Research Article

pubs.acs.org/acscatalysis

Metal-Free and Solvent-Free Oxidative Coupling of Amines to Imines

with Mesoporous Carbon from Macrocyclic Compounds
Bo Chen,†,‡ Lianyue Wang,† Wen Dai,† Sensen Shang,†,‡ Ying Lv,† and Shuang Gao*,†
†
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023,
China
‡
University of the Chinese Academy of Sciences, Beijing 100049, China
*
S Supporting Information

ABSTRACT: A new series of carbon-based heterogeneous catalysts aiming at the

oxidative coupling of amines to imines is disclosed here, which are easily synthesized
by pyrolysis of macrocyclic compounds, including phthalocyanine and porphyrin
under different temperatures. Silica colloid or ordered mesoporous silica SBA-15 is
employed as the hard template to fulfill the mesoporous structures. The most active
catalyst fabricated from phthalocyanine and silica colloid shows remarkable catalytic
activity, excellent selectivity, and robust stability toward the imine formation in the
presence of molecular oxygen under neat conditions. Kinetic analysis demonstrates
that the apparent activation for benzylamine oxidation is 47.6 kJ mol−1 and that
cationic species are involved in the reaction. The unprecedented performance of
mesoporous carbon catalysts can be attributed to their high surface area, profitable
pore volume, as well as homogeneous distribution of defect sites.
KEYWORDS: imines, aerobic oxidation, heterogeneous catalysis, metal-free, mesoporous carbon

1. INTRODUCTION that hinder the practical application of these catalysts are

Imines and their derivatives are among the most important and remaining. For example, the graphene oxide presented by
valuable building blocks for a variety of fine chemicals,1 Huang18a suffers from the tedious preparation and high catalyst
pharmaceuticals,2 and molecular motors.3 Among the reported loading (50 wt %). The boron- and nitrogen-codoped hoely
strategies for the imine fabrication,4 the oxidative coupling of graphene reported by Li18d has the drawback of great
amines provides an attractive alternative to the conventional consumption of the volatile precursor. Besides, addition of
synthetic protocols, which often require unstable aldehydes and external hetroatom-containing molecule into the carbon source
acid catalysts.5 Although significant progress has been made for
this coupling reaction during the past decade,6 key challenges is not an effective way to obtain heteroatom doped carbon
still exist, as follows: the intermediates generated from amines catalysts.
may rapidly dehydrogenate into nitriles’ byproducts and result Inspired by the achievements of electro-catalyst derived from
in poor selectivity;5b,7 the involvement of an organic solvent macrocyclic compounds and the advantages of these com-
makes the separation and purification of unstable imines very pounds with a relatively high thermal stability as well as
difficult and also brings environmental issues. Furthermore, the molecular-level containing C and N elements.19 Herein, we
mainly reported catalytic systems were based on metal catalysts, select phthalocyanine or porphyrin as a precursor and silica as a
such as Au,8 Pd,9 Ru,10 V,11 Cu,12 and Fe.13 Undoubtedly, the
hard template to prepare the mesoporous carbon materials
presence of metal incurs cost problems and metal contaminants
in the final products, particularly for the pharmaceutical which, for the first time, exhibit high catalytic activity toward
reagents. Therefore, the development of highly selective and the oxidative coupling of amines. Various amines are smoothly
cost-effective heterogeneous metal-free catalysts for the transformed into the desired imines in high yields (up to 99%)
oxidative coupling of amines under solvent-free conditions is with molecular O 2 as oxidant under neat conditions.
highly desirable. Furthermore, the catalyst is easily recycled and retains excellent
Recently, mesoporous carbon materials have shown great activity in a 100 mmol scale test with 0.47 wt % catalyst loading.
potential as sustainable catalysts for organic synthesis.14 The
Additionally, the relationship between the physicochemical
outstanding catalytic behaviors of these materials are related to
the high surface area and pore volume,15 the facile physical and property and catalytic behavior of the catalysts is discussed.
chemical modification of the surface,16 and the tunable electron
features by doping with other elements (such as B, N, S, P).17 Received: February 5, 2015
Although fewer carbon-based catalysts have been currently Revised: March 19, 2015
developed for the oxidative coupling of amines,18 limitations Published: March 20, 2015

