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INTRODUCTION
Iron catalyst for ammonia synthesis was the object of research
A model of interactions between iron nanocrystallites and
promoters and the explanation of the resulting nanometric
performed in order to verify the eectiveness of a new method structure is presented elsewhere.4,5
for determining the physical and chemical properties of By studying the kinetics of the nitriding of nanocrystalline
nanomaterials. The fused iron catalyst for ammonia synthesis iron, it was found that the reaction rate was limited by the rate
is industrially prepared by melting iron oxides with structural of dissociative adsorption of ammonia on the surface of iron. A
promoters (Al2O3, CaO) and an activating promoter (K2O). By reaction model of nanocrystalline materials with a gas phase
reduction with hydrogen of the resultant alloy, an active form of was elaborated, wherein the chemical process rate is limited by
the catalyst having nanocrystalline structure is obtained.1,2 a surface reaction rate.13 According to this model, in the
Metal oxide (mainly Al2O3, CaO) bridges connecting the nitriding process with ammonia, each nanocrystallite forming a
individual crystallites of iron form the 3-dimensional (3D) solid solution of nitrogen in -iron, -Fe(N), after reaching the
structures.3 Promoters placed on the surface of the crystallites critical concentration of nitrogen undergoes a phase transition
form the 2-dimensional (2D) structures.4 In the active iron in its whole volume to a phase -Fe4N. The phase transition of
catalyst, there is a thermodynamic equilibrium between iron nanocrystallites occurs in the order from the smallest to the
nanocrystallites and promoters located in the 2D and 3D largest in size.14
structures.4,5 Therefore, the structure of the active iron catalyst, Based on studies of nitriding of nanocrystalline iron and
due to the presence of structural promoters, is stable at high reduction of obtained nanocrystalline nitrides of iron at a
temperatures. The structure of the catalyst after xing at a given constant temperature and at dierent nitriding potentials, it was
temperature did not change at lower temperatures.6 found1518 that for each composition of the mixture of
The surface of iron nanocrystallites is wetted by a layer of K ammonia and hydrogen steady states were xed. In these
+O, and iron atoms are combined with potassium atoms by states, the reaction rate in the solid was zero (constant content
oxygen bridges. The presence of activating promoter (K2O) of nitrogen in the solid sample), and the rate of catalytic
after the reduction process increases the number of active sites ammonia decomposition reaction was constant. Additionally, in
on the catalyst surface, which is dependent on the chemical
composition of the surface of the catalysts and temperature.79 Received: September 22, 2016
Oxygen atoms prevent the extraction of potassium from the Revised: April 4, 2017
surface during the processes.312 Published: April 5, 2017
iron nitriding and reduction of the obtained iron nitrides in a out in hydrogen ow of 9 dm3/h at atmospheric pressure, poly
controlled way in states close to chemical equilibrium. During thermally, increasing the process temperature to 500 C at 10
the studies, the CPPR method was applied using thermog- C/min and then the sample was annealed for 0.5 h in order to
ravimetry and XRD. stabilize the nanocrystalline structure of the catalyst.
EXPERIMENTAL SECTION
Industrial prereduced triply promoted nanocrystalline iron
The change in mass of the sample in the thermogravimetric
measurements was expressed by nitriding degree, , dened as
the mass ratio of nitrogen attached at a given moment of time
catalyst for ammonia synthesis in the form of irregular particles during the chemical process with respect to the initial weight of
with a diameter of 1.01.2 mm was studied.43 By atomic iron contained in the solid sample (XN/XFe [mol/mol]).
emission spectrometry with inductively coupled plasma using Nitriding process of iron and reduction of the obtained iron
the spectrometer PerkinElmer Optime 5300DV, the chemical nitrides were carried out at varying nitriding potentials.
composition of the catalyst was determined. The catalyst in Nitriding potential values of the gas mixture at a given moment
addition to the metallic iron contained (wt %) 3.3 Al2O3, 2.8 of the process were calculated from the equation
CaO, and 0.65 K2O. By X-ray diraction using a Philips X-ray pNH
diractometer XPert X-ray with a copper lamp and using the P = 3/23 [Pa0.5]
Rietveld method, the average crystallite size of iron (45 nm) pH (1)
2
was determined. Apart from that, using X-ray diraction,
nanoCSD was determined by means of the method proposed where pNH3 and pH2 represent partial pressures of ammonia and
by Pielaszek.44 Fityk software45 as well as an online calculator hydrogen, respectively, in the gas phase.
