pubs.acs.

org/Langmuir
© 2009 American Chemical Society

Catalytic Role of Cu Sites of Cu/MCM-41 in Phenol Hydroxylation

Guoying Zhang, Jinlin Long, Xuxu Wang,* Zizhong Zhang, Wenxin Dai, Ping Liu, Zhaohui Li,
Ling Wu, and Xianzhi Fu*
Research Institute of Photocatalysis, State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University,
Fuzhou 350002, P. R. China

Received July 7, 2009. Revised Manuscript Received November 9, 2009

Four types of copper-containing MCM-41 mesoporous silicas were synthesized by the surface organometallic
chemistry (SOMC) procedure (Cu/MCM-41-S), mechanical mixing (Cu/MCM-41-M), impregnation (Cu/MCM-41-I),
and the hydrothermal technique (Cu/MCM-41-H). The resultant samples were characterized in detail by X-ray
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via VIRGINIA COMMONWEALTH UNIV on December 21, 2023 at 22:20:09 (UTC).

diffraction (XRD), N2 physical adsorption, transmission electron microscopy (TEM), UV-vis diffuse reflectance
spectroscopy (UV-vis DRS), temperature-programmed reduction (TPR), and infrared spectroscopy (IR) of NO
adsorption. Catalytic behaviors of these samples for hydroxylation of phenol with H2O2 were evaluated. The results
revealed that depending on the preparation methods the samples contain different copper-oxo species and thus show
different catalytic behaviors. Among these samples, the one prepared by SOMC contains a predominant amount of
isolated Cu2þ and exhibits the most excellent catalytic activity and selectivity. The amount of isolated copper species
decreases in the order of Cu/MCM-41-S > Cu/MCM-41-H > Cu/MCM-41-I > Cu/MCM-41-M, while the amount of
copper oxide clusters increases in a reversal order. The difference in the catalytic activity and product selectivity of these
four samples could be rationally explained by the distinction of chemical states of copper species. The highly dispersed
isolated Cu2þ species are identified as the active sites in the phenol hydroxylation, while the nonisolated Cu2þ clusters or
oxide are responsible for the deep oxidation of primary product HQ and the decrease of product selectivity. The
mechanism of the copper-catalyzed phenol hydroxylation was proposed.

1. Introduction species are inclined to heterogeneously distribute both inside and

Dihydroxybenzenes, such as catechol (CAT) and hydroqui-
none (HQ), are high value chemicals. Using H2O2 as an oxidant
for hydroxylation of phenol is the most doable way for producing
the dihydroxybenzenes. Compared to the homogeneously cata-
lytic hydroxylation of phenol with mineral acids, simple metal
ions, and their complexes as catalysts, the heterogeneously
catalytic hydroxylation with a solid catalyst has attracted more
interest due to its eco-friendly nature and catalyst recoverability.
Pure metal oxides or composite oxides, such as Fe2O3, Co3O4,
Fe2O3/Al2O3, CuO/SiO2, MoO3, V2O5, etc., were shown to be
active for the reaction, but neither the catalytic activity nor the
product selectivity of these catalysts is satisfactory.1 Since the
finding of TS-1 molecular sieve and its commercial application for
phenol hydroxylation in 1986,2 increasing attention has been paid
on the development of other metal-modified molecular sieves in
order to acquire higher reaction rate and better selectivity of
dihydroxybenzenes. Various metals, such as iron, copper, tita-
nium, tin, vanadium, etc., substituted or supported molecular
sieves have been extensively investigated.3,4 The loaded metal ion
or metal species have been established to be catalytically active
sites of the hydroxylation reaction. However, these catalysts often
show considerable difference in phenol conversion or in product
selectivity, depending on the chemical composition and prepara-
tion method. The main reason for the difference is that the metal
*To whom correspondence should be addressed: e-mail xwang@fzu.edu.cn,
Fax þ86-(0)591-83779251 (X.W.); e-mail xzfu@fzu.edu.cn, Fax þ86-(0)591-
83738608 (X.F.).
(1) Yu, R. B.; Xiao, F. S.; Wang, D.; Liu, Y.; Pang, G. S.; Feng, S. H.; Qiu, S. L.;
Xu, R. R.; Ma, S. J. Catal. Lett. 1997, 49, 49.
(2) Martens, J. A.; Buskens, P.; Jacobs, P. A. Appl. Catal., A 1993, 99, 71.
(3) Notari, B. Catal. Today 1993, 18, 163.
(4) Dai, P.-S. E.; Petty, R. H.; Ingram, C. W.; Szostak, R. Appl. Catal., A 1996,
143, 101.
outside the framework of molecular sieves. They can be dispersed
inside the framework as isolated and clustered metal-oxygen
units or on the surface as the metal-oxygen clusters with different
nuclearity. The insight into the inherent relationship between the
catalytic function and the structure of active component is
essential for the design and synthesis of catalysts with high
efficiency, while clear identification of chemical state of metal
atoms present in the catalysts is pivotal.
In the recent decade, the copper-modified molecular sieves,
such as CuAPO-11,5 Cu/Y,6 Cu/ZSM-5,7 CuO/MCM-48,8 Cu/
MCM-41,9 Cu/HMS,10 CuSBA-15,11 etc., have also been showed
to be excellent catalysts for the hydroxylation of phenol with
H2O2. But these studies have mainly focused on the synthesis and
activity evaluation of catalysts for phenol hydroxylation; only
limited information is available for understanding fully the effect
of copper states on the reaction. A few studies on the Cu-
incorporated mesoporous materials involved in brief this subject.
Sobczak et al. showed that copper incorporated into the skeleton
of MCM-41 exhibits different properties in comparison to the one
located in the extra-framework cationic positions.9 Qi et al.
suggested that the Cu2þ in the framework of CuAPO-11 is the
active center for phenol hydroxylation.5 For Cu2þ-modified
(5) Qi, X.; Zhang, L.; Xie, W.; Ji, T.; Li, R. Appl. Catal., A 2004, 276, 89.
(6) Wang, J.; Park, J.-N.; Jeong, H.-C.; Choi, K.-S.; Wei, X.-Y.; Hong, S.-I.;
Lee, C. W. Energy Fuels 2004, 18, 470.
(7) Villa, A. L.; Caro, C. A.; d. Correa, C. M. J. Mol. Catal. A 2005, 228, 233.
(8) Lou, L.-L.; Liu, S. Catal. Commun. 2005, 6, 762.
(9) (a) Sobczak, I.; Ziolek, M.; Renn, M.; Decyk, P.; Nowak, I.; Daturi, M.;
Lavalley, J.-C. Microporous Mesoporous Mater. 2004, 74, 23. (b) Franco, L. N.;
Perez, I. H.; Pliego, A.; Franco, A. M. Catal. Today 2002, 75, 189.
(10) Fu, Z.; Chen, J.; Yin, D.; Yin, D.; Zhang, L.; Zhang, Y. Catal. Lett. 2000,
66, 105.
(11) Wang, L.; Kong, A.; Chen, B.; Ding, H.; Shan, Y.; He, M. J. Mol. Catal. A
2005, 230, 143.

