Applied Clay Science xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Applied Clay Science

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

Research paper

Photocatalytic microreactors based on nano TiO2-containing clay

colloidosomes
Sen Lina,b, Shiyong Suna,b,c,⁎, Kexuan Shena,b,c, Daoyong Tana,b, Hongping Zhanga, Faqin Donga,c,
Xiaoxin Fuc
a
Institute of Non-metallic Minerals, Key Laboratory of Solid Waste Treatment and Resource Recycle of Ministry of Education, Southwest University of Science and
Technology, Mianyang 621010, China.
b
Sichuan Engineering Lab of Non-metallic Mineral Powder Modification & High-value Utilization, Mianyang 621010, China
c
Low-cost Wastewater Treatment Technology International Sci-Tech Cooperation Base of Sichuan Province, Mianyang 621010, China

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

Keywords: Photocatalytic microcompartments have attracted increasing interests in the field of photocatalytic degradation.
Montmorillonite This work focused on the construction and characterization of a novel photocatalytic microsystem comprising
Microreactor polydopamine-modified TiO2 nanoparticles (NPs) dispersed in clay-based colloidosomes, utilizing partially hy-
Photocatalysis drophobic montmorillonite particles as building blocks for colloidosome membrane assembly. Assessment of
Colloidosome
photocatalytic activity was performed by photocatalytic degradation of methylene blue and rhodamine B, with
TiO2
the small molecule dyes decomposing within the compartmentalized microsystems. Encapsulation of TiO2 NPs
within the clay colloidosomes enhanced the efficiency of photocatalytic degradation. The results showed a se-
lective degradation of methylene blue in the presence of rhodamine B, with associated λMB/λRhB of 2.04. The
present study indicates that photocatalytic semiconductor NPs encapsulated in clay colloidosomes form a pro-
mising microsystem with great potential for application in environmental remediation.

1. Introduction
Living systems, particularly eukaryotic cells, contain many micro-
compartmentalized organelles with specific functions for synthesizing
materials or transferring energy to sustain life. One challenge in ma-
terials science is to mimic subcellular organelles to construct micro-
reactors with specific functions using a bio-inspired bottom-up ap-
proach (Koo and Velev, 2013; Hansen et al., 2016; Tamate et al., 2016;
Buddingh and van Hest, 2017). These functions include photocatalysis,
which is emerging as a new area of environmental science (Das and
Srivastava, 2016). Photocatalysts that are encapsulated in microsystems
have advantages over photocatalysts suspended in a liquid medium,
including simple separation from aqueous conditions, controlled dif-
fusant transport rates into or out of solutions, and enhanced reactant
conversion efficiency (Rosenberg and Dan, 2011; Dan, 2012; Koo and
Velev, 2013; Gao et al., 2017). As such, encapsulation has been re-
cognized as an effective strategy for designing photocatalytic micro-
reactors (Ma et al., 2014; Das and Srivastava, 2016).
Clay minerals and their derived nanocomposites have long been used
as a class of effective and economically feasible materials for removal of
pollutants such as dyes, heavy metals and organic substances from was-
tewater (Selvam et al., 2008; Zhou and Keeling, 2013; Zhou et al., 2016).
However, conventional physical adsorption methods have suffered from
the limitations, including incomplete precipitation and sludge generation
with further desorption treatment often required. One of most promising
alternatives for the removal of various dyes from wastewater is photo-
catalysis, which achieves removal and decomposition of dyes in a single
step under light illumination. To combine the excellent adsorptive ad-
vantages of clays with improved photocatalytic reactivity, semiconductors
such as TiO2-supported clay nanocomposites have been developed for
synergistic photocatalytic adsorption of organic dyes (Ngoh and Nawi,
2016; Mishra et al., 2017a,b). Several immobilization strategies have been
used for preparation of such TiO2-clay hybrid nanocomposites, including
TiO2 nanoparticles (NPs) loaded on the mineral surface (Li et al., 2009;
Hajjaji et al., 2016; Szczepanik, 2017), TiO2 NPs intercalated into pillared
clay (Damardji et al., 2009; Sun et al., 2015), and TiO2 NPs deposited on
the exfoliated clay surface(Nakato et al., 2016; Tobajas et al., 2017).
However, TiO2-clay nanocomposites are generally utilized in powder
form. Consequently, there are difficulties with separation and recovery of
TiO2-clay nanocomposites from aqueous suspensions.

