Journal of Alloys and Compounds 783 (2019) 898e918

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Review

A review on bidirectional analogies between the photocatalysis and

antibacterial properties of ZnO
Junli Liu a, Yuhan Wang a, Jianzhong Ma b, *, Yi Peng c, Aiqin Wang d
a
School of Materials Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
b
College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
c
Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 96064, USA
d
Key Laboratory of Clay Mineral Applied Research of Gansu Province, Center of Eco-material and Green Chemistry, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou 730000, PR China

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

Article history: As a multi-functional biosafety material with outstanding anti-ultraviolet property, good photocatalytic
Received 10 August 2018 property as well as antibacterial activity, ZnO shows promising practical applications in both researches
Received in revised form and developments. It has been widely used in the fields such as photocatalysis, antibacterial, UV pro-
26 December 2018
tecting and so on. The unique photoelectric properties of ZnO promise it an effective photocatalyst. And it
Accepted 28 December 2018
plays an important role in many fields such as organic matter, pollution treatment, environmental
Available online 29 December 2018
cleaning materials and biological medicine. In this review, we discussed the key factors which may affect
the photocatalytic and antibacterial properties of ZnO based on the working mechanisms. Also, the
Keywords:
ZnO nanoparticles
methods that can be used to improve the performance of ZnO have been summarized. This review not
Photocatalytic performance only investigated the recent progress in the ZnO research and application development as photocatalysis
Antibacterial properties and antibacterial, but also provided some useful information for researchers who are interested in en-
Influence factors gineering ZnO as photocatalysis and antibacterial agent.
Advanced strategies © 2018 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
2. Photocatalytic and antibacterial mechanisms of ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
2.1. Photocatalytic mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
2.2. Antimicrobial mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 900
2.2.1. The production of reactive oxygen species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 900
2.2.2. The releasing of Zn2þ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
3. Effect factors on photocatalytic and antibacterial activities of ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
3.1. Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
3.2. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 902
3.3. pH of the solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
3.4. Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
3.5. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.6. Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.7. Surface defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
3.8. Other factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
4. Methods to improve the photocatalytic and antibacterial activities of ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906
4.1. Controlling the size and morphology of ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906
4.2. Doping with metal and nonmetal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 907
4.2.1. Doping with transition metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 907

* Corresponding author.
E-mail address: majz@sust.edu.cn (J. Ma).

https://doi.org/10.1016/j.jallcom.2018.12.330
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918 899

4.2.2. Rare earth metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908

4.2.3. Doping alkali metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
4.2.4. Alkaline earth metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
4.2.5. Doping with nonmetal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
4.3. Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
4.4. Heterojunction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
4.5. Semiconductor coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
5. Remarks and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 913
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914

1. Introduction cytotoxic effect on normal human astrocytes. Similarly, ZnO

nanoparticles induced the death of breast and prostate cell lines
Today, environmental pollution and public health are the most carried with cancer, but had no significant effect in healthy breast
important issues for our human beings. For one thing many in- and prostate cell lines [12]. These results indicated that the po-
dustrial activities such as the textile, pulp, dyes and bleaching in- tential utilization of ZnO nanoparticles in the treatment of cancer
dustries can introduce a wide variety of persistent organic and autoimmunity for potential pathogenic cells. Besides these
pollutants (POPs) into natural waters if lack of proper treatment, advantages, the photocatalytic and antibacterial properties of
and thus destroying the environmental sustainability and also nanosize ZnO have become a hot research topic. According to the
causing high toxicity and damaging to human beings and other literature, different structures of ZnO such as one-dimensional
creatures in the ecosystem [1,2]. For another, infectious diseases nanorods, two-dimensional nanosheets and three-dimensional
remain one of the biggest health challenges in the world. Moreover, snowflakes can be synthesized under certain growth conditions.
traditional environmental purification and antibacterial material And the morphology and/or size of ZnO can directly affect their
not only have side effects but also are becoming less effective for photocatalytic and antibacterial activities [13e15]. For example,
many pollutants and bacteria because they have developed resis- flower-like ZnO has strong absorption in the ultraviolet range and
tance [3]. With the fast development of science and technology, good photocatalytic activity, hollow ZnO nanometer microspheres
developing materials with the features like “lighter”, “higher” and indicates good surface permeability and unique optical properties,
“stronger” becomes the primary goals of materials scientists. four acicular ZnO because of its cutting-edge parts has smaller
Compared to traditional materials, nanomaterials have small par- nanoscale can efficiently kill bacteria and has significant antibac-
ticle size, large specific surface area, high surface energy, and a large terial active effect [16]. However, the unsatisfactory utilization ef-
proportion of surface atoms [4e6]. That has prompted nano- ficiency of visible light and the fast combination of electron-hole
engineering of materials to become one of the most promising pairs of ZnO often limit the photocatalytic and antibacterial activity
technologies involving in the photocatalytic degradation of organic [17]. Overall, many factors such as particle size, surface defects, and
pollutants and in treatment of bacterial diseases [7]. external factors including illumination, pH and temperature
ZnO is a n-type semiconductor with a band-gap of 3.37eV, and a commonly affect the photocatalytic and antibacterial activity of
significantly large free exciton binding energy of 60 meV allows for ZnO [18e20]. In terms of antibacterial properties, different types of
efficient exciton emission at room temperature [8]. Due to these bacteria have different sensitivities to ZnO. Therefore, how to
photoelectric features, it has potential applications as a photo- improve the photocatalytic and antibacterial properties of ZnO will
catalytic degrading agent and bacteriostatic agent under visible be the focus of this review.
light and becomes one of the most important semiconductors in To our knowledge, no work has been reported about the dif-
this field. Actually, ZnO has been widely used in the treatment of ference and relationship between the photocatalytic and antibac-
varieties of contaminants in wastewater such as completely terial properties of nanosized ZnO. Previous reports about the
degradation of organic matter (or chlorine) and controlling the factors and methods to increase the photocatalytic and antibacte-
spread and infection of various strains. And these successful ap- rial properties of nanosized ZnO are rarely seen either. In this re-
plications are largely benefit from the high specific surface area, view, the following parts were summarized including the
excellent hydrophobicity and oxidizing ability of ZnO. At the same photocatalytic and antibacterial mechanisms of ZnO, the key fac-
time, ZnO can be adsorbed on the surface of bacteria and thus tors which can influence the photocatalytic and antibacterial
effectively inhibit the growth of microorganisms in the process of properties, as well as the methods that can improve the perfor-
wastewater treatment and purification. When ZnO particles are mances of ZnO. Through the bidirectional analogies between the
reduced to nanoscale size, they are toxic to most bacteria and can photocatalytic and antibacterial properties of ZnO, it will promote
kill them rapidly [9]. While they are not toxic to human body and the development and application of ZnO in related fields more
can be biocompatible with human's cells. Shantikumar Nair et al. effectively.
studied the toxicity effects of particle size, surface coverage and
aspect ratio of ZnO particles on prokaryotic and eukaryotic cells. 2. Photocatalytic and antibacterial mechanisms of ZnO
Cytotoxicity against mammalian cells was investigated using hu-
man osteoblastic carcinoma cell lines. It was found that ZnO was 2.1. Photocatalytic mechanism
much more toxic to human cancer cells than other primary cells,
indicating the selective toxicity of ZnO to cancer cells [10]. Cory Photocatalysis is a process using the nature of solar energy
Hanley et al. observed that ZnO nanoparticles had a strong transforming into chemical energy to generate catalytic reaction to
advantage in killing cancerous T cells compared to normal cells [11]. excite the surrounding oxygen and water molecules to form highly
Ostrovsky et al. found that ZnO nanoparticles has cytotoxic effect oxidizing radicals [21]. It can decompose almost all organic sub-
on human glioma cell lines A172, U87, LNZ308, LN18, LN229, but no stances and some inorganic substances which are harmful to
900 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
human beings and environment. Photocatalysis not only can
accelerate the reaction, but also can apply nature's law since it
doesn't cause resource waste or additional pollution.
When the energy absorbed by the ZnO particles is higher than
the bandgap, the highly oxidizing radicals will be generated on the
surface via the light irradiation and the photocatalytic reactions
would occur [22]. As showed in Fig. 1, the zinc vacancy near the
valence band captures the hole, while the oxygen vacancy near the
conduction band captures the electron. Photogenerated electrons
are lifted from the valence band to the conduction band, forming
positively charged holes and negatively charged electrons on the
surface of ZnO. Due to the generation of positive holes and negative
electrons, redox reactions occur at the surface of semiconductors.
Negatively charged electrons can interact with the oxygen on the
surface of ZnO, generating reactive oxygen species including su-
peroxide and elemental oxygen. The presence of superoxide and
elemental oxygen as an electron scavenger extends the recombi-
nation of electron-hole pairs and forms superoxide radicals (O
The reaction of the valence band hole (hþ VB) with water molecules
may leads to the formation of hydroxyl radicals(OH) attached on
the surface of ZnO. The hydroxyl radical is an extremely strong,
non-selective oxidant which leads to the partial or complete
mineralization of organics. Reactive oxides such as superoxide and
elemental oxygen can mineralize organic pollutants into CO2, H2O
and inorganic acids [23]. Furthermore, the reactive oxygen species
which are constantly being produced lead to the degradation of
organic pollutants. In addition, the high oxidation potential of holes
in photocatalyst can oxidize the reaction active intermediate of
organics [24]. Superoxide anion free radicals are further protonated
to produce hydrogen and oxygen free radicals (HOO.) and H2O2
[25]. Hydrogen superoxide also acts as an electronic cleaner to
capture the conducting electrons and further delay the recombi-
nation process. Overall, the presence of zinc and oxygen vacancy
improved the photocatalytic performance [26]. In general, nano-
particles with larger superficial area and smaller crystallite size can
increase the oxygen vacancy and as a result generating more
reactive oxygen species and thus improve the photocatalytic ac-
tivity [27].
2.2. Antimicrobial mechanisms
Recently, antibacterial and anticancer properties of ZnO
Fig. 1. Photocatalytic mechanism of ZnO.
nanoparticles have been studied. Various mechanisms are pro-
posed to explain the antibacterial effects of ZnO nanoparticles,
including the production of living reactive oxygen species, the
releasing of zinc ions, the dysfunction of the cell membrane, and
the penetration of the cell envelope and the internalization of
nanoparticles [28]. While, the most commonly accepted antibac-
terial mechanisms of zinc oxide are the production of living reactive
oxygen species and the release of zinc ions. Kalyani Ghule et al.
reported that active oxides produced from the surface of ZnO such
as hydrogen peroxide (H2O2) and superoxide (O2) are considered
to be the main chemical substances that contributed to the occur-
rence of antibacterial activity [29]. And the nature of this mecha-
nism is attributed to the photocatalytic activity of ZnO. Herein, this
article will present the two different antibacterial mechanisms of
ZnO separately so the readers could understand the common points
and differences between the photocatalytic and antibacterial
mechanism of ZnO.
2 ).
2.2.1. The production of reactive oxygen species
Reactive oxygen species(ROS) may be the most important
contributor for antibacterial activity [30]. The band gap between
the conductive and valence electrons in a semiconductor plays an
allocating role in the production of ROS, which caused the damage
on the surface of the microorganism membrane and destroyed the
integrity of the bacterial cells [31]. It is reported that the antibac-
terial effect of ZnO nanoparticles was due to the membrane lipid
peroxidation caused by the oxidation of reactive oxygen species
produced by the interaction of ZnO nanoparticles and Escherichia
coli resulting in cell wall dysfunction [32,33]. Many studies have
distinctly shown that ZnO nanoparticles in aqueous solution can
produce a variety of reactive oxygen species, such as hydroxyl
radical (OH) and single or superoxide anion (O2 -) as well as
hydrogen peroxide (H2O2) (in the left part of Fig. 2.) [34]. Hydroxyl
radicals and hydrogen peroxide can cause the damages of DNA and
cellular proteins, and even lead to the death of molecules. There-
fore, ZnO nanoparticles with high yield of reactive oxygen species
would result in hardly breathe [35].
In the past studies on the sensitivity of E. coli to antibiotics, H2O2
is one of the main factors affecting the antibacterial activity of ZnO
nanoparticles [36]. The formation of hydrogen peroxide also be-
longs to the production of reactive oxygen species. The production
process of H2O2 on the surface of ZnO is displayed in Fig. 3. Under
ultraviolet light, the electrons in the valence band of nano-ZnO are
Fig. 2. Antibacterial mechanisms of ZnO.
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Fig. 3. The production process of H2O2 on the surface of ZnO.
excited to the conduction band, forming free-moving negatively
charged electrons and positively charged holes [37] (step 1). The
holes decompose the H2O molecules into hydroxide ion (OH) and
Hþ in the ZnO suspension (Step 2). Dissolved oxygen molecules are
converted into superoxide radicals (O þ
2 ), and reacted with H to
.
form (HO2) radicals, which then collided with electrons to produce
hydrogen peroxide anions (HO.2) (Step 3 and 4). At last, H2O2
molecules were produced by the reaction of hydrogen ions and
hydrogen peroxide anions (Step 5). Hydroxyl radicals and super-
oxide are negatively charged particles, which could not seep into
the cytomembrane to maintain immediate contact with the outside
surface of the bacteria. However, H2O2 could infiltrate into the cells
and kill bacteria [35,38]. The production of H2O2 largely lies on the
surface grain of ZnO, which results in a large number of oxygen
species on the surface and smaller nanoparticles have higher
antibacterial activity [39]. The whole antibacterial process and the
related mechanism are similar to that of photocatalysis activity.
2.2.2. The releasing of Zn2þ
In enzyme and protein solutions, Zn2þ plays a fatal role in the
production of ionic signals between various cells and intercellular
cytoplasmic organoids [40]. The homeostasis of metal ions is
important for bacterial life, because they are involved in accom-
modating various supersession functions such as dehydrogenase,
cofactor and catalytic agents, as well as structural stabilizing agent
for enzymes and DNA binding proteins [41]. However, excessive
metal or metal ions are poisonous to bacterial cells. Therefore, some
bacteria have formed mechanisms to regulate indraught and effu-
sion of metal ions including Zn2þ to maintain stable intracellular
ion concentration [42]. ZnO nanoparticles with positive zeta po-
tential can destroy the cytomembrane of gram-negative Escherichia
coli [43,44]. Contacting of ZnO powder with bacteria makes Zn2þ
release slowly. Since zinc ions have oxidation ability, Zn2þ not only
reacts with organic functional group (thioglucoside, carboxyl, hy-
droxyl), but also combines to the bacterial cell and membrane
protein (the right part of Fig. 2). It enters the bacterial cell and
damages its electron transfer system to resist the enzyme and
protein gene expression function (Fig. 4), which resulted in the
targeted anti-bacteria [45].
Through the comparison, it can be concluded that the antibac-
terial activity of nano-ZnO is the synergistic effect of photocatalysis
901
Fig. 4. Metal ions cause the damage of cell [46].
and metal oxide particle dissolution. The production of reactive
oxygen species usually requiring light conditions, but the metal ion
dissolution mechanism can work without light.
3. Effect factors on photocatalytic and antibacterial activities
of ZnO
From the perspective of semiconductor photochemistry, it is
clear that the role of photocatalysis is to trigger or accelerate spe-
cific oxidation-reduction reaction in the presence of a radiation-
emitting semiconductor. Optical absorption and the subsequent
optical excitation of electron-hole pairs take place when the energy
of the incident photon is equal to or greater than the band gap
energy [47]. It is generally believed that the particle size and
morphology, the reaction temperature, pH of the solution, the
concentration of catalysts, light, surface defects are the main factors
that affecting the photocatalytic activity of ZnO [48]. Besides, there
are also many other factors that decide the photocatalytic proper-
ties of ZnO, such as the oxygen in the solution, anions, the standard
of the CB, the intensity of ultraviolet radiation. Furthermore, the
photocatalytic degradation is affected by different reaction pa-
rameters, such as the type and concentration of organic matter [49].
Compared to the photocatalytic activity, the antibacterial ac-
tivity of ZnO depends on both intrinsic and extrinsic factors.
Inherent factors include particle size and morphology, specific
surface area, the crystallinity and concentration of nanoparticles.
External factors include the chemical equilibrium of the solution
(concentration, pH, chemical composition, temperature of the re-
agent) [50,51]. Researches display that the antimicrobial activity is
linearly related to the surface area in contact with the microor-
ganism. Larger surface areas, such as nanoparticles, ensure a wide
range of possible bio-organisms absorb on the cell surface as well as
a wide range of possible responses from environmental and organic
species [52]. Therefore, the following paper will introduce the ef-
fect factors on the photocatalytic and antibacterial properties of
ZnO in detail.
3.1. Size
The quantum size effect is defined as the phenomenon that the
electron energy level near the Fermi level changes from continuous
to discrete, and the gap between the highest occupied molecular
orbital (full band) and the lowest unoccupied molecule become
narrow when the particle size is diminished to a certain value [53].
The quantum size effect of ZnO greatly enhances its photocatalytic
activity. Junmei Wang et al. believed that the smaller size ZnO
particles required the wider band gap and the shorter wavelength
of ultraviolet light [54]. Due to the influence of quantum size, the
conduction band becomes more negative, the valence band be-
comes more positive, the energy gap of the semiconductor
902 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918

