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Chemical Engineering Journal 240 (2014) 434442

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Chemical Engineering Journal


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Aerobic oxidation of benzyl alcohol to benzaldehyde catalyzed by carbon


nanotubes without any promoter
Jin Luo a,b, Hao Yu a, Hongjuan Wang a, Haihui Wang a, Feng Peng a,
a
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China
b
College of Chemistry Science and Technology, Zhanjiang Normal University, Zhanjiang 524048, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Carbon nanotubes (CNTs) can Carbon nanotubes (CNTs) as a metal-free catalyst exhibited high activity and excellent stability for the
catalyzes benzyl alcohol (BzOH) to selective oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) in solution phase with molecule
benzaldehyde (BzH). oxygen as the terminal oxidant in the absence of any promoter.
 A reasonable mechanism for the
liquid-phase oxidation of BzOH on
CNTs is proposed.
 Electron transfer in graphene
skeletons plays an important role.
 Nitrogen doping efciently enhances
the catalytic activity of CNTs for BzOH
to BzH.
 Carbon catalyst displays outstanding
recyclability.

a r t i c l e i n f o a b s t r a c t

Article history: Carbon nanotubes (CNTs) were used as metal-free catalysts for selective oxidation of benzyl alcohol
Received 9 October 2013 (BzOH) to benzaldehyde (BzH) with molecular oxygen as the terminal oxidant in the absence of any pro-
Received in revised form 27 November 2013 moter. The effects of reaction conditions, solvent and surface chemistry of CNTs on the catalytic perfor-
Accepted 30 November 2013
mances have been investigated. The results showed that the solvent has a remarkable effect on oxidation
Available online 10 December 2013
of BzOH. The effect of the CNTs surface chemistry on the catalytic activity was revealed, and the surface
carboxylic groups were particularly detrimental for the catalytic activity. A reasonable mechanism
Keywords:
responsible for the liquid-phase oxidation of BzOH on CNTs was proposed, and electron transfer in graph-
Heterogeneous catalysis
Carbon nanotubes
ene skeletons played an important role. Nitrogen doping efciently enhanced the catalytic activity of
Benzyl alcohol CNTs for aerobic oxidation of BzOH, arising from improving electron transfer. In addition, the NCNTs
Aerobic oxidation revealed outstanding recyclability and exhibited excellent potential for industrial application of the BzOH
oxidation to BzH.
2013 Elsevier B.V. All rights reserved.

1. Introduction research and industrial manufacturing [14]. Especially, the selec-


tive oxidation of benzyl alcohol (BzOH) to higher-value added prod-
Selective oxidation of alcohols to their corresponding aldehydes uct benzaldehyde (BzH) has received increasing attention, because
or ketones is one of the most important and challenging functional the BzH has tremendous application in perfumery, pharmaceutical,
group transformations in organic synthesis, both for fundamental dyestuff and agrochemical industries [57]. Commercially, the BzH
is synthesized by the hydrolysis of the benzal chloride and the va-
por/liquid-phase oxidation of toluene [3,810]. However, in the for-
Corresponding author. mer process, traces of chlorine inevitably exist in the product BzH,
E-mail address: cefpeng@scut.edu.cn (F. Peng).

1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.11.093
J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442 435

