Journal of Colloid and Interface Science 565 (2020) 142–155

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Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

N self-doped ZnO derived from microwave hydrothermal synthesized

zeolitic imidazolate framework-8 toward enhanced photocatalytic
degradation of methylene blue
Li Sun a, Qian Shao a,⇑, Yu Zhang a, Heyun Jiang a, Shengsong Ge a, Siqi Lou a, Jing Lin b,⇑, Jiaoxia Zhang c,
Shide Wu d, Menyao Dong e,f, Zhanhu Guo f,⇑
a
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
b
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
c
School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
d
Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No. 136, Science Avenue, Zhengzhou 450001, China
e
Key Laboratory of Materials Processing and Mold (Zhengzhou University), Ministry of Education, National Engineering Research Center for Advanced Polymer Processing
Technology, Zhengzhou University, Zhengzhou, China
f
Integrated Composites Laboratory (ICL), Department of Chemical & Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Zeolitic imidazolate framework-8

(Zif-8) was prepared by a facile
microwave hydrothermal method.

The N doped ZnO was synthesized by
one-step controllable pyrolysis of Zif-8.

The N doped ZnO exhibited a higher
photocatalytic degradation of
methylene blue (MB) under solar-
simulated light.

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

Article history: The precursor particles were successfully prepared by a facile microwave hydrothermal method.
Received 7 October 2019 Compared with solvothermal and precipitation method, microwave hydrothermal method can greatly
Revised 6 December 2019 shorten the reaction time and increase the product yields. Nitrogen (N) doped zinc oxide (ZnO) nanopar-
Accepted 24 December 2019
ticles were derived via one-step controllable pyrolysis of zeolitic imidazolate framework-8 (Zif-8) precur-
Available online 26 December 2019
sors under 550 °C. The powder X-ray diffraction (XRD) analysis, elemental mapping image, energy
dispersive spectrometry (EDS) spectra and X-ray photoelectron spectroscopy (XPS) analysis proved that
Keywords:
Zif-8 particles were converted to ZnO and the N atoms were successfully doped into ZnO lattice. The
Microwave hydrothermal method
Zif-8
scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results demonstrated
N doped zinc oxide that N doped ZnO retained the morphology of Zif-8 with a particle size of approximately ~70 nm and the
Photocatalysts UV–visible diffuse reflectance spectra (UV–vis DRS) showed that the as-prepared N doped ZnO possessed
a lower band gap (3.16 eV) than commercial ZnO (3.26 eV). The photocatalytic activities of

⇑ Corresponding authors.
E-mail addresses: shaoqian@sdust.edu.cn (Q. Shao), linjing@gzhu.edu.cn (J. Lin), zguo10@utk.edu (Z. Guo).