becomes wide, and the band gap of the semiconductor increases
with the decreasing of particle size. Hjerrild et al. found changing
the particle size enhanced the oxidation-reduction potential of the
valence pores and conduction electrons [55]. As the potential en-
ergy of redox increased, the driving force of photocatalytic reaction,
the redox ability of photoelectrons and holes all increased, and the
absorption light wave shifts blue increased photocatalytic activity
of semiconductors. Soudi et al. found that shorten the diffusion
length of small-sized particle carriers and the time for electrons to
diffuse from the core to the surface could reduce the chance of
recombination, which was more conducive for electron acquisition
and loss. Therefore, the higher catalytic activity of ZnO could be
obtained with the better charge separation effect [56]. Yuan et al.
pointed out when the molecular size became smaller, more atoms
were adsorbed on the surface to greatly increased their specific
surface area and adsorption capacity, and the active substances on
the surface of the particles were more likely to contact with organic
or water molecules to make small particles had good dispersibility
and high transmittance in water [57]. It is obvious that the reduc-
tion of particle size is usually beneficial to the surface related
photocatalytic activity. Jadhav et al. indicated that was because it
could enhance the active site of a special surface area [58]. Although
the size of small particles represents a short distance from the
carrier to the surface, the migration needs to be migrated from the
core of the particle to the surface with the appropriate concentra-
tion gradient or the potential gradient [59]. The comparisons of size
on the photocatalytic performance of ZnO were shown in Table 1.
The size of ZnO also affects its antibacterial property mainly
because the specific surface area, surface atoms, optical absorption
rate and adsorption capacity of ZnO change with its' size. The
smaller size ZnO particles have large specific surface area, a lot of
surface atoms, high light absorption rate and strong adsorption
ability. Therefore, it is easier to reach the surface of bacteria, cause
cell membrane leakage and damage the large molecules in the cell.
What's more, small size ZnO nanoparticles produced more ROS
(·OH), increasing the endochemical effect of bacterial cells and the
damage of bacterial cells. At last, smaller particles could penetrate
into bacterial cells to kill bacteria more effectively [60]. With the
diminish of ZnO particle size, the range of inhibition area increased
significantly [61]. People realized that the vitality of living cells
decreased significantly as the size of ZnO nanoparticles decreased.
The reason may be that the small size of ZnO nanoparticles can
increase the reaction to bacteria, because the number of H2O2 de-
pends mainly on the surface area of ZnO [62]. What's more, the
utility activity of nanoparticles in catalytic or biological application
is greatly influenced by particle size [63]. The size of nanoparticles
probably has a greater influence on their activity, because the
accumulation of small nanoparticles in the cytomembran and
tenuigenin is more [64]. With the increase of specific surface area
and the decrease of particle size and crystallinity, the activity be-
comes stronger [65]. The comparisons of size on the antibacterial
properties of ZnO were shown in Table 2.
3.2. Morphology
The morphology of ZnO plays a key role in influencing its pho-
tocatalytic activity [66]. When photochemical catalysis occurs on
the catalyst surface, the high surface area to volume ratio is
important for increasing the decomposition rate. Besides, the ox-
ygen vacancy of ZnO can be used as a potential trap to capture one
or two electrons to help electron-hole pairs separate and increase
the photocatalytic activity. When the size of the catalyst is in
nanometer level, it would reach the reaction sites rapidly and
further reduce the chance of recombination of electron-hole pairs
generated by light, finally effectively increase the photocatalytic
activity of ZnO nanotetrapods [67]. In addition, the photocatalytic
activity is further improved by controlling the crystal growth di-
rection, the specific surface area, and the morphology of the ma-
terial. For example, Boppella et al. found the rod-shaped structure
ZnO was conducive to the adsorption of OH.Thus, it promoted the
generation of OH from ZnO to show good photocatalytic effect [68].
Compared with the nanorods, Li et al. showed the mesoporous ZnO
hollow microsphere had high specificity area and porosity ranged
in 2e50 nm [69]. In the process of inducing surface reaction,
mesoporous hollow structure provided the efficient molecular
transport way for its surface and increased the surface reaction area
where the catalyst carrier induced and suppress nanostructure
materials gathered, this would greatly facilitate the surface energy
of chemical reaction and the active site to promote the photo-
catalytic efficiency. According to the literature, different morphol-
ogies of ZnO have different photocatalytic activity and ultraviolet
shielding efficiency [70]. Our group confirmed that sea-urchin like
ZnO had higher photocatalytic performance than flower-shape and
loose ZnO, because of its unique structure and high specific surface
area to volume ratio [71]. Beyond that, Kilic et al. showed ZnO nano
flower had a unique three-dimensional structure, which enabled
ultraviolet light could be multi reflected at the terminals of the
surface, thus improving the capture ability and conversion effi-
ciency of ultraviolet light and the photocatalytic efficiency [72]. Liu
et al. also found that ZnO/ZnS/ZnIn2S4 nanotubes had the best
photoelectrocatalytic performance compared to ZnO nanowires
and nanorods, which resulted from the broaden absorption spec-
trum and improved separation ability of the photogenerated elec-
tron and hole [73,74]. The comparisons of morphology on the
photocatalytic efficiency of ZnO were shown in Table 3.
The morphology of ZnO not only influences its photocatalytic
efficiency, but also directly decides its antibacterial action [75e77].
Different shapes of ZnO exhibit different antibacterial activities.
Our group has reviewed and considered the antibacterial effect of
mulberry-shaped ZnO, lamellar-shaped ZnO and flower-shaped
ZnO on candida albicans. The results showed that the inhibition
rate of mulberry-shaped ZnO, lamellar-shaped ZnO and flower-
shaped ZnO to candida albicans was 90%, 85% and 50% respec-
tively. The main reason was that mulberry-shaped ZnO was easy to
spread and adsorb on the surface of the bacterial cell membrane,

Table 1
Effect of size on photocatalytic performance of ZnO.