and in the latter, the selectivity to BzH is very poor. Alternatively, treatment in a horizontal tubular quartz furnace with 4 cm inner
direct oxidation of BzOH in liquid phase is a promising route for diameter under owing argon at 600 C or 900 C for 2 h, and then
the manufacture of BzH, because it completely overcomes the samples were cooled under argon to room temperature prior to
major drawbacks of as above mentioned. Recently, such transfor- exposure to air, denoted as CNTs-4 or CNTs-5, respectively [37].
mation with molecular oxygen as the terminal oxidant and water Nitrogen-doped carbon nanotubes (NCNTs) were produced by
as the sole by-product has received enormous attention [11]. chemical vapour deposition (CVD) using FeMo/Al2O3 as catalyst
Consequently, a remarkable number of metal-catalyzed aerobic and a mixture of xylene as carbon source and aniline as nitrogen
processes, especially based on noble metals, such as Ru [12,13], source in a horizontal tubular quartz furnace in 4 cm inner diameter
Pd [14,15], Pt [16,17], Ag [18,19], Au [20,21], have been developed. [35]. Typically, 10 mL mixtures of aniline and xylene, which the con-
However, considering the high cost of the noble metals, it would be centration of aniline in the mixture was 30 v%. When the tempera-
still desirable to develop metal-free catalysts to carry out BzOH oxi- ture of reaction region reached 800 C, the solutions were injected
dation. Comfortingly, carbon nanotubes (CNTs), owing to their un- by a syringe pump at a rate of 2.5 mL h 1 for 4 h, accompanied
ique pp electrostatic interactions, excellent electrical and thermal with 300 sccm Ar. To remove residual FeMo/Al2O3 catalyst, the
conductivity, high specic surface areas, good chemical stability prepared catalysts were stirred in concentrated HCl using magnetic
and recyclability, environmental acceptability, readily surface mod- stirrer for 6 h, diluted in water, ltered, washed with deionized
ication and low cost [2226], have been proved promising as new- water until pH 67 was reached, and dried in air at 110 C overnight,
generation metal-free catalysts for a broad range of important the as-prepared sample was denoted as NCNTs. For comparison, un-
chemical transformations, such as the oxidative dehydrogenation doped carbon nanotubes were also produced using the same proce-
(ODH) of aromatic hydrocarbons [27] and alkanes [28], oxygen dure with xylene as precursor without aniline, denoted as CNTs-6.
reduction reaction [29], oxidation of hydrocarbons [30,31] or phe- Activated carbon (AC) was purchased from Liyang Convoy
nols [32], as well as decomposition of ammonia [33]. It is of partic- Activated Carbon Factory, then the AC was subjected to heat
ular interest to know whether it is possible to oxidize benzyl treatment in a horizontal tubular quartz furnace with 4 cm inner
alcohol (BzOH) to get higher-value added product benzaldehyde diameter under owing argon at 900 C for 2 h, and then samples
(BzH) by using cheap CNTs catalysts. were cooled under argon to room temperature prior to exposure
To this end, in our very recent work [34,35], we have reported to air, denoted as AC-900.
that CNTs as a metal-free catalyst could successfully catalyze the FeOx was loaded on the CNTs-3 in the same way as described in
oxidation of BzOH to BzH using molecular oxygen as the terminal the literature [30,38], and the loading of FeOx was controlled at
oxidant and a small number of nitric acid (HNO3) as the promoter 4.1 wt.% by atomic adsorption spectroscopy.
under atmospheric pressure. Unfortunately, CNTs alone could not
catalyze oxidation of BzOH with molecular oxygen at atmospheric 2.2. Characterization of catalysts
pressure. Moreover, considering the strongly acidic nature and
recycling issues of HNO3, it is impractical for industrial use. In this The BET specic surface areas were measured by N2 adsorption
letter, we have extended our studies on CNTs in the liquid phase at liquid N2 temperature in an ASAP 2010 analyzer. Raman spectra
aerobic oxidation of BzOH in the absence of any additives at a rel- were obtained in a LabRAM Aramaic micro Raman spectrometer
ative low operational pressure (1.5 MPa O2). The main goal of this with an excitation wavelength at 633 nm with 2 lm spot size to
work is to reveal the effect of the CNTs surface chemistry and dop- investigate the carbon nanotubes structure. The Fe content of
ing nitrogen atoms into the carbon lattice on the catalytic activity, puried sample was measured by atomic adsorption spectroscopy
and propose a reasonable mechanism pathway of BzOH oxidation (Shimadazu AAS-6800). The Ni content of puried sample was
over CNTs. In addition, the effects of reaction temperature, O2 pres- measured by electron probe micro-analyzer (EPMA-1600) with
sure, catalyst amount, reaction time and solvent on the catalytic the accelerating voltage of 15 kV and beam current of 10 nA.
performances of CNTs were investigated in detail in the selective X-ray photoelectron spectroscopy (XPS) were performed with a
oxidation of BzOH. These results provide an attractive metal-free Kratos Axis ultra (DLD) spectrometer equipped with an Al Ka
alternative to noble-metal-catalyzed systems for BzOH oxidation, X-ray source, and the binding energies (0.2 eV) were referenced
and push forward the research on carbon catalysis. to the C1s peak at 284.6 eV. SEM images were obtained in a LEO
1530VP scanning electron microscope. TEM and HRTEM images
were obtained in a JEM-2100 microscope operating at 200 kV.
2. Experimental Specimens for TEM and HRTEM were prepared by ultrasonically
suspending the sample in acetone and depositing a drop of the sus-
2.1. Preparation of catalysts pension onto a grid with amorphous carbon lm.

