Letter

pubs.acs.org/acscatalysis

Efficient Metal-Free Catalytic Reaction Pathway for Selective

Oxidation of Substituted Phenols
Yangming Lin,†,‡ Bo Li,† Zhenbao Feng,† Yoong Ahm Kim,§ Morinobu Endo,∥ and Dang Sheng Su*,†,⊥
†
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016
People’s Republic of China
‡
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, 230001 People’s Republic of
China
§
School of Polymer Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu Kwangju, 500-757 Republic of
Korea
∥
Carbon Institute of Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano, 380-8553 Japan
⊥
Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, Berlin, 14195 Germany
*
S Supporting Information

ABSTRACT: Selective oxidation of substituted phenols to p-

benzoquinones is known to be inefficient because of the
competing C−O coupling reaction caused by phenoxy radicals.
The poor stability of conventional metal-based catalysts
represents another bottleneck for industrial application. Here,
we describe a metal-free reaction pathway in which onion-like
carbon (OLC) as a low-cost catalyst exhibits excellent catalytic
activity and stability in the selective oxidation of mono-, di- and
trisubstituted phenols to their corresponding p-benzoquinones,
even better than the reported metal-based catalysts (e.g., yield,
stability) and industrial catalysts for particular substrates.
Together with XPS, Raman, DFT calculations, and a series of comparative experiments, we demonstrate that the zigzag
configuration as a type of carbon defects may play a crucial role in these reactions by stabilizing the intermediate phenoxy
radicals.
KEYWORDS: onion-like carbon, molecular model catalysts, phenol, selective oxidation, metal-free

N atural products with a benzoquinone structure typically

play an important role in biomedicine and the synthesis
of fine chemical compounds.1,2 For example, 2,6-di-tert-butyl-1,
cumbersome preparation processes, inactivation and structure
shrinkage of the catalysts, high toxicity of the catalysts, and
required strongly acidic/highly corrosive conditions. Develop-
4-benzoquinone (DTBQ) is a highly active antioxidant with ment a new catalytic system with high efficiency and a smaller
antiaging properties.3 2-Methyl-1,4-naphthoquinone (MNQ, environmental footprint for the production of various p-
vitamin K3) is a kind of popular coagulant.4,5 2,3,5-Timethyl- benzoquinones is therefore demanded.
1,4-benzoquinone (TMBQ) is an important key intermediate Metal-free nanocarbon materials have been shown to be
of vitamin E. Traditionally, selective oxidation preparation of p- alternative candidates to conventional metal-based catalysts for
benzoquinones from the substituted phenols is known to be some important reactions.30−34 Onion-like carbon (OLC)
inefficient because of the rather favorable C−O coupling obtained by a high-temperature thermal treatment (1500−
reaction, as facilitated by phenoxy radicals.6,7 Current studies
1800 °C; see Figure S8 of the Supporting Information) of
have focused on various metal-based catalysts, such as Co(II)−
nanodiamond in a graphite furnace exhibits a quasi-spherical
Schiff base complexes,8 supported heteropolycompounds,9,10
molecular sieves,11−14 heteropoly acids,15 and noble metal morphology consisting of multiple closed concentric fullerene-
catalysts.16 For the reaction pathways, alternative routes in the like shells and possesses some unique chemical and physical
presence of H2O2 or O2 have been developed to improve the properties.35,36 OLC have been widely investigated for gas-
yields of desired products in a homogeneous catalytic phase catalytic reactions, magnetic materials, electrode
environment. The yields of target p-benzoquinones by these materials, and supercapacitors.37−40
approaches could reach to ∼55−93%.4,17−29 Despite this, the
drawbacks of these methods involve low selectivity of the Received: June 11, 2015
desired p-benzoquinones, the overproduction of byproducts Revised: September 2, 2015
(e.g. dimeric or polymeric C−O coupling products), Published: September 2, 2015