Size Photocatalytic efficiency Ascension causes References

Smaller size
Changing the particle size
Shorten the diffusion length
Becoming smaller
Enhanced photocatalytic activity
Influencing the photocatalytic activity
Higher catalytic activity
Beneficial to the photocatalytic activity
Required the wider band gap and the shorter Junmei J Wang et al. [54]
wavelength of ultraviolet light
Enhanced the oxidation-reduction potential of Hjerrild et al. [55]
the valence pores and conduction electrons
Reducing the chance of recombination Abdelhadi Soudi et al. [56]
Increased specific surface area and adsorption YunFei Yuan et al. [57]
capacity
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Table 2
Effect of size on antibacterial properties of ZnO.
Size Antibacterial Properties Ascension causes
Smaller size ZnO Excellent antibacterial property Having a lot of surface atoms, high light absorption rate and strong adsorption ability
Small size of ZnO nanoparticles can increase the reaction to bacteria
The accumulation of small nanoparticles in the cytomembran and tenuigenin is more
Increasing the specific surface area
Table 3
Effect of morphology on photocatalytic efficiency of ZnO.
Morphology Photocatalytic efficiency
Rod-shaped structure ZnO Good photocatalytic effect
ZnO hollow microsphere Promoting the photocatalytic efficiency
Sea-urchin like ZnO Higher photocatalytic performance
ZnO nano flower Improving the photocatalytic efficiency
ZnO/ZnS/ZnIn2S4 nanotubes The best photoelectrocatalytic performance
changing the bacterial cell membrane permeability. In addition,
smaller size ZnO could permeate into bacteria cell, destroy the
bacteria's genetic material to prevent gene expression and inhibit
the reproduction of bacteria [78]. In the shapes of ZnO with
spherical assemblies, nanorods assemblies, cauliflower compo-
nents and mushroom components, the cauliflower component
exhibited excellent antibacterial activity. This might be related to
the particle size and specific surface area of ZnO. The specific sur-
face area, the amount of particles per unit volume and the released
hydrogen peroxide concentration of ZnO increased with the
decreasing of particle size, which resulting in a better antibacterial
effect [79]. In addition, nano ZnO with larger specific surface area
and higher surface energy might lead to the stronger adsorption
effect on bacteria, thereby exhibiting better antibacterial efficacy.
Ohira et al. suggested that the growth orientation of ZnO also
affected its biological activity [80]. The results showed that
randomly oriented ZnO nanowires had higher antibacterial activity
than conventional ZnO nanowires because the different spatial
arrangements of ZnO resulted in different bioactive activities. Zang
et al. prepared flower-like zinc oxide nanoparticles with high sta-
bility and water solubility, and demonstrated the potential appli-
cation prospects of water-soluble ZnO nanoparticle. These results
not only effectively apply colloidal ZnO nanoparticles in biolumi-
nescence imaging, but also promote their application in targeted
drug delivery [81]. The comparisons of morphology on the anti-
bacterial properties of ZnO were shown in Table 4.
3.3. pH of the solution
The pH changes will affect the adsorption of OH and Hþ on the
surface of photocatalyzer and the formation of ZnO surface charge.
Increasing the pH value of a solution, on the one hand is conducive
Table 4
Effect of morphology on antibacterial action of ZnO.
Morphology Antibacterial action
Mulberry-shaped ZnO Bacteria inhibition rate was 90%
Lamellar-shaped ZnO Bacteria inhibition rate was 85%
Flower-shaped ZnO Bacteria inhibition rate was 50%
Oriented ZnO nanowires Higher antibacterial activity
903
References
G. Applerot et al. [60]
F. Elmi et al. [62]
L.zhang et al. [64]
H. Zhao et al. [65]
Ascension causes References

Be conducive to the adsorption of OH Ramireddy Boppella et al. [68]
Increased the surface reaction area and provided the Y Li et al. [69]
efficient molecular transport way for its surface
The unique structure and high specific surface area to Junli Liu et al. [71]
volume ratio
The unique three-dimensional structure enabled Kilic et al. [72]
ultraviolet light could be multi reflected at the terminals
of the surface
Improved separation ability of the photogenerated Zhifeng Liu et al. [73,74]
electron and hole
for photocatalyzer combine OH and hþ to produce OH, on the
other hand, nano protons(hþ) adsorbed on the surface could leave
away from the catalyst and leave electronic, the existence of surface
electron is conducive to adsorb O2 and then produce hydroxyl free
radicals OH [82].
Naimi-Joubani et al. showed that the low pH value of aqueous
solutions was critical to the reduction of Cr (VI) and the reduction of
protonation on photocatalyst surfaces [83]. Rayerfrancis et al. found
pH value had a great influence on the morphology and composition
of nano ZnO [84]. ZnO had the best photocatalytic effect when
pH ¼ 12, the degradation rate of methyl orange under 2h light was
as high as 99% [85]. Soni et al. believed that the efficiency of pho-
tocatalytic oxidation and degradation of rhodamine B increased as
the pH value rise [86]. Comparisons of pH on the photocatalytic
efficiency of ZnO were shown in Table 5.
In addition, the antibacterial action is also influenced by pH [87].
Zheng et al. demonstrated that people were more easily infected by
bacteria or got cancer at low pH due to the rapid dissolution of ZnO
under acidic conditions [88]. Amornpitoksuk et al. indicated that
the antibacterial efficiency of ZnO decreased because of its disso-
lution at acidic solution, while OH in the solution may facilitate
the photogeneration of hydroxyl radicals in alkaline media [89].
Saliani et al. indicated that higher antibacterial activity was
observed at acidic pH levels with the maximum toxicity at pH ¼ 4
and pH ¼ 5 for E. coli O157: H7 and S. aureus, respectively. This was
due to the increased solubility of ZnO nanoparticles and the
maximum total Zn2þ concentration, as well as the presence of
biological components such as amino acids and peptides under
acidic conditions [90]. The comparisons of pH on the antibacterial
properties of ZnO were shown in Table 6.
Ascension causes References
Mulberry-shaped ZnO was easy to spread and adsorb on Junli Liu et al. [78]
the surface of bacterial cell membrane, changing the
bacterial cell membrane permeability
Different spatial arrangements of ZnO Tetsuya Ohira et al. [79]
904 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Table 5
Effect of pH on photocatalytic efficiency of ZnO.
pH Photocatalytic efficiency
Low pH value Be critical to the reduction of Cr (VI)
pH ¼ 12 The degradation rate of methyl orange under 2h light
was as high as 99%
Rising pH The efficiency of photocatalytic oxidation and
degradation of rhodamine B increased
Table 6
Effect of pH on antibacterial action of ZnO.
pH Antibacterial action
low pH The antibacterial efficiency of ZnO decreased
pH ¼ 4 Show the higher antibacterial activity of E. coli O157: H7
pH ¼ 5 Show the higher antibacterial activity of S. aureus
3.4. Light
The structure, luminescence mode and life of light source are
closely related to the efficiency of photocatalytic oxidation. The
effects of light sources on the reaction include wavelength and light
intensity. While the band gap width of ZnO determines the wave-
length range of incident light required. The photonic electrons and
holes that are active can only be excited within the range of
wavelengths needed.
Light intensity is another factor that affecting the photocatalytic
degradation. Generally speaking, higher degradation efficiency of
organic compounds would be obtained with the stronger light. It is
because higher light intensity could enhance the ability of photo-
hydrogenize hydrogen with the same reaction time. Many studies
have shown that increasing the intensity of light from the range of
ultraviolet to visible wavelength could promote photocatalytic re-
actions. Akira Fujishima et al. found that the reaction speed con-
stant increased rapidly with the increasing of luminous intensity in
photodegradation of paracetamol [91]. Khokhlova et al. proposed
that the catalytic reaction rate at low light intensity was propor-
tional to the luminous intensity. At medium luminous intensity, the
reaction rate was proportional to the square root of light intensity
[92]. Meanwhile, the photocatalytic degradation rate will increase
with the extension of illumination time. It is because nanoparticles
will obtain more energy under long irradiation through more
electron-hole pairs and hydroxyl radicals to accelerate the degra-
dation of organic compounds. However, the degradation rate de-
creases slightly after too prolonged exposure, which may be caused
by the aggregation of small molecules in the higher concentration
system. Comparisons of light type on the photocatalytic efficiency
of ZnO were shown in Table 7.
Table 7
Light types on the photocatalytic efficiency of ZnO.
Types Photocatalytic efficiency
Light intensity Stronger light intensity could promote
photocatalytic reactions
Increasing illumination time The photocatalytic degradation rate would
increase
Ascension causes References
The pH affected the adsorption of OH and Hþ on Mohammad Naimi-Joubani et al. [84]
the surface of photocatalyzer and the formation of
ZnO surface charge
Increasing the pH value of a solution was conducive H. Zhu et al. [85]
for photocatalyzer combine OH and hþ to produce

