Materials Today Energy 13 (2019) 125e133

Contents lists available at ScienceDirect

Materials Today Energy

journal homepage: www.journals.elsevier.com/materials-today-energy/

MOF confined in macroporous-mesoporous-TiO2 for light-boosting

electrocatalytical oxygen production
Zhenxing Li a, **, Xiaofei Xing a, Junmei Chu a, Kai-Li Wang b, Chengcheng Yu a,
Zhiting Wei a, Yangyang Wen a, Hui Sun a, Zhao-Kui Wang b, *
a
State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, Key Laboratory of Biogas Upgrading Utilization,
China University of Petroleum (Beijing), Beijing, 102249, China
b
Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM),
Soochow University, Suzhou, Jiangsu, 215123, China

a r t i c l e i n f o a b s t r a c t

Article history: A novel multiscale pore structure material is firstly synthesized by means of the MOF confined in ordered
Received 4 March 2019 macroporous-mesoporous-TiO2 (FeCoNi-MOF@TiO2). We have successfully achieved that three-scale
Received in revised form ordered porous structures are integrated into one material, and the porous sizes are 400 nm, 5.1 nm
30 April 2019
and 3.4 nm, respectively. A photo-based electrocatalytic OER catalytic system was designed, and the
Accepted 15 May 2019
FeCoNi-MOF@TiO2 as a catalyst exhibits high catalytical activity for OER under the irradiation of UV light.
The electrons of macroporous-mesoporous-TiO2 are excited and transferred to the loaded FeCoNi-MOF,
when the macroporous-mesoporous-TiO2 absorbs the UV light, which can improve the conductivity of
Keywords:
MOF
the FeCoNi-MOF. The photo-induced electron of macroporous-mesoporous-TiO2 significantly boosts the
TiO2 electrocatalytic active of FeCoNi-MOF. These results provide a promising route on enhancing the catalytic
Oxygen evolution reaction activity of MOFs in electrocatalytic reaction.
Conductivity © 2019 Elsevier Ltd. All rights reserved.
Ultraviolet light

1. Introduction materials breaks the limitations of a single pore structure [3]. These
materials meanwhile possess excellent mass transport perfor-
Hierarchically porous materials are a new type of porous ma- mance, multiple pore structures, low bulk density, large pore vol-
terials, which has been developed on the basis of microporous ume and high specific surface areas [7,8]. Based on the above
zeolite, mesoporous materials and macroporous aerogel in recent advantages, the hierarchically porous materials can be widely used
years [1e3]. According to the International Union of Pure and in adsorption, separation, catalysis, load, sensing and other realms
Applied Chemistry (IUPAC), the porous materials can be classified [9e13]. For the past few years, a lot of multi-level pore materials
into three types based on the porous size, including microporous have been studied, such as macroporous-mesoporous materials,
materials with a porous size of less than 2 nm, mesoporous mate- macroporous-microporous materials, mesoporous-microporous
rials with porous size between 2 and 50 nm, and macroporous materials, etc., however, the report on three-scale pore materials
materials with the porous size greater than 50 nm [4]. However, the is still rarely reported [13e17].
smaller pore size of the microporous materials are not conducive to With the accelerated consumption of energy, it is extremely
the diffusion of larger molecules, and the mesoporous materials urgent to look for a sustainable solution for energy storage and
usually exhibit weak acidity and low hydrothermal stability, and conversion devices [18e20]. Producing hydrogen by water elec-
the macroporous materials show the low active surface areas [5,6]. trolysis is promising future development directions of renewable
Apparently, the single pore structure restricts their application in energy [21e24]. Nevertheless, oxygen evolution reaction (OER) in
more fields. It is worth mentioning that hierarchically porous ma- the water electrolysis reaction involves the transfer of four elec-
terials are composed of two or more pore sizes, and this kind of trons and the formation of OeO bond, resulting in a very sluggish
kinetic process, which is the main barrier of the water electrolysis
reaction [25,26]. Therefore, it is a challenging problem to explore
the electrocatalyst with low-costing and superior performance to
* Corresponding author.
** Corresponding author. reduce the overpotential of OER as soon as possible [27]. At present,
E-mail addresses: [email protected] (Z. Li), [email protected] (Z.-K. Wang). most electrocatalysts used in OER are noble metals and their oxides

https://doi.org/10.1016/j.mtener.2019.05.008
2468-6069/© 2019 Elsevier Ltd. All rights reserved.
126 Z. Li et al. / Materials Today Energy 13 (2019) 125e133