© 2015 American Chemical Society 2788 DOI: 10.1021/acscatal.5b00244

ACS Catal. 2015, 5, 2788−2794
ACS Catalysis Research Article

2. EXPERIMENTAL SECTION 3. RESULTS AND DISCUSSION

2.1. General. All chemicals were purchased from To explore the activity of the prepared mesoporous carbon
commercial sources and used without further purification. catalysts in the oxidative coupling of amines, solvent-free
Products were confirmed by GC-MS (Agilent 7890A GC/5973 oxidation of benzylamine (1a) with O2 balloon, which often
MS, SE-54 capillary column) and GC calculations of yields employed the precious metal catalysts, was chosen as the model
were performed on Agilent 7890A (SE-30 capillary column, reaction. No product was detected in the absence of catalyst at
100 °C (Table 1, entry 1). Interestingly, performing the
FID detector) using N2 as carrier gas.
2.2. Synthesis of Mesoporous Carbon Catalysts.
Table 1. Oxidative Coupling of Benzylamine Promoted by
Briefly, 2.5 g of silica colloid (Ludox HS-40, 40 wt %
Different Catalystsa
suspension in H2O) was dispersed in a mixture of ethanol
and chloroform (v/v = 3:1) under vigorous stirring. Then 1 g of
phthalocyanine was added, and the whole mixture was stirred at
room temperature for 1 h. After evaporation of the solvent at
90 °C, the obtained phthalocyanine/silica colloid was pyrolyzed
at 800 °C (or 600, 700, 900 °C, ramp rate: 5 °C min−1) for 2 h entry catalyst conversion [%]b selectivity [%]b
under flowing nitrogen and then cooled naturally to room 1 - - -
temperature. The obtained powders were treated with 10 wt % 2 Pc 20.6 97.1
3 Pc-Ludox-6 53.6 95.9
hydrofluoric acid for 12 h, and this procedure was repeated
4 Pc-Ludox-7 75.3 99.9
once for removing the silicon template completely. Finally, the
5 Pc-Ludox-8 90.9 99.1
powders were thoroughly washed to neutral with water and
6 Pc-Ludox-9 89.6 98.4
dried in vacuum at 100 °C overnight. The mesoporous carbon 7 Pc-SBA15-8 77.3 96.5
materials were donated as Pc-Ludox-X (Pc was the abbreviation 8 Pc-8 3.5 97.2
of phthalocyanine, Ludox represented the Ludox HS-40 silica 9 TPP-Ludox-8 55.4 99.8
colloid, and X referred to the carbonization temperature). 10 mpg-C3N4 19.5 96.4
2.3. Procedures for the Oxidative Coupling of 11c Pc-Ludox-8 63.8 99.5
Amines. In a typical oxidation, 20 mg of catalyst and 5 12d Pc-Ludox-8 32.3 97.2
mmol of benzylamine were introduced into a 10 mL Schlenk 13e Pc-Ludox-8 4.1 97.5
tube with a magnetic bar. The tube was vacuumed and purged a
Reaction conditions: 1a (5 mmol), catalyst (20 mg), O2 balloon, 5 h,
with oxygen three times before it was finally connected with an 100 °C. bDetermined by GC using diphenyl as the internal standard
oxygen balloon. Subsequently, the tube was stirred at the and confirmed by GC-MS. c80 °C. dAir balloon. eN2 balloon.
desired temperature. After completion of the reaction, the
catalyst was separated by centrifugation. Both 250 mg of reaction with the commercially available phthalocyanine
internal standard (biphenyl) and 12 mL of CH3CN were resulted in 20% conversion with 97% selectivity (Table 1,
added. The crude mixtures’ analyses were performed on GC entry 2). To our delight, the mesoporous carbon catalysts
and confirmed by GC-MS. derived from phthalocyanine showed high activity and excellent
2.4. Large-Scale and Recycling Test. The reaction was selectivity toward the reaction, and Pc-Ludox-8 exhibited the
highest efficiency affording the desired imine in 90% yield
conducted in a 100 mL autoclave equipped with a pressure
(Table 1, entries 3−6). Upon employing SBA15 instead of
control system, and 50 mg of catalyst and 100 mmol of Ludox as the template, the yield was decreased to 75% (Table
benzylamine were added into the autoclave. The autoclave was 1, entry 7). Notably, direct carbonization of phthalocyanine
sealed, purged with O2 to exclude the air three times, charged without any template led to an inactive catalyst (Table 1, entry
the O2 pressure to 0.5 MPa, and kept constant during the 8). Besides, when tetraphenylporphyrin (TPP) was chosen as
reaction. Then, the reaction was stirred at 120 °C for 24 h. The the precursor, the catalyst also showed a moderate activity for
liquid reaction mixtures were analyzed by GC and confirmed by the reaction (Table 1, entry 9). For comparison, mesoporous
GC-MS. The catalyst was filtered and washed thoroughly with graphitic carbon nitride (mpg-C3N4) in our case gave 18% yield
ethanol. Finally, the recovered catalyst was dried under vacuum (Table 1, entry 10). Subsequently, the reaction conditions were
at 100 °C overnight and reused in the subsequent recycling investigated. Whether the reaction was conducted at 80 °C or
reaction. in air balloon, the conversion of 1 was gradually decreased
2.5. Instruments. N2 sorption isotherms were measured at (Table 1, entries 12−13). Once the reaction was performed in
77K using a QuadraSorb SI4 Station, and the samples were nitrogen atmosphere, only 4% yield of the desired product was
degassed at 300 °C for 6 h before the measurements. Scanning obtained (Table 1, entry 14), ensuring that O2 as oxidant was
electron microscope (SEM) images were conducted on a JSM- essential for the reaction.
Encouraged by these promising results, we further tested the
7800F microscope operating at an acceleration voltage of 20
effectiveness and stability of the present system. A 100 mmol-
kV. Transmission electron microscope (TEM) images were scale synthesis of N-benzylidene benzylamine (2a) was
acquired with JEM-2100 microscope. Surface compositions performed on Pc-Ludox-8 to investigate its large-scale
were determined by X-ray photoelectron spectroscopy (XPS) production under solventless conditions. As shown in Figure
using Thermo Scientific ESCALAB 250Xi instrument with Al 1, the oxidative coupling reaction proceeded smoothly, and the
Kα radiation anode (hv =1486.6 eV), and the C 1s line (284.6 corresponding 2a was obtained in 95% yield. Besides, the
eV) was used as the reference to correct the binding energies catalyst can be easily recovered by filtration and reused at least
(BE). five times without any obvious loss of activity on this 100 mmol
2789 DOI: 10.1021/acscatal.5b00244
ACS Catal. 2015, 5, 2788−2794
ACS Catalysis Research Article