OH Harsh Soni et al. [86]
Ascension causes References
Its dissolution in acidic solution P Amornpitoksuk et al. [89]
The increased solubility of ZnO nanoparticles and the Mahsa Saliani et al. [90]
maximum total Zn2þ concentration
At the same time, researches displayed that the antibacterial
properties of ZnO were diversity under different illuminated con-
ditions. Some scholars have compared the effect of light conditions
on the antibacterial performance of ZnO, and they found that the
antibacterial efficiency of ZnO was as followed: UV light > simu-
lated sunlight > no light [93e95]. The main reason for samples
under UV light and simulated sunlight had better antibacterial
activities than the corresponding sample under dull conditions was
that ZnO produced stronger photocatalysis properties with the
irradiation. Joe et al. showed that the adhesion of ZnO nanoparticles
to the bacterial cell wall under dark conditions posed a significant
risk to environmental microbes due to the addition of ZnO nano-
particles to lead Zn2þ ions in the bacterial cytoplasm [96]. However,
hydroxyl radicals and superoxide anion free radicals and other
materials with high reactivity could be produced under simulated
light. The larger amount of active materials produced under illu-
minated condition could react with the component of bacteria and
destroy its structure, thereby effectively inhibited the growth and
reproduction of bacterial. Moreover, ZnO could better response to
ultraviolet light and highly absorb it. Thus its conductivity was
significantly enhanced, which activated the interaction between
ZnO and bacteria.
Furthermore, high intensity radiation at specific wavelengths
can kill microorganisms. The experimental results showed that the
pathogen such as Acinetobacter Bauman, Pseudomonas aeruginosa
and Escherichia coli could be lethal by direct irradiation of 400 nm
light in the wound, and 405 nm light could make the Helicobacter
pylori inactive. Salmonella typhimurium could be sterilized by
521 nm light in 431 J/cm2 [97,98]. Comparisons of light on anti-
bacterial properties of ZnO were shown in Table 8.
Ascension causes References
Higher light intensity could enhance the ability Akira Fujishima et al. [91]
in the same reaction time and the ability to VA Khokhlova et al. [92]
photohydrogenize hydrogen
Nanoparticles would obtain more energy under VA Khokhlova et al. [92]
long irradiation though more electron-hole
pairs and hydroxyl radicals to accelerate the
degradation of organic compounds
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Table 8
Effect of light on antibacterial properties of ZnO.
Light Antibacterial properties
Different light condition UV light > simulated sunlight > no light
High intensity radiation Acinetobacter Bauman, Pseudomonas
aeruginosa and Escherichia coli could be lethal
by direct irradiation of 400 nm light,
405 nm light could make the Helicobacter pylori
inactive
Salmonella typhimurium could be sterilized by
521 nm light in 431 J/cm2
3.5. Reaction temperature
Reaction temperature of ZnO has certain influence on its pho-
tocatalysis and antibacterial properties. Zhifeng Liu et al. showed
that the effect of temperature on the acceleration of electro-
chemical reaction kinetics was obvious during the initial
nucleation-growth stage [99,100]. He et al. evaluated the photo-
catalytic properties of zinc oxide nanorods by photodegradation of
methyl orange (MO) and 4-nitrophenol (4-NP). It was found that
the photocatalytic activity of the ZnO sample decreased signifi-
cantly as the heating rate increased, which might be due to the
simultaneous reduction of the oxygen vacancies and the type of
surface adsorbed oxygen [101]. Usually, increasing the calcination
temperature of nanoparticles leads to the decrease of catalytic ac-
tivity. It is because the increased temperature will significantly
reduce the specific surface area and surface adsorption of ZnO.
Furthermore, the raised temperature will cause the crystal trans-
formation of ZnO to a certain degree.
High temperature treatment of ZnO particles also significantly
affects its antibacterial activity. The antibacterial activity of ZnO
decreased with the decreasing of treatment temperature [102].
Novikov reported antimicrobial tests against Klebsiella pneumoniae
and Staphylococcus aureus, and the results showed that the main
driving force for increasing antimicrobial properties was the tem-
perature and concentration of antimicrobial agents, followed by the
crosslinked formula used [103]. Therefore, rational control of
temperature could greatly improve the performance of ZnO. In
general, the effect of heating rate and calcination temperature on
the photocatalytic and antibacterial activity of zinc oxide samples
may be the combined effects of morphology, optics and surface
properties, especially the types of oxygen vacancies and surface
adsorbed oxygen.
3.6. Concentration
The concentrations of catalyst also play an important role in the
photocatalytic activity of ZnO is due to the surface area and the
contact chances between organic matter and catalyst would be
increased with the increasing of the concentration [104]. Usually,
the initial reaction rate increases rapidly with the increasing of
catalyst concentration, but the reaction rate will be decreased when
the dosage is too large. It is because catalysts would cover with each
other for the excessive addition, and block the transmission depth
of ultraviolet light and cause the scattering of light [105,106]. There
is an optimal value for organic catalyst with different
concentrations.
Moreover, many studies strongly suggest that the antimicrobial
activity of ZnO nanoparticles also depends on its concentration. Liu
et al. pointed out that increasing the concentration of nanoparticle
resulted in the higher antibacterial activity against Escherichia coli,
it was because a larger quantity of H2O2 generated on the surface of
905
Ascension causes References
The larger amount of active materials produced Y.G. Cheng, W. Zhang et al. [93e95]
under illuminated condition could react with the
component of bacteria and destroy its structure
Large light intensity can enhance the ability M.Y. Yang, P.V. Lakshmi et al. [97,98]
ZnO [107]. Jalal showed that low concentration of ZnO nanofluids
unable to inhibit the merisis of bacteria. But the antibacterial ac-
tivity of ZnO increased in the wake of the increased concentration
and time [108]. The antibacterial activity depended on the exterior
area and concentration [109]. The concentration of ZnO nano-
particles plays an important role in the photocatalytic activity and
antibacterial activity. As several studies have shown, the activity is
dependent on many factors, but it is also affected by the concen-
tration of nanoparticles. The larger surface area and the higher
concentration are in favor of the photocatalytic and antibacterial
activity of ZnO.
3.7. Surface defects
The complex and abundant surface defects (morphology,
thickness, roughness) of ZnO have the important influence on its
physical and chemical properties. V. Lakshmi and other researchers
found that the activity of nanoscale ZnO was higher than that of
micro ZnO. It was because there was a sealed end between nano-
scale ZnO, which highlighted the important role of surface defects
in the formation of ROS [98]. Saha et al. showed that the increasing
of Zn gap defects in the ZnO films deposited at higher pressure
increased the conductivity and enhanced the electron transfer
ability [110]. Wang et al. considered that oxygen vacancies could act
as active centers of catalysts, which could capture photoinduced
electrons and effectively inhibit the recombination of photoin-
duced electrons and holes. Because of the high oxygen vacancy
content of nanomaterials, the photocatalytic activity of ZnO nano-
materials was higher [111]. However, to date, there has been rela-
tively little research conducted on the influence of surface defects
on the antibacterial activity of ZnO.
3.8. Other factors
Except the above factors, there are also some other factors that
influence the activities of ZnO. Firstly, the photocatalytic activity of
the catalyst could be greatly improved by injecting oxygen into the
solution. Oxygen can be used as an electron capture agent to cap-
ture electrons and form superoxide ion free radicals. Superoxide
ion free radical has strong oxidation property which can oxidize
and degrade pollutants in water to improve the degradation rate.
The oxygen required for different catalytic reaction systems is
mainly provided by oxygen dissolved in water from the air
[112,113].
Secondly, anions can be used as electron capture agents to
improve separating efficiency of photogenic electrons and holes in
order to improve the photocatalytic reaction rate [17,114]. Besides it
becomes scavengers of hydroxyl radicals to form anion radicals. The
activity of anion free radical is lower than that of hydroxyl free
radical, so the existence of anion will affect the degradation of
organic matter [115,116].
906 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Moreover, the standard of CB is closely related to the capability
of reducing H2O and O2, and therefore should be also come into
notice. When CB is at an appropriate level, the photogenerated
electrons in CB can reduce the production of H2 or combine with O2
to form a highly oxidized O2 free radical in the aspect of water
decomposition and elimination of organic pollutants [117].
Last but not the least, the structure of bacteria directly in-
fluences the antibacterial activity of the material. It is known that
the cytoderm of most malignant bacteria are composed of sophis-
ticated surface proteins which used for adhesion and colonization,
as well as components such as polysaccharides and phosphoric
acid, which can prevent host defenses and ambient conditions
[118]. These components are large molecules with charge, so a
specific group of groups can be triggered on the surface of the
microorganism to trigger specific interactions that destroy their
main functions and positions [119]. Therefore, the antibacterial
effects of ZnO on gram positive bacteria and gram negative bacteria
are quite different due to the different cytoderm structure.
As showed in Fig. 5a, the cell walls of gram-positive bacteria
consist of thick and dense peptidoglycan and teichoic acid. How-
ever, gram-negative bacteria have cell walls with three layers of
membrane structure as displayed in Fig. 5b. The outer layer is
composed of membrane protein, porin, phospholipids and lipo-
polysaccharides. The middle layer is composed of peptidoglycan.
The inner plasma membrane consists of phospholipids and protein.
Therefore, the negatively charged Escherichia coli have electrostatic
interactions with ZnO nanoparticles [120]. Because the negative
charge on the cell surface is higher, the interaction between
nanoparticles is stronger than gram-positive bacteria [121]. It was
found that the electrostatic interaction between bacteria surface
and nanoparticles can reduce the growth of Klebsiella pneumoniae.
And the antimicrobial activity of ZnO nanoparticles depended on
the nature of the interface interaction between NP and cytomem-
brane. Besides, Escherichia coli have a weaker antioxidant cell
content, causing a lower resistance to ROS resulting in the treat-
ment of ZnO to Escherichia coli is more sensitive than Staphylococcus
aureus. Compared with gram-negative bacteria, gram-positive
bacteria have thicker cell wall and do not have the phosphoric
acid, so active substances produced by ZnO is not easy to break the
cell wall or through the cell wall to reach and destroy bacteria cell.
In addition, some other factors, such as the differences in par-
ticle and cell membrane binding, the dissolution of ZnO and the
ability to extract harmful Zn2þ ions, and the permeability of the cell
should also be taken into consideration [122]. This dependence is
attributed to morphological and structural differences among
distinguished types of bacteria and their concentration discrepancy
[123].
Fig. 5. Different structures of Gram-positive bacteria and Gram-negative bacteria.
4. Methods to improve the photocatalytic and antibacterial
activities of ZnO
With the development of industry, various poisonous and
harmful organic dyes, such as rhodamine B, methylene blue and
methyl orange cause serious environmental pollution through the
discharge of sewage from the textile industry. Besides, unreason-
able applications of antibiotics lead to the production of various
superbugs and drug-resistant bacteria, which seriously affect hu-
man health. Therefore, it is urgent to find a strategy to solve the
above problems quickly and effectively. Semiconductor photo-
catalytic technology is a promising, efficient and environmental
friendly technology that can remove dyes from wastewater and
rapidly kill the bacteria in an economical, convenient and complete
manner. As a common semiconductor material, nano ZnO has been
widely used in the process of photocatalytic purification of pol-
lutants and the antibacterial treatment. However, the disadvan-
tages of ZnO, such as the rapid recombination of photogenerated
electrons and holes, the low quantum rate in aqueous solution
seriously affect its application fields [124]. Therefore, numerous
methods such as controlling the size and morphology of ZnO,
doping metal and nonmetal ions, coupling semiconductor, con-
structing heterojunction and surface modification have been used
to increase the activity of ZnO [125].
4.1. Controlling the size and morphology of ZnO
As discussed in part 3.1 and 3.2, size and morphology of ZnO
play the important role in determining its photocatalytic and
antibacterial activity. Therefore, many researchers improved the
photocatalytic and antibacterial activity of ZnO by specific design
and control the size and morphology of ZnO [126,127].
Our group's research indicated that flower-like ZnO had better
UV absorption properties and photocatalytic activity than ZnO in
other morphology such as spherical-like and rod-like. The flower-
like ZnO had more tip or step or kink loci than the rod-like nee-
dle-like ZnO, so more Zn atoms in the defect were able to extend
the N atom in the Rhodamine B (RB) molecule and catalyzed it. In
addition, the large surface area of flower-like ZnO with open porous
nanostructures actively promoted the diffusion and mass trans-
ferred to dye molecules and oxygen [128]. We also found ZnO
hollow microspheres had good Cr(VI) (86%) removal efficiency and
good photocatalytic stability. This phenomenon was attributed to
the surface trapped holes (hþ) of photocatalyst could react with
organic pollutants, inhibiting the electron-hole recombination
[129]. The qualitative ZnO nanoplate-nanowire (ZNP-ZNW) pre-
pared by Xu et al. had a higher surface oxygen deficiency than the
single-morphous nano zinc oxide structure, which could
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918 907

