Microporous and Mesoporous Materials 264 (2018) 133–138

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Microporous and Mesoporous Materials

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Synthesis and properties of ferrocene confined within UiO-67 MOFs T

∗
Shucheng Liu, Jiao Xu, Engao Dai, Junjie Qiu, Yi Liu
School of Physical Sciences, Guizhou University, Guiyang 550025, China

A R T I C L E I N F O A B S T R A C T

Keywords: Ferrocene was encapsulated into the cavities of the metal-organic framework UiO-67 using a solvent-free eva-
Porous materials poration method. The obtained host-guest compounds were characterized by XRD, TEM, EDS, TG, XPS, N2
Metal-organic frameworks adsorption-desorption, magnetic hysteresis and cyclic voltammetry studies. The results show that the micropores
Ferrocene of UiO-67 are successfully occupied by ferrocene molecules and the ferrocene@UiO-67 composite shows an
interesting ferromagnetic behavior at room temperature. Both the oxidation and reduction peak are observed in
cyclic voltammograms due to the reversible conversion between Fe2+ and Fe3+ of ferrocene confined within
UiO-67 framework. The results reveal that the novel properties of ferrocene embedded inside MOFs carries a
substantial potential with regard to the synthesis of ferro-magnet or catalytic materials.

1. Introduction robust materials because of their designable framework structures

modularly built from metal clusters as nodes and organic ligands as
Ferrocene is a sandwich compound composed of a pair of planar struts [7–10]. Recent work on host-guest chemistry of MOFs is mostly
cyclopentadienyl ring of 6p-electrons and 6d-electrons on Fe(II) atom focused on desorption and storage features of small gas molecules, i.e.
[1–4]. Ferrocene is capable of engaging in electron transfer processes. CO2, H2, CH4 and NH3 as guests inside MOFs. In view of developing
Therefore, ferrocene has frequently been used as an electron transfer molecular-based switching systems, control of large guest molecular
mediator for various electro-catalytic reactions. Previous studies have motions inside the cavity by external stimuli is an attractive task.
demonstrated that hollow structures (cages, bowls, capsules etc.) with FeCp2(∼5 Å diameter) is an ideal probe molecule for adsorption studies
nanometer-sized cavities have ability to encapsulate large guest mole- due to its chemical and thermal robustness [11–15].
cules and can regulate specific reactions inside the cavities. In parti- In this work, we have started a study to investigate the host-guest
cular, encapsulation of ferrocene in carbon nanotubes (NTs) can com- chemistry of MOFs by introducing volatile ferrocene using the solvent-
bine both advantages of NTs and novel properties of ferrocene. The free gas phase infiltration method. The result reveals that the redox
electronic properties of ferrocene-filled NTs are greatly modified due to properties of ferrocene embedded inside MOFs are very interesting and
the charge transfer between ferrocene molecules and NTs [5]. Inter- carries a substantial potential with regard to the synthesis of ferro-
calation and exfoliation of graphene oxide using covalently attached magnet or catalytic materials. Herein, we choose UiO-67 as the pre-
ferrocene was achieved and the composites showed interesting mag- sentative example of host materials. UiO-type MOFs (UiO stands for
netic behavior [1]. Recently, the organometallic host-guest chemistry of University of Oslo), which is composed of {Zr6O4(OH)4} oxo cluster
porous crystalline organic frameworks (COF) was studied by infiltration nodes and dicarboxylate linkers, are known for their excellent thermal
of ferrocene. The structure of the inclusion compound (FeCp2)4@COF- and chemical stabilities [16–23]. Among these types of MOFs, UiO-67
102 has a unique arrangement of FeCp2 molecules which replicates the crystal is based on the Zr6O4(OH)4 building unit, forming lattices by a
host structure [6]. These works extend the scope of these new classes of 12-fold connection through the biphenyl dicarboxylic acid (BPDC)
low dense materials for possible applications in the fields like catalysis linkers, resulting in a face centered cubic (f c c) structure (a = 27.1 Å).
and sensing. The structure of UiO-67 contains two types of cages: an octahedral cage
Metal-organic frameworks (MOFs) with high surface areas and well- (Φ ∼18 Å) that is face sharing with 8 tetrahedral cages (Φ ∼ 11.5 Å)
defined pore structures have been demonstrated as novel functional and [17,19], as showing in Scheme 1.