by Pielaszek46 were used to analyze the diraction patterns. Chemical processes were performed at a constant ammonia
The surface area of the catalyst determined by the BET method ow rate, V NH3 = const, and hydrogen ow changing constantly
using a Quadrasorb SI apparatus (Quantachrome Instruments, according to the following expression
Automated Surface Area & Pore Size Analyzer) was 12 m2/g.47
Nanocrystalline iron nitriding process and reduction of the 3
t cm
VH 2 = V0H
resulting nanocrystalline nitrides of iron were conducted using 2 H2
min (2)
gases supplied by Air Liquide: ammonia having a purity of
99.998% and hydrogen of 99.999%. where H2 is the hydrogen ow acceleration and V 0H2 is the
Nanocrystalline iron nitriding process and reduction of the initial hydrogen ow at t = 0.
resulting nanocrystalline nitrides of iron were carried out in a The change of the nitriding potential of ammoniahydrogen
dierential tubular reactor35 connected to a system for mixture during the conducted processes can be expressed as
regulating gas ows (Figure 1). Processes were carried out at follows:
(VNH
VNH t )0.5
+ V0H
H
[Pa0.5]
3 3 2 2
P(t ) =
pat0.5 (V0H
t )1.5
2 H (3)
2
Figure 1. Experimental setup used in the CPPR method: 1, sample The change in hydrogen ow at the inlet to the reactor and the
holder; 2, single layer of grains; 3, reactor furnace; 4, reactor wall; 5, calculated (eq 4) participation of hydrogen in a nitriding
thermocouple; 6, electronic owmeters. mixture for one of the processes carried out at a constantly
changing ow rate of hydrogen (H2 = 0.4 cm3/min2) and the
350 C, which was measured with a thermocouple placed in the ow of ammonia (V NH3 = 35 cm3/min) are shown in Figure 2.
vicinity of the sample. The measurement setup was equipped Nitriding processes of nanocrystalline iron were initiated
with a system to stabilize and control the temperature during from xing the initial nitriding potential in the system, which
the processes. The reactor was equipped with a magnetic sensor was lower than the minimum nitriding potential necessary for
system to measure sample mass. A sample of the catalyst of the development of phase -Fe4N. The minimum nitriding
approximately 1 g was placed in a platinum basket in a form of potential of the gas mixture was determined based on data
a single layer of grains. The reactor was fed by the reaction gas obtained for nanocrystalline iron nitriding process performed in
mixture of varying composition. The change in the composition the stationary states at 350 C, which was described in previous
of the nitriding mixture was carried out by a system of papers.22,24 A gas mixture of the determined initial nitriding
electronic mass owmeters (by Brooks) connected to a potential was fed to the reactor to establish the steady state.
computer. The computer was equipped with software that After the composition of the reaction mixture was xed in the
allows simultaneous control of ows on all owmeters reactor, the ow of hydrogen was reduced constantly in the
according to predened programs. The hydrogen content in nitriding process. The processes of nitriding were carried out
the outlet gas of the reaction space was determined by means of up to the moment when the nitriding potential corresponding
katharometric method. with the obtaining of saturated with nitrogen -Fe4N phase in
A test sample was preprepared by the reduction of the the nitriding process conducted in stationary states was
passive layer of the catalyst. The reduction process was carried achieved.
8550 DOI: 10.1021/acs.jpcc.6b09607
J. Phys. Chem. C 2017, 121, 85488556
The Journal of Physical Chemistry C Article
Figure 5. Dependence of (a) the nitriding process rate and (b) the reduction process rate on the nitriding degree for the processes conducted at
dierent hydrogen ow accelerations
Figure 6. Dependence of (a) the nitriding process rate and (b) the reduction process rate on the natural logarithm of the nitriding potential for the
processes carried out at dierent hydrogen ow accelerations.
