Green Synthesis of ZnFe2O4 Nanoparticles Using Plant Extracts and Their

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Science of the Total Environment 872 (2023) 162212

Contents lists available at ScienceDirect

Science of the Total Environment


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

Review

Green synthesis of ZnFe2O4 nanoparticles using plant extracts and their


applications: A review
Ngoan Thi Thao Nguyen a, Thuy Thi Thanh Nguyen b, Duyen Thi Cam Nguyen a, , Thuan Van Tran a,
⁎ ⁎
a
Institute of Applied Technology and Sustainable Development, Nguyen Tat Thanh University, 298-300A Nguyen Tat Thanh, District 4, Ho Chi Minh City 755414, Viet Nam
b
Department of Chemical Engineering and Processing, Nong Lam University, Thu Duc District, Ho Chi Minh City 700000, Viet Nam

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Green synthesis and multiple applications


of ZnFe2O4 nanoparticles were high-
lighted.
• The effect of bio-mediated synthesis con-
ditions on properties of ZnFe2O4 nanopar-
ticles was discussed.
• Green ZnFe2O4 nanoparticles showed
good photocatalytic, adsorption, and bio-
medical performance.
• Several limitations and prospects of green
ZnFe2O4 nanoparticles were proposed.

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

Editor: Huu Hao Ngo Magnetic nanoparticles, particularly ZnFe2O4 are of enormous significance in biomedical and water treatment fields.
However, chemical synthesis of ZnFe2O4 nanoparticles endures some major limitations, e.g., the use of toxic sub-
Keywords: stances, unsafe procedure, and cost-ineffectiveness. Biological methods are more preferable approaches since they
ZnFe2O4 nanoparticles take advantages of biomolecules available in plant extract serving as reducing, capping, and stabilizing agents. Herein,
Biosynthesis
we review plant-mediated synthesis and properties of ZnFe2O4 nanoparticles for multiple applications in catalytic and
Plant extract
Applications
adsorption performance, biomedical, catalyst, and others. Effect of several factors such as Zn2+/Fe3+/extract ratio,
and calcination temperature on morphology, surface chemistry, particle size, magnetism and bandgap energy of ob-
tained ZnFe2O4 nanoparticles was discussed. The photocatalytic activity and adsorption for removal of toxic dyes, an-
tibiotics, and pesticides were also evaluated. Main results of antibacterial, antifungal and anticancer activities for
biomedical applications were summarized and compared. Several limitations and prospects of green ZnFe2O4 as an al-
ternative to traditional luminescent powders have been proposed.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Green synthesis of ZnFe2O4 using plant extracts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Advantages of plant extracts for ZnFe2O4 synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Selection of plant sources for ZnFe2O4 synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

⁎ Corresponding authors.
E-mail addresses: ntcduyen@ntt.edu.vn (D.T.C. Nguyen), tranvt@ntt.edu.vn ttran@gradcenter.cuny.edu (T.V. Tran).

http://dx.doi.org/10.1016/j.scitotenv.2023.162212
Received 1 December 2022; Received in revised form 18 January 2023; Accepted 9 February 2023
Available online 14 February 2023
0048-9697/© 2023 Elsevier B.V. All rights reserved.
N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

2.3. The presence of phytochemicals in different plant extracts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3


2.4. Reducing power of different plant extracts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.5. Formation of plant-mediated ZnFe2O4 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Properties of green ZnFe2O4 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Particles size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Surface chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.4. Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.5. Optical bandgap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Applications of green ZnFe2O4 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Photocatalytic performance of green ZnFe2O4 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2. Adsorption performance of green ZnFe2O4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.3. Electrochemical applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.4. Biomedical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.5. Catalysis applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Prospects of green ZnFe2O4 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6. Limitations and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Funding information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Compliance with ethical standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Code availability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Ethics approval . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Consent to participate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Consent for publication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Availability of data and material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

1. Introduction et al., 2021), sonication methods (Yadav et al., 2021), etc. However,
these methods are generally energy intensive and toxic, adversely influenc-
Nowadays, the advent of nanotechnology has contributed positively to ing human health and the environment. For example, reducing agents such
solving critical global problems such as climate change and pandemic dis- as citric acid, NaBH4 and oleyl amine are corrosive, formaldehyde, CO,
eases. Nanotechnology allows to manipulate/design nanometric scaled par- N2H4 are very toxic, flammable and irritating (Soni et al., 2021). Therefore,
ticles; thereby, accessing to structural characterization and exploring the synthesis of ZnFe2O4 nanoparticles through biological mediation
unprecedented results. As the size of particles is nano-scaled down, they ex- (plants, microorganisms, algae, etc.) has more advantages of high biocom-
hibit superior characteristics in comparison with bulk particles (Ghaffari- patibility, non-toxic reagents, low energy requirements, and fast, easy-to-
Moghaddam et al., 2014). As a result, nanoparticles have been increasingly handle, easy-to-scale, and facile synthesis of nanoparticles than chemical
playing a central role in catalysis (Ndolomingo et al., 2020), chemical in- and physical synthesis pathways. In other word, plants have been used as
dustry (Pagar et al., 2020), electronics and electro-optical (Hashim, a “biofactory” in the production of metal nanoparticles because they are in-
2020), biomedical (Malik et al., 2022), and agricultural devices (Hazarika expensive with local availability. Important phytochemical components
et al., 2022). (terpenoids, flavonoids, etc.) with functional groups like amine, hydroxyl,
There are different types of metallic nanoparticles such as copper, zinc, and carboxylic available in plant extract acts as reducing agent in the syn-
titanium, magnesium, gold, and silver (Roseline and Arunkumar, 2022). thesis of ZnFe2O4 nanoparticles (Devi et al., 2020; Singh, 2022). They are
Besides, spinel ferrite nanoparticles with transition metal sites (e.g., Mn, also well known as a natural stabilizer to ensure the long-term reactivity
Cu, Co, Zn, …) have attracted great attention, due to their special proper- of ZnFe2O4 nanoparticles. For instance, Amani et al. (2022) synthesized
ties, such as ferromagnetic, and electrical properties (Soufi et al., 2021). ZnFe2O4 nanoparticles using rutin from Ruta graveolens extract with the
Each spinel ferrite includes a tight arrangement of oxygen ions in a unit magnetization of 5.9 emu/g. Ghoran et al. (2020) reported that the biosyn-
cell. Interstitial space lies on between the layers of oxygen ions, forming thesis of ZnFe2O4 nanoparticles using polyphenol-rich extract of Citrus
two types including tetrahedral sublattice (A) and octahedral sublattice aurantium flowers. Fabiani et al. (2021b) indicated flavonoid group in
(B), which are based on the coordination of the nearby neighboring oxygen Antidesma bunius fruit extract could act as reducing and stabilizing agents
ions (Tatarchuk et al., 2019). Among spinel ferrites, ZnFe2O4 is one of the of ZnFe2O4 nanoparticles.
most prominent thanks to a perfect combination of Fe-and Zn-based mate- This review concentrates majorly on the plant extract-mediated fabrica-
rials. Non-magnetic Zn2+ cations are located at the A sites and the magnetic tion using natural compounds extracted from plants and potential of
Fe3+ cations are located at the B sites (Thavarani et al., 2022). Zn has stable ZnFe2O4 nanoparticles. Specifically, some structural characteristics of
biocompatibility while Fe has an outstanding ferromagnetism. This advan- ZnFe2O4 nanoparticles are discussed with the emphasis on surface chemis-
tage makes ZnFe2O4 useful for biomedical and electrochemical applications try, particle size, magnetic and optical properties. Prominent applications
(Sonu et al., 2021). include biomedical, catalysis, adsorption, photocatalysis, and even electro-
Over the past years, many physical and chemical methods have been chemical applications. Some prospects of green ZnFe2O4 nanoparticles in
proposed to synthesize ZnFe2O4 nanomaterials such as solvothermal agriculture and latent fingerprints are also highlighted, marking a step for-
(Shaterian et al., 2021), hydrothermal (Tiwari et al., 2022), sol-gel ward for this material in the future. To our best knowledge, this is the first
(Hossain et al., 2021), co-precipitation (Jyothish et al., 2022), thermal de- critical review on the plant extract-mediated synthesis and application of
composition (Tomar and Jeevanandam, 2020), solution combustion (Guo green ZnFe2O4 nanoparticles for a wide range of applications.

