The Ti3AlC2 MAX Phase as an Efficient Catalyst for Oxidative Dehydrogenation of n-Butane

Article abstract of DOI:10.1002/anie.201702196

Dehydrogenation or oxidative dehydrogenation (ODH) of alkanes to produce alkenes directly from natural gas/shale gas is gaining in importance. Ti₃AlC₂, a MAX phase, which hitherto had not been used in catalysis, efficiently catalyzes the ODH of n-butane to butenes and butadiene, which are important intermediates for the synthesis of polymers and other compounds. The catalyst, which combines both metallic and ceramic properties, is stable for at least 30 h on stream, even at low O₂:butane ratios, without suffering from coking. This material has neither lattice oxygens nor noble metals, yet a unique combination of numerous defects and a thin surface Ti_1?yAl_yO_2?y/2 layer that is rich in oxygen vacancies makes it an active catalyst. Given the large number of compositions available, MAX phases may find applications in several heterogeneously catalyzed reactions.

Full text of DOI:10.1002/anie.201702196

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Ti3AlC2 MAX-phase as an efficient catalyst for oxidative
dehydrogenation of n-butane.
Authors: Wesley Ng, Edwin Gnanakumar, Gadi Rothenberg, Erdni
Batyrev, Sandeep Sharma, Pradeep Pujari, Heather Greer,
Wuzong Zhou, Ridwan Sakidja, Michel Barsoum, and N. R.
Shiju
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201702196
Angew. Chem. 10.1002/ange.201702196
Link to VoR: http://dx.doi.org/10.1002/anie.201702196
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Angewandte Chemie International Edition
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COMMUNICATION
Ti
3
AlC MAX-phase as an efficient catalyst for oxidative
2
dehydrogenation of n-butane
[
a]
[a]
[b]
[c]
Wesley H. K. Ng, Edwin S. Gnanakumar, Erdni Batyrev, Sandeep K. Sharma, Pradeep K.
[
c]
[d]
[d]
[e]
[a]
Pujari, Heather F. Greer, Wuzong Zhou, Ridwan Sakidja, Gadi Rothenberg, Michel W.
[
f]
[a]
Barsoum* and N. Raveendran Shiju*
Abstract: Light alkenes are important raw materials for the synthesis
of polymers and other chemical products. Traditionally they are
obtained mainly from steam cracking and catalytic cracking units.
However, dehydrogenation or oxidative dehydrogenation (ODH) of
alkanes is gaining more importance to produce alkenes directly from
drops linearly with decreasing temperatures. They conduct heat
and electricity like metals, yet they are elastically stiff, strong,
brittle, and some are heat-tolerant like ceramics.[6]
Numerous studies have been published on the electrical,
3 2
natural gas/shale gas. Here we report that Ti AlC , a MAX phase,
thermal and mechanical properties of MAX phases.[
7-12]
However,
which hitherto had not used in catalysis, efficiently catalyses the ODH
of n-butane to butenes and butadiene, important intermediates for the
synthesis of polymers and other compounds. The catalyst, which
combines both metallic and ceramic properties, is stable for at least
to the best of our knowledge, no catalytic applications have been
reported so far. Considering the combination of metallic and
ceramic properties and high stability, we anticipated that these
materials could be good catalysts. Moreover, the fact that they
differ from most “conventional” catalytic materials (because they
are neither oxides nor pure metals) triggered our curiosity. Such
different materials may open reaction pathways that are
unavailable to traditional catalysts.
2
30 h on stream, even at low O :butane ratios without suffering from
coking. This material has neither lattice oxygens nor noble metals, yet
a unique combination of numerous defects and a thin surface Ti1-
y y
Al O2-y/2 layer that is rich in oxygen vacancies makes it an active
catalyst. Given the large number of compositions available, MAX
phases may find applications in several heterogeneously catalysed
reactions.
