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Phân Hủy Kháng Sinh Oxytetracycline Bằng Chất Xúc Tác Quang TiO2 Tái Tạo Bề Mặt

This study presents the development of a visible light-responsive photocatalyst, Tb/Cu doped TiO2 (TCTP), which demonstrates a degradation rate of oxytetracycline that is three times higher than bare TiO2. The co-doping of terbium and copper enhances photocatalytic activity by reducing the bandgap energy and increasing oxygen vacancies, leading to improved charge separation. The optimal doping ratio of Tb to Cu is found to be 1:1, making TCTP a promising candidate for photocatalytic applications under various light sources.
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0% found this document useful (0 votes)
15 views11 pages

Phân Hủy Kháng Sinh Oxytetracycline Bằng Chất Xúc Tác Quang TiO2 Tái Tạo Bề Mặt

This study presents the development of a visible light-responsive photocatalyst, Tb/Cu doped TiO2 (TCTP), which demonstrates a degradation rate of oxytetracycline that is three times higher than bare TiO2. The co-doping of terbium and copper enhances photocatalytic activity by reducing the bandgap energy and increasing oxygen vacancies, leading to improved charge separation. The optimal doping ratio of Tb to Cu is found to be 1:1, making TCTP a promising candidate for photocatalytic applications under various light sources.
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Applied Surface Science 687 (2025) 162244

Contents lists available at ScienceDirect

Applied Surface Science


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

Full Length Article

Degradation of antibiotic oxytetracycline using surface reconstituted


TiO2 photocatalyst
Chan-Seo You a , Jun-Young Noh a , Yunju Choi b, Sang-Chul Jung a,*
a
Department of Environmental Engineering, Sunchon National University, 255 Jungang-ro, Sunchon, Jeonnam, 57922, Republic of Korea
b
Busan Center, Korea Basic Science Institute, Busan 46742, Republic of Korea

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

Keywords: In this study, we successfully developed a photocatalyst that can respond to visible light and exhibit excellent
Oxytetracycline activity by doping terbium and copper simultaneously into TiO2 powder using the liquid phase plasma method.
Tb/Cu doped TiO2 photocatalyst When Tb/Cu doped TiO2 photocatalyst (TCTP) was used as a visible light source, the degradation rate increased
Liquid-phase plasma: Oxygen vacancies
by up to three times compared with that of bare TiO2. In the case of co-doped TiO2, an apparent synergistic effect
Photocatalyst reusability
of co-doping was confirmed compared to the single-component doping of Tb or Cu. The absorption edge moved
to the visible light region owing to simultaneous doping with Tb and Cu, and the greatest bandgap energy
reduction was achieved. In addition, Tb and Cu doping induced more oxygen vacancies, reducing the electron-
hole recombination rate by forming a charge imbalance. This is believed to improve photocatalytic activity by
adsorbing more oxygen molecules and inducing the formation of active radicals. The optimal Tb-Cu doping ratio
in this study was confirmed to be 1:1, and it can be used as a potential photocatalyst that can be activated by all
light sources, including UV and visible light.

1. Introduction extensively studied because they can decompose and remove various
types of organic chemical pollutants, are non-toxic and harmless to the
Various types of antibiotics are used to prevent and treat diseases in natural environment, and have high economic efficiency. Although TiO2
humans and animals. These antibiotics cannot be completely absorbed photocatalysts have various applications in pollutant destruction, their
or decomposed in the body and are excreted through urine and feces into efficiency is limited by two factors. First, owing to its high bandgap
aquatic ecosystems such as surface water, groundwater, and wastewater energy (3.1 eV for P-25), photocatalysis can be efficiently applied only in
[1,2]. Tetracycline antibiotics are widely used worldwide because they the UV region of the solar spectrum. Second, the recombination of
are effective against both Gram-positive and Gram-negative bacteria. electron-hole pairs occurs during the photocatalysis of TiO2 [4]. To
Different types of tetracycline (TC) and oxytetracycline (OTC) exist. overcome these limitations, the light absorption area is expanded, and
Most antibiotics are non-degradable; therefore, complete decomposition the efficiency is promoted through the optical modification of TiO2.
through wastewater treatment facilities, such as physicochemical or Various studies have been conducted, including dye sensitization,
biological treatments, is difficult. Additionally, only 4.3 to 72 % of TC combining carbonaceous materials, and doping with metals, non-metals,
and less than 50 % of OTC are processed, and the rest is discharged. metals/non-metals, and rare-earth elements [4].
Tetracycline antibiotics are detected in various places at concentrations In particular, methods for doping TiO2 with dopants are being
of approximately 0.1 to 460 µg/L [3]. Antibiotics that remain in aquatic studied in diverse ways through various changes to the dopant. Several
ecosystems owing to their non-degradable properties are potentially methods for TiO2 doping include the sol–gel method, electrophoretic
harmful to the ecosystem and humans, as they contribute to occurrence deposition, sputtering deposition, microemulsion calcination, and me­
of resistant bacteria and toxicity. Therefore, various advanced oxidation chanical mixing [5]. These methods have disadvantages such as high
processes (AOPs) have been studied and applied for the treatment of manufacturing costs, long reaction times, high-temperature treatments,
antibiotics. toxic organic solvent use, and volatile toxic substances [4,6]. The liquid
Among them, the method using TiO2 photocatalysts has been phase plasma (LPP) process is a recently introduced method to address

