Ceramics International 42 (2016) 9519–9526
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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
Mesoporous ZnO nanoclusters as an ultra-active photocatalyst
Nirmalya Tripathy a,1, Rafiq Ahmad b,1, Hyeon Kuk a, Yoon-Bong Hahn b, Gilson Khang a,n
a
Department of BIN Fusion Technology, Department of Polymer-Nano Science & Technology and Polymer BIN Research Center, Chonbuk National University,
567 Baekje-daero, Deokjin-gu, Jeonju 561-756, Republic of Korea
b
School of Semiconductor and Chemical Engineering, Chonbuk National University, 567 Baekje daero, Deokjin-gu, Jeonju 561-756, Republic of Korea
art ic l e i nf o a b s t r a c t
Article history: Morphology modulation of nanostructured materials are highly crucial for various applications including
Received 25 January 2016 photocatalysis, drug delivery, etc. In this study, mesoporous zinc oxide (ZnO) nanoclusters (MZN) were
Received in revised form synthesized via a simple, cost-effective, low-temperature wet chemical route and further sucessfully
4 March 2016
utilized for photodegradation of Rhodamine B (RhB). Firstly, polystyrene (PS) nanospheres ( 300 nm)
Accepted 4 March 2016
were prepared by polymerization of styrene in aqueous solvent. Then the MZN were achieved by for-
Available online 5 March 2016
mation of ZnO nanoparticles-shell over the surface of PS nanospheres via esterification of zinc acetate
Keywords: dihydrate in isopropyl alcohol followed by toluene dissolution of PS core. The as-synthesized MZN were
ZnO spherically-shaped, porous in nature with a diameter of 400 nm and composed of well-arranged
Mesoporous
highly-crystalline ZnO nanoparticles ( 5 nm). The MZN also exhibited a high surface area of
Nanoclusters
78.3 75.4 m2 g 1 and an average pore diameter of 26 nm. Furthermore, this unique structure de-
Photocatalytic
Rhodamine B monstrates an expeditious photodegradation of RhB under UV illumination, monitored by UV–visible
spectroscopy at different time intervals until the dye was completely degraded to colorless end products.
Fast RhB decomposition was observed with a degradation rate of 98% within initial 40 min which can
be attributed to the porous nature, large specific surface area and excellent electron accepting features of
the engineered nanoclusters.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
1. Introduction Conventionally, several innovative technologies such as adsorp-
tion, biodegradation, catalytic wet oxidation, advanced oxidation
Rhodamine B (RhB), among various organic dyes, is an processes (AOPs), etc. have been applied for harmful dyes removal/
important dye mainly discharged from textile, printing and degradation [7,8]. Among these techniques, photocatalytic
dyestuff industries. The dye, being chemically stable with low degradation of organic pollutants under UV irradiation has re-
water degradability ( 10–15%) severely damage aquatic ecosys- ceived much attention for pollutants removal and environment
tem and thus results in environmental imbalance [1]. The colored purification.
RhB dye effluents potentially inhibit sunlight penetration into Photocatalytic performances of nanomaterials are strongly
water bodies and streams affecting the natural disinfection pro- related to the desired specific material, its morphology, and
cess, and leading to high pH and temperature fluctuations, re- shape/size, etc. Especially, inorganic mesoporous and hollow
nano-/micro-structures have been widely researched for targeted
duced photosynthesis in underwater plants and slow damage to
design of an efficient photocatalyst. Because of their well-defined
various life forms [2]. Moreover, the dye is reported to possess
morphology, large specific surface area, low density, uniform size,
carcinogenicity, neurotoxicity, developmental toxicity and chronic
nanostructured wall, hollow architecture and good surface
toxicity towards both humans and animals [3]. Recently, RhB usage
permeability, inorganic mesoporous structures provide feasible
is banned in several consumer products as it has been corrobo- environment for organic pollutants transport and enhanced cata-
rated as potentially toxic and carcinogenic material, especially for lytic activity [9–11]. For instance, various engineered metal oxides
pregnant women and children [4]. Therefore, treatment of RhB dye such as TiO2, ZnO, SnO2, WO3, Cu2O, CuO, metal halides, sulfides,
containing effluents from industrial wastewater is highly desirable etc. have been fabricated as photocatalysts for degradation of
below environmentally accepted levels prior to its disposal [5,6]. organic pollutants and hydrogen generation [12–15]. Referring to a
highly active photocatalyst, ZnO is an extensively studied material
n
Corresponding author.
