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org/journal/acsodf Article

Effects of Calcination Temperature on the Phase Composition,

Photocatalytic Degradation, and Virucidal Activities of TiO2
Nanoparticles
Min Gu Kim, Jeong Min Kang, Ji Eun Lee, Kang Seok Kim, Kwang Ho Kim, Min Cho,*
and Seung Geol Lee*

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ABSTRACT: The application of TiO2 nanoparticles in the

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photocatalytic treatment of chemically or biologically contaminated

water is an attractive, albeit unoptimized, method for environ-
mental remediation. Here, TiO2 nanoparticles with mixed
brookite/rutile phases were synthesized and calcined at 300−
1100 °C to investigate trends in photocatalytic performance. The
crystallinity, crystallite size, and particle size of the calcined
materials increased with calcination temperature, while the specific
surface area declined significantly. The TiO2 phase composition
varied: at 300 °C, mixed brookite/rutile phases were observed,
whereas a brookite-to-anatase phase transformation occurred above
500 °C, reaching complete conversion at 700 °C. Above 700 °C, the anatase-to-rutile phase transformation began, with pure rutile
attained at 1100 °C. The optical band gaps of the calcined TiO2 nanoparticles decreased with rising calcination temperature. The
mixed anatase/rutile phase TiO2 nanoparticles calcined at 700 °C performed best in the photocatalytic degradation of methylene
blue owing to the synergistic effect of the crystallinity and phase structure. The photocatalytic virus inactivation test demonstrated
excellent performance against the MS2 bacteriophage, murine norovirus, and influenza virus. Therefore, the mixed anatase/rutile
phase TiO2 nanoparticles calcined at 700 °C may be considered as potential candidates for environmental applications, such as water
purification and virus inactivation.

