Direct Synthesis, Structural Features, and Enhanced Catalytic Activity of the Basolite F300-like Semiamorphous Fe-BTC Framework

Article abstract of DOI:10.1021/acs.cgd.5b00755

Paradoxically, one of the most widely and successfully tested metal-organic framework (MOF)-based catalysts, i.e., the Fe-BTC material commercialized as Basolite F300, entails a certain "mystery": Its structure is unknown and only an indirect and complex preparation method has been reported. This work describes an easy preparation method of a Basolite F300-like material. Furthermore, this synthesis procedure is carried out under environmentally and economically sustainable conditions: at room temperature, in a few minutes and using water as the unique solvent. Several characterization techniques indicate that both commercial and lab-made Fe-BTC materials are very much similar in so many physicochemical properties. However, the herein reported Fe-BTC possesses better textural properties, especially regarding the external surface area. Both Fe-BTC materials catalyze the oxidation of cyclohexene with very similar selectivity. However, the sample prepared in the laboratory gives a notably higher conversion, which was attributed to its external surface area. Iron leaching, if any, was negligible, and no significant structural transformation was detected. Finally, this paper also gives valuable structural information about the semiamorphous Fe-BTC: it exclusively contains the smallest mesocages of MIL-100(Fe), which provides an important input for interpreting the role of these Fe-BTC materials in any application demanding high porosity. (Graph Presented).

Full text of DOI:10.1021/acs.cgd.5b00755

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Article
Direct synthesis, structural features and enhanced catalytic activity
of the Basolite F300-like semi-amorphous Fe-BTC framework
Manuel Sánchez-Sanchez, Iñigo de Asua, Daniel Ruano, and Kenya Díaz
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00755 • Publication Date (Web): 11 Aug 2015
Downloaded from http://pubs.acs.org on August 13, 2015
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Direct synthesis, structural features and enhanced catalytic activity of the
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Basolite F300-like semi-amorphous Fe-BTC framework
Manuel Sanchez-Sanchez,* Iñigo de Asua, Daniel Ruano and Kenya Diaz
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Instituto de Catálisis y Petroleoquímica, ICPꢀCSIC, C/ Marie Curie 2, 28049 Madrid, Spain.
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ABSTRACT. Paradoxically, one of the most widely and successfully tested MOFꢀbased
catalysts, i.e. the FeꢀBTC material commercialized as Basolite F300, entails certain ‘mystery’: Its
structure is unknown and only an indirect and complex preparation method has been reported.
This work describes an easy preparation method of a Basolite F300ꢀlike material. Furthermore,
this synthesis procedure is carried out under environmentally and economically sustainable
conditions: at room temperature, in a few minutes and using water as the unique solvent. Several
characterization techniques indicate that both commercial and labꢀmade FeꢀBTC materials are
very much similar in so many physicochemical properties. However, the herein reported FeꢀBTC
possesses better textural properties, especially regarding the external surface area. Both FeꢀBTC
materials catalyze the oxidation of cyclohexene with very alike selectivity. However, the sample
prepared in the laboratory gives a notably higher conversion, which was attributed to its external
surface area. Iron leaching, if any, was negligible and no significant structural transformation
was detected. Finally, this paper also gives valuable structural information about the semiꢀ
amorphous FeꢀBTC: it exclusively contains the smallest mesocages of MILꢀ100(Fe), what
provides an important input for interpreting the role of these FeꢀBTC materials in any application
demanding high porosity.
Textural properties
Catalytic activity
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Basolite F300-like
Laboratory
Basolite F300-like
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OH
O
TBHP
Basolite F300
Commercial
Basolite F300
Commercial
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Time / h
Dr. Manuel Sánchez-Sánchez
Instituto de Catálisis y Petroleoquímica, ICP-CSIC
C/ Marie Curie, 2, 28049 Madrid, Spain
Tel.: +34-915854795; Fax: +34-915854760
E-mail: manuel.sanchez@icp.csic.es
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Direct synthesis, structural features and enhanced
catalytic activity of the Basolite F300ꢀlike semiꢀ
amorphous FeꢀBTC framework
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Manuel Sanchez-Sanchez,* Iñigo de Asua, Daniel Ruano and Kenya Diaz
Instituto de Catálisis y Petroleoquímica, ICPꢀCSIC, C/Marie Curie, 2 28049, Madrid, Spain
Eꢀmail address: manuel.sanchez@icp.csic.es
KEYWORDS. Room temperature preparation, Basolite F300, FeꢀBTC, cyclohexene oxidation,
diffusional problem.
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ABSTRACT. Paradoxically, one of the most widely and successfully tested MOFꢀbased
catalysts, i.e. the FeꢀBTC material commercialized as Basolite F300, entails certain ‘mystery’: Its
structure is unknown and only an indirect and complex preparation method has been reported.