possessing a direct band gap (3.37 eV), large exciton binding en-
E-mail address:
[email protected] (G. Khang). ergy (60 meV) at room temperature and high electron mobility
1
Authors contributed equally to this work. ( 115–155 cm 2 V 1 s 1) [16–21]. Previously, various ZnO nano-/
http://dx.doi.org/10.1016/j.ceramint.2016.03.030
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
9520 N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526
micro-structures were designed using vapour phase and wet (0.2 g) and H2O were added into conical flask. The suspensions
chemical approaches owing to its low-cost and high-yield, ren- were magnetically stirred in dark for 30 min to stabilize RhB ab-
dering outstanding features in material science [22–26]. The un- sorption over the photocatalyst surface. Afterwards, the photo-
ique architecture of porous nanostructures allows enhanced dye reaction vessel was exposed to UV light under ambient conditions
adsorption and thus results in highly-efficient photodegradation of and stirred. At specific time intervals, the photoreacted suspen-
harmful dyes [27]. Notably, ZnO hollow spheres have presented a sions (∼3 mL) were taken out and change in the absorption peak
remarkable catalytic performance due to its large specific surface maximum in the UV–visible spectra of RhB was monitored using
area and mesoporosity, which are the critical factors desired for an UV–visible spectrophotometer (2550-Shimadzu, Japan).
improved photocatalytic performance [28–30].
Inspired by those features, herein, we successfully synthesized
mesoporous ZnO nanoclusters (MZN) photocatalyst via dissolution 3. Results and discussion
of PS@ZnO core–shell nanospheres. The MZN exhibits remarkably
higher photocatalytic activity towards RhB with a degradation rate 3.1. Morphology and structural properties of MZN
of 98% within initial 40 min. In addition, the formation me-
chanism of MZN and its photocatalytic activity were discussed in Mesoporous ZnO nanoclusters were synthesized via two-step
detail. solution process i.e. (i) formation of PS@ZnO core–shell nano-
spheres through esterification of zinc acetate dihydrate in iso-
propyl alcohol and (ii) synthesis of MZN by toluene dissolution.
2. Experimental details Fig. 1(a–d) shows the FESEM characterized morphology of PS na-
nospheres and aqueous ammonia concentration dependent
2.1. Synthesis of ZnO mesoporous nanoclusters morphologies of PS@ZnO core–shell nanospheres. The FESEM
images (low- and high-magnification) shows that the PS nano-
All the chemicals used in this study were of analytical grade. spheres comprise a smooth surface and uniform sphere size with a
Synthesis of MZN was accomplished using PS nanospheres as core. diameter of 300 nm (a). From the images (b-d), it can be clearly
First, PS nanospheres were prepared via emulsifier-free emulsion seen that after the formation of ZnO nanoparticles-shell over PS
polymerization with slight modifications [31]. Further, a layer of nanospheres, the surface morphology changes from smooth to
ZnO nanoparticles was formed over PS nanospheres by mixing rough consisting of well-arranged nanoparticles. A change in the
zinc acetate dihydrate (0.1 g) and PS (0.5 g) in a beaker containing as-formed ZnO-shell over the PS core is noticed as a function of
100 mL distilled water and isopropyl alcohol (IPA) in 1:1 ratio ammonia concentration, which implies with an increase in am-
under ultra-sonication. The mixed solution was then transferred monia concentration, the thickness of ZnO-shell also increases.
into a three-necked flask followed by NH4OH addition and heated Interestingly, it seems that several nanoparticles were arranged
for 1 h at 65 °C with magnetically stirring. In addition, the reaction over the PS core forming ZnO-shell. The EDX spectrum (Fig. 1d,
was carried out with varying NH4OH concentration, i.e. 1, 2, and bottom) confirms the presence of zinc and oxygen species on the
3 mL while keeping all the precursors amount and reaction tem- outer surface of PS nanospheres.