MAX phases, a term coined in the late 1990s, are a family of
ternary carbides and nitrides with layered hexagonal crystal
structures. Their name reflects their chemical formula: Mn+1AX
where M is an early transition metal, A is an A-group element
mostly groups 13 and 14), X is carbon and/or nitrogen, and n =
, 2, or 3 (see Figure 1). Most of these phases were discovered
n
—
(
1
in powder form already in the 1960s, though the synthesis of
phase-pure bulk samples was only achieved in 1996.[ MAX
phases are interesting because they exhibit a unique combination
1]
[
2-4]
of ceramic and metallic properties.
Their bonding is a
[
5]
combination of covalent and metallic. The density of states at
the Fermi level is substantial and dominated by the d-d orbitals of
[
5]
the M-element. The electrical resistivity is metal-like in that it
[
a]
W. H. K. Ng, Dr. E. S. Gnanakumar, Prof. Dr. G. Rothenberg, Dr. N.
R. Shiju, Van't Hoff Institute for Molecular Sciences, University of
Amsterdam, P.O. Box 94157, 1090GD Amsterdam, The
Netherlands. E-mail: n.r.shiju@uva.nl
Figure 1. Hexagonal crystal structure of a 312 MAX phase. Ti atoms have two
I
different sites, denoted Ti and TiII. Every fourth layer is interleaved with layers
of pure A-group element.
[
[
b]
c]
Dr. E. Batyrev, Tata Steel, R&D, Ijmuiden, The Netherlands.
Dr. S. K Sharma, Dr. P. K. Pujari, Radiochemistry Division, Bhabha
Atomic Research Centre, Mumbai 400 085, India.
Considering the layered structure with alternating metals and
non-metals and thermal stability, we opted to study the catalytic
[
[
d]
e]
Dr. H. Greer, Prof. Dr. W. Zhou, School of Chemistry, University of
St Andrews, St Andrews KY16 9ST, UK.
Dr. R. Sakidja, Dept. of Physics, Astronomy and Materials Science,
Missouri State University, 901 South National Ave., Springfield, MO
application of MAX phases in oxidative dehydrogenation
[13-18]
(ODH).
Specifically, we examined the oxidative
65897.
dehydrogenation of butane to butenes and 1,3-butadiene
(Scheme 1). Butenes, and especially butadiene are important
industrial precursors for producing synthetic rubbers and plastics.
This reaction has recently gained importance with the advent of
[
f]
Prof. Dr. M. W. Barsoum, Drexel University, Department of Materials
Science & Engineering, Philadelphia, Pennsylvania 19104, United
States. E-mail: barsoumw@drexel.edu
Supporting information (full experimental details, PALS, TEM, XPS,
EDX results, modelling procedures and results) for this article is
given via a link at the end of the document.
shale gas and the increased use of natural gas as a cleaner
[15, 19-29]
carbon source.
The problem is that the typical conditions
1
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Angewandte Chemie International Edition
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COMMUNICATION
that can activate alkanes often lead to low alkene selectivity,
[
a]
o
because the products oxidise further to CO and CO
report the discovery that Ti AlC2, a commercially available MAX
2
. We now
Reaction conditions: temperature = 550 C; flow rate = 17 mL/min; catalyst
0.1 g; total pressure = 1 bar. [ trace amounts of ethylene and methane
b]
=
3
#
o
2
were also produced. The remainder is CO and CO . Temperature = 500 C.
phase, is a highly active and selective catalyst for butane ODH. It
gives high yields of C4 alkenes, especially 1,3-butadiene.
Such high selectivity for butadiene is rarely achieved in butane
ODH. At the same conversion of butane, Ti AlC was more
selective for butenes and butadiene than Mg or Mg
that are amongst the best catalysts reported so far for this
reaction.[29] Remarkably our Ti
AlC catalyst was still active and
stable at O :butane ratios ≤ 1:1 (see Table 1 and Figure S1).
3
2
3
V
2
O
8
3 2 7
V O ,
3
2
2
Typical metal oxide catalysts require ratios ≥ 2:1 to prevent severe
deactivation due to coke deposition.[
29]
Scheme. 1. The catalytic oxidative dehydrogenation of butane can give butenes,
butadiene, CO and CO .