https://doi.org/10.1016/j.jcis.2019.12.107
0021-9797/Ó 2020 Elsevier Inc. All rights reserved.
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155
the as-prepared samples were evaluated by the degradation rate of methylene blue (MB) upon irradiation
with solar-simulated light. The photocatalytic degradation efficiency of N doped ZnO was 95.3% after
80 min illumination, which was much higher than that of other samples prepared by other methods.
Quenching tests proved that the photo-generated holes (h+) played a main role in the photodegradation
of MB under solar-simulated light irradiation.
1. Introduction
In recent years, due to the rapid development of industrial man-
ufacturing, and increasing demand of new advanced materials and
consumption of energy [1–12], a large number of pollutants
[13–16] especially refractory industrial wastewater and dyeing
wastewater have been produced, and has caused great pollution
to the water ecosystem [17–20]. Many methods include physical
adsorption, biodegradation, membrane, and photocatalysis have
been explored to treat dye wastewater [21–25]. Among these
methods, photocatalysis arouses more attention owing to the high
degradation efficiencies, easy preparation of catalyst and no sec-
ondary pollution [26,27].
Nanometer oxide semiconductor materials as the favorable
photocatalysts have received extensive attention due to their high
efficiencies and environmentally friendliness [28–33]. Zinc oxide
(ZnO) with a wide band gap (3.37 eV) as a II-VI semiconductor is
a high-efficiency photocatalyst for the degradation of organic pol-
lutants due to its nontoxic, environment and economic-friendly
characteristics [34–36]. Nevertheless, the practical application in
remedying the environmental pollution by ZnO has been restricted
due to its narrow light-absorption range and the high-speed com-
bination of photogenerated electron-hole pairs [37]. Therefore, a
plenty of efforts have been devoted towards solving these two
problems such as the doping of ZnO with precious metal (i.e., Ag,
Au, Pt), g-C3N4, carbon, nitrogen, etc. to increase the visible-light
photocatalytic activity [38]. For example, Ramos-Corona et al. syn-
thesized nitrogen doped ZnO composited with graphene which
possessed higher photocatalytic activities than pristine ZnO under
visible light irradiation [39]. Gao et al. reported the high efficiency
photocatalytic performance of Au@ZnO composites for the degra-
dation of tetracycline [40]. Sindhuja et al. fabricated ZnO/g-C3N4/
Ag composites via a homemade automated jet nebulizer spray
technique and showed excellent photocatalytic performance for
the photodegradation of methylene blue [41].
Nitrogen can easily substitute oxygen atom and dope into ZnO
lattice [42]. The better overlap of N 2p orbital with Zn 3d orbital
or the mixing N 2p orbital with O 2p orbital can reduce the band-
gap energy of ZnO and suppress the rapid recombination of elec-
trons and holes, which have been proved to enhance the
photocatalytic performance [43–45]. So far, various methods of
achieving nitrogen-doping in ZnO nanoparticles have been
explored, such as thermal nitridation [46], in-situ synthesis [47],
chemical vapor deposition (CVD) [48,49], etc. However, some dis-
advantages exist in these methods like the strict synthesis condi-
tions, random distribution of elements and additional nitrogen
sources. Thus, finding a facile element doping method is still a
challenge.
Metal-organic frameworks (MOFs), porous coordination materi-
als composed of metal ions/cluster and organic ligands with large
specific surface area, excellent water/chemical stability, are widely
used as gas storage materials, adsorbents, sensors, etc. [50–54]. In
addition, some types of MOFs can be used as photocatalysts [55], it
can also be used as the precursors to obtain the desired oxide semi-
conductor materials by pyrolysis treatment [56,57]. The zeolite
imidazolate framework (Zif) is a type of MOFs, being formed
through the coordination of transition metals ions [Zn(II), Co(II)]
143
Ó 2020 Elsevier Inc. All rights reserved.
and imidazole. They have aroused extensive research interests
due to excellent thermal and chemical stability over other MOFs
[58]. Zif-8 as a Zn-containing C, N-rich ZIF constructed by the link
of Zn(II) and 2-methylimidazole ligands has attracted more atten-
tion than other ZIFs [59]. It can be used as the source of nitrogen to
achieve self-doping of N element without other functional precur-
sors. For example, Du et al. fabricated porous ZnO by thermal treat-
ment of Zif-8 and showed efficient photocatalytic activities for the
degradation of MB under UV light [28]. Lang et al. synthesized
carbon-nitrogen-doped ZnO via the pyrolysis of Zif-8 in three dif-
ferent ways which showed an improved photocatalytic activity
than pure ZnO [60], but the cumbersome pyrolysis process and
the higher pyrolysis temperature still limit its practical application.