1. INTRODUCTION for photocatalytic applications because of their facile syn-

Although industrial production is critical to our world thesis.16 In contrast, brookite has been rarely investigated as a
economy, the wastewaters generated during various production photocatalyst because it is not readily accessible in its pure
processes can result in serious water pollution. Other sources form.17−19 However, it has been reported that the photo-
of fouled water can be traced to biocontaminants such as catalytic performance of brookite is superior to those of
viruses and bacteria.1,2 To solve these growing threats to health anatase and rutile.20,21
and safety, the development of semiconductor-based photo- Generally, the photocatalytic activity of TiO2 is affected by
catalysts that can effectively degrade organic or biological its phase structure, crystallite size, specific surface area, and
pollutants has been intensively studied in recent years.3−8 pore structure.22−28 Although rutile has a smaller band gap
Among these photocatalysts, titanium dioxide (TiO2) nano- (3.0 eV) than anatase (3.2 eV), its photocatalytic activity is
particles are fascinating materials with the desirable properties inferior to that of anatase because rutile exhibits a faster
of chemical stability, nontoxicity, high photoreactivity, electron (e−) and hole (h+) recombination rate, larger grain
corrosion resistance, and cost-effectiveness.9−12 TiO2 naturally size, and smaller specific surface area.29−32 The lifetimes of
occurs in three distinct crystalline phases with different electrons and holes generated upon photon absorption are
physical and chemical properties: brookite (orthorhombic
crystal structure), anatase (tetragonal crystal structure), and
rutile (tetragonal crystal structure).13,14 Under ambient Received: January 4, 2021
conditions, bulk rutile is thermodynamically stable, whereas Accepted: March 17, 2021
anatase and brookite are thermodynamically metastable.15 Published: March 25, 2021
Thus, these phases can be accessed through thermally driven
phase transformations, as may occur during calcination.
Among the three phases, anatase and rutile are widely used
© 2021 The Authors. Published by
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longer for anatase than rutile, enhancing the surface chemical accelerating voltage and current of 40 kV and 30 mA,
reaction rate of the photoexcited species in anatase. Although respectively. The 2θ scanning range was 20−80° and the step
anatase has several advantages as a photocatalyst, its perform- size was 0.01°. The crystallite sizes of the anatase, brookite,
ance is limited by its fast e−/h+ recombination rate. and rutile phases were estimated using Scherrer’s equation (D
Several researchers have shown that phasic mixtures of TiO2 = Kλ/β cos θ), where K = 0.93, λ = 0.154059 nm, β = full
exhibit substantially higher photocatalytic performance than width at half-maximum (FWHM) in radians, and θ = the Bragg
single-phase TiO2. The different band alignments of mixed angle.41 The characteristic peaks of the phases (anatase (101)
TiO2 phases can facilitate charge transfer at the interface. This peak at 2θ = 25.3°, brookite (121) peak at 2θ = 30.8°, and
enhances e−/h+ separation and reduces e−/h+ recombina- rutile (110) peak at 2θ = 27.5°) were used to calculate the
tion.16,33−35 A well-known example is Degussa P25, a widely crystallite sizes in the samples.9,42 The weight fraction of each
used commercial TiO2 photocatalyst containing 75% anatase phase was obtained using the following eq 141,43
and 25% rutile phases.36 Upon irradiation of P25 with UV
light, photoexcited electrons from the anatase phase are KAAA KBAB
WA = , WB = ,
transferred to the rutile phase, which has a lower conduction KAAA + AR + KBAB KAAA + AR + KBAB
band energy, thus inhibiting the recombination of electrons AR
and holes.37 However, the mixing ratios of the different TiO2 and WR =
phases must still be explored to optimize photocatalytic KAAA + AR + KBAB (1)
performance.38−40
In this study, we investigate the effects of calcination where WA, WB, and WR represent the weight fractions of the
temperature on the particle and crystallite sizes, phase anatase, brookite, and rutile phases of TiO2, respectively. AA,
transformations, and photocatalytic performance of as- AB, and AR are the integrated intensities of the anatase (101),
prepared TiO2 nanoparticles. The samples before and after brookite (121), and rutile (110) peaks of the TiO 2
calcination were characterized using X-ray diffraction (XRD), nanoparticles, respectively. The terms KA and KB are
Brunauer−Emmett−Teller (BET) specific surface area and coefficients with values of 0.886 and 2.721, respectively.41,43