2
We synthesized the Ti
synthesis route and confirmed its structure by X-ray diffraction
see Supporting Information for full experimental details). It
consists of a c-axis stacking sequence where two layers of edge
sharing CTi octahedra are sandwiched between planar layers of
Al. The butane ODH study with Ti AlC was carried out at different
temperatures, varying the O :butane ratio from 0.25:1 up to 1:1.
The product mixture contained 1-butene, 2-butene, butadiene,
propene, CO and CO. Control experiments without a catalyst
yielded <1% of alkenes. At an O :butane ratio of 0.25:1 and
50 °C, Ti AlC gave nearly 35% selectivity for butenes and 25%
selectivity for butadiene at 10% conversion (Table 1). At higher
/butane ratios of 0.5 and 1, conversion increased to 20% and
4%, respectively, without significant loss in selectivity for
3 2
AlC MAX phase by a ceramic
(
6
3
2
2
2
2
5
3
2
O
2
2
butenes and butadiene. Even at 24% conversion, the partial
oxidation (butenes+butadiene) selectivity is close to 50%, which
is remarkable. The catalyst was stable, retaining its selectivity
during a long-time test (Figure S1). XRD analysis after the
reaction did not show any major structural changes further
confirming the stability of the phase (Figure S2).
3 2
Figure 2. HRTEM images of Ti AlC MAX phase. (a) A thin pale contrasted
amorphous surface layer (marked by arrow). (b) Higher magnification HRTEM
image of a selected area in (a) showing many point defects (marked by arrows).
(
c) HRTEM image showing many disordered layer defects. (d) HRTEM image
showing many partially ordered layer defects. The inset shows the
corresponding SAED pattern. The marked d-spacings are indexed to the unit
cell of Ti AlC .
3 2
Table 1. Performance of the Ti
3
AlC
2
in butane ODH
Total Selectivity
O
2
:butane
Butane
conversion,
%
Selectivity
of propene
%[
[a]
molar ratio
selectivity
of butenes,
%
of 1,3-BD
%
b]
The initial steps of the ODH reaction (O
2
and alkane
activation), normally follow a Mars–Van Krevelen mechanism for
metal oxides, wherein the lattice oxygen is the reactive species.
This means that the activity of metal oxide catalysts towards
hydrocarbons depends on the strength of the metal–oxygen bond
of the catalyst. In our case, there are no bulk lattice oxygens
available, making the adsorption of oxygen on the catalyst surface
to generate active oxygen species inevitable for the reaction to
occur. This adsorption depends strongly on the defect sites at the
catalyst surface. The HRTEM analysis indeed showed that the
catalyst particles contain many defects, most commonly domain,
point and layered ones (Figure 2). These defects might act as
adsorption as well as reaction sites. Positron Annihilation Lifetime
0
.25:1
10.1
20.3
24.2
13.8
35.0
29.0
27.0
20.7
25.0
21.0
19.5
16
1.2
1.4
1.7
1.6
0
.5:1
1:1
1
:1#
2
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COMMUNICATION
Spectroscopic investigation (PALS) of our catalyst showed two
positron lifetime components (see Table S1 and Figure S3), which
are higher than the bulk positron lifetime in titanium carbide (107
y
Al
y
)O2-y/2, creating a mole of oxygen vacancies for every two
moles of alumina that is added. Previous studies indicated that,
after high temperature oxidation, a (Ti1-yAl )O2-y/2 layer is formed
y
on the surface of Ti
[
30]
[32-33]
ps) indicating positron annihilation from defect sites. The first
lifetime component (189.7±6.1 ps) is very close to the positron
lifetime for monovacancy of Ti indicating the existence of Ti
vacancy defects. The second lifetime component (300.9±9 ps) is
attributed to defects with larger open volume like vacancy clusters
and voids. This agrees well with the HRTEM observation of
layered defects. Positron trapping to these defects will lead to
higher lifetime value. The corresponding intensities of the positron
lifetime components indicate that concentration of mono vacancy
defects are higher than the layer defects. HRTEM further shows
a thin amorphous layer (5–10 nm) on the surface (Figure 2a),
which according to EDX spectra contains a very high oxygen
content compared to the inner bulk material (see Figure S4,
Supporting Information). The X-ray from oxygen has very low
energy and can be easily absorbed so the oxygen content in an
EDX spectrum may not be accurate, therefore quantitative data
analysis is not provided. Further confirmation of a high oxygen
content in the amorphous surface layer was provided through
EDX elemental mapping (Figure 3).