Pristine commerical carbon nanotubes (CNTs-0, dout = 3050 nm, 2.3. Selective oxidation of BzOH
din = 612 nm) was purchased from Shenzhen Nanotech Port Co., Ltd.
(Shenzhen, China). One grams of pristine carbon nanotubes was The oxidation reactions were carried out in a Teon-lined
placed in a 500 mL round bottom ask and 200 mL of concentrated 100 mL stainless steel autoclave equipped with a magnetic stirrer,
HCl was added, then the mixture was stirred using magnetic stirrer at 1100 rpm. 5 mL of BzOH, 30 mL of DMF as solvent were added
for 24 h to remove residual metal impurities, subsequently, diluted into the autoclave, and the air in the reactor was ushed over three
in deionized water, ltered, washed with deionized water until cycles with Argon. Then, the reactor was heated to a stable opera-
pH = 67, and dried in air at 110 C overnight [36], denoted as tional temperature, and subsequently pure O2 was fed into the
CNTs-1. Subsequently, 0.5 g of the CNTs-1 were dispersed in reactor, and the pressure was kept constant by supplying pure O2
100 mL of 9 mol L 1 HNO3 in a 250 ml round bottom ask equipped during the reaction. Oxygenated products were identied by
with a condenser and the dispersion was reuxed under magnetic GCMS and quantitated by GC. GCMS analysis was performed
stirring for 2 or 4 h to introduce oxygen-containing groups into sur- on a SHIMAZDU GCMS-QP2010. GC analysis was performed on
face of CNTs-1, then diluted in deionized water, ltered, washed with an Agilent GC-6820 equipped with a 30 m  0.25 mm  0.25 lm
deionized water until pH 6-7 was reached, and dried in air at 110 C HP-5 capillary column and a ame ionization detector using naph-
overnight, the corresponding materials were denoted as CNTs-2 or thalene as the internal standard [34]. Furthermore, for the test of
CNTs-3, respectively. In addition, CNTs-3 was subjected to heat reusability, the used catalyst was removed from the reaction
436 J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442

mixture by ltration and washed with deionized water, ethanol


(a) BzOH BzA BzH
100
and acetone, and dried in air. 30

Conversion (%)
80

Selectivity (%)
3. Results and discussion 20 60

3.1. Effect of reaction conditions on BzOH oxidation 40


10
20
Fig. 1 shows the effect of the reaction temperature, O2 pressure,
the amount of catalyst, reaction time and solvent on BzOH oxida- 0 0
tion. As shown in Fig. 1a, the effect of the reaction temperature 100 105 110 115 120 125 130 135
o
on the conversion of BzOH is very strong. BzOH conversion and Temperature ( C)
benzoic acid (BzA) selectivity largely increased but BzH selectivity
signicantly decreased with increasing reaction temperature, indi- (b) 30 BzOH BzA BzH
100
cating that the reaction was favored by higher temperature. It is

Conversion (%)
noted that the reaction was hardly carried out to give a BzOH con- 80

Selectivity (%)
version as low as 3.7% when the temperature was 100 C. BzOH 20
60
conversion increased from 14.1% to 25.2% when the temperature
was elevated from 120 to 130 C, but if the temperature increased 40
10
to 135 C, the deeply oxidized byproduct BzA became more signif-
icant. Therefore, 130 C was regarded as the appropriate reaction 20

temperature.
0 0
As shown in Fig. 1b, increasing O2 pressure had a strong inu- 1.0 1.2 1.4 1.6 1.8
ence on the BzOH conversion and also showed a marked effect O2 pressure (MPa)
on the BzH and BzA selectivity. It is noted that the reaction was un-
able to carry out when O2 replaced by N2 and the pressure was kept (c) BzOH BzA BzH
100
1.5 Mpa, indicating that the role of O2 pressure in the BzOH oxida- 30
Conversion (%)
tion is crucial. BzOH conversion rapidly improved from 14.3% to