respectively capture photogenerated electrons and holes for
decomposing organic pollutants. In the degradation process of
methyl orange (MO), its photocatalytic activity was significantly
enhanced [130]. Sun et al. indicated that compared with other ZnO
nanostructures, thin needle pattern exhibited better photocatalytic
properties. The high surface area and mesoporous structure of thin
needle flowers provided an opportunity for effective diffusion and
transport of degradable organic molecules and hydroxyl radicals,
which would lead to the enhanced photocatalytic properties of ZnO
[131]. The comparisons of different sizes and morphologies on the
photocatalytic properties of ZnO were shown in Table 9.
In the aspect of antibacterial activities, our group reported that
mulberry-like ZnO showed the strongest antibacterial activity in
ZnO test. This might be explained by the fact that small size
mulberry-like ZnO could diffuse and adhere to the membrane
surface of bacteria more easily, which led to membrane protein
denaturation, changed membrane permeability and further
destroyed the membrane structure of bacteria cells. In addition, the
smaller size of ZnO could also penetrate into bacterial cells and bind
to DNA and RNA molecules in the cell to block genome replication.
Moreover, antibacterial test results reported by our group showed
that the drug-loaded hollow ZnO nanospheres could significantly
improve the antibacterial properties of casein films. In addition, it
could also prevent migration of fungicides [132]. Wu et al. found
that the antibacterial activity of ZnO nanowires decorated with ZnO
quantum dots (ZnO QDs/NWs) in the dark may be attributed to the
release of Zn2þ ions from ZnO QDs. Zn2þ ions were implanted into
the microbial solution to resist the growth of bacteria, thereby
destroying the microorganisms [112].
4.2. Doping with metal and nonmetal ions
The effects of doping metal atoms such as rare earth metal, alkali
metal, precious metal and transition metal on the crystalline host
lattice of ZnO crystals were studied step by step. And it has been
become the research hotspots gradually. Metal doped with ZnO
may expand the range of visible light response of ZnO and improve
its quantum efficiency. Therefore, the use of metal doping could
improve the photocatalytic and antibacterial activities of ZnO
[133,134]. In ZnO nanoparticles, the dopant results in the formation
of new electronic states in the gap, which can be used as the
electron trap sites [135]. Referring to the related literature, the
trapped electrons or holes in the redox reaction of the dye mole-
cules in the photocatalytic degradation process will be migrated to
the surface of the catalyst to participate in the reaction thereby
suppressing the recombination of electrons and holes and greatly
enhancing the photodegradation efficiency [136]. Therefore, we
believe the using of dopants to suppress the recombination of
electrons and holes could be a very helpful method to enhance the
antibacterial of ZnO nanoparticles.
4.2.1. Doping with transition metal
Metal oxide-doped transition metal will increase its crystal
defects and transfer its light absorption to the visible region [137].
Through the use of various transition metals or precious metals
such as Cu, Ni, Co, Mn, Ag [138e140], the band gap energy and the
average particle size of metal oxide will be decreased, and the
charge separation between the photogenerated electrons and the
hole pair will be improved.
In group III atoms, Ga has an ion radius of 0.62 Å and a covalent
radius of 1.26 Å, which are closest to the ion radius of Zn (0.74 Å and
1.31 Å). Therefore, Ga atoms are more likely to enter ZnO matrix
and lead to changes in the performance of ZnO photocatalyst [141].
The introduction of Ga could increase the specific surface area of
ZnO and gradually decrease the surface hydroxy oxygen concen-
tration, which determines the photocatalytic performance of Ga
doped ZnO photonic crystal. Chongsri et al. reported that the optical
response of devices had improved significantly with the increase
doping amount of Sn. The photocatalytic experiment confirmed
that the photodegradation percentage increased to 2.0% and then
decreased with the change of Sn concentration [142]. Srinivasan
et al. have confirmed that Cu-doped ZnO nanoparticles had better
photodegradation efficiency than undoped ZnO. The visible light
activity strongly depends on the position of the impurity state in
the band gap, and Cu doping can effectively separate the photo-
electron and hole to obtain high photocatalytic activity [143,144].
Giahi et al. doped Fe into ZnO matrix by sol-gel method, and found
that the presence of Fe ions could affect the photocatalytic activity
of ZnO. This result could be explained by the promotion of the
valence band of Fe doped ZnO to conduction band under ultraviolet
radiation [145]. Our team successfully prepared Fe doped sea
urchin-like ZnO nanoparticles (ZnO NPs) with different [Fe]/[Zn]
molar ratios. The results showed that the shape of crystals changed
with the increase of doping amount. In addition, doping 5% Fe
reduced the light band gap, and increased the absorption spectrum
in the visible region and the photocatalytic activity of ZnO [146].
Dubey et al. reported that compared with undoped ZnO, the pho-
tocatalytic activity of Mn doped ZnO was increased because Mn in
ZnO lattice could form impurity levels and promote the migration
of charge carriers [147]. She et al. reported that Al doped ZnO
nanoflowers had effective photochemical catalysis of helianthine B.
The fine photocatalytic performance should be related to the large
surface area of nanoflowers and the free supporter in Al doped ZnO
introduced by the doping agent [148].
Obviously, the presence of a certain amount of dopant ions can
enhance the photocatalytic activity of ZnO. However, excessive
doping of ions is harmful. Saleh and others believe that ZnO
nanoparticles doped with 12 at.% of Mn and Co ions exhibited the

Table 9
Effects of different sizes and morphologies on the photocatalytic properties of ZnO.

Morphology Photocatalytic performance Ascension causes References

Flower-like ZnO
ZnO hollow microspheres
ZnO nanoplate-nanowire
Thin needle pattern ZnO
Better UV absorption properties and
photocatalytic activity
Good Cr(VI) (86%) removal efficiency and good
photocatalytic stability
Photocatalytic activity was significantly
enhanced
Exhibited better photocatalytic properties
More tip or step or kink loci JunLi Liu et al. [128,129]
The photocatalyst surface trapped holes (hþ) could react
with organic pollutants, inhibiting the electron-hole
recombination
It had higher surface oxygen deficiency content, which Feng Xu et al. [130]
could respectively capture photogenerated electrons and
holes
The high surface area and mesoporous structure of fine Hongyu Sun et al. [131]
needle flowers provided an opportunity for effective
diffusion and transport of degradable organic molecules and
hydroxyl radicals
908 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918

maximum photodegradation efficiency because the charge capture metal would be a widely used technology to extend the acquisition
state caused by doping is a determinant, rather than the gap be- wavelength and the absorption range of ZnO, so as to improve its
tween the average particle size and the high doping concentration photocatalytic and antibacterial activity.
[49].
In the process of doping metal ions into ZnO to enhance its
4.2.2. Rare earth metals
antibacterial properties [149], researchers found that Ta doped ZnO
Recent studies have shown that doping rare earth ions in ZnO
nanoparticles exhibit more valid sterilizing effect in the dark
can broaden its visible light response [157], besides the interaction
environment than pure ZnO, which could be attributed to the
of rare earth metals and semiconductors can improve its photo-
enhancement of surface bioactivity and the synergistic effect of the
catalytic performance, because the ability to delay electron-hole
increased static electricity due to the admixture of Ta5þions into
pair recombination during excitation through the functional
ZnO [150]. Matai et al. estimated the MIC and MKC values of Ag-ZnO
groups interaction of rare earth metals [158]. Zhao et al. proved that
nanocomposites by detecting the growth of Staphylococcus aureus
doping Nd into ZnO would lead to an increase of photocatalytic
and Escherichia coli. The results showed that compared with Ag and
activity, and it reached the optimal value at the doping concen-
ZnO nanopowders alone, the Ag-ZnO nanocomposite had a strong
tration of 3% (mol fraction). The strong visible light emission and
bactericidal potential as a whole. The interaction of the nano-
enhanced photocatalytic activity could be explained by the increase
composites and the cell wall resulted in enhanced permeability of
of electron-hole pairs and induction defects of antiphase oxygen
the cell membrane, allowing them to enter the cell, which might
and interstitial oxygen caused by Nd doping [65].
result in cell death [151,152]. Manikandan et al. revealed that cobalt
Compared to ZnO nanoparticles doped with other rare ele-
doping in ZnO strengthened the antibacterial properties of ZnO.
ments, Nd doped ZnO nanoparticles in the PL emission signal
The results were based on the lattice compatibility theory. The
shows significant quenching, which proves Nd doping can lead to
surface morphology study showed that ZnO nanoparticle presented
better separation efficiency. The weak PL response leads to a slower
hexagonal particles. Co doping led to the production of needle-like
recombination rate, thus extending the life of photogenic charge
and disc particles [153]. Ravichandran and others showed that
and improving the photocatalytic activity. Besides, doping Nd can
when the Fe doping level was 8 wt%, the antibacterial efficiency of
increase the surface area of ZnO nanoparticles and thus improve
Escherichia coli and Pseudomonas aeruginosa was the highest. When
the photocatalytic activity. The degradation rate of methylene blue
the Fe doping level reached 8%, the size of the grain decreased
(MB) catalyzed by ZnO with different rare earth metals was Nd-
significantly to the nanometer level. Smaller particles could make
ZnO > Sm-ZnO > Dy-ZnO > La-ZnO, which confirmed the highest
more active surface areas interact with bacteria, resulting in better
activity for Nd-doped ZnO [158]. Zhang et al. argued that Eu-doped
antibacterial efficiency [154]. Thomas et al. showed the minimum
ZnO nanoparticles had higher photocatalytic activity than pure ZnO
inhibitory regions for pure ZnO and Cd/ZnO to Serratiamarcesens
nanoparticles in the degradation of MO under ultraviolet light. That
were 8.4 mm and 10.8 mm respectively. The production of H2O2
was because Eu3þ doping agent could act as electron scavenger,
from ZnO caused particles to infiltrate into the bacterial cell
which partially inhibited the photonic charge carrier recombina-
membrane, leading to bacterial death [155]. Our group also indi-
tion. Furthermore, Eu-doped ZnO nanoparticles were easy to
cated that the doping of Fe ions in the ZnO lattice promoted the
recycle and reuse, which was essential for environmentally
growth of ZnO along the (002) plane, forming a sea-urchin like
amicable and sustainable processes [124]. Rare earth metals are
structure and enhancing its antibacterial activity. 5% iron doped sea
doping in ZnO acts as the electron capture center and inhibit the
urchin-like ZnO had the strongest antibacterial activity against
recombination of electron and hole, thus leading to the production
Candida albicans (94%) and Aspergillus flavus (81%) [71]. Further-
of ROS and improving the photocatalytic activity of ZnO [157].
more, Kumar et al. found the holes generated in the valence band
In the process of doping rare earth metals into ZnO to enhance
and the Cu2þ species generated during the interfacial charge
its antibacterial properties, our group found that the increasing of
transfer process might be attribute to the inactivation of bacteria as
cerium dopants by more than 0.8% led to the decrease of the optical
showed in Fig. 6 [156].
band gap (3.06 eV) of ZnO, and the enhanced antibacterial activity
Therefore, it can conclude that doping transition and precious
of ZnO to Candida albicans (75%) and Aspergillus flavus (80%) under

Fig. 6. The mechanism of degradation of E.coil by Cu2þ-modified ZnO [156].

