Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

Article abstract of DOI:10.1002/cssc.201601364

Catalytic oxidation of alcohols often requires the presence of expensive transition metals. Herein, it is shown that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O₂in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H₂. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but addition of 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.

Full text of DOI:10.1002/cssc.201601364

Accepted Article
Title: Selective Aerobic Oxidation of Alcohols over Atomically-
dispersed Non-Precious Metal Catalysts
Authors: Jiahan Xie, Kehua Yin, Alexey Serov, Kateryna Artyushkova,
Hien Pham, Xiahan Sang, Raymond Unocic, Plamen
Atanassov, Abhaya Datye, and Robert Davis
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ChemSusChem
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COMMUNICATION
Selective Aerobic Oxidation of Alcohols over Atomically-
dispersed Non-Precious Metal Catalysts
Jiahan Xie, Kehua Yin, Alexey Serov, Kateryna Artyushkova, Hien N. Pham, Xiahan Sang, Raymond R.
Unocic, Plamen Atanassov, Abhaya K. Datye and Robert J. Davis*
[
9]
Abstract: Catalytic oxidation of alcohols often requires the presence
of expensive transition metals. Herein, we show that earth-abundant
Fe atoms dispersed throughout a nitrogen-containing carbon matrix
catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural
encapsulated or supported Fe complexes, but these catalysts
often require the addition of peroxides ， which is likely the
consequence of the poor ability of the catalyst to activate
dioxygen. As an Fe-N-C catalyst has previously demonstrated
excellent ORR performance, we hypothesized that it might also
be a promising catalyst for the aerobic oxidation of alcohols. In
fact, Jagadeesh et al. have reported the aerobic oxidative
nitrification of various alcohols over Fe-N-C and identified
by O
2
in the aqueous phase. The activity of the catalyst can be
. An observed kinetic isotope
regenerated by a mild treatment in H
2
effect indicates β-H elimination from the alcohol is the kinetically-
relevant step in the mechanism, which can be accelerated by
substituting Fe with Cu. Dispersed Cr, Co and Ni also convert
alcohols, demonstrating the general utility of metal-nitrogen-carbon
materials for alcohol oxidation catalysis. Oxidation of aliphatic
alcohols was substantially slower than that of aromatic alcohols, but
addition of 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with
Fe can significantly improve the reaction rate.
[10]
aldehydes as intermediates.
To the best of our knowledge,
however, the exploration of Fe-N-C and other platinum group
metal-free analogues as potential catalysts for alcohol oxidation
in water to produce aldehyde or acid products has not been
reported and the mechanism of alcohol oxidation remains
unclear. The current study relates extensive materials
characterization results to catalytic performance, explores the
kinetics of alcohol oxidation in liquid water, examines the
regenerability of the catalysts and compares a variety of non-
precious metal, atomically-dispersed M-N-C catalysts.
Precious metal catalysts are widely used in petrochemical
refineries,
pharmaceutical
production
facilities
and
[1]
environmental remediation devices. In particular, the aerobic
oxidation of biomass-derived alcohols to corresponding
aldehydes and acids in the aqueous phase using heterogeneous
precious metal catalysts, such as Au, Pt, Pd and Ru, has
received growing attention because it offers a green and
[
2]
sustainable route to value-added chemicals.
annual production and very high price of the metals, however,
can be significant barrier to commercialization of new
The limited
a
[
3]
processes. Therefore, replacement of precious metals with
more earth-abundant metals would be quite advantageous.
Recently, non-precious metal catalysts confined in a
nitrogen-containing carbon matrix, which were prepared by
pyrolysis or a ball milling method, exhibited decent activity in
[4]
[5]
electrochemical reactions
and organic synthesis.
For
example, the efficient activation of dioxygen has been reported
with Fe-containing, nitrogen-doped carbon (Fe-N-C) in the
2
electrochemical O reduction reaction (ORR), with a comparable
[6]
activity to the well-known Pt ORR catalysts. Alcohol oxidation
reactions can also be catalyzed by the Fe-based catalysts, such
[
7]
[8]
2 3
as Fe-containing polyoxometalates, nano-Fe O particles and
Figure 1. Aberration-corrected STEM images of a) fresh and b) used Fe-N-C;
c) fresh and d) used Cu-N-C. Used catalysts were recovered after 8 h of
benzyl alcohol oxidation reaction, washed and dried.
