Materials Letters 156 (2015) 50–53

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Self-template synthesis of core–shell ZnO@ZIF-8 nanospheres

and the photocatalysis under UV irradiation
Bo Yu a,b, Feifei Wang a,b, Weibing Dong c,d, Jie Hou a,b, Pingchao Lu a,b, Junbo Gong a,b,d,n
a
State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b
Collaborative Innovation Center of Chemistry Science and Engineering, Tianjin University, Tianjin 300072, PR China
c
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, PR China
d
Tianjin Key Laboratory of Modern Drug Delivery & High-Efficiency, Tianjin University, Tianjin 300072, PR China

art ic l e i nf o a b s t r a c t

Article history: Core–shell ZnO@zeolitic imidazolate frameworks-8 (ZnO@ZIF-8) nanospheres was synthesized via a self-
Received 13 February 2015 template method. Spherical ZnO is employed not only as the template but also as Zn(II) for the
Accepted 27 April 2015 composition of zeolitic imidazolate frameworks-8 (ZIF-8). Core–shell ZnO@ZIF-8 showed molecule size
Available online 6 May 2015
selectivity and good photocatalytic activity under UV irradiation, and the outer ZIF-8 shell dominated the
Keywords: photocatalysis via ligand metal charge transfer mechanism during the degradation of methylene blue
ZnO (MB). Photocatalysis of core–shell metal–organic frameworks (MOFs) will facilitate new efforts in the
ZIF-8 treatment of pollutants.
Photocatalysis & 2015 Elsevier B.V. All rights reserved.
Nanocomposites
Optical materials

1. Introduction peroxide and ascorbic acid in the electrolyte solution [6]. Although
various core–shell MOFs have been synthesized, morphological
Metal–organic frameworks (MOFs) with high specific surface structure of MOFs shell is still amorphous and difficult to be
area and well-defined porous structure have attracted consider- controlled.
able attention due to their potential applications in sensors, Previous studies suggested that MOFs were semiconductors or
catalysis, separation and gas storage [1–4]. MOFs integrated with photocatalysts with band gaps determined by the highest occup-
metals, metal oxides and other functional materials show great ied molecular orbital (HOMO)-lowest unoccupied molecular orbital
advantages due to their heterostructures [5–7]. The heterostruc- (LUMO) gaps of the organic ligand molecules [12,13]. The photocata-
tures integration can be achieved by deposition of metal (oxide) lysis of MOFs is considered to be achieved by the electron transfer
into pores of MOFs [5], and coating MOFs as a shell on metal from the photoexcited organic ligands to metallic clusters within
(oxide) as well [8–10]. Recently, MOF-based core–shell structures MOFs, which is termed as ligand to cluster charge transfer (LCCT)
have attracted increasing attention. Au@MOFs and Fe3O4@MOFs [14–16]. However, few attentions have been paid to the photocatalysis
have been synthesized by a step-by-step method and show the of the core–shell metal oxide@MOFs and photocatalytic performance
enhanced catalytic activity for the reduction of 4-nitrophenol in is still not clear.
the presence of NaBH4 [8–10]. However, in order to achieve the Considering that ZnO show various morphologies at nanoscale
growth of MOFs on the surface of template and prevent the direct (such as nanorods, nanobelts, nanotetrapods, nanospheres, nano-
nucleation of MOFs in solution, surface modification (specific combs and nanopyramids) [17], ZnO nanospheres and ZIF-8 are
functional groups such as –COOH and –SO3H) is always required employed as core and MOFs shell, respectively. We herein pre-
on the template in the step-by-step method [7,11]. By contrast, pared core–shell and morphological controlled core–coronal–shell
ZnO@zeolitic imidazolate frameworks-8 (ZnO@ZIF-8) nanorods ZnO@ZIF-8 nanospheres by self-template method, and the photo-
have been obtained by self-template method, where the ZnO catalysis of core–shell ZnO@ZIF-8 nanospheres was investigated
nanorods not only exist as the template but also provide zinc ions during the photocatalytic degradation of methylene blue (MB)
for the formation of ZIF-8 (Zn(2-methylimidazole)2
2H2O), and under UV irradiation.
show a good photoelectrochemical response towards hydrogen

