DOI: 10.1002/slct.

202000111 Full Papers

z Catalysis

A Catalyst of Pd@MIL-101@SGO Catalyzes Epoxidation and

Hydroxymethoxylation Tandem Reactions of Styrene
Hong Tang, Mei-Li Zhou, Xin Li, Yu-Yang Zhang,* and Zheng-Bo Han[a]

Brönsted acid and metal nanoparticles are important catalytic FT-IR, TGA, and nitrogen physisorption measurements. Tandem
functional groups. In this work, a bifunctional heterogeneous heterogeneous catalysis of Pd@MIL-101@SGO was investigated
catalyst with both strong Brönsted acid and metal nano- for the one-pot direct conversion of styrene into β-alkoxy
particles was prepared. First Brönsted acid groups were alcohol. The catalyst retained high catalytic activity after 5
obtained by sulfonating graphene oxide, next metal organic times of reuses in aqueous solutions. No loss of crystal structure
frameworks MIL-101 (Cr) grew on sulfonated graphene oxide was detected by PXRD and no leakage of Pd was detected by
(SGO), then palladium nanoparticles (NPs) were encapsulated ICP-AES. Therefore, Pd@MIL-101@SGO proved to be an effective
in MIL-101@SGO composites. The catalyst was characterized by recyclable heterogeneous catalyst for synthesizing β-alkoxy
a variety of different techniques including XRD, SEM, TEM, EDS, alcohol and exhibited potential application in industry.

101 to obtain a MNPs-Brönsted acid bifunctional heteroge-

Introduction
neous catalyst of Pd@MIL-101@SGO.
Metal organic frameworks (MOFs) composed of inorganic metal β-alkoxy alcohols are used as valuable organic solvents,
ions and organic ligands have attracted more and more finechemicals, versatile synthons, and pharmaceutical
attention in recent years, owing to their large specific surface intermediates.[32–35] The main strategy to synthesize β-alkoxy
areas, designable micro-mesoporous structures and excellent alcohols is a two-step reaction that epoxidation of olefins and
stability.[1–5] MOFs have versatile applications, such as gas sequential alcoholysis of epoxides under acidic conditions.[34,36,
storage and separation,[6,7] carbon capture,[8,9] sensing,[10,11] drug 37]
However, heterogeneous catalysts for this one-pot tandem
delivery,[12,13] heterogeneous catalysis,[14–16] etc. MIL-101 (Cr) reaction have rarely been reported. In this work, palladium
consisting of chromium ions and terephthalic acid ligands is an nanoparticles were used to catalyze the epoxidation of
unique MOFs with stable chemical properties, huge specific styrene,[38,39] and SGO with -HSO3 was used to catalyze the
surface areas and retractable pore structures,[17–21] which is an hydroxymethoxylation of epoxide. Pd@MIL-101@SGO catalyzed
ideal carrier for palladium nanoparticles.[17,19, 22, 23] Sulfonated the one-pot tandem reaction directly synthesized β-alkoxy
graphene oxide (SGO) was reported by Hou et al.,[24] which is a alcohols with styrene, improving production efficiency, reduc-
functional sheet structure material. SGO tends to grow MIL-101 ing energy consumption and simplifying the product separa-
(Cr) on its surface due to the acidic groups on the surface. tion.
However, it is not suitable as a carrier of palladium nano-
particles, because palladium nanoparticles are difficult to load
Results and Discussion
and easy to agglomerate.
The insertion of groups on the benzene ring of MIL-101 (Cr) Fourier transform infrared spectroscopy (FT-IR) spectra of
ligand is an important strategy for its application in samples were recorded with the Nicolet 5DX spectrometer in
catalysis.[25–27] MOFs with basic groups such as MIL-101-NH2 range 4000–400 cm 1 using KBr pellets. The X-ray powder
have been widely used.[28–30] However, applications of MOFs diffraction (PXRD) measurements of samples were detected by
with acidic groups such as MIL-101-HSO3 were limited, because Bruker AXS D8 advanced automated diffractometer with Cu Kα
ligands with -HSO3 are difficult to obtain.[27,31] To obtain a radiation. The high-angle annular dark field scanning trans-
porous composite material with strong Brönsted acid site, a mission electron microscopy (HAADF-STEM) images were
MIL-101@SGO composite material came into being. Then recorded on a JEM-2100F electron microscope operated at
palladium nanoparticles were encapsulated in the pores of MIL- 200 kV. Energy-dispersive spectra (EDS) of samples were
collected with a field emission instrument of the type SU8010.
Transmission electron microscopy (TEM) graphics of samples
[a] H. Tang, M.-L. Zhou, X. Li, Dr. Y.-Y. Zhang, Prof. Z.-B. Han were acquired on JEM-1200EX electron microscope with an
College of Chemistry operating voltage of 120 kV. The N2 sorption properties of
Liaoning University
samples were analyzed by the Brunauer Emmett Teller (BET)
Shenyang 110036, P. R. China
E-mail: [email protected] method at 77 K. The contents of Pd in Pd@MIL-101@SGO were
Supporting information for this article is available on the WWW under quantified by inductively coupled plasma atomic emission
https://doi.org/10.1002/slct.202000111 spectroscopy (ICP-AES). Thermogravimetric analyses (TGA) were