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

2. Green synthesis of ZnFe2O4 using plant extracts compound formed is proportional to the concentration of reducing sugars
within a certain range (Teixeira and Santos, 2022). The flavonoid content
2.1. Advantages of plant extracts for ZnFe2O4 synthesis can be determined based on the aluminum chloride colorimetric method.
Accordingly, the extract is mixed with AlCl3 and CH3COOK, the absorbance
Among the abundant natural resources, plants are readily available re- can be measured spectrophotometrically to detect the presence of flavo-
sources, convenient, cost-effective and especially effective in synthesizing noids (Nguyen et al., 2020). As such, the selection of plant species should
nanomaterials. Recently, the green synthesis of nanomaterials such as be partly screened by these developed techniques before the synthesis of
ZnFe2O4 often uses plant tissues instead of other biological sources such ZnFe2O4 nanoparticles using plant extract can initiate.
as bacteria, fungi, lichen and algae (Ghoran et al., 2020). It is known that
the use of plant-biomediated materials is less harmful to health, because 2.3. The presence of phytochemicals in different plant extracts
some fungi or bacteria can release several toxins during the process (Xu
et al., 2020). In addition, the culturing of microorganisms often takes Over the past centuries, many botanicals have been studied in the phar-
long time and great effort, while many types of strange colonies may ap- maceutical field, as well as found useful for conventional human treatment
pear. The abundance of phytochemicals found in any part (e.g., leaves, therapies because they contain a large number of bioactive compounds act-
flowers, stems, bark, fruits, roots, etc.) of the plant, makes it easy to collect ing as natural medicines. Many antioxidant compounds including phenolic
(Bao et al., 2021). Some components such as reducing sugar, flavonoids, acids, flavonoids, alkaloids, terpenoids and tocopherols, etc. can be also de-
quercetin, amino acids and vitamins, saponins are present available in tected in the plant species (Rao et al., 2021). Several major phytochemicals
plant extracts, which are key to synthesis material (Salachna et al., 2021). are considered to confer antioxidant activity to plants, making significant
The phytochemicals in plant extract act as reducing, complexing and stabi- contributions in the fight against many pathological conditions such as can-
lizing materials (Aldeen et al., 2022). The total duration for the synthesis of cer, diabetes, aging, cardiovascular and other degenerative diseases (Singh
metal nanoparticles can be as short as a few minutes or a few hours, com- Makhaik et al., 2021). In some cases, phytochemicals in plants are extracted
pared with many days for microorganism-biomediated methods as a result to produce the aroma of essential oils. In general, most plant species contain
of culture and incubation. high levels of phytochemicals such as flavonoids, phenolic acids, amino
acids and reducing sugars. For example, Yu et al. (2021) reported that the
2.2. Selection of plant sources for ZnFe2O4 synthesis total high phenolic acids content of rosemary leaf (7.46 mg g−1), sage
leaf (7.09 mg g−1), pomegranate leaf (16.22 mg g−1) with a variety of de-
On Earth planet, thousands of plant species are currently growing and rivatives including gallic acid, vanillic acid, caffeic acid, chlorogenic acid,
developing in a variety of ways. They are strongly adaptable, reproductive, and neochlorogenic acid. For flavonoid, total flavonids contents were deter-
and spreading creatures. Therefore, plant sources offer a feasible option for mined at 14.35, 37.65, 49.21 mg g−1 for rosemary leaf, rue leaf and stem,
the synthesis of nanoparticles using their extracts. The selection of plant peppermint leaf and stem extracts, respectively. In another study,
species for the synthesis of ZnFe2O4 nanoparticles can be considered Nasiruddin and Sinha (2020) also pointed out that Gynura procumbens
based on some criteria to reach critically green, safe and effective targets. shows that the main chemical components including amino acids
The first criterion is that suitable plant species should be locally available (16.34 mg g−1), soluble sugars (1.81 mg g−1), total chlorophyll
and easy to harvest. This requirement aids to lessen transportation and har- (0.52 mg g−1), chlorophyll-a (0.34 mg g−1), chlorophyll-b
vesting costs. Indeed, many studies have recently carried out the selection (0.145 mg g−1). In addition to the common phytochemicals found in
of locally plant species as raw materials for the synthesis of ZnFe2O4 many different plant species, there are also unique phytochemicals that
based nanomaterials (Dhiman et al., 2023; Hassanisaadi et al., 2021; Tran are specific to each plant type. For example, hesperidin is a flavanone gly-
et al., 2022b). Secondly, selecting plant species for the synthesis of coside (flavonoid) found in citrus fruits such as oranges, lemons, grapefruit,
ZnFe2O4 should avoid allergenic and highly toxic species that affect and tangerines (Gandhi et al., 2020). Lee et al. (2022) reported that about
humans and animals upon contact. More importantly, as-synthesized 35.5–95.3 % of hesperidin exists in the extracts of 7 citrus species involving
ZnFe2O4 based nanomaterials regarding human trials must be strictly con- yuzu, bitter orange, satsuma mandarin, lime, grapefruits, lemon, orange.
sidered for the toxicity of origin plant extracts, which are used to synthesize Camphor is also considered to be a unique component of the wood of the
them. Ultimately, the selected plants should contain many important phyto- camphor tree (Cinnamonum camphora) or a few other related trees in the
chemicals that exhibit high chelating and reducing functions for green syn- laurel family, notably Ocotea usambarensis of East Africa (Ahmad et al.,
thesis of ZnFe2O4. 2016).
According to Table S1, several plants are very rich in natural com- The content of phytochemicals present in plant extracts depends signif-
pounds such as phenolic acid, quercetine, flavonoids, isoflavones, etc. To icantly on external factors such as climatic conditions, water and soil condi-
determine these compounds from plant extracts for synthesis purposes, a tions, geography, nutrient, etc. The same plant species but grown in
number of qualitative and quantitative methods have been developed different places and different geography may have different types or con-
(Dias et al., 2021). Specifically, micellar electrokinetic capillary chromatog- centrations of phytochemicals. For example, Ekiert et al. (2020) conducted
raphy (MEKC) is a commonly used method for the detection of naturally oc- a survey on the content of phytochemicals in the plant extracts of Artemisia
curring polyphenols in plant extracts (Yu et al., 2022). For reducing sugars, vulgaris grown in different countries. As a result, Artemisia vulgaris grown in
evaporative light scattering detection combined with high pressure liquid Brazil had 37.45 % caryophyllene and 16.17 % germacrene D in their ex-
chromatography is helpful to separate and identify phytochemicals in the tracts. In France, the main components of this plant are 1,8-cineole
plant species (Bai et al., 2022). In addition to the mentioned techniques, (23 %) and terpinen-4-ol (19 %). Meanwhile, Artemisia vulgaris grown in
the presence of functional compounds in plant extracts can be tested Italy had the highest camphor content (47 %). In Vietnam, components
quickly and conveniently by colorimetric method. For example, polyphenol such as β-caryophyllene (24 %), β-cubebene (12 %) and β-elemene (6 %)
content can be determined according to the Folin–Ciocalteu colorimetric are the main components found in this plant extract. In another work,
method. In this method, the Folin–Ciocalteu reagent oxidizes the −OH Debasish et al. (2021) conducted a survey on the content of active ingredi-
groups in the plant extract, giving the extract a blue color (Sun et al., ents present in the extracts of Hygrophilla difformis plants grown in two
2022). Moreover, reducing sugars are aldose-containing sugars that are ca- places (Uluberia and Kharagpur) in West Bengal, India. According to the
pable of acting as a reducing agent and can be recognized by 3,5- main findings, the total vitamin C content extracted from the plants culti-
dinitrosalicylic acid (DNS) reagents. This method is based on the chromo- vated in Uluberia (189.9 mg g−1) was twice higher than those cultivated
genic reaction between reducing sugars and DNS reagents. The color inten- in Kharagpur (89.77 mg g−1). These results suggested that the difference
sity of the formed compound is determined by UV–Vis spectrophotometer in the external condition can lead to the difference in the phytochemical
and easy to convert into numerical values. The color intensity value of the contents in the same plants.

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

2.4. Reducing power of different plant extracts Resveratrol-3-O-glucoside with adjacent OH− groups on the aromatic
ring, demonstrating a high chelating power in the synthesis of nanoparti-
The difference in reducing power between plant extract may be due to cles (Nguyen et al., 2023). Quercetin is known to be a highly chelating com-
the specificity of each plant species, which is influenced by many natural pound that supports the formation and growth of crystals as well as the
factors such as climate, soil, water, and season. Different plant species stability of nanoparticles. Tambunan et al. (2017) pointed out that Ageratum
may not contain the same chemical composition, resulting in the fact that conyzoides exhibits predominantly quercetine content in the range of
the reducing power of plant extracts from different species can vary. More- 40.7–54.9 ppm with main compounds such as quercetin-3-O-glycoside,
over, phytochemicals from plant extract play a different role in the synthe- quercetin-3-O-glycoside, hyperoside, kaempferol-3-O-pentose, kaempferol-
sis of nanoparticles. Indeed, the extract from several plant parts such as 7-O-rhamnopyranoside, eupalestin, luteoline, quercetin-3-O-rutinoside,
berry fruits and guava leaves may contain phenolic acids, polyphenols, fla- luteolin-7-O-glucuronide, apigenin. Therefore, these plants may have higher
vonoids, vitamin C, etc., which exhibit a strong reducing power (Nguyen chelating power and lower reducing power than other plants.
et al., 2022a). Other plant species can contain high levels of active ingredi-
ents such as quercetine, daidzein, chlorogenic acid, and etc. are dominant, 2.5. Formation of plant-mediated ZnFe2O4 nanoparticles
which exhibit a strong chelating power.
For instance, Dittrichia viscosa is proved to have the presence of 18 phy- The precursor salts used for the synthesis of green ZnFe2O4 nanoparti-
tochemical compounds with 20.54 % of trimethylsilyl-meso-inositol as a cles or ZnFe2O4 based composite are mainly Fe(NO3)3, FeCl2, FeCl3, Zn
main compound with a good antioxidant capacity (Mssillou et al., 2022). (CH3CO2)2, and Zn(NO3)2 as shown in Fig. 1. Typically, Fe2+ or Fe3+
Other compounds such as 5(4H)-thebenidinone (16.80 %) and bis ions together with Zn2+ undergo complexation with the help of plant ex-
(methylthio)-4-(2-phenylethenyl) (9.76 %) are alkaloid compounds with tracts and calcination, then ZnFe2O4 nanoparticles are formed (Surendra
antioxidant and anti-free radical activity. As a result, this plant can supply et al., 2020b). Normally, the precursor/extract ratio (g/mL) was reported
many compounds with high reducing power for green synthesis of nanopar- to be 1:2, 1:3, and 1:10 (Fabiani et al., 2020; Fabiani et al., 2021;
ticles. At the same trend, Ibrahim et al. (2022) discovered that Rosmarinus Korotkova et al., 2019). It can be divided into two main periods of
officinalis contains high levels of phenolic diterpenes, e.g., rosmanol, ZnFe2O4 material synthesis, i.e., (i) complexation stage and (ii) calcination
carnosol, carnosic, and rosmadial acids and triterpenoids, e.g., betulinic, stage. Complexation stage is under reaction of precursor salt and plant ex-
oleanolic, and ursolic acids representing as the most abundant compound tract, which takes between 10 min and 120 min to complete. During this
(~50 %). Therefore, the authors suggested that this plant species might process, the interaction between the metal ions and the phytochemicals
offer a better reducing power. in the plant extract takes place. Biomolecules in the extract such as rutin,
By contrast, Cissus quadrangularis is found to contain high concentra- flavonoids, saponins, vitamins and proteins can act as reducing agents
tions of active ingredients such as quercetine, daidzein and trans- and complexing with metal ions (Rajeshkumar and Bharath, 2017). To be

Fig. 1. An illustration of synthesis procedure of ZnO-doped ZnFe2O4 by green bio-hydrothermal method with some steps; (i) Zn2+ and Fe3+ were dissolved with surfactant in
H2O, (ii) the guava leaf extract was added under stirring magnetically to obtain a brown precipitate, (iii) this solid was then transferred to Teflon-lined stainless autoclave at
180 °C for 12 h, (iv) the solid was calcined at high temperature to obtain ZnO-doped ZnFe2O4 nanocomposites.
Reprinted from reference Sahoo et al. (2021).

