Pillared Sn-MWW Prepared by a Solid-State-Exchange Method and its Use as a Lewis Acid Catalyst

Article abstract of DOI:10.1002/cctc.201600120

Pillared Sn-MWW (Sn-MWW(SP)-SSE) was prepared through a solid-state-exchange (SSE) route. The pillared structure was inherited from pillared B-MWW, and Sn was inserted in the framework by boron leaching and solid-state-exchange with tin tetrachloride pentahydrate. The Sn-MWW(SP)-SSE with framework Sn sites exhibits Lewis acidity and good catalytic performance for the Baeyer-Villiger oxidation, and mono- and disaccharide isomerizations.

Full text of DOI:10.1002/cctc.201600120

DOI: 10.1002/cctc.201600120
Communications
Pillared Sn-MWW Prepared by a Solid-State-Exchange
Method and its Use as a Lewis Acid Catalyst
Limin Ren+,[a] Qiang Guo+,[a] Marat Orazov,[b] Dandan Xu,[a] Dorothea Politi,[d]
Prashant Kumar,[a] Saeed M. Alhassan,[c] K. Andre Mkhoyan,[a] Dimitrios Sidiras,[d]
Mark E. Davis,[b] and Michael Tsapatsis*[a]
Pillared Sn-MWW (Sn-MWW(SP)-SSE) was prepared through
a solid-state-exchange (SSE) route. The pillared structure was
inherited from pillared B-MWW, and Sn was inserted in the
framework by boron leaching and solid-state-exchange with
tin tetrachloride pentahydrate. The Sn-MWW(SP)-SSE with
framework Sn sites exhibits Lewis acidity and good catalytic
performance for the Baeyer–Villiger oxidation, and mono- and
disaccharide isomerizations.
stacks.[7–10] Compared with delamination, pillaring leads to
a more uniform and ordered structure.[11] It is performed by
placing oxide pillars between adjacent layers to create meso-
pores.[7]
Pillared MWW in its aluminosilicate form (called MCM-36)
was first introduced in the 1990s by pillaring the layered pre-
cursor (MCM-22(P)) in an effort to combine the Brønsted acidi-
ty of zeolites with accessibility to bulky molecules.[7] Since
then, numerous studies have attempted the structural charac-
terization of pillared aluminosilicate MWW and to find its corre-
lation with catalytic activity.[11,12] To obtain pillared layered ma-
terials with highly crystalline layers, the conditions under
which the swelling step is performed are decisive and should
be well-controlled. For example, mild swelling of MCM-22(P)
results in a pillared material with improved structural preserva-
tion of the 2-dimensional MWW layers, which has been corre-
lated with improved catalytic performance.[13]
As a Lewis acid catalyst,[14–21] Sn-MWW has attracted atten-
tion from both the synthetic and catalytic perspectives.
Hensen et al. developed a “re-growth” method for preparing
Sn-MWW, which was highly active for the conversion of trioses
to methyl lactate and lactic acid.[14] Hydrothermal synthesis of
Sn-MWW and its transformation to an MCM-56 analog were re-
ported by Wu’s group.[15a] Zones et al. studied delaminated Sn-
MWW as an effective solid Lewis acid catalyst for the Baeyer–
Villiger oxidation.[15b]
Zeolites[1–3] are important heterogeneous acid catalysts. Among
them, there is a set with structures consisting of lamellar
sheets.[4] These 2-dimensional (2D) layered zeolites, which can
be manipulated by calcination, swelling, pillaring, or exfoliation
(delamination), are regarded as promising catalysts for reac-
tions involving bulky molecules.[4–7] Swelling followed by de-
lamination or pillaring are routes for creating mesoporosity in
between the 2D layers. Generally, swelling is a step performed
to expand the inter-layer spacing; it is achieved by using long
chain surfactants that interact with the silanols between the
layers.[4,7] Usually, this step may be performed under aggressive
conditions, which may lead to partial dissolution and destruc-
tion of the layers. Delamination or exfoliation is performed
after swelling to obtain individual layers or few-layer
[a] Dr. L. Ren,+ Dr. Q. Guo,+ D. Xu, P. Kumar, Prof. K. A. Mkhoyan,
Prof. M. Tsapatsis
Here, we present the preparation of pillared Sn-MWW with
well-preserved intra-layer crystallinity and compare its per-
formance with that of other catalysts for the Baeyer–Villiger ox-
idation and mono- and disaccharide isomerizations. Table 1
lists the zeolite samples prepared in this study. Detailed infor-
mation regarding their synthesis can be found in the Support-
ing Information.
