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3D PRINTING AND ADDITIVE MANUFACTURING

Volume 4, Number 4, 2017


ª Mary Ann Liebert, Inc.
DOI: 10.1089/3dp.2017.0033

ORIGINAL ARTICLE

3D Printed Hierarchical Gyroid Structure with Embedded


Photocatalyst TiO2 Nanoparticles
Wonjin Jo, Bum Joon Yoon, Hyebin Lee, and Myoung-Woon Moon

Abstract

Natural hierarchical structures, such as tree leaves or butterfly wings, have been broadly studied due to their
exclusive functions, including ultralight nature, higher surface area-to-volume ratio, and high chemical reaction
efficiency. In this study, we develop a 3D printed hierarchical gyroid structure with embedded TiO2 nano-
particles (NPs) to investigate its effective photocatalytic structural performance for long-term application.
Fused deposition modeling 3D printing is used to fabricate a gyroid structure with a functionalized photode-
gradable polylactic acid (PLA) containing embedded TiO2 NPs. The porous and 3D network gyroid structure
provides more light pathways and surface area, which increases the contact interface and rapid mass trans-
portation under UV irradiation. In addition, as the PLA is photodegraded at the surface over time, improved
hierarchies are created within the structure. It allows the embedded TiO2 NPs to be continuously exposed to the
surface along the hierarchical structure. As a result, the hierarchical gyroid structure not only maintains its
reaction efficiency but also exhibits better adsorption and faster photocatalytic ability by the formation of
additional voids as the reaction time is prolonged. This structural and material design approach will suit well for
various applications, such as drug-eluting devices, water purification filters, or energy-harvesting devices.

Keywords: 3D printing, hierarchical structure, gyroid structure, TiO2 nanoparticle, photocatalyst, PLA
degradation

Introduction terference ultraviolet filter,10 electrochromic devices,11 or a


photonic system.6 The ability to mimic these 3D network
Hierarchical structures found in various natural sys- structures with high surface-to-volume ratios is of great im-
tems have been adopted in several fields due to features such portance in many areas of surface science and technology. In
as their ultralight nature, higher surface area-to-volume ratio, particular, when the material is highly porous, the 3D net-
and rapid chemical reaction kinetics by nanoscale agents.1–3 work structure is expected to provide accessibility for surface
Animal bones are known to possess several hierarchies in chemical agents to react with water or other targets. By
which nanoscale structures improve chemical reactions, mimicking natural smart systems, various fabrication meth-
whereas micro- or macro-scale structures play an important ods have been developed for the proper realization of
role in reducing the structures’ total weight and supporting hierarchical and/or 3D network structures.12–15 Therefore,
impact resistance.4,5 Single gyroid (GA, I4132) is a fascinat- simultaneous control over a structure’s properties, including
ing example that is found in certain tropical butterfly spe- its porosity and connectivity, is essential in fabrication sys-
cies.6,7 Gyroid possesses unique properties, including (1) a tems to mimic or even surpass natural designs. 3D hierar-
network structure characterized by an infinitely connected chical and porous structures with a large void space have
triply periodic surface containing no straight lines,8,9 (2) a multiple potential applications in diverse fields, such as filtra-
lack of planes of reflectional symmetry, and (3) a GA phase tion, energy-harvesting devices, medical scaffolds, or catalysts.
with typically high pore volumes. These highly organized Several attempts have been made to fabricate controllable
gyroid structures with a large surface area and high connec- 3D shapes and sizes using lithography16–18 or templating.19,20
tivity have been recently used as an angle-independent in- Even though a scalable route to design and fabricate 3D

3D Printing Group, Computational Science Research Center, Korea Institute of Science and Technology (KIST), Seoul, Republic of
Korea.

1
2 JO ET AL.