⁎
Corresponding author at: Institute of Non-metallic Minerals, Key Laboratory of Solid Waste Treatment and Resource Recycle of Ministry of Education, Southwest University of Science
and Technology, Mianyang 621010, China
E-mail address: shysun@swust.edu.cn (S. Sun).

http://dx.doi.org/10.1016/j.clay.2017.08.022
Received 24 April 2017; Received in revised form 19 August 2017; Accepted 22 August 2017
0169-1317/ © 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Lin, S., Applied Clay Science (2017), http://dx.doi.org/10.1016/j.clay.2017.08.022
S. Lin et al.
Fig. 1. The optical microscopy images of PDA-TiO2@clay colloidosomes in water-in-oil
continuous phases (a, b) and transferring into aqueous phase (c, d).
Fig. 2. SEM observations of PDA-TiO2@clay colloidosomes. The SEM image (a), The
enlarged image of selected area (b), EDS analysis of PDA-TiO2@clay colloidosomes (c).
Fig. 3. CLSM images of PDA-TiO2@clay colloidosomes. The fluorescence image (a), the
optical transmission microscopy image (b), the overlay image of (a) and (b) (c).
Rhodamine B was used of 100 μg mL− 1.
Bio-inspired photocatalytic microsystems based on semi-permeable
colloidosomes(microcapsules) have been reported using various em-
bedded photocatalysts, including TiO2, ZnO, and Pt/ZnO (Hanczyc
et al., 2003; Li et al., 2009; Subramaniam et al., 2011; Huo et al., 2014;
Das and Srivastava, 2016; Nakato et al., 2016). In our previous work,
we successfully prepared novel cross-linked water-in-water clay-based
colloidosomes using modified montmorillonite particles as a building
2
Applied Clay Science xxx (xxxx) xxx–xxx
block to produce Pickering emulsion droplets (Sun et al., 2016). Here, a
novel light-driven mimetic microreactor system has been demonstrated,
in which where photocatalytic TiO2 NPs are encapsulated in clay-based
colloidosomes to combine the hybrid advantages of clay-based colloi-
dosomes and wide band-gap semiconductors. The photocatalytic ac-
tivities and stabilities of the TiO2 NP-containing clay colloidosomes
(TiO2@clay colloidosomes) were investigated in detail. The photo-
catalytic performance of the TiO2@clay colloidosomes was further
tested via degradation experiments with methylene blue (MB) and
rhodamine B (RhB) using TiO2@clay colloidosomes as photocatalysts.
2. Materials and methods
2.1. Materials
The octadecyl trimethyl ammonium bromide (OTAB)-modified mon-
tmorillonite (HFGEL-310, organic bentonite) was provided by Zhejiang
Fenghong New Materials Co., Ltd. (see detailed XRD pattern in Fig. S1,
Supporting information). P25-type TiO2 NPs were purchased from
Degussa, Germany. Dopamine hydrochloride, MB and RhB were pur-
chased from Shanghai Aladdin Biochemical Technology Co., Ltd. Tris
(hydroxymethyl)aminomethane hydrochloride (Tris-HCl), hydrochloric
acid, toluene, and tetraethoxysilane (TEOS) were purchased from Chengdu
Kelong Chemical Reagent Company. All chemical reagents were of ana-
lytical grade unless otherwise specified. All solutions were prepared with
ultrapure Milli-Q water (resistance > 18.2 MΩ·cm).
2.2. Surface modification of TiO2 NPs
The surfaces of the TiO2 NPs were modified with polydopamine
(PDA), formed by the polymerization of dopamine under alkaline
conditions, in order to improve their hydrophilicity and photocatalytic
activity (Mao et al., 2016). TiO2 NPs (0.5 g) and dopamine hydro-
chloride (0.05 g) were added to 100 mL of 0.1 M Tris buffer solution
(pH 8.0). The pH of the suspension was slowly adjusted to 8.5 by the
addition of ammonium hydroxide (NH3·H2O). The reaction mixture was
kept in the dark for 24 h at room temperature with magnetic stirring
(1300 rpm). The PDA-coated TiO2 NPs (PDA-TiO2 NPs) were isolated by
centrifuging the reaction mixture at 8000 rpm for 5 min. The collected
TiO2 NPs were washed 3 times with water and 3 times with ethanol.
2.3. Preparation of PDA-TiO2@clay colloidosomes
The PDA-TiO2@clay water-in-oil colloidosomes were prepared by a
Pickering emulsion method (Sun et al., 2016). Typically, an aqueous
solution containing a PDA-TiO2 NPs dispersion was added to 10 mL
toluene containing 1 mg·mL− 1 of modified montmorillonite dispersion,
with a TiO2/clay weight ratio of between 0.4 and 20 and a water/to-
luene volume fraction of 0.5. The mixture was homogenized for 1 min
using a homogenizer (Fluko, F10) at 10,000 rpm. Following cross-
linking by hydrolytic reaction with 60 μL of TEOS, the water-in-oil
PDA-TiO2@clay colloidosomes were transferred into a continuous
water phase to prepare water-in-water PDA-TiO2@clay colloidosomes.
2.4. Photocatalytic dye degradation
Photocatalytic dye degradation experiments were performed by
mixing 300 μL of a stock solution of MB (0.5 mg·mL− 1, Absmax = 668 nm)
or RhB (0.5 mg·mL− 1, Absmax = 555 nm) with 29.7 mL of Milli-Q quality
(18.2 MΩ·cm) water and adding 100 mg of PDA-TiO2@clay colloidosome
dispersion, followed by exposure to an ultraviolet (UV) lamp
(365 ± 10 nm at 18 W). At 10 min intervals, 2 mL aliquots were
S. Lin et al. Applied Clay Science xxx (xxxx) xxx–xxx