Department of Chemical Engineering and Materials Science
University of Minnesota
421 Washington Avenue SE
Minneapolis, MN, 55455 (USA)
E-mail: tsapatsis@umn.edu
[b] M. Orazov, Prof. M. E. Davis
Chemical Engineering
Swelling of the layered precursor, B-MWW(Pr), was per-
formed under mild conditions to avoid destruction of the
intra-layer crystallinity. As shown by the XRD patterns in Fig-
ure 1A, traces a and b, the (001) peak shifted from 2q=3.25
to 2.58, corresponding to an increase in layer spacing. Intra-
layer peaks (220) and (310) are clearly observed in the swollen
material, indicating that the crystallinity of the layers was pre-
served.[13] Figure 1A, trace c, shows the XRD pattern of the pil-
lared material, B-MWW(SP). The low-angle (001) peak at 2q=
2.068 (corresponding to a d spacing of 43 Š, which is character-
istic of MCM-36) indicates that B-MWW(SP) is successfully pil-
lared. The (002) and (003) peaks reflect ordered inter-layer
stacking. In the wide-angle range, the (100), (220), and (310)
California Institute of Technology
Pasadena, CA, 91125 (USA)
[c] Prof. S. M. Alhassan
Department of Chemical Engineering
The Petroleum Institute, Abu Dhabi (UAE)
[d] Dr. D. Politi, Prof. D. Sidiras
Laboratory of Simulation of Industrial Processes
Department of Industrial Management and Technology
University of Piraeus
80 Karaoli & Dimitriou
GR-18534 Piraeus (Greece)
[+] These two authors contributed equally.
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
cctc.201600120.
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Table 1. Nomenclature and description of synthesized materials.
Samples
Description
B-MWW(Pr)
B-MWW layered precursor, Si/B=13
B-MWW(3D)
B-MWW(S)
3D B-MWW obtained by calcination of B-MWW(Pr), Si/B=13
Swollen B-MWW obtained by swelling of B-MWW(Pr) with surfactant
Pillared B-MWW obtained by swelling and pilling of B-MWW(Pr)
De-boronated, pillared B-MWW obtained by acid leaching of the B-MWW(SP)
Pillared Sn-MWW with Si/Sn=125 obtained from De-B-MWW(SP) by the SSE method
Sn-MWW layered precursor, Si/Sn=94
B-MWW(SP)
De-B-MWW(SP)
Sn-MWW(SP)-SSE
Sn-MWW(Pr)
Sn-MWW(3D)
Sn-BEA-F
3D Sn-MWW obtained by calcination of Sn-MWW(Pr), Si/Sn=94
Sn-BEA prepared by a fluoride-based hydrothermal synthetic method, Si/Sn=125
SSE process. Figures S3A and S3B (in the Supporting Informa-
tion) show the SEM and TEM images of Sn-MWW(SP)-SSE,
showing plate morphology and an ordered stacking of crystal-
line layers. As expected, Ar adsorption (Figure S4 in the Sup-
porting Information) of Sn-MWW(SP)-SSE compared with Sn-
MWW(3D) is lower at low pressures and higher at high pres-
sures.
