Documente Academic
Documente Profesional
Documente Cultură
17
7.17.1
7.17.2
7.17.3
7.17.4
7.17.4.1
7.17.5
7.17.6
7.17.7
References
7.17.1
Introduction
The Ammonia Synthesis Process
Reaction Mechanism, Active Sites, and Reaction Kinetics
Micro-Kinetic Models of Catalytic Ammonia Synthesis
Activity Trends
Discovery of New Catalysts for Ammonia Synthesis
New Perspectives in Ammonia Synthesis
Conclusion
Introduction
459
460
462
465
468
470
471
473
473
http://dx.doi.org/10.1016/B978-0-08-097774-4.00725-7
459
460
7.17.2
100
80
5
4
60
3
40
2
20
1
0
1900
0
1925
1950
Year
1975
461
CO2
Air
H2O
450
500 C
0 C
Natural gas
400
500 C
300 C
350 C
NH3
300 C
1200 C
KMR
KM
400 C
200 C
1000 C
800 C
325 C
100 C
220 C
Desulphurization
Primary
reforming tubular
Secondary
reforming
Shift
Purge
synthesis
Methanator
% NH3
% NH3
350
450
550
Temperature (C)
350
450
550
Temperature (C)
Figure 3 The schematic picture of an internally cooled reactor and of an adiabatic three-bed reactor, cooled by two heat exchangers. The equilibrium
and operational lines are shown in the ammonia concentration versus temperature plot. The corresponding operation lines for that reaction in that
particular reactor is also shown. Reprinted with permission from Jacobsen, C. J. H.; Dahl, S.; Boisen, A.; Clausen, B. S.; Topse, H.; Logadottir, A.;
Nrskov, J. K., J. Catal. 2002, 205, 382387.
In such reactors, the ammonia concentration and the temperature vary in the two (or three) beds, as shown in Figure 3. The
position of the optimal operation lines depends on the type of
catalyst; however, the differences are small and the lines are
generally positioned 3060 C below the equilibrium curve.
The absolute reaction rate is much more dependent on the
catalyst of choice and, in Section 7.17.5, we will discuss how
the reactor volume can also be minimized by choosing different
catalysts in different parts of the reactor.
0.5N2 + 1.5H2
17
0
Potential energy/kJ mol-1
462
Fe
~21
46
0.5N2-* + 1.5H2
50
-100
NH3
~41
~33 NH -*
3
-200
NH2-* + H-*
259
106
-300
N-* + 3H-*
NH-* + 2H-*
surfaces are the most active.61 This was attributed to the access
to the so-called C7 active site (surface atoms with seven
nearest neighbors, Figure 5). Activity measurements at high
pressure on similar single-crystal surfaces showed that Fe
crystal faces with C7 sites have significantly higher catalytic
activity for ammonia synthesis than other Fe crystal faces
(Figure 5).54 These findings, together with the investigations
of elementary reaction steps45,62 and the effects of catalyst
support and additives,55,62 were important in establishing
an understanding of industrial ammonia synthesis based on
surface science.
First-principles studies63,64 show that the adsorption energy
of N on Fe(100) is higher compared to the more close-packed
(111) and (110) surfaces. Especially, the adsorbed phase c
(2 2)-N/Fe(100) is particularly stable, indicating that this
phase will form under high pressure of nitrogen. Consequently,
at higher coverage of N, the surfaces (111) and (110) might very
well reconstruct to form a stable c(22)-N/Fe(100) overlayer.
Furthermore, the dissociation of N2 on Fe(111) has, essentially,
two different pathways: one with a low energy barrier but with a
large entropic barrier, and the other with a high energy barrier.64
The low-energy-barrier path includes several precursor states,
which results in a complicated dissociation path. Under normal
ammonia synthesis conditions, the low-barrier, high-entropy
path will dominate, but at the highest temperatures, the highbarrier process may become more effective.
After studying ammonia synthesis over iron, the attention
turned to ruthenium, which is a more active catalyst than iron,
especially at high ammonia concentrations. This gave rise to
industrial interest in ruthenium-based ammonia catalysts in
the 1990s.
