Ceramics International 47 (2021) 16170–16177

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Fructose-regulated ZnO single-crystal nanosheets with oxygen vacancies for

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

Keywords: ZnO-based photocatalysts have been widely applied to photocatalytic reactions. However, the pure phase ZnO is
Fructose rarely used in degradation of refractory pollutants and photocatalytic hydrogen evolution due to its poor photo-
ZnO redox ability. In this study, we develop a novel surface atom regulation strategy using fructose molecules con­
Oxygen vacancies
taining hydroxyl groups to improve photo-oxidation ability of ZnO. Interestingly, the fructose-regulated ZnO
Hydroxyl
Phenol
nanosheets with oxygen vacancies exhibit more positive surface valence band maximum than that of pristine
Hydrogen ZnO. The photogenerated holes with strong oxidation capacity can be formed on the fructose-regulated ZnO
nanosheets. The fructose-regulated ZnO nanosheets can rapidly degrade high concentration of phenol and other
organic pollutants, which is difficultly achieved by the pristine ZnO nanosheets. In addition, photocatalytic H2
production activity is also found on our pure phase ZnO. This work provides a new design strategy for modifying
the surface structure of photocatalysts to improve photocatalytic performance.

1. Introduction phenol. The interface design allows phenol to be degraded due to the
photogenerated carrier separation. Wang et al. [13] developed a direct
Environmental problems are becoming serious with the rapid Z-scheme heterojunction between ZnO and TiO2 to degrade Rhodamine
development of industry. Photocatalysis is a potential green technology, B (RhB). Khalid et al. [14] reported Al and Fe co-doped ZnO nanorods
which is extensively applied in clean energy production and water for degrading methylene blue (MB). In previous works, most of studies
treatment [1–4]. Among numerous developed photocatalysts, ZnO is focused on ZnO-based photocatalysts to obtain better photocatalytic
regarded as a potential metal oxide semiconductor in the photocatalysis performance [15–17]. The preparation processes of these complexes
field due to its advantages such as high electron mobility, environ­ were somewhat complicated, easily resulting into the unsatisfactory
mentally friendly feature, easy preparation, and low cost [5–7]. How­ effect. Therefore, the study on improving photocatalytic activity of pure
ever, developing ZnO with high photocatalytic performance is still a phase ZnO via a facile surface regulation strategy is still desirable.
challenging and fascinating field, particularly its application in the During photocatalytic research of ZnO for the degradation of pol­
degradation of high concentration of pollutants and H2 production, lutants, only a few reports on the photodegradation of phenol using pure
because of high recombination rate of electrons and holes and poor phase ZnO are found and the effect of degrading phenol is not ideal [18].
surface redox ability. As an important chemical raw material, phenol is widely used in the
Various attempts, such as the construction of a heterostructure, pharmaceutical, plastic, and paint industries. Correspondingly, phenol
morphology control element doping, and noble metals as cocatalysts, brings water pollution as the high stability and toxicity. The degradation
have been widely researched to improve the photocatalytic capacity of of high concentration phenol by ZnO is still interesting. Although Y2O3
ZnO in the photodegradation of organic pollutants and water splitting and TiO2-based catalysts can degrade phenol in previous reports [19,
[8–11]. Jiang et al. [12] reported Pt@BiOI/ZnO with enhanced photo­ 20], the concentration of phenol is not high. The high concentration of
generated charge transfer properties for efficient photodegradation of phenol is very difficult degraded. Pristine ZnO with poor photooxidation

* Corresponding author.
** Corresponding author.
E-mail addresses: wangxuewen@[Link] (X. Wang), rbzhang@[Link] (R. Zhang).

[Link]
Received 9 December 2020; Received in revised form 4 February 2021; Accepted 5 February 2021
Available online 25 February 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
X. Wang et al. Ceramics International 47 (2021) 16170–16177

Fig. 1. (a) The mechanism diagram of fructose-regulated ZnO nanosheets. (b) SEM image of ZnO–F nanosheets. (c) TEM image of ZnO–F and its SAED pattern. (d)
HR-TEM image of ZnO–F. XRD patterns (e) Raman spectra (f), and ESR spectra (g) of pristine ZnO and ZnO–F.