[*]
Prof. R. J. Davis
Department of Chemical Engineering, University of Virginia,
02 Engineers’ Way, Charlottesville, VA 22904, (USA)
1
E-mail: rjd4f@virginia.edu
3 3
An Fe-N-C catalyst synthesized by pyrolysis of Fe(NO )
J. Xie, K. Yin
and nicarbazin (details provided in the supplementary
information) was investigated in the aqueous-phase aerobic
alcohol oxidation reaction. Although the catalyst has been
Department of Chemical Engineering, University of Virginia,
Charlottesville, VA 22904, (USA)
Dr. A. Serov, Dr. K. Artyushkova, Dr. H. N. Pham, Prof. P.
Atanassov, Prof. A. K. Datye
Department of Chemical and Biological Engineering and Center for
Micro-engineered Materials, University of New Mexico,
Albuquerque, NM 87131, (USA)
3
leached with acid to remove Fe or Fe C nanoparticles, some
nanoparticles (5 – 30 nm) were still observed (Figure S1a),
which has also been observed by others using similar synthesis
methods and shown to be covered by a graphitic carbon
[
5e,11]
shell.
Extensive prior characterization of our Fe-N-C
Dr. X. Sang, Dr. R. R. Unocic
Center for Nanophase Materials Sciences, Oak Ridge National
Laboratory, Oak Ridge, TN 37831, (USA)
catalyst by X-ray photoelectron spectroscopy (XPS), Mössbauer
spectroscopy and in-situ X-ray absorption spectroscopy
indicates that ~90% of the iron is atomically-dispersed as
Supporting information for this article is given via a link at the end of
the document.
x
nitrogen-coordinated Fe (Fe-N ) species and are proposed to be
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ChemSusChem
10.1002/cssc.201601364
COMMUNICATION
[
12]
the ORR active sites.
The predominant existence of
amount of Fe-N-C. The low observed catalytic activity of N-C,
compared with Fe-N-C, is likely related to the nitrogen sites on
the carbon, which have been reported to participate in the partial
atomically-dispersed Fe in the sample used here was confirmed
by aberration-corrected scanning transmission electron
microscopy (AC-STEM) (Figure 1a). The weight loading of Fe
was determined to be 1.2 wt% from XPS (Table S1) and 1.5
wt% from inductively coupled plasma atomic emission
spectroscopy (ICP-AES) (Table S2), respectively. A similar
metal loading from XPS (surface-sensitive) and ICP-AES (bulk)
is consistent with the atomically-dispersed iron species
composing a large fraction of the total iron on the catalyst.
[13]
reduction of O
carbon matrix is much larger than that of Fe (n
Fe-N-C is about 500% more active than N-C, we propose that
the Fe-N sites are the primary active sites for benzyl alcohol
oxidation.
The reaction orders with respect to O
were evaluated over the range of 0.3 – 1 MPa O
.1 M benzyl alcohol. As illustrated in Figures S2a,b and
summarized in Table 2, the reaction orders were close to zero,
indicating the saturated adsorption of O and benzyl alcohol. To
further explore the reaction mechanism, the kinetic isotope effect
utilizing deuterated alcohol (C CD OH) was evaluated. As
2
.
Considering the loading of nitrogen in the
[
12]
N
:nFe ~ 21 ) and
x
2
and benzyl alcohol
and 0.025 –
2
0
Table 1. Rates of benzyl alcohol oxidation over fresh, used and regenerated
[
a]
M-N-C catalysts
2
Rate
TOF
[
b]
Entry
Catalyst
Treatment
-
8
-1
-1
-3 -1 [c]
(
10 mol s
g
cat
)
(10 s )
6
H
5
2
summarized in Table 2, a significant kinetic isotope effect of 4.8
was observed, indicating β-H elimination is a kinetically-relevant
step during benzyl alcohol oxidation over Fe-N-C. For
comparison, the KIE was measured to be 1.8 over commercial
carbon-supported Pt catalyst (Pt/C), which is a well-studied
1
2
3
4
5
Cr-N-C
Fe-N-C
Co-N-C
Ni-N-C
Cu-N-C
Fresh
Fresh
Fresh
Fresh
Fresh
84
6.5
0.78
15
17
180
64
3.1
34
[
14]
material for alcohol oxidation. Moreover, the influence of tert-
204
butanol and 1,4-benzoquinone, known scavengers for hydroxyl
6
7
8
9
Cr-N-C
Fe-N-C
Co-N-C
Ni-N-C
Cu-N-C
Used
Used
Used
Used
Used
46
11
21
7.3
21
3.6
0.52
1.7
[15]
and superoxide radicals,
on the rate of benzyl alcohol
oxidation was examined over Fe-N-C and Pt/C. As revealed in
Table S4, the introduction of the radical scavengers did not
substantially change the rate of alcohol oxidation over either Fe-
N-C or Pt/C. These results suggest that hydroxyl and superoxide
radicals are not involved in the benzyl alcohol oxidation over Fe-
N-C.
