Cite this paper: Vietnam J. Chem.

, 2023, 61(S2), 52-59 Research Article

DOI: 10.1002/vjch.202300061

Synthesis of Al-doped and Fe–doped ZnO nanoparticles as UV filters in

sunscreens
Nhu Quyen Huynh Le1,2, Tram Anh Nguyen Ngoc1,2, Ngoc Quynh Hoa Nguyen1,2,
Ngoc Bich Nguyen3, Tien Khoa Le1,2*
1
Faculty of Chemistry, University of Science, 227 Nguyen Van Cu road, district 5, Ho Chi Minh City 70000,
Viet Nam
2
Vietnam National University of Ho Chi Minh City, Vo Truong Toan road, Linh Trung district, Thu Duc City,
Ho Chi Minh City 70000, Viet Nam
3
Center for Practice and Experimental, Dong Thap University, 783 Pham Huu Lau, ward 6, Cao Lanh City,
Dong Thap Province 87000, Viet Nam
Submitted February 18, 2023; Revised May 22, 2023; Accepted June 22, 2023

Abstract
In this work, Al-doped ZnO and Fe-doped ZnO nanoparticles have been synthesized through the coprecipitation-
annealing method to create new and safer UV filters for sunscreen. The effects of metal doping on phase composition,
crystal structure, surface morphology, specific surface area, and elemental composition were characterized by X-ray
diffraction, Raman spectroscopy, field emission electron scanning microscopy, nitrogen adsorption-desorption
experiments and energy-dispersive X-ray spectroscopy, respectively. The optical properties and photocatalytic activity of
prepared powders were studied through UV-visible diffuse reflectance spectroscopy and photocatalytic degradation of
methylene blue under UV radiation. According to the experimental results, Al or Fe-doped ZnO nanoparticles showed
better UV absorption but significantly lower photocatalytic activity than the undoped ZnO sample, which enables the
metal doped ZnO samples to become more effective and safer UV filter in sunscreen. The decline of photocatalytic
activity can be attributed to the bulk defects caused by the insertion of Al 3+ or Fe3+ ions in ZnO lattice. In particular, the
sunscreen formulations using the metal doped ZnO nanoparticles display high SPF values and diverse colors changing
from ivory to yellow-brown, preventing leaving white cast on the skin, which is very suitable as sunscreen for people of
color.
Keywords. ZnO, Al-doping, Fe-doping, sunscreen, reduced photocatalytic activity.

1. INTRODUCTION nanoparticles can produce various reactive oxygen

Over recent decades, the need to protect human skin
from ultraviolet (UV) radiation has attracted
considerable attention, especially for scientists in the
field of cosmetics. Many works reported that UVA
radiations (λ = 320-400 nm) and UVB radiations (λ =
290-320 nm) from the sunlight can cause sunburn,
skin aging and even skin cancer.[1,2] One of the
traditional solutions to protect skin against UV
radiation is using sunscreen based on ZnO
nanoparticles, which are able to strongly absorb UV
light.[3] Accordingly, ZnO nanopowders will be
dispersed in a water-oil emulsion containing
emollients, preservatives, rheological agents,
moisturizers, etc. to create sunscreen cream that can
be applied directly on human skin.
However, under UV light irradiation, these ZnO
species such as hydroxyl radicals via photocatalytic
mechanism,[4,5] resulting in concerns about the safety
of sunscreens since they can damage our skin cells.[6]
Therefore, the synthesis of ZnO nanoparticles with
suppressed photocatalytic activity without modifying
their good UV absorption has become a top target for
researchers in the field of sunscreen. In the literature,
polymer coatings, such as chitosan, were proposed as
a promising method for this research purpose. They
were expected to envelop the surface of
semiconductor particles, thereby hindering the
formation of oxidative free radicals.[7,8] However, the
preparation of coating layers on nanoparticle surface
often requires complicated procedure while the
quality and durability of coatings were usually not
mentioned in these studies. Another solution is metal
doping into the crystal structure of ZnO in order to