The diffuse reflectance UV/visible (DR-UV/vis) spectrum of
Sn-MWW(SP)-SSE exhibits a main peak centered at 205 nm
(Figure S5 in the Supporting Information), which is assigned to
the tetrahedrally coordinated Sn species.[15b,23a] The Lewis
acidic properties of Sn-MWW(SP)-SSE were probed with
adsorption of deuterated acetonitrile, followed by FTIR spec-
troscopy (Figure 2A). CÀN stretching vibration peaks corre-
sponding to physisorbed (ꢀ2261 cmÀ1), silanol-bound
(ꢀ2273 cmÀ1), and Lewis-acid-bound (ꢀ2305 cmÀ1) deuterat-
ed acetonitrile are evident.[23] Similar CÀN stretching vibrations
of adsorbed deuterated acetonitrile were also observed for Sn-
MWW(3D) as shown in Figure 2C. The IR spectra of pyridine
adsorbed on Sn-MWW(SP)-SSE after evacuation at different
temperatures are shown in Figure 2B. In addition to the bands
attributed to Lewis acid sites (1449, 1489, 1607, and the
Figure 1. A) XRD patterns of B-MWW(Pr) (trace a), B-MWW(S) (trace b),
B-MWW(SP) (traces c and d. The intensity of trace d is increased five-times
compared with that in trace c); B) Ar adsorption/desorption isotherms of
B-MWW(3D) and B-MWW(SP) (inset shows pore-size-distributions obtained
by using non-local (NL)-DFT);[22] C) SEM image and D) TEM image of
B-MWW(SP).
reflections are retained (Figure 1A, trace d), suggesting preser-
vation of the intra-layer structure.
shoulder peak 1613 cmÀ1), there are bands (1489, 1543, and
faint peak 1636 cmÀ1) corresponding to pyridine adsorbed on
Brønsted acid sites.[14,24] Loss of the intensity after evacuation
at 3508C, suggests a weaker Brønsted acidity than that associ-
ated with Al Brønsted acid sites.[24] The weak Brønsted acidity
was also observed in Sn-MWW(3D) (Figure 2D). The Brønsted
acidity of both samples can be attributed to boron remaining
after acid leaching. Ratios of Si/Bꢀ200 for Sn-MWW(3D) and
Si/Bꢀ300 for Sn-MWW(SP)-SSE, determined by inductively
coupled plasma optical emission spectrometry (ICP-OES), fur-
ther support this hypothesis.
The argon adsorption (Figure 1B) isotherm indicates a pore
size distribution centered around 3.0 nm for the pillared
sample, whereas no such peak was detected in the mesopore
range for B-MWW(3D). The SEM image of B-MWW(SP) shows
that the original morphology of B-MWW(Pr), as seen in Fig-
ure S1 in the Supporting Information, was retained (Figure 1C).
The TEM image of B-MWW(SP) shows regularly spaced layers
with high crystallinity (Figure 1D).
After swelling and pillaring, the 12 membered ring (MR)
MWW semi-cups, which are present on the external surface of
MWW layers, will be accessible through the mesopores. For Sn
incorporation using the solid-state-exchange (SSE) approach
shown in Scheme S1 (in the Supporting Information), first
boron removal from B-MWW(SP) was performed by acid treat-
ment[14] and then SSE Sn insertion was performed by contact-
ing with tin tetrachloride pentahydrate followed by high tem-
perature calcination.[16a] Figure S2 (in the Supporting Informa-
tion) shows the XRD patterns of B-MWW(SP), De-B-MWW(SP),
and Sn-MWW(SP)-SSE, indicating that the pillared arrangement
and intra-layer order were retained after acid leaching and the
Sn-MWW(SP)-SSE was tested as a catalyst for the Baeyer–Vil-
liger oxidation of the cyclic ketone 2-adamantanone and com-
pared with various zeolite catalysts (Table 2, Table S1 in the
Supporting Information). There is no lactone produced over
bulk Sn-MFI,[25] as the 10 MR channels are too small to accom-
modate 2-adamantanone, which has an estimated size of
7.0 Š.[26] Sn-MWW(3D) shows 49.4% conversion and 48.2%
yield of lactone after 4 h reaction. The activity is mainly attrib-
uted to Sn sites located on the external surface as the intra-
layer 10 MR should not be accessible to such bulky molecules
and the large super cage (with an inner diameter of approxi-
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Figure 2. FTIR spectra of deuterated acetonitrile adsorbed on A) Sn-MWW(SP)-SSE and C) Sn-MWW(3D). The arrows indicate the desorbing sequence of deu-
terated acetonitrile in vacuo. FTIR spectra after pyridine adsorption and evacuation at different temperatures on B) Sn-MWW(SP)-SSE and D) Sn-MWW(3D).