3
AlC
2
.
It is reasonable to assume that the
oxygen vacancies should also act as active oxygen ‘creators’ from
gas phase oxygen, which can explain the catalytic activity. The
adsorbed oxygen species formed upon activation of gas-phase
2
O on surface oxygen vacancies can activate n-butane. These
species are most likely monoatomic, and therefore more selective
for partial oxidation.[
28]
3 2
Figure 4. Al2p, Ti2p, O1s and C1s XPS of Ti AlC , showing different types of
possible species on the surface. Besides individual carbide and oxide, the
surface has a significant amount of mixed oxide (Al-Ti-O).
We used N
estimate the concentration of oxygen vacancies using the fact that
metallic sites will split adsorbed N O at required activation
temperature, leading to the oxidation of metal to metal oxide.
2
O chemisorption coupled with XPS analysis to
2
[
34]
-7
Thus, we first reduced the Ti
at 500 °C, creating oxygen vacancies and subsequently exposed
the reduced surface to N O. We then examined the re-oxidised
3 2
AlC MAX phase in UHV (10 mbar)
Figure 3. HAADF STEM image (top left) and elemental maps for Al + O (top
right) and Ti, Al, C and O on the Ti AlC MAX phase (bottom).
3 2
2
surface by XPS. The amount of Ti that undergoes oxidation can
be estimated by linear extrapolation of the subsurface (diffusion
dependent oxidation) uptake to t=0 (see Figure S5),[ which
gives 3.5 at%. The corresponding oxygen amount is 7.0 at%.
Using this, we can estimate the concentration of oxygen
35]
Based on the analysis of EDX spectra and mapping, we
reason that the thin layer on the catalyst surface is a mixed oxide
of Al-Ti-O. Alternatively, we considered it may be pure alumina or
alumina/titania but this appears to be less likely according to our
EDX mapping data. We believe that this thin layer, coupled with
the large electron reservoir below it, holds the key to the catalytic
26
3
vacancies as 9x10 /m (see Supporting information and Figure
S6 for more details).
To further prove the role of oxygen vacancies, we also tested
[
31]
another MAX phase Ti
Al layers are replaced by Si.
alumina and titania, silica and titania do not form a solid solution.
Hence, if our hypothesis that the (Ti1-yAl )O2-y/2 layer is responsible
for the catalysis, Ti SiC should be much less selective in ODH. A
3
SiC
2
,isostructural with Ti
3
AlC
2
wherein the
activity. To confirm this, we studied the catalyst by XPS (see
Figure 4), which has indeed proved that, besides the individual
carbide peaks, the surface has a significant amount of mixed
oxides as well as oxidized Al and Ti. This supports our hypothesis
that the surface layer observed by TEM is a mixed Al-Ti-O.
Alumina and titania can form a solid solution with the formula, (Ti1-
[
1, 36]
The difference here is that unlike
y
3
2
series of control experiments at varying temperatures proved that
3
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Angewandte Chemie International Edition
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COMMUNICATION
to be true. Ti
to 16 % at 600 °C compared to 24% at 550 °C for Ti
3
SiC
2
gave lower conversion (from 4 % at 450 °C up
AlC ) and the
atoms from butane onto the surface yielding adsorbed water
molecule/forming OH bonds is favourable on the Al TiO surface:
2 5
3
2
total yield of butene and butadiene was only 1–2 % (Table S2,
Supporting Information). This confirms that the lack of sufficient
anion vacancies in Ti SiC due to the inability to form a non-
3 2
C
C
4
H
10(g)+ O(surface)  C
4
H
8(g) +H
2
O
(ads)
ΔH = -2.5 eV (Figure 5c)
4
H10(g)+ 4O(surface)  C
4
H6(g) + 4OH(ads) ΔH = -4.8 eV (Figure 5d)
stoichiometric surface over layer leads to non-selective oxidation
in this case. Kondratenko et al. recently reported enhanced
selectivity for propene in non-oxidative dehydrogenation of
propane by deliberately increasing the concentration of defect
As shown in reaction # 2 in SI, the overall desorption reaction
(ads) is slightly endothermic, with ΔH = 0.9 eV.