52 Wiley Online Library © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH

Vietnam Journal of Chemistry
create trapping sites for photogenerated electrons and
holes, preventing the formation of hydroxy free
radicals. In fact, when ZnO nanoparticles are doped
with Al3+[9] or Na+,[10] their photocatalytic activity was
significantly reduced, making these materials more
promising for sunscreens.
Nevertheless, most of studies only examined the
UV absorption capacity of metal-doped ZnO powders
without investigating their sun protection factor
(SPF), especially when these powders were dispersed
into a water-oil emulsion of sunscreen. Another
drawback of sunscreens contaning ZnO nanoparticles
is the fact that they often show the prominent white
color, which leaves white cast on the skin. As a
consequence, it is less suitable for people of color to
ultilize. To address these problems, we proposed to
insert Al3+ or Fe3+ ions into the lattice of ZnO
nanoparticles and then used them to prepare
sunscreen creams which are expected to offer more
safety and better sun protection. Additionally, the
selection of Al3+ or Fe3+ ions as doping agent also
allows us to control the color of the powder, making
the sunscreen more appropriate for people of color.
In general, the method of synthesis plays a key
role in the effectiveness of the doping process.
According to previous works, Al-doped, Fe-doped or
Al and Fe-codoped ZnO thin films were successfully
prepared by different methods such as RF magnetron
sputtering,[11] spray pyrolysis,[12] or dip-coating sol-
gel.[13,14] Although effective, both these techniques
usually require complicated procedures, expensive
chemicals and instrumental set-up. They also seem to
be more suitable for the synthesis of thin film
synthesis than that of nanoparticles used in sunscreen
formulations. Hence, in this study, we chose the
simple coprecipitation-annealing method to
synthesize Al or Fe-doped ZnO nanoparticles as new
UV filters for sunscreen products.
2. MATERIALS AND METHODS
2.1. Synthesis of Al-doped or Fe-doped ZnO
nanoparticles
In our work, Fe-doped ZnO nanoparticles was
prepared by a simple coprecipitation-annealing
method. First, 16.71 g ZnSO4.7H2O was mixed with
0.73 g Fe(NO3)3.9H2O and then dissolved in
deionized water to obtain 100 mL of transparent
solution containing Zn2+ (0.582 mol L-1) and Fe3+ ions
(0.018 mol L-1) with the molar Zn/Fe ratio of 97/3.
Next, 1.0 mol L-1 Na2CO3 solution was slowly added
to this mixture until pH 7 under continuous magnetic
stirring to produce a yellow-brown precipitate. The
visosity of the solution containing this precipitate
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Tien Khoa Le et al.
(measured by using a Zahn cup 3) was found to be
263.2 cSt. The precipitate was subsequently washed
with deionized water to remove all trace amounts of
ions from the surface. After that, the obtained
precipitate was dried at 150°C for 2 hours, finely
ground. Finally, the powder was annealed in air at
400°C for 2 hours and labelled as ZnO-Fe.
The undoped ZnO sample (labelled as ZnO) and
Al-doped ZnO nanopowder (labelled as ZnO-Al)
were also synthesized by the same procedure as
above, without using Fe(NO3)3.9H2O (for ZnO) or
using 0.60 g Al2(SO4)3.18H2O (corresponding to
0.018 mol L-1 Al3+ solution) instead of
Fe(NO3)3.9H2O (for ZnO-Al).
2.2. Preparation of sunscreen cream using Al/Fe-
doped ZnO nanoparticles
In order to prepare 20 g of sunscreen cream, ZnO or
ZnO-Fe or ZnO-Al nanopowders were mixed with
commercial ingredients. In a typical experiment, 0.60
g of glycerin and 0.20 g of SEPNOVTM EMT 10
thickener (hydroxyethyl acrylate) were blended each
other and added to 13 mL of deionized water. This
mixture was regularly stirred until a swollen state was
reached, called mixture A. Next, 3.00 g of ZnO/ZnO-
Fe/ZnO-Al nanopowder was mixed with 2.00 g of
EMO SMARTTM L19 softener (C15-C19 alkane
mixture) for 10 min, and then 0.60 g of
EASYNOVTM emulsifier (mixture of PEG-30 and
dipolyhydroxystearate) was added to obtain the
mixture B. The mixture B was mixed with the mixture
A and stirred for 20 minutes to form a fine mixture.
Finally, 0.3 g of glycerin and 0.16 g of EUXYL PE
9010 preservative (a mixture of phenoxyethanol and
ethylhexylglycerin) were added to the mixture and
stirred for 25 minutes to obtain sunscreen products,
labelled as cream-ZnO, cream-ZnO-Fe and cream-
ZnO-Al, respectively corresponding to undoped ZnO,
Fe-doped ZnO, and Al-doped ZnO. It was recognized
that all these sunscreen products have a pH of
approximately 7.
2.3. Materials characterization
The crystal structures of ZnO, ZnO-Al and ZnO-Fe
nanopowders were studied by X-ray diffraction
(XRD) on an EMPYREAN (PANalytical), using the
monochromatized Cu Kα radiation with λ = 1.54184
Å. The average crystallite size of our samples was
calculated using the Scherrer formula (Eq. 1):
kλ
d= (1)
βcosθ
where d is the crystallite size corresponding to the
53