© 2015 American Chemical Society 5921 DOI: 10.1021/acscatal.5b01222

ACS Catal. 2015, 5, 5921−5926
ACS Catalysis Letter

Table 1. Catalytic Oxidation of 2,3,6-Trimethylphenol (TMP) over Various Samples under Different Conditionsa

sel. (%) yield (%)

entry catalyst SBET (m2 g−1) T (°C) conv. (%) TMBQ HMPQ PPO TMBQ
1b 80 16.5 13.9 3.1 81.1 2.3
2 OLC-1 463 80 99.8 82.5 15.7 trace 82.3
3 OLC-2 476 80 91.6 72.1 25.2 trace 66.1
4 OLC-3 459 80 88.6 72.3 25.8 trace 64.1
5 OLC-4 430 80 60.1 45.5 52.2 trace 27.4
6 AC 1178 80 52.4 30.4 66.7 trace 15.9
7 graphite 80 30.3 24.9 73.2 trace 7.5
8 UDD 305 80 65.5 13.4 84.3 trace 8.8
9 HHT 35 80 40.1 32.3 61.6 trace 13.0
10c graphene 520 80 81.4 58.9 39.2 trace 47.9
11d OLC-1 463 80 44.8 13.5 81.7 trace 6.0
12e OLC-1 463 80 97.3 42.5 55.4 trace 41.4
13f Ti-HMS 60 97 87 84.3
14g Ti-HMS 60 3 66.7 2
15h Ti−Si 1288 80 100 100 100
16i Ti−Si 1288 80 90 99 89
17j OLC-1 463 80 99.1 76.7 19.7 trace 76.0
18k 40% H2SO4 60−70 >99 >85 >85
19l CuCl2 MgCl2 80 >99 >90 >90
a
Reaction conditions: 8 mg of catalyst, 0.1 mmol of substrate, 0.36 mmol of tert-butyl hydroperoxide (TBHP), 5 mL of TFT solvent, t = 12 h.
b
Conducted in the absence of catalyst. cObtained from ref 42, the SBET was recorded on the Micromeritics ASAP2020 analyzer. dThe reaction
conditions are the same as in footnote a, except the oxidant is 30% H2O2. eThe reaction conditions are the same as in footnote a, except the oxidant
is cumyl hydroperoxide. fReference16, 200 mg of catalyst, t = 240 min, n(H2O2)/n(phenol) = 1, MeOH as solvent. gThe reaction conditions are the
same as in footnote f, except the oxidant is TBHP. hReference 11, 20 mg of catalyst, t = 40 min, 0.1 mmol of substrate, 0.44 mmol of H2O2, 1 mL of
CH3CN solvent. iThe seventh cycle test of catalyst under the footnote h conditions. j7 g of catalyst, 12 g of substrate, 3.6 equiv of TBHP, 200 mL of
TFT solvent, t = 12 h. kMnO2 as oxidant. lO2 as oxidant. Desired product: 2,3,5-timethyl-1,4-benzoquinone (TMBQ). Byproducts: 2,2,3,3,5,5-
hexamethyl-4,4-diphenoquinone (HMPQ), polyphenylene oxide (PPO).

In the present study, we demonstrate the excellent catalytic OLC-1 (treated at 1500 °C) exhibited the best catalytic
acitivity of OLC for selective oxidation of representative performance, with a TMBQ yield of 82.3% under the optimized
substituted phenols (seven examples) to their corresponding p- reaction conditions (entry 2). In contrast, some other carbon
benzoquinones. To the best of our knowledge, it is the first materials, such as activated carbon (AC, entry 6), graphite
time that the substitute phenol has been catalyzed by metal-free (entry 7), UDD (entry 8), HHT (a commercial high-
nanocarbons with decent activity. From XPS, Raman, and other temperature-treated nanocarbon fiber with well graphitized
comparative experiments, we show that the zigzag configuration structure; entry 9 Figure S11;), and graphene (G250, entry
rather than the oxygen species is responsible for the enhanced 10),42 showed a lower yield of TMBQ (∼7.5−47.9%) under
activities for these catalytic reactions. the same reaction conditions. In addition, the dependences of
Figure S9A−D shows the structures of various OLC samples catalytic performance on time, the amount of TBHP,
consisting of multilayer sp2 fullerene-like shells. The identified temperature, the solvent type, and the oxidant were studied
interlayer spacing of ∼0.340 nm in the shell of OLC is assigned in detail, and the results are listed in Figure S12 and Table 1,
to the (002) of turbostratic carbon graphite.41 The particle sizes entries 11−12. Long reaction times; elevated reaction temper-
of all OLC samples are ∼5−8 nm, and some lattice disorder can atures; and increased amounts of TBHP and other oxidants,
be observed on the OLC samples (Figure S9, marked by red including cumyl hydroperoxide and hydrogen peroxide, were
arrows). Regarding the N2 physisorption results, there is only a not favorable for improving the selectivity of TMBQ over
small difference in the surface area of the OLC samples (Figure OLC-1.
S10 and Table 1). As shown in Figure 1A, the conversion of TMP over OLC-1
Table 1 displays the catalytic performances of various carbon is 99.2% along with a TMBQ selectivity of 81.4% after seven
materials for the selective oxidation of 2,3,6-trimethylphenol successive runs, indicating that OLC-1 can be repeatedly used.
(TMP) to 2,3,5-trimethyl-1,4-benzoquinone (TMBQ) under This catalyst stability was further demonstrated by a low
different conditions. Without catalysts, only 2.3% of TMBQ conversion experiment (the initial conversion of TMP was
yield was obtained (Table1, entry 1) and the main byproduct maintained at ∼20%, Figure 1B). Although the OLC-1 did not
was polyphenylene oxide (PPO). The TMP conversion and the exhibit better catalytic activity than the reported Ti-HMS and
selectivity of the desired TMBQ over the four kinds of OLC Ti−Si catalysts using H2O2 as oxidant, it had a remarkable
samples were at reasonably high levels (Table1, entries 2−5). stability in the selective oxidation of TMP (Table 1, entries 11,
Among the four OLC samples treated at different temperatures, 12, 15, 16). Interestingly, the activity of OLC-1 was far more
5922 DOI: 10.1021/acscatal.5b01222
ACS Catal. 2015, 5, 5921−5926
ACS Catalysis Letter