ability cannot degrade organic pollutants such as phenol that require regulated by the introduction of oxygen vacancies to obtain a more
strong oxidation. Therefore, a method that enhances the photocatalytic positive valence band maximum (VBM), which can generate more
ability of ZnO must be developed. The construction of oxygen vacancies photoexcited holes with strong oxidation capability and provide more
into ZnO can effectively regulate the surface structure, thereby suitable surface reaction sites [22]. Compared with general ZnO, the
improving its performance [21]. The regulation of a surface band fructose-regulated ZnO single-crystal nanosheets with oxygen vacancies
structure is feasible to enhance its photocatalytic capacity. In particular, can effectively degrade phenol. Interestingly, the high concentration of
a more positive valence band position is favorable for obtaining phenol and other organic pollutants are also rapidly photodegraded, and
photoexcited holes with a strong oxidation capability [22]. Further­ hydrogen evolution is also observed. This study paves a new way to
more, photocatalytic hydrogen evolution using pure phase ZnO is rarely achieve considerably improved photocatalytic activity through a
reported due to high carrier recombination rate and poor reduction re­ surface-regulation strategy using a trace amount of fructose molecules.
action [23,24].
In a surface regulation strategy, doping heteroatoms is widely used to 2. Preparation of samples
modify surface atom structure [25]. In addition, the functional groups,
such as hydroxyl including empty orbits, may combine with ions Preparation of fructose-regulated ZnO nanosheets: 30 mL aqueous
including lone pair electrons to achieve surface reconstruction. There­ solutions were formulated in four beakers containing 0.0001 mg, 0.001
fore, the functional groups should be feasible for reconstructing surface mg, 0.1 mg, and 1 g fructose. 2.19 g (0.01 mol) of zinc acetate dihydrate
structure. To date, the study about using hydroxyl groups to obtain more was added into different fructose solutions, respectively. Subsequently,
reaction sites and adjust surface band structure is still novel. Recently, 20 mL aqueous solution containing 1.6 g (0.02 mol) sodium hydroxide
we have confirmed that hydroxyl-regulated BiOI nanosheets can obtain was added into the abovementioned solution. The system was stirred for
considerably improved visible-light photocatalytic performance as the 20 min to reach the reaction adequate. The products were washed
surface atomic structure is modified by the hydroxyl groups [26]. several times with deionized water and then dried at 80 ◦ C for 12 h in
The hydroxyl groups play a key role in the regulation of surface atom vacuum, and the product without calcination was recorded as ZnO–U.
and valence band structure. Thus, in this study, polyhydroxy-containing The other obtained products were calcined at 500 ◦ C for 20 min to
fructose is deliberately selected to modulate the surface nanostructure of remove the trace fructose. The product prepared using 0.001 mg fruc­
ZnO. A facile method of using fructose is displayed to synthesize single- tose (2 × 10− 5 g L− 1) was recorded as ZnO–F. In addition, the products
crystal ZnO nanosheets. Only a trace amount of fructose (2 × 10− 5 g L− 1) prepared using fructose of 2 × 10− 6 g L− 1, 2 × 10− 3 g L− 1, and 20 g L− 1
is added in preparing the solution; the ZnO nanosheets after hydroxyl were recorded as ZnO–F-1, ZnO–F-2, and ZnO–F-3, respectively.
adjustment exhibit considerably enhanced photo-oxidation capacity. Reference ZnO without fructose was prepared by a same method but
After a thermal treatment, the surface structure of ZnO nanosheets is without the addition of fructose.

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Fig. 2. UV–vis DRS (a) and Kubelka-Munk-transformed reflectance spectra (b), Mott− Schottky plots (c), and energy band structures (d) of the pristine ZnO
and ZnO–F.