0.36
3.5
10
11
12
13
14
15
Cr-N-C
Fe-N-C
Co-N-C
Ni-N-C
Cu-N-C
Regenerated
Regenerated
Regenerated
Regenerated
Regenerated
67
19
5.2
0.90
11
Table 2. Kinetic isotope effect and orders of reaction for benzyl alcohol
133
14
oxidation
0.70
5.0
[b]
TOF
D
TOF
H
n
dioxygen
[
c]
Catalyst
nalcohol
31
-3 -1 [a]
(
10 s )
/TOF
D
0.3 – 1 MPa
1 – 2 MPa
Fe-N-C
Cu-N-C
0.16
16
4.9
2.2
0
0
0
0
0
[
0
a] Reaction conditions: 353 K, 10 mL 0.05 M benzyl alcohol aqueous solution,
.0400 g Fe-N-C or 0.0130 g M-N-C (M = Cr, Co, Ni, Cu), 1 MPa O . Reaction
2
0.7
profiles are shown in Figure S2. [b] The used catalysts were recovered after 8
h of benzyl alcohol oxidation reaction, washed and dried; The regenerated
catalysts were recovered after 8 h of oxidation reaction, washed, dried and
treated in dihydrogen flow at 573 K for 3 h. [c] The turnover frequency (TOF)
-
1
-1
[a] The turnover frequency (TOF) [mol alcohol converted (mol metal) s ] was
derived from the initial rate calculated from conversion after 30 min of reaction,
which was below 10% in all cases. Reaction conditions: 353 K, 10 mL 0.05 M
-
1
-1
[mol alcohol converted (mol metal) s ] was derived from the initial rate
deuterated benzyl alcohol (C
.0130 g Cu-N-C, 1 MPa O
b: Reaction conditions: 353 K, 10 mL 0.05 M benzyl alcohol aqueous solution,
.0400 g Fe-N-C or 0.0130 g Cu-N-C, 0.3 – 2 MPa O . The dependence of
TOF on O pressure was shown in Figure S3.
c: Reaction conditions: 353 K, 10 mL benzyl alcohol aqueous solution (0.025 –
.1 M), 0.0400 g Fe-N-C or 0.0130 g Cu-N-C, 1 MPa O
6 5 2
H CD OH) aqueous solution, 0.0400 g Fe-N-C or
calculated from conversion after 30 min of reaction, which was below 10% in
all cases (Figure S2).
0
2
.
0
2
The rate of benzyl alcohol oxidation over Fe-N-C under
2
2
mild conditions (353 K, 1 MPa O , aqueous solution) was
0
2
.