Figure 7. Dependence of hydrogen ow accelerations, H2, on the nitriding potential for two maximum values of nitriding degree observed during
(a) nitriding process and (b) reduction process.
For the conducted processes of nitriding of nanocrystalline higher value, the greater step H2 is applied, so the chemical
iron and reduction of the obtained nitride -Fe4N a similar, reaction will be faster as well. For the process carried out in
bimodal pattern of changes in the rate of chemical reactions as a stationary states (H2 = 0), the rates of nitriding and reduction
function of the nitriding degree was observed (the same are zero because the value of P in eqs 5 and 6 are equal to P0.
number of peaks occurring and similar values of the nitriding Based on the determined dependences of the process rate on
degree corresponding to the maximum rate). The observed the H2 parameter value one can evaluate how far the process
maxima of the reaction rate correspond to the phase transition conducted with a specic change in nitriding potential diers at
of a fraction of nanocrystallites most abundant in the sample. a given moment from the process carried out in stationary
Nitriding and reduction rate depend on H2 with which the conditions.
process was conducted. The higher the H2 parameter value, the For maxima of the dependence of the nitriding and reduction
process rate for processes carried out with dierent hydrogen
higher reaction rates corresponding to dierent nitriding
ow acceleration on the nitriding degree the dependence of the
degrees. hydrogen ow acceleration on the nitriding potential is shown
At a constant process temperature (k = const) and at a given in Figure 7. The minimum nitriding potential, required to
Sac, i
nitriding degree ( = const), the expression (P P0) has the complete the conversion of iron nanocrystallites saturated with
mi
8552 DOI: 10.1021/acs.jpcc.6b09607
J. Phys. Chem. C 2017, 121, 85488556
The Journal of Physical Chemistry C Article
Figure 8. Crystallite mass distribution determined using reaction rate data for (a) nitriding and (b) reduction processes carried out at dierent
hydrogen ow accelerations
Figure 9. Crystallite size distributions determined using reaction rate data for (a) nitriding and (b) reduction processes carried out at dierent
hydrogen ow acceleration rates. For comparison, the results obtained using Pielaszeks method44 were added.
nitrogen, -Fe(N), having a size corresponding to a specic CMD = f() curve was equal to unity. On the basis of previous
nitriding degree (in this case there are crystallites of sizes studies on nitriding of nanocrystalline iron catalyst by means of
prevailing in the test samples) to the phase of iron nitride - XRD, it was assumed that nanocrystallite size range was 20
Fe4N, was extrapolated. The maxima for the dependence of the 100 nm and a shape factor, Sact,i/(mi 1), as for the sphere.
nitriding and reduction process rate for processes carried out With the selected range of diameters of crystallites the mean
with dierent hydrogen ow acceleration shown in Figure 5 are crystallite size calculated based on the obtained CSD is equal to
present at a specic nitriding degree. A similar dependence as the average diameter obtained by XRD. The obtained CSDs are
shown in Figure 7 can be determined for any value of the shown in Figure 9 together with CSDs obtained using
nitriding degree. Pielaszeks method.44
On the basis of the presented dependences of the rates of For all the processes carried out with continuously variable
nitriding and reduction processes carried out in conditions nitriding potential by constant variation of the hydrogen ow
close to the stationary ones, nanocrystallite mass distributions with varying acceleration H2 bimodal distributions of
(CMD) for single-stage phase transition -Fe(N) -Fe4N
crystallites were observed. These distributions were observed
and -Fe4N -Fe(N) were determined using a method
regardless of the phase transformation direction in a region of
described elsewhere28 (Figure 8). The nitriding degree, XN/XFe
-Fe(N) and -Fe4N. Increasing the hydrogen ow accel-
[mol/mol], as the conversion degree, [mol/mol], of the
eration in the nitriding mixture during the conducted process
phase -Fe(N) to -Fe4N was presented on the x-axis. The
resulted in reduced accuracy of the resulting size distribution of
conversion degree is dened as a ratio of mass of nitrogen in
crystallites present in the system. Determination of the
iron at a given moment of reaction to the nitrogen mass in -
Fe4N. crystallite size distribution with maximum accuracy is possible
The symmetry of the above plots leads to a very interesting in the case of processes performed in the equilibrium states.
conclusion. During reduction of iron nitrides under conditions Processes carried out at low H2 values make it possible to
close to equilibrium nanocrystalllites undergo a phase transition obtain approximate information on the shape of distribution in
in the order of their size from the biggest to the smallest. The a shorter time compared to the processes in stationary states.
same order was previously observed during the nitriding As presented in Figure 9, results obtained by XRD Pielaszeks
reaction. However, as far as reduction is considered, that was method do not show the real structure of the studied iron
the rst time such a phenomenon was observed. catalyst, since the maximum no. 2 is not detected.