[28], although noble metals exhibit higher oxygen evolution ac- Then the white emulsion solution was transferred into the oven
tivity in alkaline media, these noble metals show poor stability in under 30  C to evaporate solvent. After aging for five days, the gel
oxygen evolution polarization, are prone to corrosion and are quite product was taken in the tube furnace with nitrogen atmosphere
high-costing [29]. Metal-organic framework materials (MOFs) are under the 350  C for 3 h, then grounded into powder and heated at
the promising candidate electrocatalysts. MOFs are a sort of coor- 400  C in the muffle furnace for 4 h. Finally, the white powder
dination polymer that has been developed rapidly in the last products can be obtained.
decade, which refer to the crystal porous materials with periodic
network structures formed by self-assembly of transition metal 2.3. Synthesis of FeCoNi-MOF
ions and organic ligands [30,31]. MOFs exhibit high porosity, low
density, large specific surface areas, channel regularity, adjustable In a typical synthesis process [41], 8.3 mg of terephthalic acid
porous size, topological diversity and tailorability [32,33], which were dissolved in 12 ml of Dimethylacetamide (DMA) in a Teflon
makes them widely application in many domains, such as separa- vessel, then 40 mg of Ni(NO3)2, 14 mg of FeCl3 and 5.8 mg of
tion, catalysis, electrochemistry, biomedicine, gas absorption and Co(NO3)2 were added to the above solution, which was stirred at
storage, etc. [34e36] A mixed metaleion MOF (Fe/Co) synthesized room temperature for 2 h. The vessel was then transferred to a
by wang et al. was investigated through cyclic voltammetry and stainless steel autoclave and placed in an oven for 3 h at 150  C.
linear sweep voltammetry for OER and ORR, and the rotating disk After cooling at room temperature, the precipitate was washed
electrode (RDE) results revealed two-electron pathway of oxygen three times with ethanol and water and dried under vacuum at
reduction occurred at
0.35 to
0.55 V [37]. Even so, the low 60  C for 12 h to obtain the yellow powder sample.
intrinsic conductivity and poor stability in water of MOFs are an
indisputable fact and will inevitably affect their further application 2.4. Synthesis of FeCoNi-MOF@TiO2
in OER [38e43]. Herein, a novel multiscale pore structure material
was firstly synthesized by means of the MOF confined in ordered 0.05 g of macroporous-mesoporous-TiO2 and 8.3 mg of ter-
macroporous-mesoporous-TiO2 (FeCoNi-MOF@TiO2), and both ephthalic acid were dissolved in 12 ml of ethanol solution, then
macroporous and mesoporous structure were highly ordered. We 40 mg of Ni(NO3)2, 14 mg of FeCl3 and 5.8 mg of Co(NO3)2 were
have successfully achieved that three-scale ordered porous struc- added to the above solution, which was stirred at room tempera-
tures were integrated into one material. The FeCoNi-MOF@TiO2 ture for 2 h. Then the solution was dried at 30  C for 48 h to obtain a
was used as a catalyst for OER under the irradiation of Ultraviolet yellow powder sample. The product FeCoNi-MOF@TiO2 was ob-
(UV) light. The electrons of macroporous-mesoporous-TiO2 were tained after the yellow powder sample was washed with N, N-
excited and transferred to the loaded FeCoNi-MOF, when the Dimethylformamide (DMF) and ethanol for three times.
macroporous-mesoporous-TiO2 absorbed the UV light, which
significantly improved the conductivity of the FeCoNi-MOF. The 2.5. Synthesis of Fe-MOF@TiO2
high electrocatalytic active of FeCoNi-MOF@TiO2 was attributed to
the excellent conductivity with the induction of macroporous- 0.05 g of macroporous-mesoporous-TiO2 and 8.3 mg of ter-
mesoporous-TiO2 and rich electrocatalytic active sites and large ephthalic acid were dissolved in 12 ml of ethanol solution, then
specific surface areas of FeCoNi-MOF. These results provide a 14 mg of FeCl3 was added to the above solution, which was stirred
promising route on enhancing the catalytic activity of MOFs in at room temperature for 2 h. Then the solution was dried at 30  C
electrocatalytic reaction. for 48 h to obtain a yellow powder sample. The product FeCoNi-
MOF@TiO2 was obtained after the yellow powder sample was
2. Experimental washed with DMF and ethanol for three times.

2.1. Synthesis of 455 nm PS microspheres 2.6. Electrochemical measurement

During the synthetic process, styrene was washed by 20 ml of The electrochemical experiment of the prepared catalysts was
NaOH solution and distilled water for four times respectively until measured using an electrochemical workstation (CHI 760). A
the pH ¼ 7. Then, 12 ml of the above washed styrene and 160 ml of graphite electrode was used as the counter electrode, the catalyst-
deionized water were added into a 250 ml three-necked flask, and coated glassy carbon electrode (GCE) was used as the working
N2 was bubbled for 15 min to remove oxygen in the flask. After that, electrode (5 mm in diameter), and a saturated calomel electrode
10 mL of K2S2O8 (0.007 g mL
1) was added when the solution was (SCE) was used as the reference electrode. Then 2.5 mg catalyst was
heated to 70  C. Next, the mixture was continued under magnetic dispersed into a mixture solution of 980 mL ethanol and 20 mL of 5%
stirring for 28 h, then the colloidal solution of PS microspheres was Nafion solution. After sonicating for 30 min, a droplet of 10 mL
obtained. The colloidal solution was again washed with deionized catalyst ink containing 0.025 mg (0.127 mg cm
2) of catalyst was
water and ethanol for three times respectively. Finally, the white dropped on the surface of the GC working electrode and then dried
powder PS microspheres were obtained after drying at 30  C. in air. All electrochemical measurements were implemented in
acidic alkaline conditions that contained a 1 M KOH solution. Linear
2.2. Synthesis of the ordered macroporous-mesoporous-TiO2 sweep voltammetry (LSV) was conducted at the potentials between
1.2 V and 1.8 V (versus RHE) at a scan rate of 5 mV s
1. Electro-
In a typical synthesis process, 1.2 g of pluronic F127 was dis- chemical impedance spectra (EIS) were obtained by AC impedance
solved in 15 ml of ethanol, then 1.2 g of acetic acid (99.0%, AR) and with an amplitude of 5 mV in the frequency range from 105 to
1.2 g of hydrochloric acid (36%, AR) were added to the above so- 0.01 Hz in a solution of 1 M KOH. All potentials were converted
lution. The mixture was sealed with polyethylene film and using the formulae: ERHE ¼ ESCE þ0.924 V. Electrochemical
continued stirring for 2 h at room temperature until F127 was measurement under the UV light radiation: LSV and EIS measure-
completely dissolved. Next, 3.5 g of PS microspheres were added to ment were performed, when the irradiation with a 365 nm UV light
the solution and stirring it for another 7 h to ensure the complete (100 W) was carried out the GC electrode. LSV measurement
dispersion of PS microspheres. 1.7 g of tetrabutyl titanate was without the UV light radiation: The GC electrode was firstly irra-
added into the solution and stirring at room temperature for 3 h. diated under the 365 nm UV light (100 W) for 5 min, and then the
 Z. Li et al. / Materials Today Energy 13 (2019) 125e133 127

