energy to release electrons which are transferred into
cells to cause chemical synthesis reaction so that solar energy is
stored up [121].
At room temperature and atmospheric pressure using water
as a hydrogen source and solar energy as energy, a photocata
lytic way to directly transform the nitrogen in air into ammo
nia: N2 + 3H2O 2NH3 + 1.5O2, need to resolve the solar energy
input and photocatalysts of problems.
These two reactions are both thermodynamically non
spontaneous reactions, and N2 is activated the harder than CO2,
but their photocatalysis are both theoretically achievable.
Whichever the natural CO2 reduction reaction or artificial wa
ter reduction (producing H2) and oxidation (producing O2)
reaction, is a very complex catalytic process that usually occurs
through multiple electrons pathway, and combinations of ele
mentary reactions. Michel and Deisenhofer who cowinners of
the Nobel Prize in Chemistry in 1988 [122,123] used theoreti
cal calculations to conclude that the common effect of asym
metric nuclear Frankcondon factors and the electronic cou
pling is likely the main reason for unidirection electron trans
fer. The study results of mechanism of photosynthesis and its
center structure will provide inspiration for photocatalytic
ammonia synthesis.
The research on photocatalysis has more than 50 years of
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4. Conclusions
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Graphical Abstract
Chin. J. Catal., 2014, 35: 16191640 doi: 10.1016/S18722067(14)601182
Ammonia synthesis catalyst 100 years: Practice, enlightenment and challenge
Huazhang Liu *
Zhejiang University of Technology
22
(NH3) / %
P = 15 MPa, SV = 30000 h1
425 oC
400 oC
20
Fe1-xO
18
16 Fe3O4
14
12
0
4
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Fe2+/Fe3+
10
The achievement and progress of the ammonia synthesis catalysts in theory and practice during about 100 years, and a new challenge in
face of a biomimetic ammoniasynthesis path at room temperature and atmospheric pressure, including electrocatalysis, photocatalysis
and biocatalysis, are presented. Understanding the mechanism and the translation of the knowledge into technical perfection has become
a fundamental criterion for scientific development in catalysis research.
1630
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Page numbers refer to the contents in the print version, which include
both the English and Chinese versions of the paper. The online version
only has the English version. The pages with the Chinese version are only
available in the print version.