Fig. 4. Spectral characterization of TiO2 NPs, PDA-TiO2 NPs and PDA-TiO2@clay colloidosomes with varied ratios of PDA-TiO2 NPs to clay from 0.4 to 16. UV–vis adsorption spectra (a),
FTIR spectra (b).

3. Results and discussion

600 (a)TiO2 NPs
(a)
(b) (b)PDA-TiO2 NPs Clay water-in-oil Pickering emulsions were constructed using OTAB-
(k)
500
(j) (c)Clay colloidosomes modified montmorillonite particles as a stabilizer at the water-toluene
(i)
(d)0.4 interface. Before the emulsifying experiments, characterizations of P25-
(h) (e)0.8 type TiO2 NPs showed their distinctive characteristics including anatase/
400 (f)1.6
(g) rutile ratio of 4:1 in the mineral phase, and average diameter of 24 nm (see
Intensity

(f) (g)3.2
(e) (h)4.8
details in Figs. S2–S4, Supporting information). Photocatalytic micro-
300
(d) (i)6.4 reactors were constructed by encapsulating aqueous PDA-TiO2 NP dis-
(c) (j)8 persions in clay colloidosomes. The optical microscopy observations, to-
200 (k)16 gether with our previous results, show that the average diameter of the
spherical water-in-oil clay colloidosomes depends on the volume/weight
100 ratio of the interior aqueous phase and the clay stabilizer (Sun et al.,
2016). The average size of the emulsion droplets of PDA-TiO2@clay col-
loidosomes was approximately 30 μm when using a water/toluene volume
0
450 500 550 600 fraction of 0.5 (Fig. 1a and b). The resulting water-in-water PDA-TiO2@
-1 clay colloidosomes were structurally stable after being cross-linked by
Wavenumber (nm)
TEOS and transferred into the aqueous phase (Fig. 1c and d). SEM images
Fig. 5. The photoluminescence spectra of TiO2, PDA-TiO2, PDA-TiO2@clay colloidosomes of the dried PDA-TiO2@clay colloidosomes show clay layers with creased
with varied ratios of PDA-TiO2 to clay from 0.4 to 16. surfaces (Fig. 2a and b). The rough textures on the surfaces of the PDA-
TiO2@clay colloidosomes were similar to those obtained when tetra-
collected from the solution and measured by UV–vis spectroscopy (EV300, methoxysilane (TMOS) was used as a cross-linker (Sun et al., 2016). En-
Thermo Scientific Instruments). Photocatalytic dye degradation experi- ergy dispersive spectrometer (EDS) analysis showed that these specific
ments were carried out for both dyes using 100 mg PDA-TiO2@clay col- PDA-TiO2@clay colloidosomes contained Ti components, indicating that
loidosome dispersions with TiO2/clay weight ratios of between 0.4 and 16. the TiO2 NPs dispersions had been encapsulated by the clay-based col-
Control degradation experiments involving the dyes in the presence of loidosomes (Fig. 2c).
TiO2 NPs were also performed. Exponential decay constants (λ) and cat- To assess the permeabilities of the clay membranes of the water-in-