UV light was immediately turned off and LSV was measured inside the macropores and the size of FeCoNi-MOF was 50e80 nm,
without UV. Similarly, the LSV curves at 10 min, 15 min, 20 min, that was smaller than the pure FeCoNi-MOF (100 nm, Figure S3),
25 min, 30 min and 35 min can be also obtained according to the resulting from the confined effect of macroporous-mesoporous-
above method. TiO2, and the ordered mesoporous structure with porous size of
5.1 nm in the macroporous walls, which was also consistent with
2.7. Characterization the construction of macroporous-mesoporous-TiO2, proving the
morphology of the macroporous-mesoporous-TiO2 was well
The scanning electron microscopy (SEM) observations were retained in the FeCoNi-MOF@TiO2. The high-resolution trans-
measured by Hitachi SU8010 scanning electron microscopy (SEM, mission electron microscope (HRTEM) image disclosed the mes-
Japan) at 200 kV. The transmission electron microscopy (TEM) were oporous walls were highly crystalline and the lattice spacing of the
performed on a JEM 2100 LaB6 at an accelerating voltage of 200 kV. FeCoNi-MOF@TiO2 was 0.24 nm and 0.36 nm, which was corre-
The small-angle and wide-angle X-ray diffraction (XRD) patterns sponded to the (103) and the (101) crystal facets of anatase TiO2
were carried out on a Burker D8-advance X-ray power diffrac- respectively (Fig. 1e). Moreover, the uniformly ordered meso-
tometer operated at 40 kV and current of 40 mA with Cu-Ka radi- porous structure of the composite FeCoNi-MOF@TiO2 was further
ation (l ¼ 1.5406 Å). The X-ray photoelectron spectrometer (XPS) confirmed by the small angle X-ray diffraction (SAXRD) pattern. As
was taken at an ion-pumped chamber (evacuated to 2  10
9 Torr) Fig. 1f showed, there were a strong diffraction peak at 2q ¼ 0.99
of an Escalad5 spectrometer, employing Mg KR radiation (BE) and two weaker peaks at 2q ¼ 1.65 and 1.99 , which can be
1253.6 eV. The energy-dispersive X-ray spectroscopy (EDS) was assigned to (100), (110) and (200) reflection by the explanation of
recorded on a Hitachi SU8010 scanning electron microscopy under p6mm hexagonal symmetry. This result agreed well with the
a working voltage of 200 kV. The UVevisible absorption spectrum SAXRD pattern (Figure S4) of the macroporous-mesoporous-TiO2,
was recorded on a Hitachi U-3010 spectrometer after dissolving the whose diffraction peak also located at 2q ¼ 0.99 ,1.65 and 1.99 .
solid photocatalyst powder in ethanol. Thermal gravimetric anal- As for the wide-angle X-ray diffraction (WAXRD) pattern (Fig. 1g),
ysis (TGA) was recorded on Mettler Toledo TGA/DSC the diffraction peaks of TiO2 located at 25.38 , 37.97,
3 þ thermogravimetric analyzer under argon atmosphere at a 48.09 ,54.38 , 62.71, 69.80 , 75.30 and 82.70 can be indexed to
heating rate of 10  C min-1 in the temperature range of the (101), (004), (200), (105), (204), (220), (215) and (224) re-
100e700  C. Nitrogen sorption isotherms and pore size adsorption flections of anatase TiO2 (JCPDS card No. 21e1272), and the
curves were determined at 77 K with a Micromeritics ASAP 2460 diffraction peaks of FeCoNi-MOF located at 9.3 , 12.5 and 17.8 . It
analyzer (USA). Before the measurement, the samples were was worth noting that the diffraction peaks FeCoNi-MOF@TiO2
degassed in a vacuum for 6 h. The Brunauer-Emmett-Teller (BET) combined all the peaks of FeCoNi-MOF and macroporous-meso-
method was utilized to calculate the specific surface areas. By using porous-TiO2, and the peaks at 9.26 , 12.49 and 17.80 were
the Barrett-Joyner-Halenda (BJH) model, the pore volumes and belonged to the pure FeCoNi-MOF, while the peaks at 25.40 ,
pore size distributions were derived from the adsorption branches 38.05 , 48.21, 54.61, 62.74 , 69.82 and 75.18 were attributed to
of isotherms. the anatase TiO2.
In order to investigate the distribute of FeCoNi-MOF in the
3. Results and discussion FeCoNi-MOF@TiO2, the scanning transmission electron microscopy
(STEM) mode was used on a macropore of the FeCoNi-MOF@TiO2.
The schematic diagram of the formation of FeCoNi-MOF@TiO2 The high-angle annular dark field (HAADF)-STEM image and
was illustrated in Fig. 1a. The metal ions and ligand were dissolved energy-dispersive X-ray spectroscopy (EDX) elemental mapping
into DMA to form a homogeneous solution, and then the macro- (Fig. 2) clearly showed that Ti and O were uniformly dispersed on
porous-mesoporous-TiO2 was added to above solution. The mac- the macroporous walls, while the Fe, Co and Ni mostly dispersed
roporous-mesoporous-TiO2 was used as a template, and the inside the macropore. The above results strongly indicated that the
growth of FeCoNi-MOF was confined in the macroporous structure FeCoNi-MOF (red circles) was mainly concentrated in the macro-
of the macroporous-mesoporous-TiO2. From the scanning electron porous structure, which was good agreement with the SEM and
microscopy (SEM) of the prepared macroporous-mesoporous-TiO2 TEM result. The EDX analysis showed the ratio of Fe, Co and Ni was
(Figure S1a), the macroporous structure was well-organized, and about 5:1:12 (Table S1), which was consistent with the feeding
the porous size was 400 nm, which was smaller than that of the PS ratio.
microspheres (455 nm, Figure S2), because of the shrinkage during The porous property of these prepared samples was further
the calcining process to remove the PS microspheres. The corre- characterized by N2 adsorption-desorption isotherms and pore size
sponding transmission electron microscopy (TEM) of macro- distribution curves (Fig. 3). The N2 adsorption-desorption iso-
porous-mesoporous-TiO2 showed that the ordered mesoporous therms of macroporous-mesoporous-TiO2, FeCoNi-MOF and
channel was on the macroporous walls (Figure S1b). The SEM FeCoNi-MOF@TiO2 were all assigned to the typical type IV curves
image of FeCoNi-MOF showed that the average size of FeCoNi- with hysteresis loops in the relative pressure (P/P0) range of
MOF particle was 100 nm (Figure S3). The three-scale pore 0.1e0.9, 0.4e1.0 and 0.4e1.0, respectively, suggesting the presence
structure of the FeCoNi-MOF@TiO2 was demonstrated in Fig. 1. The of the homogeneous mesoporous structure (Fig. 3a, b and c). And it
SEM image of the FeCoNi-MOF@TiO2 showed that the well- can be calculated from the nitrogen absorption curve that the
ordered close-packed macroporous structures were belonged to Brunauer-Emmett-Teller (BET) surface area of FeCoNi-MOF@TiO2
a classic face centered cubic (fcc) close-packed arrangement was 80 m2 g
1. From these three corresponding pore size distri-
(Fig. 1b). The high-magnification SEM image exhibited that the bution curves derived from the adsorption portion (Fig. 3d), the
FeCoNi-MOF was uniformly distributed in the macropores (Fig. 1c), pore size distribution curve of FeCoNi-MOF@TiO2 showed a strong
indicating that the FeCoNi-MOF successfully growed in the mac- peak (3.4 nm) and a broad peak (5.1 nm), which was attributed to
ropores of macroporous-mesoporous-TiO2 as the schematic dia- the FeCoNi-MOF, and macroporous-mesoporous-TiO2, respectively,
gram described (Fig. 1a). The diameter of the macropores was illustrating the FeCoNi-MOF@TiO2 had two kinds of mesoporous
400 nm, which was corresponding to the prepared macroporous- structure. Based on the SEM, TEM and pore size distribution result,
mesoporous-TiO2. The TEM image of the FeCoNi-MOF@TiO2 the FeCoNi-MOF@TiO2 exhibited three-scale pore structure, and
(Fig. 1d) showed the existence of FeCoNi-MOF (red circle areas) the porous size were 400 nm, 5.1 nm and 3.4 nm, respectively. The
128 Z. Li et al. / Materials Today Energy 13 (2019) 125e133