The 2008C spectra are multiplied by a factor of three to enhance the visibility of the peaks. Absorption band characteristics for specifically adsorbed pyridine
are denoted by H for hydrogen-bonded pyridine, B for adsorption on Brønsted sites, and L for Lewis acid sites.
(>50%) and high FRU selectivity (around 70%) at similar GLU
Table 2. Baeyer–Villiger oxidation of 2-adamantanone catalyzed by differ-
ent catalysts.[a]
conversions of around 75% (Figure 3, Figure S6 in the Support-
ing Information) after 24 h of the reaction. This is comparable
to the previously reported performance of Sn-SPP and much
higher than that of Sn-BEA-F (Table S2 in the Supporting Infor-
mation).[29] As can be seen from Figure 3, the yield of fructose
on Sn-MWW(SP)-SSE exceeds 50% after about 8 h, whereas
with Sn-MWW(3D), it reaches comparable levels after 24 h. It is
reasonable to attribute this difference to the alleviated diffu-
sion limitations on Sn-MWW(SP)-SSE compared with Sn-
MWW(3D), as similar acidic properties of the two catalysts have
been confirmed by FTIR, and the reaction appears to proceed
with a similar mechanism in both catalysts as discussed next.
The isotopic identity (H or D) at the C1 position was deter-
mined by 13C NMR spectroscopy for fructose generated
through glucose isomerization catalyzed by Sn-MWW(SP)-SSE
in methanol with inverse isotopic enrichment at the C2 posi-
tion of the starting glucose (e.g., for glucose with natural
abundance H at C2, the reaction was run in [D4]MeOH). No iso-
topic scrambling with the solvent was observed (Figures S7, S8
in the Supporting Information), strongly suggesting that this
isomerization proceeds primarily through a 1,2-intramolecular
hydride shift that has been associated with the framework
Lewis acidic “open” Sn sites in Sn-BEA,[30] rather than through
an enolization mechanism that prevails on SnO2 and homoge-
neous bases in methanol.[31,32] Similarly, it is demonstrated that
in the presence of Sn-MWW(3D), the isomerization reaction
proceeds by way of an intramolecular hydride shift (Figures S7,
S8).[30–32]
Catalysts
Si/Sn
Conversion
[%]
Yield
[%]
Selectivity
[%]
Sn-MWW(3D)
Sn-MWW(SP)-SSE
Sn-BEA-F
94
125
125
125
49.4
90.5
82.3
<3
48.2
85.1
79.4
–
97.6
94.0
96.5
–
Sn-MFI
[a] Reaction conditions: ketone 1 mmol, 30 wt% H2O2 1.5 mmol, Sn/
ketone=0.66%, dioxane 3.09 g, 908C, 4 h.
mately 7.1 Š and height of approximately 18.2 Š) can only be
reached through the 10 MR channels.[5,27] As expected, Sn-
MWW(SP)-SSE shows much higher activity (90.5% conversion
and 85.1% yield of lactone) than that of Sn-MWW(3D). Further-
more, Sn-MWW(SP)-SSE shows even better catalytic per-
formance when compared with that of the state-of-art catalyst
Sn-BEA-F (82.3% conversion and 79.4% yield of lactone).