Barrett−Joyner−Halenda (BJH) pore size analyses, field Raman analysis was conducted by a Raman spectrometer
emission scanning electron microscopy (FE-SEM), high- (JASCO Co., NRS-5100, Tokyo, Japan) at room temperature
resolution transmission electron microscopy (HR-TEM), and with a solid-state laser at 532 nm with a notch filter grating of
UV−vis spectrophotometry. To evaluate photocatalytic per- 1800 g/mm.
formance as a function of catalyst calcination temperature, the The BJH pore size distributions and BET surface areas were
degradation of methylene blue dye as an organic pollutant obtained from nitrogen adsorption−desorption isotherms
surrogate was tested with TiO2 in aqueous solution. Finally, (Quantachrome, Autosorb-iQ & Quadrasorb SI, Boynton
the photocatalytic virus inactivation capabilities of the catalysts Beach, FL). The surface morphologies of the TiO2 nano-
were estimated against the MS2 bacteriophage, murine particles were analyzed by FESEM using a Carl Zeiss SUPRA
norovirus, and influenza virus using a TiO2/cotton fabric 40VP instrument (Oberkochen, Germany). The microstruc-
system. tures of the TiO2 nanoparticles were observed by HR-TEM
(FEI Co., TALOS F200X, Hillsboro, OR). The TiO 2
2. EXPERIMENTAL METHODS nanoparticles were dispersed in ethanol and then mounted
on a copper grid with formvar. The particle size of each sample
2.1. Materials. Titanium tetrachloride (TiCl4, 99%), nitric
was also measured by the particle size distribution histogram of
acid (HNO3, 60%), and methylene blue were purchased from
HR-TEM.
Junsei Chemical Co. Ltd., Japan. Sodium hydroxide pellets
2.4. Photocatalytic Degradation Tests. The photo-
(NaOH, 98%) were obtained from Dae-Jung Chemicals Ltd.,
catalytic performance of the calcined TiO2 nanoparticles was
South Korea. Poly(ethylene glycol) (PEG) with a molecular
evaluated by decomposing methylene blue (MB). Calcined
mass of 600 was purchased from Merck, Germany.
TiO2 nanoparticles (0.5 wt %) were added to aqueous MB
Commercially bleached cotton fabric was employed in this
solution (20 ppm, 20 mL, pH 7), and the suspension was
study. All chemicals were of analytical grade and used as
ultrasonicated and stirred for 60 min under dark conditions.
received without further purification.
The suspension was then irradiated under UV light (8 W × 4
2.2. Synthesis Process. TiCl4 was used as a starting
lamps) at room temperature. During the process of
material to prepare TiO2 powder. A stock solution of TiOCl2
degradation, solution aliquots (2 mL) were withdrawn via a
(4.0 M in Ti4+) was prepared by the careful dropwise addition
syringe at 30 min intervals up to 180 min. UV−vis spectra were
of aqueous HNO3 (1.0 M) into vigorously stirred TiCl4 at 0
collected for these samples in the 300−800 nm range,
°C. To prepare TiO2, the stock solution was diluted with
measuring the absorbance with a single-beam UV−vis
aqueous HNO3 (5.0 M) and heated at 80 °C for 15 h. After
spectrophotometer (Shimadzu, model UV-1280, Kyoto,
cooling to room temperature, the pH of the solution was
Japan). The photocatalytic performance was calculated
adjusted to pH 7 by adding NaOH solution (1.0 M). The
according to eq 2.
white precipitates were collected on a membrane filter and
ji C − Ct zyz
conversion (D%) = jjj 0 z × 100%
washed, first with dilute HNO3 solution (1.0 M) to eliminate
j C0 zz
k {
titanium hydroxide and then with distilled water. After drying
at 100 °C, samples were calcined at 300, 500, 700, 900, and (2)
1100 °C (heating rate of 9 °C/min) for 2 h.
2.3. Characterization of TiO2 Photocatalysts. The where C0 is the initial absorbance and Ct is the absorption at a
phase compositions of the synthesized TiO2 nanoparticles certain irradiation time t of the MB solution (λ = 665 nm). All
were identified using a Philips X’pert 3 X-ray diffractometer of the analyses were conducted using a quartz cuvette as the
(Eindhoven, Netherlands) with Cu Kα radiation and an sample holder.
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2.5. Photocatalytic Virus Inactivation Test. The dip- The MS2 bacteriophage (ATCC 15597) was quantified by
padding method was used to coat TiO2 nanoparticles onto the the soft agar overlay (double-agar layer) plaque assay method45
cotton fabric (area: 100 mm × 100 mm) to evaluate the with Escherichia coli C3000 as host bacteria, cultured using 10
photocatalytic virus inactivation performance. To remove g/L tryptone, 1 g/L glucose, 1 g/L yeast extract, 8 g/L NaCl,
residual impurities, the cotton fabric sample was boiled and 0.8 g/L CaCl2. The top and bottom agars for the plaque
successively for 30 min with sodium carbonate solution (2.0 assays contained 7 and 15 g/L agar, respectively.
