Article

pubs.acs.org/IC

Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in

Air with High Conversion and Selectivity
Gong-Jun Chen,* Jing-Si Wang, Fa-Zheng Jin, Ming-Yang Liu, Chao-Wei Zhao, Yan-An Li,
and Yu-Bin Dong*
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for
Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong
Normal University, Jinan 250014, P. R. China
*
S Supporting Information
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ABSTRACT: A new 3D porous Cu(II)-MOF (1) was

synthesized based on a ditopic pyridyl substituted diketonate
ligand and Cu(OAc)2 in solution, and it features a 3D NbO
motif which is determined by the X-ray crystallography.
Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-
MOF (2) was prepared based on 1 via solution impregnation,
and its structure was confirmed by HRTEM, SEM, XRPD, gas
adsorption−desorption, and ICP measurement. 2 exhibits
excellent catalytic activity (conversion, 93% to >99%) and
selectivity (>99% to benzaldehydes) for various benzyl alcohol
substrates (benzyl alcohol and its derivatives with electron-
withdrawing and electron-donating groups) oxidation reac-
tions in air. In addition, 2 is a typical heterogeneous catalyst,
which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its
catalytic activity and selectivity.

■ INTRODUCTION
Selective catalytic oxidation of benzyl alcohols to the
corresponding benzaldehydes is one of the most important
issues in modern synthetic chemistry and chemical industry.
Hitherto, a great deal of research effort has been devoted to
finding novel and efficient catalysts for this type of reaction.1−3
Over the past decades, nanoparticles (NPs) have been
intensively pursued in a wide range of important catalytic
processes owing to their large surface area-to-volume ratios. For
example, Cu,4−6 Ru,7 Pd,8−11 Au,12−16 and Au−Pd alloy
NPs17−22 were demonstrated to be the efficient species for
alcohol oxidation. Among these NPs, Pd NPs have attracted
more attention owing to their excellent catalytic perform-
ance.23,24 Although Pd NPs show good catalytic behaviors for
many useful reactions under reaction conditions, Pd NPs are
prone to aggregation and form Pd black because of their high
surface energy.25 Therefore, the immobilization of Pd NPs in
porous supports is regarded as one of the most practical ways to
address this problem. So far, various inorganic materials, such as
CeO226−28 SiO2,29−34 ZrO2,35 and porous carbon,36−40 and
organic materials, such as polystyrene,41 amphiphilic resin,42
and copolymers,43 have been utilized as supports to incorporate
Pd NPs. However, the inorganic−organic hybrid materials as a
heterogeneous supporting matrix for metal NPs have not yet
attracted much attention.
Metal−organic frameworks (MOFs) are a new class of
inorganic−organic hybrid materials composed of inorganic
metal nodes and organic linkers. The structurally ordered and
molecularly tunable features make them an ideal scaffold to
integrate various functional moieties. Their incorporation
between distinct individual doped species will endow such
composite materials with great potential applications, especially
in the catalytic field. High surface areas, controllable pore sizes,
and tunable pore environments of MOFs would facilitate the
MOF supports to entrap various NPs.44−50 In addition, the
crystalline porous structure together with heteroatom donors
on MOFs would effectively limit the aggregation and migration
of small active catalytic NPs in the solid state, consequently,
making the NPs involved NPs@MOFs catalysts to be highly
active and reusable.51,52
In this contribution, we report the synthesis and structure of
a new porous Cu(II)-MOF (1) and its Pd NPs-embedded
composite Pd@Cu(II)-MOF (2) via solution impregnation
(Scheme 1). Notably, 2 can be a highly active catalyst to
promote the aerobic oxidation of various benzylic alcohols in
air with high conversion rates (93% to >99%) and chemo-
selectivity (aldehydes, >99%).53 Moreover, the catalyst can be
easily recovered and reused due to its heterogeneous catalytic
nature.
Received: December 25, 2015
Published: March 9, 2016