Fig. 1. (a) Schematic illustration of the synthesis procedure of the FeCoNi-MOF@TiO2. (b) SEM image of the prepared FeCoNi-MOF@TiO2. (c) High-magnification SEM image of
the prepared FeCoNi-MOF@TiO2. (d) TEM image of the prepared FeCoNi-MOF@TiO2 (red circle areas are the FeCoNi-MOF). (e) HRTEM image of the prepared FeCoNi-MOF@TiO2.
(f) SAXRD pattern of the prepared FeCoNi-MOF@TiO2. (g) WAXRD patterns of simulated MIL-53, macroporous-mesoporous-TiO2, FeCoNi-MOF and FeCoNi-MOF@TiO2.
 Z. Li et al. / Materials Today Energy 13 (2019) 125e133 129

Fig. 2. EDX element mappings of the prepared FeCoNi-MOF@TiO2 (red circle areas are FeCoNi-MOF).

Fig. 3. N2 adsorption-desorption isotherms recorded for the prepared macroporous-mesoporous-TiO2 (a), FeCoNi-MOF (b) and FeCoNi-MOF@TiO2 (c). (d) The corresponding pore
size distribution curves of macroporous-mesoporous-TiO2, FeCoNi-MOF and FeCoNi-MOF@TiO2.

abundant pore structure of the FeCoNi-MOF@TiO2 has a large EDX result and feeding ratio. The detailed Fe 2p spectrum (Fig. 4b)
specific surface area and provides more reactive sites. appeared doublet peaks at 712.06 and 725.27 eV, which can be
For the purpose of further confirming the composite structure of belong to Fe 2p3/2 and Fe 2p1/2 and the valence state was Fe3þ
FeCoNi-MOF@TiO2, the X-ray photoelectron spectroscopy (XPS) [40,41]. The spectrums of Co 2p3/2 and Co 2p1/2 were situated at
was used to analyze the surface chemical composition and valence 782.03 and 798.02 eV, which were assigned to Co 2p3/2 and Co 2p1/2
state in Fig. 4. The wide-scan XPS survey spectrum revealed the and ascertained the composite involved Co2þ (Fig. 4c) [41]. Fig. 4d
appearance of Fe, Co, Ni, Ti and O in Fig. 4a, verifying that the showed Ni 2p3/2 and Ni 2p1/2 peaks were located at 855.89 and
FeCoNi-MOF and the macroporous-mesoporous-TiO2 were com- 873.56 eV, along with the satellite peaks at 861.66 and 879.92 eV,
bined together successfully, and the elemental ratio of Fe, Co and Ni indicating the presence of Ni2þ. Fig. 4e showed Ti 2p3/2 and Ti 2p1/2
calculated by XPS was about 5:1:12, which matched well with the peaks separately lied at 458.37 and 464.07 eV, accounting for the
130 Z. Li et al. / Materials Today Energy 13 (2019) 125e133