perature constant. The suspensions were aged overnight at room Further, the PS@ZnO core–shell nanospheres were suspended
temperature, washed and dried. The powder was then dispersed in toluene to achieve MZN and characterized in detail using FESEM
into excessive toluene solution and stirred slowly for 2 h followed and TEM, shown in Fig. 2. The typical FESEM (a1) and TEM (a2)
by alcohol washing and air-dried. Then, the products were an- images of MZN grown using 1 mL ammonia solution showed
nealed at 400 °C for 2 h to remove residual PS. distorted nanostructures. In case of MZN synthesized using 2 mL
ammonia solution, the as-formed nanoclusters are spherical in
2.2. Characterizations shape with less porosity (b1, b2). However, the images (c1, c2) of
as-synthesized MZN using 3 mL ammonia solution demonstrated
Morphological and structural characterizations of the as-grown well-arranged ZnO nanoparticles in spherically-shaped na-
products were performed using field-emission scanning electron noclusters with good mesoporosity. Also, the HRTEM image (inset
microscopy (FESEM, HITACHI S-4800), transmission electron mi- of c2) taken from the edge and centre of a single MZN further
croscopy (TEM) and high-resolution TEM (HRTEM, JEOL JEM- confirms the porous nature of nanoclusters made up of ZnO na-
2010UHR) at an acceleration voltage of 200 kV. The crystalline noparticles. The nanoclusters were observed to be 400 nm in
structure and composition of samples were determined by X-ray diameter constructed with 5 nm ZnO nanoparticles. The EDX
diffractometer (XRD) measured with Cu-Kα radiation spectrum (inset of c1) reveals that the as-grown MZN were com-
(λ ¼1.54178 Å) in the range of 10–80° with 8°/min scanning speed posed of Zn and O elements. The corresponding selected area
and infrared (IR) absorption spectroscopy at room temperature in electron diffraction (SAED) pattern (lower inset of c2) shows the
the range of 400–4000 cm 1, respectively. The optical properties polycrystalline nature of the nanoclusters.
were characterized by Raman-scattering measurements with Ar þ Fig. 3a shows the typical XRD pattern of PS nanospheres,
(513.4 nm) as the exciton source. Thermogravimetric analysis PS@ZnO core–shell nanospheres and MZN. For bare PS nano-
(TGA, TGA Q50 thermal analyzer) was performed at the tem- spheres, a single broad peak is ascribed to PS amorphous phase
perature range of 23–750 °C (heating rate¼20 °C/min) under an which is well-matched with the previously reported studies
oxygen atmosphere. Nitrogen adsorption-desorption analysis [32,33]. The XRD pattern of PS@ZnO core–shell nanospheres dis-
(ASAP 2010 analyzer at 77 K) and Brunauer–Emmett–Teller (BET) plays all the diffraction peaks corresponding to wurtzite ZnO
were measured to gain insights into the porous structure and pore phase along with the broad peak of PS, which indicates the growth
size distribution of the samples. of ZnO nanoparticles over the PS surface. The XRD pattern of MZN
displays good wurtzite crystallinity suggesting that the na-
2.3. Photocatalytic degradation of Rhodamine B noclusters have a single crystal structure. All the obtained dif-
fraction peaks in the (100), (002), (101), (102), (110), (103) and
The photocatalytic degradation of RhB was performed in a (112) planes, with higher intensity in the (101) plane suggests the
conical flask using as-synthesized MZN as photocatalyst under UV formation of nanoclusters along the [0001] direction. Also, no
illumination for 50 min. RhB solution (100 mL of 100 mg/L), MZN peaks indicating impurities such as PS were observed, confirming
N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526 9521
Fig. 1. (a) Low-magnification FESEM image of polystyrene (PS) spheres. Low-magnification FESEM images of ammonia solution concentration dependent morphologies of
PS@ZnO core–shell, keeping all the other parameters constant: (b) 1 mL, (c) 2 mL, and (d) 3 mL. Inset of (a), (b), (c) and (d, top) shows high-magnification FESEM image of the
respective spheres. Inset of (d, bottom) shows EDX spectra of PS@ZnO core–shell.
the presence of pure ZnO. Furthermore, the FTIR spectra of PS 44 wt% of the PS@ZnO core–shell nanospheres (after reducing the
nanospheres, PS@ZnO core–shell nanospheres and MZN were first mass loss %) and the remaining wt% of MZN is approximately
studied and shown in Fig. 3b. In case of PS nanospheres, all the 27%. Next, Fig. 4b presents the N2 adsorption-desorption isotherms
FTIR peaks were well-expressed according to the PS standard [34]. and pore size distribution of MZN based on the BJH (Barrett–Joy-
Where, the peaks at 1400–1600 cm 1, 2935 cm 1, 3130 cm 1 and ner–Halenda) model. It is well-reported that smaller size of pores
680–905 cm 1 were assigned to the C¼ C stretching, C–H will provide higher specific surface area [38]. The MZN were found
stretching, sp2 C–H stretching and C–H bending, respectively. The to possess large surface area and pore volume owing to its narrow
peak at 3400–3700 cm 1 is because of adsorbed water. The FTIR pore size distribution. A H1 hysteresis loop (IUPAC classification) in
spectrum of PS@ZnO core–shell nanospheres showed a peak at the range of 0.7–0.9 P/P0 in the isotherm curve was noticed which
430 cm 1 corresponding to the stretching vibration of ZnO along further indicates the mesoporous features of MZN. From N2 ad-
with all the PS peaks which further confirms the presence of ZnO sorption-desorption isotherm, the BET surface area was calculated
on the PS surfaces. As well, the FTIR spectrum of MZN shows the as 78.37 5.4 m2 g 1. The average pore diameter of MZN was ob-
ZnO stretching peak (430 cm 1). In addition, a broad absorption served as 26 nm according to the pore size distribution curve
band at 3420–3440 cm 1 in the samples is ascribed to O–H ranging from 5 to 200 nm (inset of Fig. 4b).