 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
the visible light source [159]. Other researchers have also done the
correlation studies. Li et al. argued that after adding Ce4þ, the
antibacterial activity of nano ZnO was significantly improved, and
the antibacterial rate against Escherichia coli and Staphylococcus
was above 97%. The uniform distribution of doping ions effectively
prevented the recombination of electron-hole pairs, prolonged the
existence of photoinduced electrons and holes, and improved the
hydroxyl position of the surface and the photocatalytic efficiency of
ZnO, thus making it more effective in bactericidal and bacteriostasis
[160]. Zhao et al. reported that La3þ/ZnO rare earth composite
antibacterial agent had good antibacterial properties against gram-
negative Escherichia coli and gram-positive Staphylococcus aureus,
and its antibacterial property was enhanced by the synergistic ef-
fects of La3þ and ZnO crystal lattices [161]. Shally et al. found that
the rare earth doped ZnO nanoparticles exhibited great antibacte-
rial activity against gram-negative bacteria Escherichia coli, the
maximum antibacterial activity was obtained with 1% wt % Nd and
Gd doped ZnO nanoparticles [162].
In conclusion, rare earth doped ZnO nanoparticles have good
photocatalytic activity and can be used as ideal catalysts for
degrading harmful organic dyes such as rhodamine B, bright yel-
low, methylene blue and methyl violet. At the same time, rare earth
doped ZnO nanoparticles have good antibacterial activity against
both gram-positive and gram-negative strains.
4.2.3. Doping alkali metals
Group I main family elements (Li, Na and K) have active physical
and chemical properties. In some studies, they have been used as
dopant to regulate the performance of ZnO, which can be used as
both the receptor and donor in ZnO [104]. Such as Li doped ZnO is
the most active photocatalyst and has high photocatalytic activity
for the degradation of p-nitrophenol (P-NP). Enhanced photo-
catalytic activity of Li doped ZnO is mainly due to the electron
capture of lithium metal ions. Besides, the small particle size, large
superficial area and high surface coarseness of the photocatalyst
are also very important. Benhebal et al. showed that the photo-
catalytic activity test of ZnO photocatalyst doped lithium had
favorable photocatalytic activity, and the maximum degradation
rate was 97%. The doping of alkali metal ions could form P type ZnO
semiconductor, and the doped ions might enter the gap position
[163]. Wang et al. found that Na doping can increase the photo-
catalytic hydrogen production of ZnO hollow spheres. The highest
photocatalytic generation rate of H2 reached to 1380 mol g1 h1
used by 0.7% Na-ZnO/Pt, which was 51 times higher than pure ZnO/
Pt hollow balls, because Na doping could increase the photo-
catalytic hydrogen production of ZnO hollow spheres [164]. Be-
sides, researches showed that Kþ doping led to the increase of ZnO
lattice, and the morphology of ZnO changed from lamellar to
granular. Compared with pure ZnO, Kþ doped ZnO microcrystals
showed higher specific surface area and visible light absorption,
lower optical band gap. Under visible light irradiation, Kþ doped
ZnO microcrystals also had enhanced photocatalytic activity than
pure ZnO [104]. Ganesh et al. reported that Al and Li co-doped ZnO
powder showed excellent photocatalytic activity in the experiment
of MB degradation under simulated sunlight exposure. In Al and Li
co-doped ZnO nanoparticles, the activity of these photocatalysts
increased to 10% as the concentration of Li increased. ZnO showed P
type semiconductor behavior with the doping of Li, because Liþ (ion
radius is 90 mm) could replace Zn2þ(ionic radius 88pm) atom, and P
type semiconductor material was more resistant to corrosion than
N type material [165].
Alkali metal doped ZnO is also an effective method to improve
the antibacterial properties of ZnO. Prasanna found that Na doped
nano ZnO released the highest amount of reactive oxygen species,
followed by nano ZnO, N doped micron ZnO, and micron ZnO. The
909
concentration of the vacancy was also in the same order. This
directly indicated the correlation between reactive oxygen species
and oxygen vacancies in pure ZnO and doped ZnO [166]. Due to the
high oxygen vacancy concentration, hydroxyl radicals produced by
Na doped ZnO increase, resulting in better antibacterial properties.
Although the researches about alkali metal doping ZnO to enhance
its antibacterial properties is relatively less, it is not difficult to see
that the doping of alkali metal is effective and cheap method to
improve the photocatalytic and antibacterial properties of zinc
oxide in the future.
4.2.4. Alkaline earth metals
Alkaline earth metal doping has also contributed a lot to the
process of improving photocatalytic performance of ZnO [167].
Kumaran et al. confirmed the enhanced visible light catalytic ac-
tivity of Sr doped ZnO nanoparticles was obtained, and the pho-
tocatalytic activity of Sr2þ doped ZnO was much higher than pure
ZnO. The interaction of doping ions and ZnO destroyed a part of the
original lattice and formed the lattice defect, which played an
important role in improving the catalytic activity of ZnO [168]. Raj
et al. found that all Sr doped ZnO nanoparticles photocatalysts had
stronger light absorption in the ultraviolet ray and medium light
absorption in the visible light region. In addition, photocatalytic
efficiency of RhB dye was improved with the increasing of the
doping concentration. This may be due to the Sr dopant reduced
electron hole recombination in the ZnO environment. Thereby
capturing photoexcited electrons on the conduction band [137,169].
In terms of antibacterial activity, JavedIqbal et al. found that the
growth of staphylococcus aureus could be successfully eliminated
by changing the doping level of Mg in ZnO. The enhancement of
antibacterial activity of Mg doped ZnO might be due to the change
in grain size, morphology and soluble Zn2þ ions. The optical results
showed that the band gap energy of ZnO increased significantly
after doping Mg [170]. Snega et al. found the antibacterial activity of
the doped ZnO film was significantly enhanced with the increasing
of Mg concentration. This would lead to the production of H2O2 and
O2, respectively, resulting in oxidative damage inside the cell
membrane or cells [171]. Hameed et al. studied on a group of strains
showed that alkali metal ions (Mg2þ, Ca2þ, Sr2þ, Ba2þ) doped ZnO
nanoparticles (NPs) had obvious antibacterial effects, while Mg-
doped ZnO NPs had stronger antibacterial effect than other alkali
metal ions doped ZnO. This was because the replacement of Mg in
the Zn position lead to the highest level of the strength compared to
I (100)/I (002), so a greater proportion of (0001) Zn polar surfaces
enhanced the diffusion capacity of Zn2þ ions, leading to the higher
ROS in the Mg doped sample [172]. However, the antibacterial
properties of other alkaline earth metal doped ZnO were less
studied.
Comparisons of some doped metal on the photocatalytic and
antibacterial properties of ZnO were displayed in Tables 10 and 11.
4.2.5. Doping with nonmetal
Recent studies have demonstrated that doping C, N, F or S re-
duces band gaps in various metal oxides. In order to increase the
photocatalytic activity of ZnO under visible light, non-metal such as
nitrogen or sulfur could be doped into ZnO. Researchers observed
that non-metallic impurities (N, S, C) interfere with the crystalli-
zation of ZnO could improve the photocatalytic activity by
enhancing the absorption of light and the transport efficiency of
photogenerated charge carriers [173]. Besides, the photocatalytic
test showed that the C-doped ZnO nanofibers had much higher
degradation rate to rhodamine B than pure ZnO nanofibers in
visible light. It was because the doping of carbon might reduce the
band gap of ZnO, and the formation of new energy state led to the
enhancement of photocatalytic activity [174]. Ganesh et al. found
910 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918

Table 10
Effects of different types of metal on the photocatalytic properties of ZnO.

Type of doped metal Photocatalytic performance Ascension causes References

Ga Increased the photocatalytic performance Changed the morphology of ZnO, and increased the Junbo Zhong et al. [141]
photoelectric charge separation rate
Cu Better photodegradation efficiency The synergistic effect of Cu and ZnO Srinivasan ANANDAN et al. [143]
Fe Increased photocatalytic activity 5% Fe doped ZnO NPs had smaller size, more uniform Junli Liu et al. [146]
dispersion
Mn and Co Increased photocatalytic activity Formed impurity levels and promoted the migration of Deepak Kumar Dubey et al. [148]
charge carriers
Al Effective photochemical catalysis of helianthine B Changed the crystal cell parameters Guangwei et al. [133]
Nd Increased photocatalytic activity Extended the life of photogenic charge Zhen zhao et al. [65]
Eu Higher photocatalytic activity Acted as the electron scavenger to inhibit the photonic Yangqing Zhang et al. [124]
charge carrier recombination
Li The maximum degradation rate was 97% The electron capture of lithium metal ions Hadj Benhebal et al. [163]
K Increased photocatalytic Higher specific surface area, visible light absorption and J. Lv et al. [104]
lower optical band gap

Table 11
Effects of different types of metal on the antibacterial properties of ZnO.