In the first attempts to measure the N2 dissociation rate on
different Ru surface facets, the process was found to be structure insensitive.65 As with the case of iron, it was possible to
model the activity of technical catalysts at high-pressure conditions based on the surface-science results,60 so there seemed
to be some consistency. However, there was one problem;
experimentally, the activation energy for the dissociation reaction was found to be around 0.40 eV on the Ru(0001) surface,
which disagrees with a calculated barrier of 1.36 eV.66 The
answer to this discrepancy was found in a joint experimental
and theoretical effort,67 where dissociative adsorption of N2
over a closed packed Ru(0001) surface was revisited. Measurements were done on both clean and Au-passivated surfaces. In
the latter case, small amounts of Au (12% on the surface)
were deposited on the surface, where they preferentially decorate reactive step sites. The results show that the presence of Au
reduces the N2 dissociation rate almost completely, demonstrating the high structure sensitivity of N2 dissociation on Ru.
Based on the measurements, it was concluded that the reaction
takes place solely at the step sites, with a dissociation barrier of
0.4 eV. The rate on the planar terrace was measured to be at
least nine orders of magnitude smaller than that at the steps at
500 K. The first ab initio calculations supported this and they
gave a corresponding 1.5-eV barrier difference. Laser-assisted
associative desorption of N2 from Ru(0001) also confirmed
the reactivity difference between step and terrace atoms.68
Fe(111)
Fe(210)
C4
C4
C7
C5
C8
C7
14
T = 400 C
12
463
Fe(100)
10
C4
C8
8
6
Fe(211)
Fe(110)
C5
C6
C7
2
0
(111) (211) (100) (210) (110)
Surface orientation
The first layer
Figure 5 Produced ammonia over different Fe facets (left) and the corresponding structures (right). Reprinted with permission from Somorjai, G. A.;
Li, Y. Proc. Natl. Acad. Sci. 2011, 108, 917924.
-10
Ru(0001)
Ea = 0.4 0.1 eV
-12
-13
TS
2.0
DE [eV/N2]
log S0
-11
1.0
0.0
N2,ad
2Nad
12% Au on Ru(0001)
Ea = 1.3 0.2 eV
-1.0
-14
0.0015
0.0020
0.0025
1/T (1/K)
0.0030
0.0035
Figure 6 (Left) An Arrhenius plot of measured thermal sticking coefficients of N2 on a clean Ru(0001) surface and the same surface covered with
0.010.02 mL of gold. (Right) Results from density-functional calculations comparing N2 dissociation on a terrace and at a step on Ru(0001). The upper
curve shows the adsorption and transition-state energies for the dissociation on the terrace, whereas the lower curve shows the same energies at the step.
The energy zero is taken to be the energy of the N2 molecule in the gas phase. Reprinted figure with permission from Dahl, S.; Logadottir, A.; Egeberg, R. C.;
Larsen, J. H.; Chorkendorff, I.; Tornqvist, E.; Nrskov, J. K. Phys. Rev. Lett. 1999, 83, 1814. Copyright 1999 by the American Physical Society.
464
200
N2
100
E tot (eV/molecule)
700 K
500 C
350 C
TSterrace
3H2
-1.00
k4
NH3
0
NH3
k1
0
-2.00
-3.00
-4.00
0
TSstep
-5.00
*
*
*
*
*
*
*
3
3
6H + 5H + 4H + 3H + 3H + 2H + H NH NH
+3 +3 +3 +
+ +2
3
*
*
*
*
H
*
*
2
3
3
*
N
*
N 2 2N 2N NH NH 2 NH 3 NH NH + N H 3
*+
N
+
+
+ N *+
+
* H2*
N* N* N*
H
N
N
H2
H2
H2
0.001
0.0015
0.002
0.0025
0.003
0.0035
-1
1/T [K ]
Figure 7 (left) The comparison of potential energy landscape for ammonia formation over terrace and step sites on Ru(0001). The plot shows
that the step effect is less pronounced for the hydrogenation step, which results from the fact that transitions states are similar on both surfaces. (Right)
The comparison of the rate constants for NH2 hydrogenation and N2 dissociation over stepped Ru. Despite that the hydrogenation barrier is higher
than the dissociation barrier, N2 dissociation is by far the slowest step due to the entropic effects. The rate constants were estimated with harmonic
transition-state theory. Reprinted with permission from Logadottir, A.; Nrskov, J. K. J. Catal. 2003, 220, 273279.