* Corresponding author.
E-mail address: [email protected] (S.-C. Jung).

https://doi.org/10.1016/j.apsusc.2024.162244
Received 9 September 2024; Received in revised form 17 November 2024; Accepted 27 December 2024
Available online 28 December 2024
0169-4332/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
C.-S. You et al. Applied Surface Science 687 (2025) 162244

Table 1 method. Copper and terbium precursors were copper chloride dihydrate
Various initial precursor concentrations and LPP process conditions for the (CuCl2⋅2H2O, Junsei Chemical Co.) and terbium (III) chloride hexahy­
production of Tb/Cu-doped TiO2 photocatalyst. drate (TbCl3⋅6H2O, Sigma Aldrich Co.), which were prepared by dis­
Samples Initial precursor concentration LPP process condition solving in deionized water (Daejung Chemicals & Metals Co., Ltd.)
(mM) without any additional treatment and were used as aqueous reactants.
Tb(Cl)3 Cu(Cl)2 The photocatalytic activity of the modified TiO2 photocatalysts was
Bare TiO2 0 0 • Power evaluated for the decomposition characteristics of oxytetracycline hy­
Tb2.0-TiO2 1.5 0 • voltage (250 V) drochloride (OTC, C22H24N2O9⋅HCl, Tokyo Chemical Industry Co.).
Tb1.5Cu0.5-TiO2 1 0.5 • frequency (30 kHz)
Tb1.0Cu1.0-TiO2 0.75 0.75 • pulse width (5 μs))
Tb0.5Cu1.5-TiO2 0.5 1 • LPP reaction time: 1 hr 2.2. Method
Cu2.0-TiO2 0 1.5

2.2.1. Preparation and characterization of TCTP


these limitations [7,8]. The LPP method allows the simultaneous doping In this study, the LPP method was used to simultaneously dope Tb (a
of a single- or multi-component dopant even with a short process time rare-earth element) and Cu (a transition metal) on the surfaces of TiO2
and can complete the doping process without post-treatment [9]. photocatalysts. The configuration of the LPP process and device was
Among the materials used as TiO2 dopants, rare earth elements are based on a previous study by our research team (Fig. S1(a)) [7,8]. The
one of the materials that are receiving attention as dopants owing to LPP process conditions and precursor injection concentrations for
their ability to promote autocatalytic or catalytic reactions because of reforming TiO2 photocatalysts are listed in Table 1. After completely
their 4f and 5d orbitals. However, rare-earth elements are expensive, dissolving TbCl3 and CuCl2 at certain concentrations in 250 mL of
and their widespread use is limited. To overcome these limitations, deionized water, P-25 (0.5 g) was added to the prepared solution, which
methods for doping rare-earth elements with other materials that can was stirred and sonicated to obtain a uniformly dispersed LPP reaction
produce synergistic effects are being studied, and inexpensive transition solution. The LPP reaction was performed after filling the LPP reactor
metals, in particular, are attracting attention. Transition metal doping with a completely dispersed and dissolved aqueous solution into the LPP
reduces the band gap energy and increases electron-hole recombination, reactor in Fig. S1(a). After completion of the LPP process, it was filtered
thereby reducing the efficiency of TiO2 as a photocatalyst. Co-doping (membrane filter, 0.45 µm pore size) and dried (vacuum oven, 24 h, 373
with various combinations such as metal/nonmetal, metal/metal, K), then recovered and used as TCTP. Analysis equipment was used to
nonmetal/nonmetal, etc. can produce catalysts with superior perfor­ evaluate the physicochemical properties of TCTP, and the analysis de­
mance, such as photocatalytic reactivity, based on synergy effects vices used are listed in Table S1.
compared to single doped catalysts. It is necessary to develop a method
of co-doping rare earth elements and transition metals to reduce the cost 2.2.2. Photocatalytic degradation tests
of rare earth elements while maintaining the advantages of single- The photocatalytic activities of TCTP and bare TiO2 (P-25) were
component doping [10]. Accordingly, in this study, by exploiting the compared to determine the effects of doping. The light source for the
LPP process, TiO2 was modified by doping with rare-earth elements and photocatalytic decomposition reaction was an LED lamp module man­
transition metals. Therefore, in this study, we attempted to decompose ufactured using 100 units of blue LED (NSPB519BS) and UV LED
and treat antibiotics (OTC), which have recently attracted attention as (NSPU510CS) purchased from Nichia. A schematic representation of the
water pollutants, by producing TiO2 that can undergo photocatalytic photocatalytic degradation test is shown in Fig. S1(b), and the target
action under sunlight and has low recombination (electron-hole pair). material for degradation was oxytetracycline (OTC), one of the antibi­
otics. In this photocatalytic decomposition reaction, the initial concen­
2. Materials and methods tration of OTC solution was 5 mg/L. A photocatalyst (0.2 mg mL− 1) was
added to the OTC solution at the same concentration, placed in a
2.1. Materials decomposition reaction vessel, and circulated at a rate of 500 mL min− 1.
Photocatalytic decomposition occurred when the reaction solution was
The Tb/Cu doped TiO2 photocatalyst (TCTP) used Degussa P-25 circulated through a quartz photodecomposition reactor installed inside
(nanopowder, 21 nm primary particle size (TEM), ≥99.5 % trace metals the LED lamp module. The reactant aqueous solution was collected at
basis) as a substrate and was doped with dopant Tb and Cu using the LPP each decomposition reaction time interval, and the photocatalyst
dispersed in the aqueous reaction solution was removed by

Fig. 1. X-ray diffraction pattern of bare TiO2 and Tb/Cu doped TiO2 photocatalys.