Fig. 4. (a) Wide-scan XPS spectrum of the prepared FeCoNi-MOF@TiO2. (b) Fe 2p XPS spectrum of the prepared FeCoNi-MOF@TiO2. (c) Co 2p XPS spectrum of the prepared FeCoNi-
MOF@TiO2. (d) Ni 2p XPS spectrum of the prepared FeCoNi-MOF@TiO2. (e) Ti 2p XPS spectrum of the prepared FeCoNi-MOF@TiO2. (f) TGA curves of the prepared FeCoNi-MOF@TiO2
and FeCoNi-MOF.

presence of Ti4þ in TiO2 [42]. Thermogravimetric analysis (TGA, UV light radiation in 1 M KOH electrolyte, for comparison, the same
Fig. 4f) compared the weight loss of FeCoNi-MOF@TiO2 and FeCoNi- examination was carried out on FeCoNi-MOF. The FeCoNi-MOF@-
MOF. The first mass loss of the FeCoNi-MOF@TiO2 occurred before TiO2 and FeCoNi-MOF were evaluated by depositing the catalyst on
200  C, which may be the volatilization of water and DMF enriched a glassy carbon (GC) electrode. Before the electrochemical test, the
in the pores with a mass loss of 2.7%. The second weight loss ranged electrodes underwent an activation treatment by several linear
from 200 to 370  C, and the mass loss was 5.2% due to the sweep voltammetry (LSV) until a stable curve was achieved. In
decomposition of terephthalic acid. At temperatures of order to understand the high catalytic activity of the FeCoNi-
370e600  C, the MOF structure in the composite is gradually MOF@TiO2 with UV light radiation toward OER, the mass activity
destroyed, resulting in a mass loss of 34%. The decomposition was calculated to compare catalytic activity of FeCoNi-MOF@TiO2
temperature of FeCoNi-MOF@TiO2 is higher than FeCoNi-MOF, with (FeCoNi-MOF@TiO2-UV) and without (FeCoNi-MOF@TiO2-
suggesting that the FeCoNi-MOF@TiO2 was beneficial to the NUV) UV light radiation. Figure S9a shows the LSV curves of
improvement of thermal stability of FeCoNi-MOF. The UVevis ab- FeCoNi-MOF@TiO2 at a scan rate of 10 mV s
1. The overpotential of
sorption spectra of FeCoNi-MOF@TiO2 and macroporous-meso- the FeCoNi-MOF@TiO2-UV was only 629 mV versus RHE at a cur-
porous-TiO2 were also analyzed in Figure S5. Both FeCoNi- rent density of 10 mA cm
2 mg
1, which was much smaller than the
MOF@TiO2 and macroporous-mesoporous-TiO2 had a strong ab- 635 mV for the FeCoNi-MOF@TiO2-NUV after 5 min of UV light
sorption peak at 323 nm, indicating that the FeCoNi-MOF@TiO2 and radiation. Apparently, the overpotential of FeCoNi-MOF@TiO2-UV
macroporous-mesoporous-TiO2 had a strong UV absorption was much lower than FeCoNi-MOF@TiO2-NUV, suggesting the UV
capacity. light radiation can improve significantly the activity of OER. The
According to the optical and porous property of FeCoNi- same referential measurements were conducted using the FeCoNi-
MOF@TiO2, we firstly designed a new photo-based electrocatalytic MOF (Figure S9b), and the OER activity was almost no change in the
OER catalytic system. A typical three-electrode system was used to presence or absence of UV light radiation. In order to verify the
evaluate the OER performances of the as-prepared catalysts with effect of UV light radiation rather than temperature on the
 Z. Li et al. / Materials Today Energy 13 (2019) 125e133 131

Fig. 5. (a) Potential-time curves of FeCoNi-MOF@TiO2 with (FeCoNi-MOF@TiO2-UV) and without (FeCoNi-MOF@TiO2-NUV) UV light radiation obtained at the working current of
10 mA cm
2 mg
1. (b) EIS of FeCoNi-MOF@TiO2 with (FeCoNi-MOF@TiO2-UV) and without (FeCoNi-MOF@TiO2-NUV) UV light radiation. (c) Schematic diagram of the OER reaction
process on FeCoNi-MOF@TiO2.