∗
Corresponding author.
E-mail address: yliu9@[Link] (Y. Liu).

[Link]
Received 23 July 2017; Received in revised form 9 December 2017; Accepted 12 January 2018
Available online 17 January 2018
1387-1811/ © 2018 Elsevier Inc. All rights reserved.
S. Liu et al. Microporous and Mesoporous Materials 264 (2018) 133–138

2.3. Physical measurements

X-ray powder diffraction (XRPD) patterns were recorded using a

PANalytical X'Pert powder diffractometer with CuKα radiation.
Transmission electron microscope (TEM) measurement was performed
by use of a FEI Tecnai G2 F20. Thermogravimetric analysis (TGA) were
performed using a Simultaneous Thermal Analyzer (STA 449C,
NETZSCH) in the temperature range between 30 °C and 800 °C in a N2
atmosphere. X-ray photoelectron spectroscopy (XPS) was measured
with Thermo Escalab 250Xi. Nitrogen adsorption/desorption isotherms
were measured at 77 K using surface area and pore size analyzer (3H-
2000PS2). The magnetic properties of sample were determined using a
vibrating sample magnetometer (VSM, VersaLab, Quantum Design) at
room temperature.
Scheme 1. Illustration of ferrocene confined in UiO-67 MOFs.

2.4. Electrochemical measurements

5 mg of ferrocene@UiO-67 powder was dispersed in a 1 mL mixture

of distilled water and ethanol (3: 1 v/v). Then, 10 mL of 5 wt% Nafion
was added to the above mentioned solution. The mixed solution was
sonicated for at least 30 min to form a homogeneous ink. 5 mL of the
mixed solution was drop-cast onto a glassy carbon electrode with a
diameter of 5 mm for the electrochemical measurements. All the elec-
trochemical measurements were performed on an electrochemical
workstation (CHI 660E, CHI Instruments Inc., Shanghai) using a typical
three-electrode mode with an electrolyte solution of 6 M KOH, a Pt
counter electrode, an Ag/AgCl (saturated KCl) reference electrode, and
a modified glassy carbon working electrode. For comparison, the elec-
trochemical measurements of UiO-67 and blank glassy carbon electrode
as work electrode were performed under the same conditions.

3. Results and discussion

Powder X-ray diffraction patterns (Fig. 1) of ferrocene@UiO-67

suggested that the crystal structure of UiO-67 is maintained without
damage when ferrocene molecules are encapsulated into the cavity of
Fig. 1. XRD patterns of UiO-67 and ferrocene@UiO-67.
UiO-67. Inspection of the PXRD-data reveals that all peaks are at the
same position of the pristine powder, which indicates that no contrac-
tion or change in the symmetry of the crystals happens due to the ri-
gidity of UiO-67. A change in Bragg peak intensity at low angle was
2. Experimental noticed, which can be associated to the presence of ferrocene molecules
within the pores of UiO-67. This is explained by taking account of
2.1. Synthesis of UiO-67 scattering factors due to loading of ferrocene. Moreover, the powder
pattern did not show any reflections corresponding to FeCp2, which
Synthesis of UiO-67 was performed by dissolving 1.2 mmol of zir- rules out the presence of crystals of FeCp2 outside the framework.
conium (IV) chloride (ZrCl4), 1.2 mmol of 4,4′-Biphenyl dicarboxylic TEM (Fig. 2) show that the framework of UiO-67 are maintained by
acid (H2BPDC) and 30 equivalents of acetic acid (CH3COOH) in 30 mL the loading of ferrocene, which exhibit a well-defined mono disperse
of N,N-dimethyformamide (DMF) at room temperature. The mixture octahedral microcrystals with particle size in the range of 150–300 nm.
was placed in a 100 mL Teflon-lined stainless steel autoclave and heated The element composition of the sample is qualitatively determined by
at 120 °C for 48 h. The product was cooled to room temperature, wa- EDS attached to TEM. Confine of ferrocene within UiO-67 was further
shed three times with DMF, and dried at room temperature. Excess confirmed by EDS analysis of ferrocene@UiO-67 which showed the
H2BPDC and DMF in the pores were removed using a high temperature presence of Fe peaks in the spectrum (Fig. 2c). The relative atomic
treatment at 300 °C for one day. A pale yellow powder was obtained. percentage of 0.19%, 90.72%, 6.34% and 1.49% for Fe, C, O and Zr
respectively were obtained by the EDS analysis (Table 1). Moreover, the
EDS mapping of ferrocene@UiO-67 (Fig. 2f) also confirms that the
2.2. Synthesis of ferrocene @UiO-67 ferrocene are uniformly distributed in the frameworks.
Fig. 3 shows the thermal behavior of ferrocene in UiO-67 frame-
150 mg of dry and activated UiO-67 and 300 mg of ferrocene were work. The thermogravimetric analysis (TGA) profile of ferrocene@UiO-
placed in two separate glass boats in a Schlenk bottle. The bottle was 67 exhibits no weight drop until 110 °C. Above 110 °C, there was a 25%
then evacuated to 10−3 mbar for 5 min and sealed. The reaction bottle weight loss until temperature reached 280 °C, which was attributed to
was kept at 110 °C for 72 h. the release of ferrocene from the UiO-67 channels. The curve shows a