alytic efficiencies (Λ) were evaluated by fitting exponential decay curves water PDA-TiO2@clay colloidosomes, fluorescent dye RhB was added
to the normalized time-dependent photocatalytic dye degradation data. to the external continuous aqueous phase. CLSM images showed that
the negatively charged clay membranes had significant uptakes of the
positively charged RhB molecules from the exterior environment
2.5. Characterization through electrostatic interactions, indicating that as well as size-selec-
tive permeability, the clay membranes were capable of charge-selective
The morphologies of the PDA-TiO2@clay colloidosomes were ob- adsorption (Fig. 3).
served by optical microscopy (DM 2000, Leica), scanning electronic TiO2 is an excellent photocatalyst that has long been used for light-
microscopy (SEM, Ultra 55, Zeiss), and confocal laser scanning micro- driven photochemical reactions (Dariani et al., 2016; Mao et al., 2016;
scopy (CLSM, TCS SP8, Leica). The spectral properties of PDA-TiO2@ Yang et al., 2016). Surface modification of TiO2 NPs by PDA can improve
clay colloidosomes, TiO2 NPs, and PDA-TiO2 NPs were characterized light activation of PDA-TiO2@clay colloidosomes, was confirmed by
using a UV–vis diffuse reflectance spectrophotometer (UV-DRS, UV spectral characterization (Fig. 4) (Mao et al., 2016). The commercial P25-
3150, Shimadzu) and a photoluminescence (PL) spectrometer (OmniPL, type TiO2 NPs showed absorption in the UV region, with no visible ab-
Beijing Zhuolihanguang Instrument). Fourier transform infrared (FTIR) sorption above 400 nm. UV–vis adsorption spectra of PDA-TiO2 NPs
spectra were recorded on an FTIR spectrometric analyzer (Spectrum showed obvious, strong visible-light absorption, suggesting that solar en-
One, PE). ergy conversion efficiency was enhanced after PDA surface modification of

3
S. Lin et al. Applied Clay Science xxx (xxxx) xxx–xxx

a 1.0 b 1.0

0.8 0.8

0.6 0.6
-1 -1
C/C0

C/C0
0.1mg.ml 0.1mg.ml
-1 -1
0.2mg.ml 0.2mg.ml
0.4 -1 0.4 -1
0.4mg.ml 0.4mg.ml
-1 -1
0.6mg.ml 0.6mg.ml
-1 -1
0.8mg.ml 0.8mg.ml
0.2 -1 0.2 -1
1mg.ml 1mg.ml
-1 -1
2mg.ml 2mg.ml
-1 -1
4mg.ml 4mg.ml
0.0 0.0

0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time/min Time/min

c 1.0 d 1.0

0.8 0.8

0.6 0.6
-1 -1
C/C0
C/C0

0.1mg.ml 0.1mg.ml
-1 -1
0.2mg.ml 0.2mg.ml
0.4 -1 0.4 -1
0.4mg.ml 0.4mg.ml
-1 -1
0.6mg.ml 0.6mg.ml
-1 -1
0.8mg.ml 0.8mg.ml
0.2 -1
0.2 -1
1mg.ml 1mg.ml
-1 -1
2mg.ml 2mg.ml
-1 -1
4mg.ml 4mg.ml
0.0 0.0

0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time/min Time/min

Fig. 6. Photocatalytic degradation of MB (a, c) and RhB (b, d) by PDA-TiO2@clay colloidosomes (a, b) and PDA-TiO2 NPs dispersions (c, d) with various concentrations of PDA-TiO2 NPs
from 0.1 to 4 mg·mL− 1.

