Liquid-phase oxidation of alkanes with molecular oxygen catalyzed by high valent iron-based perovskite

Article abstract of DOI:10.1039/c8cc02185f

Hexagonal BaFeO_3-δ containing high valent iron species acted as an efficient heterogeneous catalyst for the aerobic oxidation of alkanes without the need for additives. The activity of BaFeO_3-δ was much higher than that of typical Fe³⁺/Fe²⁺-containing iron oxide-based catalysts, and the recovered catalyst could be reused without significant loss of catalytic performance.

Full text of DOI:10.1039/c8cc02185f

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DOI: 10.1039/C8CC02185F
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Liquid-phase oxidation of alkanes with molecular oxygen
catalyzed by high valent iron-based perovskite
Satomi Shibata,a Kosei Sugahara,a Keigo Kamata*a,b and Michikazu Haraa,c
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Hexagonal BaFeO3–δ containing high valent iron species acted as structures and physicochemical properties can be controlled
an efficient heterogeneous catalyst for the aerobic oxidation of by changing the composition.7b,7c Despite their superiority,
alkanes without the need for additives. The activity of BaFeO3–δ application to perovskite-catalyzed liquid-phase organic
was much higher than that of typical Fe3+/Fe2+-containing iron reactions is still limited. We have very recently reported the
oxide-based catalysts, and the recovered catalyst could be reused amino acid-aided synthesis of high-surface-area perovskite
without significant loss of catalytic performance.
catalysts that contain alkaline earth metals as A-site elements.8
Hexagonal SrMnO3 could act as an efficient heterogeneous
catalyst for the aerobic oxidation of various substrates.8 We
envisaged that an iron-based perovskite containing Fe4+ would
likely act as an efficient catalyst for alkane oxidation because
high valent iron-oxo species have been postulated to be strong
active oxidants under mild conditions.9 Here, we report that
hexagonal 6H-BaFeO3–δ, which consists of face-sharing dimeric
Fe2O9 units linked by single corner-sharing FeO6 units along the
c axis (Fig. 1(a)), could act as an efficient, recyclable and
Catalytic oxidation of the aliphatic C–H bond of alkanes to
produce useful chemicals remains a significant and challenging
subject of research in the chemical industry.1 The development
of effective catalysts with well-defined active sites for the
oxidation of alkanes using activated oxidants such as organic
peroxides/peracids and hydrogen peroxide is expected to lead
to remarkable activity and selectivity.2 In contrast to such
processes, catalytic oxidation with molecular oxygen (O2) as an
oxidant offers environmental and economic advantages;
however, the control of O2 activation and selectivity remains a
problem to be solved.3 Functionalized adamantane derivatives
can be biologically active compounds and functionally hybrid
materials;4 therefore, several catalytic systems for the aerobic
oxidation of adamantane have been developed (Table S1,
ESI).5,6 Most of these systems are homogeneous and typically
require additives (radical initiator, reductant, etc.) or photo- or
microwave irradiation.5 There are only a few examples of
recoverable and reusable heterogeneous Ru- and V-based
catalysts with O2 as the sole oxidant.6
heterogeneous catalyst for the oxidation of adamantane (1a
)
with 0.1 MPa of O2 as the sole oxidant. This study provides the
first example of a naturally abundant iron oxide-based
heterogeneous catalyst for the aerobic oxidation of 1a without
the need for any additives.