Selectivity (%)
80
25.2%, while BzH selectivity decreased from 95.4% to 88.4% when
20
the O2 pressure was elevated from 1.0 to 1.5 Mpa. However, further 60

increasing O2 pressure to 1.8 Mpa, BzH selectivity decreased to


40
85.7%. Therefore, 1.5 Mpa was regarded as the appropriate O2 10
pressure. 20
As shown in Fig. 1c, in the blank experiment in the absence of
0 0
CNTs-1, the conversion of BzOH was 7.8% with 85.2% selectivity 0 50 100 150 200
for BzH at 130 C for 10 h. Notably, increasing the amount of CNTs-1 amount (mg)
CNTs-1 to 50 mg rapidly improved BzOH conversion to 19.7% and
BzH selectivity to 90.7%, showing that the catalytic role of CNTs- (d) BzOH BzA BzH
100
1 in the BzOH oxidation is crucial. Further increasing the amount
Conversion (%)

of CNTs-1 to 100 mg increased BzOH conversion to 25.2%.

Selectivity (%)
20 80
However, the excess amount of the CNTs-1 (200 mg) rapidly
caused decrease of selectivity to BzH, which was likely attributed 60

to further oxidation of BzH into BzA. 40


10
As shown in Fig. 1d, the initial conversion of BzOH sharply in-
creased with the reaction processing and reached a plateau, 20
whereas the selectivity for BzH decreased with increasing reaction
0 0
time. No signicant difference in the BzOH conversion was ob- 2 4 6 8 10
served when the reaction time was prolonged over 8 h, but the Reaction time (h)
selectivity for BzH slightly decreased implied that the prolonged
reaction time may also cause further oxidation of BzH into BzA. (e) 50 BzOH BzA BzH
100
These results reveal that an 8 h reaction period is adequate.
As shown in Fig. 1e, the behaviour of BzOH oxidation in various 40
Conversion (%)

80
Selectivity (%)

solvent is conspicuously different. The room temperature dielectric


30
constants for N,N-dimethyl formamide (DMF), acetonitrile (A), tol- 60

uene (T), benzene (B) and n-hexane (H) are 37, 36, 2.4, 2.3 and 1.9, 20 40
respectively, due to the dipole moment of the solvent molecules
[39,40]. BzOH conversion obviously increases with the solvent 10 20
dielectric constant increasing. DMF with the highest dielectric
constant was recognized the best solvent, i.e. 24.1% BzOH conver- 0 0
DMF A T B H
sion with 89.5% BzH selectivity were obtained at 130 C, while Solvent
n-hexane with the lowest dielectric constant was the worst one.
It is noted that, although acetonitrile has the higher dielectric Fig. 1. Effect of the reaction temperature (a), O2 pressure (b), the amount of catalyst
constant, BzOH conversion was much lower than that in DMF, it (c), reaction time (d) and solvent (e) on the conversion and selectivity for the
oxidation of BzOH. Reaction conditions: 5 mL BzOH, 30 mL DMF, 100 mg CNTs-1,
may be caused by its low solubility of O2 and low boiling point 130 C, 1.5 MPa O2, 8 h or 10 h.
(81.1 C). In addition, the observed much lower BzOH conversion
J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442 437

Table 1
Catalytic performance of the different catalysts for BzOH aerobic oxidation.a