The traditional methods of synthesizing Zif-8 such as solvothermal
method [61] and precipitation method [62] have the defects of low
yield, long synthesis time and uneven heating, which limit the
practical applications. In recent years, microwave hydrothermal
technology has received extensive attention in nanomaterial syn-
thesis fields because of its rapid, uniform heating, high product
yield [63].
In this work, Zif-8 precursor was prepared by microwave
hydrothermal method with methanol as polar solvent which has
a stronger absorbing microwave ability than non-polar solvents
[64]. Subsequently, N doped ZnO was obtained by one-step directly
calcining Zif-8 precursor at 550 °C for 2 h in the presence of air.
Compared with the ZnO derived from the precursors prepared by
solvothermal and precipitation method, the N doped ZnO obtained
by calcining Zif-8 precursor prepared by microwave hydrothermal
method showed more outstanding photocatalytic activity of
methylene blue (MB) upon irradiation with solar-simulated light.
The doping of N reduced the band gap energy of ZnO and improved
light utilization which enhanced the photocatalytic activities.
Moreover, the reaction time was substantially shortened and the
product yields were increased. In addition, after five recycle exper-
iments, the as-prepared N doped ZnO can still maintain a high-
efficiency degradation capacity.
2. Experimental
2.1. Materials
Zinc nitrate hexahydrate (Zn(NO3)26H2O), 2-methylimidazole
(Hmim), sodium formate (HCOONa), anhydrous ethanol, methy-
lene blue (MB), isopropyl alcohol (IPA), p-benzoquinone, EDTA-
2Na and methanol were all commercial analytical grade reagents
and used as received without any further treatment or purification.
2.2. Synthesis of ZIF-8.
Zif-8 was prepared by microwave hydrothermal method.
Briefly, 0.59 g of Zn(NO3)26H2O was dissolved in 40 mL methanol,
then another 40 mL methanol containing 1.28 g of Hmim and
0.08 g of HCOONa was added slowly. The mixture was poured into
a Teflon-reactor (100 mL capacity) and transferred into a micro-
wave hydrothermal parallel synthesizer (XH-800S, Beijing Xian-
gHu Science and Technology Development Co., Ltd, China) and
144 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155
heated at 120 °C for 2 h. After the reaction was finished, the white
precipitate was harvested by centrifugation and was washed three
times with anhydrous ethanol and dried in the oven at 70 °C for
12 h. The as-prepared sample was denoted as M-Zif-8. For compar-
ison, Zif-8 particles were also fabricated by solvothermal [65] and
traditional precipitation method [66], the samples were designated
as S-Zif-8, P-Zif-8, respectively.
2.3. Fabrication of the ZIF-8 derived N-ZnO
The N doped ZnO was obtained by putting the as-prepared Zif-8
in a covered crucible and placing it in a muffle furnace at desired
temperature in air for 2 h at a ramp rate of 9 °C/min, and recorded
separately as M-ZnO-n, S-ZnO-n, P-ZnO-n, where ‘‘M”, ‘‘S” and ‘‘P”
represent the microwave hydrothermal method, solvothermal
method and precipitation method, respectively, and n corresponds
to the calcining temperature. For example, the N doped ZnO pre-
pared by pyrolysis of the Zif-8 precursor (obtained by microwave
hydrothermal method) at 550° C is denoted as M-ZnO-550.
2.4. Characterizations
The morphology and structural analysis of the samples were
examined by a scanning electron microscope (SEM, S-4800, Hita-
chi, Japan) and transmission electron microscope (TEM, JEM-
2100F, Japan). The crystal structures of the products were tested
by powder X-ray diffraction (XRD, ultima IV, Rigaku, Japan). Ele-
mental composition information of samples was examined by an
ESCALAB 250Xi X-ray photoelectron spectrometer (XPS, Thermo
Scientific, USA). The UV–Vis diffuse reflectance spectra of the sam-
ples were analyzed by UH4150 UV–Vis spectrophotometer (Hita-
chi, Japan). The Brunauer–Emmett–Teller (BET) results were
obtained at 77.350 K using a micromeritics surface area and pore
volume analyzer (TriStar II 3020, USA).
2.5. Photocatalytic activity measurement
The photocatalytic activities of photocatalysts were examined
by MB degradation experiments under solar-simulated light irradi-
ation. A xenon lamp (200 W, k = 320–1100 nm) was employed as
the light source. In a typical photocatalytic degradation experi-
ment, 50 mg of photocatalyst powders were added into a 100 mL
aqueous solution of MB (20 mg/L). Before illumination, the suspen-
sion was magnetically stirred in dark for 0.5 h to obtain the adsorp-
tion/desorption equilibrium of MB dye on the surface of the
sample. Then the catalyst was exposed under the xenon lamp. At
a certain regular interval, 4 mL reaction solution was sampled
every 20 min and promptly centrifuged for three minutes to sepa-
rate the photocatalyst particles. The absorbance of MB aqueous
solution was measured by UV9000 UV–vis absorption spectropho-