Type of doped metal Antibacterial Properties Ascension causes References

Ta Exhibited more valid sterilizing effect The enhancement of surface bioactivity and the BingLei Guo et al. [150]
synergistic effect of the static electricity
increased
Fe Inhibition rate to Candida albicans (94%) and Promoted the growth of ZnO along the (002) Junli Liu et al. [71]
Aspergillus flavus (81%) plane forming a sea urchin like structure
Ce Inhibition rate to Escherichia coli and Led to the decrease of the optical band gap YanXia Li et al. [160]
Staphylococcus was above 97%
La Good antibacterial properties Entered a variety of synergistic ZnO crystal Shanyang Zhao et al. [161]
lattices
Na Improved antibacterial properties Released the highest amount of reactive oxygen V. Lakshmi Prasanna et al. [162]
species

that many oxygen vacancy and zinc vacancy generated in the pro-
cess of S doped ZnO [165]. The vacancy could promote the
adsorption of O2 and capture photoelectron, so as to achieve high
photocatalytic efficiency. Besides, S doped ZnO could produce more
electron-hole pairs under the same conditions, which improve the
utilization rate of sunlight. In the actual sample of S doped ZnO, the
existence of O and Zn vacancy defects has enabled the introduction
of S dopant to realize the photocatalytic application of ZnO in the
range of ultraviolet and visible light [175]. Moreover, other research
displayed nitrogen doped ZnO microspheres had highly improved
photocatalytic activity, which could degrade corrosive acids (humic
acid HA) under visible light. Nitrogen could be incorporated into
the ZnO lattice instead of interstitial sites, which was the reason for
the improved visible light absorption and photocatalytic activity
[176]. In addition to the energy level matching between the
selected materials, the design and manufacture of the right heter-
ojunction on the interface of composite materials also play an
important role in photocatalysis [177]. Comparisons of dopant
atoms on the photocatalytic properties of ZnO were shown in
Table 12.
For the studies on the improvement of antibacterial properties
by doping nonmetal, Gupta et al. found N doped ZnO showed
enhanced bioactivity against Escherichia coli [178]. Behzadnia et al.
indicated N doped nanoscale ZnO produced some positive species
and microorganism cell surface negatively charged residues, which
resulted in changes in cell permeability, and the normal meta-
bolism of microbes resulted in the death of microbes [179]. Pod-
porska et al. found that F-doped ZnO was effectively against
Staphylococcus aureus and Escherichia coli under visible light irra-
diation because the doping increased the production of reactive
oxygen species [180]. Snega et al. also indicated the prepared ZnO: F
film from the initial solution of 20 at.% F concentration showed high
transparency and good antibacterial properties. With the
increasing of F doping level, the band gap of ZnO increased slightly,
and the grain size decreased. F doped ZnO films produced a lot of
surface defects, and the antibacterial efficiency was improved
[181]. Comparisons of dopant atoms on the antibacterial properties
of ZnO were shown in Table 13.
Doping of non-metal in ZnO will change the electronic absorp-
tion properties of ZnO. The band gap is narrowed and the optical
absorption of ZnO is extended to the visible region. Nonmetallic
doping enables ZnO to gain more photons and enhance its

Table 12
Effects of dopant atoms on the photocatalytic properties of ZnO.

Dopant atoms Photocatalytic performances Ascension causes References

C doped ZnO nanofibers Much higher degradation rate to rhodamine B Reduced the band gap of ZnO and the formation of new L. Pan et al. [174]
energy state
S doped ZnO Achieved high photocatalytic efficiency Produced more electron-hole pairs under the same H. Zhang et al. [175]
conditions
N doped ZnO Highly improved photocatalytic activity Nitrogen could be incorporated into the ZnO lattice H. Sudrajat et al. [176]
instead of interstitial sites
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Table 13
Effects of dopant atoms on the antibacterial properties of ZnO.
Dopant atoms Antibacterial properties
N doped ZnO Enhanced bioactivity against Escherichia coli
F doped ZnO Effectively against Staphylococcus aureus and
Escherichia coli under visible light irradiation
ZnO: F film Good antibacterial properties
photocatalytic activity. ZnO band gap also plays a role in the gen-
eration of ROS. The resulting ROS causes oxidative damage on the
surface of microbial membranes. Besides, ZnO nanoparticles could
destroy the cell membrane of bacteria and released Zn2þ ions cause
lysosome and mitochondria damage leading to bacterial cell death.
4.3. Surface modification
Since the small size nanoparticles are easy to agglomerate and
further affect its antibacterial properties, therefore surface modi-
fication is very important [182e187]. Inorganic nanoparticles can
be modified via coupling agents, such as titanate, aluminate and
silicone hydride. The different antimicrobial effect between modi-
fied and unmodified ZnO nanoparticles can be attributed to the
difference in the number of oxygen vacancies, which is a typical
characteristic of ZnO [188]. Zhang et al. found that PVC modified
ZnO not only had good antibacterial properties but also retained
the favorable performance of PVC. Meanwhile, ZnO modified by
PVP had good dispersibility than unmodified nano ZnO. This might
because the modified sample enhanced the bacterial adhesion
ability to cause a good antibacterial effect [189]. The antibacterial
activity of modified ZnO nanoparticles promotes cell wall pene-
tration due to its high surface area and volume ratio [183].
Thanks to the generation of active oxygen and the release of
Zn2þ ions both occur on the surface of the nanomaterials, and the
surface properties also affect the interaction between ZnO and the
cell wall of the bacteria. All possible mechanisms of antibacterial
activity may be affected by surface modification. Leung et al. found
that nanoparticles coated with different surface modification
agents show higher or lower toxicity than bare ZnO, depending on
the surface modifier used [190]. Besides, different surface modifi-
cation molecules lead to differences in the release of Zn2þ ion and
the production of reactive oxygen species. Different amine func-
tional groups have been shown in the past such as benzylamine
could increase the production of reactive oxygen species in cells,
and long chain amine containing amines, such as cationic peptides
and polythene derivatives showed better antibacterial activity
[191].
It can be seen that the proper surface modification of ZnO not
only solve the agglomeration of nanoparticles, but also enhanced
antibacterial activity of ZnO.
4.4. Heterojunction
For semiconductor photocatalysts, the coupling heterojunction
can improve its photocatalytic efficiency by increasing charge
separation and the life of the charge carrier as well as extending its
optical response range [192e196]. For example, Ag2CO3 has been
used to improve the photocatalytic activity of semiconductors. The
coupling of Ag2CO3 with ZnO could form n-n heterogeneous
structure, achieving significant separation efficiency of charge and
improved charge pair life, thus improving the photocatalytic ac-
tivity of ZnO. Xiang et al. demonstrated that modified ZnO with
Ag2CO3 could significantly promote the visible light drive activity of
911
Ascension causes References
Produced some positive species and microorganism cell Amir Behzadnia et al. [179]
surface negatively charged residues
Increased the production of reactive oxygen species Podporska-Carroll J et al. [180]
F doped ZnO films produced a lot of surface defects S. Snega et al. [181]
photocatalyst. The coupling of ZnO and Ag2CO3 could over-
whelmingly promote the simulated solar photocatalytic activity of
ZnO derived from accelerated separation of photogenic charge pairs
[197]. The ZnO@AgI nanostructures prepared by Huang et al.
showed high photocatalytic activity. This was because the hetero-
junction structure between AgI nanoparticles and ZnO nanosheets
reduced the recombination of photogenerated electron hole pairs
in the conduction band (CB) and valence band (VB) of AgI nano-
particles by transferring electrons from CB of AgI nanoparticles to
CB of ZnO nanosheets [198]. Tong et al. showed that the photo-
catalytic activity of ZnO@BiOI composites was significantly
enhanced. The enhancement of photocatalytic activity was due to
the formation of ZnO@BiOI heterojunction structure, which facili-
tated the separation of photoinduced charge carriers [199].
In addition, the photocatalytic activity of SnO2/ZnO hetero-
junction to methyl orange was much higher than SnO2 and ZnO
samples. This could be attributed to the pore structure and high
surface area of SnO2/ZnO heterojunction led to higher photo-
catalytic activity of the sample [200]. Zhang et al. pointed out that
the photocatalytic activity of composite electrospun NiO/ZnO
nanofibers to Rhodamine B (RB) was much higher than that of pure
ZnO nanofibers, which could be attributed to the formation of p-n
heterojunction. The original Ni/Zn mole ratio of p type NiO/ZnO
heterojunction nanofibers had the best catalytic activity, which
might be due to their high separation efficiency for photoelectrons
and holes [201]. Ma et al. proposed that the heterojunction be-
tween ZnO and ZnGa2O4 promoted charge separation, and it was
the reason for the improved photocatalytic activity. Photocatalytic
test showed that ZnO/ZnGa2O4-0.2 showed about 82% of methyl
orange (MO) degradation efficiency within 70 min, far higher than
ZnO (6%) and ZnGa2O4 (47%) [202]. Bai et al. showed that ZnS/ZnO
photocatalysts had significantly higher photocatalytic activity than
pure ZnS and ZnO due to their high surface area and effective
charge separation [203]. The comparisons of the above results were
shown in Table 14.
While the construction of heterojunction could also improve the
antibacterial properties of ZnO. Mao et al. showed that Ag/Ag@AgCl
nanostructures enhanced the photocatalytic and antibacterial ac-
tivities of ZnO by enhancing active oxygen through visible light
[204], the antibacterial process was shown in Fig. 7. Zhang et al.
displayed that ZnO/ZnAl2O4 nanocomposites had good activity in
the inactivation of E. coli under simulated sunlight irradiation due
to the formation of ZnO and ZnAl2O4 heterojunction structure.
E. coli inactivation rate was 99.8% within 60 min The inactivation
reaction might be due to the DNA damage caused by the reactive
oxygen species (ROS) produced by radiation [205]. Guo and others
reported that the spongy ZnO/ZnFe2O4 heterostructure enhanced
the antibacterial properties and the possibility of light induced
charge separation and broadened the absorption of visible light.
The high specific surface area of spongy ZnO/ZnFe2O4 hetero-
structure and a large number of pores in the cavernous structure
were not only beneficial to the surface absorption of visible light
and mass transfer, but also provided more active catalytic sites,
resulting in high ROS production to enhance its antibacterial
912 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918

Table 14
Effects of different types of heterojunction on the photocatalytic properties of ZnO.

Different types Photocatalytic performances Ascension causes References

Ag2CO3/ZnO heterojunction
ZnO@AgI nanostructures
ZnO@BiOI composites
SnO2/ZnO heterojunction
NiO/ZnO nanofibers
ZnO/ZnGa2O4-0.2
Improved the photocatalytic activity Formed n-n heterogeneous structure, achieving Z. Xiang et al. [197]
significant separation efficiency of charge and
improved charge pair life
Showed high photocatalytic activity Reduced the recombination of photogenerated He Huang et al. [198]
electron hole pairs in the conduction band (CB) and
valence band (VB)
Significantly enhanced The formation of ZnO@BiOI heterojunction Zhifang Tong et al. [199]
structure, which facilitated the separation of
photoinduced charge carriers
The photocatalytic activity to methyl orange was much The pore structure and high surface area of SnO2/ L. Zheng et al. [200]
higher ZnO heterojunction
The photocatalytic activity to Rhodamine B (RB) was High separation efficiency for photoelectrons and Zhenyi Zhang et al. [201]
much higher holes
Showed about 82% of MO degradation efficiency The heterojunction between ZnO and ZnGa2O4 Baojun Ma et al. [202]
promoted charge separation

Fig. 7. The antibacterial process of Ag/Ag@AgCl/ZnO hybrid nanostructures [204].

activity [206]. Wu et al. displayed R factor inhibitory activity of
AgxZn1xOZnO heterojunction nanowires to Escherichia coli
under visible light (400e775 nm) could reach 5.6. This could be
attributed to various reactive oxygen species generated by light
excitation of AgxZn1-xO-ZnO nanowires [207]. Ponnuvelu et al.
found that the synergistic antibacterial activity of coreeshell
ZnO@Ag heterojunction nanorods to gram-negative bacteria was
more prominent. The reasonable reason for this enhanced anti-
bacterial activity could be attributed to the physical damage caused
by the interaction between the material and the outer cell wall
resulting from the electron transfer between the ZnO interface
[208]. The comparisons of the above results were shown in
Table 15.
4.5. Semiconductor coupling
Semiconductor oxide could be optimized to improve the sepa-
ration efficiency of the photo-generated carrier of electric charge,
thereby improving the photocatalytic performance [209]. These
semiconductor coupling structures include CdS-ZnO [210], CdSe-
ZnO [211] and SnO2-ZnO [212]. Researchers found that due to the
spatial nature of the nano-bonding point between the cadmium
chalcogenide and the zinc oxide crystal phase, different degrees of
ion exchange between the two crystals could alleviate the larger
lattice mismatch and promote hole transport in the catalytic pro-
cess to promote exciton separation [213]. Eley et al. showed that
CdS-ZnO and CdSe-ZnO which were the composites of ZnO and
other semiconductors with suitably matched band energy. Type-II

Table 15
Effects of different types of heterojunction on the antibacterial properties of ZnO.