Using CMD plots for transitions taking place in both Nowadays, a better understanding of the structure and
directions the CSD for each of the processes carried out with properties of catalysts containing nanoparticles as active species
dierent hydrogen ow acceleration was determined. Ratios of is a key factor in many industries. Size distribution of
individual fractions were chosen so that the area under the nanoparticles can be measured by, e.g., electron microscopies
8553 DOI: 10.1021/acs.jpcc.6b09607
J. Phys. Chem. C 2017, 121, 85488556
The Journal of Physical Chemistry C Article
(SEM, TEM, STM)48 and atomic force microscopy. The the end of the chemical reaction) should be zero between one
measurement is performed directly by measuring the length of and another crystallographic phase.
nanoparticle. It is also possible to determine the shape of the Each technique uses dierent assumptions which results in
observed objects. However, these techniques require a lot of dierences between e.g. volumetric and surface methods.
grains to be observed and analyzed due to inhomogeneity of Agglomerates of small crystallites in the surface method can
nanomaterials.17 Apart from that, it can be dicult to be treated as one large crystallite. In turn, XRD-based
distinguish borders inside the agglomerates of nanoparticles methods use a sometimes very complicated mathematical
and, therefore, the analysis by means of microscopies may be apparatus and assume a rather unimodal distribution of
sometimes sort of subjective. Using techniques based on gas particles. This is, however, correct only for some cases, because
sorption measurements49 we obtain information related to the many times one deals with substances that are characterized by
surface area of the whole solid sample. However, agglomerates bi- or trimodal distributions.17,35,56,57 An example of such a
and single particles are not distinguished which may lead to substance is iron ammonia synthesis catalyst (Figure 9).
incorrect information about the solid structure. Methods based Therefore, results obtained by means of dierent methods
on X-ray diraction can be applied to characterize the whole should not be strictly compared with each other, because this
can lead to dierent conclusions.
sample of nanocrystalline substances. Generally, XRD-based
methods are related to the volume of a crystallite. One of these
methods uses the Scherrers equation for determining the CONCLUSIONS
average size of nanocrystallites. The Rietveld method,50 By using the CPPR method it was possible to conduct kinetic
originating from Hall method, enables us to determine the studies in states close to chemical equilibrium. Several
average crystallite size together with lattice strains. To accelerations of nitriding potential change have been applied
determine size distributions of nanocrystallites, the whole during investigations of the nitriding process of nanocrystalline
diraction line prole has to be analyzed.44,5154 As an example, iron -Fe(N) to iron nitride -Fe4N and reduction of the
Pielaszek44 presented a method for determining the nano- obtained iron nitride. Critical nitriding potentials, at which
crystallite size distribution which is a modication of classical phase transformations of nanocrystallites of a certain size occur
methods for determining the mean size of crystallites. Other in the above-mentioned reactions, have been determined.
XRD-based techniques for determination the crystallite size Furthermore, hysteresis phenomenon for a dependence of the
distribution are the WarrenAverbach method or the method iron nitriding degree on nitriding potential has been conrmed.