stretching vibration due to the presence of adsorbed water mo-
lecules [35]. The peak at 1390–1410 cm 1 is mainly attributed to 3.2. Formation mechanistic details of MZN
the symmetric and asymmetric O–C–O stretching vibration of the
adsorbed carbonate anion during synthesis of ZNPs [36,37]. Also, Fig. 5 schematically illustrates the formation mechanism of
the peaks at 2937 and 2871 cm 1 correspond to C–H stretching mesoporous ZnO nanoclusters, synthesized using PS sacrificial
vibration. core followed by toluene dissolution. In step-I, the PS sacrificial
Thereafter, TGA analysis was carried out to assess the mass core were synthesized via polymerization reaction. The zeta po-
ratio between PS and ZnO (Fig. 4a). For PS@ZnO core–shell nano- tential of the PS nanospheres in aqueous solution at pH ¼7 was
spheres, the mass loss profile displays a three-step mass loss i.e. observed as 20.63 mV, which confirms the presence of negative
(i) the first mass loss (19%) below 200 °C due to trapped solvent charges over the as-synthesized nanospheres. In step-II with the
evaporation and other two mass losses at 300–360 °C (32%) and solution containing zinc acetate dihydrate, polystyrene, isopropyl
370–420 °C (12%) were ascribed to the decomposition and com- alcohol and NH4OH, a layer of ZnO nanoparticles deposition takes
plete removal of PS. The weight loss patterns of MZN showed a place over the PS nanospheres surfaces. We hypothesize that (i) at
single decrease in mass over 220–280 °C which is ascribed to first, a coupling reaction between zinc acetate dihydrate and iso-
desorption of physically adsorbed water from the surface of MZN propyl alcohol produces initial OH ions via esterification reaction
[38]. Thus, the total PS weight loss above 200 °C was calculated as between CH3COO and alcohol; (ii) then, instant nucleation and
9522 N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526
Fig. 2. (a1), (b1) and (c1) FESEM and (a2), (b2) and (c2) TEM images of spherically-shaped mesoporous ZnO nanoclusters obtained after toluene-dissolution of PS@ZnO core–
shell synthesized using 1, 2 and 3 mL ammonia solutions, respectively. Inset of (c1) and (c2) shows EDX spectra, and HRTEM image (top) with SAED pattern (bottom) of ZnO
nanoclusters, respectively.
growth of Zn(OH)2 nuclei takes place over the nanospheres owing mechanism, the growth of ZnO is due to high basicity of reaction
to a reaction between Zn2 þ cations and free OH ions, serving as solution resulting in an increased precursors (zinc hydroxide
basic building units for the formation of PS@ZnO core–shell complexes) concentration as well as an increase in the chemical
nanospheres. potential of OH ions [40]. In addition, NH4OH also reacts with
In the latter part of reaction, NH4OH plays a crucial role by Zn(OH)2 and penetrates the shell giving a mesoporous appearance
dissociating and providing OH ions slowly by the following to the PS@ZnO core–shell nanospheres [41]. Thereafter, the MZN
chemical reaction: NH4OH⇔NH4 þ þOH , since NH4OH is a weak
were obtained by dispersing PS@ZnO core–shell nanospheres
base with an equilibrium constant of Kb ¼1.89 10 5 at 60 °C [39].
(synthesized using 3 mL ammonia solution) in excessive toluene,
From Figs. 1 and 2, it is evident that the thickness of ZnO nano-
where toluene penetrates the porous ZnO-shell and dissolves the
particles-shell over the PS nanospheres increases with an increase
in NH4OH concentrations, and as well plays a vital role in MZN PS core efficiently [42]. Notably, the dispersion of PS@ZnO core–
formation. The ample presence of OH ions leads to the formation shell nanospheres synthesized using 1 and 2 mL ammonia solution
of Zn(OH)2 complexes, which ultimately results in the ZnO nano- in excessive toluene resulted in either almost distorted or irregu-
particles formation through condensation process. Furthermore, at larly formed nanoclusters due to inadequate thickness of ZnO
an appropriate reaction temperature and time, Zn(OH)2 results in nanoparticles-shell over PS nanospheres core, supported by FES-
ZnO nanoparticles formation. According to the above proposed EM and TEM images in Figs. 1 and 2.