Table 2. Catalytic Oxidation of Various Substituted Phenols

over OLC-1 Catalysta

Figure 1. (A) Recycling test of OLC-1 for selective oxidation of TMP

to TMBQ. Reaction conditions: 8 mg of catalyst, 0.1 mmol of
substrate, 0.36 mmol of TBHP, 5 mL of TFT solvent, T = 80 °C, t =
12 h. (B) Recycling test of OLC-1 for selective oxidation of TMP to
TMBQ. Reaction conditions: 8 mg of catalyst, 0.1 mmol of substrate,
0.36 mmol of TBHP, 5 mL of TFT solvent, T = 40 °C, t = 30 min.

than the Ti-HMS catalyst using TBHP as an oxidant (Table 1,

entry 14). It should be noted that OLC-1 still displayed the
good catalytic performance at preparative production scale
(entry 17). Compared with the conventional homogeneous
industrial catalysts (40% H2SO4 and CuCl2 + MgCl2), OLC-1
not only showed a competing catalytic performance but also
represented a smaller environmental footprint for the
production of TMBQ (Table 1, entries 18, 19).
Following the success of TMP oxidation, we applied OLC-1
to a series of phenols with mono-, di-, and other trisubstituted
structures (Table 2). For all these derivatives, there was a
reasonable conversion and selectivity output. For instance,
TMBQ was produced efficiently from 2,3,5-trimethylphenol
a
(2,3,5-TMP) and had a conversion of around 100% and Reaction condition: 8 mg of OLC-1 catalyst, 0.1 mmol of substrate,
selectivity of 87.5% at 100 °C after 12 hours (Table 2, entry 1). 0.36 mmol of TBHP, 5 mL of TFT solvent, T = 80 °C, t = 4 h. bT =
The selective oxidation for di-substituted phenols, including 100 °C, t = 14 h. ct = 5 h. dt = 8 h. e0.05 mmol of substrate, T = 70 °C,
2,6-dimethylphenol (DMP), 2,6-dimethylphenol (2,5-DMP) t = 12 h. fReference 9, 1 mmol of substrate, 5 mLof acetone, 0.02
and 2-methyl-1-naphthol (MNL) resulted in ∼80.9−85.7% mmol of Cs3H1M11PV1 heterogeneous catalyst, 22 mmol H2O2, T =
20 °C, t = 7 h. gReference 16, 200 mg of Ti-HMS catalyst, n(H2O2)/
yield of the corresponding p-benzoquinones under the n(phenol) = 1, MeOH as solvent, T = 60 °C, t = 24 h. hThe reaction
optimized reaction conditions (Table 2, entries 2, 4, 6 and conditions are the same as in footnote f, except the oxidant is TBHP.
Figure S14). Compared with the reported metal-based catalysts i
CrO3/ CH3COOH/H2SO4 catalyst, T = 60−90 °C
and the industrial homogeneous catalyst (CrO3/CH3COOH/
H2SO4),9,16 OLC-1 exhibited an excellent catalytic performance
in the selective oxidation of DMP, 2,6-di-tert-butyl phenol similar XPS O 1s spectral profiles (only C−O/C−OH group)
(DTBP) and MNL under similar reaction conditions (Table 2, showed different activities (Table 1, entries 2−4); hence, there
entries 2, 3, 6). Moreover, a good catalytic performance for the is no simple correlation between the oxygen species and the
oxidation of mono-substituted phenol, 2-methylphenol (MP), observed catalytic performance. These results indicate that