This work describes an easy preparation method of a Basolite F300ꢀlike material. Furthermore,
this synthesis procedure is carried out under environmentally and economically sustainable
conditions: at room temperature, in a few minutes and using water as the unique solvent. Several
characterization techniques indicate that both commercial and labꢀmade FeꢀBTC materials are
very much similar in so many physicochemical properties. However, the herein reported FeꢀBTC
possesses better textural properties, especially regarding the external surface area. Both FeꢀBTC
materials catalyze the oxidation of cyclohexene with very alike selectivity. However, the sample
prepared in the laboratory gives a notably higher conversion, which was attributed to its external
surface area. Iron leaching, if any, was negligible and no significant structural transformation
was detected. Finally, this paper also gives valuable structural information about the semiꢀ
amorphous FeꢀBTC: it exclusively contains the smallest mesocages of MILꢀ100(Fe), what
provides an important input for interpreting the role of these FeꢀBTC materials in any application
demanding high porosity.
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INTRODUCTION
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The catalytic potential of MetalꢀOrganic Frameworks (MOFs) has already been reflected in so
many investigations.1ꢀ6 At the same time, the progress in their catalytic applications seems to be
limited by certain aspects, such as their controversial stability in the reaction media, the lack of
systematic studies or the subsequent scarce number of works affording some correlation between
structural features of the MOF materials and their catalytic behavior. 7ꢀ10
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Probably, the maximum exponent of this disparity between the possibilities and the soꢀfar
reduced development of MOFs as catalysts is found in the case of the FeꢀBTC material,
commercialized as Basolite F300. There are tens of publications remarking the notable catalytic
performance of this material2, 11ꢀ22 in reactions requiring either acidic or redox centers. Moreover,
this material has been used as raw material to generate highly active and stable FischerꢀTropsch
catalysts.23 It is particularly noteworthy that its catalytic behavior has been systematically
compared with that of the wellꢀknown MILꢀ100(Fe) in a large number of reactions.2, 14, 20, 22, 24, 25
MILꢀ100(Fe) material is also formed by iron and trimesic acid, that is, it is also a FeꢀBTC
material, having two types of cages in the range of mesopores. 26 Wide and detailed comparison
between both materials concluded that they are similar but essentially different from a physicoꢀ
chemical point of view. 27 Accordingly, both FeꢀBTC materials catalyze the same reactions but
giving different activity/selectivity, in such a way that the semiꢀamorphous FeꢀBTC generally
results more active in reactions requiring acidic centers (whereas the opposite trend was found in
the redox reactions),14 despite the former possesses lower textural properties, maybe because
defects also play an essential catalytic role.28, 29 This overcoming its homologous highlyꢀporous
MILꢀ101(Fe) gives an idea of the potential of this material, which of course deserves to be
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deeply investigated. In this sense, a very recent and meritorious study provides some insights
into the Fe clusters in Basolite F300 material as well as into the influence of the
hydratation/dehydration process on the Fe sites environment. 30
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Improving the performance of a catalyst is quite often based on changing the experimental
conditions of its preparation, ideally taking into account the knowledge about the role and/or the
environment of the active centers. However, the development of the catalytic potential of this Feꢀ
BTC material is seriously limited by both the lack of reported synthesis methods and by the
unsolved structure. Nevertheless, the preparation of a similar material was already reported albeit
through an indirect method including the previous preparation and isolation of the Fe precursor,
a mixed Fe2+/Fe3+ layered double hydroxide. 20 In this context, this article addresses two
important advances in both synthesis procedure and structural knowledge of this semiꢀ
amorphous FeꢀBTC material. On one hand, it is described a direct, sustainable, cheap and almost
instantaneous synthesis of a Basolite F300ꢀlike material, which opens so many possibilities of
studying the influence of synthesis parameters on the final properties and adsorption/catalytic
behavior of the resultant materials. As an example, the optimized labꢀprepared FeꢀBTC is shown
to enhance the catalytic activity of its commercial homologue in the oxidation of cyclohexene.
The synthesis procedure used in this work for preparing the FeꢀBTC materials is based on the
sustainable and widely applicable via to obtain carboxylateꢀbased MOF materials recently
described by our group, 31, 32 which for instance allows to achieve these materials at room
temperature and in water as the unique solvent. On the other hand, a detailed and combined
characterization of semiamorphous (Basolite F300ꢀlike) and crystalline (MILꢀ100(Fe)) FeꢀBTC
materials by means of N2 adsorption/desorption isotherms, lowꢀangle XRD and TG analyses
have made clear that the former possesses just one of the two types of cages present in the latter.