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C.-S. You et al. Applied Surface Science 687 (2025) 162244

Table 2 anatase (JCPDS card no. 21–1272) and rutile (JCPDS card no. 21–1276)
Crystalline Size of Tb/Cu- doped TiO2. (110) peak which was observed [11,12]. No additional impurity peaks
Sample DA(101) (nm) DR(110) (nm) due to the dopant were observed in the XRD patterns of the prepared
TCTPs, indicating that Tb and Cu occupied major positions in the TiO2
Bare TiO2 18.89 24.52
Tb2.0-TiO2 19.11 25.07 lattice [13]. As a result of the enlarged analysis of the anatase crystal
Tb1.5Cu0.5-TiO2 19.49 25.18 (101 peak) and the rutile crystal (110 peak), bare TiO2 was 25.26◦ and
Tb1.0Cu1.0-TiO2 19.69 25.50 27.37◦ at 2θ. Meanwhile, Tb1.0Cu1.0-doped TiO2 prepared through the
Tb0.5Cu1.5-TiO2 19.92 25.48 LPP process moved 0.04◦ and 0.05◦ to the right to 25.30◦ and 27.47◦ .
Cu2.0-TiO2 21.36 25.24
The diffraction peaks are believed to be displaced by stress or strain
effects [14]. Using the Scherrer equation from the XRD patterns, the
centrifugation and a syringe filter. Samples of the reactant solution from average crystal sizes related to the anatase (1 0 1) and rutile (1 1 0) peaks
which the TCTP powder was removed were analyzed at the maximum were calculated using the following equation:
absorption wavelength of OTC (355 nm) using a UV–vis spectrometer to Kλ
evaluate the decomposition efficiency. The reactive species generated Crystallite size, D = (1)
βcosθ
during the photodegradation process were analyzed by optical emission
spectroscopy (OES) and isopropyl alcohol (IPA, 500 mM), benzoquinone where λ is 1.5406 (Cu-source), β is FWHM (full width at half maxima,
(BQ, 2 mM), ethylenediaminetetraacetic acid (EDTA-2Na, 100 mM), and measured in radians), K is the shape coefficient of 0.94, and θ is the
methanol (Me-OH, 100 mM) were used as scavengers to investigate the Braggs angle of the diffraction peak [14,15]. Crystallite size calculation
radicals. results are shown in Table 2, which confirmed that the crystal size
increased owing to doping. In particular, when comparing the size of DA
3. Results and discussion (101) with bare TiO2, Tb2.0-TiO2, and Cu2.0-TiO2, the crystallite size
increased by 0.22 nm for Tb doping and 2.48 nm for Cu doping. Thus, Cu
3.1. Characterization of TCTP doping had a considerable effect on the crystallite size.

3.1.1. X-ray diffraction analysis 3.1.2. TEM analysis


X-ray diffraction (XRD) measurements were used to confirm the HR-FETEM analysis was performed to examine the structure and
phases and structures of the manufactured photocatalysts, and the elemental distribution of the TCTPs prepared using the LPP process. The
measurement results of TCTPs and bare TiO2 are shown in Fig. 1. The mapping results for Ti, O, Tb, and Cu for Tb1.0Cu1.0-doped TiO2 are
XRD pattern of bare TiO2 was the same as the diffraction pattern of shown in Fig. 2(a), and the dots for each element are distributed in the
typical P-25, with strong peaks of (200), (004), and (101), including same shape as in the real image. This indicates that the Tb and Cu ions in

Fig. 2. (a) The actual image of Tb1.0Cu1.0-doped TiO2 and the mapping image of each element and the image observed with a field emission energy filtering
transmission electron microscope(b-g).

Table 3
Chemical composition of Bare TiO2 and Tb1.0Cu1.0-doped TiO2 prepared by LPP method.
Sample Initial precursor Concentration (mM) Titanium Oxygen Terbium Copper
Tb(Cl)3 Cu(Cl)2 Wt. % At. % Wt. % At. % Wt. % At. % Wt. % At. %

Bare TiO2 0 0 58.66 32.16 41.34 67.84 0.00 0.00 0.00 0.00
Tb1.0Cu1.0-doped TiO2 1.0 1.0 56.91 31.37 41.27 68.11 0.94 0.16 0.87 0.36

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C.-S. You et al. Applied Surface Science 687 (2025) 162244

Fig. 3. Photoluminescence spectrum of bare TiO2 and Tb/Cu doped TiO2 photocatalys.