n
2. Materials and methods
Corresponding author at: State Key Laboratory of Chemical Engineering, School
of Chemical Engineering and Technology, Tianjin University, Tianjin 300072,
PR China. ZnO nanospheres were synthesized via hydrolysis of 100 mL
E-mail address: junbo_gong@tju.edu.cn (J. Gong). 0.1 M zinc acetate diethylene glycol solution with stirring at 150 1C

http://dx.doi.org/10.1016/j.matlet.2015.04.142
0167-577X/& 2015 Elsevier B.V. All rights reserved.
 B. Yu et al. / Materials Letters 156 (2015) 50–53 51

for 1.5 h. ZnO nanospheres were collected by centrifugation and core–shell structure of nanospheres, where the inner core with dark
dried at 60 1C for 12 h after washing by water and ethanol for contrast is ZnO and the outer shell with light contrast is ZIF-8
several times. Core–shell ZnO@ZIF-8 nanospheres were synthesized (Fig. 2c–f). No freestanding ZIf-8 is found during the formation of
by a modified method that described by Zhan et al. [6]. In a typical ZnO@ZIF-8, which suggesting that the growth of ZIF-8 is strictly
experiment, 2 mmol 2-methylimidazole was dissolved in 15 mL N, limited to the surface of ZnO. The outer coating ZIF-8 of core–shell
N-dimethylformamide (DMF) and the solution was pre-heated at ZnO@ZIF-8 is compact and the thickness is about 100 nm, while the
70 1C. After that, 5 mL ZnO suspension (0.25 mmol ZnO dispersed in diameter of the inner ZnO core is about 200 nm (Fig. 2c and d). In
5 mL water) was added into the pre-heated solution and the mixed order to expose more ZnO on the surface for further modification,
suspension was heated at 70 1C with stirring for 5 h. The size of the ordered shell gaps are obtained in the core–coronal–shell ZnO@ZIF-8.
nanosphere and the thickness of ZIF-8 shell were controlled by ZIF-8 cubes (50–100 nm) are individual with each other and coronal
heating time. As for synthesis of core–coronal–shell ZnO@ZIF-8, grew on the surface of ZnO cores (200–250 nm) (Fig. 2e and f).
0.2 mL 25 mM cetyltrimethylammonium bromide (CTAB) DMF Self-template synthesis of ZnO@ZIF-8 is a process that consists of
solution was required and added into the system after the addition the dissolution of ZnO and the formation of ZIF-8. Before formation of
of ZnO suspension, and the reaction was allowed at 70 1C for 2 h. the ZIF-8 shell, diameter of ZnO nanospheres is 300 nm (Fig. 2a and b),
White products were collected by centrifugation and dried at 60 1C which is in agreement with the diameter of the core–shell ZnO@ZIF-8
for 12 h after washing by ethanol for several times. The schematic (Fig. 2c and d). However, the ZnO cores become smaller than before,
illustration of ZnO@ZIF-8 synthesized via the self-template method and the difference of diameters between ZnO and ZnO@ZIF-8 is shown
has been shown in Fig. 1a. as the new-formed ZIF-8 shell (Fig. 2c–f). Significant change of the ZnO
Morphology of the synthesized nanospheres was characterized by diameter suggests that 2-methylimidazole ligands are able to pass
high-resolution analytical transmission electron microscopy (TEM, Fei through pores of the ZIF-8 and catch the surface of the ZnO core,
Tecnai G2 F20). The crystalline structures of the synthesized nano- where small ZnO nanocrystallites are dissolved and the dissolved Zn
spheres were investigated by powder X-ray diffraction (XRD, Rigaku (II) coordinates with organics to form ZIF-8 [6]. TEM analysis of core–
D/max-2500). coronal–shell ZnO@ZIF-8 shows larger particles than core–shell ZnO@-
Photocatalytic performance was investigated via MB degradation ZIF-8 with similar thickness of ZIF-8 shells, suggesting that the
using a Model XPA-VII photocatalytic reactor (Xujiang Electrome- dissolved Zn(II) can also diffuse outward and connect with the
chanical Plant, Nanjing, China). UV light was provided by a 300 W organics at the outer layer of ZIF-8 shells [6].
high pressure Hg lamp. In a typical experiment, 10 mg catalyst was Photocatalytic performance of core–shell ZnO@ZIF-8 was inves-
added into 20 mL 10 ppm MB solution and the mixture was stirred tigated during the photocatalytic degradation of MB under UV
under UV irradiation. The concentration of MB was 40 ppm during irradiation (Fig. 3). Removal of MB by the core–shell ZnO@ZIF-8
the photocatalytic degradation in the presence of 0.5 M H2O2. was insignificant through adsorption process without UV irradia-
During the irradiation, 0.5 mL suspension was taken out regularly tion (Fig. 3a). However, significant degradation of MB was
and the supernatant was centrifuged for the determination of MB obtained during the photocatalysis under UV irradiation. Absor-
concentrations at 664 nm by a UV–vis spectrophotometer (Mapada, bance of MB at 664 nm decreased rapidly with the increase of
UV-6300). irradiation time, and 94.1% of MB was degraded after 240 min
under UV irradiation (Fig. 3b). Photocatalytic degradation kinetics
of MB catalyzed by ZnO, ZIF-8 and core–shell ZnO@ZIF-8 are
3. Results and discussion shown in Fig. 3c. It is found that the first-order degradation rate
of core–shell ZnO@ZIF-8 was similar with that of ZIF-8, suggesting
Powder XRD analysis of ZnO@ZIF-8 shows main diffraction that the photocatalytic mechanism of ZIF-8 is dominating towards
peaks signed as # and n, which are in good agreement with ZIF-8 the degradation of MB during the photocatalysis of core–shell
and ZnO (JCPDS, No. 36-1451), respectively (Fig. 1b). It suggests ZnO@ZIF-8. Previous studies suggested that ZnO@ZIF-8 nanorods
that the synthesized ZnO@ZIF-8 is a composite, which consists of showed different photoelectronic responses towards hole scaven-
ZIF-8 and ZnO with different crystalline structures. gers with different molecule sizes, and some hole scavengers (such
TEM analyses of the synthesized ZnO, core–shell and core– as ascorbic acid) decreased the photoelectronic response due to
coronal–shell ZnO@ZIF-8 in Fig. 2 indicate that formation of ZnO@- their larger molecule sizes than the pore aperture of ZIF-8 [6]. As
ZIF-8 is in agreement with the self-template synthesis process the molecule size of MB is larger than the pore aperture of ZIF-8,
described in Fig. 1a. Zinc oxides formed during the hydrolysis of Zn pores of ZIF-8 could be obstructed, which results in the restrained
(II) are spherical particles (300 nm) and aggregate of numerous small diffusion of H2O to ZnO cores and an inhibitory effect on forming
nanocrystallites (Fig. 2a and b). TEM analysis of ZnO@ZIF-8 suggests a peroxide radical for the degradation of MB. Though activity of