Figure 2b, the interconnected vesicle-like frameworks of the

catalyst were obvious, and the pore sizes had a range from
several to dozens of nanometers. The selected-area electron
diffraction (SAED) image revealed the multicrystalline
structure of the sample (Figure 2c). Large-scale elementals
mapping analysis demonstrated the uniform distribution of C,
N, O and excluded the possible presence of other elements
(Figure 2d). Well-defined linear array of mesoporous structure
was observed for Pc-SBA15−8 (Figure 2e), reflecting that the
structure of SBA-15 was successfully transferred into the
catalyst. For comparison, bulk aggregations were presented in
Pc-8 prepared without using any template, and the smooth
surface implied their poor porosity (Figure 2f). Therefore, the
catalysts with discrepant morphologies were prepared via
different templates under the same pyrolysis temperature and
Figure 1. Pc-Ludox-8-catalyzed 100 mmol scale of the oxidative presented significantly different activities toward the oxidative
coupling of benzylamine. Reaction conditions: 1a (100 mmol), catalyst coupling of amines. Thus, it was deduced that the micro-
(50 mg), 0.5 MPa O2, 24 h, 120 °C. Yields were determined by GC. structure of the catalysts played important roles in the reaction.
To unveil the underlying factors affecting the catalytic
scale experiment. Note that the catalyst loading here was only activity, the microstructure of the catalysts were analyzed by N2
about 0.47 wt % and was one magnitude lower than that of sorption (Figure 3). The isotherms of Pc-Ludox-8 displayed an
reported carbocatalysts.18 IUPAC type-IV curve and H4-type hysteresis loop, suggesting
Representative scanning electron microscopy (SEM) micro- the mesoporous nature of the catalyst. The Brunauer−
graph for Pc-Ludox-8 was displayed in Figure 2a, clearly Emmett−Teller (BET) surface area and pore volume were
indicating the introduction of pore structures into the resulting 751 m2/g and 2.2 m2/g, respectively. A broad pore size
carbons. Further detailed structural information was obtained distribution of Pc-Ludox-8 was presented in the entire testing
by transmission electron microscopy (TEM). As shown in range (3−60 nm), and the major pore size was centered at 17