© 2016 American Chemical Society 3058 DOI: 10.1021/acs.inorgchem.5b02973

Inorg. Chem. 2016, 55, 3058−3064
Inorganic Chemistry
Scheme 1. Synthesis of Cu(II)-MOF (1) and Pd@Cu(II)-
MOF (2)a
a
The photographs of 1 and 2 are inserted.
■
EXPERIMENTAL SECTION
Materials and Instrumentation. The reagents and solvents
employed were commercially available and used without further
purification. Ligand (HL = 4,4,4-trifluoro-1-(4-(pyridin-4-yl)phenyl)-
butane-1, 3-dione) was synthesized according to our reported
procedure.54 Elemental analyses for C, H, and N were obtained on
a PerkinElmer analyzer model 240. The powder diffractometer (XRD)
patterns were collected by a D8 ADVANCEX-ray with Cu Kα
radiation (λ = 1.5405 Å). Electron spin resonance (ESR) spectra were
obtained from a Bruker A300-10/12/S-LC. Infrared (IR) samples were
prepared as KBr pellets, and spectra were obtained in the 400−4000
cm−1 range using a PerkinElmer 1600 FTIR spectrometer. The total
surface areas of the catalysts were measured by the BET (Brunauer−
Emmett−Teller) method using carbon dioxide adsorption at 195 K.
This was done by the Micromeritics ASAP 2000 sorption/desorption
analyzer. ICP-LC was performed on an IRIS Interpid (II) XSP and
NU AttoM. HRTEM (high-resolution transmission electron micros-
copy) analysis was performed on a JEOL 2100 electron microscope at
Figure 1. (a) Simulated and measured XRPD patterns of 1. (b) Coordination sphere of Cu(II) in 1. (c) Single cubic unit of 1. (d) 3-fold
interpenetrating NbO-net of 1 with 1D channel down the crystallographic c axis.
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an operating voltage of 200 kV. Scanning electron microscopy (SEM)
analysis was performed on a Gemini Zeiss Supra 55. Gas
chromatography (GC) analysis was performed on an Agilent 7890B
GC.
X-ray Crystallography. Diffraction data for the complex were
collected at 293(2) K, with a Bruker Smart 1000 CCD diffractometer
using Mo−Kα radiation (λ = 0.71073 Å) with the ω-2θ scan
technique. An empirical absorption correction was applied to raw
intensities.55 The structure was solved by direct methods (SHELX-97)
and refined with full-matrix least-squares technique on F2 using the
SHELX-97.56 The hydrogen atoms were added theoretically, and
riding on the concerned atoms and refined with fixed thermal factors.
The details of crystallographic data and structure refinement
parameters are summarized in Table S1. The selected bonds lengths
and angles for 1 are summarized in Table S2. CCDC 1443366
contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_requeat/
cif.
Synthesis of Cu(II)-MOF (1). A solution of Cu(OAc)2 (2.4 mg,
0.01 mmol) in MeOH (1 mL) was layered onto a solution of HL (4.8
mg, 0.02 mmol) in CH2Cl2 (2 mL). The solutions were left for about 3
days at room temperature, and compound 1 was obtained as bright
green crystals (Scheme 1). Yield, 75%. IR (KBr pellet, cm−1):
3068(w), 1607 (s), 1569 (s), 1536 (s), 1458 (m), 1299 (m), 1250
(m), 1193 (s), 1145 (s), 1073 (m), 787 (s), 701 (s). Elemental
analysis (%) calcd for C96H54Cu3F18N6O18 (desolvated): C, 54.59, H,
2.58, N, 3.98; Found: C, 54.48, H 2.71, N 3.96.
Synthesis of Pd@Cu(II)-MOF (2). 1 (100 mg, 0.02 mmol) was
added to a CH3CN (10 mL) solution of palladium nitrate (90 mg, 0.2
mmol). The mixture was stirred for 1 h at room temperature. The
resulting solid was isolated by centrifugation and washed with CH2Cl2.
The obtained green-yellow crystalline solids (Figure S1) were mixed
with NaBH4 (50 mg, 1.3 mmol) in water (4 mL), and the mixture was
stirred for an additional 15 h to afford 2 as a dark brown solid (Scheme
1). The obtained crystalline solids were washed with water and EtOH
and dried in air. ICP measurement indicated that the encapsulated
amount of Pd NPs in 2 is up to 5.1% (mass fraction).
The General Catalytic Reaction Procedure. The catalytic
activity of 2 for the aerobic oxidation of benzyl alcohol to
benzaldehyde was tested in air. A mixture of benzyl alcohols (25 μL,
0.21 mmol), 2 (20 mg, 5% Pd), and xylene (3.0 mL) was stirred at 130
°C for 25 h in the air (monitored by gas chromatography (GC)) to
afford the corresponding aldehydes. The conversion and selectivity
were determined by GC. 2 was recovered by centrifugation. After it
was washed with ethanol (3.0 mL × 3) and dichloromethane (3.0 mL
DOI: 10.1021/acs.inorgchem.5b02973
Inorg. Chem. 2016, 55, 3058−3064
Inorganic Chemistry
Figure 2. Left: SEM and elemental maps of Cu and Pd images of 2. Simulated and measured XRPD patterns of 2. Right: HRTEM image of 2.
Figure 3. Left: CO2 adsorption isotherms for Cu(II)-MOF (1) and Pd@Cu(II)-MOF (2) at 195 K. Right: The pore widths of 1 and 2 are centered
at 1.3 and 0.9 nm, respectively.
× 3) and dried at 90 °C in vacuum, 2 was used in the next run under
the same reaction conditions.
Leaching Test. The solid catalyst Pd@Cu(II)-MOF (2) was
separated from the hot solution right after reaction for 5 h. The