3. Results and discussion The crystal structure of as-prepared pristine ZnO and ZnO–F is
analyzed by X-ray diffraction (XRD) (Fig. 1e). Both the synthesized ZnO
3.1. Design and structural characterization of fructose-regulated ZnO and ZnO–F can be indexed well to the hexagonal phase of ZnO (JCPDS:
single-crystal nanosheets No. 36-1451). The samples are thermally treated at high temperature to
remove fructose and improve crystallinity of ZnO–F. Raman spectro­
Fructose is used as a surface regulated agent to reconstruct single- scopic analysis is performed on pristine ZnO and ZnO–F to study their
crystal ZnO nanosheets. The surface regulation strategy is shown in structure and residual carbon. The corresponding data are presented in
Fig. 1a. The hydroxyl groups in fructose are nucleophilic and tightly Fig. 1f. The Raman spectra of ZnO nanosheets show peaks at 437, 586,
bound to zinc ions during the growth route of Zn(OH)2 [27,28]. Notably, 834, 937, and 1100 cm− 1. The peak at 437 cm− 1 is a characteristic peak
the hydroxyl groups are adsorbed during the formation of zinc hy­ of ZnO. The peak at 586 cm− 1 corresponds to oxygen vacancies and
droxide instead of zinc oxide. Zinc hydroxide is easily converted into interstitial zinc. The peaks at 937 and 834 cm− 1 are assigned to the
ZnO via a dehydration process. If fructose is added after the full syn­ vibrational mode that is caused by the two-phonon combination E2
thesis of zinc hydroxide, then no evident change on photocatalytic ac­ (high) þ A1(TO) and E1(TO) þ E2(LO), respectively [31]. The peaks
tivity is found (Fig. S1), indicating that the regulation of fructose occurs between 1050 and 1150 cm− 1 correspond to the two-phonon modes
in the growth of Zn(OH)2. (2LO) characteristic of this II–IV semiconductor. The peak positions of
The SEM image of ZnO–F is shown in Fig. 1b. ZnO prepared using ZnO–F nanosheets are consistent with the pure phase ZnO, and no
fructose is a sheet-like structure with average thickness of ca. 20 nm, characteristic modes of carbon are found on the ZnO–F after a thermal
which is similar to ZnO without fructose (Fig. S2). Furthermore, the TEM treatment [32], indicating that fructose has been completely removed.
images of ZnO–F nanosheets are used to detect the microstructure and During calcination, the carbon is oxidized to take away oxygen of
crystalline state. Numerous pores are observed on the ZnO–F nanosheets ZnO–F, and the oxygen vacancies are formed on the surface of ZnO–F.
(Fig. 1c). The selected area electron diffraction pattern suggests that the The evidence of oxygen vacancies can be explored using ESR spectra
ZnO–F nanosheet is a single-crystal rather than polycrystalline. This (Fig. 1g). Compared with the pristine ZnO, the ZnO–F nanosheets show a
structure will considerably reduce a recombination rate of photoexcited stronger electron spin resonance (ESR) signal around g = 2.0, corre­
carriers due to the absence of grain boundary [29]. Fig. 1d reveals that a sponding to oxygen vacancies [33]. The ZnO–F nanosheets have abun­
clear fringe with a lattice spacing of 0.247 nm is corresponding to dant oxygen vacancies after 500 ◦ C thermal treatment. In addition, the
d-spacing of plane (101) of ZnO [30], indicating the high crystallinity of treatment temperature plays a key role in controlling the content of
ZnO–F. oxygen vacancies [34]. Oxygen vacancies on the surface can serve as

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Fig. 3. XPS spectra of (a) Zn 2p, and (b) O 1s in ZnO and ZnO–F.

Fig. 4. (a) UV–vis absorption spectra of phenol degraded using ZnO–F with light irradiation time. (b) Photodegradation curves of phenol degraded using the pristine
ZnO; ZnO–F prepared different fructose concentrations. (c) Cycling degradation curves of phenol using the ZnO–F.