structures is highly desirable, the development of a facile NP attachment, and (3) a large amount of pores. The gyroid
and time-saving method remains a challenge, especially for offers improved hierarchies by enhanced photocatalytic re-
structures composed of porous micro- or nanoscale subunits actions to the TiO2 NPs, and this structural and its chemical
for advanced applications. In the case of gyroid, most of the synergy could generate more powerful and efficient photo-
existing methods have been fabricated as nano-sized gyroids catalytic degradation results over a long period.
by using self-assembly of block copolymers as templates21 or
metal deposition and thermal oxidation methods.11 However, Materials and Methods
due to the complicated shape of gyroid, the conventional
Filament fabrication
processing methods have been limited to produce a large
micro- or macro-sized gyroid. Recently, 3D printing tech- The TiO2 NP-embedded PLA filament was produced by
nology has come under the spotlight because of its ability to using a custom-made filament extruder. TiO2 NPs were ob-
create sophisticated 3D objects with multilength in a tained from Cho et al.’s group of Korea Institute of Science and
simple way.22–28 Due to the cost-effectiveness, fused de- Technology. Briefly, the TiO2 NPs were synthesized by a flame
position modeling (FDM) or material extrusion is a widely aerosol method in which the precursor vapors, titanium (IV)
implemented method to create 3D structures by deposition of isopropoxide (TTIP), and flammable gases such as CH4 were
sequential layers of semi-molten thermoplastic filament. As a burnt together in a combustion reactor at around 1200C. The
raw material in FDM, PLA (polylactic acid) is the most manufacturing method and the characterization of TiO2 NPs
broadly used thermoplastic filament because of its excellent were described in detail elsewhere.49 They reported that the
biocompatibility29 and biodegradability.30 PLA can be de- Brunauer, Emmett, and Teller (BET) surface area for the well-
graded by thermal depolymerization or hydrolysis in the crystalline TiO2 NPs was found to be 20 m2/g and the average
ground or in water because it is derived from renewable re- particle size was 39 nm. After setting the temperature to 180C
sources, such as corn starch.31,32 PLA’s properties can be for extrusion and allowing the instrument to warm up, a mix-
readily modified by coupling with specific nanoscale mate- ture of a transparent PLA powder and TiO2 NPs (10:1 g/g) was
rials such as graphene, wood, metal, or biomaterials.33–35 poured in the hopper. Once the temperature was set, the
Various FDM materials with desirable functionalities have gearmotor was turned on, and a white filament was extruded
been produced by mixing PLA with functional nanoscale through the melt extruder nozzle (dia.: 1.75 mm).
materials, which provides the material with improved dura-
bility, high strength, conductivity, magnetic behavior, and FDM printing processes
chemical reactivity.36 Among the specific nanomaterials,
All shapes were designed by using a 3D CAD program,
TiO2 nanoparticles (NPs) can be a useful and attractive ma-
and they were exported in an STL (standard tessellation
terial because of its photocatalytic property that decomposes
language) file format. The total gyroid size (64 U cells ar-
various organic compounds, including polymers and pollut-
ranged 4 · 4 · 4) was 3 · 3 · 3 cm with a fixed unit cell size of
ants.37–40 Immobilized TiO2 NPs in organic polymers have
0.75 cm. For a more detailed derivation for the gyroid model,
been reported to be powerful in practical photocatalytic ap-
see the paper by Wohlgemuth et al.50 The size of the plate fin-
plications because a significant increase in degradability
shaped structure was the same as that of the gyroid, and the
under solar or UV irradiation can be achieved.31,41–43 In
thickness of each pin was 0.23 cm. Then, each file was im-
addition, Torrado Perez et al. fabricated the TiO2-ABS (ac-
ported into 3D printing software (CreatorK; ROCKIT, Inc.,
rylonitrile butadiene styrene) nanocomposites instead of PLA
Republic of Korea) to slice the STL file into printer-readable
and made 3D printed dogbone structures. It showed that the
g-code. All the structures were printed on a commercially
tensile stress was increased by TiO2 NPs addition compared
available FDM 3D printer (3DISON Plus; ROCKIT, Inc.)
with pure ABS.44 Skorski et al. also proved that the 3D
with the following settings: temperature of 210C, print
printed TiO2-ABS nanocomposite structure could photo-
speed of 150 mm/s, and layer thickness of 0.1 mm.
catalyze the degradation of a rhodamine 6G in solution.45 The
advantageous behavior of TiO2 NPs has allowed the prepa-
Photocatalytic activity test
ration of PLA/TiO2-NP composites for use in biomedical and
environmental applications.46–48 All structures were placed into the center of glass beakers
Here, we developed 3D hierarchical gyroid structures with with 130 mL of MB. The MB solution was prepared by di-
embedded TiO2 NPs (E-gyr) to investigate the possibility of luting 1 mL of 0.05% MB (Sigma-Aldrich) with 500 mL of
their efficient photocatalytic structural performance for long- distilled water. The photocatalytic activities of the structures
term application. We investigated the UV light photocatalytic were evaluated by measuring the degradation of the MB
activities of these structures in the degradation of methylene under UV light irradiation (CT-UVT, UV-B type; Dongseo
blue (MB), as well as their reaction performance with respect Science Co., Ltd., South Korea). A 15 W UV lamp at the
to the PLA degradation rate. The 3D printed hierarchical irradiation wavelength range of 280–360 nm was used as the
porous networks created by the gyroid structure contained UV source. To evaluate the gyroid structure and height ef-
more surface area for the TiO2 NPs, which enhanced the fects, the solution was only illuminated from the top by
contact interface and rapid mass transportation under UV covering the side and bottom areas of the glass beakers with
irradiation. Moreover, the E-gyr maintained its reaction ef- aluminum tape. The distance between the UV lamp and the
ficiency with controlled exposure of the photocatalyst over bottom of the beaker was 140 cm. To compare the long-term
time, as the supporting PLA was degraded from the surface photodecomposition efficiency of E-gyr, the structure was
due to its photodegradable and hydrolytic nature. We found first exposed to UV light in all directions in distilled water to
that the E-gyr possesses particular strengths: (1) high con- induce UV degradation, and then, water was replaced with an
nectivity, (2) enormous contact surface areas for functional MB solution to measure the photodecomposition efficiency.
3D PHOTOCATALYTIC HIERARCHICAL GYROID STRUCTURE 3