To further explore the active sites of Sn-MWW catalysts and
their accessibility, mono- and disaccharide isomerizations in-
volving larger molecules were investigated. Glucose (GLU) iso-
merization was performed in ethanol by following the reaction
sequence reported in ref. [28]. According to this procedure
(Scheme S2 in the Supporting Information), GLU is first reacted
to produce a mixture of fructose (FRU; GLU isomerization
product) and ethyl fructoside (FRU ketalization product with al-
cohol). Upon addition of water, hydrolysis of the fructoside
yields FRU.[28,29] With this approach, the FRU yield could be in-
creased compared with that achieved by isomerization in
water. By performing GLU isomerization in this way, both Sn-
MWW(3D) and Sn-MWW(SP)-SSE have shown high FRU yield
We also tested the long-term stability of the Sn-MWW(SP)-
SSE catalyst by performing reactions over recycled and cal-
cined catalysts. It was found that the catalyst retains its glu-
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Figure 3. A and B) GLU isomerization reaction profiles as a function of time. A) Sn-MWW(3D) and B) Sn-MWW(SP)-SSE as catalyst. C and D) FRU yield versus
reaction time and FRU yield versus GLU conversion over different catalysts. Reaction conditions: 1 wt% GLU (0.05 g) in ethanol (4.95 g), GLU/Sn=74, 908C.
After quenching the reactor in an ice bath, 6.45 g of deionized water was added to hydrolyze the ethylated sugars at 908C for 24 h. The fructose and man-
nose (MAN) concentrations and yields were obtained after the indicated reaction time followed by hydrolysis. Reaction time is the time for reaction in ethanol
before the addition of water (see the Supporting Information).
cose isomerization activity after at least five runs (Figure S9 in
Table 3. Maltose isomerization to maltulose over different catalysts.[a]
the Supporting Information). Moreover, the ordered layer struc-
ture and intra-layer crystallinity of the used zeolite catalyst
after the fifth run are still preserved as confirmed by XRD and
Ar adsorption/desorption isotherms (Figure S10 in the Support-
ing Information).
Catalysts
Solvent
Conversion
[%]
Yield
[%]
Selectivity
[%]
Sn-BEA-F
ethanol
ethanol
ethanol
n-propanol
n-propanol
n-propanol
8.9
40.5
79.4
8.0
38.9
75.6
6.7
33.6
61.1
6.1
28.9
59.1
75.3
83.0
77.0
76.3
74.3
78.2
Sn-MWW(3D)
Sn-MWW(SP)-SSE
Sn-BEA-F
Sn-MWW(3D)
Sn-MWW(SP)-SSE
Next, maltose, which is a much larger molecule, was also
used as the isomerization substrate to probe the accessibility
of the active sites of the Sn-BEA-F and Sn-MWW catalysts. Simi-
larly to GLU isomerization, when maltose (MAL) to maltulose
(MALTU) isomerization was performed in alcohols (such as eth-
anol and n-propanol), intermediates, which can be converted
back to the isomerized sugar through a hydrolysis step, were
observed (Scheme S3 in the Supporting Information). As pre-
sented in Table 3, after 24 h of reaction, Sn-BEA-F shows MAL
conversion of 8.9% in ethanol and 8.0% in n-propanol, which
are much lower than that of Sn-MWW(3D) (40.5% conversion,
33.6% yield in ethanol and 38.9% conversion, 28.9% yield in
n-propanol) and Sn-MWW(SP)-SSE (79.4% conversion, 61.1%
[a] Reaction conditions: 1 wt% maltose in 3 g of alcohol (ethanol or n-
propanol) at 908C for 24 h. Sn/MAL=1/35. After quenching the reactor in
an ice bath, 4 g of deionized water was added to perform the hydrolysis
at 908C for 48 h. The MALTU yields are those obtained after the reaction
time of 24 h and 48 h of hydrolysis at 908C.
yield in ethanol and 75.6% conversion, 59.1% yield in n-propa-
nol). Compared with Sn-MWW(3D), Sn-MWW(SP)-SSE shows
higher MALTU yields both in ethanol and n-propanol (Table 3).