Figure 2. (a) SEM image, (b) TEM image, (c) selected area electron diffraction (SAED) pattern of the edge area, and (d) large-area SEM image
along with the corresponding C-Ka, N-Ka, and O-Ka elemental maps of Pc-Ludox-8; (e) TEM image of Pc-SBA15−8; (f) SEM image of Pc-8.

2790 DOI: 10.1021/acscatal.5b00244

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molecules and substrates in oxidation reactions.18d,e,21 Here,

we might attribute the benefits to the increase of graphitic N
species, which promoted the oxidative coupling of amines with
molecular oxygen. In addition, a certain amount of oxygen
implanted by the inorganic template was present in these
catalysts,22 which were divided into three peaks centered at
530.6, 532.2, and 533.8 eV (Figure 4b). According to the
literature,23 the peaks at 530.6 and 532.2 eV were assigned to
the absorbed oxygen-containing components and CO
groups, respectively, whereas the peak at 533.8 eV belonged
to the C−OH and/or C−O−O-H groups. It was noteworthy
that the carboxylic acid groups with large π-conjugation system
Figure 3. (a) N2 sorption isotherms and (b) the corresponding BJH in graphene oxide played an important role in activation of the
pore size distribution plots of Pc-Ludox-8, Pc-SBA15-8, and Pc-8. substrates.18c In order to evaluate the possible effects of these
carboxylic acid groups, the Pc-Ludox-8 was treated with NaOH
nm according to the Barrett−Joyner−Halenda (BJH) model. or NaBH4, respectively. However, we did not observe any
Similarly, Pc-SBA15-8 also exhibited a type-IV sorption appreciable change in both activity and selectivity compared
isotherm with a weak type H4 hysteresis loop. The BET with the fresh Pc-Ludox-8 (Table S1). Therefore, the
surface area was up to 789 m2/g, whereas the corresponding contribution of carboxylic acid groups to the reaction can be
pore volume and the major pore size were 1.0 m2/g and 2.7 excluded. The C 1s spectrum of Pc-Ludox-8 were deconvoluted
nm, respectively, much smaller than that of Pc-Ludox-8. In into four peaks centered at 284.6, 285.7, 286.5, and 288.0 eV
contrast, no evident mesopore was detected for Pc-8. This (Figure 4c), corresponding to the CC, C−N, C−O, and O−
structural information was consistent with the SEM and TEM CO groups, respectively.23b Furthermore, as the pyrolysis
observations (Figure 2 and Figure S4). It was widely accepted temperature raised from 600 to 900 °C, the contents of carbon
that the catalyst with a high surface area and pore volume was increased from 87.4 to 89.7 atom % along with the reduction of
beneficial for mass transfer and exposure of more catalytic N or O atoms linked directly to the C atoms (Table 2). As a
active sites, which played important roles in promoting the result, more defect sites derived from the restacking of C atoms
reaction activity.20 Although the surface area of Pc-Ludox-8 was were originated, which can remarkably enhance the reaction
slightly lower than Pc-SBA15-8, the advantages of pore volume activity. Previous works also proposed the mesoporous carbon
and pore size might assist it to gain a better performance. From catalysts owned more active sites for oxygen adsorption and
this perspective, the Pc-8 showed low activity toward the activation than that of oxygen-inert mpg-C3N4,24 which might
reaction was reasonable. explain why mpg-C3N4 showed low activity for the coupling of
In spite of similar pore structures and surface areas (Table 2), amines.
the Pc-Ludox-X (X = 6, 7, 8, 9) presented different reaction With the optimized conditions (Table 1, entry 5), the yield
activities toward the amine oxidation. Thus, it was necessary to of 2a can be further increased to 94% without loss of the
discuss the relationship between their components and the selectivity by simply prolonging the reaction time to 5.5 h
activities. The element components of the samples were (Table 3, entry 1). Then, a series of amines with different
determined by X-ray photoemission spectroscopy (XPS) substituted groups was tested, and the results are listed in Table
analysis. The contents of nitrogen were reduced from 8.5 to 3. In general, benzylamines substituted with electron-donating
5.1 atom % as the pyrolysis temperature increased from 600 to groups (Me, OMe) or electron-withdrawing groups (F, Cl, Br,
900 °C, indicating a high degree of agglomeration was obtained CF3) were suitable substrates for the reaction, affording the
and more nitrogen atoms were incorporated into the carbon corresponding imines in excellent yields. However, the
matrix. The high-resolution N 1s spectra of Pc-Ludox-8 and electronic properties of the substituents on the phenyl ring
other samples can be fitted with four peaks, including pyridinic have some effects on the efficiency of the reaction, the former
N (398.1 eV), pyrrolic N (399.6 eV), graphitic N (400.7 eV), (Table 3, entries 2−3) was more favored to be oxidized than
and pyridine N oxide (403.2 eV) (Figure 4a). As the pyrolysis the latter (Table 3, entries 6−9). Moreover, it was found that
temperature increased to 900 °C, the contents of graphitic N the reaction was sensitive to the steric hindrance of the
increased while the contents of the pyridinic N decreased, substituents on the phenyl ring, and para-substituted amine
suggesting graphitic N was more stable than pyridinic N, and exhibited a higher activity than meta- and ortho-substituted
the latter may be transformed into the former under higher isomers (Table 3, entries 3−5). Note that heterocyclic amines,
temperature (Figure S7). Previous studies have shown that the including 2-furfurylamine and 3-picolylamine, which might
introduction of nitrogen into the carbon-based catalyst can poison the metal catalyst due to the coordination with the
induce the electron relocalization to activate the oxygen metal active sites, could also be transformed into the