g/L), followed by sodium dodecylbenzene sulfonate (2.0 g/L),
and then washed with distilled water and air-dried at room 3. RESULTS AND DISCUSSION
temperature. A PEG−TiO2 sol was prepared by mixing TiO2 3.1. Phase Structure. The XRD patterns of the TiO2
nanoparticles (0.3 g) and PEG-600 (50 mL) in an ultrasonic nanoparticles before and after calcination at temperatures from
mixer for 5 h. The pretreated fabric was immersed in the 300 to 1100 °C are shown in Figure 1. The samples were
prepared PEG−TiO2 sol for 1 min and then passed through a
two-roller laboratory padding machine at a nip pressure of 4
bar to ensure a constant amount of TiO2 on the fabric. After
padding, the fabric was immediately dried at 100 °C for 5 min
in a preheated oven and finally cured at 120 °C for 3 min.
The virus inactivation experiments were conducted in a deep
Petri dish using phosphate buffer solution (20 mL, pH 7.0, 10
mM) with the target virus (MS2 bacteriophage, murine
norovirus, or influenza virus) and a TiO2/cotton fabric pad (50
mm × 100 mm). The initial populations of the virus in the
disinfection experiments were controlled to about 106 plaque
forming units (PFU)/mL. In the UV light experiments,
illumination was provided by 3 Blacklight Blue lamps (BLB,
4 W, Philips Co.; light intensity: 1.8 × 10−6 Einstein/l s),
which emitted in the 300−400 nm range.
Typically, three samples (1.0 mL) were collected over 40
min to measure the viable virus; each sampled solution was
diluted to 1/10 and 1/100. Three replicate plates were used at
each dilution. All disinfection experiments were repeated three
times and their averaged values with statistical deviations were
used for the data analysis. The same experiments were also
carried out with para-chlorobenzoic acid (pCBA), a well-
known OH radical probe, to investigate the role of OH radicals
in virus inactivation for the TiO2/cotton fabric system. The
concentration of pCBA (initial concentration: 300 ppb) was
analyzed by HPLC (Waters Co.). A reverse-phase C18 column
(XTerra Rp-18, 5 μm, 150 mm × 2.1 mm) was used with a UV
detector (UV−vis 151, Gilson Co.) at 230 nm.
Murine norovirus-1 strain CW1 (MNV1) was propagated in
confluent monolayers using the murine macrophage cell line
RAW264.7, which was cultured in HyClone Dulbecco’s Figure 1. (a) XRD patterns and (b) Raman spectra of TiO2
nanoparticles: as-prepared and calcined at different temperatures.
modified Eagle’s medium (DMEM)/high glucose (GE Health-
care Life Sciences, Logan, UT). 44 The culture was
supplemented with 10% fetal bovine serum (FBS, Invitrogen, designated as as-prepared, HTi-1, HTi-2, HTi-3, HTi-4, and
Carlsbad, CA) containing penicillin/streptomycin and incu- HTi-5 according to calcination conditions (untreated, 300,
bated at 37 °C in a 5% CO2 chamber. The virus was incubated 500, 700, 900, and 1100 °C, respectively). Each sample
for 2 days, subjected to 3 freeze−thaw cycles, and finally displays the main characteristic peaks of the anatase, brookite,
harvested by low-speed centrifugation at 1000g for 30 min. To and rutile phases at 25.3, 30.8, and 27.5°, respectively, as
concentrate the virus, the supernatant was filtered using an referenced from the Joint Committee on Powder Diffraction
Amicon Ultra-15 centrifugation unit (Merck Millipore, Ire- Standards (JCPDS card numbers: anatase, 21-1272; brookite,
land). 29-1360; and rutile, 21-1276). At low calcination temperatures
The influenza A (H3N2) virus was obtained from the Korea (<500 °C), broad XRD peaks are observed owing to the
Bank for Pathogenic Viruses (KBPV, Seoul, South Korea). The amorphous structure of the TiO2 nanoparticles. With
virus was propagated in Madin−Darby canine kidney increasing calcination temperature (>500 °C), the XRD
(MDCK) cells (American Type Culture Collection (ATCC), peaks steadily narrow and sharpen. This may be attributed to
Manassas, VA) and assessed by plaque titration. Cells were the elimination of grain boundary defects during calcination at
maintained in DMEM supplemented with 10% FBS containing high temperatures, which therefore increases the crystallinity of
100 U/mL penicillin, 100 μg/mL streptomycin (HyClone), the TiO2 nanoparticles.46 Further, the crystallite size of all of
0.2% bovine serum albumin (BSA, Gibco, Waltham, MA), and the samples increases with calcination temperature, as shown
25 mM HEPES (Gibco) in a humidified atmosphere in Table 1. The crystallite size of each phase was calculated
containing 5% CO2 at 37 °C. using Scherrer’s equation, and the weight fractions of the
10670 https://doi.org/10.1021/acsomega.1c00043
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Table 1. Physical Properties of TiO2 (HTi) Nanoparticles as a Function of Calcination Temperature