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Fig. 2. TEM of UiO-67(a); ferrocene@UiO-67 (b,d,e); EDS and EDS mapping of ferrocene@UiO-67 (c,f).

Table 1
The element composition of ferrocene@UiO-67 determined by EDS.

Element Weight % Atomic % Uncertainty % Correction k-Factor

C(K) 76.869 90.719 1.073 0.173 6.279

O(K) 7.161 6.344 0.188 0.514 1.980
Fe(K) 0.737 0.187 0.052 0.994 1.480
Cu(K) 5.648 1.259 0.143 0.997 1.757
Zr(K) 9.583 1.489 0.281 0.999 3.927

stability plateau in the range of 280–450 °C before a second step of an

additional 28% weight loss occurs (450–600 °C), which corresponds to
the thermal decomposition of the UiO-67 framework.
The chemical state of materials was investigated using X-ray pho-
toelectron spectroscopy (XPS) to probe the properties of the inner-shell
electrons (Fig. 4). High-resolution narrow-scan spectra were obtained
for the C1s, O1s, Zr3d and Fe2p core levels. As observed from C1s
spectra, the most prominent peak at 284.7 eV is assigned to sp2-hy-
bridized carbon (C=C) on the benzene ring. The peak at 288.6 eV is
Fig. 3. TGA of UiO-67 and ferrocene@UiO-67 under a N2 atmosphere.
attributed to HO−C=O groups of the BPDC linkers. The O1s spectrum
reveals only one peak at 531.8 eV, which can be attributed to the
oxygen components on the carboxylate groups of the BPDC linkers. The are shown in Fig. 5 and the textural parameters are also listed in
two peaks at 182.6 and 185.0 eV in the Zr3d spectrum can be ascribed Table 2. For UiO-67, the adsorption-desorption isotherms exhibit type-I
to the Zr-O bonds. For the Fe2p spectrum, two peaks at 711.2 and isotherm with typical microporous characteristics. The specific BET
724.3 eV corresponded to Fe 2p3/2 and Fe 2p1/2, are typical of fer- surface area of UiO-67 was measured as 1662 m2 g-1. The pore size
rocene. All of these results further confirm the coexisting chemical distribution curve of UiO-67 using the BJH model exhibits narrow pores
states of ferrocene and UiO-67 in the composites. distribution centered at 1.99 nm with the total pore volume 0.94 cm3 g-
1
The N2 adsorption-desorption isotherms and pore size distributions . N2 adsorption of ferrocene @UiO-67 was also measured at 77 K and

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Fig. 4. XPS of ferrocene@UiO-67.

Table 2
Porosity characteristics of samples.

Sample SBET d pore Vpore Smicropore Vmicropore

(m2g−1) (nm) (cm3g−1) (m2g−1) (cm3g−1)

UiO-67 1662 2.26 0.94 1566 0.61

ferrocene @UiO-67 26 20.47 0.13 0 0

that the 86.2% of pores in UiO-67 are occupied by ferrocene.