Table 1. Long-Term Photodecomposition Fastcam Mini UX50 high-speed camera (Photron USA, Inc.)
Test Conditions for E-gyr with a PMS-Z65C 6.5 · zoom lens (Pomeas Optical Tech-
nology) at 250 frames/s. The contact angle (CA) was mea-
UV irradiation time (h) sured from the captured image and determined by using the
Cycle no. Distilled water MB solution ImageJ software package with a DropSnake plugin. All CA
values were averaged over three different spots on each sample.
1 0 12
2 48 8 Dark adsorption test. All samples were kept in the dark
3 48 8
4 96 8 for 12 h and then exposed to the UV lamp for 12 h. The test
5 144 8 solution extraction was carried out after the dark treatment
6 144 8 for 12 h and after 6 and 12 h for the UV irradiation, respec-
7 144 8 tively. Each absorbance was measured by using a UV-vis
spectrophotometer.
MB, methylene blue.
Results
The process was repeated by following the cycle conditions Figure 1 shows the flow chart for the resulting E-gyr
shown in Table 1. For the photocatalytic activity test, adequate structure according to the following stepwise processes: (a–c)
aliquots of the MB solution (1 mL) were withdrawn after peri- fabrication of the TiO2 NP-embedded PLA filament with the
odic time intervals of irradiation, and absorbance was measured filament extruder, (d) design of the E-gyr to mimic unique
by using a UV-vis spectrophotometer (Varian Cary 100). The natural structures allowing UV light passing though the
photodecomposition efficiency was calculated at the maxi- macropores, (e–f) fabrication of an infinitely connected gy-
mum absorption of light at 664 nm. After UV irradiation for a roid porous structure embedded with TiO2 NPs by an FDM
given period, the structure was periodically removed, washed printer, and (g) generation of hierarchical structure by PLA
with distilled water, and dried completely, and weight loss photodegradation in aqueous condition. The surface for the
was determined as described in the section ‘‘Weight loss.’’ as-printed E-gyr was shown to be flat without no presenting
noticeable TiO2 NPs (Fig. 1f), whereas after UV exposure
Weight loss. After each cycle of the photodecomposition time of more than 24 h, the TiO2 NPs or clusters appeared on
test, the E-gyr was removed, washed several times with the surface (Fig. 1g). To evaluate the effect of E-gyr on
distilled water, dried completely, and weighed at room tem- the photodecomposition efficacy, we compared the gyroid
perature on a semi-micro balance with a precision of 0.1 mg. structure with a plate fin-shaped structure (Fig. 2a) after the
The percentage of weight loss (WL%) was computed by using upper surfaces were exposed to UV light for 12 h in MB
the following equation: solution (Fig. 2b). As shown in Figure 2c, we found that the
MB decomposition rate of the E-gyr was *1.42 times
WLð%Þ ¼ 100 ðW0  Wr Þ=W0 , (57.4% vs. 81.5%) faster than that of the plate fin-shaped
structure. Even though the entire top surface was exposed to
where W0 and Wr are the initial E-gyr weight before water UV, the reaction rate was found to be higher even at the initial
exposure and after water exposure, respectively. decomposition rate. This increase in photocatalytic perfor-
mance of E-gyr could be attributed to the connected surfaces
Degradation tests and porous structure of the gyroid. It allowed a large number
of more effective paths for UV light, resulting in more sur-
Scanning electron microscope analysis. Degradation faces for a photocatalytic reaction with the MB solution.
tests were performed with the TiO2 NP-embedded PLA ras- Although it could not accurately analyze the actual light path
ters (dia.: 300 lm) in 50 mL of distilled water under UV ir- and the UV-responsive area, it is considered that the structure
radiation. Here, the raster refers to the strand from which the enhanced light harvesting and, consequently, increased the
filament is loaded through the nozzle. The rasters were re- quantity of electrons and holes photogenerated by the TiO2
moved daily, washed with distilled water, and dried com- NPs, which allowed them to participate in the photocatalytic
pletely. The morphological shapes were examined by using a degradation of the MB molecules. In addition, the photo-
field emission-scanning electron microscope (SEM) (Nova catalytic efficiency of the E-gyrs was proportional to the
NanoSEM 200, FEI) with an electron-acceleration voltage of structure height (Fig. 2d, e). The improved photocatalytic
5 kV. Before SEM imaging, the samples were coated with Pt performance of the E-gyr resulted from an increase in the
for 120 s to prevent electron charging of the PLA material. surface area along its height. As the height increased, the
For the cross-section view of rasters after the degradation E-gyr possessed larger specific surface areas, and, thus, it
treatment, each structure was fractured in nitrogen gas. offers more active catalytic sites for TiO2 NP attachment.
To further evaluate the advantage of E-gyr in photo-
Contact angle measurement. The surface wettability of catalytic reactions over time, experiments were performed
the 3D printed cuboid shaped structures (E-plate: 15 · 15 · for the photocatalytic activity of the gyroid. As shown in
1 mm) was comprehensively characterized. Before mea- Figure 3a, a prominent change in the adsorption capacity was
surement, each structure in distilled water was removed from observed over time by the E-gyr. The decomposition time
the UV chamber daily, washed with distilled water, and dried was significantly shortened from more than 12–8 h for cycles
completely. The dynamic behavior of a 2 lL water droplet on 1 and 2, respectively, demonstrating further reductions for
the surfaces was recorded and captured after 10 s by using a increasing cycles. Although the saturation phenomenon
4 JO ET AL.