-7
-1
-1
measured to be 1.7×10 mol s
gcat (Table 1, Entry 2), which is
-1
equivalent to a turnover frequency (TOF) of 0.00078 s based
on total Fe atoms. As control experiments, the conversion of
benzyl alcohol was evaluated under identical conditions in the
presence of Norit activated carbon and activated-carbon-
supported Fe (Fe/C) with similar Fe loading and nanoparticle
size compared to Fe-N-C (Figures S1). In addition, metal-free
nitrogen-containing carbon (N-C) was evaluated for benzyl
Slight deactivation was observed after 8 h of reaction. As
shown in Table 1, Entries 2 and 7, ~35% of the initial activity of
Fe-N-C was lost after recovery from the reactor compared to the
fresh catalyst. To investigate the cause of deactivation, the used
catalyst was characterized by AC-STEM and ICP-AES. High-
resolution electron microscopy (Figure 1b) revealed atomically-
x
dispersed Fe-N sites remained on the used catalyst and
3
+
alcohol oxidation in the absence and presence of soluble Fe
Fe(NO ) (Table S3). The conversion of benzyl alcohol over
elemental analysis of the fresh and recovered catalysts
confirmed that the Fe loading was unaffected by reaction (Table
S2). Moreover, the concentration of Fe in the reaction medium
after 8 h was less than 0.03 mM, consistent with less than 2% of
available iron being leached into the solution. Indeed, the
(
3 3
)
activated carbon and supported Fe nanoparticles was negligible
whereas the reaction rate over N-C (with or without the presence
3
+
of Fe ion) is ~20 % of that observed with the equivalent
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ChemSusChem
10.1002/cssc.201601364
COMMUNICATION
catalytic activity can be almost fully regenerated by a reductive
A related study on the oxidative nitrification of alcohols by
treatment in H
that the Fe-N
the deactivation is likely the result of strongly adsorbed species
on active sites, which were removed during the H treatment.
This was also supported by an extra peak at around 573 K
observed during H -temperature-programmed reduction of a
used Fe-N-C catalyst (Figure S4). similar deactivation
behavior was also observed during alcohol oxidation over a Pt
2
(Table 1, Entries 2, 7, 12). These results suggest
sites are stable under the reaction conditions and
Jagadeesh et al. revealed Fe and Co catalysts exhibited the
[18]
x
best activity and selectivity. As shown in Table 1, Entries 1-5,
benzyl alcohol was also efficiently converted over all of the M-N-
C catalysts in this work. The activity of these M-N-C (M = Cr, Co,
Ni, Cu) catalysts was much greater than that of Fe-N-C, among
which Cu-N-C was the most active catalyst with a TOF of 0.034
2
2
-1
A
s (~50 times greater than that of Fe-N-C and only about one
order of magnitude lower than Pt). As shown in Figure 1c, the
high-resolution STEM image confirmed the atomic dispersion of
Cu, which likely resides in nitrogen-coordinated sites. Similar to
[16]
catalyst.
The oxidation of other alcohols, including 5-
hydroxymethylfurfural (HMF), ethanol, 1,6-hexanediol and
glycerol, was also investigated over the Fe-N-C catalyst. As
shown in Figure 2, benzyl alcohol and HMF were efficiently and
selectively converted to benzyl aldehyde and 2,5-diformylfuran
Fe-N-C, the reaction order with respect of O
was close to 0 in the range of 1 – 2 MPa O
2
and benzyl alcohol
and 0.025 – 0.1 M
2
benzyl alcohol over Cu-N-C (Figures S2c and S2d). However, at
lower O pressure (0.3 – 1 MPa), the O reaction order was ~0.7.
The higher O reaction order over Cu-N-C versus Fe-N-C is
possibly correlated to the observed lower activity of Cu-N-C in
(
DFF), respectively. The selectivity to benzyl aldehyde and DFF
2
2
was 92% and 82% at the conversion of 79% and 49%,
respectively. Less than 3% conversion of ethanol, 1,6-
hexanediol and glycerol was observed under the same
conditions, which is likely the result of either more difficult
activation of β-H in the aliphatic alcohols or severe catalyst
deactivation.
2
[
18]
ORR as reported by Serov et al. Interestingly, a much weaker
kinetic isotope effect was observed during oxidation of
deuterated benzyl alcohol over Cu-N-C compared to Fe-N-C
(2.2 versus 4.9) (Table 2), which might be related to a more
facile β-H elimination on the Cu catalyst.
The stability of M-N-C catalysts was also investigated.
Similar to the behavior of Fe-N-C, loss of activity was observed
over M-N-C (M = Cr, Co, Ni, Cu) after 8 h of benzyl alcohol
oxidation (Table 1, Entries 1-10). More specifically, only ~10% of
the initial activity was observed with recycled Co-N-C, Ni-N-C
and Cu-N-C catalysts. Microscopy revealed that Cu remained
atomically dispersed throughout the reaction (Figure 1d) and
negligible Cu leaching was observed by ICP-AES (Table S2). In
Selectivityaldehyde /%
Conversion /%
Selectivityacid /%
1
00
7
5
2
5
0
5
0
an attempt to regenerate the activity of used M-N-C, H
2
treatment at 573 K was performed on the recovered catalysts.