anatase brookite rutile
sample no. calcination temperature (°C) size (nm) content (%) size (nm) content (%) size (nm) content (%)
as-prepared 0 6.35 81 4.80 19
HTi-1 300 10.10 81 10.70 19
HTi-2 500 17.01 39 13.45 41 18.17 20
HTi-3 700 28.19 79 26.69 21
HTi-4 900 46.10 12 51.90 88
HTi-5 1100 77.60 100

Figure 2. FE-SEM images of TiO2 nanoparticles calcined at different temperatures: (a) HTi-1, (b) HTi-2, (c) HTi-3, (d) HTi-4, and (e) HTi-5.

anatase, brookite, and rutile phases were estimated using eq 1. °C), the rutile phase content increases from 21 to 100%, with
A mixture of brookite and rutile phases is observed for the as- the higher thermal stability of the rutile phase driving the
prepared sample and HTi-1 (Figure 1a and Table 1). Since the transformation at high temperatures.51 These data suggest that
anatase (101) diffraction peak at 25.3° overlaps the brookite an increasing calcination temperature leads to higher
(120) diffraction peak at 25.3°, Raman spectroscopy analysis is crystallinity, a larger crystallite size, and phase transformation
needed to check the potential presence of anatase. Identi- in the TiO2 nanoparticles.
fication of the composition of each phase was conducted by 3.2. SEM and TEM Analyses. FE-SEM and HR-TEM
comparing the observed vibration modes with the litera- analyses were performed to investigate the effect of calcination
ture.47−50 In Figure 1b, HTi-1 shows characteristic signals of temperature on the morphology and particle size of the TiO2
brookite at 153 (A1g) and 247 (A1g) cm−1 and characteristic nanoparticles. Figure 2 shows the FE-SEM images of the
signals of rutile at 447 (Eg) and 612 (A1g) cm−1. Meanwhile, calcined TiO2 nanoparticles. Clearly, the calcination temper-
HTi-2 presents characteristic signals of brookite and rutile as ature does not influence the morphology of the nanoparticles,
well as the signals of anatase at 399 (B1g), 516 (A1g), and 639 which retain their irregular spherical shapes after calcination.
(Eg) cm−1. Upon increasing the calcination temperature from However, the particle size increases with calcination temper-
300 to 500 °C, the brookite phase is transformed into the ature, as shown in Table 1 and Figure 2.
anatase phase (HTi-2). At 700 °C (HTi-3), the characteristic Figure 3 shows the morphology, d-spacing values, and
brookite (121) peak at 30.8° disappears, indicating the selected area electron diffraction (SAED) patterns of the
complete phase transformation from brookite to anatase. calcined TiO2 nanoparticles subsequent to their HR-TEM
With further increases in calcination temperature (to 1100 analyses. The particle and crystallite sizes of the nanoparticles
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Figure 3. HR-TEM images and SAED patterns of TiO2 nanoparticles calcined at different temperatures: (a) HTi-1, (b) HTi-2, (c) HTi-3, (d)
HTi-4, and (e) HTi-5.