We used vibrating sample magnetometer (VSM) to measure the
magnetic hysteresis curve of the samples. Fig. 6 shows the hysteresis
loop of ferrocene and ferrocene filled UiO-67 obtained at the room
temperature, respectively. The shape of the hysteresis of ferrocene@
UiO-67 indicates that the composites are ferromagnetic at room tem-
perature. The hysteresis exhibits an average coercivity of
HC = 0.9499 T and the saturation magnetization is measured to be 1.0
emu/g. The observed value of HC and saturation magnetization for the
present composites is compared to that of the bulk ferrocene [5]. In
Fig. 5. N2 adsorption isotherms of UiO-67and ferrocene@UiO-67 at 77 K. The inset shows consideration of micropore volume (0.61 cm3 g-1 by the N2 adsorption
the BJH pore size distribution curve.
measurement) of UiO-67, we can estimate that the magnetization per
pore volume is about 1.49 emu/cm3 in ferrocene@UiO-67.
the N2 adsorbed amount decreased drastically as compared to UiO-67. The electrochemical behaviors of ferrocene@UiO-67 composites
Especially, it was observed that, when ferrocene was introduced, the were tested by a three-electrode system using 6 mol/L KOH as the
micropore surface area and the micropore volume of UiO-67 decreased electrolyte at different scan rates in a potential range of 0–600 mV (vs.
to 0. The results suggested that ferrocene molecules occupied the mi- Ag/AgCl) (Figs. 7 and 8). Notably, a pair of symmetric redox peaks
cropore spaces of UiO-67. From value of pore volume, it is estimated (240 mV and 375 mV at scan rate of 10 mV/s, respectively) appeared in

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CV curves and were not observed in UiO-67 and blank glassy carbon
electrode, which was attributed to the reversible conversion between
Fe2+ and Fe3+ in ferrocene [24]. When the scan rate is fast enough, the
redox peak position shifts to high potential, and the peak currents are
greatly enhanced. The linear relationship between the peak current and
the scan rate indicates that the electrode is reversible (Fig. 8b). The
behavior of cyclic voltammograms of the ferrocene-loaded MOF can be
explained by a charge-hopping mechanism [24], where the ferrocene
molecules remain localized in the pores of the MOF and mediate elec-
tron transport across the layer. In this case, the Fe2+/Fe3+ redox re-
action takes place at the MOF-electrolyte interface. The redox processes
corresponding to the conversion between different irons oxidation
states can be described by following reactions:

Fe 2 + + OH− ↔ Fe3 + (OH ) + 2e−

This process is illustrated in Scheme 2. The small size of an an-

chored ferrocene molecule (∼5 Å) relative to the channel diameter of
UiO-67(∼18 Å and ∼11.5 Å) permits ferrocene to install in channels
and the electrochemical reaction occurs in the channels. Under the
Fig. 6. Magnetic hysteresis curves of ferrocene and ferrocene@UiO-67.
oxidation process, OH− is adsorbed on ferrocene, as a result, some free
electrons are released to contribute the oxide current peak. Under the
reduction process, OH− is released to contribute the redox current
peak. The results show that the installed ferrocene molecules are elec-
trochemically reversible, implying effective site-to-site redox hopping
and potential usefulness as a redox shuttle in electro catalytic systems.

4. Conclusions

In summary, we have shown that UiO-67 can be filled with ferro-

cene as identified by XRD, TEM, EDS, TG and XPS. The magnetic
measurements reveal that the magnetic structure of UiO-67 is sig-
nificantly modified, and ferromagnetic behavior are formed due to
ferrocene encapsulation. The oxidation and reduction peak are ob-
served in cyclic voltammograms due to the conversion between Fe2+
and Fe3+ in ferrocene. The combined findings have important im-
plications for the use of this MOF composite as electro-catalysts and
electro-analytical devices in electrochemical cells.

Acknowledgements
Fig. 7. Cyclic voltammograms of UiO-67, ferrocene@UiO-67 and glassy carbon electrode.
This work was supported by the National Natural Science
Foundation of China (21261006).

Fig. 8. Cyclic voltammograms of ferrocene@UiO-67(a); The linear relationship between the peak current and the scan rate (b).

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Scheme 2. Illustration of conversion between different irons oxida-

tion state in ferrocene.

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