Fig. 1. Self-template synthesis of core–shell and core–coronal–shell ZnO@ZIF-8 (a) and XRD analysis of the synthesized ZnO@ZIF-8 (b).
52 B. Yu et al. / Materials Letters 156 (2015) 50–53

Fig. 2. TEM analysis of synthesized ZnO (a, b), core–shell (c, d) and core–coronal–shell (e, f) ZnO@ZIF-8.

Fig. 3. Photocatalytic degradation of MB. Adsorption (a) and photocatalytic degradation (b, c) of MB by ZnO@ZIF-8 and (d) in the presence of H2O2.

ZnO@ZIF-8 nanospheres is shown to be the same as that of ZIF-8 Photocatalytic activity of ZnO@ZIF-8 was even higher than that
during the degradation of MB, ZnO@ZIF-8 shows good response to of ZnO during the degradation of MB in the presence of H2O2
hole scavengers with small molecule size (such as H2O2) [6]. (Fig. 3d).
 B. Yu et al. / Materials Letters 156 (2015) 50–53 53

the activity of ZnO@ZIF-8 nanospheres is shown to be the same as that

of ZIF-8 during the degradation of MB, but ZnO@ZIF-8 shows higher
photocatalytic activity of than that of ZnO during the degradation of
MB in the presence of H2O2. As the molecule size of MB is larger than
the pore aperture of ZIF-8, the degradation is mainly controlled by
LMCT photocatalytic mechanism of the outer ZIF-8 shell.

Acknowledgement

We are grateful to the financial support of National Natural

Science Foundation of China (NNSFC, nos. 21176173 and 21376164)
and National High Technology Research and Development Pro-
Fig. 4. Photocatalytic mechanism of ZIF-8 shell within core–shell ZnO@ZIF-8.
gram (863 program, no. 2012AA021202).

The photocatalytic mechanism of ZIF-8 within core–shell ZnO@-

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