reaction was continued with the filtrate in the absence of 2 for an
additional 15 h. No further increase in either the conversion of benzyl
alcohol or the selectivity of aldehyde was detected, which confirms that
the catalytically active sites for this oxidation reaction were located on
2.
■
RESULTS AND DISCUSSION
Synthesis and Structural Analysis of Cu(II)-MOF (1)
and Pd@Cu(II)-MOF (2). The combination of HL with
Cu(OAc)2 in a CH2Cl2/MeOH mixed solvent system to afford
1 ([Cu3(L)6]) as bright green crystals in 75% yield. Simulated
and measured XRPD patterns match each other very well,
indicating that 1 was obtained in pure phase (Figure 1a).
Compound 1 crystallizes in the hexagonal space group R3̅. Each
Cu(II) center in 1 adopts a 4 + 2 octahedral coordination
sphere (Figure 1b), in which two coplanar chelating β-diketone
units form the square (Cu−O distances of 2.107(3)−2.124(3)
Å), and the axial positions are occupied by two pyridyl N-
donors (Cu−N distance of 2.016(3) Å). As shown in Figure 1c,
octahedral Cu(II) centers are linked together by L to a 4-
connected 3D NbO network. The shortest opposite Cu(II)···
Cu(II) distance in a single cubic unit is 26.6139(4) Å. Notably,
1 is 3-fold interpenetrating, and the three sets of NbO
frameworks are displaced by ca. (1/3, 1/3, 1/3) relative to each
other so that the large hexagonal channels appear along the
crystallographic c axis (Figure 1d). The opposite Cu···Cu
distance in the channel is 22.9330(3) Å. All the fluorine atoms
on the framework face toward the center of the channels, and
the opposite F···F distance is 14.4423(3) Å. In addition, solvent
molecules are located in 1, and the encapsulated solvent
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molecules can be removed at 110 °C based on the TGA trace
(Figures S2 and S3). The desolvated sample of 1 is stable up to
ca. 200 °C (demonstrated by XRPD, Figure S4). The high
thermal stable feature of 1 would make it suitable to be a
catalyst support for uploading active NPs to promote organic
reactions at relative high temperature.
Palladium-embedded Pd@Cu(II)-MOF (2) was prepared by
the impregnation with the Pd(NO3)2 in CH3CN for 5 h,
yielding Pd(II)@Cu(II)-MOF (Scheme 1). The Pd NPs-loaded
Pd@Cu(II)-MOF (2) was obtained by the reduction of Pd(II)
@Cu(II)-MOF with NaBH4 in aqueous solution. The uploaded
amount of Pd, as determined by inductively coupled plasma
(ICP) measurement, is up to 5.1 wt %. Presumably, the
generated Pd NPs might be stabilized by the multitudinous F
atoms in the framework. The energy-dispersive X-ray spectrum
(EDS) measurement (Figure 2) shows that the uploaded
palladium homogeneously distributes in 2. In addition, the
structure of Cu(II)-MOF (1) remained intact after the Pd
uploading and no changes in the XRPD patterns were detected,
which supports that Cu(II)-MOF (1) was chemically stable
during the palladium reducing process (Figure 2). In addition,
the ESR spectra show that no valence state change of the
Cu(II) in Pd@Cu(II)-MOF (2) was observed after the
treatment by NaBH4 in aqueous solution under the reaction
conditions (Supporting Information, Figure S5).
To get a further insight into the structure of 2, high-
resolution transmission electron microscopy (HRTEM) was
used to investigate the dispersion and size distribution of the Pd
NPs in 2. HRTEM analysis revealed that the Pd NPs were
crystalline and highly dispersed with an average particle size of
ca. 2 nm (Figure 2). The lattice fringes had an interplanar
spacing of 0.24 nm, corresponding to 1/3 (4 2 2) fringes of
face-centered cubic (fcc) Pd.57
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Inorganic Chemistry
BET Surface Area Measurement of 1 and 2. In order to
investigate the BET surface area of Cu(II)-MOF (1) and Pd@
Cu(II)-MOF (2), gas adsorption−desorption experiment was
performed on 1 and 2. A N2 adsorption isotherm was first
measured, but it exhibits negligible uptake by the framework
even at low temperature. Such a phenomenon has been
observed for some MOFs.58 However, CO2 adsorption of 1 and
2 at 195 K revealed a typical type IV mode, showing pore
condensation with pronounced adsorption−desorption hyste-
resis (Figure 3). It indicates the existence of mesopores in 1;
meanwhile, 2 shows no adsorption−desorption hysteresis,
indicating that 2 is microporous. The surface areas of 1 and
2 are 1129.24 and 373.24 m2/g, respectively. The different
adsorption capacities and behaviors of 1 and 2 are clearly
caused by the Pd NPs doping. The mesopore size distribution
curve, calculated from Barrett−Joyner−Halenda analysis, shows
a narrow pore diameter distribution at ca. 1.3 nm and ca. 0.9
nm for 1 and 2, respectively (Figure 3), which is well consistent
with the single-crystal analysis of 1. Thus, most of the Pd NPs
might not be located inside the MOF cavity, as they are larger