tometer (METASH, China) at a wavelength of 664 nm, and the con-
centration was calculated by the Beer-Lambert law.
3. Results and discussion
3.1. Characterization of the products
The XRD patterns of the as-prepared Zif-8 precursors synthe-
sized by different methods and N-doped ZnO obtained by calcining
precursors at 550 °C are shown in Fig. 1A. It can be seen that the
diffraction peak positions of all Zif-8 precursors are consistent with
reported literature [67], and the diffraction peaks of M-Zif-8 are
higher and stronger than that of P-Zif-8 and S-Zif-8. The diffraction
peaks of M-ZnO-550, S-ZnO-550 and P-ZnO-550 at 2h 31.8°, 34.4°,
36.2°, 47.5°, 56.6°, 62.9°, 66.4°, 67.9°, 69.1° can be assigned to
(1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2)
and (2 0 1) crystal planes, which are identified being consistent
with the hexagonal wurtzite structure of ZnO (JCPDS 79-2205).
No peaks of Zif-8 are observed in the diffraction patterns of M-
ZnO-550, S-ZnO-550 and P-ZnO-550, indicating that Zif-8 had
completely changed into ZnO. However, there are no peaks related
to nitrogen-containing phase in the XRD patterns, this may be due
to the doping of nitrogen into the lattices of ZnO [45]. Fig. 1B shows
the XRD patterns of M-ZnO-550 and commercial ZnO on the (0 0 2)
crystal faces, the diffraction peak angle of M-ZnO-550 is shifted to
the left as compared to commercial ZnO and the lattice constants
and d-spacing (0 0 2) of M-ZnO-550 (a = 3.2490, c = 5.2051,
d = 0.2602) are larger than those of commercial ZnO (a = 3.2454,
c = 5.1974, d = 0.2596), which can be resulted from nitrogen atom
instead of oxygen atom or inserted nitrogen atom into interstitial
sites between the zinc atom and the oxygen atom [37,45,68].
The morphologies of the as-prepared Zif-8 precursors obtained
by different methods and (M, S, P)-ZnO-550 were investigated by
SEM (Fig. 2). The morphologies of M-Zif-8, S-Zif-8, P-Zif-8 are
shown in Fig. 2A, B, C, respectively. All Zif-8 particles are uniform
approximately rhombic dodecahedron facets, which are in consis-
tent with those reported in the literature [69]. It is worth noting
that these three Zif-8 particles have different sizes. The particle
sizes of P-Zif-8, S-Zif-8, M-Zif-8 are ~56, ~75, ~97 nm, respectively.
In addition, M-Zif-8 has a tendency to grow into larger particles
which proved that the nucleation and crystallization process of
Zif-8 particle growth can be accelerated by the microwave radia-
tion assistance [70]. After calcination, it can be seen that M-ZnO-
550, S-ZnO-550, P-ZnO-550 present smooth irregular polygon mor-
phologies (Fig. 2D-F), which can be attributed to the contraction of
M-Zif-8 skeleton and some rod-like particles were formed due to
the co-growth of partial particles. It indicates that the ZnO with
special morphology can be obtained by calcining Zif-8 particles.
Fig. 3 shows the low magnification TEM and the high-resolution
transmission electron microscopy (HRTEM) images of M-ZnO-550.
As shown in Fig. 3A and B, it can be clearly seen that the M-ZnO-
550 is formed with irregular polygon morphologies and the aver-
age diameter of about 70 nm, which is corresponding to the SEM
result. Fig. 3C and D show the HRTEM images of M-ZnO-550. The
obvious lattice planes of the nanocrystals demonstrate the high
crystallinity of M-ZnO-550. The interplanar spaces of 0.25 and
0.28 nm match well with the (1 0 1) and (1 0 0) plane of ZnO,
respectively [71]. The observed slight lattice disorder and disloca-
tion at the edge of M-ZnO-550 (the part of dotted box in Fig. 3D)
prove the existence of oxygen vacancy [72]. Fig. 4 shows the ele-
mental mapping images and EDS spectrum of M-ZnO-550. It can
be seen that C, N, O and Zn elements are evenly distributed in
the as-prepared sample, indicating that N atoms have been suc-
cessfully doped into ZnO.
To survey the chemical states and compositions of Zn, O, N and
C species, the XPS determination of M-ZnO-550 was carried out
(Fig. 5). As depicted in Fig. 5A, the full survey spectrum shows
the constitution elements of Zn, C, N and O, no other peaks related
to Zn and O elements, indicating that the highly purity of the as-
prepared catalyst. Fig. 5B records the high- resolution spectrum
of C 1s, where the three symmetric peaks are situated at
284.9 eV, 286.6 eV and 288.9 eV. The main peak at 284.9 eV corre-
sponds to sp2-hybridized carbon from CAC or contamination car-
bon [73], the two fitting peaks are assigned to the CAO and
O@CAO band, respectively [74]. However, no peak appeared at
the binding energy (283 eV) suggested the non-existence of C as
Zn-C band. The observed only one fitting peak at 399.4 eV between
the sp2-hybridized nitrogen (396–397 eV) [75] and the oxynitride
(above 400 eV) [76] is attributed to N-Zn-O band (Fig. 5C). The
existence of N-Zn-O band indicates that nitrogen atoms have been
successfully doped in ZnO by replacing the oxygen atoms.
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155 145