TiO2 NPs (Fig. 4a). The bare clay colloidosomes had no absorption above
350 nm, whereas the PDA-TiO2@clay colloidosomes showed clear evi-
dence of the characteristics of both PDA-TiO2 and the clay colloidosomes,
with enhanced light utilization efficiency across the whole absorption
range, implying that the photo-responsive PDA-TiO2@clay colloidosome
microsystem could be used in practical applications utilizing natural solar
irradiation. The FTIR spectra of the PDA-TiO2@clay colloidosomes showed
the characteristic peaks of PDA-TiO2 and indirectly revealed the existence
of encapsulated PDA-TiO2 NPs in the colloidosomes (Fig. 4b). PL emission
spectroscopy was used to identify the charge transport and separation
properties at an excitation wavelength of 365 nm (Fig. 5). Compared with
pure TiO2 NPs, the obvious decrease in the fluorescence intensity of the
PDA-TiO2 NPs indicated a lower electron-hole recombination rate and
faster charge transfer between the dopamine molecules and the surface of
the TiO2 NPs upon electronic excitation (Mao et al., 2016; Yang et al.,
2016). Larger amounts of TiO2 NPs in the colloidosomes yielded lower
emission intensity.
TiO2 NPs can photocatalytically degrade dyes via decomposition of
H2O2 into hydroxyl radicals (Dariani et al., 2016; Yang et al., 2016). Given
that a range of dye molecules had been successfully sequestered into clay
colloidosomes, we exploited these host-guest PDA-TiO2@clay colloidosome
systems as photocatalytic microreactors (Sun et al., 2016). The photo-
catalytic performances of PDA-TiO2@clay colloidosomes were assessed
through the degradation of MB (initial concentration 0.05 mg·mL− 1) and
RhB (initial concentration 0.05 mg·mL− 1) under UV light (365 ± 10 nm
at 18 W) at various PDA-TiO2 NP-to-clay ratios (Fig. 6a and b) and pH
values (Fig. 7a and b). We also employed PDA-TiO2 suspensions as re-
ference photocatalysts under similar experimental conditions for the pur-
poses of comparison (Figs. 6c, d and 7c, d).
All samples showed exponential decay, with the decay constants for
MB (λMB) being larger than those for RhB (λRhB), as shown in Table 1.
Similarly, the catalytic efficiency values obtained for MB (ΛMB) were
larger than those seen for RhB (ΛRhB), as shown in Table 2. Interest-
ingly, photocatalysis was enhanced when PDA-TiO2 NPs were en-
capsulated into clay colloidosomes (Fig. 6). The photodegradation ef-
ficiency of the PDA-TiO2@clay colloidosomes increased with increasing
PDA-TiO2 NP content. However, the interior solutions became more
turbid when more PDA-TiO2 NPs were encapsulated in the colloido-
somes, making it difficult for the UV light to penetrate the PDA-TiO2@
clay colloidosomes. Large quantities of encapsulated PDA-TiO2 NPs
(above 0.4 mg·mL− 1) resulted in lower irradiation by UV light, and
hence reduced photonic efficiencies of the PDA-TiO2@clay colloido-
somes (Lv et al., 2015; Dariani et al., 2016).
When changing the pH value, the photocatalytic efficiency for MB
increased as the pH value was increased from 3 to 11 (Fig. 7, Tables 3 and
4). Slight changes in the photocatalytic efficiency of RhB degradation were

4
S. Lin et al. Applied Clay Science xxx (xxxx) xxx–xxx

a 1.0 1
b 1.0 1
3 3
5 5
0.8 0.8 7
7
9 9
11 11
0.6 0.6 13
13

C/C0
C/C0

0.4 0.4

0.2 0.2

0.0 0.0

0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time/min Time/min
c 1.0 d 1.0

0.8 0.8

0.6 0.6
C/C0
C/C0

1 1
3 0.4 3
0.4
5 5
7 7
9 0.2 9
0.2
11 11
13 13

0.0 0.0

0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time/min Time/min

Fig. 7. Photocatalytic degradation of MB (a, c) and RhB (b, d) by PDA-TiO2@clay colloidosomes containing 0.1 mg·mL− 1 PDA-TiO2 (a, b) and 0.1 mg·mL− 1 PDA-TiO2 NPs dispersions (c,
d) with various pH values.