trapping sites of photogenerated electrons for photochemical reactions. [41,42]. However, the binding energies of O 1s in ZnO–F shift to higher
Thus, the recombination rate of photogenerated electrons/holes can be energy direction and increase by 0.7 eV, which is caused by the for­
prevented by the oxygen vacancies, which improve the photocatalytic mation of oxygen vacancies [43]. In addition, the nitrogen
activities of ZnO. Moreover, oxygen vacancies may cause more positive adsorption-desorption isotherms are shown in Fig. S3. The microstruc­
surface VBM and significantly enhance the photo-oxidation ability [22, tures of pristine ZnO and ZnO–F are analyzed.
35–37].
3.3. Photodegradation of high concentration of organic pollutants
3.2. Surface energy band structure of fructose-regulated ZnO
Phenol is used to evaluate the photocatalytic performances of the
The UV–vis diffuse reflectance spectra (DRS) of ZnO and ZnO–F are ZnO–F nanosheets. Different from most reported pollutant concentra­
shown in Fig. 2a and Kubelka− Munk-transformed reflectance spectra tion (2 × 10− 5 M), 10-fold concentration of phenol (2 × 10− 4 M) is used
are shown in Fig. 2b to estimate their light response range and bandgaps. to study the photodegradation ability of the hydroxyl-regulated ZnO and
The bandgap of ZnO–F is slightly widened to 3.22 eV from 3.2 eV of pristine ZnO. ZnO–F nanosheets with oxygen vacancies can rapidly
pristine ZnO, suggesting that the bulk structure is not changed by degrade phenol molecules in 2 h (Fig. 4a). The main bands of phenol
fructose molecules. The Mott–Schottky spectra show the conduction approximately 271 nm gradually disappear with light irradiation time.
band minimum (CBM) positions of the ZnO and ZnO–F in Fig. 2c to The photodegradation curves of phenol by ZnO and oxygen-deficient
estimate their conductive band positions. The CBM positions of the ZnO–F are compared in Fig. 4b. Different from the poor phenol photo­
ZnO–F and pristine ZnO are − 0.52 and − 0.56 eV, respectively. Com­ degradation activity of pristine ZnO, the oxygen-deficient ZnO–F
bined with their bandgaps and CBM positions, the VBM position of nanosheets exhibit effective photodegradation for phenol. The oxygen-
ZnO–F is slightly promoted from 2.64 eV of pristine ZnO to 2.7 eV. On deficient ZnO–F prepared using a low fructose content of 2 × 10− 5 g
the basis of the abovementioned results, the obtained band structures of L− 1 shows the highest phenol degradation rate, reaching a phenol
ZnO–F and pristine ZnO are summarized in Fig. 2d. A more positive VBM removal rate of 95.4%. The mineralization rate is 86.2% by the TOC
position in the ZnO–F can provide a photogenerated holes with strong analysis. The most reported phenol concentration (2 × 10− 5 M) can be
oxidative capability during a photocatalytic reaction [38–40]. also rapidly degraded by our catalysts (Fig. S4a). Photodegradation
Photocatalytic reactions are considerably affected by the surface stability is studied via three cycling photodegradation (Fig. 4c). During
atomic structure and chemical state of materials. The chemical binding the third cycle of reaction, the ZnO–F still can rapidly degrade phenol.
energies of ZnO and ZnO–F are analyzed by using XPS spectra in Fig. 3 to No evident decay of activity is found in a long-term reaction. Moreover,
study the surface chemical state. The binding energies of Zn 2p1/2 and Zn the crystal structure is not changed before and after the reaction in
2p3/2 are not changed in ZnO and ZnO–F. Surface-adsorbed and lattice Fig. S4b. These results prove the high stability of ZnO–F as
oxygen are located at 531.1 and 529.6 eV in pristine ZnO, respectively photocatalysts.

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Fig. 5. Degradation curves of (a) MB and (b) RhB over pristine ZnO and oxygen-deficient ZnO–F. Photodegradation cycles of (c) MB and (d) rhodamine B over the
oxygen-deficient ZnO–F nanosheets.

Fig. 6. (a) Photocatalytic H2 evolution rates over methanol, pristine ZnO and ZnO–F. (b) Different contents of co-catalyst Pt on hydrogen production over ZnO–F. (c)
Cycles of photocatalytic H2 evolution over 1 wt% Pt-loaded ZnO–F.

Apart from phenol, RhB and MB with the high concentration of 4 × (Fig. 5c and d), MB and RhB can be still effectively degraded in 80 and
10− 4 M, that is, over 10 times that of most reported [44], are selected to 60 min, respectively. The abovementioned results indicate that
test the catalytic activity of the oxygen-deficient ZnO–F (Fig. 5 and oxygen-deficient ZnO–F nanosheets can be widely suitable for degrading
Fig. S5). Compared with the pristine ZnO, the oxygen-deficient ZnO–F organic pollutants and are stable in a long-term catalytic reaction.
nanosheets exhibit gratifying photodegradation performances for high
concentrations of organic dyes. The mineralization rate of MB and RhB
are 89.2% and 96%, respectively. These results are basically consistent 3.4. Hydrogen production performance of catalysts
with the results from the UV–vis spectra. After three degradation cycles
In previous studies, various attempts, such as the ZnO-based

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Fig. 7. (a) PL and (b) transient fluorescence spectra of ZnO and ZnO–F nanosheets. (c) Electrochemical impedance spectra of the ZnO and ZnO–F. (d) Current curves
of the pristine ZnO and ZnO–F.