1362 DOI: 10.1021/la902436s Published on Web 11/25/2009 Langmuir 2010, 26(2), 1362–1371
Zhang et al.
zeolites, Wang et al. reported that not only the isolated Cu2þ
species but also a small amount of clustered Cu2þ species is neces-
sary to improve the product selectivity,6 while the clustered copper
ions are thought to be inactive in the oxidation of the aromatic ring
but accelerate the nonproductive decomposition of hydrogen
peroxide.11 The role of copper states in the phenol hydroxylation
has been uncertain to date. Because of a variety of different surface
sites of catalyst, the exact states of metal species are difficult to
identify by physicochemical methods,12 especially after the catalyst
was already obtained by the conventional methods such as ion
exchange, impregnation, and hydrothermal process. Preparation
of well-defined metal species on the surface of molecular sieves may
be an alternative strategy for gaining insight into relationship
between the catalytic function and the chemical state of metal.
The surface organometallic chemistry method (SOMC) can be
used for the surface modification at an atomic and molecular level
and for the design of catalysts with definite active sites.13,14 As a
zeolite molecular sieve was treated under vacuum conditions, a
large amount of isolated hydroxyls would be left on the surface of
support, which offers a scaffold for molecular engineering of
isolated metal sites.15,16 In previous work, we constructed success-
fully isolated tin-, iron-, or titanium-oxo species on the frame-
work surface of the zeolite molecular sieves by this strategy.17-19
Recently, we studied the deposition mechanism of Cu[OCH-
(Me)CH2NMe2]2 on the surface of MCM-41 under in situ
condition.20 The study revealed that owing to the intervention
of surface hydroxyl groups, the isolated copper complexes with
different chemical compositions could be anchored on the surface
dependent on the thermal treatment temperature. It arouses our
interest in preparation of well-defined copper-oxo sites on
the surface of MCM-41 for identifying catalytic role of the
copper-oxo sites with different chemical structures.
In this work, four types of copper-containing MCM-41 meso-
porous silicas were synthesized by surface organometallic chem-
istry (SOMC), mechanical mixing, impregnation, and hydro-
thermal technique. The copper states in the resultant samples
were characterized in detail by UV-vis diffuse reflectance spec-
troscopy (UV-vis DRS), temperature-programmed reduction
(TPR), and in situ infrared spectroscopy of NO adsorption
(IR). The catalytic behaviors of these samples for hydroxylation
of phenol with H2O2 were compared. The results show that
isolated copper species are predominant on the Cu/MCM-41
catalyst with the best catalytic activity, prepared by the SOMC
method. The isolated copper species are identified as the active
sites of phenol hydroxylation. A possible pathway for the copper-
catalyzed reaction was discussed in detail.
2. Experimental Section
2.1. Catalyst Preparation. Dimethylamino-2-propanol and
CuO were purchased from Merk-Schuchardt and Alfa-Aesar,
(12) Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.;
Chorkendorff, I. Science 2007, 317, 100.
(13) Coperet, C.; Chabanas, M.; Saint-Arroman, R. P.; Basset, J. M. Angew.
Chem., Int. Ed. 2003, 42, 156.
(14) Lefebvre, F.; Mallmann, A.; Basset, J. M. Eur. J. Inorg. Chem. 1999, 361.
(15) Long, J.; Wang, X.; Zhang, G.; Dong, J.; Yan, T.; Li, Z.; Fu, X. Chem.;
Eur. J. 2007, 13, 7890.
(16) Long, J.; Wang, X.; Ding, Z.; Zhang, Z.; Lin, H.; Dai, W.; Fu, X. J. Catal.
2009, 264, 163.
(17) Wang, X.; Xu, H.; Fu, X.; Liu, P.; Lefebvre, F.; Basset, J. M. J. Mol. Catal.
A 2005, 238, 185.
(18) Wang, X.; Long, J.; Yan, G.; Zhang, G.; Fu, X.; Basset, J. M.; Lefebvre, F.
Microporous Mesoporous Mater. 2008, 108, 258.
(19) Wang, X.; Lian, W.; Fu, X.; Basset, J. M.; Lefebvre, F. J. Catal. 2006, 238,
13.
(20) Zhang, G.; Wang, X.; Long, J.; Xie, L.; Ding, Z.; Wu, L.; Li, Z.; Fu, X.
Chem. Mater. 2008, 20, 4565.
Langmuir 2010, 26(2), 1362–1371
Article
respectively. Other reagents were purchased from Guangzhou
Chemical Reagent Corp., China. MCM-41 was synthesized by a
typical hydrothermal procedure using CTAB as a surfactant and
TEOS as a source of silica, followed by calcination under flowing
oxygen at 813 K for 20 h. Cu[OCHMeCH2NMe2]2 was synthe-
sized by an alcohol-exchange reaction described in the literature.21
The reaction of copper methoxide, Cu(OMe)2, with dimethyla-
mino-2-propanol was performed in pentane at room temperature.
After evacuation to remove the solvent, the product was purified
by sublimation under vacuum (10-4 Torr) at 333 K. The purple
solid Cu[OCHMeCH2NMe2]2 was acquired, as checked by the IR
spectrum,22 and preserved in a glovebox full of N2 from hydrolysis
prior to use.
The organo-copper-grafted MCM-41 was prepared by the reac-
tion of MCM-41 with Cu[OCHMeCH2NMe2]2 (SOMC method)
at a temperature of 353 K. The preparation was performed in a
homemade glass tube connected to a vacuum line. The neat MCM-
41 powder was pretreated in the glass tube under dynamic vacuum
(10-4 Torr) at 773 K for 4 h and then was cooled to room
temperature. A given amount of Cu[OCHMeCH2NMe2]2 in pen-
tane solution was introduced into the tube with a syringe via a
septum. After removing the solvent at room temperature by
evacuation, the system was kept at 353 K for 10 h and then treated
under dynamic vacuum at the same temperature for 2 h to eliminate
physisorbed species. The resulting solid Cu[OCHMeCH2NMe2]2/
MCM-41, the composition and structure of which were character-
ized in detail in our previous work,20 was calcined at 773 K for 10 h
in flowing dry oxygen. The as-prepared copper supported MCM-
41 sample was denoted as Cu/MCM-41-S.
For comparison purposes, other three copper-supported
MCM-41 catalysts were prepared by traditional methods as
follows. (1) The sample denoted as Cu/MCM-41-M was prepared
by a mechanical mixing of CuO with MCM-41 followed by
calcination in air at 773 K for 10 h. (2) The sample denoted as
Cu/MCM-41-I was prepared by impregnation of MCM-41 with
an aqueous solution Cu(NO3)2, dried for 12 h at room tempera-
ture, and finally calcined in air at 773 K for 10 h. (3) The sample
denoted as Cu/MCM-41-H was synthesized by the hydrothermal
method by taking a quantitative amount of TEOS and Cu(NO3)2
add to a solution of CTMABr and NaOH under vigorous
stirring.23 After adjusting the pH value by the diluted H2SO4
(0.1 M), the resulting mixture was transferred into a stainless steel
autoclave equipped with a Teflon linear and aged at 383 K for
2 days. The powder was recovered, washed with deionized water,
dried, and calcined in air at 773 K for 10 h.
The loading amount of copper in the four Cu/MCM-41
samples was controlled by addition of the copper precursor
(Cu[OCHMeCH2NMe2]2, CuO, and Cu(NO3)2) in the above-
mentioned process and determined by atomic absorption spectro-
photometry (AAS).