FIG. 1. The conceptual flow chart for the 3D printing of gyroid for photocatalytic applications. (a–c) fabrication of the TiO2
NP-embedded PLA filament with the filament extruder (PLA—black color, TiO2 NP—yellow color), (d) design of the E-gyr,
(e) FDM-printed E-gyr, and (f, g) SEM images of surface morphology of E-gyr before and after UV treatment in water,
respectively. FDM, fused deposition modeling; NP, nanoparticles; PLA, polylactic acid; SEM, scanning electron microscope.

occurred during some later cycles, the MB degradation rate was most likely due to PLA degradation at the gyroid surface
gradually increased as the E-gyr was exposed to UV light accelerated by UV exposure (Fig. 3c). The improvement of
over time. It has been also confirmed that as the cycles were the photodegradation effect and the weight loss of the E-gyr
repeated under UV irradiation, the weight of the E-gyr de- over time resulted from the effect of the hierarchical structure
creased (Fig. 3b). This gradual weight loss by the structure formed by the decomposition of PLA by the TiO2 NPs. As

FIG. 2. Effect of the structure shape and height on the photocatalysis of MB solution. (a) The 3D printed gyroid structure
and plate fin-shaped structure, (b) top view images of the two structures in the MB, (c) photodecomposition rate/irradiation
time dependence for the two structures under top-side UV illumination, (d) the height of each structure was 0.75, 1.5, 2.25,
and 3.0 cm, respectively, and (e) photodecomposition rate/irradiation time dependence for the different structure heights
under top-side UV illumination. The scale bars are 1 cm. MB, methylene blue.
3D PHOTOCATALYTIC HIERARCHICAL GYROID STRUCTURE 5

FIG. 3. Measurement results for (a) the photodecomposition rate and (b) the weight loss as a function of photocatalytic
reaction cycle for the E-gyr, (c) schematic of the photodegradation behaviors of the gyroid design with spatially embedded
TiO2 NPs.