the reaction solution that dissociated from the precursor by the LPP plane (ICDD: 00–001-0562), 3.24 Å TiO2 rutile (1 1 0) plane (ICDD:
reaction were evenly doped on the TiO2 surface. Here, the numbers after 00–001-1292), 2.51 Å CuO( − 1 1 1) plane (ICDD: 00–001-1117), 2.19 Å
Tb and Cu represent the mM concentrations of the precursor when Tb2O3 (422) plane (ICDD: 00–023-1418), 1.84 Å TbO2 (220) plane
producing TiO2 via the LPP process. Table 3 shows the chemical (ICDD: 01–075-0209), and 1.74 Å Cu2O (211) plane (ICDD: 03–065-
composition of Tb1.0Cu1.0-doped TiO2 prepared at a concentration of 1 3288) were confirmed.
mM Tb and 1 mM Cu, as analyzed using Energy Dispersive X-ray Spec­
troscopy (EDS). The atomic percentage ratio was doped with Tb 0.16 % 3.1.3. Photoluminescence spectra analysis
and Cu 0.36 %, which are believed to be doped on the TiO2 surface, as Tb Fig. 3 shows the photoluminescence (PL) spectra of bare TiO2 and
and Cu ions are reduced by chemically active species generated during TCTPs measured at an excitation wavelength (350 nm) within the
the LPP process [16]. measurement range of 380–630 nm. Photoluminescence emission is
For a detailed structural analysis of Tb1.0Cu1.0-doped TiO2, the FE- derived from the recombination of holes and excited electrons, and the
EF-TEM (Field Emission Energy Filtering Transmission Electron Micro­ PL spectrum shows the separation of photoinduced pairs. Therefore, it
scope) measurement results are shown in Fig. 2(b)–(f); (b) and (c) show can be used to identify the charges separated by the dopant (Tb and Cu)
TEM images, and (d), (e), and (f) show enlarged lattice images. (d) ions doped into TiO2 [17,18]. When comparing bare TiO2 and TCTP in
shows the lattice spacings of the TiO2 anatase (1 0 1) plane (ICDD the PL spectrum shown in Fig. 3, the intensity of bare TiO2 was higher
00–001-0562), (e) the (422) plane (ICDD 00–023-1418) of Tb2O3, and and that of TCTP was significantly reduced. The spectrum of the Cu-
(f) the ( − 1 1 1) plane (ICDD 00–001-1117) of CuO, which were 0.352, doped TiO2 changed only in intensity, and a new emission peak was
0.219, and 0.251, respectively. The Selected Area Electron Diffraction not generated in the same way as in the results of previous Cu-doped
(SAED) pattern analysis results to confirm the Tb and Cu planes that TiO2 manufacturing studies [18]. In the PL spectra of Tb-doped TiO2
were not identified in the XRD pattern are shown in Fig. 2(g). By and TCTP, new emission peaks were observed at 490, 544, 587, and 622
comparing the observed discontinuous concentric diffraction ring with nm, which are believed to be due to Tb doping. This is due to the typical
d values for each plane of the ICDD card, 3.52 Å TiO2 anatase (1 0 1) radiative electronic transitions of doped Tb3+ and are the peaks

Fig. 4. (a) UV–Vis absorbance spectra, (b) band gap energy of bare TiO2 and Tb/Cu doped TiO2 photocatalys.

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C.-S. You et al. Applied Surface Science 687 (2025) 162244

Fig. 5. XPS spectrum of Tb1.0Cu1.0-doped TiO2 prepared using the liquid phase plasma method.