Fig. 1. (A) XRD patterns of M-Zif-8, S-Zif-8, P-Zif-8, commercial ZnO, M-ZnO-550, S-ZnO-550 and P-ZnO-550 particles, (B) the (0 0 2) planes of M-ZnO-550 and commercial
ZnO intercepted from (A).

Fig. 2. SEM images of M-Zif-8 (A), S-Zif-8 (B), P-Zif-8 (C), M-ZnO-550 (D), S-ZnO-550 (E) and P-Zif-8-550 (F).
146 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155

Fig. 3. Low magnification TEM images (A and B) and HRTEM images (C and D) of M-ZnO-550.

Fig. 4. SEM images of M-ZnO-550 (A), elemental mapping of M-ZnO-550 with the homogeneous distribution of C, N, O and Zn (B–E), and EDS measurement of the plotted area
of M-ZnO-550 (F).
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155 147

Fig. 5. XPS spectra of M-ZnO-550: full survey spectrum (A), high-resolution spectra of C 1s (B), N 1s (C), O 1s (D) and Zn 2p (E).

The same results are proved by the elemental mapping image and
EDS spectrum (Fig. 4). Three fitting peaks at 530.1 eV, 531.4 eV and
532.4 eV of O 1 s are shown in Fig. 5D. The lowest bind energy fit-
ting peak at 530.1 eV can be assigned to O2– ions which are from
the ZnO lattice [77]. The other two fitting peaks at 531.4 eV and
532.4 eV are associated with the O2– ions in the oxygen vacancy
in ZnO and the OAH bonds from molecular water, respectively
[78,79]. Fig. 5E shows the XPS spectra of Zn 2p, two fitting peaks
at binding energy of 1021.15 eV and 1044.2 eV can be observed,
corresponding to Zn 2p3/2 and Zn 2p1/2 [80].
3.2. Influence of calcination temperature
The controlled pyrolysis of Zif-8 plays a vital role in obtaining N
doped ZnO, the effect of calcination temperature on the formation
of N doped ZnO was explored. Fig. 6 shows the XRD patterns of the
commercial ZnO and M-ZnO-n obtained by pyrolyzing the M-Zif-8
precursors at 400 °C-650 °C. When the calcination temperature is
400 °C, the diffraction peak of M-Zif-8 at 17° is still retained and
the weak peaks of ZnO appears. With increasing the calcination
temperature to 450 °C, the peaks of Zif-8 completely disappear,
148 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155
Fig. 6. XRD patterns of M-ZnO-400, M-ZnO-450, M-ZnO-550 and M-ZnO-650.
but the crystallization of ZnO is low. The intensity of the diffraction
peaks of ZnO becomes stronger as the calcination temperature con-
tinues to increase. The crystallite size of samples was roughly cal-
culated by Scherrer formula (1) [81]:
Fig. 7. SEM images of (A) M-ZnO-400, (B) M-ZnO-450, (C) M-ZnO-550 and (D) M-ZnO-650, and nitrogen elements mapping images of (E) M-ZnO-400, (F) M-ZnO-450, (G) M-
ZnO-550 and (H) M-ZnO-650.
D ¼ 0:89k=b cos h ð1Þ
where D stands for the crystallite size of M-ZnO-550, k represents
the X-ray wavelength of Cu Ka radiation, b is the half width of
the main peak and h is the half of the diffraction angle 2h. The
crystallite sizes of commercial ZnO, M-ZnO-400, M-ZnO-450,
M-ZnO-550 and M-ZnO-650 estimated by the formula are
~54.8 nm, ~ 13.2 nm, ~ 15.8 nm, ~ 32 nm and ~45.3 nm, respectively.
It can be seen that the crystallite size of M-ZnO becomes larger as
the pyrolysis temperature increases.
The morphologies of M-ZnO-n (n = 400, 450, 550 and 650) are
shown in Fig. 7. From Fig. 7A and B, it can be seen that both the par-
ticles of M-ZnO-400 and M-ZnO-450 have agglomerated and still
maintain the morphologies of M-Zif-8 particles. When raising the
calcination temperature to 550 °C, the morphology of M-ZnO-550
(Fig. 7C) has changed to irregular polygon shape. Compared with
M-Zif-8, the particle size reduction of M-ZnO-400 (~45 nm), M-
ZnO-450 (~50 nm), M-ZnO-550 (~70 nm) is attributed to the shrink
of the M-Zif-8 skeleton. Compared with M-ZnO-n (n = 400, 450,
550), the larger particle size of M-ZnO-650 (~200 nm) can be
attributed to the co-growth of partial particles. As shown in
Fig. 7 (E ~ H), the distribution of nitrogen element become sparse
as the of calcination temperature raise. The N atomic percentages
of M-ZnO-400, M-ZnO-450, M-ZnO-550 and M-ZnO-650 are listed
in Table 1, it can be seen that the retention of nitrogen is decreased
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155 149

Table 1
N atom [%] of M-ZnO-400, M-ZnO-450, M-ZnO-550, M-ZnO-650.

Samples M-ZnO-400 M-ZnO-450 M-ZnO-550 M-ZnO-650

N atom [%] 27.04 16.21 7.13 2.91

as the increase of pyrolysis temperature. Combined with the
results of XRD patterns, in order to obtain nitrogen retention, high
crystallization and good morphology of N doped ZnO, the calcina-
tion temperature needs to reach 550 °C.
Fig. 8 shows the N2 adsorption-desorption isotherms of M-Zif-8,
M-ZnO-n (n = 400, 450, 550 and 650) and the specific surface area
and pore structure of these as-prepared samples are evaluated by
the isotherms. The adsorption-desorption isotherms of all samples
are consistent with the type IV isotherm according to the IUPAC
classification [82]. As shown in Fig. 8A, B and C, M-Zif-8 has a large
adsorption to nitrogen at low relative pressures, M-ZnO-400 and
M-ZnO-450 also have adsorption of nitrogen at low relative pres-
sure, but the adsorption capacity is much lower than that of M-
Zif-8. The result suggests that M-ZnO-400 and M-ZnO-450 still
retain the crystal structure of Zif-8. Table 2 shows the specific sur-
face areas, pore performance data and pore volume of all samples.

Fig. 8. N2 sorption isotherms and pore size distribution of (A) M-Zif-8, (B) M-ZnO-400, (C) M-ZnO-450, (D) M-ZnO-550 and (E) M-ZnO-650.
150 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155

Table 2
Specific surface area, pore diameter, pore volume and band gap of samples.
a
Samples SBET (m2/g) a
Dpore (nm) a
Vpore (cm3/g) b
Eg (eV)
M-Zif-8 1222.43 2.26 0.690 5.21
M-ZnO-400 32.67 7.52 0.075 2.21
M-ZnO-450 31.82 9.41 0.061 3.12
M-ZnO-550 9.66 5.25 0.013 3.16
M-ZnO-650 3.33 5.09 0.004 3.18
S-ZnO-550 3.19
P-ZnO-550 3.17
Commercial ZnO 3.26
a
Estimated by BET N2 adsorption method (Fig. 8).
b
Estimated by UV–vis diffuse reflectance spectra (Fig. 9).