Table 1
Exponential decay constants (λ) in Fig. 6 determined for the photocatalytic degradation of dyes of MB and RhB molecules in the presence of PDA-TiO2@clay
colloidosomes or free PDA-TiO2 NPs dispersions with various concentrations of PDA-TiO2 NPs from 0.1 to 4 mg·mL− 1.

PDA-TiO2 NPs PDA-TiO2@clay colloidosomes Free dispersions

concentrations/
mg·mL− 1 λMB/ λRhB/ λMB/min− 1 λRhB/min− 1
min− 1 min− 1

0.1 0.072(4) 0.025(2) 0.064(4) 0.014(3)

0.2 0.217(3) 0.037(1) 0.070(2) 0.021(4)
0.4 0.104(1) 0.031(1) 0.080(3) 0.029(4)
0.6 0.163(1) 0.024(4) 0.043(4) 0.012(5)
0.8 0.053(2) 0.020(1) 0.039(3) 0.027(1)
1 0.036(1) 0.015(3) 0.034(4) 0.006(3)
2 0.023(1) 0.010(2) 0.028(2) 0.005(3)
4 0.012(2) 0.003(2) 0.012(1) 0.004(2)

observed under analogous conditions. Previous studies have suggested that
pH is an important factor in the adsorption process (Skoric et al., 2016). In
general, variation of the pH can change the charges on the surface of the
PDA-TiO2 NPs, as well as altering the potentials of catalytic reactions.
Under alkaline conditions, TiO2 possesses a negative charge and the ca-
tionic MB and RhB molecules can be easily adsorbed (Dariani et al., 2016).
Thus, photocatalytic efficiency generally accelerates with increasing pH
value. However, in the microsystem where clay is present, other factors
can influence the adsorption of the dye. The negatively charged surface of
the montmorillonite increases the number of adsorbent sites owing to the
silanol groups on the surface, which are deprotonated as the pH rises
(Almeida et al., 2009). However, the maximum adsorption of RhB by

5
S. Lin et al. Applied Clay Science xxx (xxxx) xxx–xxx

Table 2
Catalytic efficiency (Λ) in Fig. 6 determined for the photocatalytic degradation of dyes of MB and RhB molecules in the presence of PDA-TiO2@clay colloi-
dosomes or free PDA-TiO2 NPs dispersions with various concentrations of PDA-TiO2 NPs from 0.1 to 4 mg·mL− 1.

PDA-TiO2 PDA-TiO2@clay colloidosomes Free dispersions

concentrations/
mg·mL− 1 ΛMB/ ΛRhB/ ΛMB/ ΛRhB/
min− 1 mg− 1 min− 1 mg− 1 min− 1 mg− 1 min− 1 mg− 1

0.1 0.089(3) 0.056(2) 0.080(4) 0.043(1)

0.2 0.136(2) 0.023(1) 0.044(2) 0.038(4)
0.4 0.032(1) 0.010(2) 0.027(3) 0.015(4)
0.6 0.010(1) 0.006(4) 0.009(2) 0.009(5)
0.8 0.008(3) 0.003(2) 0.006(2) 0.006(2)
1 0.004(2) 0.002(3) 0.004(3) 0.003(3)
2 0.001(1) 0.001(2) 0.002(2) 0.001(2)
4 0.001(3) 0.001(2) 0.001(2) 0.001(1)

Table 3
Exponential decay constants (λ) in Fig. 7 determined for the photocatalytic degradation of dyes of MB and RhB molecules in the presence of PDA-TiO2@clay
colloidosomes or free PDA-TiO2 NPs dispersions with various pH values.

pH values PDA-TiO2@clay colloidosomes Free dispersions

−1 −1
λMB/min λRhB/min λMB/min− 1 λRhB/min− 1

1 0.110(7) 0.067(2) 0.051(1) 0.041(1)

3 0.044(7) 0.026(1) 0.081(2) 0.012(1)
5 0.059(4) 0.023(4) 0.053(3) 0.009(5)
7 0.070(4) 0.033(2) 0.040(5) 0.011(1)
9 0.109(1) 0.081(4) 0.021(4) 0.029(2)
11 0.395(3) 0.049(5) 0.032(1) 0.015(5)
13 0.313(1) 0.113(1) 0.048(1) 0.014(3)