Vietnam Journal of Chemistry
(hkl) plane, k is the constant depending on crystallite
shape (0.94[15]), λ is the wavelength of CuKα radiation
(1.5406 Å), β is the full width at half maximum
(FWHM) of the most intense peaks (assuming
Gaussian shape[16]) and θ is its diffraction angle.
Moreover, from the XRD patterns, the dislocation
density (δ, line m-2) and the micro-strain (ε) in the
crystal structure of our samples were determined via
Eq. 2[17] and Eq. 3 (based on Williamson-Hall
method[18]), respectively.
1
δ= (2)
d2
kλ
βcosθ = + 4ε × sinθ (3)
d photocatalytic activity of ZnO was investigated
The Raman spectra of these powder samples were
recorded by a HORIBA Scientific LabSpec6 at room
temperature, using the visible laser with λ = 543 nm
to investigate their lattice defects. The particle size
and surface morphology of these samples was
examined by field emission scanning electron
microscopy (FE-SEM) images, recorded on a
HITACHI S-4800 microscope with an acceleration
voltage of 10 kV and a working range of 7.6 mm.
Their Brunauer–Emmett–Teller surface area (SBET)
and Barret–Joyner–Halenda pore size (dBJH) were
estimated by using N2 adsorption-desorption
isotherms taken at 77 K on a Quantachrome NOVA
1000e analyzer. Simultaneously, the elemental
composition was determined by energy-dispersive X-
ray spectroscopy (EDS), also recorded on the
HITACHI S-4800 instrument with the acceleration
voltage of 10 kV.
The UV-visible light absorption of the powders
and the sunscreen samples was investigated by UV-
visible diffuse reflection technique on a Shimadzu
UV 2600 instrument at room temperature. From the
UV-visible absorption spectrum of the powder
samples, their band gap values were estimated by
using Tauc equation (Eq. 4).[18,19]
αhν = A(hν – Eg)2 (4)
where α stands for the absorption coefficient, h is
Planck’s constant, ν represents the frequency of
photon, A is a proportionality constant, and Eg is the
bandgap value (eV).
Likewise, the SPF index of our sunscreen samples
was calculated according to the following equation
(Eq. 5):[20,21]
∑400
290 E(λ)ε(λ)
SPF = (5)
∑400
290 E(λ)ε(λ) /MPF(λ)
where E(λ) is the solar spectral irradiance, ε(λ) is the
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Synthesis of Al-doped and Fe–doped …
CIE erythemal spectral effectiveness, and MPF(λ) is
the inverse of the transmission (1/T) at a given
wavelength.
In addition, the colors of sunscreen samples was
also evaluated via the CIE L*a*b* color coordinates
(where L*, a*, and b* values stand for the lightness,
the green(–)/red(+) color component and the blue
(–)/yellow(+) color component, determined by the
Color Grab colorimeter application on a Samsung
Galaxy A32 device.
2.4. Photocatalytic tests
The diminished effects of Al or Fe-doping toward the
through the degradation of methylene blue (MB)
under UV radiation in the presence of ZnO, ZnO-Fe
and ZnO-Al samples. First, 0.125 g each of
nanopowders was dispersed into 2×10-5 mol L-1 MB
solution (250 mL). The suspension was stirred
without illumination for 60 minutes to ensure the
adsorption-desorption equilibrium of dye molecules
on oxide surface. Subsequenly, the reaction
suspension was irradiated by UV light (9W Radium
78 lamp). During the experiment, the pH of solution
was found to be 7. The reaction temperature was also
maintained at approximately 30°C using a water
circulation system. At a interval of 5 minutes, 5 mL
of reaction mixture was collected, centrifuged to
separate the powder from the solution. The remained
MB concentration in the solution was determined by
UV-visible absorption spectroscopy at 664 nm on a
Helios Omega UV-VIS spectrophotometer (Thermo
Fisher Scientific).
3. RESULTS AND DISCUSSION
3.1. Crystal structure
Figure 1 depics the XRD patterns of ZnO, ZnO-Al,
and ZnO-Fe powder samples. Their XRD patterns
show characteristic and intense peaks at 2θ angles of
31.70, 34.46, 36.24, 47.58 and 56.67°, respectively
corresponding to the (1 0 0), (0 0 2), (1 0 1), (1 0 2)
and (1 1 0) lines of wurtzite ZnO (zincite) phase. No
impurity phase was found in these XRD patterns,
indicating that the Al or Fe-doping did not alter the
phase composition of ZnO nanoparticles. However,
the diffraction peaks of ZnO-Fe and ZnO-Al samples
are less symmetrical and wider than those of ZnO
nanoparticles, suggesting that the metal doping can
reduce the crystallinity of ZnO, create various types
of structural defects in ZnO lattice as well as decrease
the crystal size. In fact, table 1 compares the cell
parameters (determined by Rietveld refinement on
54
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Vietnam Journal of Chemistry Tien Khoa Le et al.