generated during the electric dipole transitions from 5D4 to 7F6, 7F5, 7F4, photocatalyst utilization under visible light.
and 7F3 [19]. The peak appearing at 390 nm is a peak due to the emission
of the bandgap transition corresponding to the bandgap energy of TiO2 3.1.5. X-ray photoelectron spectroscopy analysis
anatase. Oxygen vacancies typically cause electron trapping dynamics, X-ray photoelectron spectroscopy (XPS) characterization was per­
resulting in a decrease in peak intensity or an unobservable state. In formed to clarify the chemical composition and chemical bonding state
TCTPs, the intensity at 390 nm was reduced or not observed, which is of TCTP prepared via the LPP process. Fig. 5 shows the analysis results
thought to be due to increased oxygen vacancies [20]. As observed from for the bare TiO2 and Tb1.0Cu1.0-doped TiO2. Fig. 5(a) shows the Ti2p
the TEM-SAED results, the decrease in the intensity of TCTP was due to region spectrum, with the main peak of Ti4+ oxidation state at 458.6
the formation of a charge imbalance in the combination of Ti-O-Tb and (Ti2p3/2) eV and 464.3 (Ti2p1/2) eV for bare-TiO2, and the peak of 457.6
Ti-O-Cu, which were uniformly distributed on the TiO2 surface and in (Ti2p3/2) eV for Ti3+ oxidation state; Ti-C peak was detected at 459.8 eV.
the lattice gap. To rectify this, hydroxyl groups are adsorbed on the TiO2 In the Ti2p region spectrum of Tb1.0Cu1.0-doped TiO2, two major peaks
surface, facilitating oxidation. Thus, the photogenerated electrons and corresponding to the Ti4+ oxidation state of Ti2p3/2 and Ti2p1/2
holes effectively improve the separation state or suppress recombina­ appeared at binding energies of 458.9 and 464.7 eV, respectively, and
tion, thereby improving the photocatalyst performance [21,22]. the Ti3+ state at 457.9 and 463.6 eV peaks were detected. In particular,
the Ti3+ peak, which was not detected for bare TiO2, was detected at
3.1.4. UV–vis diffuse reflectance spectra analysis 463.6 eV [25,26]. The energy separation of Ti2p1/2 and Ti2p3/2 in the
Fig. 4 shows the UV-DRS analysis results of bare TiO2 and TCTPs. Ti4 + oxidation state was 5.7 eV, which agrees with the P-25 peak re­
Fig. 4(a) shows the UV–vis diffuse reflectance absorption spectra, indi­ ported in previous studies [27–29]. Comparing the positions of the
cating that the absorption of TCTPs from 400 to 700 nm was evidently detected peaks of bare-TiO2 and Tb1.0Cu1.0-doped TiO2, the positions
higher than that of bare TiO2. This indicates that doping creates a strong of the peaks shifted by approximately 0.3 eV, possibly because some Ti
absorption ability in the visible and UV light regions, expanding the light ions were replaced by dopant ions in the lattice [25].
response range to the visible light region [21]. Fig. 4(b) shows the Fig. 5(b) shows the O1s region spectrum. In bare TiO2, only two
bandgap energy (BGE) calculated using the Kubelka–Munk equation. peaks were detected: 530.3 eV of the Ti-O bond, which is lattice oxygen,
Bare TiO2 showed a value of 3.10 eV, which is similar to that reported in and 532.1 eV, a surface contamination peak such as OH. Tb1.0Cu1.0-
previous studies [23,24]. The BGE of TCTP was Tb2.0-doped TiO2 (2.89 doped TiO2 prepared by the LPP process was additionally confirmed to
eV), Tb1.5Cu0.5-doped TiO2 (2.95 eV), Tb1.0Cu1.0-doped TiO2, have a new peak, a chemisorbed oxygen peak of 533.8 eV [30]. Because
Tb0.5Cu1.5-doped TiO2 (2.86 eV), and Cu2.0-doped TiO2 (2.93 eV). of doping, the Ti-O-Tb bond appeared at the lattice oxygen peak, and the
Compared with bare TiO2, the BGE decreased in all cases owing to Ti-O-Cu bond appeared at the same peak as the surface contamination
doping. A maximum reduction of 0.24 eV was observed compared to peak. Meanwhile, as in the Ti2p spectrum, a peak shift of 0.2 to 0.4 eV
bare TiO2. This result shows that Tb and Cu doping reduces the distance was observed due to doping [31,32].
between the valence and conduction bands, thereby improving Fig. 5(c) shows the high-resolution XPS spectrum of the Tb3d region,

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C.-S. You et al. Applied Surface Science 687 (2025) 162244

where Tb2O3, Tb3d5/2 (1242.7 eV), and Tb3d3/2 (1274.0 and 1277.4
eV), were observed. Additionally, a peak corresponding to Tb3+ in the
TbO1.5 state was observed. Furthermore, the Tb4+-related peaks by the
TbO2 and TbO1.82 states were confirmed at 1244.6 (Tb3d5/2) and 1281.7
(Tb3d3/2) eV [33–35]. These results were confirmed by TEM analysis
and suggested that the doped Tb exists in one or more oxidation states:
Tb3+ and Tb4+.
As shown in Fig. 5(d), Cu2P3/2 was observed at a binding energy of
933.0 eV, and Cu2P1/2 at a binding energy of 952.7 eV. These peaks
were caused by Cu+, indicating that Cu existed as Cu2O but not as CuO
[36]. These values are consistent with the Cu2O values reported in
previous studies [37,38]. Although two forms of Cu2O and CuO were
observed in the TEM SAED pattern, only the peak of Cu2O was observed
in the XPS analysis. This is considered to be detected only in the form of
Cu+, which exists in a relatively high form owing to the low peak height
resulting from the small amount of Cu doped on the TiO2 surface [39].
Colón reported that Cu+ has a better effect on photocatalytic activity
than Cu2+ and acts as a photoactive species that avoids the recombi­
nation of electron holes [40]. These results are expected to positively
affect the photocatalytic activity of TCTP doped in Cu+ through the LPP
process.
Fig. 6. Changes in the ratio of the peak areas of Ti4+, Ti3+, Ti-C and oxygen Fig. 6 shows the change in the ratio of peak areas of Ti4+, Ti3+, Ti-C,
vacancies in Ti2p, O1s during the doping process through the LPP process.
and oxygen vacancies in Ti2p and O1s during the doping process via the
LPP process. By comparing three types of TiO2, namely bare TiO2, Tb2.0-
doped TiO2, and Tb1.0Cu1.0-doped TiO2, the effects of doping and co-

Fig. 7. Oxytetracycline decomposition behavior of bare TiO2 and Tb/Cu doped TiO2 under UV LED light and blue LED light.