Figure 4. Isomerization of MAL to MALTU in n-propanol. A) MALTU yield versus MAL conversion and B) MALTU yield versus reaction time over Sn-MWW(3D)
and Sn-MWW(SP)-SSE. Reaction time is the time for reaction in n-propanol before the addition of water (see the Supporting Information).
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[9] a) I. Ogino, M. M. Nigra, S.-J. Hwang, J.-M. Ha, T. Rea, S. I. Zones, A. Katz,
J. Am. Chem. Soc. 2011, 133, 3288–3291; b) I. Ogino, E. A. Eilertsen, S.-J.
Hwang, T. Rea, D. Xie, X. Ouyang, S. I. Zones, A. Katz, Chem. Mater.
2013, 25, 1502–1509.
[10] X. Ouyang, S.-J. Hwang, R. C. Runnebaum, D. Xie, Y.-J. Wanglee, T. Rea,
S. I. Zones, A. Katz, J. Am. Chem. Soc. 2014, 136, 1449–1461.
[11] a) W. J. Roth, C. T. Kresge, J. C. Vartuli, M. E. Leonowicz, A. S. Fung, S. B.
McCullen, Stud. Surf. Sci. Catal. 1995, 94, 301–308; b) Y. J. He, G. S. Ni-
varthy, F. Eder, K. Seshan, J. A. Lercher, Microporous Mesoporous Mater.
1998, 25, 207–224.
[12] S. Laforge, P. Ayrault, D. Martin, M. Guisnet, Appl. Catal. A 2005, 279,
79–88.
[13] a) S. Maheshwari, E. Jordan, S. Kumar, F. S. Bates, R. L. Penn, D. F. Shantz,
M. Tsapatsis, J. Am. Chem. Soc. 2008, 130, 1507–1516; b) S. Maheshwari,
C. Martínez, M. T. Portilla, F. J. Llopis, A. Corma, M. Tsapatsis, J. Catal.
2010, 272, 298–308.
For a more detailed comparison of the catalytic performance
of these two materials, the reaction in n-propanol was fol-
lowed as a function of time. Sn-MWW(SP)-SSE exhibits higher
MAL conversion and MALTU yield over all the reaction times
(4 h to 30 h) but both materials show similar selectivity and
their yield versus conversion curves overlap and complement
each other (Figure 4).
In conclusion, it was demonstrated that mesoporous pillared
Sn-MWW (Sn-MWW(SP)-SSE) with ordered inter-layer stacking
and preserved intra-layer crystallinity was obtained through
a solid-state-exchange method. It was found to be an active
and regenerable catalyst for the Baeyer–Villiger oxidation and
mono- and disaccharide isomerization, and, in certain cases,
superior to other Sn-based zeolites.
[14] Q. Guo, F. Fan, E. A. Pidko, W. N. P. van der Graaff, Z. Feng, C. Li, E. J. M.
Hensen, ChemSusChem 2013, 6, 1352–1356.
[15] a) G. Liu, J.-G. Jiang, B. Yang, X. Fang, H. Xu, H. Peng, L. Xu, Y. Liu, P. Wu,
Microporous Mesoporous Mater. 2013, 165, 210–218; b) X. Ouyang, S.-J.
Hwang, D. Xie, T. Rea, S. I. Zones, A. Katz, ACS Catal. 2015, 5, 3108–
3119.
Acknowledgements
This work was supported as part of the Catalysis Center for
Energy Innovation, an Energy Frontier Research Center funded by
the U.S. Department of Energy, Office of Science, Basic Energy Sci-
ences under Award DE-SC0001004. Q.G.’s postdoctoral fellowship
was partially supported by the Petroleum Institute of Abu Dhabi.
[16] a) C. Hammond, S. Conrad, I. Hermans, Angew. Chem. Int. Ed. 2012, 51,
11736–11739; Angew. Chem. 2012, 124, 11906–11909; b) C. Hammond,
D. Padovan, A. Al-Nayili, P. P. Wells, E. K. Gibson, N. Dimitratos, Chem-
CatChem 2015, 7, 3322–3331.