Entry Catalyst SBET (m2/g) Raman (ID/IG)b COOHc (%) Xd (%) Selectivitye (%) rwf rsg
BzH BzA
1 CNTs-0 88.7 23.6 89.9 10.1 16.92 0.191
2 CNTs-1 92.6 1.65 2.77 24.1 89.5 10.5 18.24 0.197
3 CNTs-1h 92.6 4.7 98.2 1.8
4 CNTs-1i 92.6 30.3 89.4 10.6 24.12 0.260
5 CNTs-2 106.2 1.78 5.66 10.8 97.9 2.1 5.16 0.049
6 CNTs-3 120.7 1.96 7.95 6.4 98.4 1.6 4.32 0.036
7 CNTs-3 j 7.5 96.6 3.4
8 CNTs-4 127.1 1.81 2.65 17.6 93.9 6.1 16.56 0.130
9 CNTs-5 130.6 1.67 2.28 24.9 90.2 9.8 20.28 0.155
10 AC 1187 15.9 95.7 4.3 9.48 0.008
11 AC-900 1201 22.2 93.6 6.4 12.23 0.010
12 CNTs-6 45.7 1.01 24.2 97.1 2.9 18.12 0.396
13 NCNTs 60.3 1.18 44.7 94.1 5.9 30.24 0.501
a
Reaction condition: 30 mL DMF, 5 mL BzOH, 100 mg catalyst, 1.5 MPa O2, 130 C, 8 h.
b
The excitation wavelength was 633 nm.
c
The atomic content of carboxylic groups on the surface of CNTs from XPS.
d
BzOH conversion at 8 h.
e
Selectivity of major products at 8 h.
f
Initial rate of BzOH consumption per gram of catalyst at 4 h, mmol g 2 h 1.
g
Initial rate of BzOH consumption per m2 of catalyst surface at 4 h, mmol m 2 h 1.
h
Added p-benzoquinone (3 wt% of BzOH).
i
Added TBHP (3 wt% of BzOH).
j
4.1% FeOx was loaded on the CNTs-3 by atomic adsorption spectroscopy.

Fig. 2. Plausible mechanism pathway of BzOH oxidation with O2 over CNTs.

in the presence of toluene or benzene or n-hexane as a solvent is


also probably attributed to its low solubility of O2 and relative
low boiling point.
1000 CNTs-5 (ID/IG=1.67)

500
3.2. Catalytic mechanism discussion
0
To prove the dominant role of radical species in our system, CNTs-4 (ID/IG=1.81)
p-benzoquinone as a typical radical scavenger or tert-butyl 500
hydroperoxide (TBHP) as a typical free-radical initiator was added
0
to the reactor, and the results are summarized in Table 1. The
Intensity (a.u.)

1000
reaction was almost totally suppressed to give a conversion as CNTs-3 (ID/IG=1.96)
low as 4.7% with the addition of p-benzoquinone (Table 1, Entry 500
3). Moreover, BzOH conversion and the initial reaction rates of
0
CNTs-1, normalized by BET surface area, were increased from
1000
24.1% to 30.3% and 0.197 to 0.260 mmol m 2 h 1 with the addition CNTs-2 (ID/IG=1.78)

of TBHP (Table 1, Entries 2 and 4), respectively. The results strongly 500
suggested that the oxidation of BzOH proceeds by a free-radical 0
mechanism in our system, it is obviously different from our
1000 CNTs-1 (ID/IG=1.65)
previous report about the aerobic oxidation of BzOH catalyzed by
CNTs-HNO3 system under atmospheric pressure, which is not a 500

free-radical mechanism [34]. It is probable that aH-atom of BzOH 0


was difcultly activated to produce benzyl alcohol radical under 800 1000 1200 1400 1600 1800 2000
atmospheric pressure and low temperature (90 C), because the Raman shift (cm-1)
aforementioned CNTs-1 was unable to effectively catalyze the
BzOH oxidation under the low O2 pressure and low temperature. Fig. 3. Raman spectra of the catalysts.
438 J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442

Recently, Peng et al. revealed that the nature of the radical car-
(a) C1s
bon catalysis origins from a weak interaction between radicals and 400000

Intensity (a.u.)
graphene skeletons, which connes the radicals around the sur- CNTs-1
CNTs-2
300000
faces of CNTs and thus enhances the electro-transfer catalysis of CNTs-3
CNTs-4
peroxides to yield alcohol and ketone for the aerobic oxidation of O1s CNTs-5
200000
cyclohexane [41]. Similarly, CNTs provide solidliquid reaction
interfaces in our system, which connes the radicals around the 100000
surfaces of CNTs, at the solidliquid interfaces, the electron trans-
fer between radicals and CNTs is facilitated, thereby the larger rad- 0
200 400 600 800
ical chain-length improved the formation of BzH. Therefore, a Binding energy (eV)
plausible mechanism pathway of BzOH oxidation over CNTs is pro-
(b) 80000
posed in Fig. 2. 70000