Fullprof Suite 2009 software), the crystallite sizes, the Table 1: Cell parameters, average crystallite size (d),
micro-strain, and the dislocation density of three micro-strain (ε), and dislocation density (δ) of ZnO,
powder samples. It was observed that ZnO-Al and ZnO-Al, and ZnO-Fe samples
ZnO-Fe exhibit higher cell parameters (a and c) as
Cell δ×103
well as higher dislocation densities and micro-strains
Sample parameters d (nm) ε×103 (line
than those of ZnO sample, but the crystal size of ZnO
a (Å) c (Å) nm-2)
is larger than that of doped samples. According to
Shannon,[22] the ionic radius of Al3+ (r = 0.39 Å) and ZnO 3.248 5.203 30.59 0.001 0.64
Fe3+ (r = 0.49 Å) are lower than that of Zn2+ (r = 0.60 ZnO-Al 3.250 5.210 14.50 0.013 4.84
Å). Hence, these evolutions of crystal structure and ZnO-Fe 3.252 5.209 17.15 0.015 3.44
crystal size found in ZnO-Al and ZnO-Fe samples 474 474
470
may be related to the successful insertion of Al3+ and
Fe3+ ions into interstitial sites of ZnO lattice. As a

Intensity (a.u.)
result, the unit cell of ZnO is expanded, causing the
increase in cell parameters, micro-strain and making
ZnO crystals difficult to grow. 436 436
580 432
576

ZnO ZnO-Al ZnO-Fe

300 350 400 450 500 550

-1
600 650 300 350 400 450 500 550 600 650 300 350 400 450 500 550 600 650
Raman shift (cm ) -1
Raman shift (cm ) Raman shift (cm )
-1

Figure 2: Raman spectra of ZnO, ZnO-Al, and

ZnO-Fe samples
ZnO-Fe
Intensity (a.u.)