heterojunctions, and element doping, have been widely applied in 3.5. Separation and migration of photogenerated carriers
photocatalytic water splitting [45,46]. Lots of ZnO-based photocatalysts
show photocatalytic hydrogen performance. Guan et al. [47] reported The intensity of fluorescence depends on the recombination of
that the MoS2-RGO/ZnO composite photocatalysts had high H2 pro­ photoexcited carriers. A strong PL emission intensity indicates a high
duction via solvothermal process. recombination possibility, which is unfavorable in photocatalytic ac­
However, few reports indicate that pure phase ZnO can produce tivity. The PL spectra are shown in Fig. 7a and used to estimate the
hydrogen by photocatalysis. Fig. 6a shows that neither the sacrificial separation efficiency of photoexcited carriers [49]. The low fluorescence
agent, such as methanol, nor the pristine ZnO with Pt loading in a intensity of ZnO–F implies that the recombination rate of electrons and
methanol solution has hydrogen production performance. By contrast, holes is lower than that of ZnO, and the separation efficiency of electrons
the Pt-loaded oxygen-deficient ZnO–F nanosheets (Fig. 6a and Fig. S6) and holes is higher than that of ZnO. In addition, The transient fluo­
can produce H2 in a methanol aqueous solution. Pt, as a co-catalyst, rescence and positron lifetimes of both ZnO and ZnO–F nanosheets are
plays a key role in capturing photoexcited electrons and reducing the shown in Fig. 7b. The electron lifetimes in the ZnO–F (τ1 = 1.72 ns; τ2 =
activation energy of H2 production. The contents of Pt loading are 14.65 ns) are prolonged compared with those of ZnO (τ1 = 1.12 ns; τ2 =
optimized in Fig. 6b. When the content of Pt is 1 wt%, the optimal 5.63 ns). The mean lifetimes of fluorescence, that are calculated using
amount of hydrogen is obtained. Fig. 6c depicts the photocatalytic following equation (Q1), were obtained by using an exponential decay
performance of ZnO–F for five-run reused tests in 5 days. The hydrogen function [50].
production rate is not reduced, even after being reused for the fifth run.
A1 xτ1 2 + A2 xτ2 2
The stable reusability test suggests the outstanding stability of oxygen- 〈τ〉 = Q1
A1 xτ1 + ​ A2 xτ2
deficient ZnO–F nanosheets. The performance of hydrogen production
must be attributed to the reducibility of excited electrons. In addition, The mean lifetimes of photoexcited electrons in the pristine ZnO and
the oxygen vacancies can serve as an interface electron transfer mediator ZnO–F were calculated to 2.03 ns and 3.11 ns, respectively. After
to enhance charge transition to the conduction band [48]. introduction of oxygen vacancies, the vacancy states in the bandgap
restricted the photoexcited electrons and holes recombination and
contributed to the improved catalytic activity [51]. Consequently,

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Fig. 8. ESR spectra of DMPO–•OH adducts on ZnO and ZnO–F nanosheets in the dark (a) and under UV–vis light for 4 min (b). (c) Fluorescence spectra of 2-hyrox­
yterephthalic acid using the ZnO and ZnO–F under light for 1 h.

photoexcited carriers with long lifetimes in the ZnO–F will become easy ability. The hydroxyl groups play a key role in regulating the surface
to participate in the photocatalytic reaction [52]. The photo­ atomic structure suitable for photocatalytic reaction. This result signif­
electrochemical behaviors of the pristine ZnO and ZnO–F are tested to icantly works out the limitation that the pure phase ZnO cannot produce
study the separation and transport of photoexcited carriers in the cata­ hydrogen and effectively photodegrade phenol. In this work, only the
lysts. Their charge-carrier transport rate is explored by EIS plots trace low-cost fructose is used to provide hydroxyl groups to achieve a
(Fig. 7c). The result indicates that the arc radius on the plots of ZnO–F is considerable degradation effect, which can be applied in the design of
smaller than that of the pristine ZnO, resulting in significantly improved other new photocatalysts and used in large-scale wastewater treatment
transport efficiency in internal resistance measurements [53]. The factories.
ZnO–F exhibits an improved current intensity, which is seven times that
of pristine ZnO (Fig. 7d). The fructose-regulated ZnO–F also displays
better photoelectrochemical stability than that of the pristine ZnO. The Declaration of competing interest
results indicate that photogenerated electrons and holes in ZnO–F are
easily separated and migrated to the surface for catalytic reaction. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
3.6. Mechanism of surface photocatalytic reaction
Acknowledgements
In previous reports, phenol is difficultly degraded by pristine ZnO.
However, the oxygen-deficient ZnO–F can effectively degrade high The financial support from National Natural Science Foundation of
concentration of phenol after the surface regulation by fructose mole­ China (51862023, 51662030, 21868016), the Natural Science Founda­
cules. The amount of fructose added in this test is only trace, but it plays tion of Jiangxi Province (2018BCD40004).
a vital role. The •OH as a single-electron structure is very active and has
high oxidizing property. The ESR spectra are tested to determine the
Appendix A. Supplementary data
active species in catalysts during the photocatalytic oxidation pathway.
5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) is used as a spin trap to
Supplementary data to this article can be found online at [Link]
stabilize radicals. The investigation of •OH radicals in ZnO and ZnO–F is
org/10.1016/[Link].2021.02.193.
conducted in the experiment. DMPO-•OH signals are not found in the
dark (Fig. 8a). After light irradiation, four characteristic peaks with in­
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