[17] A. Corma, L. T. Nemeth, M. Renz, S. Valencia, Nature 2002, 412, 423–
425.
[18] M. Renz, T. Blasco, A. Corma, V. FornØs, R. Jensen, L. Nemeth, Chem. Eur.
J. 2002, 8, 4708–4717.
Keywords: isomerization · layered materials · Lewis acids ·
solid-state-exchange · zeolites
[19] H. Y. Luo, L. Bui, W. R. Gunther, E. Min, Y. Romµn-Leshkov, ACS Catal.
2012, 2, 2695–2699.
[20] M. Moliner, Y. Romµn-Leshkov, M. E. Davis, Proc. Natl. Acad. Sci. USA
2010, 107, 6164–6168.
[21] C. M. Osmundsen, M. S. Holm, S. Dahl, E. Taarning, Proc. R. Soc. London
Ser. A 2012, 468, 2000–2016.
[22] P. I. Ravikovitch, A. V. Neimark, Colloids Surf. A 2001, 187–188, 11–21.
[23] a) S. Roy, K. Bakhmutsky, E. Mahmoud, R. F. Lobo, R. J. Gorte, ACS Catal.
2013, 3, 573–580; b) M. Boronat, P. Concepción, A. Corma, M. Renz, S.
Valencia, J. Catal. 2005, 234, 111 –118.
ˇ
[1] a) J. Cejka, A. Corma, S. I. Zones, Zeolites and Catalysis Synthesis Reac-
tions and Applications, Wiley-VCH, Weinheim, 1996, pp. 1–57; b) H. van
Bekkum, E. M. Flanigen, J. C. Jansen, Introduction to Zeolite Science and
Practice, Elsevier, Amsterdam, 1991, pp. 5–10; c) R. Xu, W. Pang, J. Yu,
Q. Huo, J. Chen, Chemistry of Zeolite and Related Porous Materials, Wiley,
Singapore, 2007, pp. 1–6; d) R. M. Barrer, Hydrothermal Chemistry of
Zeolites, Academic Press, London, 1982, pp. 1–10.
[24] a) O. M. Busch, W. Brijoux, S. Thomson, F. Schüth, J. Catal. 2004, 222,
174–179; b) B. Chakraborty, B. Viswanathan, Catal. Today 1999, 49,
253–260; c) F. de Clippel, M. Dusselier, R. Van Rompaey, P. Vanelderen, J.
Dijkmans, E. Makshina, L. Giebeler, S. Oswald, G. V. Baron, J. F. M. Denay-
er, P. P. Pescarmona, P. A. Jacobs, B. F. Sels, J. Am. Chem. Soc. 2012, 134,
10089–10101.
[25] N. K. Mal, V. Ramaswamy, P. R. Rajamohanan, A. V. Ramaswamy, Micropo-
rous Mater. 1997, 12, 331–340.
[26] S. P. Elangovan, K. Inoue, T. Okubo, A. Kojima, M. Ogura, Ind. Eng. Chem.
Res. 2007, 46, 1039–1044.
[27] V. Narkhede, H. Gies, Chem. Mater. 2009, 21, 4339–4346.
[28] S. Saravanamurugan, M. Paniagua, J. A. Melero, A. Riisager, J. Am. Chem.
Soc. 2013, 135, 5246–5249.
[29] L. Ren, Q. Guo, P. Kumar, M. Orazov, D. Xu, S. M. Alhassan, K. A. Mkhoy-
an, M. E. Davis, M. Tsapatsis, Angew. Chem. Int. Ed. 2015, 54, 10848–
10851; Angew. Chem. 2015, 127, 10998–11001.