465
1 nm
Step atom
2.5
Step A
step A
step B
step C
step D
Energy/eV
1.5
1
0.5
0
Step B
-0.5
-1
Small
crystal
1.5
300 K
Step C
0.1
Edge atoms
Step D
Active sites
0.01
0
4
6
8
Crystal size (nm)
10
2.5
3
3.5
4
Bond length / angstrom
700 K
4.5
1200 K
Ru(0001)
surface
D
D
B
B
B
2.0
3.0
4.0
Diameter/nm
5.0 2.0
3.0
4.0
Diameter/nm
5.0 2.0
3.0
4.0
5.0
Diameter/nm
466
10.0
Calculated ammonia concentration (%)
10-1
10-2
1 atm
10-3
10-3
150 atm
300 atm
10-2
10-1
Experimental exit NH3 mole fraction
1.0
0.1
0.1
1.0
Measured ammonia concentration (%)
10.0
Figure 10 Ammonia concentration predicted from two micro-kinetic models,56,89 plotted as a function of the measured ammonia concentration.
Reprinted figure with permission from Stoltze, P.; Nrskov, J. K. Phys. Rev. Lett. 1985, 55, 2502. Copyright 1985 by the American Physical Society;
Sehested, J.; Jacobsen, C. J. H.; Tornqvist, E.; Rokni, S.; Stoltze, P. J. Catal. 1999, 188, 8389.
467
10
7000
5000
x (29N2) (ppm)
6000
0.1
4000
3000
2000
1000
0.01
0.01
0.1
0
450
10
500
550
600
650
700
750
800
T (K)
1
0.1
0.01
0.001
0.001
0.01
0.1
1
10
Experimental
ammonia
output
(NH
-%)
(a)
3
(c)
10
10
1
0.1
0.01
0.001
0.001
0.01
0.1
1
10
Experimental
ammonia
output
(NH
-%)
(b)
3
10
100
1
0.1
0.01
0.001
0.001
0.01
0.1
10
Figure 11 Comparison between measured and calculated NH3 production for the Ru/MgA1204 catalyst: pressure, 1100 bar; H2:N2 ratio, 6:11:4;
temperature, 320440 C. The solid line is the calculated outlet concentration of 29N2 when an inert gas containing 0.67% 29N2 and 0.60% 30N2 is
passed over 138 mg of catalyst containing 20 mmol g1 of active sites. The flow is 50 Nml min1 and the reactor is treated as a plug flow reactor.
The conditions are equal to the ones used by Hinrichsen et al.92 over the Ru/MgO catalyst, and the open circles are their results. Reprinted with
permission from Dahl, S.; Sehested, J.; Jacobsen, C. J. H.; Tornqvist, E.; Chorkendorff, I. J. Catal. 2000, 192, 391399.
(d)
10
1
0.1
0.01
0.001
0.0001
0.0001 0.001 0.01
0.1
10
100
Figure 12 The calculated ammonia synthesis/decomposition output as calculated from the first-principles model and compared to measurements on
an industrially supported Ru-based catalyst. Reprinted with permission from Hellman, A.; Honkala, K.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.;
Dahl, S.; Christensen, C. H.; Nrskov, J. K. Surf. Sci. 2009, 603, 17311739.
468
Productivity (NH3-%)
7.17.4.1
Activity Trends
Measured
Calculated
Measured
Calculated
Measured
Calculated
1
1
0.1
0.1
0.01
580 600 620 640 660 680 700 720
Temperature (K)
(a)
40
60
(b)
4:1
1:1
1:3
1:5
Ratio (N2:H2)
(c)
100
Ru
10
1.0
Os
Rh
0.01
Re
Mo
0.1
Co
Ni
Pt
40
(a)
Fe
Ir
80
120
Figure 13 Ammonia productivity as a function of (a) temperature, (b) flow, and (c) ratio. The synthesis conditions are (a) N2:H2 (1:3), 30 Nml min1
(STP); (b) 713 K, N2:H2 (1:3); (c) 713 K, 30 N ml min1 (STP), all at a total pressure of 50 bar. Reprinted with permission from Hellman, A.; Honkala, K.;
Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Nrskov, J. K. Surf. Sci. 2009, 603, 17311739.