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 Full Papers

Scheme 1. preparation of catalyst. Reagents and conditions: a) graphite powder, 1)H2SO4, H3PO4, KMnO4, 323 K, 2) H2O2, water, RT; b) Cr(NO3)3, H2BDC, water,
493 K; c) Na2PdCl4, NaBH4, methanol, RT.

taken on a Perkin-Elmer Pyrisl (298-1073 K, 5 K⋅min 1, flowing reported by Férey et al.[41]) As shown in Figure 2 SEM image, (a)
N2). The catalytic reaction products were analyzed and pure SGO had a clean sheet structure, (b) MIL-101@SGO-2 did
identified by SP-2100 A gas chromatograph (GC, equipped with not maintain the sheet structure of SGO, (c) MIL-101@SGO-3
a Kromat-Bond Series capillary column and a flame ionization maintained the sheet structure of SGO, and MIL-101 crystals
detector). grew on the surface of SGO. Then, palladium nanoparticles
Preparation of Pd@MIL-101@SGO was illustrated in were encapsulated in MIL-101@SGO via a capillary impregna-
Scheme 1. Firstly, SGO was obtained according to a slightly tion-reduction method.[42] As shown in Figure S1, as-synthe-
modified literature procedure.[40] Purchased graphite powder sized Pd@MIL-101@SGO still retained the Brönsted acidic
was sulfonated and oxidized. As shown in Figure S1, the groups of SGO. As shown in Figure 1, the PXRD patterns of as-
synthesized SGO had obvious infrared absorption peaks of synthesized Pd@MIL-101@SGO were consistent with the PXRD
O C-O (1386 cm 1), S=O (1060 cm 1), C S (747 cm 1), and C O- patterns of MIL-101@SGO, proving that palladium nanoparticles
C (595 cm 1), which proved that the graphite powder had been had little effect on the overall crystal structure, which were
successfully sulfonated and oxidized.[24] Next, MIL-101 (Cr) was similar to the results reported by Jiang et al.[21] As shown in
grown on SGO by hydrothermal method, and MIL-101@SGO of Figure 2 (d) SEM image, Pd@MIL-101@SGO kept the structure
MIL-101@SGO-1, MIL-101@SGO-2, MIL-101@SGO-3, MIL- of MIL-101@SGO. As shown in Figure 3 (a) TEM image, under
101@SGO-4 were synthesized respectively. (They were different low magnification TEM, it was mainly observed that MIL-101
from the weight of SGO added during synthesizing MIL- crystals grew on SGO, and palladium nanoparticles grew in
101@SGO.) As shown in Figure S1, these as-synthesized MIL- pores of MIL-101. Figure 3 (b) TEM image showed specific
101@SGO retained the Brönsted acidic groups of SGO. As loading details of palladium nanoparticles either incorporated
shown in Figure 1, the PXRD patterns of as-synthesized MIL- into pores of MIL-101 or located on the framework surface of
101@SGO were compared with the PXRD patterns of MIL-101 MIL-101. As shown in Figure 3 (c), it was still observed that the
and SGO, and as-synthesized MIL-101@SGO retained structures palladium nanoparticles maintained micromorphology after 5
of both SGO and MIL-101. (Simulated pattern of MIL-101 was

Figure 1. PXRD patterns of simulated MIL-101, MIL-101, SGO, MIL-101@SGO-

1/2/3/4, Pd@MIL-101@SGO-1/2/3/4, Pd@MIL-101@SGO-2 after 5 runs and Figure 2. SEM image of as-synthesized (a) SGO, (b) MIL-101@SGO-2, (c) MIL-
Pd@MIL-101@SGO-3 after 5 runs. 101@SGO-3, (d) Pd@MIL-101@SGO-3.