Intensity (a.u.)
Firstly, BzOH is adsorbed onto the CNTs surface and activated, 60000
sp2-C
starting from a weak pp interaction between the graphene sheets 50000
40000
of CNTs and the benzene ring of BzOH [42,43]. Moreover, the rad- sp3-C
30000
ical nature of the unbound oxygen atom of the O2 molecule per- C-OH
20000
haps is enhanced consequent to O2 adsorption on CNTs. After one C=O
COOH
* stacking
10000
O-atom get bonded, the other O-atom unpaired electron density 0
is expected to mimic a radical. Thus, the CNT bonded O2 is AOAO -10000
282 284 286 288 290 292 294 296 298
in an orthogonal direction on the CNTs surface. Then a weakly
Binding energy (eV)
bonded aH-atom of activated BzOH is preferentially abstracted
by the CNTs bonded O2 to produce the benzyl alcohol radical
(c) 70000
60000

Intensity (a.u.)
(BA) and HO2 radicals, owing to the dissociation energy of aCAH 2
50000 sp -C
bond of BzOH is much lower (84 kcal mol 1) than that of the
40000
OAH bond of BzOH (103 kcal mol 1) [44]. Secondly, a compara- sp -C
3

30000
tively higher diffusive reaction propensity of a free O2 molecule 20000
C-OH

in solution is expected to help it add to the BA to form benzyl 10000


C=O
COOH * stacking

alcohol peroxyl radical (BAP). Thirdly, CNTs catalyze the BAP to 0


eliminate a HO2 radical and there form BzH [4547], arising from -10000
282 284 286 288 290 292 294 296 298
the pp interaction between the BAP and graphene sheets of the
Binding energy (eV)
CNTs. Finally, the main by-product BzA is obtained through further
oxidation of BzH in the presence of O2.
(d) 70000
Intensity (a.u.)

60000
50000
3.3. Effect of surface chemistry on BzOH oxidation 2
sp -C
40000
sp3-C
30000
Recent studies have revealed the catalytic activity was deter- C-OH
20000
mined by the nature and the surface chemistry of the carbon mate- C=O
COOH * stacking
10000
rials. For instance, surface carbonyl groups have been proposed as
0
serving as the active sites in the oxidative dehydrogenation of hydro-
282 284 286 288 290 292 294 296 298
carbons [48] and alkanes [28], while surface carboxylic acid groups
Binding energy (eV)
were identied as the active sites for the dehydration of alcohols
(e) 80000
[49] and the wet-air oxidation of phenols [32]. In our previous report 70000
Intensity (a.u.)

on the aerobic oxidation of BzOH catalyzed by CNTs-HNO3 system 60000


50000 sp2-C
[34], we found that the surface defects and surface oxygen-contain-
40000
ing groups on carbon catalyst have little impact on the BzOH conver- sp3-C
30000
sion, while having a negative effect on BzH selectivity. Consequently, C-OH
20000
it is necessary to demonstrate the role of the surface structure of the C=O
COOH * stacking
10000
carbon catalyst in the BzOH liquid-phase oxidation reaction. Herein, 0
oxidation and annealing treatments were performed to change the -10000
282 284 286 288 290 292 294 296 298
surface structure of CNTs-1. The surface structures were investigated
Binding energy (eV)
by Raman and XPS, and the results are illustrated in Figs. 3 and 4. (f) 80000
Fig. 3 shows two characteristic Raman peaks at approximately 70000
Intensity (a.u.)

1580 cm1 (G-band) and 1320 cm 1 (D-band). The G-band corre- 60000
sponds to the optical phonon modes of E2 g symmetry in graphite 50000 sp -C
2