Table 2. Results of N2 Sorption and Chemical Compositions of the Mesoporous Carbon Catalysts
sample SBET (m2 g−1) VTotal (cm3 g−1)a DPore (nm)b C content (atom %)c N content (atom %)c O content (atom %)c
Pc-Ludox-6 726 1.7 12.4 87.4 8.5 4.0
Pc-Ludox-7 745 1.8 17.9 87.6 8.5 3.9
Pc-Ludox-8 751 2.2 17.1 88.1 6.9 4.9
Pc-Ludox-9 754 2.0 17.4 89.7 5.1 5.2

a
Determined from the adsorption volume at p/p0 = 0.98. bCalculated using the BJH method. cMeasured by X-ray photoelectron spectroscopy.

2791 DOI: 10.1021/acscatal.5b00244

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ACS Catalysis Research Article

Figure 4. High-resolution XPS spectrum of Pc-Ludox-8 with the N 1s (a), O 1s (b), and C 1s (c).

Table 3. Oxidative Coupling of Various Amines to Imines over Pc-Ludox-8a

a
Reaction conditions: amines (5 mmol), catalyst (20 mg), O2 balloon, 100 °C. bDetermined by GC and confirmed by GC-MS.

corresponding imines in good yields (Table 3, entries 10−11). supervised via continuous sampling by GC. As displayed in
Attempts were made to oxidize the challenging aliphatic Figure 5a, the desired imine was the sole product during the
amines. Due to the inactive a-hydrogen of amine, a lower yield whole of the reaction, and excellent selectivity was preserved
of the product was observed (Table 3, entry 12). Furthermore, even in the above 100 mmol scale experiment. The plot for the
the catalyst was also capable of selectively oxidizing 1,2,3,4- product can be well fitted with pseudo fist-order reaction
tetrahydroiso quinoline to give the corresponding imine in 73% kinetics in the range of 0 to 1 h, and the rate constant k was 0.3
yield (Table 3, entry 13). h−1. In addition, we did not observe an induction period at the
To investigate the reaction performance with Pc-Ludox-8 in start of the reaction, which was obvious in MOF-253 catalytic
detail, the product evolution of the oxidative coupling of 1a was system.25 The presentation of free-radical scavenger (BHT)
2792 DOI: 10.1021/acscatal.5b00244
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Figure 5. (a) Reaction profiles for the oxidative coupling of benzylamine over Pc-Ludox-8. (b) Arrhenius plot for the oxidation of benzylamine. (c)
Hammet plot for the oxidative coupling of the para-substituted benzylamines, the lg(kX/kH) was obtained from the ratio of conversion with reaction
time of 40 min.