This value however is much lower than the energy required for
releasing the intermediate product of C
3.89 eV). Thus, both types of direct dissociation will not be the
easiest pathways and thus, other intermediate mechanisms must
have taken place to lower these overall energy barrier. This gives
credence to the possible role of oxygen defects and/or a higher
operating temperature to enable the reaction to proceed.
Nevertheless, the overall reactions involving further dissociations
do indicate energetically favourable conditions for oxidative
dehydrogenation of butane on a mixed Al-Ti-O surface into butane
and butadiene.
C
4
4 9(g) +
H10(g)  C H H
4 4
H9(ads) into C H9(g) (ΔH =
[37]
2
sites in unconventional oxide catalysts. They promoted ZrO ,
+
which has an unchangeable oxidation state, with other metal
oxides, which created lattice defects consisting of coordinatively
unsaturated Zr cations. Our results further confirm that the
defective structure in unconventional materials can generate
unexpected catalytic properties. Moreover, stable activity and
selectivity over several hours (Figure S1) indicate high surface
mobility of oxygen anions and consequent rapid reoxidation
3 2
apparently due to the layered structure of our Ti AlC MAX phase.
Since adsorption of butane on the surface also will influence the
reaction, we also compared the relative adsorptions of n-butane
on both samples at 250 °C (highest temperature possible in our
adsorption equipment). These experiments showed that Ti
3
AlC
2
adsorbs significantly more n-butane than Ti
apparently due to the defective structure.
SiC (Figure S7),
3 2
To understand further the experimental observations, we
evaluated computationally a number of scenarios of favourable
chemical reactions at the surface. Note that this is not an
exhaustive search. Since a previous equilibrium study has shown
that a stable ternary phase of Al
system,
2
TiO
we used the O-terminating (001) surface of this
phase as a simple model to represent the mixed-cation oxide
surface on Ti AlC MAX phase. We performed electronic structure
calculations as implemented in the Density Functional Theory
5
exists in the Ti-Al-O
[38-39]
3
2
[
40]
approximation (VASP ab initio code ) to assess the energetics
of the adsorption of butane onto the oxygen-terminating surface
at the ground state (at 0 K). Further details of the methodology,
[41]
exchange-correlation potentials used (PAW-PBE
)
and
–5
convergence criteria (electronic convergence criterion of 10 eV
and force convergence limit of 10 eV/A) are given elsewhere.[42-
–
2
4
3]
Table S3 (Supporting Information) shows the list of chemical
reactions along with the final atomic configurations.
The results show that butane adsorbs relatively easily,
through the formation of a C–O bond on the selected surface. This
is followed immediately by the dissociation of the hydrogen atom
onto the surface, captured by one of the oxygen’s dangling bonds:
C
4
H
4
10(g) + O(surface)  C H9(ads) + OH(ads); ΔH = -2.99 eV. Figure 5a
Figure 5. Atomic configurations of various steps of butane interaction with the
shows the resulting atomic configuration (A video showing the
relaxation sequence is included in the SI). This reaction releases
roughly 3 eV per molecule of butane. A possible subsequent
MAX surface, taking Al
2
TiO
5
as a model resulting in (a) C
+ H O and (d) C H
4
H9(ads) + OH(ads), (b)
6(g)
+ 4OH(ads). See the
C H + H O , (c) C H
4
8(ads)
2
(ads)
4
8(g)
2
(ads)
4
Supporting Information for more details. Ti is represented by blue balls and O
by red balls.
reaction where by the adsorbed C
8(ads) by releasing another hydrogen atom forming a water
molecule (Figure 5b) is also favoured, for an overall chemical
reaction of: C
eV. A further oxidative dehydrogenation may be facilitated by the
release of more hydrogen atoms from the adsorbed C yielding
,3 butadiene according to: C
(ads) ; ΔH = -1.39 eV. Overall, releasing two or four hydrogen
4 9
H further decomposes into
4
C H
3 2
There is no lattice or structural oxygen in Ti AlC MAX phase, and
4
4 2
H10(g) + O(surface)  C H8(ads) + H O(ads) ; ΔH = -3.35
it doesn’t contain any noble metals, yet its unique combination of
defects and very thin presumably non-stoichiometric oxide
surface layer containing oxygen vacancies resulted in O-
containing active sites and made this material catalytically active.