Perovskite BaFeO3–δ was prepared by the amino acid-aided
method (see ESI).8b Fig. 1(b) shows a powder X-ray diffraction
(a)
(b)
The versatility of perovskite oxides with formula ABO3 has
led to various applications in the fields of structural chemistry,
magnetism, superconductivity, and piezoelectrics.7a In
particular, the catalytic function of perovskite oxide-based
materials has attracted much attention because their
10
20
30
40
50
60
70
80
2θ (degree)
(d)
(c)
a.Laboratory for Materials and Structures, Institute of Innovative Research, Tokyo
Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503,
Japan. E-mail: kamata.k.ac@m.titech.ac.jp; Fax&Tel: +81-45-924-5338
b.Japan Science and Technology Agency (JST), Precursory Research for Embryonic
Science and Technology (PRESTO), 4-1-8 Honcho, Kawaguchi 332-0012, Japan.
c. JST, Advanced Low Carbon Technology Research and Development Program
(ALCA), 4-1-8 Honcho, Kawaguchi 332-0012, Japan.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [Experimental details,
Figures, 4 Tables]. See DOI: 10.1039/x0xx00000x
719 717 715 713 711 709 707 705
Binding energy (eV)
200 nm
Fig. 1 (a) Structure of BaFeO3. Brown, purple, and red spheres
represent the Fe, Ba, and O atoms, respectively. (b) XRD
patterns for BaFeO3–δ (upper) and BaFeO3 (lower, ICSD 50869).
(c) XPS Fe 3p3/2 spectrum for BaFeO3–δ and (d) SEM image.
6
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(XRD) pattern for BaFeO3–δ, which is in good agreement with various perovskites and iron oxides (Tables 1 and VSie4w, AErSticI)le. OFnoliuner
that for hexagonal 6H-BaFeO3 x [space group P63/mmc (No. products, 1-adamantanol 3a), 2-
2a), 2-adDamOIa: 1n0t.a10n3o9l/C8CC02185F
4a), and 1,3-adamantanediol 5a), were
(
(
–
194)].10 Impurity phases of other iron oxide species (FeO, adamantanone
(
(
Fe3O4, Fe2O3, and Ba2FeO4) were not observed. Elemental mainly formed. The reaction did not proceed in the absence of
analysis of BaFeO3–δ using inductively coupled plasma atomic a catalyst (entry 19). Among the catalysts tested, Fe4+-
emission spectroscopy (ICP-AES) revealed that the molar ratio containing BaFeO3–δ and SrFeO3 exhibited high catalytic
of Ba:Fe was 1:1. The average oxidation state of Fe species was activity (entries 1 and 5), and the intrinsic activity of BaFeO3–δ
determined to be 3.8 by iodometry, which indicates that the δ (with face-sharing octahedra) per surface was approximately
value in BaFeO3–δ is ca. 0.1. The X-ray photoelectron two times higher than that of SrFeO3 (with the corner-sharing
spectroscopy (XPS) Fe 2p spectrum of BaFeO3–δ showed peaks octahedra). Other Fe3+/Fe2+-containing oxides such as CaFeO2.5
with binding energies of 709.7 and 711.6 eV, which correspond LaFeO3, BaFe2O4, and simple iron oxides (FeO, Fe3O4, and
to Fe3+ and Fe4+ species, respectively (Fig. 1(c)).10,11 The specific Fe2O3) and catalyst precursors of Fe(OAc)2 and Ba(OAc) were
,
surface area of BaFeO3–δ was 11 m2 g–1, and this value was almost inactive (entries 6
larger than those (0.2–6.6 m2 g–1) reported for BaFeO3–δ (Table based perovskites (BaBO3 (B = Mn, Co, and Ru) and AMnO3 (A
S2, ESI).10 Fig. 1(d) shows a scanning electron microscopy = Ca and Sr)), oxidation did not proceed (entries 14
18). The
(SEM) image of BaFeO3–δ, where the particle sizes were total yield of 2a 5a reached 67% for the oxidation of 1a under
–13). In the presence of Ba- and Mn-
–
–
estimated to be 50−200 nm. Cubic SrFeO3 and orthorhombic optimum conditions (entry 1 in Table 2), and the value was the
CaFeO2.5 were also successfully synthesized by the amino acid- second highest among the heterogeneous systems without
aided method and were characterized by XRD, N2-adsorption, additives (Table S1, ESI). In this case, the selectivity ratio of
and elemental analyses (Table S3 and Figs. S1 and S2, ESI).
tertiary/secondary (3°/2°) C–H activation normalized to the
number of C–H bonds was 29. This value is comparable to
a
Table 1 Effects of catalysts on the oxidation of 1a with O2
those of metal-catalyzed radical-mediated oxidation catalysts
with O2.5,6,9c Although BaFeO3-based materials have been
investigated for the catalytic combustion of CH4 and CO, NOX
decomposition, and electrochemical reaction,10 their
application to liquid-phase organic reactions has not been
reported.