3.2. Morphology and elemental composition

ZnO-Al
ZnO
Zincite (ZnO)
20 30 40 50
o
2 ( )
Figure 1: XRD patterns of ZnO, ZnO-Al, and
ZnO-Fe samples
It was acknowledged that Raman spectroscopy is
also a good method to investigate the evolution of
crystal structure for solid materials. For example,
Aslan et al. successfully used Raman spectroscopy to
detect the formation of SnS2 and SnS crystalline
phases, which are often difficult to distinguish
through XRD patterns.[23] Hence, our undoped and
metal-doped ZnO samples were also analyzed by
their Raman spectra (figure 2). All samples exhibit an
intense peak at 474 cm-1 and a weak peak at about
432-436 cm-1, respectively related to the
characteristic surface mode and the high frequency
E2 mode of ZnO wurtzite phase.[24,25] Additionally,
ZnO-Al and ZnO-Fe samples also display a weak
peak at 576-580 cm-1. According to some studies,[26,27]
this weak peak could be attributed to the E1 (LO)
mode, generated by the presence of different intrinsic
defects. Hence, the metal doping is believed to be able
to significantly affect the structure of ZnO, causing
lattice distortion and creating numerous structural
defects.
© 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de
The morphology and particle size of ZnO, ZnO-Al,
and ZnO-Fe powder samples were investigated by
FE-SEM (figure 3). As shown in figure 3a, the ZnO
sample is composed of relatively uniform, spherical
particles, existing in the agglomerated state with the
60 70
particle size in the range of 20-40 nm. When Al3+ or
Fe3+ ions were incorporated into ZnO lattice (figures
3b and 3c), the changes in shape and particle size of
ZnO nanoparticles were not clearly observed.
Interestingly, the specific surface area and the pore
size were found to increase due to the metal-doping
(table 2). Since ZnO particles need to be ultrafine to
become highly transparent when dispersed in
sunscreen medium, the particle size range and the
specific surface area of these samples are believed to
be suitable for sunscreen products.
Figure 3: FE-SEM images of (a) ZnO, (b) ZnO-Al,
and (c) ZnO-Fe samples
Table 2: Brunauer–Emmett–Teller surface area
(SBET) and Barret–Joyner–Halenda pore size (dBJH)
of ZnO, ZnO-Al, and ZnO-Fe samples
ZnO ZnO-Al ZnO-Fe
SBET (m2 g–1) 43.84 62.69 60.16
dBJH (Å) 9.81 10.77 10.66
55
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Vietnam Journal of Chemistry Synthesis of Al-doped and Fe–doped …

Table 3 presents the elemental composition of
ZnO-Al and ZnO-Fe powder samples, determined by
EDS spectroscopy. The presence of Al and Fe atoms
in the samples confirms that the doping process of
Al3+ and Fe3+ ions into ZnO lattice was successfully
performed. From the EDS results, the molar Al/Zn
ratio of ZnO-Al (3.71%) and the molar Fe/Zn ratio of
ZnO-Fe (3.79%) are close to the theoretical value
when synthesizing these samples (3.00%).
Table 3: Elemental composition of ZnO-Al and
ZnO-Fe samples
% Element
Sample
a relatively strong absorption in the range of 400-650
nm, thereby displaying a yellow-brown color. The
color study of the cream samples was further
strengthened by their CIE L*a*b* coordinates (Table
4). When ZnO was doped with Fe3+ ions, the L* value
was dramatically reduced, whereas both a* and b*
values strongly increased, corresponding to the
increase in red and yellow color components.
Therefore, this sunscreen has a yellow–brown color,
which does not leave any white casts on the skin,
thereby being very appropriate for people with brown
or yellow-brown skin.
a ZnO b cream-ZnO

Zn O Al Fe
1.6 ZnO-Al 1.6 cream-ZnO-Al
ZnO-Fe cream-ZnO-Fe

ZnO-Al 42.59 55.84 1.58 1.2 1.2

Absorption (a.u.)
Absorption (a.u.)
ZnO-Fe 44.61 53.70 1.69 0.8 0.8

0.4 0.4

3.3. Optical properties and SPF values 0.0 0.0

200 300 400 500 600 700 800 200 300 400 500 600 700 800

The UV-Visible absorption spectra of the powder Wavelength (nm) Wavelength (nm)