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

more specific, functional groups such as hydroxyl or carboxyl can perform Although a high proportion of resulting ZnFe2O4 materials are spheri-
complexation and chelating of metal ions, thereby increasing the stability cally morphological as statistical data obtained from Fig. S3, the diversity
and reducing the clustering of the resulting material. Indeed, used Ruta of their morphology has been reported as show in Table 1. The morpholog-
graveolens to extract rutin - a precursor flavonoid to synthesis ZnFe2O4 ical types of ZnFe2O4 materials can be attributed to the phytochemicals
nanoparticles. Accordingly, the adjacent hydroxyl groups (–OH) in rutin from the plant extracts. These biomolecules are instituted of functional
contribute to the formation of the octahedral complex as the metal ions- groups capable of binding and chelating with metal ions; and thereby, cre-
phytochemical. Therefore, the complexation process may be safe, fast, ating phytochemical-metal ion complex with different geometric shapes.
and efficient. After calcination, as-obtained ZnFe2O4 materials have different morphol-
After complexation, calcination is carried out to form nanoparticles for ogy. By contrast, the ZnFe2O4 nanoparticles synthesized by chemical
the final step of material synthesis. The calcination temperature for the syn- methods such as solution combustion method, co-precipitation method
thesis of ZnFe2O4 nanoparticles is usually around 450, 500, and up to using alkaline solution, hydrothermal technique using surfactant, etc. are
700 °C for 60–240 min as shown in Fig. S1 in the supplementary data doc- mostly nanospheres in shape. Indeed, Nguyen et al. (2022b) fabricated
ument (Fabiani et al., 2021; Surendra et al., 2020b). The process is consid- ZnFe2O4@ZnO nanocomposite using the solution combustion method
ered to be a step that consumes the most energy and time. To address this using urea as an additive fuel had a spherical shape. In another study,
obstacle, the thermal calcination of ZnFe2O4 process can also be supported Adnan et al. (2021) synthesized ZnFe2O4 material by hydrothermal
by microwave irradiation energy (900 W). For example, Suresh Kumar et al. method, forming almost spherical nanoparticles. As a result, the control
(2021) synthesized green ZnFe2O4 material using Citrus limon extract with of the shape of ZnFe2O4 materials in the presence of plant extract is of
the support of microwave irradiation. All the calcination process took great significant for the potential applications such as adsorption,
only 15 min, saving the time considerably. Therefore, it can be suggested photocatalysis and biomedicine.
that using the microwave-assisted method to shorten the heating time
and save energy, making the synthesis of nanomaterials can be industrially 3.2. Particles size
scaled up.
Various synthesis methods are applied to produce ZnFe2O4 nanoparti- The average particle size of green ZnFe2O4 nanoparticles can be usually
cles such as alkaline addition, no alkali addition, bio-hydrothermal, probe determined by physicochemical techniques such as X-ray diffraction, dy-
sonication, green co-precipitation and microwave-assisted combustion as namic light scattering, transmission electron microscopy, etc. Almost publi-
listed in Table 1. As a statistic dataset from the previous studies, Fig. S2 cations reported that ZnFe2O4 nanoparticles tend to reach strong
shows the diversity of synthesis methods of ZnFe2O4 nanoparticles from agglomeration as a result of the magnetic interaction between the nanopar-
plant extracts. Among them, the method without addition of alkaline solu- ticles. As shown in Table 1, the particle sizes of ZnFe2O4 nanoparticles and
tion is the best applied approach (45 %). This trend is more referable to syn- their nanocomposites are distributed in a wide range, but popularly
thesize ZnFe2O4 nanoparticles because the use of toxic chemicals is not <50 nm. Some of the controllable factors that can affect the nanoparticle
required, minimizing secondary pollution into the environment as well as size include extraction fluid, calcination temperature, precursor salt/ex-
the total production cost. Methods for total green synthesis should be ap- tract ratio. The calcination temperature is a major contributor to changing
plied to reach a critically safe and clean process. the nanoparticle size. It is thought that as the calcination temperature in-
creases, the crystals tend to cluster and increase in crystallinity, resulting
in increased size of the nanoparticles (Phromma et al., 2020). Indeed,
3. Properties of green ZnFe2O4 nanoparticles Matinise et al. (2018) pointed out that the particle size of ZnFe2O4 materials
increased from 7.5 to 17.5 nm when calcination temperatures from 500 to
3.1. Morphology 700 °C. In another study, Kiruthika et al. (2022b) synthesized ZnFe2O4
nanoparticles from Actinidia deliciosa extract with a calcination temperature
The morphology of green ZnFe2O4 materials can be characterized based of 700 °C. Accordingly, the obtained results revealed an average size of
on scanning or transmission electron microscopy analysis. Some of the nanoparticles at 40 nm. Mehdipour et al. (2021) indicated that ZnFe2O4 cal-
main morphologies of ZnFe2O4 nanoparticles are spherical, flake, sheet, cined at 500 °C had a smaller particle size (~9 nm) than that of the study
cubic, and spongy as shown in Fig. 2 (Kiruthika et al., 2022; Surendra conducted by Kiruthika et al. (2022b). Regarding the plant extracts, used
et al., 2020b; Suresh Kumar et al., 2021; Yang et al., 2022). These shapes Ruta graveolens extract as green precursor to synthesize ZnFe2O4 with a par-
of ZnFe2O4 from plant extract can be chiefly controlled by synthesis factors ticle size of 18–32 nm. Using the same plant extract, Amani et al. (2022)
such as precursor salt concentration, annealing and calcination time, source again produced ZnFe2O4 nanoparticles with a larger size of 20–30 nm. In
of synthetic materials and calcination temperature (Huang et al., 2019). addition, plants from the Citrus family also attracted much attention from
Among them, the calcination temperature is often considered as one of ZnFe2O4 synthesis studies. For example, Citrus sinensis was used together
the most important factors to the morphology of the ZnFe2O4 nanoparticles. with Fe(NO3)3 and Zn(NO3)2 to synthesize ZnFe2O4 with particle size of
It was found that nanoparticles tend to have diverse shapes such as flake, 30 nm (Krishnan et al., 2021). Suresh Kumar et al. (2021) showed that Cit-
sheet, cubic, spongy or corel at the low annealing temperature in a range rus limon fruit may contain many phytochemicals suitable for ZnFe2O4 syn-
of 400–500 °C (Table 1). However, the morphology of ZnFe2O4 tends to thesis, yielding a particle size of 25 nm. Compared with the above two
be mostly spherical once increasing the calcination temperature to 600 or Citrus species, Hafez Ghoran et al. (2020) indicated that ZnFe2O4 had the
700 °C. For example, Surendra et al. (2020a) synthesized ZnFe2O4 material smallest particle size with about 15 nm by using Citrus aurantium extract
from Jatropha curcas extract with a calcination temperature of 500 °C and for the synthesis. Small-sized nanoparticles can bring more benefits to ap-
formed flake shaped nanoparticles. In another study, Surendra et al. plications such as biomedical, adsorption, photocatalysis, etc. Therefore,
(2020b) again synthesized ZnFe2O4 using Azadirachta indica extract under above concerns are set out to control the factors affecting the particle size
the calcination at a temperature of 450 °C. The morphology of obtained depending on the purpose of the study.
ZnFe2O4 was spongy-shaped. Meanwhile, Amiri et al. (2020) found Plant extracts are a key factor to control the particle size of green
ZnFe2O4 material had the shape of coral dust at a synthesis temperature ZnFe2O4 nanoparticles. According to Table 1, the particle size of green
of 500 °C. As for at 700 °C, Matinise et al. (2018) observed spherical ZnFe2O4 nanoparticles synthesized using plant extracts are mainly in the
ZnFe2O4 nanoparticles via the scanning electron spectroscopy images. At range from 5 to 50 nm. The histogram in Fig. S4 illustrates the particle
the same trend, Balasubramanian and Murali (2020) performed the synthe- size distribution of plant-mediated synthesized ZnFe2O4 nanoparticles
sis of ZnFe2O4 nanoparticles at temperatures 400–600 °C. The resulting ma- based on statistic data from the previous studies, finding an average particle
terials were spherically morphological, but tended to cluster with size of 30 nm. With such outcome, the particle size of green ZnFe2O4 nano-
increasing temperature. particles seems to be somewhat smaller than that of chemically synthesized

5
Table 1
Green synthesis of ZnFe2O4 nanoparticles using plant extracts and several physicochemical properties (particle size, morphology, bandgap, surface chemistry, magnetization) of green ZnFe2O4 nanoparticles.
N.T.T. Nguyen et al.