proposed by Vogel.55 Iron nanocrystallite size distribution in the iron ammonia
The most important feature of the proposed in this paper synthesis catalyst has been determined and it occurred to be
method is that it is a chemical method in which the whole solid bimodal. Accuracy of size distribution measurement depended
sample can be analyzed. In this method, a response of a on nitriding potential change accelerations. In comparison to
chemical system to changes in chemical potential of a gas phase other known methods of determining size distributions, the
is studied. The phenomenon that nanocrystallites of a certain proposed method is based on the relation of the active surface
Sact/V ratio undergo a phase transition at the specic chemical to the mass (volume) of a nanocrystallite. It is advantageous
potential of a gas phase is used, assuming that the chemical since it enables studying elementary processes due to
composition of the surface of each nanocrystallite is the same. connection of measured values with surface phenomena. It
This means that the obtained CSD is related to active surface was also discovered that during both the nitriding and
area. Active surface is a very important parameter when dealing reduction of iron nitrides nanocrystallites underwent phase
with processes occurring on the surface of catalytic nanoma- transition in their entire volume in the order of their sizes from
terials. However, this method also has some limitations. One of the largest to the smallest. All of the results were obtained in a
them is the requirement to operate in the close-to-equilibrium signicantly shorter period of time in comparison to the case
when processes would be carried out under conditions of
state. To show how far we can be from equilibrium let us
equilibrium state.
consider the following examples. In the region of classical
kinetics where P(t) P0(), every nanocrystallite may react
AUTHOR INFORMATION
and undergo the phase transition. We can, of course, assess the
shape of GSD under kinetics conditions,56 but the obtained Corresponding Author
result might not be accurate. On this end, we are maximally far *Tel: +48 91 449 47 30. Fax: +48 91 449 46 86. E-mail:
away from equilibrium. At the opposite end, where P(t) = rpelka@zut.edu.pl.
P0() we deal with real equilibrium. This state, however, can be ORCID
dicult to achieve. But the results obtained in equilibrium Rafa Pelka: 0000-0002-0896-8839
states are the most accurate. Therefore, we propose the CPPR
Author Contributions
method which operates in an intermediate region, viz. where
The manuscript was written through contributions of all
P(t) changes in some vicinity of P0(). The closer the
authors. All authors have given approval to the nal version of
equilibrium we operate the better. When the distance between
the manuscript.
P(t) and P0() is increased the accuracy of the method
decreases because we approach the kinetic region (Figure 9). Notes
The second limitation is connected with parameter. Namely, The authors declare no competing nancial interest.
the proposed method requires a phase transition to occur. It
means that value of must change in such a way to allow the
phase transition. If there are several phase transition then mass
ACKNOWLEDGMENTS
The scientic work was nanced by The National Centre for
increments (reaction rate in the solid phase: Figure 5, the Research and Development, program Lider, Project No.
nitriding reaction rate changes from 0 at the beginning to 0 at LIDER/025/489/L-5/13/NCBR/2014.
8554 DOI: 10.1021/acs.jpcc.6b09607
J. Phys. Chem. C 2017, 121, 85488556
The Journal of Physical Chemistry C Article
REFERENCES
(1) Liu, H. Z. Ammonia Synthesis Catalysts: Innovation and Practice;
(24) Kiebasa, K.; Arabczyk, W. Studies of the Ammonia
Decomposition over a Mixture of -Fe(N) and -Fe4N. Pol. J.
Chem. Technol. 2013, 15, 97101.
World Science Publishing Co. Ltd.: Singapore, 2013.
(25) Kiebasa, K.; Pelka, R.; Arabczyk, W. Studies of the Kinetics of
(2) Schlogl, R. In Catalytic Ammonia Synthesis, Fundamental and
Ammonia Decomposition on Promoted Nanocrystalline Iron Using
Practice; Jennings, J. R., Ed.; Plenum Press: New York, 1991.
Gas Phases of Different Nitriding Degree. J. Phys. Chem. A 2010, 114,
(3) Altenburg, K.; Bosch, H.; van Ommen, J. G.; Gellings, P. J. The
Role of Potassium as a Promoter in Iron Catalysts for Ammonia 45314534.
(26) Moszynski, D.; Moszynska, I.; Arabczyk, W. Iron Nitriding and
Synthesis. J. Catal. 1980, 66, 326334.
(4) Arabczyk, W.; Narkiewicz, U.; Moszynski, D. Double-Layer Reduction of Iron Nitrides in Nanocrystalline Fe-N System. Mater.
Model of the Fused Iron Catalyst for Ammonia Synthesis. Langmuir Lett. 2012, 78, 3234.