OH
OH
OH
+
O
catalyst
PhCF3
+
+
OH
1a
2a
3a
4a
5a
Entry
Catalyst
SBET
Yield
(%)
Selectivity (%)
(m2 g–1)
50
2a
3a
4a
5a
1
2b
3b,c
4b,d
11
11
11
11
29
30
30
31
76
7
11
6
BaFeO3–δ
BaFeO3–δ
BaFeO3–δ
40
30
82
79
77
7
7
8
6
7
7
5
7
7
BaFeO3–δ
SrFeO3
CaFeO2.5
LaFeO3
BaFe2O4
Fe2O3
Fe3O4
FeO
Fe(OAc)2
Ba(OAc)2
BaCoO3
5
6
7
8
20
28
18
14
39
12
1
–
–
19
27
<1
<1
<1
<1
<1
<1
<1
<1
<1
76
–
–
–
–
–
–
–
–
8
–
–
–
–
–
–
–
–
–
10
–
–
–
–
–
–
–
–
6
–
–
–
–
–
–
–
–
–
20
10
0
Removal of catalyst
9
10
11
12
13
14
0
48
96
144
192
240
Time (h)
Fig. 2 Effect of BaFeO3–δ removal on the oxidation of 1a
. ◆,
with BaFeO3–δ , without BaFeO3–δ as indicated by the arrow.
;
◇
Reaction conditions: BaFeO3–δ (0.1 g), 1a (0.5 mmol), PhCF3 (1
mL), pO2 (0.1 MPa), 363 K.
–
–
15
16
17
18
BaMnO3
SrMnO3
CaMnO3
25
47
11
<1
<1
<1
–
–
–
–
–
–
–
–
–
–
–
–
To verify whether the observed oxidation catalysis is due to
solid BaFeO3–δ or leached Fe or Ba species, the oxidation of 1a
was performed under the conditions described in Fig. 2. When
BaFeO3–δ was removed by hot filtration after 48 h, no further
oxidation proceeded (Fig. 2). In addition, no leaching of Fe or
Ba species in the filtrate was determined by ICP-AES analysis.
These results suggest that the observed catalysis is
heterogeneous. The BaFeO3–δ used could readily be recovered
from the reaction mixture by simple filtration. There was no
significant difference in the XRD patterns of the fresh and
recovered BaFeO3 catalyst (Fig. S3, ESI).‡ The recovered
catalyst could be reused twice without significant change in
BaRuO3
without
25
–
1
<1
>99
–
–
–
–
–
–
–
19
a
Reaction conditions: catalyst (0.1 g), 1a (0.5 mmol), PhCF3 (1
mL), pO2 (0.1 MPa), 363 K, 48 h. Yield and selectivity were
determined by gas chromatography (GC) analysis. Yield (%) =
(
2a
product (mol)/(2a
Reuse (1st). d Reuse (2nd).
+3a
+
4a
+
5a) (mol)/initial 1a (mol)
×100. Selectivity (%) =
b
c
+
3a+4a 5a) (mol) 100. 1a (1 mmol).
+
×
The aerobic oxidation of 1a in benzotrifluoride (PhCF3) at
0.1 MPa of O2 without any additives was performed using
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the total yield or the selectivity: e.g., 82% selectivity to 2a at oxygenated products (alcohols and ketones) were obtained
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DOI: 10.1039/C8CC02185F
30% total yield (fresh), 79% selectivity to 2a at 30% total yield (entries 8 and 9).