It can be seen that M-Zif-8 has the largest specific surface area
(1222.43 m2/g) and pore volume (0.690 cm3/g) but the smallest
pore size compared to other samples. The specific surface area
and pore volume of the M-ZnO-n (n = 400, 450, 550 and 650)
decreases as the increase of pyrolysis temperature. Compared with
the M-ZnO-650, M-ZnO-550 displays a larger specific surface area
(9.66 m2/g), pore size (5.25 nm) and pore volume (0.013 cm3/g).
The band gap of the catalyst is also one of the significant factors
affecting the light utilization efficiency. The UV–Vis diffuse reflec-
tance spectra of the as-prepared samples are shown in Fig. 9A. The
light absorption wavelength of the M-Zif-8 precursor corresponds
only to the UV light region below 255 nm. It is obvious that the
spectral intensities of M-ZnO-n (n = 400, 450, 550 and 650),
S-ZnO-550 and P-ZnO-550 are higher than commercial ZnO and
their absorption edges extend to the visible region, indicating that
the O2 vacancy atoms and the effect of nitrogen doping on the top
of valence band (VB) play a crucial role in expanding the absorp-
tion to the visible region [83]. The band gap energy (Eg) of the
as-prepared samples were investigated by the Kubelka-Munk Eq.
(2) [84]:


ðahv Þ ¼ K hv  Eg
2
ð2Þ
where a, hv, K and Eg represent the absorption coefficient, photon
energy, proportionality constant and band gap, respectively. From
Fig. 9B, the band gap energy (Eg) can be calculated by the normal-
ized maps (ahm)2 for the photon energy of the samples and the value
are listed in Table 2. The band gap energy of M-Zif-8 is 5.2 eV, which
corresponds to the fact that it only absorbs ultraviolet light. Com-
pared with other samples, although M-ZnO-400 and M-ZnO-450
have narrower band gaps, but it can be seen that the ZnO crystals
are not completely formed under the calcination temperature at
400 °C and 450 °C from above XRD patterns and SEM. The band
gap energy of M-ZnO-550, M-ZnO-650, S-ZnO-550 and P-ZnO-550
is 3.16 eV, 3.18 eV, 3.19 eV and 3.17 eV, respectively, which are
all lower than commercial ZnO (3.26 eV), That can be attributed
to the special morphologies of these materials and the existence
of N related defect state which is closer to the conduction band
(CB) than VB [85], and the Eg value of M-ZnO-550 is the lowest indi-
cating that M-ZnO-550 possessed the high efficiency of light utiliza-
tion. Thus, in combination with the above characterizations, the
desirable controllable calcination temperature of one-step synthe-
sizing N doped ZnO is 550 °C.
3.3. Photocatalytic activity
The photocatalytic properties of samples can be evaluated by
degradation of MB aqueous under solar-simulated light irradiation.
Before the light irradiation, the photocatalysts were added in dye
aqueous and stirring for 30 min in the dark to reach the
adsorption-desorption equilibrium. From Fig. 10A, it can be obvi-
ously seen that M-ZnO-550, S-ZnO-550 and P-ZnO-550 have the
similar adsorption efficiencies (about 5%) of MB. After 80 min of
solar-simulated light illumination, M-ZnO-550 not only shows
the higher photocatalytic degradation efficiencies (95.3%) than
S-ZnO-550 (91.8%) and P-ZnO-550 (90.8%), but the synthesis time
of the precursor of M-ZnO-550 is shorter than that of S-ZnO-550
and P-ZnO-550. Moreover, the yields of the precursor of M-ZnO-
550 are much higher than that of P-ZnO-550. Implying that micro-
wave hydrothermal technology has great potential in the field of
photocatalysts. Fig. 10B shows the degradation rates of all samples

Fig. 9. UV–vis absorption spectra of M-Zif-8, M-ZnO-400, M-ZnO-450, M-ZnO-550, M-ZnO-650, S-ZnO-550, P-ZnO-550 and commercial ZnO (A), the plotting of (ahm)2 vs. hm
based on the direct transition (B).
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155 151

Fig. 10. Photocatalytic degradation of MB (A) and (B) using various photocatalysts under solar-simulated light irradiation (photocatalyst: 50 mg, MB: 100 mL, 20 mg/L). The
photodegradation kinetic curves of various photocatalysts (C) and (D).