Materials Plant Plant Synthesis method Precursor metal Precursor/extract Calcination Calcination Particles Morphology Band gap Surface chemistry Magnetization References
species tissues ratio (g/mL) temperature time (h) size (eV) (emu/g)
(°C) (nm)

ZnFe2O4 Moringa oleifera Leaves Non-alkaline Fe(NO3)3·9H2O 1:10 (1 h 500–700 2 5–25 Spherical, Not reported Hydroxyl, phenolic Not reported (Matinise et al., 2018)
supplement Zn(NO3)2·6H2O complexation) irregular acids
ZnFe2O4 Jatropha curcas Seeds Non-alkaline Fe(NO3)3·9H2O 1:1 500 Not 5–20 Flake 1.81 Hydroxyl Not reported (Surendra et al., 2020a)
supplement Zn(NO3)2·6H2O reported
ZnFe2O4 Azadirachta indica Leaves Probe sonication Fe(NO3)3·9H2O Not reported 450 3 <100 Spongy 1.8 Hydroxyl, Not reported (Surendra et al., 2020b)
Zn(NO3)2·6H2O carboxylate
ZnFe2O4 Actinidia deliciosa Fruits Non-alkaline Fe(NO3)3·9H2O Not reported 700 4 30–40 Cubic Not reported Hydroxyl, carbonyl, Not reported (Kiruthika et al., 2022)
supplement Zn(NO3)2·6H2O alkane
2+
ZnFe2O4@Cu Aegle marmelos Fruits One-pot green Fe(NO3)3·9H2O Not reported 600 Not 20–25 Spongy Not reported Hydroxyl, carbonyl, Not reported (Surendra et al., 2021)
Zn(NO3)2·6H2O reported alkane
ZnFe2O4 Boswellia carteri Fruits Alkaline FeCl3·6H2O 1:1 (1 h 80 4 20.54 Spherical, Not reported Not reported Not reported (Imraish et al., 2021b)
supplement Zn(CH3CO2) complexation) irregular
2·2H2O
ZnFe2O4 Nyctanthes arbor-tristis Flowers Non-alkaline Fe(NO3)3·9H2O 2:1 400–600 Not 4–12 Spherical 2.08–2.17 Not reported Not reported (Balasubramanian and
supplement Zn(NO3)2·6H2O reported Murali, 2020)
ZnFe2O4 Tristaniopsis Leaves Non-alkaline Fe(NO3)3·9H2O 1:10 (1 h 700 2 9 Not Not reported Hydroxyl, phenol Not reported (Fabiani et al., 2020)
merguensis supplement Zn(NO3)2·6H2O complexation) reported
ZnFe2O4 Antidesma bunius Flowers Alkaline Fe(NO3)3·9H2O 1:2 700 Not Not Not Not reported Hydroxyl, aldehyde Not reported (Fabiani et al., 2021)
supplement Zn(NO3)2·6H2O reported reported reported
ZnFe2O4 Citrus aurantium Flowers Green FeCl2·4H2O Not reported 80 Not 9–20 Spherical Not reported Hydroxyl, 30 (Hafez Ghoran et al.,
co-precipitation FeCl3·6H2O reported aromatic, etheric, 2020)

6
Zn(CH3CO2) alkane
2·2H2O
ZnFe2O4 Ruta graveolens Leaves Non-alkaline FeCl2·4H2O 1:10 55 48 20–30 Spherical 1.93 Hydroxyl, alkane, 5.9 (Amani et al., 2022)
supplement FeCl3·6H2O amine
Zn(CH3CO2)
2·2H2O
ZnFe2O4 Citrus limon Fruits Microwave-assisted Fe(NO3)3·9H2O 1:1 Not reported 15 25 Spherical, Not reported Hydroxyl 4.23 (Suresh Kumar et al.,
combustion Zn(NO3)2·6H2O cubic 2021)
ZnFe2O4/reduced Citrus sinensis Peels Bio- hydrothermal Fe(NO3)3·9H2O 2:1 400 5 30 Spherical, 1.53 Hydroxyl, carbonyl, Not reported (Krishnan et al., 2021)
graphene oxide Zn(NO3)2·6H2O irregular carboxyl, amine,
carboxylic acid
ZnFe2O4@alginic acid Brown algae (alginic Not Alkaline Fe(NO3)3·9H2O Not reported 80 2 70 Spherical Not reported Hydroxyl, alginic 17.06 (Maleki et al., 2019)
acid) reported supplement Zn(NO3)2·6H2O acid, carboxylate
ZnFe2O4-imatinib- Teucrium polium Flower Non-alkaline Fe(NO3)3·9H2O Not reported 500 1 45 Spherical, Not reported Hydroxyl Not reported (Amiri et al., 2020)
liposome supplement Zn(NO3)2·6H2O coral
ZnO- ZnFe2O4 Psidium guajava Leaves Bio- hydrothermal Fe(NO3)3·9H2O Not reported 500 Not 10–20 Spherical Not reported Not reported Not reported (Sahoo et al., 2021)
Zn(NO3)2·6H2O reported
ZnFe2O4-CeO2/BRGO Ocimum tenuiflorum Leaves Non-alkaline Fe(NO3)3·9H2O Not reported Not reported Not 6–20 Spherical, 1.9–2.8 Hydroxyl, Not reported (Barik et al., 2021)
Direct Z-Scheme supplement Zn(NO3)2·6H2O reported flake carboxylate
ZnFe2O4@Ag Scenedesmus obliquus Leaves Non-alkaline Fe(NO3)3·9H2O Not reported Not reported Not <50 Spherical, Not reported Hydroxyl, Not reported (Jodati et al., 2023)
supplement Zn(NO3)2·6H2O reported irregular carboxylate, zinc
ferrite
ZnFe2O4-reduced Emblica officinalis Fruits Alkaline Fe(NO3)3·9H2O Not reported 200 Not 7–9 Flake 1.9–2.3 Hydroxyl, zinc Not reported (Amrutha et al., 2020)
graphene oxide supplement Zn(NO3)2·6H2O reported ferrite, graphene
oxide
ZnFe2O4@SiO2 Tragacanth gum Gum Alkaline Fe(NO3)3·9H2O Not reported 600 1 50 Rod, cubic Not reported Hydroxyl, carbonyl, 19.325 (Etemadinia et al., 2019)
supplement Zn(NO3)2·6H2O alkane 15.363
(composites)
Science of the Total Environment 872 (2023) 162212
N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

Fig. 2. Morphology SEM image of ZnFe2O4 nanoparticles from plant extract, (a) flake (from Jatropha curcas extract) (Surendra et al., 2020a), (b) spongy (from Azadirachta
indica extract) (Surendra et al., 2020b), (c) coral (from Teucrium polium extract) (Amiri et al., 2020), (d) TEM image of spherical-ZnFe2O4 nanoparticles (from Nyctanthes arbor-
tristis extract) (Balasubramanian and Murali, 2020).

ones. For example, Tomar and Jeevanandam (2022) exhibited that of ZnFe2O4 nanoparticles can increase the stability, high biocompatibility
ZnFe2O4 nanoparticles produced from the chemical synthesis via the ther- of this material, exerting better adsorption and photocatalytic performance
mal decomposition obtained a particle size of 42.8–57.1 nm. Dimri et al. (Virkutyte and Varma, 2011). Similar to morphology and particle size, the
(2021) have successfully synthesized ZnFe2O4 nanoparticles with an aver- surface chemistry of plant extract-mediated ZnFe2O4 nanoparticles may de-
age particle size of 50 nm through the citrate combustion method. In an- pend on the calcination temperature during the synthesis. During this calci-
other study, Zhang et al. (2019) reported that the particle size of ZnFe2O4 nation process, most of organic compounds are decomposed into volatiles
fabricated by the solvothermal method was very large, at 270 nm. It is con- or simple products, e.g., CO2, N2 and H2O (Tran et al., 2022a). Therefore,
ceivable that the phytochemicals from plant extract probably exert the for- if the calcination temperature is too high, the amount of remaining phyto-
mation of ZnFe2O4 in many ways. Specifically, they act as a chelating agent chemicals or surface chemistry is very tiny. Indeed, Fabiani et al. (2020)
to complex with metal ions, and hence, preventing the clustering of nano- showed that the calcination temperature at 700 °C to produce ZnFe2O4 par-
particles together during crystal nucleation. Moreover, phytochemicals per- ticles from Tristaniopsis merguensis extract can disrupt functional groups
form a capping function by coating the entire surface of the nanoparticle, such as carboxyl. At a calcination temperature of 500 °C, Krishnan et al.
enhancing functionality of green ZnFe2O4 nanoparticles. As such, the pres- (2021) showed a series of functionalization of ZnFe2O4 synthesized from
ence of phytochemicals in plant extracts takes main responsibility for the Citrus sinensis extracts such as hydroxyl, carbonyl, carboxyl, amine, carbox-
synthesis of small-sized ZnFe2O4 nanoparticles. ylic acid. Meanwhile, at calcination temperature of 900 °C, Kombaiah et al.
(2017) reported that plant extract-based ZnFe2O4 biosynthesized from
3.3. Surface chemistry Opuntia dilenii haw extract had a less diverse surface chemistry
(e.g., hydroxyl, carboxyl) than that of studied by Krishnan et al. (2021). Sur-
Several physicochemical techniques, i.e., Fourier transform infrared face functionalization can significantly increase many kinds of main inter-
spectroscopy, X-ray photoelectron spectroscopy or quantification by actions such as electrostatic attraction, hydrogen bonding, and π–π
Boehm titration are used to determine the surface chemistry of green interaction suitable for adsorption or biomedicine applications (Suresh
ZnFe2O4 nanomaterials (N.T.T Nguyen et al., 2022a). The surface chemis- et al., 2015). Therefore, much attention to the factors affecting the change
try of ZnFe2O4 nanoparticles is considered based on surface functional of surface chemistry should be paid.
groups, which play a key role in catalytic activities or adsorption perfor- It can be understood that nanoparticles from plant extracts have a coat-
mance. ZnFe2O4 nanoparticles synthesized using green synthesis method ing of phytochemicals on their surface. Phytochemicals include many func-
often exhibit a diverse surface chemistry mainly deriving from phytochem- tional compounds such as carbonyl, hydroxyl, methyl, amino, phosphate,
icals in plant extracts. Specifically, the main surface chemistry of ZnFe2O4 etc. Therefore, the surface chemistry of plant-mediated nanoparticles is
nanoparticles include hydroxyl, carbonyl, carboxylate, alkane, amine, and somewhat more diverse than those synthesized by chemical methods. Ac-
amide as summarized in Table 1. It is suggested that the functionalization cording to Table 1, the surface chemistry of green ZnFe2O4 nanomaterials