electrocatalytic activity of FeCoNi-MOF@TiO2, Figure S10 recorded and 631 mV, respectively. There was almost no change in the
the potential when the electrocatalytic reaction was exposed to UV overpotential of FeCoNi-MOF-UV and FeCoNi-MOF-NUV. From the
light radiation for 10 min, 15 min, 20 min, 25 min, 30 min and above data, it can be seen that the OER catalytic activity FeCoNi-
35 min respectively (red line), and then turn off the UV light to get MOF@TiO2 can be enhanced by the UV light radiation. To further
another potential (black line). The overpotential of the as-prepared understand the OER activity of the catalysts, electrochemical
FeCoNi-MOF@TiO2 was almost no change at a current density of impedance spectroscopy (EIS) was performed as shown in
10 mA cm
2 mg
1 with increasing the UV light radiation time, Figure S13. The Nyquist semicircle of the FeCoNi-MOF-UV and
indicating that the catalytical active of FeCoNi-MOF@TiO2 had no FeCoNi-MOF-NUV were almost the same, indicating that the UV
relationship with temperature. The as-prepared Fe-MOF@TiO2 was light radiation had no effect on the conductivity of the FeCoNi-MOF.
also used to evaluate the OER performances (Fig. S11), which was Fig. 5b showed that the Nyquist semicircle of the FeCoNi-MOF@-
almost unchanged with or without UV light radiation. In addition, TiO2-UV was much lower than FeCoNi-MOF@TiO2-NUV, indicating
the overpotential of Fe-MOF@TiO2 was 756 mV and is greater than the better electron conductivity of FeCoNi-MOF@TiO2-UV than
the overpotential of FeCoNi-MOF@TiO2. FeCoNi-MOF@TiO2-NUV, which was consistent with the results of
Fig. 5a showed that the overpotential of the FeCoNi-MOF@TiO2- Fig. 5a. For comparison experiments, the samples mixed with
UV for 5 min, 10 min, 15 min, 20 min, 30 min and 35 min were FeCoNi-MOF and TiO2 (FeCoNi-MOF&TiO2) were used to evaluate
629 mV, 629 mV, 628 mV, 627 mV, 628 mV, 627 mV and 626 mV, the OER performances (Figure S8, S14), which was almost un-
respectively, versus RHE at a current density of 10 mA cm
2 mg
1. changed with or without UV light radiation, indicating that the UV
The overpotential was stable, indicating that the catalytical active light radiation had no effect on the conductivity of physical
of FeCoNi-MOF@TiO2 was stable and was not affected by the heat mixture. When UV light was irradiated on macroporous-meso-
generated by the UV lamp. The overpotential of the FeCoNi- porous-TiO2, electrons were excited to enter the conduction band
MOF@TiO2-NUV for 5 min, 10 min, 15 min, 20 min, 25 min, 30 min from the valence band to form photoelectrons, while the holes
and 35 min were 635 mV, 636 mV, 635 mV, 634 mV, 635 mV, remained in the valence band (Fig. 5c). The photo-induced elec-
637 mV and 634 mV, respectively, versus RHE at a current density trons of macroporous-mesoporous-TiO2 can be transferred to the
of 10 mA cm
2 mg
1. The overpotential of FeCoNi-MOF@TiO2-UV loaded FeCoNi-MOF and then transferred to the circulating circuit
was a lot lower than [email protected] S12 showed to improve the electron transfer efficiency, thereby improving the
that the overpotential of the FeCoNi-MOF with UV light radiation OER catalytic performance of FeCoNi-MOF@TiO2.
(FeCoNi-MOF-UV) at a current density of 10 mA cm
2 mg
1 for
5 min, 10 min, 15 min, 20 min, 25 min, 30 min and 35 min is 4. Conclusions
630 mV, 629 mV, 624 mV, 628 mV, 634 mV, 632 mV and 629 mV,
respectively, and the overpotential of the FeCoNi-MOF without UV In summary, we firstly achieved a novel three-scale pore
light radiation (FeCoNi-MOF-NUV) at a current density of structure material by means of the FeCoNi-MOF confined in or-
10 mA cm
2 mg
1 for 5 min, 10 min, 15 min, 20 min, 25 min, 30 min dered macroporous-mesoporous-TiO2. Since the FeCoNi-MOF were
and 35 min was 632 mV, 632 mV, 626 mV, 631 mV, 637 mV, 633 mV grown in the ordered macroporous structure of macroporous-
132 Z. Li et al. / Materials Today Energy 13 (2019) 125e133