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 Full Papers

Table 1. N2 physical sorption properties of different samples.

Entry Sample BET[a] (m2/g)

1 MIL-101 2822.01
2 SGO 0
3 MIL-101@SGO-1 249.05
4 MIL-101@SGO-2 310.15
5 MIL-101@SGO-3 541.17
6 MIL-101@SGO-4 380.82
7 Pd@MIL-101@SGO-2 87.25
8 Pd@MIL-101@SGO-3 149.55

[a] BET specific surface areas were analyzed by the Brunauer Em-
mett Teller (BET) method at 77 K.

AES, which proved that palladium nanoparticles were well

loaded. As shown in Figure S2, EDS of Pd@MIL-101@SGO
further confirmed the presence of Pd and S in the catalyst. As
shown in Figure S3, TG analysis of MIL-101@SGO-3 and
Pd@MIL-101@SGO-3 showed that decomposition of the organic
ligand (BDC) occurred at about 573 K.
N2 physical adsorption experiments were carried to charac-
terize pore structures of as-synthesized complexes. As shown in
Table1, as-synthesized MIL-101 had a huge BET (Brunauer
Emmett Teller) specific surface area of 2822 m2/g, while SGO
had no adsorption for N2, consistent with previous reports.[43]
(Entries. 1–2, Table 1) MIL-101@SGO-3 had the largest BET
Figure 3. TEM image of as-synthesized Pd@MIL-101@SGO-3; (a) image of low specific surface area among all MIL-101@SGO (Entries. 3–6,
magnification, (b) image of Pd nanoparticles, (c) Pd nanoparticles after 5
runs,(d) corresponding size distribution of Pd nanoparticles, (e) correspond-
Table 1), perhaps because MIL-101 grew best in MIL-101@SGO-
ing size distribution of Pd nanoparticles after 5 runs. 3 than others, which were consistent with the morphological
results observed by SEM. After encapsulating palladium nano-
particles, the BET specific surface areas of Pd@MIL-101@SGO
were further reduced. (Entries. 7–8, Table 1) Figure 4 (a) and
reuses. As shown in Figure 3 (d) and (e), particle size of Figure S4 are N2 adsorption isotherms at 77 K of different
palladium nanoparticles inside MIL-101 were mainly distributed samples. Figure 4 (b) is pore size distribution of the samples
around 3.8 nm before and after 5 reuses (they are the statistical measured by D A (Dubinin-Astakhov) micropore method. Pore
results of Nano Measurer.) The added amount of Pd was 1.0 wt diameters of MIL-101@SGO-1/2/3/4 were 1.6 nm, 1.7 nm,
%, and loaded amount of Pd in Pd@MIL-101@SGO-1/2/3/4 were 1.9 nm, 1.7 nm, respectively. Pore diameters of Pd@@SGO-2/3
0.97, 1.01, 0.95 and 0.98 wt % respectively determined by ICP- were 1.6 nm and 1.8 nm, proving that the pore diameters of

Figure 4. (a) N2 adsorption isotherms at 77 K of different as-synthesized MIL-101@SGO, (b) Pore size distribution of as-synthesized complexes by D A (Dubinin-
Astakhov) micropore method.