Given the interesting set of properties that the MAX phases exhibit,
4 8
H
1
H O
2
4
4 6(ads)
H8(ads) + O(ads)  C H +
4
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Angewandte Chemie International Edition
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COMMUNICATION
[
17]
[a] N. R. Shiju, M. Anilkumar, S. P. Gokhale, B. S. Rao, C. V. V.
Satyanarayana, Catal. Sci. Technol. 2011, 1, 1262-1270; [b] N.R.
Shiju, V.V. Guliants, ChemPhysChem, 2007, 8, 1615-1617.
G. Rothenberg, E.A. de Graaf, A. Bliek, Angew. Chem. Int. Ed.
especially their high-temperature stability, metallic and ceramic
properties and low cost, our work has very wide scope in
heterogeneous catalysis. For an industrial process, we still need
to resolve issues such as product separation and high recycle
rate; however, we believe that our results will open new
fundamental studies of MAX phases. There are over 60 MAX
phases synthesized so far, with very different compositions. The
unique properties of these materials as catalysts or catalyst
supports in suitable reactions are waiting to be explored.
[18]
2003, 42, 3366-3368.
[
[
[
[
19]
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H. Nguyen Ngoc, H. Ngo Duc, C. Le Minh, Appl. Catal., A 2011,
407, 106-111.
M. Setnicka, R. Bulanek, L. Capek, P. Cicmanec, J. Mol. Catal. A:
Chem. 2011, 344, 1-10.
N. Madaan, N. R. Shiju, G. Rothenberg, Catal. Sci. Technol. 2016,
6, 125-133.
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[
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V. Schwartz, W. Fu, Y.-T. Tsai, H. M. Meyer, III, A. J. Rondinone,
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S. Asaoka and S. Al-Khattaf, Catal. Sci. Technol., 2015, 5, 4622-
N. R. S and E.S.G thank CAPITA ERA-NET for funding. We thank
N. J. Geels and Dr. M. C. Mittelmeijer-Hazeleger for the butane
adsorption measurements. H. F. G. and W.Z. thank the EPSRC
for a Capital Equipment Grant EP/L017008/1.
[
27]
[28]
4
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Chang and I. K. Song, J. Nanosci. Nanotechnol., 2013, 13, 8110-
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Keywords: Butadiene • heterogeneous catalysis • natural gas •
oxidative dehydrogenation • shale gas • VASP
8
B. Hausberger, Catal. Today, 2010, 156, 237-245. [f] J. C. Jung, H.
Kim, Y. S. Kim, Y.-M. Chung, T. J. Kim, S. J. Lee, S.-H. Oh and I.
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5
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201702196
COMMUNICATION
Keywords: Butadiene • heterogeneous catalysis • natural gas • oxidative dehydrogenation • shale gas • VASP
Table of Contents
COMMUNICATION
Wesley H. K. Ng, Edwin S.
Gnanakumar, Erdni Batyrev, Sandeep
K. Sharma, Pradeep K. Pujari, Heather
F. Greer, Wuzong Zhou, Ridwan
Sakidja, Gadi Rothenberg, Michel W.
Barsoum* and N. Raveendran Shiju*
Ti
3
AlC
2
, the first MAX phase to be used in heterogeneous catalysis, efficiently
Page No. – Page No.
catalyses the ODH of n-butane to butenes and butadiene, owing to its defective
structure and non-stoichiometric oxide layer on the surface.
3 2
Ti AlC MAX-phase as an efficient
catalyst for oxidative
dehydrogenation of n-butane
6
This article is protected by copyright. All rights reserved.