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The catalytic results of this work are also discussed in terms of such structural feature and the
differences in physicochemical properties between the commercialized and the labꢀmade Feꢀ
BTC materials. In the course of writing this article, a highlyꢀrelated publication appeared
addressing both a synthesis method and the structural solving of the sample A520, also
commercialized by BASF and SigmaꢀAldrich.33
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EXPERIMENTAL
2.1. Synthesis of the Fe-BTC materials
FeꢀBTC material was prepared in water at room temperature adapting the novel concepts in the
MOF synthesis31, 32 to the ironꢀtrimesate system. A typical synthesis starts with the preparation of
two solutions: (i) the colorless Solution 1 (pH = 10.9) was prepared by dissolving 0.263 g of
trimesic acid (H3BTC) in a NaOH aqueous solution composed by 10 g of H2O and 0.150 g of
NaOH; and (ii) the yellowish orange Solution 2 (pH = 1.8) was prepared by dissolving 0.508 g of
FeCl3·6H2O in 10 g of H2O. Next, Solution 2 was added dropwise over Solution 1 under
magnetic stirring, generating the immediate appearance of a brownish orange solid. The resultant
suspension (pH = 2.1) was maintained under stirring at room temperature (23 ºC) during a period
of time varying from 10 minutes to 24 hours. The molar ratio of the mixture was 1.5 Fe : 1.0
BTC : 3.0 NaOH : 880 H2O. The solids were recovered by centrifugation, washed different times
with deionized water and subsequently with ethanol, and then dried at room temperature. The
samples were denoted as FeBTCꢀtime, whereas the commercially available FeꢀBTC (supplied by
Aldrich) was designated as Basolite F300.
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A MILꢀ100(Fe) material was prepared as described elsewhere26 for comparison purposes.
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Powder Xꢀray diffraction (XRD) patterns were acquired with a Philips X’PERT diffractometer
using Cu Kα radiation. Attenuated total reflectionꢀFourier transform infrared (ATRꢀFTIR)
spectra were recorded using a Thermo Nicolet Nexus 670 FTIR spectrometer equipped with a
SensIR Technologies DurasamplIR horizontal ATR accessory and a liquid nitrogenꢀcooled MCT
detector. Thermogravimetric analyses (TGA) were registered in a PerkinꢀElmer TGA7
instrument. TG analyses were carried out at a heating rate of 20 ºC/min under air flow. Nitrogen
adsorption/desorption isotherms were measured at ꢀ196 ºC in a Micromeritics ASAP 2020
device. Before the measurement, the previously calcined sample was degassed at 150 ºC under
high vacuum for at least 18 hours. Surface areas were estimated by the BET method;
microporous and external surface areas were estimated by applying tꢀplot method; and pore size
distributions were calculated applying the BJH method corrected by KrukꢀJaroniecꢀSayari
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method 34
. Scanning Electron Microscopy (SEM) studies were carried out in an Ultraꢀhigh
Resolution FEIꢀNOVA NanoSEM 230 FESEM instrument equipped with an EDS detector for
punctual elemental microanalyses.
2.3. Catalytic reactions
Catalytic tests were run as described elsewhere.7, 35 As a previous step, FeꢀBTC samples were
placed in a round flask submerged in a silicone bath at 150 ºC, and kept overnight under constant
N2 flow. The oxidation of cyclohexene was carried out at 70 ºC under atmospheric pressure and
under stirring (400 rpm). The system was refrigerated with water at 5 ºC (cyclohexene
evaporation below 3 wt. % after 48 h of reaction). The substrate cyclohexene (10 times the
weight of the evacuated catalyst), the solvent acetonitrile (cyclohexene/acetonitrile molar ratio of
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30) and the internal GC standard toluene (the same weight than the catalyst) were added over the
catalyst. Once this mixture reached 70 ºC (temperature controlled with a thermometer in contact
with the mixture), the oxidizing agent tertꢀbutyl hydroperoxide (TBHP) was added, taking the
moment of this addition as reaction time zero. Aliquots at different reaction times (0ꢀ25 h) were
taken under stirring to follow the kinetics. These aliquots were analyzed by gas chromatography
(Varian 430 GC; capillary column of 15 m length, 0.25 mm diameter, 1 µm stationary phase
thickness; FID detector) and total reflection Xꢀray fluorescence (TXRF) after being filtered
(filter paper with pores of 0.45 µm). Identification of the nonꢀcommercial 2ꢀcyclohexenyl
peroxide product was done as described elsewhere.35 Due to the high volatility of cyclohexene,
its conversion was calculated indirectly, through the sum of the detected products. Mass balance
always had an error below 10 %.