mesoporous-TiO2, this material exhibited a highly ordered hierar- [13] X. Du, J. He, Spherical silica micro/nanomaterials with hierarchical structures:
synthesis and applications, Nanoscale 3 (2011) 3984e4002.
chical porous structure, and the porous size were 400 nm, 5.1 nm
[14] S. Lopezorozco, A. Inayat, A. Schwab, T. Selvam, W. Schwieger, Zeolitic ma-
and 3.4 nm, respectively. The ordered mesoporous structure was in terials with hierarchical porous structures, Adv. Mater. 23 (2011) 2602e2615.
the macroporous walls, while the FeCoNi-MOF was in the macro- [15] C. Triantafillidis, M.S. Elsaesser, N. Hüsing, Chemical phase separation stra-
pores. As electrocatalysts on OER, the FeCoNi-MOF@TiO2 showed tegies towards silica monoliths with hierarchical porosity, Chem. Soc. Rev. 42
(2013) 3833e3846.
high electrocatalytic performance under UV light radiation, owing [16] Z. Sun, Y. Deng, J. Wei, D. Gu, B. Tu, D. Zhao, Hierarchically ordered macro-/
to the excellent conductivity of FeCoNi-MOF with the induction of mesoporous silica monolith: tuning macropore entrance size for size-selective
macroporous-mesoporous-TiO2. The photo-induced electron of adsorption of proteins, Chem. Mater. 23 (2011) 2176e2184.
[17] W. Wang, H. Qi, H. Long, X. Wang, H. Ru, A simple ternary non-ionic tem-
macroporous-mesoporous-TiO2 improved the conductivity of plating system for preparation of complex hierarchically mesoemesoporous
FeCoNi-MOF, which can provide a guideline for enhancing the silicas with 3D-interconnected large mesopores, J. Mater. Chem. 2 (2014)
catalytic activity of MOFs in electrocatalytic reaction. 5363e5370.
[18] T. Ma, S. Dai, M. Jaroniec, S. Qiao, Metal-organic framework derived hybrid
Co3O4-carbon porous nanowire arrays as reversible oxygen evolution elec-
Declaration of interests trodes, J. Am. Chem. Soc. 136 (2014) 13925e13931.
[19] Y. Yan, Y. Luo, J. Ma, B. Li, H. Xue, H. Pang, Facile synthesis of vanadium metal-
organic frameworks for high-performance supercapacitors, Small 14 (2018)
The authors declare no competing financial interest. 1801815.
[20] X. Xiao, Q. Li, X. Yuan, Y. Xu, M. Zheng, H. Pang, Ultrathin nanobelts as an
excellent bifunctional oxygen catalyst: insight into the subtle changes in
Acknowledgment structure and synergistic effects of bimetallic metaleorganic framework,
Small Methods 2 (2018) 1800240.
[21] J. Zhou, Y. Dou, A. Zhou, R. Guo, M. Zhao, J. Li, MOF template-directed fabri-
The authors acknowledge financial supports from the Beijing
cation of hierarchically structured electrocatalysts for efficient oxygen evo-
Natural Science Foundation (Grant Nos. 2182061), Science Foun- lution reaction, Adv. Energy Mater. 7 (2017) 1602643.
dation of China University of Petroleum, Beijing (Grant no. [22] J. Xu, Y. Wang, S. Cao, J. Zhang, G. Zhang, H. Xue, Q. Xu, H. Pang, Ultrathin Cu-
2462019BJRC001) and from the Natural Science Foundation of MOF@d-MnO2 nanosheets for aqueous electrolyte-based high-voltage elec-
trochemical capacitors, J. Mater. Chem. 6 (2018) 17329e17336.
Jiangsu Province (Grant no. BK20130288). This project is also fun- [23] R.M. Ramsundar, J. Debgupta, V.K. Pillai, P.A. Joy, Co3O4 nanorodsdefficient
ded by the Collaborative Innovation Center of Suzhou Nano Science non-noble metal electrocatalyst for oxygen evolution at neutral pH, Electro-
and Technology, and by the Priority Academic Program Develop- catalysis-US 6 (2015) 331e340.
[24] X. Guo, S. Zheng, G. Zhang, X. Xiao, X. Li, Y. Xu, H. Xue, H. Pang, Nano-
ment of Jiangsu Higher Education Institutions (PAPD). structured graphene-based materials for flexible energy storage, Energy
Storage Mater 9 (2017) 150e169.
[25] X. He, F. Yin, G. Li, A Co/metaleorganic-framework bifunctional electro-
Appendix A. Supplementary data catalyst: the effect of the surface cobalt oxidation state on oxygen evolution/
reduction reactions in an alkaline electrolyte, Int. J. Hydrogen Energy 40
Supplementary data to this article can be found online at (2015) 9713e9722.
[26] Y. Wei, X. Ren, H. Ma, X. Sun, Y. Zhang, X. Kuang, T. Yan, D. Wu, Q. Wei, In situ
https://doi.org/10.1016/j.mtener.2019.05.008. formed Co(TCNQ)2 metal-organic framework array as a high-efficiency cata-
lyst for oxygen evolution reactions, Chemistry 24 (2018) 2075e2079.
[27] D.D. Babu, Y. Huang, G. Anandhababu, M.A. Ghausi, Y. Wang, Mixed-metal-
References
organic framework self-template synthesis of porous hybrid oxyphosphide for
efficient oxygen evolution reaction, ACS Appl. Mater. Interfaces 9 (2017)
[1] J. Ge, T. Huynh, Y. Hu, Y. Yin, Hierarchical magnetite/silica nanoassemblies as 38621e38628.
magnetically recoverable catalyst-supports, Nano Lett. 8 (2008) 931e934. [28] H. Xu, Z. Shi, Y. Tong, G. Li, Porous microrod arrays constructed by carbon-
[2] Y. Liang, Q. Cao, M. Zheng, H. Huo, H. Hu, H. Dong, Y. Xiao, Y. Liu, Teflon: a confined NiCo@NiCoO2 Core@Shell nanoparticles as efficient electrocatalysts
decisive additive in directly fabricating hierarchical porous carbon with for oxygen evolution, Adv. Mater. 30 (2018), e1705442.
network structure from natural leaf, ACS Sustain. Chem. Eng. 5 (2017) [29] T. Reier, M. Oezaslan, P. Strasser, Electrocatalytic oxygen evolution reaction
9307e9312. (OER) on Ru, Ir, and Pt catalysts: a comparative study of nanoparticles and
[3] X. Yang, L. Chen, Y. Li, J.C. Rooke, C. Sanchez, B. Su, Hierarchically porous bulk materials, ACS Catal. 2 (2012) 1765e1772.
materials: synthesis strategies and structure design, Chem. Soc. Rev. 46 (2017) [30] L. Tang, S. Zhang, Q. Wu, X. Wang, H. Wu, Z. Jiang, Heterobimetallic
481e558. metaleorganic framework nanocages as highly efficient catalysts for CO2
[4] L.B. Mccusker, F. Liebau, G. Engelhardt, Nomenclature of structural and conversion under mild conditions, J. Mater. Chem. A. 6 (2018) 2964e2973.
compositional characteristics of ordered microporous and mesoporous ma- [31] D. Bradshaw, S. El-Hankari, L. Lupica-Spagnolo, Supramolecular templating of
terials with inorganic hosts, Pure Appl. Chem. 73 (2001) 381e394. hierarchically porous metal-organic frameworks, Chem. Soc. Rev. 43 (2014)
[5] J. Pang, K. Qiu, Y. Wei, Recent progress in research on mesoporous materials I: 5431e5443.
synthesis, J. Inorg. Mater. 17 (2002) 407e414. [32] W.T. Koo, J.S. Jang, S. Qiao, W. Hwang, G. Jha, R.M. Penner, I.D. Kim, Hierar-
[6] Q. Zhao, Y. Mao, L. Yan, L. Lu, T. Jiang, H. Yin, Stability of Y/MCM-48 composite chical metal-organic framework-assembled membrane filter for efficient
molecular sieve with mesoporous and microporous structures, J. Asian Ceram. removal of particulate matter, ACS Appl. Mater. Interfaces 10 (2018)
Soc. 2 (2014) 347e356. 19957e19963.
[7] B. Su, C. Sanchez, X. Yang, Hierarchically structured porous materials, Adv. [33] J. Cui, N. Gao, X. Yin, W. Zhang, Y. Liang, L. Tian, K. Zhou, S. Wang, G. Li,
Funct. Mater. 22 (2012) 4634e4667. Microfluidic synthesis of uniform single-crystalline MOF microcubes with a
[8] M. Sun, C. Chen, L. Chen, B. Su, Hierarchically porous materials: synthesis hierarchical porous structure, Nanoscale 10 (2018) 9192e9198.
strategies and emerging applications, Front. Chem. Sci. Eng. 10 (2016) 1e47. [34] S. Dang, Q. Zhu, Q. Xu, Nanomaterials derived from metaleorganic frame-
[9] M. Sun, S. Huang, L. Chen, Y. Li, X. Yang, B. Su, Applications of hierarchically works, Nat. Rev. Mater. 3 (2017) 17075.
structured porous materials from energy storage and conversion, catalysis, [35] Z. Liang, Q. Chong, D. Xia, R. Zou, X. Qiang, Atomically dispersed metal sites in
photocatalysis, adsorption, separation, and sensing to biomedicine, ChemIn- MOF-based materials for electrocatalytic and photocatalytic energy conver-
form 47 (2016) 3479. sion, Angew. Chem. 130 (2018) 9750e9780.
[10] S. Fan, B. Fang, J.H. Kim, J.J. Kim, J. Yu, J. Ko, Hierarchical nanostructured [36] L. Jiao, Y. Wang, H. Jiang, Q. Xu, Metal-organic frameworks as platforms for
spherical carbon with hollow core/mesoporous shell as a highly efficient catalytic applications, Adv. Mater. 30 (2017) 1703663.
counter electrode in CdSe quantum-dot-sensitized solar cells, Appl. Phys. Lett. [37] H. Wang, F. Yin, G. Li, B. Chen, Z. Wang, Preparation, characterization and
96 (2010), 053503. bifunctional catalytic properties of MOF(Fe/Co) catalyst for oxygen reduction/
[11] X. Zhang, T. Ma, Z. Yuan, Synthesis of hierarchically meso-/macroporous ti- evolution reactions in alkaline electrolyte, Int. J. Hydrogen Energy 39 (2014)
tanium tetraphosphonate materials with large adsorption capacity of Heavy 16179e16186.
metal ions, Chem. Lett. 37 (2008) 746e747. [38] T. Fan, F. Yin, H. Wang, X. He, G. Li, A metaleorganic-framework/carbon
[12] J. Konishi, K. Fujita, K. Nakanishi, K. Hirao, K. Morisato, S. Miyazaki, M. Ohira, composite with enhanced bifunctional electrocatalytic activities towards ox-
Sol-gel synthesis of macro-mesoporous titania monoliths and their applica- ygen reduction/evolution reactions, Int. J. Hydrogen Energy 42 (2017)
tions to chromatographic separation media for organophosphate compounds, 17376e17385.
J. Chromatogr., A 1216 (2009) 7375e7383.
 Z. Li et al. / Materials Today Energy 13 (2019) 125e133 133