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C.-S. You et al. Applied Surface Science 687 (2025) 162244

Fig. 8. (a) cycling runs in the photocatalytic degradation of oxytetracycline under UV light irradiation, (b) XRD patterns of Tb1.0Cu1.0-TiO2 before and after pho­
tocatalytic reaction.

doping were also compared. The ratio of Ti4+ oxidation state decreased results of the decomposition reaction of OTC using TCTPs and bare TiO2
from 90.4 % to 71.4 % and 81.5 %, respectively, by 19.0 % and 8.9 %, as photocatalysts are shown in Fig. 7(a) and (b) under UV LED light
but it accounted for most of the oxidation states. This indicates that Ti conditions and Fig. 7(c) and (d) under blue LED light conditions. During
ions in the TiO2 lattice mainly exist in the form of Ti4+ even when the a 90 min reaction time under UV LED light conditions, 95.0 % of bare
doping process proceeds through the LPP process. The decrease in the TiO2, 87.8 % of Tb2.0-doped TiO2, 91.0 % of Tb1.5Cu0.5-doped TiO2,
area of Ti4+ and the increase in the area ratio of Ti3+ by 4.4 and 2.4 95.3 % of Tb1.0Cu1.0-doped TiO2, 82.7 % of Tb0.5Cu1.5-doped TiO2, and
times, respectively, indicate that after the LPP process, Ti ions were 80.0 % of Cu2.0-doped TiO2 decomposed. The decomposition reaction
substituted and replaced by Tb or Cu ions, or a mixed oxide structure rate constant K during the first 30 min was 3.22 × 10-2 min− 1 for bare
with an oxidation state of Ti3+ was formed by the formation of Ti-O-Tb TiO2, 4.98 × 10-2 min− 1 for Tb2.0-doped TiO2, 5.12 × 10-2 min− 1 for
structure in the TiO2 lattice, or the formation of Ti2O3 [25]. In the Tb1.5Cu0.5-doped TiO2, 5.41 × 10-2 min− 1 for Tb1.0Cu1.0-doped TiO2,
change in the peak area ratio of oxygen vacancies, the area of lattice 3.88 × 10-2 min− 1 for Tb0.5Cu1.5-doped TiO2, and 3.44 × 10-2 min− 1 for
oxygen was significantly reduced from 92.4 % in the doping process Cu2.0-doped TiO2. The decomposition reaction rate constant, K,
using the LPP process to 80.4 % for Tb2.0-doped TiO2, which was a 12 % increased from a minimum of 1.07 times to a maximum of 1.68 times
decrease, and to 66.3 % for Tb1.0Cu1.0-doped TiO2, which was a 26 % through doping, possibly because the photocatalytic performance
decrease. It can be seen that the areas of OH peak and chemisorbed improved owing to the effects of Tb and Cu doping, consistent with the
oxygen peak increased and were newly formed. In addition, an increase results predicted from the PL analysis. Under blue LED light conditions,
in surface oxygen species was confirmed, which is thought to be because during the 90 min decomposition reaction time, bare TiO2 was reduced
the dopants, Tb and Cu, substituted Ti ions or formed oxide structures by 14.6 %, Tb2.0-doped TiO2 by 37.5 %, Tb1.5Cu0.5-doped TiO2 by 40.6
such as Cu2O, CuO, TbO2, and Tb2O3. In particular, in the case of co- %, Tb1.0Cu1.0-doped TiO2 by 43.6 %, Tb0.5Cu1.5-doped TiO2 by 36.4 %,
doping, the decrease was 2.2 times larger, suggesting that more O va­ and Cu2.0-doped TiO2 by 20.6 %. The decomposition reaction could be
cancies can be formed through co-doping than through single-element activated through doping, and when Tb1.0Cu1.0-doped TiO2 was used,
doping. By confirming the change in peak area of the XPS spectrum, it the decomposition rate increased up to 3 times compared to that of bare
was confirmed that the band gap reduction and red shift in Tb and Cu TiO2. The decomposition reaction rate constant K for 90 min also
doping using the LPP process were due to the O vacancy and Ti3 + improved 3.5 times from 1.81 × 10-3 min− 1 to 6.38 × 10-3 min− 1.
formation [41]. The decomposition rate of OTC by TCTP manufactured with LPP was
considerably improved compared to that of bare TiO2 under all UV and
blue light sources. The improvement in the decomposition rate of TCTP
3.2. Photocatalytic activity of TCTP is due to the weakening of the PL emission compared to bare-TiO2 due to
the Tb and Cu dopants doped on the TiO2 surface, as confirmed by the PL
This study performed a degradation experiment to evaluate the analysis. Therefore, as the separation of electron holes increases and
photocatalytic activity of bare TiO2 and TCTPs for the antibiotic recombination is suppressed, the generation of oxidants such as hy­
oxytetracycline hydrochloride (OTC). The calculation of the decompo­ droxyl radicals can be increased, and the BGE can be reduced, thereby
sition reaction rate was assumed to follow a pseudo-first-order decom­ strengthening the photoelectric effect [42]. For co-doped TiO2, an
position reaction, and the decomposition reaction results during the first apparent synergistic effect of co-doping was confirmed compared to the
30 min of the reaction under UV light (λmax = 375 nm) conditions and single-component doping of Tb or Cu. Cu-doped TiO2 showed a signif­
the first 90 min of the reaction under blue light (λmax = 465 nm) icant decrease in the PL emission peak, while the decrease in the BGE
conditions were applied to the calculation. was the smallest. For Tb doping, the PL emission peak was reduced to a
Fig. 7 shows the results of the OTC degradation experiment using smaller extent than that of Cu, while the bandgap energy was further
TCTPs and bare TiO2 prepared by the LPP process. To test the photo­ reduced. For TCTP, the absorption edge moved to the visible light region
degradation resistance of OTC, its decomposition efficiency was inves­ owing to the effects of Tb and Cu doping, and the largest BGE reduction
tigated during light irradiation for 90 min under blue and UV LED light. was achieved. Additionally, as shown in TEM and XPS analyses, Tb and
Consequently, 2.9 % decomposed under UV LED light (Fig. 7(a)), and Cu doping replace the Ti4+ oxidation state with Tb3+ or Cu+ oxidation
only 0.7 % decomposed under blue LED light (Fig. 7(c)). Therefore, the states, which causes oxygen vacancies and charge imbalances. It is
antibiotic OTC barely decomposed after irradiation with light alone. The