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RESULTS AND DISCUSSION
The PXRD patterns of the FeꢀBTC samples prepared at room temperature after different
synthesis times are shown in Figure 1, compared to the diffractogram of the commercial MOF
Basolite F300 (supplied by SigmaꢀAldrich). The low resolution of the presented XRD patterns is
a consequence of the semiꢀamorphous nature of these materials. In any case, some relatively
broad bands were detected, and they can somehow be taken as a rough fingerꢀprinted proof of
the nature of the material. There is a very good agreement between the PXRD patterns of the Feꢀ
BTC samples prepared at the laboratory and that of the commercial Basolite F300, in terms of
the position, and both relative and absolute intensities of the XRD bands. Affording FeꢀBTC by
this method is very relevant from a sustainability viewpoint, as it can be prepared at room
temperature, in a few minutes and using water as unique solvent. From a kinetics point of view,
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two aspects should be highlighted. Firstly, the material can be formed instantaneously (it is
already formed after 10 minutes). Secondly, the samples as seen by XRD are maintained
basically invariable during the first hours (and even days) of the synthesis. In any case, because
of the low resolution of the patterns, XRD characterization is quite limited and some other
characterization techniques should be used to shed light on the similarities/differences between
the commercial and the labꢀmade FeꢀBTC materials.
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FeBTCꢀ7d
FeBTCꢀ24h
FeBTCꢀ6h
FeBTCꢀ2h
FeBTCꢀ10min
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Figure 1. XRD patterns of the commercial Basolite F300 (black line, at the bottom) and of the
FeꢀBTC materials prepared in the laboratory after different synthesis times. The patterns were
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not normalized but just moved along the Yꢀaxis. The rising background is due to the
fluorescence effect.
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In any case, the procurement of a material quite similar to the Basolite F300 is out of any doubt
at this point. Moreover, the sustainability of the methodology deserves to be remarked. The
procedure is carried out at room temperature, in a few minutes and using water as the unique
solvent. Some other energetic and/or environmental advantages of the method has been
discussed elsewhere.31 In contrast, the only reported method to prepare a similar material, which
is also carried out at room temperature, implies the previous preparation (with careful control of
the oxidation processes) for up to 24 hours and subsequent isolation of a mixed Fe2+/Fe3+ layered
double hydroxide, and an extra step to form the FeꢀBTC material including the use of a
considerable amount of ethanol.20
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Since the limited information about structural features of these semiamorphous materials, the IR
spectroscopy region of ca. 650–1800 cmꢀ1 can be also taken as a fingerprint of materials nature,
especially when they contain organic entities such as MOFs.36, 37 It was particularly useful to
identify MOFs formed by crystals so small that their characterization by XRD is uncertain.36
Unlike PXRD, which is sensitive to the structure of materials (longꢀrange information), that IR
region is rather sensitive to the conformational and/or local environment of organic molecules
(shortꢀrange information), so both techniques are somehow complementary. Figure 2 compares
the FTIR spectra of the samples Basolite F300 and FeBTCꢀ10min. The FTIR spectra of the rest
of the samples FeꢀBTC prepared in the lab at different times are practically identical to that of
FeBTCꢀ10min, so they have been omitted for clarity. Both FTIR spectra are similar but not
equal. Some differences are evident in the 800ꢀ1100 cmꢀ1 region, where the bands are rather
weak. Nevertheless, there is a very good agreement away from that region, suggesting that both
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materials are closely related to each other. Such good agreement becomes even more manifest
when the FTIR spectrum of any of both materials is compared with the spectrum of the free
trimesic acid (H3BTC), which is markedly different in spite of the fact that all samples basically
contain the same organic moiety. Therefore, not only the longꢀrange information given by XRD
but also the shorterꢀrange one indicated by FTIR studies, suggests that the nature or our FeꢀBTC
material, although different, is near to that of the commercial Basolite F300.
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Figure 2. FTIR spectra of the commercial Basolite F300 (black line, at the bottom), the sample
FeBTCꢀ10min (red, in the middle) and the free linker H3BTC (blue, at the top).
One of the most important issues of the MOF materials is their thermal stability. At the same
time, that stability as well as some other features derived from thermogravimetric (TG)
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characterization could be taken as indications about the similarity between two FeꢀBTC
materials. The thermal stability of the commercial and our FeꢀBTC materials are practically the
same and 70 ºC lower than the protonated linker H3BTC (Figure S1 and Table S1).
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In so many applications including heterogeneous catalysis, porosity of MOF materials becomes a
key parameter. Figure 3a shows the N2 adsorption/desorption isotherms of Basolite F300,
FeBTCꢀ10min and FeBTCꢀ24h. The estimated BET area of the Basolite F300 (859 m2gꢀ1, Table
1) is lower than that indicated by the supplier (1300 – 1600 m2gꢀ1) but very close to that
experimentally measured by others14, 20, 27 and substantially higher than that found very
recently.38 Although the labꢀmade FeꢀBTC possesses properties quite similar to these of Basolite
F300 according to XRD, FTIR and TG characterization, the porosity of the former is markedly
higher, particularly in the mesoporous region. The total BET area was estimated in 1092 m2gꢀ1,
more than one fourth higher than that of the commercial one. Since the main alteration between
both isotherms is found in the mesoporous region, the difference is even much higher in the pore
volume (1.30 and 0.38 cm3gꢀ1 for the samples FeBTCꢀ10min and Basolite F300, respectively).