[2] a) A. Corma, Chem. Rev. 1995, 95, 559–614; b) M. E. Davis, Nature 2002,
417, 813–821; c) C. S. Cundy, P. A. Cox, Chem. Rev. 2003, 103, 663–702;
d) M. E. Davis, Chem. Mater. 2014, 26, 239–245.
[3] a) X. Zhang, D. Liu, D. Xu, S. Asahina, K. A. Cychosz, K. V. Agrawal, Y. Al
Wahedi, A. Bhan, S. Al Hashimi, O. Terasaki, M. Thommes, M. Tsapatsis,
Science 2012, 336, 1684–1687; b) M. Choi, K. Na, J. Kim, Y. Sakamoto, O.
Terasaki, R. Ryoo, Nature 2009, 461, 246–250.
[4] a) U. Díaz, A. Corma, Dalton Trans. 2014, 43, 10292–10316; b) B. Marler,
H. Gies, Eur. J. Mineral. 2012, 24, 405–428; c) W. J. Roth, P. Nachtigall,
ˇ
R. E. Morris, J. Cejka, Chem. Rev. 2014, 114, 4807–4837; d) M. Tsapatsis,
AIChE J. 2014, 60, 2374–2381.
[5] a) M. E. Leonowicz, J. A. Lawton, S. L. Lawton, M. K. Rubin, Science 1994,
264, 1910–1913; b) P. Ayrault, J. Datka, S. Laforge, D. Martin, M. Guisnet,
J. Phys. Chem. B 2004, 108, 13755–13763.
[6] a) Y. X. Wang, H. Gies, B. Marler, U. Müller, Chem. Mater. 2005, 17, 43–
49; b) T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai, F. Mizukami, Angew. Chem.
Int. Ed. 2004, 43, 4892–4896; Angew. Chem. 2004, 116, 5000–5004.
[7] a) C. T. Kresge, W. J. Roth, K. G. Simmons, J. C. Vartuli, WO 92/11934,
1992; b) C. T. Kresge, W. J. Roth, U.S. Patent 5266541, 1993; c) C. T.
Kresge, W. J. Roth, U.S. Patent 5278115, 1994.
[8] a) A. Corma, V. Fornes, S. B. Pergher, Th. L. M. Maesen, J. G. Buglass,
Nature 1998, 396, 353–356; b) K. Varoon, X. Zhang, B. Elyassi, D. D.
Brewer, M. Gettel, S. Kumar, J. A. Lee, S. Maheshwari, A. Mittal, C.-Y.
Sung, M. Cococcioni, L. F. Francis, A. V. McCormick, K. A. Mkhoyan, M.
Tsapatsis, Science 2011, 334, 72–75; c) P. Wu, D. Nuntasri, J. Ruan, Y. Liu,
M. He, W. Fan, O. Terasaki, T. Tatsumi, J. Phys. Chem. B 2004, 108,
19126–19131; d) A. Corma, V. FornØs, J. Martínez-Triguero, S. B. Pergher,
J. Catal. 1999, 186, 57–63.
[30] R. Bermejo-Deval, M. Orazov, R. Gounder, S.-J. Hwang, M. E. Davis, ACS
Catal. 2014, 4, 2288–2297.
[31] a) Y. Romµn-Leshkov, M. Moliner, J. A. Labinger, M. E. Davis, Angew.
Chem. Int. Ed. 2010, 49, 8954–8957; Angew. Chem. 2010, 122, 9138–
9141; b) R. Bermejo-Deval, R. S. Assary, E. Nikolla, M. Moliner, Y. Romµn-
Leshkov, S.-J. Hwang, A. Palsdottir, D. Silverman, R. F. Lobo, L. A. Curtiss,
M. E. Davis, Proc. Natl. Acad. Sci. USA 2012, 109, 9727–9732.
[32] R. Bermejo-Deval, R. Gounder, M. E. Davis, ACS Catal. 2012, 2, 2705–
2713.
Received: January 30, 2016
Published online on March 23, 2016
ChemCatChem 2016, 8, 1274 – 1278
www.chemcatchem.org
1278
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