increase with calcination temperature. Figure 3a shows between the fringes are estimated as 0.290 and 0.321 nm,
nanoparticles with both spherical and rod shapes, comprising which are close to the (121) lattice spacing of brookite and the
a mixture of brookite and rutile phases. The d-spacing values (110) lattice spacing of rutile, respectively. With increasing
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calcination temperature (to 500 °C, Figure 3b), a mixture of Table 2. BET Surface Areas and Pore Volumes of TiO2
anatase (101), brookite (121), and rutile (110) phases with d- (HTi) Nanoparticles Calcined at Various Temperatures
spacings of 0.352, 0.290, and 0.326 nm, respectively, is
sample no. surface area (m2/g) pore volume (cc/g)
observed. Figure 3c,d shows mixtures of anatase (101) and
rutile (110) phases with d-spacings of 0.351 and 0.323 nm, HTi-1 101.24 0.268
respectively. Figure 3e shows the single rutile (200) phase with HTi-2 45.68 0.210
d = 0.229 nm. The SAED patterns of the calcined TiO2 HTi-3 17.61 0.132
nanoparticles confirm the mixtures of brookite and rutile HTi-4 5.32 0.026
phases, as shown in Figure 3a. After calcination at 500 °C, a HTi-5 3.25 0.015
triphasic mixture of anatase (101), brookite (121), and rutile
(110) phases is observed. The SAED patterns shown in Figure 3.4. Optical Analysis. The optical properties of the
3c,d indicate mixtures of anatase (101) and rutile (110) calcined TiO2 nanoparticles were investigated before the
phases. Finally, after calcination at 1100 °C, only the rutile photocatalytic performance tests because the UV−vis
(200) phase is observed, again confirming complete trans- absorption edge is associated with the energy band of the
formation of the anatase phase. Moreover, from the XRD semiconductor. The UV−vis absorption spectra of the TiO2
results, the crystallinity increases as a result of crystallite nanoparticles in Figure 5a clearly show that the UV−vis
growth with thermal energy input. Therefore, different phase absorption edge is shifted toward higher wavelengths with an
transformations occur depending on the calcination temper- increase in calcination temperature.
atures. The optical band gap energies of the samples were calculated
3.3. BET and BJH Analyses. Figure 4 shows the nitrogen on the basis of Tauc plots. The band gap values can be
adsorption−desorption isotherms of the calcined TiO2 nano- determined using the following equation57,58
(αhν)n = B(hν − Eg ) (3)
where α is the absorption coefficient, hv is the photon energy,
B is a constant relative to the material, Eg is the energy gap, and
n is a value that depends on the nature of the transition (n = 2
for a direct allowed transition, 2/3 for a direct forbidden
transition, and 1/2 for an indirect allowed transition). The
band gap values were calculated by extrapolating the plots of
(αhv)n versus photon energy for direct (n = 2; Figure 5b) and
indirect (n = 1/2; Figure 5c) transitions. The direct and
indirect band gap values are depicted in Table 3. The
estimated direct band gap values for the calcined TiO2
nanoparticles range from 3.05 to 2.98 eV, whereas the
estimated values for the indirect band gap vary from 2.99 to
2.91 eV. The band gap of rutile TiO2 (HTi-5) is smaller than
that of bulk rutile TiO2 (3.02 eV).59 For both direct and
indirect transitions, the optical band gap clearly decreases with
calcination temperature, and the direct band gap values are
Figure 4. Nitrogen adsorption−desorption isotherms of the TiO2 greater than the corresponding indirect band gap values. These
nanoparticles calcined at different temperatures. results can be explained on the basis of particle size, which
affects the optical band gap: for most semiconductors, a
decrease in band gap with an increase in particle size leads to a
particles. According to the IUPAC classification, the obtained red shift of the optical absorption edge.30,60
isotherms can be described as type IV52 indicating the 3.5. Photocatalytic Degradation. The photocatalytic
presence of well-developed mesopores associated with capillary performance of the calcined TiO2 nanoparticles was evaluated
condensation of the adsorbent. Adsorption isotherms of in the degradation of MB under UV light irradiation. The
mesoporous TiO2 nanoparticles are also described by degradation of a dye indicates that a photochemical reaction
hysteresis loops (H1−H4) that indicate the distribution and has occurred. Figure 6a,b presents the changes in MB
shapes of the pores within the materials.53 The calcined TiO2 absorption over time in the presence of HTi-3 (calcined at
nanoparticles present H3-type hysteresis loops, which 700 °C) and commercial Degussa P25 as a reference,
represent isotherm curves that increase slowly and then rise respectively. The maximum peak at 665 nm decreases
sharply at high relative pressure P/P0 (P: the balance pressure; progressively with elapsed UV irradiation time, and the rate
P0: saturation pressure).54 These results indicate that the pores of decrease is more rapid with HTi-3 compared to P25. This
are irregular with parallel, slit-like, and open-ended-tubular can also be observed in Figure 7a,b, which shows the
shapes. photocatalytic performance of the calcined TiO2 nanoparticles
Table 2 shows the surface areas and pore volumes of the and P25 in MB degradation. It is well known that the
TiO2 nanoparticles obtained at various calcination temper- adsorption on the surface of the catalyst affects the
atures. The surface areas of the calcined TiO2 nanoparticles are photocatalytic performance. Therefore, the adsorption capacity
101.24, 45.68, 17.61, 5.32, and 3.25 m2/g, respectively. Thus, under dark conditions of the sample was investigated before
with increasing calcination temperature, the surface areas, and the sample was exposed to the light irradiation. In Figure 7a, it
pore volumes decrease due to the crystallization of the TiO2 was observed that 7.5, 6.1, 5.8, 4.1, 2.8, 1.8, and 0.5% of MB
nanoparticles.55,56 readily adsorbed onto P25, as-prepared, HTi-1, HTi-2, HTi-3,
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Figure 6. Absorption spectra changes of methylene blue under UVA

light irradiation for different time periods: (a) HTi-3 (700 °C) and
(b) P25.