can be achieved as expected (Table 2, entry 5). Thus, a cost- oxygen species might not be the active sites in the selective
effective metal-free catalytic system to realize the selective oxidation of the substituted phenols.
oxidation of phenols has been achieved. The Raman spectra of the OLC samples have three main
To study the origin of the catalytic performance of OLC, features in the 1000−3000 cm−1 region (Figure S16A): D band
XPS was employed to investigate the surface composition of (defect-induced mode, ∼1323 cm−1), the G band (1578 cm−1),
the catalysts. Figure S15A illustrates that with an increase in the and the 2D band (2652−2678 cm−1). Compared with other
preparation temperature, the full width at half-maximum OLC samples, the decreasing fwhm of the D band on OLC-4
(fwhm) value of C 1s spectra decreases from 1.21 eV for represented a more ordered carbon network structure (Figure
OLC-1 to 1.11 eV for OLC-4. This sugguests that OLC-4 has a S16B). In contrast, OLC-1 had a more disordered carbon
more ordered graphitic structure. As shown in Figure S15B, all structure. The increased intensity, the asymmetric spectral
the catalysts have similar oxygen concentrations (0.53−0.64 at. profile, and the upshift (from 2652 to 2678 cm−1) of the 2D
%). This is also confirmed by elemental analysis (0.33−0.38 wt band of the OLC samples reflected that the carbon structures
%, Table S1). The oxygen peaks located at 530.8 and 533 eV consisting of stacked graphene layers were favorable to
were assigned to trace CO and C−O (ether group) or C− formation of an ordered carbon lattice under elevated
OH groups, respectively.35 As reported earlier, oxygen species, temperature.35,36,45 Moreover, Figure S17 illustrates that there
such as a carbonyl group, have been proven to be the active is no obvious change between fresh OLC-1 and used OLC-1,
sites in alkane oxidative dehydrogenation and nitrobenzene suggesting the structural stability of OLC-1 catalyst. The ID/IG
reduction reactions.43,44 In the present work, OLC-4 with C ratio was used to depict the number of defects, especially at
O group did not exhibit the best catalytic performacne. This graphene edges.46 The linear relationship of the activity with
signifies that CO is perhaps not critical to the phenol the ID/IG ratio in Figure 2 reveals that the ratio is proportional
oxidation reaction. In addition, the three other catalysts with to the mass-normalized activity and the area-normalized activity
5923 DOI: 10.1021/acscatal.5b01222
ACS Catal. 2015, 5, 5921−5926
ACS Catalysis Letter

Table 3. Catalytic Performance of TMP over Various Model

Molecule Catalystsa

Figure 2. Dependences of mass-normalized activity (A) and area-

normalized activity (B) on the ID/IG ratio under different reaction
conditions in the selective oxidation of TMP to TMBQ. Condition A:
80 °C, 12 h. Condition B: 70 °C, 12 h. Condition C: 60 °C, 3 h.