That difference is more easily interpreted from the pore size distributions (PSD) (Figure 3b).
Indeed, the PSD curve of the sample FeBTCꢀ10min shows a relatively narrow peak centered at
5.3 nm, which is completely absent in the PSD profile of Basolite F300. The sample FeBTCꢀ24h
also contains certain contribution in that region, although it is quite less intense and is shifted
toward smaller mesopores.
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b
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2.2 nm
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FeBTCꢀ10min
FeBTCꢀ24h
5.3 nm
FeBTCꢀ10min
FeBTCꢀ24h
Basolite F300
0
Basolite F300
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10
p/p0
log D
Figure 3. (a) N2 adsorption/desorption isotherm at ꢀ196 ºC of the samples FeBTCꢀ10min,
FeBTCꢀ24h, Basolite F300 and MILꢀ100(Fe). (b) Pore size distribution curves of the adsorption
braches of the same isotherms.
Table 1. Data estimated from the N2 adsorption/desorption isotherms and pore size distributions
from Figure 3 of the indicated samples.
Sample
Total
SBET / m2g-1
859
External
SBET a / m2g-1
63
Vp b / cm3g-1
PSD peaks c
/ nm
0.38
1.30
1.8
Basolite F300
FeBTC-10min
1092
525
1.8, 2.2, 4.5
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FeBTC-24h
a Data from t-plot. External SBET is the difference between the total SBET and the microporous SBET
.
b Pore volume measured at p/p0 = 0.98.
c
Maxima of the peaks found in pore size distribution by the applying BJH method to the adsorption
branches. The values were corrected by the KrukꢀJaroniecꢀSayari method.34
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Moreover, the PSD curves of Figure 3b present a further distinctiveness that deserves to be
analyzed in detail. The PSD curve of any of the semiꢀamorphous FeꢀBTC sample indicates the
existence of some cavities with narrow pore distribution with a diameter of 1.8 nm, very close to
the limit between micropore and mesopore according to the IUPAC classification, i. e., near 2
nm. However, it must be taken into account that the BJH method used in the generation of PSD
plots from the isotherm systematically underestimates the pore diameter.39 Despite these PSD
curves were corrected by KrukꢀJaroniecꢀSayari method,34 designed for MCMꢀ41ꢀlike materials,
it is quite probable that the PSD curves from Figure 3b still underestimates the pore diameter.
Indeed, the PSD curve (also obtained from the adsorption branch of an N2 isotherm registered
under the same conditions in our laboratory) of a MILꢀ100(Fe) material (violet curve in Figure
3b) shows two intense and narrow peaks in that region, centered at 1.8 and 2.2 nm, which were
undoubtedly attributed to the two types of wellꢀknown mesoporous cages characteristic of the
MILꢀ100(Fe) material. However, these cavities actually have diameters of 2.5 and 2.9 nm,26 so
the underestimation of the pore diameter in the soꢀgenerated PSD curve is still 0.7 nm for these
materials. It is remarkable that, according to this interpretation, Basolite F300 is differentiated
from the crystalline MILꢀ100(Fe) in possessing just the smallest one of the two mesoporous
cages of the latter.
Figure 4 displays two extra characterization proofs supporting this interpretation. The low angle
XRD patterns (Figure 4a) of both labꢀmade and commercial FeꢀBTC materials shows a broad
reflection at around 3.8 º (d = 23.2 Å) that coincides with the 2θ position of the XRD reflections
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220, 311 and 222 clearly observed in the MILꢀ100(Fe) pattern, suggesting that some mesocages
are indeed present in the semiamorphous materials. However, there is no evidence of the
reflection 111 (d = 42.3 Å) in the XRD patterns of any of the two FeꢀBTC materials, unlike in
that of MILꢀ100(Fe) material. Since the reflection 111 corresponds to the largest spacing d of the
structure, it is expected that it is related to the largest cages of the structure. Figure 4b plots the
normalized TGA derivatives curves of the three FeꢀBTC samples: Basolite F300, FeBTCꢀ10min
and MILꢀ100(Fe) in the region of the water loss (25ꢀ150 ºC). In that temperature region, TG
analysis detected two losses for the sample MILꢀ100(Fe) (centered at 46 and 72 ºC), which were
attributed to the presence of the two different cages. In good agreement with the discussion about
TGA curves of FeꢀBTC (Supporting Information), the TG derivative of either Basolite F300 or
FeBTCꢀ10min in the region 25ꢀ150 ºC presents a unique loss centered at 66 and 71 ºC,
respectively (Table S1). This loss is clearly closer to the second loss of MILꢀ100(Fe). It seems
quite logical to attribute this second weight loss to the water molecules trapped within the
smallest cages, where presumably they would be more strongly retained than in the larger ones.