HTi-4, and HTi-5, respectively, during the adsorption process

(in dark conditions). The lower adsorption capacity of MB on
the samples calcined at higher temperatures could be ascribed
to the decrease of the surface area of HTi samples (Table 2).
The calcination temperature of the TiO2 nanoparticles also has
an impact on the degradation kinetics, as shown by the
constants in Table 4. The first-order rate constants were
calculated using ln(C0/Ct) = kt, where k is the first-order
constant, C0 is the initial concentration, and Ct is the
concentration of the dye after the photocatalytic reaction for
time t. The order of MB degradation rate constants is HTi-3 >
Figure 5. (a) UV−vis absorption spectra of TiO2 nanoparticles P25 > HTi-2 > HTi-4 > HTi-1 > as-prepared > HTi-5.
calcined at different temperatures. (b) Direct and (c) indirect Tauc Although HTi-3 (anatase/rutile = 79:21) has a similar phase
plots demonstrating the band gaps of TiO2 nanoparticles calcined at composition to that of P25 (anatase/rutile = 75:25), HTi-3
different temperatures. shows the best photocatalytic performance, with a rate
constant of 3.11 × 10−2 min−1. Generally, the photocatalytic
Table 3. Direct and Indirect Band Gap Values of TiO2 performance of TiO2 nanoparticles depends on many factors,
Nanoparticles Calcined at Different Temperatures including phase composition, crystallinity, crystallite size, and
band gap (eV)
surface area.22−24 In our study, HTi-3 shows the best
2
photocatalytic performance because of its high crystallinity
sample no. direct (αhν) indirect (αhν)1/2 and anatase/rutile phase composition. Further, anatase has an
HTi-1 3.05 2.99 indirect band gap structure, while brookite and rutile have
HTi-2 3.03 2.98 direct band gap structures. The indirect band gap structure
HTi-3 3.02 2.96 provides longer e−/h+ lifetimes, leading to the lower
HTi-4 3.01 2.94 recombination of e−/h+ pairs. Despite the larger surface areas
HTi-5 2.98 2.91 in HTi-1 and HTi-2 compared to HTi-3, lower photocatalytic
performance is observed, with k values of 3.68 × 10−2 and 1.06
× 10−2 min−1, respectively. This is consistent with the study of
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Figure 7. (a) Photocatalytic degradation curve and (b) corresponding degradation kinetics for degradation of methylene blue by calcined TiO2
nanoparticles and P25. Images of methylene blue photodegradation by calcined TiO2 nanoparticles and P25: (c) initial (t = 0 min) and (d) final
(180 min).

Table 4. Kinetics Constants k for the Degradation of

Methylene Blue
sample no. k (min−1)
P25 2.99 × 10−2
as-prepared 2.97 × 10−3
HTi-1 3.68 × 10−3
HTi-2 1.06 × 10−2
HTi-3 3.11 × 10−2
HTi-4 1.02 × 10−2
HTi-5 1.59 × 10−3