shown in the SEM images, the morphological evolution of On days 4 through 7, the water droplets immediately spread
the structure differed significantly as a function of the deg- on the surface within 1 s of contact with a CA of 0.
radation time (Fig. 4a). The TiO2 NPs in the pristine E-raster Figure 5 shows the evolution of dark adsorption and the
were completely covered by PLA polymer before UV ex- photodegradation of MB as a function of time with the dif-
posure (Day 0). As the photocatalytic reaction proceeded ferent samples: (1) no gyr (MB solution only without gyroid),
continuously, the E-raster gradually developed many appar- (2) gyr (gyroid that made only PLA with no TiO2 NPs), and (3
ent pores and voids with the irradiation time as shown in the and 4) E-gyr (gyroid with embedded TiO2 NPs). As a result of
surface image (Day 2). The pores formed became larger dark adsorption measurement for 12 h, the adsorption of MB
along the entire surface over time (Days 4–7). Interestingly, was directly correlated with the specific area of PLA and
the bulk degradation of PLA generated a hierarchical porous catalyst. It appeared that the adsorption rate of the sample D
structure, as shown in the cross-section views of days 2, 4, was much higher than that of the other cases because a
and 7. The resultant surface morphology was completely considerable amount of TiO2 NPs was exposed along the
different, compared with the initial state of smooth surface hierarchical structure formed through the UV treatment over
consisting solely of the PLA matrix. The process was ac- the long period. Even in the relatively same E-gyr structure,
celerated by increasing the irradiation time during the deg- in the case of sample C, the adsorption rate and the photo-
radation in an aqueous environment. reaction rate were comparatively lower than that of the
These results corresponded with the surface wettability sample D because the surface of gyroid was initially covered
findings shown in Figure 4b. The pristine structure exhibited with PLA, and, thus, it took time to expose the TiO2 to the
hydrophilic properties with a CA of *71.7 originating from surface due to the decomposition of PLA. In the case of
the PLA surface. PLA is known to possess a naturally low samples 1 and 2, MB was decomposed despite the absence of
hydrophilic property because of its polar oxygen linkages.51 TiO2 NPs, presumably due to the property of MB photolysis
The CA taken on day 0 also indicates that the TiO2 NPs were without photocatalysis. According to Ohtani and colleagues,
not present on the structure surface. In contrast, daily surface as MB absorbs light, it shows a photoinduced reaction.52
exposure to UV illumination resulted in enhanced super- Therefore, the higher rate of the sample C and D might result
hydrophilic properties due to the TiO2 NPs exposure after in the combination of the contributions to the absorption by
significant PLA surface degradation. In addition, the rough both TiO2 NPs and MB. Also, some of the MB were adsorbed
structures with micro/nanoscale features on the hierarchical on the surface of the PLA and this MB might not actually get
surfaces might contribute to this wetting behavior. As a re- degraded. Therefore, we should note that all MB losses were
sult, water droplets were permeable through the pores. This not the result of photodegradation alone. Ideally, it is nec-
behavior was also demonstrated through a change in the CAs essary to exclude the influence of this photoadsorption by
(i.e., on day 2). The CA decreased from 72 (time = 0 s) to dye itself to evaluate the actual photocatalytic activity of
35.2 (time = 10 s) and eventually reached 3.36 (time = 20 s). photocatalysts.52 However, since we measured only MB in
6 JO ET AL.

FIG. 4. (a) SEM images of the surface and cross-section of the E-raster after various UV irradiation times, (b) water
droplets on photocatalytically treated E-plate surfaces and their contact angles measured daily.

solution, it is difficult to separate the influence of the TiO2 light, the appreciable UV light-sensitizing ability of E-gyr can
characteristics on both adsorption and photodegradation pro- be assigned mainly to the photocatalytic activity of E-gyr.
cesses. Nevertheless, the absorption and decomposition rates of
MB showed a much higher tendency in samples with TiO2 NPs,
indicating that the hierarchical structure and photocatalytic Discussion
reaction have played a significant role. Namely, even consid- From the earlier investigations, the following factors were
ering the direct contributions of the MB photoreaction by UV found to significantly affect the structures’ photocatalytic
activity. The E-gyr with a porous and infinitely connected
triply periodic surface allowed repeated and continuous light
scattering and reflection. The structure was highly effective at
improving the light-harvesting capability, thus increasing the
numbers of photogenerated electrons and holes that were
used more efficiently in the photocatalytic decomposition of
organic compounds. The large active surface area also re-
sulted in a considerable improvement by providing a large
number of active catalytic reaction sites. In addition, the hi-
erarchical structure with diverse void sizes readily allowed
the acceleration of mass transportation. This effect improved
the circumstances for the transport of reactants of different
sizes and reduced the diffusion distance of photogenerated
charge carriers.53,54 These factors were beneficial to expe-
diting the generation of more reactive oxygen species such as
hydroxyl radicals. With these synergistic features, the pho-
tocatalytic performance of the structures could be conse-
quently enhanced.
FIG. 5. Adsorption and photodegradation of MB with The extensive surface degradation reflected the combined
different samples as a function of time: (1) no gyr, (2) gyr, effect of photocatalytic degradation and hydrolysis of the
(3) pristine E-gyr, and (4) E-gyr after the cycle 7 treatment. PLA matrix. The exposed TiO2 NPs at or near the surface
3D PHOTOCATALYTIC HIERARCHICAL GYROID STRUCTURE 7