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

from plant extracts is attached by hydroxyl, phenolic acids, carboxylate, of the material and achieving a sufficient magnetism value for many prom-
carbonyl, carboxylic acid, amine, etc. Meanwhile, the surface chemistry of ising applications.
chemically synthesized ZnFe2O4 nanomaterials seems to be poor in func-
tional groups. For example, Manohar et al. (2021) reported that the surface 3.5. Optical bandgap
chemistry of ZnFe2O4 nanoparticles from chemical synthesis owns hydroxyl
and carbonyl only. At the same trend, Navidpour and Fakhrzad (2022) The valence band energy of a semiconductor is defined as a disparity be-
pointed out that the surface chemicals of ZnFe2O4 nanoparticles synthe- tween the valence band and the conduction band, i.e., the minimum photon
sized via the high-energy ball milling method include hydroxyl only de- energy required to excite an electron from the valence band to the conduc-
tected by FT-IR spectra. The variety of surface chemistry of nanoparticles tion band. This is an important value evaluating the photocatalytic ability
from plant extracts compared to chemical/physical methods could help of ZnFe2O4 in absorbing visible light or UV in photocatalytic application.
them improve their performance in different applications. Therefore, the As shown in Table 1, ZnFe2O4 nanoparticles have a band gap of ~1.8 eV,
role of phytochemicals is increasingly emphasized through the study of sur- the doped ZnFe2O4 nanoparticles have a higher band gap (1.9–2.8 eV). It
face chemistry. may be due to the addition of materials with large band gap increasing
the band gap of nanocomposites, which improve the electric properties of
3.4. Magnetism nanocomposites. Indeed, Yang et al. (2022) reported that ZnFe2O4 nano-
particles coated carbon shells with a very narrow band gap of 1.78 eV. In
Magnetic properties are considered as one of the important features of another study, Amani et al. (2022) conducted the synthesis of ZnFe2O4
ferromagnetic materials as a result of aligned interactions of unpaired elec- nanoparticles in the presence of Ruta graveolens. Accordingly, the band
trons (d and f electrons). Magnetic nanoparticles have advantages for many gap was obtained at 1.93 eV. When doping with CeO2, Barik et al. (2021)
applications such as biomedical, especially in the delivery of cancer drugs. realized that the band gap of ZnFe2O4–CeO2 increased from 1.9 to 2.8 eV.
Drug-delivering magnetic nanoparticles can precisely locate tumor sites for At the same trend, Amrutha et al. (2020) found that ZnFe2O4 synthesized
drug delivery without affecting other non-target organs (N.T.T. Nguyen from Emblica officinalis had a band gap of 1.9 eV. After doping with reduced
et al., 2022b). Moreover, magnetic nanoparticles can be easily separable graphene oxide, however, the band gap value of the nanocomposites raised
from the solution after adsorption and catalytic processes (Gao, 2019). to 2.3 eV. The authors explained that the band gap reduction results from
The magnetic value of ZnFe2O4 could be examined by the Vibrating Sample multiple-band effects on the valence and conduction bands of ZnFe2O4–
Magnetometer (VSM) analysis. The chemical synthesis method of ZnFe2O4 RGO. In semiconductors, the interaction between the free carriers and the
nanoparticles is usually highly magnetic, about 20–60 emu/g (Sripriya impurities occurs, i.e., the free carrier ion interaction leads to a hard shift
et al., 2018). For example, ZnFe2O4 nanoparticles were synthesized by gel of the band gap. To sum up, the suitable optical band gap of the material
combustion exhibiting high saturation magnetism, 44.60 emu/g plays an important role in enhancing the photocatalytic activity of the ma-
(Chavarriaga et al., 2020). also even synthesized ZnFe2O4 nanomaterials terial in the presence of visible or UV light regions.
by solvothermal method without the assistance of a template or surfactant, The band gap values of plant-mediated ZnFe2O4 nanoparticles generally
giving a saturation magnetism of 58 and 66 emu/g. Based on Table 1, plant tend to be lower than those of ZnFe2O4 nanoparticles through chemical
extract-based ZnFe2O4 from the green synthesis method have the magnetic methods. Indeed, Reddy et al. (2021) fabricated ZnFe2O4 nanoparticles
saturation ranging from 0.05 to 30 emu/g (commonly <20 emu/g), lower via conventional synthesis with a band gap of 2.12 eV. Compared with
than that of the chemical synthesis method. This could explain that the green synthesis, Krishnan et al. (2021) showed that a lower band gap
plant extract in the synthesis process can increase the decoration on the sur- (1.53 eV) value of Zn nanoparticles from Citrus sinensis peel extract. At the
face of ZnFe2O4 nanomaterials, reducing their magnetism. same trend, Amani et al. (2022) pointed out that the green synthesis of
The magnetism of ZnFe2O4 nanomaterials can be affected by factors ZnFe2O4 from Ruta graveolens extract exhibited a very low band gap of
during the synthesis of the material, including the calcination temperature. 1.93 eV. The difference in band gap between plant-mediated and chemi-
Increasing the heating temperature of materials increases their magnetic cally synthesized nanoparticles can be explained that the phytochemicals
saturation of ZnFe2O4 nanoparticles. For example, Etemadinia et al. on the surface of nanomaterials may prevent the recombination of electrons
(2019) reported that the calcination of ZnFe2O4 nanoparticles at 600 °C when moving from CB to VB region, resulting in band gap change of the
in the presence of Tragacanth gum extract. Accordingly, the magnetic satu- nanomaterials. In addition, some phytochemicals containing nonmetallic
ration of this nanomaterial was obtained 19.325 emu/g, which was higher elements such as O, N, and P can be doped into the structure of ZnFe2O4
than that (15.363 emu/g) of ZnFe2O4@SiO2. Meanwhile, Mehdipour et al. nanoparticles during the synthesis, resulting in changing the band gap of
(2021) synthesized ZnFe2O4 by green method under the calcination at ZnFe2O4.
500 °C, obtaining a magnetic saturation at 11.833 emu/g, lower than that
of study by Etemadinia et al. (2019). The increase in saturation magnetiza- 4. Applications of green ZnFe2O4 nanoparticles
tion with increasing calcination temperature can be attributed to the in-
crease in the coercivity of the individual particles, causing the 4.1. Photocatalytic performance of green ZnFe2O4 nanoparticles
nanoparticles to solidify and agglomerate (Senthil et al., 2018). As a result,
magnetic properties can lead to an increase in the average particle size of Recently, photocatalysis is an important strategy to solve the energy cri-
ZnFe2O4. Indeed, Malakootian et al. (2019) synthesized ZnFe2O4 nanopar- sis and environmental problems. This application involves the successful
ticles coated carboxymethyl cellulose carbohydrates with a saturation mag- use of photon energy (e.g., sunlight, visible light, or ultraviolet light) to gen-
netism value of 11.96 emu/g and the particle size of 25 nm. Maleki et al. erate free radicals that decompose pollutants. The proposed mechanism of
(2019) produced ZnFe2O4 from brown algal extract with a saturation mag- ZnFe2O4 nanoparticles has been investigated by many studies, especially to
netism of 17.06 emu/g. Particles size of ZnFe2O4 (70 nm) were significantly determine the role of the material band gap and the type of free radical gen-
larger than that of the study by Malakootian et al. (2019). From these obser- erated (Das et al., 2021; Huang et al., 2022). Firstly, under light irradiation,
vations, a proper route can be suggested to synthesize green ZnFe2O4 mate- ZnFe2O4 nanoparticles absorb light and excite the electrons moving from
rials with high magnetic, stable and suitable for the target application. the valence band (VB) to the conduction band (CB) (Hou et al., 2013).
However, if the magnetism of material is too high, it increases the agglom- Therefore, they leave the hole at the VB of the ZnFe2O4 material. If the ma-
eration and particles size of the material. This barrier can lead to a decrease terials are composites, the component material with the lower band gap
in surface area and active sites; thereby, reduce the effectiveness of plant- will be excited first and tend to donate electrons at CB to the other compo-
mediated ZnFe2O4 nanoparticles for adsorption and photocatalytic perfor- nent material. This helps prevent the possibility of recombination of elec-
mance. It is highlighted that the role of plant extracts in synthesizing trons and holes (L.T.T Nguyen et al., 2022). This confirms the role of
ZnFe2O4 nanoparticles can be confirmed by reducing the agglomeration ZnFe2O4 doping that has a positive contribution to the photocatalytic