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 Full Papers
the catalysts did not change significantly after loading palla- 12–14, Table 2) 343 K was a suitable reaction temperature, and
dium nanoparticles. the efficiency of the catalyst reduced significantly when the
A series of catalytic experiments were conducted. For the temperature decreased to 333 K. (Entries. 12 and 15, Table 2)
first step of epoxidation, TBHP was a suitable oxidant, other Pd@MIL-101@SGO-3 had nearly 100% of the yield, Pd@MIL-
oxidants such as H2O2 and O2 had poor oxidation effects. 101@SGO-2 had yield of about 60% and Pd@MIL-101@SGO-1
(Entries. 1–3, Table 2) Pd@MIL-101 had a weaker catalytic effect, had yield of about 40%. (Entries. 16–18, Table 2) To understand
maybe because Brönsted acid had a certain promotion effect.[44] the reaction process, the catalytic reactions were monitored
(Entries. 1 and 4, Table 2) Under the same conditions, TBHP over time. As shown in Figure 5, styrene was first formed into
could not oxidize styrene with catalyst of MIL-101@SGO, SGO, epoxide, meanwhile epoxide was also formed into β-alkoxy
MIL-101, or no catalyst. (Entries. 5–8, Table 2) For the second alcohol. The amount of epoxide was increased first and then
step of hydroxymethoxylation, SGO had extremely high decreased, and the amount of β-alkoxy alcohol had been
catalytic efficiency, 99.9% yield at 5 min (Entry. 9, Table 2) MIL- increasing.
101 had a little catalytic effect. (Entry. 10, Table 2) The reaction By analogy with the previous reports,[32,45] mechanism of the
could not proceed without a catalyst. (Entry. 11, Table 2) For tandem reaction is shown in Scheme 2. As already described
the tandem reaction, Pd@MIL-101@SGO-4 had a high yield of above, the one-pot direct conversion of styrene into β-alkoxy
95.54%, probably because the second step of hydroxymeth- alcohol requires two catalytic centers to complete the two
oxylation consumed the product of the first step of epoxida- different parts of reaction. First, in the presence of TBHP, Pd(0)
tion, and promoted reaction of the first step. (Entry. 12, Table 2) was transformed into the active peroxo species, which
Mixture of water and methanol was the best among the solvent epoxidized styrene to the styrene oxide, and this was the rate
tested for the tandem reaction, maybe because water could limiting step of the whole reaction. Then, the epoxide could be
promote the decomposition of H + at the catalyst site. (Entries. protonated by the SGO. Subsequently, methanol would attack
the most stable benzyl carbocation from the backside, giving
rise to the trans-β-alkoxy alcohol.
Pd@MIL-101@SGO-3 was selected for further cycling tests.
As shown in Figure 6, it could still maintain high activity after 5
cycles. As shown in Figure 1, PXRD patterns showed that crystal
structures of Pd@MIL-101@SGO-3 and Pd@MIL-101@SGO-2
both remained stable after 5 cycles, and ICP-AES tests showed
no leakage of palladium nanoparticles. It was proved that the
bifunctional heterogeneous catalyst maintained high catalytic
efficiency and stable structure after 5 cycles.

Conclusion
In summary, a new MNPs-Brönsted acid bifunctional heteroge-
neous catalyst was synthesized. The catalyst had high catalytic
efficiency on the one-pot direct conversion of styrene into β-

Figure 5. monitoring the catalytic reactions over time. Reaction conditions:

styrene (1.0 mmol), TBHP (2.0 mmol), Pd@MIL-101@SGO-3, 343 K, 1 mL
methanol and 3 mL water, monitored by GC.

Scheme 2. reaction mechanism diagram. Figure 6. recyclability studies of Pd@MIL-101@SGO-3 in tandem reactions.

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 Full Papers

Table 2. Yields of different reactions.

Entry Reactant Product Catalyst Oxidant Time Yield[1] / % Yield[2] / %

1 Pd@MIL-101@SGO-4 TBHP 5h 38.05 /

2 Pd@MIL-101@SGO-4 H2O2 5h 0 /

3 Pd@MIL-101@SGO-4 O2 5h 0.5 /

4 Pd@MIL-101 TBHP 5h 29.04 /

5 MIL-101@SGO-4 TBHP 5h 0 /

6 SGO TBHP 5h 0 /

7 MIL-101 TBHP 5h 0 /

8 none TBHP 5h 0 /

9[a] SGO / 5 min / 99.99

10[a] MIL-101 / 5h / 20.21

11[a] none / 5h / 0

12[a] Pd@MIL-101@SGO-4 TBHP 5h 4.45 95.54

13[b] Pd@MIL-101@SGO-4 TBHP 5h 5.95 23.90

14[c] Pd@MIL-101@SGO-4 TBHP 5h 17.99 19.00

15[d] Pd@MIL-101@SGO-4 TBHP 5h 24.66 28.61

16[a] Pd@MIL-101@SGO-3 TBHP 5h 0 99.99

17[a] Pd@MIL-101@SGO-2 TBHP 5h 29.08 60.13

18[a] Pd@MIL-101@SGO-1 TBHP 5h 49.87 39.56

Reaction conditions: reactant (1.0 mmol), oxidant (2.0 mmol or continuous oxygen), catalyst, 343 K and 4 mL water, [a] (343 K, 1 mL methanol and 3 mL water),
[b] (343 K, 1 mL methanol and 3 mL acetonitrile), [c] (343 K, 4 mL methanol), [d] (333 K, 1 mL methanol and 3 mL water); [1] epoxide, [2] β-alkoxy alcohol, the
conversion and yield of the reaction were monitored by GC.

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 Full Papers
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