was also failed to disturb the oxidation of 1a (Table S1). Thus, 61% of N-benzylidene methylamine was transformed into 2a,
we can exclude the possibility of a radical chain pathway for the and the residual substrate can be recovered from the reaction
reaction. The apparent activation for benzylamine oxidation Ea mixtures. This observation strongly supported benzylimine was
was calculated from the Arrhenius plot, and the value was 47.6 the intermediate, and the hydrolytic process to generate the
kJ mol−1 (Figure 5b), much smaller than the reported value of aldehyde was unfavorable for the reaction. Based on the results
62.8 kJ mol−1.26 Finally, the relative rates for the oxidative vide supra, the oxidative coupling of amines in the present study
coupling of para-substituted benzylamines (CF3, Br, H, Me, proceeded via the path B.
OMe) were investigated (Figure 5c). A reasonable linear
relationship between log(kX/kH) and Brown−Okamoto con- 4. CONCLUSION
stant σ+ was established,27 and the resulting reaction constant ρ
was −0.3, indicating the intermediary of cationic species were In summary, we have developed a novel and metal-free carbon-
involved in the reaction. The results in Table 3 were also based catalyst for the imine formation under solvent-free
proved that the reaction was substituent-sensitive, and the conditions. The mesoporous carbon materials are prepared by
electron-donating substituents were more likely to be oxidized. simple thermolysis of macrocyclic compounds such as
We further proposed the general reaction pathway for the phthalocyanine or porphyrin with silica templates. Applying
synthesis of imines catalyzed by these mesoporous carbon these catalysts in the oxidative coupling of amines, it affords the
catalysts (Scheme 1). In the initial phase of the reaction, both corresponding imines in good to excellent yields with molecular
O2 as oxidant. Besides, the catalysts show potential perform-
Scheme 1. Proposed Reaction Pathways for Pc-Ludox-8- ance in large-scale production and can be recycled several times
Catalyzed Oxidative Coupling of Primary Amines to Imines without loss of the catalytic efficiency. It is revealed that the
template and pyrolysis temperature influence the micro-
structure and surface compositions of the materials, respec-
tively, and further affect the behaviors of the catalysts. More
detailed studies are currently in progress in order to clarify
other factors that determine the catalytic reactivity as well as
the extensions of these catalysts to other oxidation reactions.

■
*
ASSOCIATED CONTENT
S Supporting Information

The following file is available free of charge on the ACS

Publications website at DOI: 10.1021/acscatal.5b00244.
benzylamine and molecular oxygen were activated on the defect Additional preparation of materials, characterizations for
sites of catalysts and subsequently transformed into benzyli-
mesoporous carbon materials, and controlled experi-
mine and H2O2 intermediates, respectively. As the formation of
H2O2 was not observed, we believed it reacted immediately ments (PDF)

■
with another molecular 1a to obtain benzylimine.18b,25 Given
the unstable and easily decomposed properties, the generated AUTHOR INFORMATION
benzylimine may readily transform as the following two
pathway: (a) hydrolyzed to give the aldehyde, subsequently Corresponding Author
condensing with a second molecule of 1a to produce the *E-mail: sgao@dicp.ac.cn.
desired 2a; (b) added with another molecule of 1a, successively Notes
releasing NH3 to give 2a. In the Pc-Ludox-8-catalyzed The authors declare no competing financial interest.

■
solventless reaction described here, no signal of aldehyde was
detected by GC-MS, and thus, we believed path A was
unfavorable for the reaction. To test this hypothesis, N- ACKNOWLEDGMENTS
benzylidenemethyl amine as the analogy of benzylimine was We gratefully acknowledge financial support from the National
added to 1 equiv of 1a with 20 mg of Pc-Ludox-8 (Scheme S1). Natural Science Foundation of China (21403219).
2793 DOI: 10.1021/acscatal.5b00244
ACS Catal. 2015, 5, 2788−2794
ACS Catalysis Research Article

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2794 DOI: 10.1021/acscatal.5b00244

ACS Catal. 2015, 5, 2788−2794