8
N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

activity of the material. The electrons and holes can then combine with H2O prevent the recombination of the electron-hole pair, reducing band gap,
or O2 from the outside to create a variety of free radicals (e.g., •OH−, •O−
2 , and generating more reactive oxygen species. As a result, the photocatalytic
H2O2, etc.) that degrade the pollutants in aqueous (U.T.P Nguyen et al., degradation of pollutants can be more effective. Indeed, Nguyen et al.
2022). (2023) carried out a survey to compare the photocatalytic activity of
Factors affecting the photocatalytic activity of ZnFe2O4 can include the ZnFe2O4@ZnO nanoparticles synthesized by biological and chemical
band gap of the material and the irradiation source. These two factors have methods. Accordingly, plant-mediated ZnFe2O4@ZnO nanoparticles exhib-
a correlation relationship, specifically if the band gap of the material is ited a lower band gap of 1.98 eV, compared with 2.89 eV of chemically syn-
large, they exert a good photocatalytic effect with the irradiation source thesized ZnFe2O4@ZnO. As expected, this plant-mediated catalyst achieved
being ultraviolet light. In contrast, materials with small band gap are a higher dye degradability (94.9 %) than the material synthesized chemi-
more suitable for visible light irradiation source. Indeed, Surendra et al. cally (79.6 %).
(2020a, 2020b) synthesized successfully ZnFe2O4 using Jatropha curcas ex- Phytochemicals from plant extracts contribute to not only improving
tract with band gap of 1.81 eV, achieving 98 % MG degradation under UV the photocatalytic efficiency of ZnFe2O4 nanomaterials but also enhancing
irradiation (Table 2). At the lower band gap 1.53 eV, Krishnan et al. (2021) their reusability in water treatment applications. This advantage may be at-
reported that ZnFe2O4/reduced graphene oxide nanoparticles from orange tributed to the presence of functional groups derived from phytochemicals
peel extract were suitable for visible light irradiation as evidenced by decorating on the surface of the nanoparticles, preserving the metal active
92.4 % MB degradation efficiency. In addition, materials from plant sites from leaking after each reuse. Indeed, Balasubramanian and Murali
extract-based biosynthesis methods were also compared with chemical syn- (2020) synthesized ZnFe2O4 nanoparticles using Nyctanthes arbor-tristis
thesis methods. Specifically, Surendra et al. (2020b) synthesized ZnFe2O4 flower extract for photocatalytic activity. Accordingly, the degradation effi-
material from neem leaf extract and from chemical synthesis for photocat- ciency for RhB was obtained at 100 % in the first use and still maintained a
alytic degradation of 3 dyes AR-88, AO-8, MG. According to the results, stable structure and activity after 5th reuse, at 97 %. Meanwhile, Miao et al.
ZnFe2O4 from chemical synthesis achieved 98 %, which was not signifi- (2022) reported that ZnFe2O4/CdS nanocomposites synthesized by
cantly higher than that of biological synthesis (88 %). These results also solvothermal method displayed the maximum degradation efficiency of
confirmed the role of plant extract in the synthesis of catalyst materials. 93.2 % for RhB, and only 84.96 % after 5th reuse. Xie et al. (2013) prepared
In another study, the comparison between the commercial catalyst material ZnFe2O4 nanoparticles by the chemical coprecipitation combined with
and the biosynthetic ZnFe2O4 material from the Emblica officinalis and Aloe high-temperature sintering method for MB photocatalytic degradation.
vera extract was carried out for clarification (Amrutha et al., 2020). Accord- The authors observed a lower recyclability with 4 cycles of these chemically
ingly, the photocatalytic efficiency of commercial P25 for LR dye degrada- synthesized nanoparticles. The photocatalytic degradation rate was found
tion reached 84 % while that of the biological ZnFe2O4/reduced graphene at about 70 % for the final cycle. To some extent, phytochemicals from
oxide material is 97 %. This highlights the photocatalytic efficiency of plant extracts may improve the photocatalytic performance and recyclabil-
ZnFe2O4 materials synthesized from plant extracts, they can exist many sur- ity of plant-mediated ZnFe2O4 nanoparticles compared with the chemically
face chemistry on the material surface and support the photocatalysis pro- synthesized ones.
cess. In particular, Balasubramanian and Murali (2020) also proved that The mechanism of photocatalytic degradation by plant-mediated
ZnFe2O4 biomaterial has excellent reusability with the 5th reuse still ZnFe2O4 nanoparticles can be studied by examining the generation of frag-
reaching 97 %. In addition to photocatalysts for dye degradation, ments. For example, by using gas chromatography–mass spectrometry
ZnFe2O4 nanoparticles also confirm its catalytic ability in the application (GC–MS) analysis, fragments of levofloxacin antibiotic at degradation
of biodegradation of antibiotics and pesticides. Indeed, Malakootian et al. stages can be elucidated as shown in Fig. 3. As a result, mechanism of pho-
(2019) produced ZnFe2O4 nanoparticles to decompose 87 % of ciprofloxa- tocatalytic degradation can be proposed through redox reaction to convert
cin in 120 mins under UV irradiation. In another study, Barik et al. (2021) levofloxacin antibiotic into harmless degradation products such as CO2 and
reported that ZnFe2O4-CeO2/BRGO from Ocimum tenuiflorum extract de- H2O. To sum up, green ZnFe2O4 material is one of the most effective
graded over 99 % of chlorpyrifos pesticides in aqueous under visible light photocatalysts for removal of pollutants. To enhance the degradation effi-
irradiation. ciency of pollutants, it is necessary to design new ZnFe2O4 based
The phytochemicals from the plant extracts significantly affect the photocatalysts by doping with other semiconductor materials like ZnO,
structure of green ZnFe2O4 nanoparticles as well as their photocatalytic ef- TiO2, CeO2, etc. This key development makes green ZnFe2O4 based
ficiency in the removal of pollutants. Considering the surface of ZnFe2O4 photocatalysts more preferable for removal of different pollutants.
nanoparticles, the functionality by phytochemicals on the surface can lead
to enhanced photocatalytic activity (Abdullah et al., 2021). For instance, 4.2. Adsorption performance of green ZnFe2O4
Muthuvel et al. (2020) showed that nanoparticles synthesized by chemical
method have many oxygen vacancies, leading to fast electron-hole recom- Adsorption is one of the most effective physical methods used for pollut-
bination; thereby, reducing the photocatalytic activity for the catalyst. By ant removal in aquatic environments (Ighalo et al., 2022). The main possi-
contrast, the phytochemicals present on the surface of the catalyst can ble mechanism in this method is the interactions between the contaminant

Table 2
Photocatalytic performance of green ZnFe2O4 nanoparticles for removal of pollutants.
Materials Reducing agent Source light Application References

ZnFe2O4-CMC Carboxymethyl cellulose UV Degradation of 87 % ciprofloxacin for 120 min (Malakootian et al., 2019)
carbohydrate
ZnFe2O4/reduced graphene Orange peel Visible light Degradation of 92.4 % MB for 120 min (Krishnan et al., 2021)
oxide
ZnFe2O4 Jatropha (plant) UV Degradation of 98 % MG for 180 min (Surendra et al., 2020a,
2020b)
ZnFe2O4 Neem extract UV Degradation of dyes, e.g., AR-88, AO-8, MG (88–98 %) for 180 min (Surendra et al., 2020b)
ZnFe2O4:Cu2+ Aegle marmelos UV–visible light Degradation of 94 % RhB (Surendra et al., 2021)
ZnFe2O4 Nyctanthes arbor-tristis Solar light Degradation of 100 % RhB for 30 min, still obtained 97 % at 5th recycle (Balasubramanian and
flower illumination Murali, 2020)
ZnFe2O4-CeO2/BRGO Ocimum tenuiflorum Visible light Degradation of 99 % chlorpyrifos (pesticides) for time: 60 min; (Barik et al., 2021)
Direct Z-Scheme degradation of 99 % RhB for 40 min
ZnFe2O4 Cratoxylum glaucum UV Degradation of 16.42 % RhB for 180 min (Putri et al., 2021)

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

Fig. 3. a) Fragments of levofloxacin (LVFX) antibiotic found under photocatalytic degradation of ZnFe2O4@Ag2CO3 nanoparticles, b) mechanism of photocatalytic
degradation of levofloxacin over ZnFe2O4@Ag2CO3 catalyst.
Reprinted from the reference Li et al. (2020).

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

molecule and the material surface. Many interactions, such as electrostatic achieved 73 % at 4th reuse. With high performance in terms of stability, re-
interaction, hydrophobic effect, π–π bond, hydrogen bond, ion exchange, usability and removal efficiency, bio-mediated ZnFe2O4 nanoparticles can
and Van der Waals force, have been reported to be possibly involved in be an ideal adsorbent for removal of pollutants in aqueous environment.
the adsorption of pollutants on ZnFe2O4 nanoparticles as shown in Fig. 4 In another study, Sahoo et al. (2021) synthesized ZnO and ZnO-ZnFe2O4
(Zhang and Camarena, 2020). The green ZnFe2O4 nanoparticles can fulfill nanoparticles by green bio-hydrothermal method in the presence of Psidium
the requirements for a good adsorbent because they have many outstanding guajava extract. According to the obtained results, the dye removal efficien-
properties in terms of surface, stability and environmentally friendly syn- cies of ZnO were 64 % for Congo red and 58 % for methylene blue, while
thesis. In particular, ZnFe2O4 is highly magnetic, helping better recovery those of ZnO-ZnFe2O4 nanocomposites were 96 % for Congo red and
after use. These features exert ZnFe2O4 to develop industrial scale with 90 % for methylene blue. The adsorption capacities of plant-mediated
higher treatment efficiency. ZnO-ZnFe2O4 nanoparticles were calculated at 90.35–120 mg g−1, com-
Plant extract-mediated ZnFe2O4 nanoparticles can be highly effective in pared with 42.12–70.12 mg g−1 of plant-mediated ZnO nanoparticles.
the adsorptive removal of toxic dyes. Specifically, the biomolecules remain- This outcome confirmed the effectiveness of the material after doping of
ing on the surface of the ZnFe2O4 nanoparticles can increase active sites to ZnFe2O4, possibly because the surface area of the nanocomposites
attract pollutant molecules. The existence of functional groups on the sur- (47.34 m2/g) was larger than that of origin ZnO nanoparticles (32.12 m2/
face can also enhance the bonding between the ZnFe2O4 and the dye mole- g). To sum up, the modification of plant-mediated ZnFe2O4 nanoparticles
cules such as hydrogen bonds, hydrophobic interaction, electrostatic should be considered to improve the adsorption performance.
interactions, etc. For instance, Dehghan et al. (2019) conducted an experi-
ment to study the malachite green dye adsorption by ZnFe2O4 nanoparti- 4.3. Electrochemical applications
cles chemically synthesized via the hydrothermal method as shown in
Table S2. According to the results obtained, the maximum adsorption ca- Currently, a number of nanomaterials have been used as a sensing appli-
pacity of nanomaterials was found at 116.2 mg g−1. Meanwhile, U.T.P. cation in various fields such as gas sensing (leakage sensing and preventing
Nguyen et al. (2022) showed the potential of ZnFe2O4 nanoparticles syn- accidents that can occur when it leaks accidentally or by mistake)
thesized using Chrysanthemum spp. flower extract for adsorption of this or- (Kiranakumar et al., 2022), chemical sensor (Umar et al., 2020). In addi-
ganic dye. In this work, ZnFe2O4 demonstrated a higher adsorbtion tion, zinc ferrite materials also show outstanding potential in electrochem-
capacity of 120 mg g−1 than that of study by Dehghan et al. (2019). ical sensors, helping to support detection applications. To test their
Etemadinia et al. (2019) used tragacanth gum in combination with usability in electrochemical applications, the electrochemical performance
ZnFe2O4@SiO2 material to remove methylene blue dye. Under optimal of ZnFe2O4 materials is usually investigated by cyclic voltammetry (CV)
conditions pH 8, contact time 60 min, initial concentration 60 mg/L and ab- and electrochemical impedance spectroscopy (EIS) (Alsulami et al.,
sorbed dose 0.2 g/L, maximum adsorption capacity is 109.37 mg g−1. 2022). In addition, lithium ion battery production technology is considered
Zhang and Camarena (2020) showed that ZnFe2O4 nanoparticles can be as an excellent energy storage and power supply device (Tomaszewska
synthesized with the assistance of yeast through a simple one-pot sonica- et al., 2019). The ZnFe2O4 material is known to act as the anode in Li-ion
tion process. Accordingly, the materials exhibited a maximum Congo red batteries due to its excellent electrochemical properties such as good cy-
adsorbtion capacity of 108.3 mg g−1. More interestingly, highly magnetic cling performance, high specific capacity, good rate capability (Won
ZnFe2O4 showed an excellent recyclability with at least 4 reuses and et al., 2014). From these interesting findings, ZnFe2O4 nanoparticles have