2.2. Physicochemical Characterization. The IR experi-
ments were carried out on a Nicolet Nexus 670 FTIR spectro-
meter with a DTGS detector. In situ IR spectra of NO adsorbed
on ca. 15 mg of self-supporting wafer were recorded at the given
partial pressures of NO with a homemade in situ IR cell equipped
with CaF2 transparent windows at room temperature. In all
experiments, the IR spectrum collected before gas dosage was
used as background. All reported spectra of NO adsorption are
background-subtracted. Each spectrum consists of 32 scans taken
at 4 cm-1 resolution. Typically, the sample was first pretreated
under dynamic vacuum at 473 K for 1 h and then cooled to room
temperature in vacuum (pressure lower than 10-6 mbar) prior to
contacting with NO.
XRD spectra were recorded on a Bruker D8 Advance X-ray
diffractometer using Cu KR radiation. Elemental analysis was
(21) Goel, S. C.; Kramer, K. S.; Chiang, M. Y.; Buhro, W. E. Polyhedron 1990,
9, 611.
(22) Young, V. L.; Cox, D. F.; Davis, M. E. Chem. Mater. 1993, 5, 1701.
(23) Huo, Q.; Margolese, D. I.; Stucky, G. D. Chem. Mater. 1996, 8, 1147.
DOI: 10.1021/la902436s 1363
Article
performed on a PerkinElmer Analyst 800 atomic absorption
spectrometer. Transmission electron microscopy (TEM) was per-
formed with a JEM-200 CX microscopeoperated at 200 kV.
UV-vis DRS spectra were recorded on a Varian 500 spectrometer.
The spectra were collected at 200-800 nm referenced to BaSO4 and
were transformed into the Kubelka-Munk function, F(R¥).
Nitrogen adsorption-desorption isotherms were measured at
77 K with ASAP2020 M (Micromeritics Instrument Corp.). Tem-
perature-programmed reduction was performed on a Micromeri-
tics AutoChem 2910 instrument with 45 mg of catalyst at heating
rate of 10 K min-1 in H2(10%)/He gas flow (30 mL min-1).
2.3. Hydroxylation of Phenol by H2O2. Phenol hydroxyla-
tion with H2O2 was carried out in a 100 mL of three-necked
round-bottom flask fitted with a reflux condenser. In a standard
reaction, ∼1.0 g of phenol and ∼0.05 g of catalyst were first added
in 20 mL of deionized water in the reactor. Hydrogen peroxide
(H2O2, 30% aqueous solution) was added through a transfer pipet
to the magnetically stirred phenol solution containing catalyst
(molar ratio of phenol to H2O2 = 1:1, stirring rate = 1000 rpm).
The reaction mixture was sampled periodically by syringe and
analyzed by liquid chromatography (Waters 2487) equipped with
a Merck C18 column. The mixture was separated on the column
using a methanol/water mixture (60/40, volume ratio) as the
mobile phase at a flow rate of 0.6 mL/min and detected at UV
wavelength of 245 and 271 nm. The identification and quantifica-
tion of reactant and products were performed using standard
compounds (phenol, hydroquinone, and catechol).
The determined concentration data of phenol, CAT, HQ, and
BQ were further treated with expressions given as follows,6 where
the conversion of phenol is expressed by Xphenol:
Xphenol ð%Þ ¼ 100  ðCi, phenol -Cf , phenol Þ=Ci, phenol
where Ci,phenol and Cf,phenol are the molar concentrations of
phenol before and after the reaction, respectively. The selectivity
to product is shown by Sj
Sj ð%Þ ¼ 100  Cj =ðCi, phenol -Cf , phenol Þ
where Cj is the molar concentration of product; j = catechol
(CAT), hydroquinone (HQ), and p-benzoquinone (BQ). The total
selectivity of products
Sproduct ð%Þ ¼ SCAT ð%Þ þ SHQ ð%Þ þ SBQ ð%Þ
The availability of H2O2
H2 O2;eff ð%Þ ¼ 100  ðCf , CAT þ Cf , HQ þ Cf , BQ Þ=C0, H2 O2
where Cf,CAT, Cf,HQ, and Cf,BQ are the molar concentrations
of CAT, HQ, and BQ, respectively.
3. Results and Discussion
3.1. Characterization of Cu/MCM-41. 3.1.1. Chemi-
cal Composition, N2 Adsorption/Desorption, XRD, and
TEM Studies. The copper contents and the texture parameters
of the four copper-supported MCM-41 catalysts, prepared by
different methods, are summarized in Table 1. The four copper-
supported MCM-41 catalysts contain the almost same copper
content (ca. 1.5 wt %), but their textural parameters are markedly
different from those of the nude MCM-41. The BET surface area
and pore volume are deceased in the order MCM-41 > Cu/
MCM-41-S > Cu/MCM-41-H > Cu/MCM-41-I > Cu/MCM-
41-M, but these samples have the same adsorption isotherm
characteristics: typical of a type IV with a hysteretic loop
(IUPAC classification). It indicates that copper loading does
not destroy the mesoporous structure of MCM-41, which will be
further conformed by XRD and TEM below. However, the
1364 DOI: 10.1021/la902436s
Zhang et al.
Table 1. Physicochemical Characteristics of Copper-Modified
MCM-41 Samples
copper SBET/m2 pore pore
sample content/wt % g-1 volume/mL g-1 diameter/nm
MCM-41 0 1047 1.05 3.01
Cu/MCM-41-S 1.50 971 0.7593 2.97
Cu/MCM-41-H 1.48 936 0.7247 2.99
Cu/MCM-41-I 1.53 895 0.6494 2.85
Cu/MCM-41-M 1.50 883 0.5691 2.83
Figure 1. Nitrogen adsorption-desorption isotherms of the syn-
thesized samples (a) MCM-41, (b) Cu/MCM-41-S, (c) Cu/MCM-
41-H, (d) Cu/MCM-41-I, and (e) Cu/MCM-41-M. The inset is the
corresponding pore size distributions.
difference in the pore size for several copper-contained samples
is obvious. Cu/MCM-41-S and Cu/MCM-41-H have very narrow
pore diameter (2.97 and 2.99 nm), slightly smaller than that of
MCM-41. Whereas for Cu/MCM-41-I and Cu/MCM-41-M the
average pore diameter of ca. 2.8 nm is notably smaller than that
of the Cu/MCM-41-S, Cu/MCM-41-H, and nude MCM-41, the
pore radius distribution also becomes broader.
Distinctly, the preparation method affects the texture of Cu/
MCM-41. In view of the almost same copper content, the dis-
crepancy of samples maybe result from the different states of
copper species on the mesopore surface. For the Cu/MCM-41-S
prepared by the SOMC method, the highest surface area and pore
volume can be attributed to the high dispersity of copper species on
the mesoporous wall of MCM-41. The Cu/MCM-41-S sample was
prepared with Cu[OCHMeCH2NMe2]2/MCM-41 as precursor.
Bonding of the Cu and O atoms in the precursor to the MCM-
41 framework20 could hinder conglomeration of copper-oxo
species to clusters during calcination and thus avoids the blockage
of the channels of MCM-41. For other three samples, the con-
glomeration of copper on the surface could be unavoidable in the
calcination process, especially for the Cu/MCM-41-I and Cu/
MCM-41-M. The conglomeration or low dispersity undoubtedly
results in pore blockage and therefore decreases in the BET surface
area, the pore diameter, and the pore volume.
The crystalline structure of the four Cu/MCM-41 samples was
characterized by XRD, as shown in Figure 2. No major change in
the structure of MCM-41 is observed after copper modification.
Within the low angle area, all the samples exhibit a main peak at 2.2
indexed as [100] due to the hexagonal array of parallel mesoporous
tubes.24 The incorporation of Cu2þ ions causes merely a little
(24) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.;
Schmitt, K. D.; Chu, C. T. W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.;
Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834.
Langmuir 2010, 26(2), 1362–1371
Zhang et al.
Figure 2. XRD patterns of (a) Cu/MCM-41-S, (b) Cu/
MCM-41-M, (c) Cu/MCM-41-I, (d) Cu/MCM-41-H, and (e) nude
MCM-41.
decrease in the intensity of all diffraction peaks. No other
diffraction peaks arising from crystalline copper oxide (35.6 and
38.8) are observed in the high angle (not shown); this shows
that copper may be dispersed highly onto the mesoporous wall of
MCM-41 to form isolated copper ions and/or oligonuclear CuO
clusters.
The microstructure of the four Cu/MCM-41 samples was
further studied by TEM, as shown in Figure 3. The existence of
order-oriented mesoporous channels is very clear. This indicates
that these modified MCM-41 materials retains a highly ordered
two-dimensional hexagonal mesophase. No copper oxide nano-
particles confined in mesoporous channels are observed, suggest-
ing that copper oxides are dispersed on the MCM-41 surface.
These results are quite consistent with the XRD results above.
3.1.2. UV-vis DRS Spectroscopy. UV-vis diffuse reflec-
tance spectroscopy (UV-vis DRS) is known to be a very sensitive
technique for identification of the chemical states of metal ions.
Figure 4 gives a comparison of the UV-vis DRS spectra of the
four Cu/MCM-41 samples. The Cu/MCM-41-S sample shows a
single strong absorption peak at ca. 225 nm, which is assigned to
the charge transfer transition between isolated Cu2þ ion and
oxygen (Figure 4c).25,26 No significant absorption peak above
300 nm is observed, suggesting that Cu/MCM-41-S is free of
copper oxide oligomers or clustered copper species. It indicates
that Cu2þ ions are present in the isolated form in the Cu/MCM-
41-S. Very differently, both the Cu/MCM-41-I and the Cu/
MCM-41-M show a resolvable shoulder absorption to a different
extent between 275 and 350 nm besides the one at ca. 225 nm. The
absorption was attributed to the charge transfer between cluster
Cu2þ and oxygen in [Cu-O-Cu]n surface species,27 indicating
the presence of the extra-framework copper oligomers or the
aggregated copper oxide clusters in the Cu/MCM-41-M and Cu/
MCM-41-I samples. On the basis of the intensity of the absorp-
tion, the amount of oligonuclear Cu clusters in the Cu/MCM-41-I
is more than the Cu/MCM-41-M. In addition, a very broad
absorption in about 400-800 nm, attributing to the d-d transi-
tion of Cu2þ in the pseudo-octahedral ligand oxygen environ-
ment,28,29 is markedly observed for the Cu/MCM-41-M sample,
indicating the presence of CuO particles. As for the Cu/MCM-41-
H, its UV-vis DRS spectrum is similar to that of Cu/MCM-41-S,
(25) Komatsu, T.; Nunokawa, M.; Moon, I. S.; Takahara, T.; Namba, S.;
Yashima, T. J. Catal. 1994, 148, 427.
(26) Schoonheydt, R. A. Catal. Rev.;Sci. Eng. 1993, 35, 129.
(27) Prasad, M. R.; Kamalakar, G.; Kulkarni, S. J.; Raghavan, K. V. J. Mol.
Catal. A 2002, 180, 109.
(28) Marion, M. C.; Garbowski, E.; Primet, M. J. Chem. Soc., Faraday Trans.
1990, 86, 3027.
(29) Shimokawabe, M.; Takezawa, N.; Kobayashi, H. Appl. Catal. 1982, 2, 379.
Langmuir 2010, 26(2), 1362–1371
Article
but the trailing toward higher wavelength indicates the presence
of a few oligonuclear Cu clusters.
3.1.3. In Situ IR Spectroscopy of NO Adsorption. The Cu-
oxo species in the four Cu/MCM-41 samples are further identified
by infrared spectroscopy using NO as probe molecule. Figure 5
demonstrates the IR spectra of NO adsorption at room tempera-
ture. All of the spectra exhibit two main bands at 1885 and ca. 1630
cm-1. On the basis of the literature,30-32 the band at 1885 cm-1 is
confessedly ascribed to Cu2þ-NO, while the band at ca. 1630
cm-1 is assigned to bridged bidentate nitrate species Cu2þ-
O-NO-O-Cu2þ. The formation of nitrate species is due to the
equilibrium characteristic of NO: 3NO T NO2 þ N2O, which is
shifted toward the right upon increasing pressures. No difference in
the IR spectra in the region 1750-1950 cm-1 is observed for these
four samples, whereas the IR spectra in the range of 1450-1750
cm-1 show some significant differences. (1) The band at ca. 1630
cm-1 is decreased in intensity in the order of Cu/MCM-41-M >
Cu/MCM-41-I > Cu/MCM-41-H. The generation of bridged
bidentate nitrate [Cu2þ-O-NO-O-Cu2þ] species (IR band at
1630 cm-1) upon NO adsorption requires the presence of cationic
metal pairs. It implies the presence of the oligonuclear copper
cluster in the three samples and that its amount deceases in the
same order, as seen from the UV-vis DRS spectrum in Figure 4.
In contrast, for Cu/MCM-41-S the band occurs at 1620 cm-1
rather than at 1630 cm-1, indicating that its copper states are
different from that of other three samples. (2) Two bands at 1578
and 1620 cm-1, belonging to monodentate [Cu2þ-O-NO2] and
chelating bidentate [Cu2þ-O2N-O] nitrate species formed as a
result of NO2 adsorption on isolated copper-oxygen species,
respectively,9a,33 are clearly observed upon NO adsorption on
the Cu/MCM-41-S sample (Figure 5a), while one band occurs at
1560 cm-1 is observed upon NO adsorption on the Cu/MCM-41-
H sample (Figure 5c). The difference in the IR spectra may be
originated from the different local structures of isolated copper
species dependent on the preparation method. Isolated copper
species in the Cu/MCM-41-S sample are absolutely exposed on the
surface, whereas a majority of isolated copper ions in the Cu/
MCM-41-H sample may be buried in the framework of MCM-41.
The wide band at about 1508-1490 cm-1 has been rarely reported
for other copper-containing materials, which can be related to
special structure of copper species in our sample. The assignment
of this band is controversial in the literature. We speculate that it
maybe belong to N-O stretches in nitrito (-O-N-O) or (-NO2)
complex coordinated to Cu2þ, based on the wavenumber of IR
absorption.9a These results are in good agreement with the UV-vis
DRS results reported above.
3.1.4. TPR Analysis. Temperature-programmed reduction
(TPR), containing some information about the surface structure
of the catalysts, has been extensively applied to the characteriza-
tion of reducible catalysts including metal and metal oxide system.
It is especially suitable for studying highly dispersed systems with
low loading. According to the literature,34,35 the following reduc-
tion processes can be considered:
CuO þ H2 f Cu0 þ H2 O
ðH2 -TPR peak in the 440-480 K rangeÞ ðIÞ
(30) London, J. W.; Bell, A. T. J. Catal. 1973, 31, 32.
(31) Hadjiivanov, K.; Kn€ozinger, H. Phys. Chem. Chem. Phys. 2001, 3, 1132.
(32) Giamello, E.; Murphy, D.; Magnacca, G.; Morterra, C.; Shioya, Y.;
Nomura, T.; Anpo, M. J. Catal. 1992, 136, 510.
(33) Ziozek, M.; Sobczak, I.; Nowak, I.; Daturi, M.; Lavalley, J. C. Top. Catal.
2000, 11/12, 343.
(34) Shanbhag, G. V.; Joseph, T.; Halligudi, S. B. J. Catal. 2007, 250, 274.
(35) Richter, M.; Fait, M. J. G.; Eckelt, R.; Schreier, E.; Schneider, M.; Pohl,
M.-M.; Fricke, R. Appl. Catal., B 2007, 73, 269.
DOI: 10.1021/la902436s 1365
Article Zhang et al.