than the pore size. Therefore, these Pd NPs are presumably
sandwiched in the crystallite matrix of Cu(II)-MOF (1) and
partly stabilized by F atoms on the framework.
Oxidation of Benzyl Alcohol in Air. Reaction Con-
ditions. The aerobic oxidation reactions (with 2, 5% Pd) of the
benzylic alcohols with different substituted groups in xylene
were carried out in air (monitored by GC). We found that the
temperature, solvent system, and reaction time are the key
parameters for this Pd@Cu(II)-MOF-catalyzed oxidation
reaction. The optimized reaction conditions are obtained
based on the benzyl alcohol oxidation in atmospheric air
(Table 1). The reaction temperature was first investigated for
Table 1. Oxidation of Benzyl Alcohol in Different Solvent
Systems at Different Temperaturesa
entry T (°C) solvent t (h) conv. (%) select (%)
1 25 xylene 25 0 0
2 70 xylene 25 15 >99
3 110 xylene 25 88 >99
4 130 xylene 25 95 >99
5 110 toluene 25 88 91
6 70 CH3CN 25 15 95
a (Figures S22 and S23).
Reaction conditions: air, benzyl alcohol (0.21 mmol), Pd@Cu(II)-
MOF (2) (5% Pd), solvent (3 mL).
the impact on the efficiency of oxidation reactions in air. As
shown in Table 1, upon increase of the reaction temperature
from 25 to 130 °C in xylene (entries 1−4), the conversion of
benzyl alcohol dramatically enhanced. Notably, >99% selectiv-
ity toward benzaldehyde was maintained during the temper-
ature increasing process. It should be noted that an excellent
yield (95%) was achieved when the reaction was carried out at
130 °C (Table 1, entry 4). However, the chemoselectivity to
benzaldehyde is still >99% at this temperature, which was
confirmed by GC analysis (Figures S6−S11). It, therefore,
appears that 130 °C is the optimum temperature for this
benzaldehyde oxidation reaction. In addition, we also
investigated the effect of the solvent system and found that
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xylene is the best solvent for this oxidation reaction in
atmospheric air. As shown in Table 1 (entries 5 and 6), the
reaction conversion and selectivity (to benzaldehyde) in
toluene (110 °C, 25 h, Figure S12) are 88% and 91%,
respectively. Meanwhile, the corresponding conversion and
selectivity in CH3CN (70 °C, 25 h, Figure S13) are 15% and
95%, respectively. Besides benzaldehyde, benzoic acid and an
unidentified species were also detected in entries 5 and 6 by
GC.
The conversion and the selectivity of benzyl alcohol to
benzaldehyde in xylene at different reaction times are shown in
Figure 4. The initial conversion of benzaldehyde is continu-
Figure 4. Reaction time examination (black line) and leaching test
(red line) for benzyl alcohol reaction catalyzed by 2. Reaction
conditions: air, Pd@Cu(II)-MOF (2) (5% Pd), benzyl alcohol (0.21
mmol), xylene (3 mL). The solid catalyst was filtrated from the
reaction solution after 5 h, whereas the filtrate was transferred to a new
vial and reaction was carried out under the same conditions for an
additional 15 h.
ously increased, and the maximum yield (95%) appeared at 25
h (Figures S14−S19). No more obvious changes in the
conversions can be detected after 25 h; the TON and TOF are
19 and 0.76 h−1. In order to gain insight into the heterogeneous
nature of 2, the hot leaching test was carried out. As indicated
in Figure 4, no further reaction took place without 2 after
ignition of the oxidation reaction at 5 h (Figures S20 and S21).
This finding demonstrated that no leaching of the catalytically
active sites occurs and that 2 exhibits a typical heterogeneous
catalyst nature (Figure 4). In addition, the catalytic activities of
Cu(II)-MOF (1) and treating it with NaBH4 without Pd NPs
as the catalysts for this oxidation reaction were also examined
under the same reaction conditions; however, the benzyl
alcohol conversions are only up to 16% and 15%, respectively
Recyclability Studies. Reusability of catalysts is very
important for industrial applications. The recyclability of 2
was tested. The Pd@Cu(II)-MOF (2) was recycled seven times
for benzyl alcohol oxidation (Figure 5). After each run, the
solid catalyst was easily collected by centrifugation, washed with
ethanol/dichloromethane, dried at 90 °C, and reused in the
next run under the same conditions. Interestingly, the reaction
conversion increased from 95% at the first run to >99% at the
4−6 runs (Figures S24−S29). Although we distance ourselves
from any type of explanation and say forthright that we do not
know why the conversion enhanced after three catalytic cycles,
it is possible because of some smaller solid catalyst particles
formed and dispersed more uniformly in the MOF matrix
during the reactions (Figure S30). The size and dispersion of
the Pd NPs in 2 did not show any detectable aggregation after
six runs, and the atomic lattice fringes (0.24 nm) corresponding
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Inorganic Chemistry Article