to MB as follow: blank (without catalytic) 15.4%, photosensitiza- Table 3

tion (M-ZnO-550) (soaking M-ZnO-550 with high concentration The kinetic constant k and correlation coefficient (R2) of MB degradation by all
MB for 2 h) 96.3%, commercial ZnO 66.9%, M-ZnO-400 90.4%, M- samples.
ZnO-450 72.9%, M-ZnO-550 95.3%, and M-ZnO-650 75.8%, respec- All samples K (h1) R2 Efficiencya (%)
tively. The photosensitization effect of MB hardly enhances the
Commercial ZnO 0.012 0.9798 66.9
photocatalytic performance of M-ZnO-550. The relatively high Blank (without catalyst) 15.4
degradation rate of M-ZnO-400 can be attributed to the adsorption Photosensitization of MB 96.3
to MB during dark processing. The photocatalytic degradation rate S-ZnO-550 0.031 0.9920 91.8
of M-ZnO-550 to MB reaches 95.3% after 80 min under the simu- P-ZnO-550 0.029 0.9924 90.8
M-ZnO-400 0.019 0.9865 90.4
lated sunlight illumination, much higher than that of commercial
M-ZnO-450 0.014 0.9411 72.9
ZnO (66.9%), which indicates that nitrogen doping of ZnO can M-ZnO-550 0.040 0.9955 95.3
improve the catalytic activity of photocatalyst. M-ZnO-650 0.016 0.9807 75.8
In order to better research the reaction kinetics of the photocat- a
The MB dye degradation efficiency by using different photocatalysts under
alytic reaction process, according to Pseudo-first-order kinetic solar-simulated light irradiation for 80 min.
models, the photocatalytic degradation kinetics of all photocata-
lysts were investigated (Fig. 10 (C and D)). The pseudo-first- order
kinetic model is as the following Eq. (3) [86]: preparation process and excellent photocatalytic effect of N doped
ZnO prepared by microwave hydrothermal method.
ln ðC 0 =C t Þ ¼ kt ð3Þ The reusability of photocatalyst plays a crucial part in practical
applications. Thus, the M-ZnO-550 was used to investigate the
where C0 and Ct are the initial concentrations of MB aqueous solu- recycle photocatalytic degradation ability (Fig. 11). After five recy-
tions and the reaction concentrations at time t, respectively. k is the cle experiments, the photocatalyst can still maintain a high-
reaction rate constant, t is the time that catalysts exposed under the efficiency degradation capacity of around 95%. The slight decrease
light irradiation. The value of k and correlation coefficient (R2) of all of photocatalytic degradation rate indicated that the superior
samples are summarized in Table 3. According to the value of R2, it reusability and chemical stability of the M-ZnO-550 photocatalyst.
can be clearly observed the pseudo-first-order kinetic liner relation-
ship between the concentration of MB aqueous solutions and the
irradiation time. 3.4. Photodegradation mechanism
Table 4 shows the comparison of the preparation method, reac-
tion time, dosage, methods of N doping and photocatalytic activity In the process of degradation dye, the irradiation leads to the
of various reported ZnO. The sharp contrast proves the time saving generation of active radicals (e.g. hydroxyl radicals (OH), superox-
152 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155

Table 4
Comparison of the preparation method, reaction time, dosage, method of N doping and photocatalytic activity of different ZnO.

Preparation method Reaction Pyrolysis method Catalysts Method of N Dye Light source Efficiency (%) Ref.
of precursor time (dosage) doping (concentration) irradiation time
Hydrothermal 48 h None N-ZnONCBs Additional MB (3.75 mg/L) 250 W UV ~99/80 min [83]
(100 mg) nitrogen source 400 mL lamp
Chemical 1h Two step pyrolysis N-ZnO 8C120 Self-doping MB (10 mg/L) 300 W Xe ~100/90 min [60]
coprecipitation (50 mg) 200 mL lamp
Chemical 10 min One step pyrolysis N doped ZnO Additional RHB (10 mg/L) 300 W Xe ~60/180 min [38]
coprecipitation (550 °C for 3 h) (40 mg) nitrogen source 40 mL lamp
Hydrothermal 24 h One step pyrolysis ZnO@N-NpC In situ fabrication MB (24 mg/L) 300 W UV 99/80 min [47]
(700 °C for 2 h) (25 mg) 500 mL Hg lamp
Chemical 4h One step pyrolysis ZnO (100 mg) None MB (8 mg/L) 18 W UV 76/60 min [28]
coprecipitation (500 °C for 5 h) 100 mL lamp
Microwave 2h One step pyrolysis N doped ZnO Self-doping MB (20 mg/L) 200 W Xe 97.1/80 min this
hydrothermal (550 °C for 2 h) (50 mg) 100 mL lamp work

Fig. 11. Cycling runs for the photodegradation of MB over M-ZnO-550. Fig. 12. Effects of scavengers (IPA, P-Benzoquinone and EDTA-2Na) on photodegra-
dation of MB in an aqueous solution.