Figure 3. HRTEM images of (a) Cu/MCM-41-S, (b) Cu/MCM-41-H, (c) Cu/MCM-41-I, and (d) Cu/MCM-41-M.

540-670 K is an indicative of the two-step reduction of isolated

Figure 4. UV-vis DRS spectra of samples (a) Cu/MCM-41-I, (b)
Cu/MCM-41-H, (c) Cu/MCM-41-S, and (d) Cu/MCM-41-M.
isolated:
1 3.2. Catalytic Activity for Phenol Hydroxylation.
Cu2þ þ H2 f Cuþ þ Hþ ð>480 KÞ ðIIÞ
2
1 catalysts prepared by different methods, we selected the Cu/
Cuþ þ H2 f Cu0 þ Hþ ð>600 KÞ ðIIIÞ
2 MCM-41-S sample as a representative catalyst to examine the
Reactions I and II occur at lower temperature than reaction III.
As shown in Figure 6, all of the TPR of samples occurs in the
temperature range of 400-700 K. The low-temperature peak at
482 K may be due to reduction of the copper-oxygen phase
(not necessary CuO). The two reduction peaks at 480-540 and
Cu2þ species. Two reduction peaks at higher temperature are
observed for both Cu/MCM-41-S and Cu/MCM-41-H, of which
the one at low temperature may be corresponding to the reduction
of Cu2þ to Cuþ and the one at the high temperature may to the
reduction of Cuþ to metallic copper. It suggests that the majority
of copper species in the Cu/MCM-41-S and Cu/MCM-41-H are
presented as highly dispersed isolated Cu2þ species. An extremely
minor amount of copper clusters may coexist. The shift to higher
temperature of the two-step reduction in the sample Cu/MCM-
41-H may be because of the incorporation of the copper ions to
the framework of support. As for the Cu/MCM-41-I and Cu/
MCM-41-M samples, only one main reduction peak appears at
the low temperature and a shoulder peak appears at the high
temperature, which are comparable with the TPR result of pure
CuO reported in the literature.36 This indicates that large CuO
clusters are predominant, while the isolated Cu2þ species may
be in a minor proportion, in the Cu/MCM-41-I and Cu/MCM-
41-M.
3.2.1. Effect of the Reaction Conditions. Prior to comparison
of catalytic performance of the four copper-containing MCM-41
effect of various factors including solvent, phenol/H2O2 molar
ratio, and reaction temperature on phenol hydroxylation, in order
(36) W€ollner, A.; Lange, F.; Schmelz, H.; Kn€ozinger, H. Appl. Catal., A 1993,
94, 181.