Fig. 4. Several interactions, such as electrostatic interaction and hydrogen bond involving in the adsorption of pollutants on ZnFe2O4 nanoparticles.
Reprinted from reference Sahoo et al. (2021).

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

become the subject of maximum potential exploitation in electrochemical has a lower charge transfer resistance because the presence of Cu2+ accel-
applications. erates the surface charge transfer.
Matinise et al. (2018) have studied the synthesis of ZnFe2O4 materials
from Moringa oleifera extracts and examined their electrochemical proper- 4.4. Biomedical applications
ties. Accordingly, the time constant and exchange current of ZnFe2O4 nano-
materials from EIS analysis were calculated and found to be In recent time, ferrite materials with transition metal sites including Zn,
5.2001 × 10−4 s/rad and 6.59432 × 10−4 A, respectively. Based on the Co, Ni, Fe, Mn, and Mg have been extensively studied for possible biomed-
electrochemical results, the authors confirmed that the ZnFe2O4 electrode ical applications. Among ferrites, the biomedical applications of ZnFe2O4
from plant extract exhibits good potential response and it becomes a prom- nanoparticles are preferred due to the biocompatibility of Zn2+ ions with
ising electrode for electrochemical applications. Indeed, Kiruthika et al. the tissues of human body (Hoque et al., 2016). Thereby, ZnFe2O4 nanopar-
(2022) shown that ZnFe2O4 synthesized from Actinidia deliciosa fruit extract ticles have been used as antibacterial, antifungal, anti-cancer, drug delivery
could be the anode for Li-ion batteries. The positive results obtained from and disease diagnosis agents. For disease diagnosis, ZnFe2O4 shows a tre-
the CV plot show a sharp and reversible redox pair due to the formation mendous potential of enhanced magnetic resonance imaging (MRI) for
of the ZnLi alloy, which stabilizes the anode. This achievement has high- early detection of lesions or tumors in the body (Gupta et al., 2014).
lighted the potential to replace toxic chemical materials of biological The plant-mediated ZnFe2O4 nanoparticles are also applied in anti-
ZnFe2O4 in electrochemical applications. In addition, the electrochemical inflammatory cells by inhibiting proinflammatory mediators. Imraish
ability of ZnFe2O4 nanoparticles can also be applied to sensing drugs such et al. (2021a) synthesized ZnFe2O4 material in the presence of Boswellia
as Paracetamol, Dolo-650 and some drugs that stimulate the uterus to carteri to anti-inflammation resin extract. In this study, biological ZnFe2O4
avoid abuse such as Mifepristone and Misoprostol. Specifically, Surendra nanoparticles exhibited excellent anti-inflammatory activity by inhibiting
et al. (2020a, 2020b) used ZnFe2O4 electrode prepared from Jatropha ex- the mRNA expressions of IL-1b, IL-6 and TNF-α proteins. It is expected
tract with platinum (opposite electrode) in 0.1 M KCl electrolyte with a pe- that ZnFe2O4 nanoparticles can be one of the promising candidates for
riod of −1.24 V to 0.4 V at a scan rate of 10–50 mV/s to detect different many biomedical applications.
drugs. According to the results, the capacitance values of ZnFe2O4 electrode The support of phytochemicals during the bio-mediated synthesis could
was observed for Dolo 650, Paracetamol, and Mifepristone – Misoprostol enhance the biomedical performance of ZnFe2O4 nanoparticles. The
sensor chemicals were 208, 269, and 91 Ω respectively at scan rate of phytochemicals coating on the surface of nanomaterials can increase the
40 mV as shown in Fig. 5 Similarly, Surendra et al. (2021) synthesized biocompatibility and biostability, penetrating the cell membrane of micro-
ZnFe2O4-Cu2+ material from Aegle marmelos extract for electrochemical organisms easier, and thus, having higher efficiency than nanoparticles syn-
sensing application. Accordingly, the arc radius of the ZnFe2O4-Cu2+ nano- thesized without plant extracts as shown in Table S2. For example, Zhang
particles for Mifepristone – Misoprostol is 380 Ω higher than that of study et al. (2022) synthesized the ZnFe2O4 nanoparticles through a surfactant-
by Surendra et al. (2020a, 2020b). This shows that the doped material assisted hydrothermal technique for antibacterial applications. In this

Fig. 5. CV plots for prepared ZnFe2O4 nanoparticles with different sensors.


Reprinted from reference Surendra et al. (2020a, 2020b).