(reuse 1st), and 77% selectivity to 2a at 31% total yield (reuse
The BaFeO3–δ-catalyzed oxidation of 1a under the
2nd) (entries 2–4 in Table 1),§ which indicates the durability of conditions of entry 1 in Table 1 proceeded with an induction
BaFeO3–δ
.
period and was completely suppressed by the presence of a
radical scavenger (2,6-di-tert-butyl-4-methylphenol, 1 equiv.
Table 2 Oxidation of various substrates catalyzed by BaFeO3–δ with respect to 1a). The oxidation of 1a did not proceed under
a
with O2
an Ar atmosphere (Fig. S4, ESI), which indicates that BaFeO3–δ
did not act as a stoichiometric oxidant but as a catalyst. A good
correlation between the logarithm of the reaction rate
normalized on a per hydrogen basis (logR0’) for the oxidation
of alkylarenes and C–H bond dissociation energy (BDE) was
observed (Fig. 3).14 A kinetic isotope effect (kH/kD) value of 5.0
was observed for the oxidation of 1f and 1f-d10 at 363 K. All
these data including the catalyst effect, 3°/2° value for 1a, and
the stereospecificity for 2d indicate that the present oxidation
proceeds via a radical-mediated oxidation mechanism and that
H-abstraction (likely by high valent iron oxo species in BaFeO3–
δ) is the rate-determining step (Fig. S5). The high 18O content
(96–97 %) in 2a (18O-labeled 2a/total 2a) was observed from
the initial stage of the BaFeO3–δ-catalyzed oxidation of 1a at
0.1 MPa of 18O2 (97 atom%, Fig. S6),§§ supporting the reaction
mechanism.
–0.5
xanthene
9,10-dihydroanthracene
–1.0
–1.5
–2.0
–2.5
–3.0
–3.5
fluorene
ethylbenzene
a
70
75
80
85
90
Reaction conditions: BaFeO3–δ (0.2 g),
1 (1.0 mmol), PhCF3 (1
BDE (kcal mol–1
)
mL), pO2 (0.1 MPa), 363 K. Ketones (6% yield). c Ketones (5%
yield). d n-Octane (1 mL), 353 K.
b
Fig. 3 Plot of logR0’ versus BDE for the oxidation of alkylarenes.
Reaction conditions: BaFeO3–δ (0.1 g), substrate (1 mmol),
PhCF3 (1 mL), pO2 (0.1 MPa), 363 K.
The present system could be applied to the oxidation of
various hydrocarbon substrates with O2 as the sole oxidant
(Table 2). The tertiary C–H bonds of 1a, as well as its
In conclusion, hexagonal iron-based perovskite BaFeO3–δ
synthesized by the amino acid-aided method could
heterogeneously catalyze the aerobic oxidation of various
alkanes and alkylarenes without the need for any additives.
This work was supported by the PRESTO program (No.
JPMJPR15S3) of the Japan Science and Technology Agency
(JST).
derivatives
(1-ethyladamantane
(1b
)
and
1,3-
dimethyladamantane (1c)), were mainly oxidized, and the
yields of the corresponding alcohols were 42% and 31%,
respectively (entries 2 and 3). In the case of cis-decalin (1d),
the stereoisomeric mixture of 9-decalol (2e, cis/trans = 26/74)
was obtained (entry 4), which indicates the formation and the
substantial inversion of the 9-decalyl radical intermediate in
this reaction.2b,3a,9c,13 The secondary C–H bonds of cyclooctane
Conflicts of interest
There are no conflicts to declare.
(
(
1e) was also oxidized to the corresponding alcohol and ketone
2e and 3e), while the yields were low (entry 5). This catalyst
system also efficiently catalyzed the oxidation of alkylarenes.
Fluorene (1f) and xanthene (1g) with two benzene rings were
oxidized to the corresponding ketones in 59% and 95% yields,
respectively (entries 6 and 7). In the case of tetralin (1h) and
Notes and references
‡ The slight peak shifts due to the increase of oxygen vacancies
were observed.
indan
(1i) with one benzene ring, the corresponding
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