and indicates the presence of crystalline graphite carbon, whereas 40000


3
sp -C
30000
the D-band is attributed to disorders and structural defects in the C-OH
20000
graphite structure [50,51]. The intensity ratio of D-band to G-band, C=O
COOH * stacking
10000
namely, ID/IG, is used to evaluate the defects of carbon-based nano- 0
structures [52]. The higher ID/IG ratio implies more defects in the car- -10000
282 284 286 288 290 292 294 296 298
bon-based nanostructures. As shown in Fig. 3, the ID/IG ratio
Binding energy (eV)
increased with increasing extent of oxidation and decreased with
increasing annealing temperature due to annealing treatment at Fig. 4. XPS survey spectra of the catalyst (a) and deconvolution of XPS C1s spectra
high temperatures can controllably heal the defects [53,54]. As of CNTs-1 (b), CNTs-2 (c), CNTs-3 (d), CNTs-4 (e) and CNTs-5 (f).
shown in Fig. 4a, all the samples exhibit two distinct peaks at a bind-
ing energy of 284 and 532 eV for carbon (C1s) and oxygen (O1s), increasing extent of oxidation and decreased with increasing anneal-
respectively. It is shown that the peak area at 532 eV increased with ing temperature due to annealing treatment at high temperatures
J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442 439

Table 2
Fractions of the XPS C1s functional groups and surface carboxyl group content of different catalysts.

Catalysts sp2-C (%) sp3-C (%) CAOH (%) C@O (%) COOH (%) pp stacking (%) C (at.%) COOH (at.%)
CNTs-1 58.6 26.5 4.5 3.2 2.9 4.3 95.37 2.77
CNTs-2 52.7 24.9 7.2 4.1 5.9 5.2 96.01 5.66
CNTs-3 55.1 21.8 6.3 4.9 8.1 3.8 98.09 7.95
CNTs-4 62.8 26.1 3.9 2.5 2.7 2.0 98.11 2.65
CNTs-5 61.1 24.2 6.3 2.5 2.3 3.6 99.31 2.28

can controllably remove partial unstable surface oxygen-containing adsorption strength of the oxygen-containing intermediate (BAP),
groups. Deconvolution of the C1s spectra (Fig. 4bf) gives six individ- which was supported by the 1-phenylethylperoxyl radical adsorbed
ual peaks, namely the following: sp2-hybridized graphite-like carbon on CNTs-COOH with more difculty than on CNTs [31], leading to a
atoms (284.6 eV), sp3-hybridized diamond-like carbon atoms decreased BAP elimination of HO2 to form BzH. On the other hand,
(285.3 eV), CAOH (286.1 eV), C@O (287.0 eV), COOH (288.8 eV) the introduction of carboxylic group and defects decreased conduc-
and pp stacking (290.8 eV) [5557]. The fraction of the specic tivity and electron mobility of CNTs, thereby the electron delocaliza-
functional groups and surface carboxyl group content on different tion was suppressed, thus decreased the electron transfer between
samples detected by XPS are shown in Table 2. It is indicated that CNTs and radicals [58,59].
the carboxylic groups content on the catalyst increased with increas-
ing extent of oxidation and decreased with increasing annealing 3.4. Effect of doping nitrogen on BzOH oxidation
temperature. As shown in Table 1, a strong effect of the CNTs surface
chemistry on the catalytic activity was observed (Entry 2, 5 and 6), it As mentioned above, if indeed electron transfer in graphene
is shown that the catalytic activity dramatically decreased and the skeletons plays an important role, it is farther expected that
selectivity to BzH increased with the content of surface carboxylic increasing the electron mobility of CNTs would improve its
groups increasing, which is different from that of HNO3 promoted
-0.4
CNTs catalysis [34]. As expected, the signicant improvement of CNTs-6
NCNT
the catalytic activity after thermal treatment (Table 1, Entries 8

Ln(rs) (mmol m h )
and 9) is likely attributed to the presence of fewer carboxylic groups
-1
-0.8 Ea = 65.4 kJ/mol
on the catalyst surface. Moreover, a similar behavior was observed -2
on activated carbon (AC) for the oxidation of BzOH (Table 1, Entries
10 and 11). This result is probably caused by the localization of elec- -1.2
trons as a result of the introduction of oxygen-containing groups and
Ea = 81.3 kJ/mol
defects, which may be unfavorable to the pp interaction between
the radicals and graphene planes and is supported by the improve- -1.6
ment of the catalytic activity after thermal treatment at high temper-
0.00244 0.00248 0.00252 0.00256
atures, which removed the oxygen-containing surface groups and
1/T (K)
beneted the repair of the defects. On the one hand, the introduction
of carboxylic groups on the CNTs (CNTs-COOH) surface reduced the Fig. 6. Arrhenius plot of the oxidation of BzOH over synthesized CNTs-6 and NCNTs.