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

work, the inhibition zone of chemically synthesized ZnFe2O4 nanoparticles through many reactions to synthesize bioactive compounds or some types
only reached 7.7 mm for E. coli and 8.1 mm for S. aureus. At the same con- of drug precursors or organic substances in industrial applications
ditions, Khalid Haliru and Abubakar (2021) reported that the synthesis of (Khanmohammadi-Sarabi et al., 2022). For example, ZnFe2O4 nanoparti-
ZnFe2O4 from Neem leaf extract for against Gram-negative and Gram- cles catalyze the reactions to synthesize 4H-pyrans, 1H-tetrazoles, and
positive bacteria. As a result, the zones of inhibition obtained at 31 mm their derivatives which have beneficial pharmacological activities includ-
for E. coli and 24 mm for S. aureus. This result is almost 3–4 times higher ing antitumor, diuretic, anti-HIV, antimalarial, anti-inflammatory, and hy-
than that of ZnFe2O4 material via chemical method. Studies on the use of poglycemic (Maleki et al., 2019). 1H-tetrazoles are a group of nitrogen-
other plant extract-mediated nanoparticles such as ZnO, CuO, MgO, Ag, rich heterocyclic compounds with various uses that have recently attracted
etc. also reported the same trend (Nguyen et al., 2022c, 2022b). As a result, much attention in a variety of applications including explosives, catalysis
phytochemicals have proved, to some extent, to be of considerable impor- technology, materials science, information recording systems (Aghavandi
tance in the synthesis, structure, and biomedical activity enhancement of and Ghorbani-Choghamarani, 2022).
nanomaterials. Maleki et al. (2019) synthesized ZnFe2O4 nanoparticles using alginic
One of the biomedical applications of ZnFe2O4 nanoparticles from bio- acid in brown algae extract to produce 2-amino-3-cyano-4H-pyran deriva-
synthesis is antibacterial activity. ZnFe2O4 nanoparticles can contact bacte- tives. In this study, the synthesis of 4H-pyrans derivatives catalyzed by
ria through the electrostatic interaction mechanism between the bacterial bio-mediated ZnFe2O4 nanoparticles was facile with excellent yields
cell membrane and the material. Thanks to their biocompatibility, (83–95 %) in short reaction time (10–20 min). The authors also reported
ZnFe2O4 nanoparticles easily cross cell membranes, inhibiting important the good reusability of this green catalyst with a high yield of 85 % for
metabolic functions and ultimately inactivating bacterial cells (Zhang the 6th run. Thanks to functionality by phytochemicals from plant extract,
et al., 2020). Surendra et al. (2020a, 2020b) synthesized successfully ZnFe2O4 materials can acts as a catalyst with higher efficiency than the
ZnFe2O4 from jatropha extract to against P. aeroginosa and E. coli. In this chemically synthesized ones as shown in Table S2. For example,
study, the inhibition percentages were obtained of 85.20 % and 28.60 % Kombaiah et al. (2017) prepared the ZnFe2O4 catalyst synthesized using
for P. aeroginosa and E. coli, respectively. In general, the ability of Opuntia dilenii haw extract and synthesized by the chemical method to con-
ZnFe2O4 to eliminate E. coli bacteria is still limited. In another study, vert glycerol to formic acid. As a result, 97 % formic acid was obtained and
Krishnan et al. (2021) took advantage of the photocatalytic ability of the selectivity of the main product also increased to 99 % using plant-
ZnFe2O4/reduced graphene oxide from orange peel extracts to support mediated ZnFe2O4. Meanwhile, only 85 % formic acid was produced with
the fight against E. coli. E. coli cell cultures treated with ZnFe2O4/rGO had lower selectivity using chemically synthesized ZnFe2O4. The authors con-
the percentage survival rate of 81.15 %, while the survival rate of bacteria cluded that the catalyst synthesized from plant extracts exhibited higher
reached only 29.43 % when exposed to sunlight. It is explained that the catalytic activity and better selectivity. It could be explained that the parti-
photocatalytic activity of ZnFe2O4 material under sunlight irradiation en- cle size (32 nm) of the plant-mediated catalyst was so far smaller than that
hances the generation of ROS that kill bacteria. (73 nm) of the catalyst synthesized by the chemical method, suppling more
Another potential biomedical application of ZnFe2O4 nanoparticles is catalytic active sites, having higher catalytic activity. To sum up, the phyto-
anticancer activity. Indeed, ZnFe2O4 nanoparticles from orange peel chemicals in plant extracts bring ZnFe2O4 nanomaterial good performance
could against lung cancer cell line (A549) (Krishnan et al., 2021). Accord- in catalytic activity.
ingly, the half maximal inhibitory concentration (IC50) value for A549
cells was found to be 249.9 μg/mL. In another study, Jodati et al. (2023) re- 5. Prospects of green ZnFe2O4 nanoparticles
ported anti-breast cancer cells activity of ZnFe2O4@Ag nanocomposites
from Scenedesmus obliquus extracts. In this study, IC50 value for MCF-7 This review provides an insight into the efforts and approaches towards
was obtained of 111 μg/mL, lower than that of the study by Krishnan applications of ZnFe2O4 nanoparticles from plant extracts. Plant extracts
et al. (2021). The better effect may be due to Ag nanodoping and the pres- not only play an important role in replacing chemical reducing agents,
ence of plant extracts that have functional components required for cancer but also contribute to the applicability of ZnFe2O4 materials (Ghoran
cell elimination. In addition to the normal ability to kill cancer cells, et al., 2020). In addition, the biocompatibility of ZnFe2O4 can be attributed
ZnFe2O4 nanoparticles can also treat cancer through hyperthermia therapy. to the functional components present in the plant extracts remaining in the
Cancer cells can be killed by selectively raising the temperature of the le- surface of the material (Kiruthika et al., 2022). In particular, the capping
sion to about 42–45 °C while healthy cells remain unaffected (Manohar and material stabilization of plant extracts help ZnFe2O4 to reduce cluster-
et al., 2021). ing and dispersion (Fabiani et al., 2021). Thanks to these benefits, ZnFe2O4
Among biomedical applications, ideally nanomagnetic ZnFe2O4 can be nanoparticles from plant extract have potential in many applications such
preferentially targeted for delivery to disease sites in cells. For example, as biomedical (Amani et al., 2022), photocatalysis (Balasubramanian and
Amiri et al. (2020) synthesized liposome-doped ZnFe2O4 nanoparticles Murali, 2020), adsorption (Etemadinia et al., 2019), agriculture (El
from Teucrium polium extract and coated with hyaluronic acid. In this Messaoudi et al., 2022), and even electrochemistry, sensing (Surendra
study, the material was used to deliver the drug imatinib - a cancer treat- et al., 2021). In addition, the potential of doping ZnFe2O4 materials along
ment drug against U87 cell lines (human primary glioblastoma cell with some other semiconductor materials also contributes to the future ex-
line). Accordingly, the percentage of drug release to the tumor site in pansion of ZnFe2O4 in a variety of applications.
the presence and absence of the magnetic medium was 92.12 % and Recently, ZnFe2O4 nanoparticles can be an alternative to traditional lu-
79.02 %, respectively. In another study, confirmed that rutin present minescent powders for safe detection and quality improvement of latent
in plant extracts has the potential to synthesize chitosan-coated fingerprints (LFP) deposited on various surfaces (Renuka et al., 2021). Dur-
ZnFe2O4 materials for doxorubicin drug delivery applications. Accord- ing a crime scene investigation, exposure of a fingerprint specialist to pow-
ing to the results, the percentage of drug loading and drug release dered formulations would be a health hazard. Therefore, the alternative use
reached 78.6 % and 87.4 % respectively. It is believed that the prepara- of ZnFe2O4 nanoparticles from plant extracts is safe and magnetic, which is
tion of ZnFe2O4 nanoparticles for drug delivery could be an effective so- easy to remove by magnetic brush. Indeed, Amrutha et al. (2020) synthe-
lution for the pharmaceutical industry. sized ZnFe2O4-reduced graphene oxide material from Emblica officinalis
fruit extract as a labeling agent to detect LFP on various surfaces such as
4.5. Catalysis applications phone screens, glass, and marble. Enhanced fingerprints were captured
under the 254 nm UV light band using a Nikon D3100-lens digital camera.
ZnFe2O4 nanoparticles can be an effective tool to direct the construction According to the results, the enhanced fingerprint displays a well-resolved
of complex structures from simple starting materials (Amini et al., 2021). ridge and flow profile with a clear resolution between light ridges and dark
The good catalytic ability of the ZnFe2O4-based materials has been reported background as shown in Fig. 6.

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

Fig. 6. (a) LFP stained by ZnFe2O4-reduced graphene oxide; (b–e) several small ridges of latent fingerprints were identified and images displayed.
Reprinted from reference Amrutha et al. (2020).

Besides, the role of ZnFe2O4 nanoparticles in the field of agricultural may not have much magnetism compared to others such as CoFe2O4 and
biotechnology is very meaningful in increasing crop yield and creating MnFe2O4, so recovery after use is even less. ZnFe2O4 materials may not
plant immunity. Sahoo et al. (2021) used a bio-hydrothermal method to be as efficient in adsorption and photocatalysis as other advanced multi-
synthesize ZnFe2O4 nanoparticles in the presence of Psidium guajava ex- functional materials. It is necessary to do more doping studies of compo-
tract. In this study, Nicotiana benthamiana was selected to test the ability nent materials with large surface area or to adjust the band gap to match
of ZnFe2O4 nanoparticles to enhance plant immunity. The amount of the irradiation source. Because of their stubs, the scalability of green
water lost (% of original fresh weight) in plants treated with nanoparticles ZnFe2O4 nanoparticles for commercial use needs to be evaluated to reduce
was found to be lower than that of the control plants, especially the protein the total cost of production.
levels of defense-related genes were increased. In addition, colonization of The significance of plant extract-mediated ZnFe2O4 nanoparticles in dif-
expressed bacterial colonies was significantly reduced compared with con- ferent applications can be debased if the problems of solid wastes possibly
trol plants when infected with Pseudomonas syringae. However, the specific generated from bio-mediated synthesis (e.g., cellulose residues) and utiliza-
mechanism of the plant immune effect has not been elucidated. In another tion (spent adsorbent or catalyst) are not solved sufficiently. To deal with
study, Korotkova et al. (2019) reported that zinc ferrite nanoparticles were these solid wastes, we suggest a feasible solution towards circular economy.
synthesized by green method using Petroselinum crispum in seed germina- In other word, the solid wastes should be converted into useful products for
tion. Accordingly, the highest percentage of seed germination of Triticum other applications or other fields. For solid cellulose residues, methods of
vulgare was 53 %, higher than that of the control sample (~40 %). Along pyrolysis and modification can be helpful to transform them into biochars,
with these prospects, the use of ZnFe2O4 nanoparticles in various fields is activated carbons, porous carbons, and nanocomposites, which are used for
expected to increase in the future research. wastewater treatment. Solid cellulose residues can become a precursor for
renewable biofuels and bioenergy production fields (Khoo et al., 2020).
6. Limitations and challenges For spent ZnFe2O4 nanoparticles, it is suggested that modification process
with focus on improving their structure and activity should be considered
Apart from the future prospects of ZnFe2O4 materials have been stated, to minimize disposal solid waste into the environment. To sum up, the cir-
some knowledge gaps are still not clear in the paper. The fundamental role cular economy principles in this case can be applied in combination with
of each phytochemical in the biology of ZnFe2O4 nanoparticles is still not biofuel and material technologies to create more value-added products as
fully understood. There are also very few studies comparing the effective- well as harmonize the benefits between environmental protection and sus-
ness of chemically and biologically synthetic nanoparticles. Therefore, tainable economy development (Pacurariu et al., 2021; Tran et al., 2022c).
more future works should focus on these aspects. Furthermore, the specific
mechanisms of ZnFe2O4 nanoparticles in each of their collected applica- 7. Conclusions
tions have not been elucidated and studied specifically. This can cause
many obstacles in the process of improving the efficiency of materials. In In summary, the plant-mediated synthesis and potential utilizations of
addition, the studies on this material are still modest, there are no in- plant extract-based ZnFe2O4 nanoparticles have been reviewed. It was
depth and focused studies on them. This type of spinel ferrite material found that biosynthesis conditions such as Zn2+/Fe3+/extract ratio, and

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N.T.T. Nguyen et al. Science of the Total Environment 872 (2023) 162212

calcination temperature significantly affect the morphology, surface chem- Declaration of competing interest
istry, particle size, magnetism and bandgap energy of obtained ZnFe2O4
nanoparticles. With low bandgaps and high surface areas, plant-mediated The authors declare that there are no conflicts of interest.
ZnFe2O4 and its nanocomposites exhibited high photocatalytic activities
during degradation of toxic dyes, antibiotics, and pesticides. With diverse Acknowledgment
surface chemistry, they also showed good adsorption performance through
plausible mechanisms such as electrostatic interaction, and hydrogen bond- The authors would love to appreciate the effort of researchers all over
ing. Plant-mediated ZnFe2O4 were proved as promising antibacterial, anti- the world in the fight against the COVID-19 pandemic. We also acknowl-
fungal and anticancer agents for biomedical applications. In addition, plant- edge Mina Rees Library, The Graduate Center of the City University of
mediated ZnFe2O4 could be heterogeneous catalyst for synthesis of valued New York (CUNY) for granting access to databases, Freepik company pro-
compounds. We also suggest several prospects of plant-mediated ZnFe2O4 jects at www.freepik.com, and Canva® graphic design platforms at www.
as an alternative to traditional luminescent powders for safe detection in canva.com for many graphic resources reproduced in this work.
improved latent fingerprints.
Appendix A. Supplementary data
Funding information
Supplementary data to this article can be found online at https://doi.
There was no external funding for this study. org/10.1016/j.scitotenv.2023.162212.

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