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This result is of great importance for understanding the differences in adsorption and/or catalytic
behavior of both FeꢀBTCꢀbased materials. For instance, MILꢀ100(Fe) but not Basolite F300
could catalytically process within its cages molecules having kinetic diameter between 4.7/5.5 Å
and 8.6 Å, which are the window openings of the small and large cages, respectively.26 It is also
worth to underline that the labꢀmade FeꢀBTC samples, unlike the commercial one, contain
certain amount of the largest cages of MILꢀ100(Fe), according to their PSD (Figure 4b).
Therefore, the difference in textural properties between the commercial and the hereinꢀprepared
FeꢀBTC materials is not exclusively due to the presence of high external surface area. To
conclude the discussion of the N2 isotherms, it is noteworthy that the characterization of either
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amorphous or semiꢀamorphous MOF material by means of adsorption/desorption isotherms is by
far the most helpful, informative and revealing tool for any application that requires high
porosity, even providing indirect but trustable structural information considering the limitations
of XRD techniques for these scarcelyꢀordered materials.
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a
b
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Simulated
MILꢀ100(Fe)
311
MILꢀ100(Fe)
222
MILꢀ100(Fe)
FeBTCꢀ10min
Basolite F300
FeBTCꢀ10min
Basolite F300
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50 100
T / ºC
150
2θ / º
Figure 4. (a) Simulated low angle XRD pattern of the simulated MILꢀ100(Fe) (top) and
experimental low angle XRD patterns of the samples Basolite F300, FeBTCꢀ10min and MILꢀ
100(Fe). (b) Normalized TG derivative curves of the same samples.
Taking into account that labꢀmade and commercial FeꢀBTC samples have different textural
properties especially manifest in the external surface, it was expected that some differences could
be somehow apparent in their particle morphology and/or size. Some representative SEM images
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of Basolite F300 and FeBTCꢀ10min are shown in Figure 5. Basolite F300 is formed by two types
of particles of similar sizes (around 10 µm), as they can be seen in Figure 5a. The predominant
particles are the ones appearing at the top of Figure 5a. An enlargement of one of this type of
particles is shown in Figure 5b. They are formed by nanocrystals or at least these nanocrystals
efficiently cover the surface of bigger particles. The less predominant particles (the particle at the
bottom of Figure 5c is a good example) scarcely contain some nanocrystals on the surface.
Contrasting with this morphology heterogeneity, the sample FeBTCꢀ10min is formed by
particles having uniform appearance. These particles have size in the range 10ꢀ50 µm. The
images of Figure 5d and 5e, registered at different magnifications, shows that the particles have
not only homogenous appearance from a distance but also they are homogenously composed by
much smaller nanoparticles of very similar shape and size. These nanoparticles are agglomerated
generating some relativelyꢀordered ‘intercrystalline’ mesoporosity, in good agreement with the
significant N2 adsorption and the existence of a hysteresis loop in the mesoporous region of the
isotherm (Figure 3b).
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The samples were also studied by EDS elemental microanalysis, integrated into the microscope.
Apart from Fe, O and C, the FeꢀBTC samples prepared in our laboratory showed some traces of
Cl, which is not surprising since FeCl3·6H2O was the iron source in the synthesis procedure. On
the other hand, Basolite F300 showed some traces of S as an unexpected element, suggesting that
any Sꢀcontaining Fe source, probably iron sulfate, was used in the unreported synthesis
procedure of this commercial material.
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Figure 5. SEM images of FeꢀBTC samples: (a), (b) and (c) Basolite F300; (d) and (e) FeBTCꢀ
10min. The limited resolution at high magnifications was probably due to the magnetic character
of the Feꢀrich samples.
To prove the benefits of labꢀmade FeꢀBTC samples against the commercial Basolite F300, which
has been pointed out by some characterization techniques, these samples were tested in the most
widely used and successful application of these materials so far, i.e. as heterogeneous catalysts.
In particular, the tested reaction was the oxidation of cyclohexene with peroxides in liquid
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media. This test reaction was chosen because cyclohexene can be oxidized through two different
routes: epoxidation and allylic oxidation, which imply the oxidation of C atoms of the double
bond and the adjacent C atoms to the double bond, respectively (Scheme 1).7, 35 Therefore, both
mechanisms yield different oxidation products, and can provide important information about the
performance of the catalysts. Thus, this reaction was recently selected to provide key insights
into the redox catalytic role of the metal ion M in the isostructural series of MꢀMOFꢀ74 catalysts
(M = Mn, Co, Ni, Cu, Zn), concluding that the radicalꢀroute oxidation is governed by the surface
area of the material as long as M is a redox metal ion, whereas the epoxidation catalytic activity
was related to the reduction potential of the redox metal.7 Figure 6 shows the total yield (solid
lines) of products resulting from the oxidation of cyclohexene with no catalysts (blank
experiment) and in the presence of an activated catalyst, either FeBTCꢀ10min or Basolite F300.