samples and the sunscreen samples are displayed in
figures 4a and 4b, respectively. It can be seen that all
three powder samples (ZnO, ZnO-Al, and ZnO-Fe)
strongly absorbed radiations in the UV region (200-
400 nm). No significant difference of UV absorption
intensity was found between them, demonstrating
that the Al or Fe-doping did not alter the UV
absorption capacity of ZnO. Only small red shifts in
band gap were found for doped samples since the
bandgap of ZnO powder is 3.23 eV while ZnO-Al and
ZnO-Fe show the band gap of 3.19 and 3.16 eV,
respectively. In particular, when powder samples
were dispersed into the cream base, the suncreens
using doped ZnO powders showed higher UV
absorption than that containing undoped ZnO.
Besides, the SPF indexes of cream-ZnO-Al and
cream-ZnO-Fe were also higher than that of cream-
ZnO (table 4). These results should be explained by
the good dispersion of doped ZnO powder samples in
the cream base. In fact, when ZnO nanoparticles were
doped with Al3+ or Fe3+ ions, their crystallite size
significantly decreased, which improves their specific
surface area. Consequently, the crystals can be well
dispersed in the cream base, thereby improving the
interactions between doped ZnO nanoparticles and
UV radiations.
For the visible light region, the absorption spectra
show that ZnO and cream-ZnO samples almost did
not absorb visible light. Likewise, ZnO-Al and
cream-ZnO-Al samples slightly absorbed the visible
light in the range of 400-500 nm and showed no
absorption in the 500-800 nm region. Hence, these
Al-doped samples displayed an ivory color. In
contrast, ZnO-Fe and cream-ZnO-Fe samples shows
Figure 4: UV-visible absorption spectra of (a)
ZnO, ZnO-Al, ZnO-Fe samples and (b) cream-ZnO,
cream-ZnO-Al, cream-ZnO-Fe samples
Table 4: SPF index and L*a*b* color coordinates of
suncreen creams
Sample SPF L* a* b*
cream-ZnO 25.9 99.5 -0.7 -0.2
cream-ZnO-Al 35.6 97.9 -4.2 5.5
cream-ZnO-Fe 31.2 65.9 23.1 48
3.4. Photocatalytic activity
Prior to photocatalytic experiments, the adsorption of
MB dye on the surface of ZnO, ZnO-Al, and ZnO-Fe
powder samples was investigated in the dark,
showing that the MB adsorption capacity of these
samples is negligible (table 5). Then their
photocatalytic activity was evaluated through MB
degradation under UV light (figure 5). The rate
constant of MB degradation was also calculated from
the Ln([MB]0/[MB]) versus time plots (figure 6) and
shown in table 5. As depicted in figure 5, MB
molecules were clearly degraded over undoped ZnO
within 1 hour whereas they were scarcely removed in
the presence of ZnO-Al and ZnO-Fe samples. Among
all three samples, the undoped ZnO exhibited the best
photocatalytic activity with a rate constant (k) up to
1.284 h–1. When Al3+ and Fe3+ ions were incorporated
into ZnO lattice, the rate constant of MB degradation
impressively decreased to 0.131 h–1 and 0.368 h–1,
respectively. These results prove that the metal
doping successfully reduced the photocatalytic

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Vietnam Journal of Chemistry Tien Khoa Le et al.

activity, but still ensured the effective UV absorption alcohol as a hydroxyl radical scavenger.[29] In the
of ZnO nanoparticles. presence of this alcohol (10-4 mol L-1 or 10-3 mol L-1),
the performance of undoped ZnO nanoparticles for
MB degradation was gradually decreased (figure 7),
1.4
0 min 0 min 0 min
10 min a 1.4
10 min b 1.4
10 min c
1.2 20 min 20 min 20 min
30 min 1.2 30 min 1.2 30 min

demonstrating the essential role of hydroxyl radicals

40 min 40 min 40 min
1.0 50 min
50 min 1.0 50 min 1.0
60 min 60 min 60 min
Absorbance

Absorbance
Absorbance

0.8
0.8 0.8

0.6 0.6

0.4
0.6

0.4
in their photocatalytic activity.
0.4

0.2 0.2
0.2

0.0
0.0 0.0 1.5
400 500 600 700 800 400 500 600 700 800 400 500 600 700 800 -1
Wavelength (nm) Wavelength (nm) Wavelength (nm) ZnO k = 1.284 h
Figure 5: UV-visible absorption spectra of MB
-4 -1
ZnO + tert-butyl alcohol (10 mol L )
-1
k = 0.811 h
degradation with different degradation times under -3 -1
ZnO + tert-butyl alcohol (10 mol L )
UV light over (a) ZnO, (b) ZnO-Al, and (c) ZnO-Fe 1.0 k = 0.230 h
-1