Table 4
Catalytic efficiency (Λ) in Fig. 7 determined for the photocatalytic degradation of dyes of MB and RhB molecules in the presence of PDA-TiO2@clay colloi-
dosomes and free PDA-TiO2 NPs with various pH values.

pH values PDA-TiO2@clay colloidosomes Free dispersions

ΛMB/ ΛRhB/ ΛMB/ ΛRhB/

min− 1 mg− 1 min− 1 mg− 1 min− 1 mg− 1 min− 1 mg− 1

1 0.017(2) 0.008(2) 0.006(2) 0.005(2)

3 0.005(3) 0.003(1) 0.010(2) 0.002(3)
5 0.007(4) 0.003(2) 0.007(3) 0.001(1)
7 0.009(3) 0.004(1) 0.005(1) 0.001(2)
9 0.014(2) 0.010(4) 0.003(4) 0.004(3)
11 0.049(3) 0.006(3) 0.004(2) 0.002(2)
13 0.039(1) 0.014(1) 0.006(3) 0.002(3)

montmorillonite occurs at pH 7, while that of MB occurs at pH 11 (Selvam 4. Conclusions

et al., 2008; Almeida et al., 2009). Therefore, an increase in pH enhances
the photocatalytic efficiency of MB degradation more effectively than that
of RhB degradation.
Dye selectivity was determined by performing simultaneous dye
degradation experiments on mixtures of MB and RhB (Fig. 8). Si-
multaneous photocatalytic degradation was monitored by changes in
the visible absorption bands at 668 nm (MB) and 555 nm (RhB). Time-
dependent reductions were observed in both the 668 and 555 nm ab-
sorption bands, with an associated λMB/λRhB ratio of 2.04. Therefore, it
was possible to achieve selective degradation of MB in the presence of
RhB by spatial confinement of the dye molecules specifically within the
PDA-TiO2@clay colloidosomes.
A novel photocatalytic microsystem based on clay colloidosomes
containing PDA-TiO2 NPs was developed. The PDA-TiO2@clay colloi-
dosomes effectively stabilized the TiO2 NPs compared with free aqu-
eous dispersions. Moreover, the PDA-TiO2@clay colloidosomes ex-
hibited versatility for enhancing the photocatalytic degradation of
organic dyes. Our results suggest that PDA-TiO2@clay colloidosomes
can selectively sequester and degrade the organic dye MB in the pre-
sence of RhB. The demonstrated photocatalytic microreactor needs
further in-depth studies to determine its potential applications in the
field of environmental remediation.

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S. Lin et al. Applied Clay Science xxx (xxxx) xxx–xxx

0.0
a 1.2 0 min b-0.2 Methylene blue
10 min Rhodamine B
-0.4
20 min
-0.6
1.0 30 min
-0.8
40 min
-1.0
50 min
0.8 -1.2
Intensity/A.U.

60 min
-1.4

lnC/C0
0.6 -1.6
-1.8
-2.0
0.4
-2.2
-2.4
0.2 -2.6
-2.8
0.0 -3.0
450 500 550 600 650 700 750 0 10 20 30 40 50 60
Wavelength/nm Time/min

c 1.2 0 min d 0.0 Methylene blue

10 min -0.2 Rhodamine B
20 min
1.0 -0.4
30 min
40 min -0.6
50 min
0.8
Intensity/A.U.

60 min -0.8
lnC/C0
-1.0
0.6
-1.2

0.4 -1.4

-1.6
0.2
-1.8

0.0 -2.0
450 500 550 600 650 700 750 0 10 20 30 40 50 60
Wavelength/nm Time/min
Fig. 8. Selectivity of photocatalytic degradation of mixture of MB and RhB in 0.1 mg·mL− 1 PDA-TiO2@clay colloidosomes (a, b) and 0.1 mg·mL− 1 PDA-TiO2 NPs dispersions(c, d). The
experimental pH value is 7.0.

Acknowledgments
The present work was supported by the National Natural Science
Foundation of China (41672039, 41502027) and Postgraduate
Innovation Fund Project of Southwest University of Science and
Technology (17ycx044).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.clay.2017.08.022.
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