Fig. 5. TEM (a) and HRTEM (b) images of the NCNTs. Survey (c) and N1s (d) XPS spectrum of the NCNTs.
440 J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442

BzOH BzA BzH NCNTs (ID/IG=1.18)


50
100 NCNTs used for 4th cycle (ID/IG=1.19)
250

Selectivity (%)
40
80
Conversion (%)

200

Intensity (a.u.)
30 60 150

20 100
40
50
10 20
0
0 0
1 2 3 4 800 1000 1200 1400 1600 1800 2000
Cycle Raman shift (cm )
-1

Fig. 7. Recyclability of NCNTs in liquid-phase BzOH oxidation. Fig. 8. Raman spectra of NCNTs and the used NCNTs.

and oxygen (O1s) at a binding energy of 284, 400 and 532 eV,
activity. Consequently, we modied the electronic characteristics respectively. In Fig. 5d the N 1s spectrum deconvoluted into ve
by doping electron-rich nitrogen atoms into the carbon lattice. main component peaks, namely, pyridine N (398.5 eV), pyrrolic N
Nitrogen doped CNTs (NCNTs, 1.02 at.% N by XPS) were synthe- (400 eV), quaternary N (400.9 eV), N-oxides (402.3 eV) and chemi-
sized by chemical vapor deposition with xylene as carbon source sorbed N (405.3 eV) is shown [62,63], the major functionalities of
and aniline as nitrogen source [35]. As shown in Fig. 5a and b, NCNTs are quaternary N and pyridine N, which may be responsible
the typical morphology of NCNTs with compartments in bamboo- for the activity of NCNTs [64,65]. It is worth noting that nitrogen
like nanolaments was observed [60,61]. Fig. 5c shows that the doping markedly improves the activity, such as BzOH conversion
NCNTs have three distinct peaks of carbon (C1s), nitrogen (N1s) was increased from 24.2% to 44.7% when undoped CNTs-6 was

Fig. 9. SEM (a and b), TEM (c and d) and HRTEM (e and f) images of the NCNTs (a, c and e) and used NCNTs for 4th cycle (b, d and f).
J. Luo et al. / Chemical Engineering Journal 240 (2014) 434442 441

replaced by NCNTs. Especially, the initial reaction rates of NCNTs, and exhibited excellent potential for industrial application of the
normalized by catalyst weight and BET surface area, were 1.7 BzOH oxidation to BzH. These results not only provide an attractive
and 1.3 times as high as those of the undoped CNTs-6, respectively metal-free alternative to noble-metal-catalyzed systems but also
(Table 1, E12 and 13). In addition, the value of the apparent activa- give new insights into the effect of surface chemistry on carbon-
tion energy (Ea) for oxidation of BzOH is 81.3 kJ/mol using catalyzed reactions, to push forward the research on carbon
undoped CNTs-6 as a catalyst, which is close to that (84 kJ/mol) catalysis.
reported for the ammonium molybdate-catalyzed aerobic BzOH
oxidation using H2O2 as oxidant [66]. As expected, the value of
the Ea for oxidation of BzOH is 65.4 kJ/mol using NCNTs as a Acknowledgements
catalyst, which is lower than that for the undoped CNTs-6
(Fig. 6), showing that the oxidation of BzOH is promoted by the This work was supported by the National Natural Science
nitrogen doping. It strongly suggested that the nitrogen doping Foundation of China (Nos. 21133010 and 21273079), the Guang-
has indeed contributed to the considerable improvement of dong Provincial Natural Science Foundation (No. S20120011275),
activity, which is attributed to enhancing electron transfer. the Program for New Century Excellent Talents in Universities of
It may be argued whether Fe species played important role in China (NCET-12-0190) and the Research Fund of the Guangdong
the oxidation reaction due to NCNTs were produced by the CVD Provincial Key Laboratory of Green Chemical Product Technology
method over a FeMo/Al2O3 catalyst. Therefore, the effect of residual (GC201205).
Fe species on the catalytic activity of NCNTs for the oxidation of
BzOH should be excluded properly. We previously demonstrated References
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