[39] J. Shen, P. Liao, D. Zhou, C. He, J. Wu, W. Zhang, J. Zhang, X. Chen, Modular and [42] C. Chen, T. Wu, D. Yang, P. Zhang, H. Liu, Y. Yang, G. Yang, B. Han, Catalysis of
stepwise synthesis of a hybrid metal-organic framework for efficient elec- photooxidation reactions through transformation between Cu(2þ) and Cu(þ)
trocatalytic oxygen evolution, J. Am. Chem. Soc. 139 (2017) 1778e1781. in TiO2-Cu-MOF composites, Chem. Commun (Camb). 54 (2018) 5984e5987.
[40] H. Ali-Lo€ytty, M.W. Louie, M.R. Singh, L. Li, H.G.S. Casalongue, H. Ogasawara, [43] Q. Qian, Y. Li, Y. Liu, L. Yu, G. Zhang, Ambient fast synthesis and active sites
E.J. Crumlin, Z. Liu, A.T. Bell, A. Nilsson, Ambient-pressure XPS study of a Ni-Fe deciphering of hierarchical foam-like trimetal-organic framework nano-
electrocatalyst for the oxygen evolution reaction, J. Phys. Chem. C 120 (2016) structures as a platform for highly efficient oxygen evolution electrocatalysis,
2247e2253. Adv. Mater. 5 (2019) 1901139.
[41] F. Li, Q. Shao, X. Huang, J. Lang, Nanoscale trimetallic metal-organic frame-
works enable efficient oxygen evolution electrocatalysis, Angew Chem. Int.
Ed. Engl. 57 (2018) 1888e1892.