Ln([MB]0/[MB])
samples
1.5
ZnO 0.5
ZnO-Fe
ZnO-Al

1.0
Ln([MB]0/[MB])

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Time (h)

0.5 Figure 7: Ln([MB]0/[MB]) versus time plot of MB

degradation on ZnO with tert-butyl alcohol at
different molar concentrations
0.0
0.0 0.2 0.4
Time (h)
0.6 0.8 1.0
However, when Al3+ and Fe3+ ions penetrate into
Figure 6: Ln([MB]0/[MB]) versus time plot of MB ZnO lattice, they can displace Zn2+ ions or enter the
degradation on undoped ZnO, ZnO-Al, and ZnO-Fe interstitial sites of Zn2+ and O2+ ions, which increases
under UV light the positive charge of system. At that time, the
material will create Zn2+ vacancies in the lattice to
Table 5: MB adsorption percentage and rate constant neutralize the positive charge. These holes can act as
of MB degradation under UV light on ZnO, ZnO-Al the trapping sites for photogenerated electrons and
and ZnO-Fe samples holes, preventing the formation of free hydroxyl
radicals.[30] Hence, the photocatalytic activity of the
Sample material was greatly reduced. For this reason, ZnO-
ZnO ZnO-Al ZnO-Fe Al and ZnO-Fe powder samples can be potentially
% MB applied to create sunscreen products that not only
1.27 2.52 1.87
adsorption effectively absorb ultraviolet light with a high SPF
k (h-1) 1.284 0.131 0.368 index but also become safer for consumers.

The decrease in photocatalytic activity should be 4. CONCLUSION

explained by the formation of structural defects inside
ZnO-Al and ZnO-Fe powder samples, as Al or Fe-doped ZnO nanopowders were successfully
demonstrated by the XRD and Raman results. In prepared by the simple coprecipitation-annealing
general, under UV illumination, ZnO semiconductor method to apply as UV filters in suncreens. The
nanoparticles will absorb UV radiations to produce experimental results showed that the doping of Al3+
photogenerated electrons and holes (Eq. 6).[28] These or Fe3+ ions into ZnO lattice did not change the phase
charged species will migrate to the surface to react composition and the UV absorption of ZnO, but
with O2 and H2O to generate free radicals (Eqs. 7 and created structural defects, leading to the great
8), such as hydroxyl radicals, which have strong decrease in photocatalytic activity under UV light,
oxidizing power. which makes these materials safer for use in
TiO2 + hν → e– + h+ (Eq. 6) sunscreens. The sunscreen creams using these doped
e– + O2 → O2●– (Eq. 7) ZnO nanoparticles also showed better UV light
h+ + H2O → ●OH + H+ (Eq. 8) absorption (with impressive SPF indexes) than the
In fact, to prove the relation between the cream using undoped ZnO powder. Moreover, Fe-
photocatalytic activity of ZnO and hydroxyl radicals, doped ZnO powder sample also gives the sunscreen a
the scavenger tests were carried out with tert-butyl yellow-brown color, which is suitable for the skin of

© 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 57

Vietnam Journal of Chemistry
Asians, especially those in the sub-equatorial region.
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Research highlights
• Al/Fe-doped ZnO nanoparticles prepared by coprecipitation-annealing method.
• Al/Fe-doping increases the dislocation density and structural defects of ZnO.
• The photocatalytic activity of ZnO was greatly reduced by Al/Fe-doping.
• Al/Fe-doped ZnO nanoparticles display high UV absorption.
• Sunscreen using Al/Fe-doped ZnO show high SPF values and ivory-brown colors.

Corresponding author: Tien Khoa Le

Faculty of Chemistry, University of Science
Vietnam National University, Ho Chi Minh City
227 Nguyen Van Cu street, District 5, Ho Chi Minh City 70000, Viet Nam
Email: ltkhoa@hcmus.edu.vn
Tel.: +84- 937293251.

© 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 59