Ozawa et al.,34 which reported that photocatalytic performance

was enhanced as WA increased and WB decreased. HTi-5
delivers the lowest photocatalytic performance with k = 1.59 ×
10−3 min−1 because this material consists of only single-phase Figure 8. Photocatalytic virus inactivation performance of calcined
rutile and has the largest crystallite size (77.6 nm) and smallest TiO2 nanoparticles (HTi-3 with cotton fabric) with MS2 bacter-
surface area (3.25 m2/g). Moreover, rutile has a direct band iophage, murine norovirus, and influenza virus.
gap structure, which leads to the fast recombination of e−/h+
pairs. These results are clearly observed in Figure 7c,d, wherein
both P25 and HTi-3 completely decompose MB after 180 min which were estimated from MS2 bacteriophage, murine
UV irradiation, while HTi-5 hardly degrades MB at all. norovirus, and influenza virus inactivation kinetics in aqueous
3.6. Photocatalytic Virus Inactivation. Since TiO2 has conditions during the 40 min BLB irradiation. In control
been shown to be capable of inactivating a broad range of experiments (without BLB irradiation), no inactivation of the
microorganisms, photocatalytic virus inactivation against MS2 targets is observed on the time scale of this study. As OH
bacteriophage, murine norovirus, and influenza virus was radicals have been shown to be major participants in microbial
evaluated for the possible antimicrobial applications in public inactivation for TiO2 systems in a previous study,61 the
settings, such as cruise ships, nursing homes, hospitals, daycare degradation of the well-known OH radical probe pCBA was
centers, etc. Figure 8 shows photocatalytic virus inactivation also assayed (Figure 8 offset) under the same experimental
profiles obtained for the HTi-3-coated cotton fabric system, conditions.
10675 https://doi.org/10.1021/acsomega.1c00043
ACS Omega 2021, 6, 10668−10678
ACS Omega http://pubs.acs.org/journal/acsodf Article

For the prepared fabrics, significant inactivation of the Ji Eun Lee − School of Chemical Engineering, Pusan National
viruses is observed. The HTi-3-coated cotton requires 40 min University, Busan 46241, Republic of Korea
to inactivate 99.9% (3 log) of the influenza virus under BLB Kang Seok Kim − Department of Organic Material and
irradiation. From the radical probe experiment in Figure 8 Science, Pusan National University, Busan 46241, Republic
(offset) and our previous assumptions61 (kexp = kOH radical, pCBA of Korea
[OH radical]ss (kexp = 0.126 s−1, kOH radical, pCBA = 5 × 109 M−1 Kwang Ho Kim − School of Materials Science and
s−1)), the steady-state concentration of OH radicals could be Engineering, Pusan National University, Busan 46241,
calculated as 2.5 × 10−11 M (=4.3 × 10−7 mg/L). Considering Republic of Korea
that the times required for 3 log inactivation of the MS2 Complete contact information is available at:
bacteriophage, murine norovirus, and influenza virus are 36, https://pubs.acs.org/10.1021/acsomega.1c00043
32, and 40 min, respectively, the required CT (disinfectant
concentration × reaction time) values for 3 log inactivation of Notes
the targets can be calculated as 1.5 × 10−5, 1.4 × 10−5, and 1.7 The authors declare no competing financial interest.

■
× 10−5 mg/L min, respectively. The results clearly demonstrate
that the HTi-3-coated cotton effectively inhibits the MS2 ACKNOWLEDGMENTS
bacteriophage, murine norovirus, and influenza virus.
This research was mainly supported by the Global Frontier
Program through the Global Frontier Hybrid Interface
4. CONCLUSIONS
Materials (GFHIM) of the National Research Foundation of
In this study, as-prepared TiO2 nanoparticles were calcined at Korea (NRF) funded by the Ministry of Science, ICT and
temperatures ranging from 300 to 1100 °C to investigate the Future Planning (No. 2013M3A6B1078882). This study was
effect of calcination temperature on photocatalytic perform- supported by the Basic Science Research Program through the
ance. The calcination temperature affected the crystallite size, National Research Foundation of Korea funded by the
crystallinity, particle size, and phase transformation in the as- Ministry of Science, ICT and Future Planning (No.
prepared TiO2 nanoparticles according to XRD, SEM, and 2017R1E1A1A01074266). This research was supported by
TEM analyses. The XRD patterns revealed that the calcined the National Research Council of Science & Technology
TiO2 nanoparticles were composed of brookite/rutile phases (NST) granted by the Korean Government (MSIP) (No.
(300 °C calcination temperature), anatase/brookite/rutile CRC-16-01-KRICT).
phases (500 °C), anatase/rutile phases (700 and 900 °C),
and rutile phase (1100 °C). Further, a reduction in surface area
from 101.24 to 3.25 m2/g was observed with increasing
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