Figure 5. Recycling catalytic test. Left: conversion and selectivity obtained at 25 h in repeated runs of the benzyl alcohol oxidation catalyzed by 2
(air, 130 °C, benzyl alcohol (0.21 mmol), 2 (5% Pd), xylene (3.0 mL)). The average conversion and chemoselectivity based on six catalytic cycles are
>97% and >99%, respectively. Right: corresponding XRPD patterns (a−g corresponding to 1−7 runs).

Table 2. Summary of the Reported Benzyl Alcohol Oxidation Reactions Using Pd NPs as the Heterogeneous Catalysts
catalyst cond. run conv. (%) select (%) ref.
Pd/NaX zeolite toluene/100 °C/O2 (3 mL/min) 1 66 97 32
Pd/hybrid SiO2 CO2/O2 (18 MPa)/O2 (8 vol %)/80 °C 1 99.5 89.8 33
Pd/A20E10 toluene/water/80 °C/air (5 bar) 1 85.6 97 61
Pd/Al2O3 solvent free/120 °C/O2 (50 mL/min) 1 80.1 94.3 62
Pd/GC solvent free/110 °C/O2 (20 mL/min) 1 72.5 98.3 36
Pd/SBA-16 water/50 °C/air or O2 11 >99 >99 63
Pd-pol water (K2CO3)/100 °C/air (1 atom) 6 93−99 >99 64
CM-CeO2-Pd-1.0 solvent free/O2 1 82.1 62.9 26
Pd/CB 353 K/O2 1 99 95 37
Pd/AC water/60 °C/O2 (1.5 atm) 1 50 >99 38
ARP-Pd water/100 °C/O2 (1 atm) 1 97 40
Pd/PEG solvent free/80 °C/O2/scCO2 1 83.1 99.8 65
Pd@U-E15 water/K2CO3/90 °C/O2 (1 atm) 1 90 90 66
Pd cluster colloid water/32 °C/air bubbling/(pH 3.5) 10 86−93 100 41
PdHAP-0 trifluorotoluene/90 °C/O2 (1 atm) 1 >99 99 67
water/110 °C/O2 (1 atm) 1 >99 90
Pd@hmC water/K2CO3/80 °C/O2 1 48 37 68
MNP−Pd toluene/K2CO3/85−90 °C/air 4 86−100 90−93 69
Pd@Cu(II)-MOF xylene/130 °C/air (atmospheric pressure) 6 95 to >99 >99 this work