1366 DOI: 10.1021/la902436s Langmuir 2010, 26(2), 1362–1371

Zhang et al.
Figure 5. FT-IR spectra of (a) Cu/MCM-41-S, (b) Cu/MCM-41-
I, (c) Cu/MCM-41-H, and (d) Cu/MCM-41-M after adsorption of
NO at room temperature.
Figure 6. TPR profiles of (a) Cu/MCM-41-S, (b) Cu/MCM-41-H,
(c) Cu/MCM-41-I, and (d) Cu/MCM-41-M.
to acquire optimal reaction conditions and gain insight into the
difference in the phenol hydroxylation activity of these catalysts.
Table 2 lists the change of phenol hydroxylation behaviors
with increasing phenol/H2O2 molar ratio in water at 333 K. As
increasing phenol/H2O2 ratio, the phenol conversion and the
CAT/HQ ratio remarkably decrease, while the selectivity of main
products CAT and HQ notably increases. Moreover, the selec-
tivity to BQ is low and almost unchanged with increasing phenol/
H2O2 molar ratio. For comparison purposes, the phenol/H2O2
ratio of 1:1 is used in all of the later experiments.
Figure 7 shows the influence of solvent on phenol hydroxyla-
tion at 333 K. It can be seen that the Cu/MCM-41-S sample is
almost inactive in acetone and ethanol, and less active in acet-
onitrile, within 6 h of reaction. When water is used as solvent
instead of the organic compounds, the phenol conversion is close
to 38%, and the CAT and HQ selectivity are 39% and 26%,
respectively. Apparently, water is the best solvent for the copper-
catalyzed phenol hydroxylation, probably because water as
solvent is advantageous to the activation of H2O2 over copper
active sites.
Figure 8 shows the effect of reaction temperature on the phenol
hydroxylation in water solution. It is observed that as increasing
reaction temperature from 313 to 353 K, the phenol conversion
gradually increases from 15.5% to 49.0%, while the BQ selectivity
gradually decreases from 10% to ca. 1.3%. For two main
products CAT and HQ, the selectivity increases gradually with
increasing temperature from 313 to 333 K, but they slightly
Langmuir 2010, 26(2), 1362–1371
Article
Table 2. Effect of Phenol/H2O2 Molar Ratios on the Conversion of
Phenol over Cu/MCM-41-Sa
phenol/ phenol CAT HQ BQ CAT/
H2O2 conversion selectivity selectivity selectivity HQ
molar ratio (%) (%) (%) (%) ratio
1:1 37.9 39.2 26.1 2.8 1.5
2:1 28.9 42.9 30 2.4 1.3
3:1 17.6 45.2 39.7 2.0 1.14
a
Reaction conditions: water 20 mL, catalyst 50 mg, 333 K, reaction
time 6 h.
decrease with further increasing temperature. This indicates that
the increase in reaction temperature in the range of 313-353 K
can enhance the phenol conversion and reduce the BQ selectivity.
But higher temperature is deleterious to the formation of CAT
and HQ which may be caused by the deep oxidation of these
products. Therefore, the optimal temperature that may be usable
for comparison of catalytic activity of these catalysts for this
catalytic reaction is 333 K.
3.2.2. Comparison of the Catalytic Behaviors of Four Cu/
MCM-41 Samples. Catalytic activities of four Cu/MCM-41
samples for phenol hydroxylation were determined in the water
solution with phenol/H2O2 ratio 1:1 at 333 K. Figure 9 shows the
conversion of phenol and the yields of CAT, HQ, and BQ as a
function of reaction time. The corresponding data during 6 h of
reaction, including phenol conversion, product selectivity, and
H2O2 availabilities, are summarized in Table 3. The nude MCM-
41 is also tested to be inactive for phenol hydroxylation. For the
four copper-contained MCM-41 catalysts, the phenol conver-
sions decrease in the order of Cu/MCM-41-S > Cu/MCM-41-H
> Cu/MCM-41-I > Cu/MCM-41-M. CAT, HQ, BQ, and black
tarry compounds are formed in liquid phase. Although the total
selectivity of the three products (SCAT þ SHQ þ SBQ) is compar-
able for these four catalysts (slightly higher for Cu/MCM-41-M),
the selectivity to single product seems to be dependent on the
preparation method of the catalysts. It is interesting to note that
the selectivity to BQ decreases in the order of Cu/MCM-41-M >
Cu/MCM-41-I > Cu/MCM-41-H > Cu/MCM-41-S; the selec-
tivity to HQ increases in the inverse order, and the selectivity to
CAT is almost comparable over all samples. Distinctly, the Cu/
MCM-41-S catalyst prepared by the SOMC method shows the
highest phenol conversion, the highest selectivity to HQ, and the
highest H2O2 availability, among all catalysts. The Cu/MCM-
41-M catalyst alone causes substantive byproduct BQ. This
indicates the dependence of the phenol hydroxylation activity
on the preparation method of Cu/MCM-41.
3.3. Roles of Copper Sites in Phenol Hydroxylation. The
results in sections 3.1 and 3.2 show that the chemical states of Cu
species and the catalytic behaviors of Cu/MCM-41 samples
depend distinctly on the preparation method. Isolated Cu2þ
species in the Cu/MCM-41-S sample prepared by SOMC route
are predominant. The conclusion is strongly supported by the
experimental results as follows: (1) the UV-vis DRS spectrum
shows only one strong absorption peak centered at ∼225 nm
(Figure 4c), (2) FTIR of NO adsorption displays the band at 1885
cm-1 ascribed to Cu2þ-NO vibration and another two bands at
1578 and 1620 cm-1 belonging to monodentate and bidentate
nitrate species formed on isolated copper-oxygen species, and (3)
the two-step reduction of the Cu/MCM-41-S sample in the H2-
TPR, and no copper oxide clusters is formed upon calcination at
773 K in air. In contrast to Cu/MCM-41-S, the Cu/MCM-41-M
sample contains predominantly copper oxide. Over the Cu/
MCM-41-H sample prepared by the hydrothermal method and
the Cu/MCM-41-I prepared by the impregnation method, copper
DOI: 10.1021/la902436s 1367
Article
Figure 7. Effect of solvent on conversion of phenol over Cu/
MCM-41-S. Reaction conditions: phenol/H2O2 molar ratio 1:1,
solvent 20 mL, catalyst 50 mg, 333 K, reaction time 6 h.
Figure 8. Effect of reaction temperature on the conversion of
phenol over Cu/MCM-41-S. Reaction conditions: water 20 mL,
catalyst 50 mg, reaction time 6 h.
is presented as both copper oxide clusters and isolated copper(II)
species. The amount of copper oxide clusters in the Cu/MCM-41-
I sample is higher than the Cu/MCM-41-H sample, as indicated
by the more intense absorption band at 320 nm in the UV-vis
DRS spectra. The amount of isolated copper species in the Cu/
MCM-41-H sample is higher than the Cu/MCM-41-I sample,
whereas these isolated copper species consist of two parts: isolated
copper species dispersed on the surface of MCM-41 and isolated
copper(II) species buried in the MCM-41 framework. In sum-
mary, the amount of isolated copper species in the four samples
with the almost same copper content decreases in the order of Cu/
MCM-41-S > Cu/MCM-41-H > Cu/MCM-41-I > Cu/MCM-
41-M, while the amount of copper oxide clusters increases in a
reversal order. The activity results in section 3.2 shows the phenol
conversion decreasing in the order of Cu/MCM-41-S > Cu/
MCM-41-H > Cu/MCM-41-I > Cu/MCM-41-M, which is in
good parallel with the amount of isolated copper species of them.
Therefore, it can be concluded that isolated species dispersed on
the surface of MCM-41 are catalytically active centers for phenol
hydroxylation.
As for the selectivity to product, the activity results in section
3.2 show that except for the Cu/MCM-41-M, other three samples
show the almost same selectivity to CAT. For the phenol hydro-
xylation reaction with H2O2, the formations of CAT and HQ are
thermodynamically parallel reactions; however, kinetically the
ortho-displacement of phenol with hydroxyl is more preponder-
ant than the para-displacement according to the quantum
1368 DOI: 10.1021/la902436s
Zhang et al.
optimizing computation.37 So, the higher selectivity to CAT can
result from the kinetic control. Noted that the selectivity to BQ is
increased in the order of Cu/MCM-41-S < Cu/MCM-41-H <
Cu/MCM-41-I < Cu/MCM-41-M; i.e., with increase in the
amount of copper oxide clusters, it is speculated that copper
oxide clusters are responsible for the formation of BQ. Interest-
ingly, the selectivity to HQ decreases with the increase in copper
oxide clusters, but the total selectivity to HQ and BQ is almost
constant and independent of catalyst. The formation of BQ is
evidently as a result of the oxidation of HQ.38 The results are
consistent with what was reported before that if the catalyst
contains isolated Cu ions, oxidation of benzene with the mixture
of N2O-H2O produces phenol with a selectivity as high as 88%,
but if copper oxide species present in the catalyst, the selectivity of
oxidation decreases to 65%.39 According to the analysis, for the
copper-catalyzed phenol hydroxylation, the phenol conversion is
decided to the amount of isolated copper-oxo, while the selec-
tivity to CAT and HQ is controlled by the inherent kinetics
nature, but the copper oxide species present in catalyst lead to the
transformation of a part of HQ to BQ and therefore to the
increase in the CAT/HQ ratio.
Moreover, the H2O2 efficiencies of the four catalysts represent
the same order as phenol conversion, i.e., Cu/MCM-41-S > Cu/
MCM-41-H > Cu/MCM-41-I > Cu/MCM-41-M. The Cu/
MCM-41-M sample containing the most copper oxide clusters
exhibits the lowest utilization rate of H2O2 (4.5%). The existence
of copper oxide clusters also leads to the low efficiency. A similar
observation was reported by Bahranowski et al.,13 who suggested
that the clustered copper species or copper oxide are inactive in
the selective oxidation but accelerates the nonproductive decom-
position of hydrogen peroxide.
3.4. Possible Mechanism for Copper-Catalyzed Phenol
Hydroxylation. 3.4.1. Analysis of Kinetics. In order to
reveal the reason for high activity of isolated copper-oxo species,
the kinetic analysis for the catalytic process is necessary. Accord-
ing to the classical Langmuir-Hinshelwood model, i.e., both
phenol (PH) and H2O2 (HP) are adsorbed on the active site and
the surface reaction between adsorbed PH and HP is rate-limiting
step. The following rate expression is obtained:
dCPH kKPH KPH CPH CHP
- ¼ ð1Þ
dt ð1þKPH CPH þKHP CHP Þ2
where KPH and KHP are the adsorption constants of PH and HP,
CPH and CHP are the concentrations of PH and HP in solution,
and k is the rate constant of PH. In the case of weak adsorption of
both PH and HP on the catalyst, eq 1 can be simplified to the
following equation:
dCPH
- ¼ kKPH K HP CPH CHP ð2Þ
dt
If CPH = CHP, then
dCPH
- ¼ kKPH K HP CHP 2 ¼ k 0 CHP 2 ð3Þ
dt
In such a case, the reaction follows second class kinetics
1=CPH ¼ k 0 t þ BðconstantÞ ð4Þ
(37) Zhang, J. M.; Feng, H. S. Chem. React. Eng. Technol. 2004, 20, 239.
(38) Wang, J.; Park, J. N.; Wei, X. Y.; Lee, C. W. Chem. Commun. 2003, 628.
(39) Bahidsky, M.; Hronec, M. Catal. Today 2005, 99, 187.
Langmuir 2010, 26(2), 1362–1371
Zhang et al. Article