were expected to actively absorb UV light, which would lead come the disadvantages found at this stage in the degradation
to rapid degradation of MB molecules, as well as the PLA of contaminants.
matrix. Simultaneously, due to the superhydrophilic property
of TiO2 NPs, they absorbed moisture faster and aided the Conclusion
hydrolysis of ester linkages in the PLA matrix, breakdown of We can take advantage of the synergistic interactions of
long macromolecular chains, formation and dissolution of the 3D printed E-gyr structures in several ways. For a long-
oligomer fragments, and so on.55–57 Importantly, hierarchical term application, which is the most case, the E-gyr is ad-
structures are known to promote the entrapment of water vantageous in that (1) other processes after printing are not
molecules in the pores on the surface, leading to the pene- required because the 3D multifunctional structure can be
tration of water molecules into the interfacial zone through created by using only the prefabricated functional filament,
voids and resulting in higher water absorption after a short (2) continuous photocatalytic reactions can occur over time
exposure time.55 Subsequently, this effect suggests that water through the continuous TiO2 NPs exposure, (3) hierarchical
absorption caused a dramatic reduction in the number of MB structures can be formed, and (4) the reaction time can be
molecules. Then, these processes repeated as the reaction adjusted to ensure that reactions occur when proper envi-
time was prolonged by the formation of additional voids ronmental conditions or the desired targets are present. More
along the hierarchical structure. Therefore, as the PLA specifically, the 3D hierarchical porous structure with the
polymer matrix was in contact with more TiO2 NPs, the TiO2 NP-embedded PLA filament is suitable for applica-
polymer chains became more susceptible to attack by water. tions in water treatment to markedly enhance performance
This effect continuously allowed the exposure of the em- by optimizing several important factors, including structure
bedded TiO2 NPs at the PLA/TiO2 interface, resulting in shape, surface area, porosity, and high reactivity of TiO2 NPs.
higher photocatalytic capacity through the TiO2 NPs. Further, this structural and material design scheme can be
It is known that the slurry reactor is effective in the water adapted for various fields and applications, such as drug-
treatment method using the TiO2 photocatalyst due to ex- eluting devices, water purification filters, energy-harvesting
cellent degradation capability, sorption of contaminants, and devices, or tissue engineering.
load-carrying capacity through the large surface area of TiO2
NPs.37 However, the suspended/slurry TiO2 NPs requires Acknowledgments
additional treatment steps, such as filtration or centrifugation
to remove the photocatalyst NPs from the solution, which The authors acknowledge support from the National Re-
adds to the overall capital and cost.37,58 In addition, the re- search Foundation of Korea (NRF) Grant funded by the
action process of TiO2 can produce a waste that is in need of Ministry of Science, ICT & Future Planning for convergent
disposal and so the method for by-product treatment should research in Development program for convergence R&D
be considered. Although TiO2 NPs are found in toothpaste, over traditional culture and current technology (NRF-
cosmetics, or biomedical parts, the safety of TiO2 NPs is still 2016M3C1B5906481). This research was also supported by
a controversial issue.59 Also, their particle size and mor- the Center for Advanced Meta-Materials (CAMM) of a
phology remains the main problem in a largescale water Global Frontier Project (CAMM No. 2014063701) and a
treatment process.60 As an alternative, catalyst immobiliza- grant (MPSS-CG-2016-02) through the Disaster and Safety
tion strategies have been developed to eliminate the need of Management Institute funded by the Ministry of Public
post-treatment removal. However, the fixation of TiO2 into a Safety and Security of Korean government. This work was
large substrate also creates a decrease in the amount of cat- supported by a KIST internal project.
alyst active sites and the 2D-based substrate shape causes
mass transfer limitations.60–62 The difference in adsorption Author Disclosure Statement
capacity between slurry and immobilization can be seen from No competing financial interests exist.
the difference in the MB decomposition rates of the samples
A and B after 12 h of UV irradiation as shown in Figure 5. References
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