160
16
Ru
14
Fe
12
Ni
Re
10
Pt
8
0
(b)
Co
Rh
40
80
120
160
Figure 14 The rate of (a) ammonia synthesis and (b) ammonia decomposition as a function of the heat of chemisorption over various metals.96
Reproduced from Aika, K.; Yamazaki, K.; Ozaki, A. Chem. Lett. (Jap.) 1973, 2, 161.
Cu(111)
5.0
Pd(211)step
3.0
ETS [eV]
Ea [eV/N2]
Pd(111)
4.0
fcc-Fe(111)
2.0
1.0
469
Ru(0001)
Fe(110)
Fe/Ru(0001)
0.0 Mo(110)
-1.0
-2.0
-3.0
Ru(0001)step
Fe(110)step
Fe(111)
Mo(110)step
-2
-2.0
-1.0
0.0
1.0
DE [eV/N2]
2.0
3.0
4.0
-6
-4
-2
Figure 15 Correlation between the energy in the transition state and the dissociative adsorption energy of nitrogen. Reprinted with permission
from Logadottir, A.; Rod, T. H.; Nrskov, J. K.; Hammer, B.; Dahl, S.; Jacobsen, C. J. H. J. Catal. 2001, 197, 229231 and Munter, T. R.; Bligaard, T.;
Christensen, C. H.; Norskov, J. K. Phys. Chem. Chem. Phys. 2008, 10, 5202.
470
20.0
CoMo
10
Ru
10
10
10
10
10
15.0
Fe
-1
TOF [s1]
TOF(s-1)
10
Co3Mo3N
17.5
Os
Co
-2
-3
Mo
12.5
Ru
10.0
7.5
5.0
Ni
-4
2.5
Fe
-5
-25.0
0.0
25.0
50.0
75.0
[DE-DE(Ru)](kJ/mol N2)
Figure 16 Turnover frequencies for ammonia synthesis as a function of
the adsorption energy of nitrogen. Reprinted from Jacobsen, C. J. H.;
Dahl, S.; Clausen, B. S.; Bahn, S.; Logadottir, A.; Nrskov, J. K. J. Am.
Chem. Soc. 2001, 123, 84048405, with permission Copyright 2001
American Chemical Society.
reaction, a universal behavior has been established, for example, the dissociative adsorption of the diatomic molecules O2,
N2, NO, and CO98 and (de)hydrogenation reactions.97 Furthermore, linear scaling relations between the adsorption energies of adsorbates that bind in a similar fashion to a surface has
been established,104 for example, the adsorption energy of NH,
NH2 that binds via the N atom to the surface scales with the
adsorption energy of N, and the slope of these linear scaling
relations can be approximately derived from simple bond
order conservation arguments.104
By combining BEP relations, scaling relations with microkinetic models, it has now been possible to construct volcano
curves for a number of reactions.105 For some reactions, it is
necessary to use not only one but two descriptors, for example,
reactions where CO is hydrogenated, since the reaction intermediates bind via both C and O, and the adsorption energy of
these does not correlate linearly. However, this still results in a
large reduction of parameters that need to be known in order
to predict the activity of a catalyst in a given reaction.
3
4
5
6
NH3 concentration (%)
7.17.6
Depleting fossil fuel resources together with severe environmental consequences caused by the combustion of carboncontaining molecules enforce us to look for new energy solutions. There are several possible options for currently employed
hydrocarbons both for storage and for use as energy carriers,109
of which the most prominent ones are hydrogen, methanol,
ethanol, and methane. Also, synthetic hydrocarbons could
h = 5%
Fe 20%
Ru
Os
102
471
Fe
Ru
Os
101
90%
TOF (s-1)
100
10-1
Co
Mo
Mo
Co
10-2
10-3
10-4
10-5
-100
-50
0
EN*-EN* (Ru) (kJ/mol N2)
50
-100
-50
0
EN*-EN* (Ru) (kJ/mol N2)
50
Figure 18 (Left panel): calculated volcano curves at 420 C, 80 bar, 2:1 H2:N2, equilibrium 17.4%NH3. (Right panel): calculated volcano curves at
450 C, 200 bar, 3:1 H2:N2; equilibrium 25.4% NH3. In both cases, the volcano curves are calculated at ammonia concentrations corresponding to a
90, 20, and 5% approach to equilibrium. Reprinted with permission from Jacobsen, C. J. H.; Dahl, S.; Boisen, A.; Clausen, B. S.; Topse, H.;
Logadottir, A.; Nrskov, J. K. J. Catal. 2002, 205, 382387.