Yield of products is given instead of direct cyclohexene conversion in order to avoid any error
due to the evaporation of the cyclohexene throughout the reaction time despite the system was
refrigerated with water at low temperature (5 ºC).35 Data of the catalytic results after ca. 24 hours
are compiled in Table 2. With no catalyst, there is certain catalytic activity (18.8 % conversion),
indicating that the reaction is spontaneous to some extent under the tested conditions. The
presence of any FeꢀBTC samples enhances the conversion of cyclohexene, certifying that they
are real catalysts of this process. Moreover, the labꢀmade FeBTCꢀ10min sample is significantly
more active than the commercial Basolite F300. Indeed, if the spontaneous conversion is
subtracted from that given by the catalysts, the activity of FeBTCꢀ10min (39.3 %) is exactly
double than that of Basolite F300 (19.5 %). Since both materials are quite similar as inferred by
different characterization techniques such as XRD, FTIR and TGA, we attributed the difference
in the catalytic activity to the substantial difference in external surface area.
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OH
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Radical
2
3
4
Oxidant
Catalyst
Epoxidation
OH
O
1
O
6
7
H2O
5
OH
OH
8
Scheme 1. Products generated from the oxidation of cyclohexene through either the radical (top)
or epoxidation (bottom) routes. 1: cyclohexene; 2: cyclohexenyl hydroperoxide or 3ꢀ
hydroperoxyꢀ1ꢀcyclohexene; 3: , 2ꢀcyclohexenꢀ1ꢀol; 4: 2ꢀcyclohexenꢀ1ꢀone; 5: cyclohexene
oxide; 6: cyclohexanol; 7: cyclohexanone; 1,2ꢀcyclohexanediol.
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FeBTCꢀ10min
Basolite F300
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No catalyst
0
5
10
15
20
25
Time / h
Figure 6. Total yield (solid lines) of cyclohexene oxidation products as a function of reaction
time, resulting from the catalytic tests in the absence of any catalyst (grey) or in the presence of
either the Basolite F300 sample (black) or the FeBTCꢀ10min sample (red). The yield of the
products through radical (dashed lines) or epoxidation (dot lines) routes of the reactions in the
presence of catalysts are also shown.
Table 2. Total yield and yield by different routes of the catalytic experiments with no catalyst or
in the presence of Basolite F300 or FeBTCꢀ10min catalysts.
Sample
Total
Radical route yield / %
Epoxidation route yield / %
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yield /
%
2a
3a
4a
Total
5a
8a
Total
6
7
38.3
29.4
1.1
3.8
34.3
0.5
3.5
4.0
Basolite F300
8
9
58.1
18.8
39.3
18.0
1.8
0.1
12.7
0.7
53.8
18.8
ꢀ
ꢀ
4.3
ꢀ
4.3
ꢀ
FeBTC-10min
No catalyst
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a Numbers indicates the chemicals according to Scheme 1. Products 6 (cyclohexanol) and 7
(cyclohexanone) were not detected.
In principle, the difference in catalytic activity (double for the FeBTCꢀ10min catalyst) seems to
be too high for being reasonably justified by the difference in surface area (27 % higher for the
same sample), especially taking into account that the oxidation by the radical mechanism, which
is extensively predominant for both FeꢀBTC catalysts (Figure 6 and Table 2), resulted directly
proportional to the surface area (either microporous or external) and independent on the metal
nature in the isostructural series of MꢀMOFꢀ74 7. However, some other aspects could influence
the global activity. Since both FeꢀBTC presumably contains only the smallest cages found in
MILꢀ100(Fe), with windows entrance as small as 4.7ꢀ5.5 Å,26 it is possible that reactants and
products have some important diffusion problems to access the these cages. For instance, both
reactants TBHP40 and cyclohexene41 have been reported to access very limitedly to the pores of
the TSꢀ1 zeolite, one of the most typical catalysts in the oxidation of light olefins with pore
diameter of precisely 5.5 Å. Although MOF structures are expected to be much more flexible
than zeolite ones, it can inferred that diffusional problems would be important and therefore
external surface area rather than microporous area would be the main responsible factor for the
catalytic activity in the oxidation of cyclohexene with TBHP. Supporting this interpretation, the
cyclohexene conversion through the epoxidation route, which requires that both TBHP and
cyclohexene meet in the neighborhood of the active sites, is really low in both FeꢀBTC catalysts
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compared to the conversion by the radical route, which requires that a unique TBHP molecule
interacts with an Fe site to convert several cyclohexene molecules due to the propagation of
radicals. Anyway, although some factors could alter the direct correlation between surface area
and catalytic activity, it is clear that the cyclohexene conversion must be especially favored by
the external surface area.