7
C.-S. You et al. Applied Surface Science 687 (2025) 162244

Fig. 9. (a) OES spectrum in each solution condition, (b) change in intensity of radicals for change in TCTPs.

believed that hydroxide ions are adsorbed on the surface of TCTP to


balance the charge, and the surface hydroxide ions combine with holes
generated by UV to induce the formation of hydroxyl radicals, thereby
reducing the speed of electron-hole recombination and improving the
photocatalytic activity [43,44]. It was thought that the OH radical
generated during this process was involved in the decomposition of
OTC. The optimal Tb-Cu doping ratio in this study was confirmed to be
1:1, and Tb1.0Cu1.0-doped TiO2 prepared through the LPP process can be
used as a potential photocatalyst that can be activated in all light
sources, including UV and visible light.

3.3. TCTP reusability and stability

A recyclability test was conducted under UV irradiation to evaluate


the reusability and stability of TCTP prepared using the LPP process.
After conducting 15 recycling tests, the XRD patterns of used TCTP were
compared and analyzed. As shown in Fig. 8(a), the TCTP photocatalytic
performance slightly decreased during the 15 reactions of 90 min each,
and the photodegradation efficiency was maintained at 83.8 % even
after 15 cycles. As shown in Fig. 8(b), the results of the XRD analysis of
TCTP used 15 times showed that the XRD patterns were almost the same Fig. 10. Comparison of decomposition rate constants by different reactive
before and after several decomposition tests. The slight decrease in species scavengers in OTC photodegradation using bare TiO2 and Tb1.0Cu1.0-
crystallinity and the 0.14 nm growth of the crystallite size from 19.69 doped TiO2.
nm to 19.83 nm (using the Scherrer equation) were presumed to be due
to the effects of the drying and purifying process after the decomposition solution, respectively. As can be confirmed from the emission spectrum
test. Reusability experiments confirmed that TCTP is a recyclable ma­ in Fig. 9(a), when the photocatalyst was administered, it was confirmed
terial that exhibits stable photocatalytic performance. that the amount of reactive active species generated was significantly
greater than that of OTC, and at this time, the reactive active species
3.4. Investigation of reactive species generated were hydroxyl radical (⋅OH, 309 nm), hydrogen radical (Hβ
486 nm, Hα 656 nm), and oxygen radical (O, 777 nm, 844 nm) [46,47].
In order to identify the reactive species involved in OTC decompo­ Fig. 9(b) shows the results of comparing the amount of active species
sition in photodecomposition using TCTP, optical emission spectroscopy produced by bare-TiO2 and TCTP types using OES intensity. When TCTP
(OES) analysis was performed, and the effect of each reactive species was used, it was confirmed that the production of all active species
was indirectly confirmed using a scavenger. OES analysis was used to increased compared to bare-TiO2, and in particular, the greatest change
detect the active species generated during the photolysis process using was observed when Tb1.0Cu1.0-doped TiO2 was used. When comparing
TCTP and to compare the indirect production amount, and the reactive each active species, the hydroxyl radical (⋅OH) at 309 nm increased 2.54
active species generated during plasma discharge were investigated and times, the hydrogen radical Hβ (486 nm) increased 4.77 times, and the
compared using the LPP system used in the production of TCTP [45]. Hα (656 nm) increased 3.23 times compared to bare TiO2. The oxygen
The OES results of the reactive active species generated through plasma radical was also detected 4.70 times at 777 nm and 4.89 times at 844
discharge by injecting bare TiO2 and TCTP into the OTC solution are nm. Through this, it was confirmed that the TCTP with the highest active
shown in Fig. 9. Fig. 9(a) shows the OES results, showing the emission species production was Tb1.0Cu1.0-doped TiO2, and it was confirmed
spectra of the OTC solution from 200 to 1000 nm and the cases where that this was consistent with the result of the photodecomposition in
bare-TiO2 and Tb1.0Cu1.0-doped TiO2 were injected into the OTC which the decomposition efficiency of Tb1.0Cu1.0-doped TiO2 was the