(27) Arabczyk, W.; Ekiert, E.; Pelka, R. Hysteresis Phenomenon an a
1999, 15, 57855789.
(5) Arabczyk, W.; Pelka, R.; Jasinska, I. Extended Surface of Materials Reaction System of Nanocrystalline Iron and a Mixture of Ammonia
as a Result of Chemical Equilibrium. J. Nanomater. 2014, 2014, and Hydrogen. Phys. Chem. Chem. Phys. 2016, 18, 2579625800.
(28) Pelka, R.; Arabczyk, W. Studies of the Kinetics of Reaction
No. 473919.
(6) Jasinska, I.; Lubkowski, K.; Arabczyk, W. Wpyw Temperatury Between Iron Catalysts and Ammonia Nitriding of Nanocrystalline
Redukcji na Powierzchnie Wasciwa i Aktywna Preredukowanego Iron with Parallel Catalytic Ammonia Decomposition. Top. Catal.
Katalizatora Z elazowego do Syntezy Amoniaku. Przem. Chem. 2003, 2009, 52, 15061516.
82, 230233. (29) Pelka, R.; Arabczyk, W. Modelling of Nanocrystalline Iron
(7) Kowalczyk, Z.; Jodzis, S.; Sroda, J.; Diduszko, R.; Kowalczyk, E. Nitriding Process Influence of Specific Surface Area. Chem. Papers
Influence of Aluminium and Potassium on Activity and Texture of 2011, 65, 198202.
Fused Iron Catalysts for Ammonia Synthesis. Appl. Catal., A 1992, 87, (30) Lehrer, E. The Equlibrium Iron-Hydrogen-Ammonia. Z.
114. Electrochem. 1930, 36, 383392.
(8) Arabczyk, W.; Narkiewicz, U.; Kaucki, K. Model of Active (31) Kunze, J. Nitrogen and carbon in iron and steel thermodynamics;
Surface of Iron Catalyst for Ammonia Synthesis. Vacuum 1994, 45, Akademie-Verlag: Berlin, 1990.
267269. (32) Du Marchie van Voorthuysen, E. H.; Feddes, B.; Chechenin, N.
(9) Paal, Z.; Ertl, G.; Lee, S. B. Interactions of Potassium, Oxygen G.; Inia, D. K.; Vredenberg, A. M.; Boerma, D. O. Low-Temperature
and Nitrogen with Polycrystalline Iron Surfaces. Appl. Surf. Sci. 1981, Nitridation of Iron Layers in NH3H2 Mixtures. Phys. Stat. Sol. (A)
8, 231249. 2000, 177, 127133.
(10) Strongin, D. R.; Somorjai, G. A. In Catalytic Ammonia Synthesis, (33) Du Marchie van Voorthuysen, E. H.; Chechenin, N. C.; Boerma,
Fundamental and Practice; Jennings, J. R., Ed.; Plenum Press: New D. O. Low-Temperature Extension of the Lehrer Diagram and the
York, 1991. Iron-Nitrogen Phase Diagram. Metall. Mater. Trans. A 2002, 33,
(11) Ertl, G.; Prigge, D.; Schlogl, R.; Weiss, M. Surface Character- 25932598.
ization of Ammonia Synthesis Catalysts. J. Catal. 1983, 79, 359377. (34) Sokoowska, A.; Rudnicki, J.; Beer, P.; Maldzinski, L.;
(12) Somorjai, G. A.; Materer, N. Surface Structures in Ammonia Tacikowski, J.; Baszkiewicz, J. Nitrogen Transport Mechanisms in
Synthesis. Top. Catal. 1994, 1, 215231. Low Temperature Ion Nitriding. Surf. Coat. Technol. 2001, 142144,
(13) Wrobel, R.; Arabczyk, W. SolidGas Reaction with Adsorption 10401045.
as the Rate Limiting Step. J. Phys. Chem. A 2006, 110, 92199224. (35) Pelka, R.; Kiebasa, K.; Arabczyk, W. Catalytic Ammonia
(14) Arabczyk, W.; Wrobel, R. Study of the Kinetics of Nitriding of Decomposition during Nanocrystalline Iron Nitriding at 475 degrees
Nanocrystalline Iron Using TG and XRD Methods. Solid State C with NH3/H2 Mixtures of Different Nitriding Potentials. J. Phys.