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Finally, despite the low conversion through the epoxidation mechanism does not allow to extract
important conclusions, it is worth to underline a relevant detail. Some cyclohexene epoxide
remains at the end of the reaction when Basolite F300 is the catalyst but not at all when the
catalyst is the sample FeBTCꢀ10min. It is wellꢀknown that the aperture of epoxides is catalyzed
by Fe acid sites.42 Therefore, the total transformation of the epoxide by the catalyst FeBTCꢀ
10min suggests that its catalytic activity is higher not only in oxidation reactions but also in
reactions requiring acidic centers. Acidic catalytic tests with these two FeꢀBTC samples are in
progress.
One of the most controversial issues about the MOF catalysts is their stability under the tested
reaction conditions. Figure 7 shows the conversion and the Fe leaching of three successive
catalytic reactions with the same portion of the sample FeꢀBTCꢀ10min as well as the XRD
patterns of the catalyst before and after the reaction. The catalytic activity is maintained or even
slightly increased along the reaction cycles. At the same time, no significant metal leaching was
detected, The reaction mixture of the first cycle only contained 0.3 ppm of Fe, which should be
considered negligible. Reaction mixture of the second and third cycles had even lower iron
content (0.015 and 0.042 ppm, respectively), whereas both the reaction mixture of the blank
experiment and that of the Basolite F300, which has no leaching after similar reaction
conditions,11, 13, 16, 22, 24 gave an Fe concentration of 0.035 ppm. That so low metal leaching
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contrasts to that found in the series of isostructural MꢀMOFꢀ74 materials, tested under exactly
the same conditions 7. The XRD pattern of the asꢀreacted one is slightly different to that
registered before reaction in terms of intensity, the presence/absence of some XRD bands/peaks,
etc. These differences could be attributed to the presence of chemical species (reactants, solvent
or products) within the pores, as the diffractogram after three reactions cycles of the filtered and
washed catalyst recoveres the diffraction features, as the commercial Basolite F300 material does
after reaction16. Therefore, FeꢀBTCꢀ10min sample is a reusable heterogeneous catalyst.
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Washed after the
third reaction cycle
61.9 %
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Asꢀreacted after the
first reaction cycle
Before reaction
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/ º
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2θ
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Figure 7. (a) Yield (black columns, left Yꢀaxis) and iron leaching (orange squares, right Yꢀaxis)
in the cyclohexene oxidation catalyzed by the FeꢀBTCꢀ10min sample. (b) XRD patterns of the
FeꢀBTCꢀ10min catalysts: before reaction (red line, at the bottom), asꢀreacted after the first
reaction cycle (green line, in the middle), and filtered and washed after the third reaction cycle.
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CONCLUSIONS
This article describes a direct (oneꢀstep), easy, rapid and sustainable preparation of a semiꢀ
amorphous Basolite F300ꢀlike FeꢀBTC MOF material. The experimental conditions include
room temperature, water as the unique solvent and synthesis time of just a few minutes.
Although, according to an extensive characterization, both the longꢀ and shortꢀrange structure
features, Fe/BTC ratio, Fe and BTC environment or the BTC conformation are quite similar in
both materials, the optimized FeꢀBTC sample prepared in the laboratory overcomes the textural
properties of the commercial Basolite F300. Such difference is due to the labꢀmade sample is
formed by small and homogeneous nanocrystals agglomerated in ordered particles containing
‘intercrystalline’ mesoporosity of about 5 nm of diameter, whereas Basolite F300 lacks
significant external surface area. The consequently expected advantages in, for instance,
avoiding diffusion problems was made clear in the catalytic oxidation of cyclohexene, as the new
FeꢀBTC sample doubled the catalytic activity given by Basolite F300, maintaining the structure
and with no iron leaching. In addition, this work also provides an important structural aspect
about the semiꢀamorphous FeꢀBTC materials. A careful N2 adsorption study makes clear that
these FeꢀBTC materials do only contain the smallest cage of the two mesoporous ones present in
the highlyꢀrelated FeꢀBTC MILꢀ100(Fe) material, which could be of substantial importance to
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understand their differences/similarities in gas adsorption, in catalytic performance or in any
other application in which porosity plays a key role.
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AUTHOR INFORMATION
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Corresponding Author
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* Dr. Manuel SanchezꢀSanchez, Telephone: +34ꢀ915854795, Fax: +34ꢀ915854760, Eꢀmail
address: manuel.sanchez@icp.csic.es
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Author Contributions
The manuscript was written through contributions of all authors. All authors have given approval
to the final version of the manuscript.
ACKNOWLEDGMENTS
Authors acknowledge Spanish Government for financial support (MATꢀ2012ꢀ31127). K. Díaz
thanks CONACyT for financial support of this research.
SUPPORTING INFORMATION AVAILABLE
TGA plots and data of the FeꢀBTC materials. This information is available free of charge via the
Internet at http://pubs.acs.org/.
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