to 1/3(422) of face-centered cubic (fcc) Pd were also clearly
observed (Figure S27).
The conversion, however, decreased to 85% (Figure S31) at
the seventh run, indicating that 2 began to be deactivated.
HRTEM analysis revealed that some of the Pd NPs in 2 began
to aggregate (Figure S32), which could be the reason for the
low catalysis efficiency of 2 after six runs. Such an observation
was further confirmed by the elemental maps of Cu and Pd in 2
after six runs (Figure S33). In addition, ICP measurement
indicated that the amount of Pd NPs in 2 has no significant
changes after six runs; the amount of Pd species, however,
dropped to 3.85% after the seventh cycle, which could be an
additional reason for the catalyst inactivation (Table S3).
The XRD patterns of 2 and that after being reused for six
cycles indicated that the structural integrity of 2 was well
preserved. Therefore, Cu(II)-MOF can be an ideal support to
upload Pd NPs, furthermore, effectively preventing their
sintering and aggregation in the solid state even at a higher
reaction temperature (Figure 5).
It has been reported that the oxidative dehydrogenation of
alcohols to the corresponding aldehydes happened on all
3062
exposed metallic palladium faces; therein, the decarbonylation
often occurred and the undesired products preferentially
formed on hollow sites of Pd particle faces.31,59 However, in
our experiments, almost no decarbonylating products were
detected during reaction, so we proposed that the sites on face-
centered cubic Pd are the primary sites for benzyl alcohol
oxidation.60,67 The distance of the H(Cα-H)−H(hydroxy) on
benzyl alcohol is about 0.21 nm, which is close to the Pd−Pd
bonding distance of 0.24 nm found in 2. This might effectively
enhance the interactions between Pd NPs and reaction
substrates, consequently, leading to a high oxidation catalytic
efficiency.
Compared to various reported Pd NPs-loaded heterogeneous
catalysts (Table 2), 2 herein exhibits good catalytic activity and
selectivity for benzyl alcohol oxidation in the air. Therefore, it
can be a valuable complement for the MOFs to heterogeneous
aromatic carbinols oxidation composite catalysts.
Oxidation of Other Substituted Benzylic Alcohols. The
scope of the oxidation catalytic system was explored by
performing the oxidation reactions of various substituted
benzylic alcohols. Table 3 summarizes the results of these
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Inorganic Chemistry
Table 3. Oxidation Reactions of Benzyl Alcohols with
Different Substituted Groups Catalyzed by 2 in Aira
a
Reaction conditions: air, 130 °C, benzylic alcohols (0.21 mmol), 2
(5% Pd), xylene (3.0 mL). Reaction conversion and selectivity are
determined based on GC analysis (Figures S34−S39).
oxidation reactions. We found that all benzylic alcohols with
both electron-withdrawing (−F, −NO2) and electron-donating
groups (−OMe, −Me) at either para- or meta-position gave
excellent conversions (93−99%). In addition, the reaction
selectivity toward benzaldehydes is basically 100% in all cases.
Therefore, Pd@Cu(II)-MOF is indeed a good heterogeneous
catalyst for aromatic carbinols oxidation.
■ CONCLUSIONS
A new porous Cu(II)-MOF (1) with a NbO network was
synthesized. Pd NPs-loaded Pd@Cu(II)-MOF (2) was
prepared based on 1 by impregnation and reduction reaction
in solution. The Cu(II)-MOF with fluorine atoms can
effectively stabilize the palladium nanoparticles in the crystals.
More importantly, the obtained Pd NPs-embedded Pd@
Cu(II)-MOF can be a highly active heterogeneous catalyst
for the oxidation of aromatic carbinols to the corresponding
benzaldehydes in the air with high conversion rates and almost
100% selectivity. The catalyst can be recovered and reused for
at least six runs without a significant loss in its activity and
selectivity. Further work on exploring new catalytic reactions
with such NPs@MOF catalytic systems is currently underway.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b02973.
Single-crystal data, TGA traces, XRPD patterns, photo-
graphs for Pd(II)@Cu(II)-MOF, ICP measurement,
HRTEM images, EDS measurement, and GC analysis
(PDF)
Crystallographic data for 1 (CIF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: yubindong@sdnu.edu.cn.
*E-mail: gongjchen@126.com.
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Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We are grateful for financial support from NSFC (Grant Nos.
21475078, 21271120, and 21301109), the 973 Program (Grant
Nos. 2012CB821705 and 2013CB933800), the Taishan
Scholar’s Construction Project, the Reward Fund for Out-
standing Young and Middle Aged Scientists of Shandong
Province (no. BS2012CL032), and the Jinan Science and
Technology Bureau (OUT_06623).
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3064 DOI: 10.1021/acs.inorgchem.5b02973

Inorg. Chem. 2016, 55, 3058−3064