Phenom. 2003, 94, 185188. Chem. C 2014, 118, 61786185.
(15) Moszynska, I.; Moszynski, D.; Arabczyk, W. Hysteresis in (36) Karch, J.; Birringer, R.; Gleiter, H. Ceramics Ductile at Low
Nitriding and Reduction in the Nanocrystalline Iron-Ammonia- Temperature. Nature 1987, 330, 556558.
Hydrogen System. Przem. Chem. 2009, 88, 526529. (37) Lojkowski, W.; Fecht, H. J. Structure of Intercrystalline
(16) Wilk, B.; Arabczyk, W. Studies on the Nitriding and Reduction Interfaces. Prog. Mater. Sci. 2000, 45, 339568.
in the Nanocrystalline Iron-Ammonia-Hydrogen System. Przem. Chem. (38) Poliakoff, M.; King, P. Phenomenal Fluids. Nature 2001, 412,
2014, 93, 10361040. 125.
(17) Wilk, B.; Arabczyk, W. Investigation of Nitriding and Reduction (39) Gleiter, H. Nanostructured Materials: Basic Concepts and
Processes in a Nanocrystalline IronAmmoniaHydrogen System at Microstructure. Acta Mater. 2000, 48, 129.
350C. Phys. Chem. Chem. Phys. 2015, 17, 2018520193. (40) Beck, I. E.; Bukhtiyarov, V. I.; Pakharukov, I. Y.; Zaikovsky, V. I.;
(18) Arabczyk, W.; Ekiert, E.; Pelka, R. Size-Dependent Trans- Kriventsov, V. V.; Parmon, V. N. Platinum Nanoparticles on Al2O3:
formation of -Fe into -Fe4N in Nanocrystalline the FeNH3H2 Correlation Between the Particle Size and Activity in Total Methane
System. J. Phys. Chem. C 2016, 120, 1798917995. Oxidation. J. Catal. 2009, 268, 6067.
(19) Wilk, B.; Kiebasa, K.; Arabczyk, W. Nitriding of Nanocrystalline (41) Pelka, R.; Kielbasa, K.; Arabczyk, W. The Effect of Iron
Iron with AmmoniaHydrogen Mixture at 300C. Przem. Chem. 2015, Nanocrystallites Size in Catalysts for Ammonia Synthesis on Nitriding
94, 18161820. Reaction and Catalytic Ammonia Decomposition. Cent. Eur. J. Chem.
(20) Moszynski, D.; Moszynska, I. Phase Transformations During 2011, 9, 240244.
Nitriding of Nanocrystalline Iron. Przem. Chem. 2013, 92, 13321335. (42) Pelka, R.; Glinka, P.; Arabczyk, W. The Influence of Iron
(21) Moszynski, D.; Moszynska, I.; Arabczyk, W. The Trans- Nanocrystallite Size on a Nitriding Process Rate. Mater. Sci.-Poland
formation of Alpha-Fe into Gamma-Fe4N in Nanocrystalline Fe-N 2008, 26, 349356.
System. Appl. Phys. Lett. 2013, 103, 253108. (43) Arabczyk, W.; Jasinska, I. The Current State of Knowledge of
(22) Moszynski, D. Nitriding of Nanocrystalline Iron in the Iron Catalysts Used in Ammonia Synthesis. Przem. Chem. 2006, 85,
Atmoshperes with Variable Nitriding Potential. J. Phys. Chem. C 130137.
2014, 118, 1544015447. (44) Pielaszek, R. FW1/5/1/4 Method for Determination of the
(23) Moszynski, D.; Kiebasa, K.; Arabczyk, W. Influence of Grain Size Distribution from Powder Diffraction Line Profile. J. Alloys
Crystallites Size on Iron Nitriding and Reduction of Iron Nitrides Compd. 2004, 382, 128132.
in Nanocrystalline Fe-N System. Mater. Chem. Phys. 2013, 141, 674 (45) Wojdyr, M. Fityk: a General-Purpose Peak Fitting Program. J.
679. Appl. Crystallogr. 2010, 43, 11261128.