ide radical (O–2) and hole (h+)) which play an essential role in the
degradation of organic pollutants [87]. Quenching tests were used
to investigate which radicals lead to the dye degradation. In this
study, as scavengers, 1 mM isopropyl alcohol (IPA), p-
benzoquinone, and EDTA-2Na were used to remove the OH, O–2
and h+, respectively. Fig. 12 shows the change of photocatalytic
activity with adding these three scavengers. It can be obviously
seen that the addition of these three scavengers all caused the
decrease of photocatalytic degradation efficiency compared to
the absence of the scavenger. With adding the p-benzoquinone,
IPA and EDTA-2Na, the degradation efficiencies of MB decreased
from 95.3% to 85.7%, 76.5% and 59.2%, respectively. EDTA-2Na
has the most obvious inhibitory effect on photocatalytic perfor-
mance, suggesting that h+ plays a leading role in the photocatalytic
process and both OH and O–2 play a secondary role. Moreover, the
increased charge density caused by the electrons accumulate in
oxygen vacancy would make the adsorbed oxygen (O2) more easily
Scheme 1. Schematic illustration of the M-ZnO-550 photodegradation mechanism
transform into O–2 [88], therefore, oxygen vacancy is the minor fac-
of MB.
tor that caused the degradation of dye.
Qiu et al. suggested that there exists a N related defect state (N
2p state) which is isolated above the VB due to the N doping [89]. ZnO ðe Þ þ O2 ! ZnO þ O2 — ð5Þ
Combined with the above experimental results, the photocatalytic
þ þ
mechanism diagram of e- and h+ transfer behaviors during the N ZnO ðh Þ þ H2 O ! ZnO þ OH þ H ð6Þ
doped ZnO degradation of MB under solar-simulated light irradia-
þ
tion is illustrated in Scheme 1. The photocatalytic degradation ZnO ðh Þ þ MB ! CO2 þ H2 O þ other degradation products
mechanism can be explained by the following Eqs. (4)–(9) [90]: ð7Þ
hv  þ
ZnO ! ZnO ðe Þ þ ZnO ðh Þ ð4Þ
O2 — þ MB ! CO2 þ H2 O þ other degradation products ð8Þ
 L. Sun et al. / Journal of Colloid and Interface Science 565 (2020) 142–155
OH þ MB ! CO2 þ H2 O þ other degradation products
From the illustration, for commercial ZnO, it can be seen that
under solar-simulated light irradiation, e- are transfer from the
VB to the conduction band (CB), the h+ are generated at VB (Eqs.
(4)) [91]. For N doped ZnO, there is a N related defect state which
is closer to CB than VB. Compared with commercial ZnO, due to the
existence of N related defect state, the bandgap between CB and VB
is shortened. Thereby, electrons require less energy to excited from
the ground state to the excited state. At the same time, due to the
existence of oxygen vacancy, the O2 can be converted into O–2 more
easily. As above discussed, the photogenerated e- and h+ would
convert O2 and H2O to O–2 and OH (Eqs. (5 ~ 6)). Finally, the radi-
cals (h+, OH and O–2) further oxidize MB to CO2, H2O and other
degradation products (Eqs. (7)-(9)).
4. Conclusion
In summary, we synthesized the Zif-8 precursors by a facile
microwave hydrothermal method and successfully fabricated N
doped ZnO by one-step controlling pyrolysis of Zif-8 precursors
for the first time. It is proved that nitrogen self-doping in zinc oxide
crystal lattice can be achieved by controlling the pyrolysis temper-
ature of Zif-8. Compared with reported literatures [38,60,83], this
work has the merits of self-doping, without additional nitrogen
sources, improved precursor preparation process, simple pyrolysis
process and enhanced photocatalytic performance. The degrada-
tion efficiency of MB solution by the as-prepared N doped ZnO
reached 95.3% after 80 min of solar-simulated light illumination.
The photo-generated holes were the main active species that
caused the degradation of MB, the doping of N reduced the energy
of e- transfer from VB to CB and improved the photocatalytic activ-
ity. In addition, the as-prepared N doped ZnO photocatalyst
showed excellent reusability. This work not only provides a facial
preparation of MOFs by microwave hydrothermal method, but also
provides a method of self-doping non-metal elements in metal
oxide by controlling the calcination temperature of MOFs. More-
over, the self-doping N in ZnO has an outstanding application pro-
spect in the respect of photocatalytic degradation of organic
pollutants in environmental water and has the potential applica-
tions in fields of gas molecule detection, lithium-ion battery, solar
cell [11,92–98].
Author contribution section
L. Sun, Y. Zhang, H. Jiang, and S. Lou prepared the samples and
the carried out the photocatalytic degradation studies. J. Zhang car-
ried out the SEM and TEM analysis. S. Wu carried out the BET and
XPS analysis. M Dong carried out the XRD analysis.
Q. Shao, S. Ge, J. Lin, and Z. Guo are in charge of the project.
All authors have prepared the paper and approved the final
publishing.
Declaration of Competing Interest
The author declare that there is no conflict of interest.
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