Figure 9. Comparison of the catalytic performance of four catalysts at 333 K in water (phenol/H2O2 molar ratio 1:1): (A) conversion of
phenol, (B) yield of catechol, (C) yield of hydroquinone, (D) yield of benzoquinone.

Table 3. Catalytic Performances of the Copper-Modified MCM-41 for the Hydroxylation of Phenola
product distribution

catalysts Xphenol (%) SCAT SHQ SBQ Sproduct (%) H2O2,eff (%) CAT/HQ

MCM-41 0.0 0.0 0.0 0.0 0.0 0.0

Cu/MCM-41-M 4.2 40.1 19.2 21.6 80.9 4.5 2.09
Cu/MCM-41-I 22.4 36.6 21.2 9.3 67.1 14.6 1.73
Cu/MCM-41-H 25.0 39.9 23.0 7.9 70.8 17.8 1.73
Cu/MCM-41-S 37.9 39.2 26.1 2.8 68.1 27.3 1.50
a
Reaction conditions: amount of catalyst 50 mg, volume of solvent (H2O) 20 mL, H2O2/phenol molar ratio 1:1, temperature 333 K, reaction time 6 h.

Figure 10A shows the change in the concentration of phenol with
reaction time at different temperature, which is determined with
the Cu/MCM-41-S as catalyst. Figure 10B is a plot of 1/CPH vs t.
It can be seen that the change of 1/CPH with reaction time t is
nonlinear, which indicates that the above hypothesis is false.
If one of reactants (assuming H2O2) has very low adsorption on
the surface and another one (phenol) has very high adsorption,
the following equation is obtained from 1:
dCPH CHP
- ¼ k0 ð5Þ
dt CPH
where k0 = kKPHKHP. As CPH/CHP molar ratio = R or CHP =
CPH/R, then formula 5 is changed into
-r0 ¼ k 0 R -1 ð6Þ
When the reaction time t = 0 min, the concentration of PH keeps
constant and only the dosage of HP is changed (CPH = C0,PH =
constant). The initial reaction rate r0 would follow eq 6 and
should be linearly correlative with the reciprocal value of PH/HP
molar ratio. Parts A and B of Figure 11 show the concentration of
phenol as a function of CPH/CHP ratio and the corresponding
r0-R-1 plot, respectively. The linear correlation shown in
Figure 11B indicates that the reaction rate r0 is proportional to
CHP/CPH molar ratio. As such, we assume that phenol has very
low adsorption on active copper sites and H2O2 has very high
adsorption; the initial reaction rate r0 also follows eq 6. In any
cases, phenol inhibits the reaction at all concentrations. We can
therefore draw one conclusion that the conversion is controlled in
fact by the concentration of H2O2 in solution.
3.4.2. Proposed Reaction Mechanism of Hydroxylation of
Phenol with H2O2. The reaction mechanism for the hydroxyla-
tion of phenol employing copper ion has been previously pro-
posed on the basis of the chemical similarity between copper and
iron.9b,11 The reaction pathway was regarded as involving hydro-
xyl radical, where the interaction of transition metal sites with
hydrogen peroxide yields HO• and HO2• species via a redox
mechanism. However, in our experiment of phenol hydroxyla-
tion, no induction period is observed (induction period is a unique
feature of the radical-type mechanism, i.e., the reaction can be
initiated after undergoing an induction period40). Furthermore, it
(40) (a) Choi, J. S.; Yoon, S. S.; Jang, S. H.; Ahn, W. S. Catal. Today 2006, 111,
280. (b) Long, J.; Wang, X.; Ding, Z.; Zhang, Z.; Lin, H.; Dai, W.; Fu, X. J. Catal. 2009,
264, 163.

Langmuir 2010, 26(2), 1362–1371 DOI: 10.1021/la902436s 1369

Article Zhang et al.