under different reaction conditions, that is, the OLC-1 catalyst

with the highest number of defects exhibits the best catalytic
performance. The same linear relationship could be observed in
the selective oxidation of DMP to DMBQ (Figure S18). In
addition, when commercial HHT with a very low ID/IG ratio
(∼0.35) was used in the oxidation reaction of TMP, a low yield
(∼13%) was obtained (Table 1, entry 9). All the results showed
that defects played a key role in these catalytic reactions.
Defects are rich in nanocarbons, and it has been reported
that many reactions are catalyzed by the defects in carbon;31,47
however, an effective method to identity the type of defect and
to give an accurate description of the amounts of each type is
lacking, even for the total number of defects per square (nano)
meter. It is a challenge to identify the actual active sites because
of the diversity of defects and technical limitations. Although
first-principles calculation was used to study the influence of the
doped Stone−Wales defect structure on ORR,48 exploring the
specific structure of active defect sites in a reaction process is
still an arduous task. Here, we applied several small molecules
a
as model catalysts to simulate the structures of carbon catalysts Reaction conditions: 8 mg of model catalyst, 0.1 mmol of substrate,
and to identify possible active sites. 0.36 mmol of TBHP, 5 mL of TFT solvent, T = 80 °C, 12 h.
b
As mentioned, the trace CO and C−O group could be Conducted in the absence of catalyst. c20 mg model catalysts. Desired
observed in OLC samples. When different loadings of benzyl product: 2,3,5-timethyl-1,4-benzoquinone (TMBQ).
ether and anthraquinone with the mimicked CO and C−O
structures were added into the reaction (Table 3, entries 2−4), is consistent with the conversion rate of TMP (16.5%),
it was found that the catalytic activities did not change as indicating the direct effect of TBHP on the TMP conversion. In
compared with the blank experiment. This again illustrates that contrast, the decomposition rate of TBHP over OLC-1 was
the surface oxygen species is inconsequential to the catalytic 85.2%, suggesting that the fullerene-like shells had an excellent
reaction. decomposition ability for TBHP. It has been reported that the
We also employed a few model catalysts with specific selective oxidation of substituted phenols may involve a
armchair and zigzag defect structures to identify the types of phenoxy radical coupling process.50−52 The hydroxyl radical
active sites. As shown in Table 3, two kinds of model catalysts derived from the decomposition of TBHP would get close to
with an armchair structure do not exhibit an enhanced catalytic the hydroxyl of the substituted phenol to abstract hydrogen
performance (entries 5, 6). It is worth noting that with an (this is also the reason for a blank experiment with the TMP
increae in the zigzag unit (Table 3, entries 7−9 and Table S2), conversion of 16.5%),33,53,54 and then the phenoxy radical was
anthracene, naphthacene, and pentacene have an increasing produced along with the release of water.50−52,55 As mentioned
yield in the selective oxidation of TMP (from 2.7% to 8.4%). A above (Table 1, entry 1), the main product of the TMP
similar activity tendency for the model catalysts was observed in oxidation was PPO (81.1% selectivity) in the absence of
the selective oxidation of DMP to DMBQ (Figure S19). All the catalyst. This result was ascribed to the C−O coupling of
facts indicated that the zigzag configuration might have a phenoxy radicals. Thus, avoiding the C−O coupling must be a
positive effect on these reactions. In addition, there was no key step.
obvious synergistic effect between the zigzag and oxygen It has been suggested in the literature that the zigzag edge
species (CO, C−O), as well as for armchair structures may be more reactive than the armchair edge due to its unique
because the yields of TMBQ were only 1.7%, 1.8%, and 2.5% electronic structure and unpaired electrons.56,57 It is therefore
on xanthenes, pentacenequinone, and coronene catalyst reasonable to expect that the phenoxy radical would be more
(entries 10−12), respectively. stable for binding at the zigzag edge than the amchair edge.
As shown in Table S3, only 4.5% TBHP (about 0.0162 To test this hypothesis, DFT calculations were performed to
mmol) decomposed under the blank reaction conditions, which study the adsorption of the phenoxy radical at the model
5924 DOI: 10.1021/acscatal.5b01222
ACS Catal. 2015, 5, 5921−5926
ACS Catalysis Letter

catalysts, as shown in Table 3. In Figure 3, the adsorption of the

phenoxy radical at the zigzag edge (five benzene rings) is
■ ACKNOWLEDGMENTS
The authors thank Dr. Linhui Yu, Bingsen Zhang, Jia Wang,
Rui Huang, and Kuang-Hsu Wu for their kind help during this
study. The authors acknowledge financial support from MOST
(2011CBA00504); NSFC of China (21133010, 51221264,
21261160487); and the “Strategic Priority Research Program”
of the Chinese Academy of Sciences, Grant No. XDA09030103.
Bo Li is grateful for a financial grant from the Institute of Metal
Research (Y3NBA211A1). The computing time was partly
allocated from ShenYang Branch, Supercomputing Center of
CAS.

Figure 3. Adsorption energies and structures of phenoxy radical

obtained from DFT calculations. (a) Armchair edge (model catalyst 6
in Table 3), (b) zigzag edge (model catalyst 9 in Table 3). The
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5926 DOI: 10.1021/acscatal.5b01222

ACS Catal. 2015, 5, 5921−5926