sensitively depends also on the reaction conditions. Interestingly, it is observed that the optimal ammonia synthesis catalyst
is never the optimal ammonia decomposition catalyst; see
Figure 19.21 This does not indicate that the principle of microscopic reversibility does not hold, but, rather, highlights that
widely different reaction conditions in ammonia synthesis and
decomposition result in very different optimal binding energies
for the two reactions, except, of course, at equilibrium. Also, for
ammonia decomposition, a combination of first-principle calculations, micro-kinetics, and surface science can lead to the
discovery of new catalysts formulations.111
One can imagine several scenarios where it would be advantageous to produce ammonia locally on a smaller scale, even if the
production costs would be higher than in the HaberBosch process. This point of view is becoming more relevant as ammonia is
used in the SCR process for removing nitrogen oxides from diesel
engine exhaust, with the recent proposal of using ammonia salts
as an energy carrier,3 or with the increased political focus on
transporting safety for hazardous chemicals. Hinnemann and
Nrskov have performed a theoretical study on the possibility to
produce ammonia under ambient temperatures and pressures. As
mentioned in the introduction, microorganisms exist in nature,
which use the enzyme nitrogenase to form ammonia from protons, electrons, and atmospheric nitrogen. In the enzyme, the
active site is an MoFe7S9 cluster, which catalyzes the reaction:
N2 8H 8e P 2NH3 H2 ;
where the nitrogen molecule is hydrogenated stepwise. The
source of energy for this reaction consists of at least 16 ATP
molecules.6 These presumably increase the chemical potential
of the electrons. It has been hypothesized that part of the
enzyme functions just like a battery.6
Since protonation reactions in particular appear to be so
well-described within the DFT methodology, it offers hope that
it is adequate also for describing electrochemical ammonia
synthesis.112 In an electrochemical cell, ammonia synthesis
on a ruthenium electrode in aqueous solution cannot proceed
via the same reaction mechanism as the HaberBosch process,
because all available ruthenium step sites for N2 dissociation
will be poisoned by strongly adsorbing oxygen atoms and OH
groups.112 The calculations show that the barrier for N2 dissociation is too high on the close-packed terraces at low electrochemical temperature. This leaves the biomimetic mechanism
-0.4
Optimal DE (eV)
472
-0.6
Synthesis
Decomposition
-0.8
-1.0
-1.2
-1.4
-1.6
0.001
0.01
0.1
1
10
Ammonia concentration (%)
100
5(
4(
+
e
+
(H
*N
H
N
*N
*NHNH
*NHNH2
H
*N
U=0V
2N
*N
2(
3(
2H
6(
*N
e
+
e
+
+
2
*N
U = -1.08 V
*N
N
H
6(
Reaction coordinate
Figure 20 Free energy for the associative mechanism of electrochemical
ammonia synthesis on a flat Ru(0001) surface obtained from DFT
calculations of the binding energy and vibrational frequencies, as well as
entropy of the gas molecules. For an electrolyte with pH0 at 300 K, this
also gives the free energy for the electrochemical reaction when there is no
applied bias, U 0 V. The most difficult step is the addition of the first
proton to the adsorbed N2 molecule. With an applied potential of U
1.08 V, all the elementary steps involve either no change or a decrease in
the free energy. Reprinted with permission from Srensen, R. Z.;
Hummelshj, J. S.; Klerke, A.; Reves, J. B.; Vegge, T.; Nrskov, J. K.;
Christensen, C. H. J. Am. Chem. Soc. 2008, 130, 86608668.
7.17.7
Conclusion
473
theoretical detail reveals promise. There is a linear correspondence between the computational power and the number of
catalyst materials that we can screen for a given reaction at the
current high level of accuracy. With the historical increase in
available computer power, it is difficult to remain skeptical of
the importance of theory in the field of catalysis, already in the
near future. It can be envisioned that, soon, theoretical modeling will not only be used for reproducing the experimentally
known facts about a given reaction on a given surface, but
could become the standard choice as the first starting point
when a new catalyst for a known reaction is desired, or even
when an unknown reaction to obtain a given product is
needed. This would be the beginning of the era of Catalysis
Informatics,113 and there are strong indications that ammonia
synthesis will continue to be the bellwether reaction in this
development.
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