Figure 11. (A) Change of phenol concentration as a function of

Figure 10. Change in the concentration of phenol with increasing reaction time. (B) Overall reaction rate as a function of phenol/
reaction time and reaction temperature. Reaction conditions: H2O2 ratio.
water 20 mL, catalyst 50 mg, phenol/H2O2 molar ratio 1:1.

is interesting to note that the conversion of phenol increases with

increasing reaction temperature. These experimental results are
distinctly different from those in the hydroxylation of phenol with
H2O2 in the presence of Fenton’s reagent (Fe2þ ions), which is
known to proceed by a free radical mechanism.41 The reaction
mechanism for the phenol hydroxylation over copper-based
catalysts needs to be further studied.
Figure 12 shows the determination result of hydroxyl radicals
in the reaction system. When DMPO is added to the solution
containing Cu/MCM-41-S and H2O2, a 4-fold peak with the
intensity ratio of 1:2:2:1 which is the typical and characteristic
EPR signal of DMPO-OH adduct is observed. However, after
adding phenol, the EPR signal is quenched. This observation is in
agreement with the literature,42 indicating that the OH of adduct
is transferred from DMPO to phenol and that these OH radicals Figure 12. ESR spectra of (Cu/MCM-41-S)-H2O2-DMPO
are important intermediates in the hydroxylation reaction over mixture after addition of phenol (A) and without addition of
phenol (B).
copper-based catalysts.
The above kinetic analysis shows that the copper-catalyzed reacts with the CuOOH intermediate to form products. It is
phenol hydroxylation with H2O2 is controlled by the concentra- certain that the formed OH radical during the decomposition of
tion of H2O2 in solution. Moreover, the phenol hydroxylation H2O2 can also react with phenol to produce HQ and CAT.
exclusively at the o- and p-positions suggests reaction to be an Such an intermediate species is very similar to that in the TS-1-
electrophilic substitution, probably involving HOþ species. We catalyzed reaction as described in Scheme 1D. In the case
now envisage the reaction to take place as described in Scheme 1 of phenol hydroxylation over TS-1 catalyst, it is well-known
(pathway 1). The interaction of H2O2 with copper-oxo species that there is a strong interaction between TS-1 and aqueous
has been reported43 to produce a CuOOH intermediate, as H2O2 to form the titanium-peroxo compounds.44 It is the
described in Scheme 1A. The CuOOH intermediate can react actual oxygen donors in the TS-1-catalyzed reaction. In methanol
further with H2O2 to form OH radical. Phenol instead of H2O2 or H2O medium, the titanium-peroxo species interacts with
solvent molecules to form a five-ring intermediate described
(41) Kurian, M.; Sugunan, S. Chem. Eng. J. 2006, 115, 139. as Scheme 1C. But in acetone or acetonitrile medium, the
(42) Sun, J.; Meng, X.; Shi, Y.; Wang, R.; Feng, S.; Jiang, D.; Xu, R.; Xiao, F. S.
J. Catal. 2000, 193, 199.
(43) Elizarova, G. L.; Matvienko, L. G.; Ogorodnikova, O. L.; Parmon, V. N.
Kinet. Catal. 2000, 41, 332. (44) Clerici, M. G.; Ingallina, P. J. Catal. 1993, 140, 71.

1370 DOI: 10.1021/la902436s Langmuir 2010, 26(2), 1362–1371

Zhang et al.
Scheme 1. Possible Pathway of the Copper-Catalyzed Phenol
Hydroxylation
titanium-peroxo species exists in the form as Scheme 1D. It is
interesting to note that in acetonitrile the Cu/MCM-41 sample
exhibits a low conversion (ca. 9.2%) and a high selectivity toward
BQ, and no HQ is formed. In ethanol and acetone, it is inactive,
but they are the best solvents over TS-1 catalyst.45 Xiao42 and
Wu46 reported also that over the catalysts of Cu-Bi-V-O and
CuAlCO3-LTLcs the change in solvents leads to the large
difference in conversion. The difference in solvent influence
maybe is mainly originated from the different coordination ability
of copper and titanium ions with oxygen-contained solvents, such
as alcohol and acetone. In ethanol or acetone medium, oxygen
atom of solvents can be strongly coordinated to copper active sites
(45) Thangaraj, A.; Kumar, R.; Ratnasamy, P. J. Catal. 1991, 131, 294.
(46) Zhu, K. Z.; Liu, C. B.; Ye, X. K.; Wu, Y. Appl. Catal., A 1998, 168, 365.
(47) Kubota, M.; Yamamoto, K. Bull. Chem. Soc. Jpn. 1978, 51, 2909.
Langmuir 2010, 26(2), 1362–1371
Article
to form stable alkoxo-copper complexes,47 which can destroy the
reactive intermediate formation and thus block the proceeding of
the reaction. Product HQ can also coordinate with copper sites
and consequently undergoes further oxidation to BQ. BQ is
further oxidized to tar materials. At high reaction temperature,
the overoxidation of products proceeds more easily. It may be the
main reason for the high content of BQ in products on the copper-
catalyzed reaction.
It is likely that there exists another path for the copper-
catalyzed phenol hydroxylation in water (pathway 2). Phenol is
adsorbed first on copper sites to form phenoxo-copper com-
plex48 and subsequently oxidized to product CAT by activated
H2O2. Distinctly, in free-oxygen solvent, acetonitrile, the hydro-
xylation of phenol mainly proceeds by this pathway.
4. Conclusions
Dependent on the preparation methods, the Cu/MCM-41
samples contain the different states of copper species, including
isolated copper species and copper oxide clusters. The amount of
isolated copper species decreases in the order of Cu/MCM-
41-S > Cu/MCM-41-H > Cu/MCM-41-I > Cu/MCM-41-M,
while the amount of copper oxide clusters increases in a reversal
order. The conversion of phenol is increased with increase in the
amount of isolated copper species for these samples. It is
suggested that the highly dispersed and isolated species on
Cu/MCM-41 surface are catalytically active centers of phenol
hydroxylation, while the presence of nonisolated Cu2þ clusters or
oxide accelerates the deep oxidation of primary product HQ and
lead to decrease of its selectivity.
Cu/MCM-41-S catalyst with the most excellent catalytic per-
formance, which contained the preponderant amount of surface
isolated copper-oxo species, can be acquired by the SOMC
strategy. The kinetic analysis shows that phenol hydroxylation
with H2O2 in water on the Cu/MCM-41 is a quasi-first-order
reaction based on the Langmuir-Hinshelwood adsorption me-
chanism, in which the surface reaction between adsorbed PH and
HP is the rate-limiting step. The catalytic results are distinctly
different from those in the hydroxylation of phenol with H2O2 in
the presence of Fenton’s reagent (Fe2þ ions), which is known to
proceed by a free radical mechanism. An ionic-type mechanism
similar to the TS-1-catalyzed reaction is proposed.
Acknowledgment. Financial support of this work by the
National Natural Science Foundation of China (Grants
20673020 and 20873022), National Basic Research Program of
China (973 Program No. 2007CB613306), and National High
Technology Research and Development Program of China (863
Program No. 2008AA06Z326) is gratefully acknowledged.
(48) Wilkenh€oner, U.; Langhendries, G.; Laar, F.; Baron, G. V.; Gammon, D.
W.; Jacobs, P. A.; Steen, E. J. Catal. 2001, 203, 201.
DOI: 10.1021/la902436s 1371