8
C.-S. You et al. Applied Surface Science 687 (2025) 162244

Fig. 11. Predicted pathway for the photocatalytic decomposition reaction of oxytetracycline using Tb1.0Cu1.0-doped TiO2.

best. 147, 139, 111, 83, and 61, which are ultimately decomposed into CO2,
Using Scavenger, the results of indirectly confirming the active H2O, and N-minerals.
species that has the greatest effect on OTC photodecomposition among
the active species are shown in Fig. 10. Isopropyl alcohol (IPA), ben­ 4. Conclusion
zoquinone (BQ), EDTA-Na, and methanol (Me-OH) were used as scav­
engers. IPA was added to remove hydroxyl radicals (•OH), BQ to remove A photocatalyst capable of responding to visible light and exhibiting
superoxide radicals (•O–2), EDTA-Na to remove holes (h+), and Me-OH to excellent activity was manufactured by doping terbium and copper
remove electrons (e-), and then photodecomposition was performed to simultaneously with TiO2 powder using the liquid phase plasma method.
confirm their respective effects [48,49]. As shown in the results in XRD analysis revealed that the crystallite size increased owing to
Fig. 10, it was confirmed that hole (h+) had the greatest effect on the doping, and Cu doping had a greater effect on the crystallite size. TEM
decomposition of OTC using TiO2 photocatalyst and was the main active analysis showed that Tb and Cu were uniformly doped on the TiO2
species. Changes due to Tb and Cu doping were confirmed by the change surface, and SAED pattern analysis confirmed the Tb2O3, TbO2, CuO,
in the ratio of OTC decomposition reaction rate constants when using and Cu2O planes. In addition, it was assumed that a Ti-O-Tb structure
bare TiO2 and Tb1.0Cu1.0-doped TiO2 according to each scavenger in­ was formed within the TiO2 lattice and that a mixed oxide structure with
jection. When ISO was used as an •OH scavenger, the decomposition the oxidation state of Ti3+ was formed by the formation of Ti2O3. Cu-
reaction rate constant of bare TiO2 decreased by 5.4 % compared to doped TiO2 exhibited a significant decrease in the PL emission peak,
before addition, whereas it decreased by 26.9 % when Tb1.0Cu1.0-doped whereas the decrease in the bandgap energy was the smallest. For Tb-
TiO2 was used. Through this, it was confirmed that when doping is doping, the PL emission peak was reduced to a smaller extent than
performed, •OH is formed in greater amounts than bare TiO2, thereby that of Cu, whereas the BGE was further reduced. It was assumed that
improving the decomposition efficiency. the band gap reduction and red shift owing to the simultaneous doping
of Tb and Cu by LPP were due to O vacancies and Ti3+ formation. When
3.5. Degradation pathways Tb1.0Cu1.0-doped TiO2 prepared by doping with LPP was used as a
visible light source, the decomposition rate increased up to three times
To better understand the degradation process of OTC using TCTP compared to that of bare TiO2. The improvement in the decomposition
photocatalyst and to detect intermediates and investigate the reaction rate of TCTP increased the generation of oxidants, such as hydroxyl
pathways generated during the degradation process, LC-MS/MS analysis radicals, by increasing the separation of electron holes and suppressing
was performed, and the expected intermediates and degradation path­ recombination by simultaneous doping with Tb and Cu, which was
ways are shown in Table S3 and Fig. 11. The decomposition experiment strengthened by reducing the band gap energy. TCTP stability and
was conducted by injecting 0.1 g of Tb1.0Cu1.0-doped TiO2 into a 5 ppm reusability tests confirmed that TCTP is a reusable and stable photo­
OTC solution and conducting photodecomposition under UV irradiation. catalytic material.
The decomposition pathway of OTC can be largely divided into two
types as shown in Fig. 11, and the main decomposition processes are CRediT authorship contribution statement
estimated to be hydroxylation, ring-opening reaction, demethylation,
and dehydration. Pathway I is a process in which the double bond at Chan-Seo You: Writing – original draft, Investigation. Jun-Young
C11a-C12 positions reacts with ⋅OH radicals through hydroxylation to Noh: Investigation, Data curation. Yunju Choi: Formal analysis. Sang-
generate a primary intermediate with m/z = 477, then the acylamino Chul Jung: Writing – review & editing, Supervision.
group, carbinol groups, and methyl groups at C2 position are lost to
generate m/z 340, and m/z 279 is generated through the removal of Declaration of competing interest
methyl groups at C6 position and the opening of benzene rings [50,51].
Pathway II forms m/z 358 through dehydration and demethylation of The authors declare that they have no known competing financial
C6, m/z 227 through deamination and opening of benzene rings, and m/ interests or personal relationships that could have appeared to influence
z 208 through removal of methyl groups in an additional reaction [52]. the work reported in this paper.
Subsequent additional reactions include ring-opening reaction and
oxidation by active species such as ⋅OH to generate substances with m/z

9
C.-S. You et al. Applied Surface Science 687 (2025) 162244

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Strategy towards Multi–functionality, ChemistrySelect. 1 (2016) 2140–2147,
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Korea (NRF) grant funded by the Korean Government (MSIT) [20] S. Chan, Y. Xiao, Y. Wang, Z. Hu, H. Zhao, W. Xie, A Facile Approach to Prepare
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