Different types Antibacterial properties Ascension causes References

ZnO/ZnAl2O4 nanocomposites
The spongy ZnO/ZnFe2O4
heterostructure
AgxZn1xOZnO heterojunction
nanowires
Coreeshell ZnO@Ag heterojunction
nanorods
Good activity in the inactivation of E. coli
Enhanced the antibacterial properties
Inhibitory activity to Escherichia coli under
visible light (400e775 nm) could reach 5.6
Antibacterial activity to gram-negative bacteria
was more prominent
The DNA damage caused by the reactive oxygen Li Zhang et al. [205]
species (ROS) produced by radiation
The high specific surface area of spongy ZnO/ Xiutong Guo et al. [206]
ZnFe2O4 heterostructure and a large number of
pores in the cavernous structure
Various reactive oxygen species generated by Jyh Ming Wu et al. [207]
light excitation of AgxZn1-xO-ZnO nanowires
The physical damage caused by the interaction Ponnuvelu DV et al. [208]
between the material and the outer cell wall
resulting from the electron transfer between
the ZnO interface
 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918 913

interfaces between semiconductors caused spatial separation and
increased lifetimes of photogenerated excitons, which reduced in-
ternal charge recombination and increases catalytic activity [214].
At the same time, the catalytic activity was increased due to the
combination of the intrinsic chemistry of the chalcogenide anion
and the heterojunction structure. It was found that the ZnO doped
with SnO2 showed significantly higher photocatalytic activity than
the single-phase SnO2 or ZnO powder synthesized with similar
processing conditions. The enhanced photocatalytic activity of
SnO2 doped ZnO could be attributed to its high specific surface area
and enhanced charge separation caused by the coupling of ZnO and
SnO2 [215].
Besides, it is a promising strategy to improve the photocatalytic
performance of semiconductor ZnO by coupling carbon materials to
form ZnO/carbon composite by proper integration method. It is
worth noting that abundant carbon material family, such as C60,
CNT and graphene, has further facilitated the synthesis of various
ZnO/carbon composite photocatalysts. In photocatalysis, the widely
recognized role of carbon materials in ZnO/carbon composites is to
store and pass photoelectron from semiconductor ZnO as a
photoelectron reservoir. Besides, the presence of carbon materials
can enhance the adsorption capacity of ZnO/carbon composites,
which also contribute to the enhancement of photoactivity [216].
As for ZnO/C60 composite materials, it has been proved that C60
can be anchored in ZnO vacancy and basically reduces the activa-
tion of surface oxygen atoms, thus inhibiting the photoinduced
corrosion of semiconductor ZnO. Luo et al. indicated the photo-
degradation efficiency of methylene blue by RGO-ZnO composites
increased by 67% due to the inhibition of charge carrier recombi-
nation by the interaction between RGO and ZnO [217]. Barpuzary
et al. studied the enhanced electron transfer with alignment of ZnO,
CdS and GO entities based on ZnO, CdS and GO in composite ma-
terials [218,219]. The ZnO nanocomposite with narrow band gap
semiconductor (such as carbon, CdS and Bi2O3) hybridization, can
activate the ZnO under visible light irradiation, and significantly
improve the photocatalytic performance of the ternary composites
compared with the binary composite materials [220,221]. We have
also prepared the composite materials of ZnO and C. The new
synthesized type of visible-light driven ZnO/graphite carbon (ZnO/
g-C) core shell nanowires promoted the separation of electron-hole
pairs, improved the photocatalytic activity and inhibited the
photoinduced corrosion. The results showed that the photocatalytic
activity of ZnO/g-CNWs was 2.4 times higher than that of pure ZnO
under UV visible light. The narrow band gap of semiconductor led
to the expansion of absorption capacity to a longer wavelength
region and improved the transportation of carrier, which enhanced
the photocatalytic performance of nanocomposites [222]. Liu et al.
prepared the ZnO/CdS gradient photoelectron chemical electrode
by continuous ion layer adsorption reaction (SILAR). Under suitable
conditions, each band gap was optimized to absorb solar light and
inject charge to improve photocurrent performance [223]. The
comparisons of the above results were shown in Table 16.
Yalcinkaya et al. indicated ZnO/TiO2 had good antibacterial ac-
tivity against Escherichia coli. The antimicrobial mechanism of
metal oxides was due to their interaction with high reactive oxygen
species, which caused damage to the outer membrane or bacterial
interior [224]. Ali et al. found ZnO/CdS nanocomposites could be
used to control and manage skin infections caused by resistant
Staphylococcus aureus. They believed that the increased antibacte-
rial activity was related to the structure of CdS and ZnO. At the same
time, ZnO had the special features over other metal oxides for
antibacterial applications. Compared with ZnO, the size of ZnO/CdS
nanocomposites was reduced, which could inhibit the growth of
Staphylococcus aureus [225]. Zirak et al. indicated that the excited
state electrons in the conduction band (CB) were transferred to the
CB of ZnO, and charge separation occurred when CdS generated
electron-hole pairs under visible light irradiation. Electrons trans-
ferred to ZnO caused the reduction of the sample, while holes
remaining in Cd could act as oxidants and/or promote the gener-
ation of hydroxyl radicals (OH), resulting in the stronger antibac-
terial activity [226]. The antibacterial activity of ZnO/graphite
composites based on photocatalytic reaction in dark conditions by
Dedkov et al. showed that Zn2þ ions played an important role in the
antibacterial activity, and there was a synergistic effect between
Zn2þ and active oxygen species, resulting in antibacterial activity
[227]. Karthik et al. found the CdO-ZnO nanocomposites had sig-
nificant antibacterial activity against a variety of pathogenic or-
ganisms. The first reason for the antibacterial activity was the
formation of hydrogen peroxide (H2O2) from the surface of CdO-
ZnO nanocomposites. The second reason was CdO-ZnO nano-
composites released the positive charge of Cd2þ and Zn2þ to attract
the negative charge on the membrane of microorganism cells. Cd2þ
and Zn2þ penetrated the cell membrane, causing the cells lose,
which led to the death of microbes [228]. Besides, the enhanced
UV-light driven antibacterial activity of ZnO/GQD nanocomposites
on Escherichia coli was found by our group. That was attributed to
the rapid generation of ROS and the effective interface charge
transfer from graphene quantum dot (GQD) to ZnO [229]. The
comparisons of the above results were shown in Table 17.
5. Remarks and outlook
In this paper, the photocatalytic and antibacterial activity of ZnO
nanoparticles as well as the factors affecting their activity are
reviewed. Till now, various potential methods such as controlling
size and morphology, doping metal and nonmetal ions, coupling
semiconductors, constructing heterostructures, surface modifica-
tion and improving the ultraviolet radiation have been used to

Table 16
Effects of different coupling types on the photocatalytic performances of ZnO.

Different Coupling types Photocatalytic performances Ascension causes References

CdS-ZnO and CdSe-ZnO
ZnO doped with SnO2
ZnO/carbon composites
RGO-ZnO composites
ZnO/graphite carbon (ZnO/g-C)
core shell nanowires
Increased catalytic activity
Showed significantly higher photocatalytic
activity
Improved the photocatalytic performance
The photodegradation efficiency of methylene
blue increased by 67%
The photocatalytic activity of ZnO/g-C increased
2.4 times
Reduced internal charge recombination Clive Eley et al. [214]
High specific surface area and enhanced charge A. Dodd et al. [215]
separation caused by the coupling of ZnO and SnO2
Reduced the activation of surface oxygen atoms, thus M. Ahmad et al. [216]
inhibiting the photoinduced corrosion of
semiconductor ZnO
The inhibition of charge carrier recombination by the QiuPing Luo et al. [217]
interaction between RGO and ZnO
The narrow band gap of semiconductor led to the JunLi Liu et al. [222]
expansion of absorption capacity to a longer
wavelength region and improved the transportation of
carrier
914 J. Liu et al. / Journal of Alloys and Compounds 783 (2019) 898e918
Table 17
Effects of different coupling types on the antibacterial properties of ZnO.
Coupling type Antibacterial properties
ZnO/TiO2 Good antibacterial activity against Escherichia coli
ZnO/CdS Good antibacterial activity
nanocomposites
CdO-ZnO Significant antibacterial activity against a variety of pathogenic
nanocomposites organisms
ZnO/GQD Enhanced antibacterial activity
nanocomposites
further improve the efficiency of photocatalytic and antibacterial
activity of ZnO, specially in the degradation of organic dyes and
POPs, as well as the treatment of harmful superbacteria and resis-
tant bacteria. Hopefully, the more satisfactory results might be
acquired by the combination of two different methods.
Besides, as we all know that for ZnO nanoparticles, the intro-
duction of intracellular ROS can lead to the enhancement of pho-
tocatalytic activity and the death of bacteria. The releasing of Zn2þ
and adhesion of ZnO nanoparticles on the cell membrane lead to
the mechanical damage of bacteria. In order to improve the pho-
tocatalytic and antibacterial properties of modified ZnO nano-
particles systematically, we still need to explore methods to further
enhance the production of ROS and the release of Zn2þ continu-
ously. We believe that the excellent performance of ZnO nano-
particles in the treatment of photodegradable organic dyes and
bacteria is of great significance to environmental remediation and
human health. Therefore, more attention should be paid to inves-
tigate the correlation among the structure, optical, chemical
properties and the activity of ZnO nanoparticles. And one day in the
future, ZnO nanoparticles can be used as an intelligent weapon
against multi drug-resistant microorganisms and a powerful sub-
stitute for antibiotics.
Acknowledgments
This investigation was supported by National Key Research and
Development Program of China (2017YFB0304700), National Nat-
ural Science Foundation of China for Young Scholar (51802185), Key
Laboratory of Clay Mineral Applied Research of Gansu Province
(CMAR-2017-03), Scientific Research Program Funded by Shaanxi
Provincial Education Department(17JK0114), Natural Science Basic
Research Plan in Shaanxi Province of China (2018JQ5083).
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