Whereas the majority of catalytic activity was recovered from Cr-
N-C, Fe-N-C and Co-N-C, the Ni-N-C and Cu-N-C samples were
not efficiently regenerated (Table 1).
Benzyl
alcohol
HMF
Glycerol
Ethanol
HDO
This work provides
a systematic evaluation of the
aqueous-phase aerobic alcohol oxidation at mild temperature
over a series of non-precious-metal M-N-C catalysts. Benzyl
alcohol and HMF were efficiently and selectively converted to
the aldehyde products over the earth-abundant Fe-N-C catalyst
with a slight loss of activity that could be fully regenerated by
Figure 2. Conversion and product distribution from oxidation of benzyl alcohol,
-hydroxymethylfurfural (HMF), glycerol, ethanol and 1,6-hexanediol (HDO)
over Fe-N-C. Reaction conditions: 353 K, 10 mL 0.05 M benzyl alcohol
aqueous solution, 0.167 g Fe-N-C, 1 MPa O , 8 h reaction time.
5
2
2
simple H treatment. The rate of aliphatic alcohol oxidation was
In an attempt to improve the rate of alcohol oxidation over
our heterogeneous catalytic system, 2,2,6,6-tetramethyl-1-
piperidinyloxy (TEMPO) was added to the reaction medium,
which has been reported as a co-catalyst when combined with
first-row transition metal complexes for homogeneous or
quite slow over Fe-N-C but can be significantly promoted by
adding a catalytic amount of TEMPO. The highest activity for
benzyl alcohol oxidation was obtained over Cu-N-C, which is
tentatively attributed to a faster β-H elimination step. Mechanistic
studies of these systems are currently underway.
[
17]
electrochemical oxidation of alcohols. As shown in Table S5,
the catalytic amount of additive TEMPO (1 mM) significantly
increased the rate of benzyl alcohol oxidation. The conversion of
benzyl alcohol after 30 min increased from 2.4 % to 12.2% with
the addition of TEMPO. More importantly, the oxidation of 1,6-
hexanediol, an aliphatic diol, was significantly promoted by
TEMPO, with 6.3% conversion after 30 min, compared to 0.5%
conversion without the addition of TEMPO.
Experimental Section
See the Supporting Information for Experimental Details, which include
Materials and Methods; Element loadings from XPS and ICP-AES;
Reaction rates over different materials; Influence of radical trap and
TEMPO addition on reaction rate; STEM images of Fe-N-C and
supported Fe catalysts; Influence of dioxygen pressure on TOF; reaction
A series of M-N-C catalysts containing other metals (M =
Cr, Co, Ni, Cu) was also prepared by the same method used to
synthesize Fe-N-C and evaluated in the benzyl alcohol oxidation.
profiles of benzyl alcohol oxidation over M-N-C; and H
fresh and used Fe-N-C.
2
TPR results from
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COMMUNICATION
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Acknowledgements
This work is supported by the US NSF under grant numbers
EEC-0813570 (Center for Biorenewable Chemicals,CBiRC) and
CBET-1157829, and in part by the US DOE-EERE Fuel Cell
Technology Program (subcontract to Northeastern University,
with PI Sanjeev Mukerjee). A portion of the microscopy research
was conducted at the Center for Nanophase Materials Sciences
in Oak Ridge National Lab, which is a DOE Office of Science
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ChemSusChem
10.1002/cssc.201601364
COMMUNICATION
COMMUNICATION
Iron atoms dispersed throughout a
nitrogen-containing carbon matrix
Jiahan Xie, Kehua Yin, Alexey Serov,
Kateryna Artyushkova, Hien N. Pham,
Xiahan Sang, Raymond R. Unocic,
Plamen Atanassov, Abhaya K. Datye
and Robert J. Davis*
catalyze alcohol oxidation by O
aqueous phase. The used catalyst
can be regenerated by mild
treatment in H . An observed kinetic
isotope effect indicates β-H
elimination is kinetically-relevant
2
in the
a
2
Page No. XXXX– Page No.XXXX
a
Selective Aerobic Oxidation of
Alcohols over Atomically-dispersed
Non-Precious Metal Catalysts
step in the mechanism, which can be
accelerated by substituting Fe with
Cu.
This article is protected by copyright. All rights reserved.