N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526 9523
Fig. 3. (a) XRD patterns and (b) FTIR pattern of PS nanospheres, PS@ZnO core–shell nanospheres and mesoporous ZnO nanoclusters, respectively.
Fig. 4. (a) TGA spectra for PS@ZnO core-shells nanospheres and MZN. (b) Nitrogen adsorption-desorption isotherm and pore size distribution (inset) of MZN.
Fig. 5. Schematic illustration of the formation mechanism of MZN using polystyrene sacrificial core followed by toluene dissolution.
3.3. Photocatalytic degradation of Rhodamine B surface of MZN as a photocatalyst are shown in Fig. 6a. From the
image, it can be clearly seen that with an increase in UV exposure
Fig. 6 illustrates the photocatalytic degradation of aqueous so- time, the intensity of RhB absorbance continuously decreases,
lution of RhB under UV light irradiation. The UV–visible spectra of which indicates decrease in RhB concentration. Additionally, the
RhB with increasing irradiation time from 0–50 min over the rate of RhB degradation (in percentage) with MZN under UV
9524 N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526
Fig. 6. (a) UV–visible absorbance spectra of decomposed RhB dye solution over highly porous MZN under UV light illumination; (b) degradation (%) versus time interval, and
(c) dye degradation pie chart as a function of time. (d) Plausible reaction mechanism involved in photocatalytic degradation of RhB by MZN.
illumination showed an increased degradation rate with increase e−CB + O2 → O2∙− (2)
in exposure time, as shown in Fig. 6b. The pie chart of RhB de-
gradation (Fig. 6c) demonstrates that almost all ( 98%) of the dyes H2 O + O2∙− → HOO + OH−
∙
(3)
were decomposed in an initial 40 min over MZN. Previously, the
RhB photodegradation ability of different ZnO structures were also 2OOH∙ → O2 + H2 O2 (4)
prominent such as nanoparticles by 95% within 70 min [43];
hierarchical flower-rod arrays 100% within 90 min [44]; nano- ∙
hamburgers 61% within 60 min; 3D ZnO microflowers 99% de-
O2∙− + dye → dye−OO (5)
gradation was achieved within 60 min [45] and hexagonal plat- ∙
forms 100% within 60 min [46] under UV irradiation. Compared OOH + H2 O + e−CB → H2 O2 + OH− (6)
with the above studies, MZN showed enhanced photocatalytic
∙
degradation efficiency of RhB because of mesoporous nature, high H2 O2 + e−CB → OH + OH− (7)
surface area and excellent electron accepting features of the en-
∙
gineered MZN. H2 O2 + O2∙− → OH + OH− + O2 (8)
Schematic illustration of RhB photodegradation with MZN is
summarized in Fig. 6d. The ultra-fast photocatalytic degradation of ∙
Dye + OH /O2∙− + ZnO → Dye degradation (9)
RhB with MZN was explained by photo-excitation of the semi-
conductor followed by the photogeneration of electron-hole In the above reactions, the photogenerated e in CB migrates to
(e –h þ ) pairs between the conduction (CB) and valence bands the surface; scavenged by the ubiquitous O2 to produce superoxide
∙
(VB). These results showed that UV light irradiation and MZN anion and simultaneous protonation produces HOO radicals.
þ
photocatalyst influences the effective decomposition of RhB dye. It While, h in VB moves to the backside of MZN surface and reacts
is well-known that the dyes color are dependent on their asso- with either H2O or OH to yield an active species such as OH∙ . The
∙
ciated chromophores (azo bonds) and auxochromes where the azo above generated active oxygen species ( O−2 , O2∙−, HOO / ∙OH) were
bonds were the most active bonds and can be oxidized by positive responsible for degradation of RhB into less harmful organic end
hole or hydroxyl radical or reduced by electron in the conduction products. Thus, MZN possessing good crystallinity and optical
band. The mechanism involved in the photocatalytic degradation properties substantially increase the reactive species over catalysts
of RhB by MZN can be illustrated through the following plausible surface leading to expeditious photocatalytic degradation of RhB
reaction sequences [47,48]: under UV illumination. In order to check the cyclic stability of MZN
photocatalyst for RhB degradation, we have conducted five cyclic
ZnO + hν → e−CB + h+VB (1)
stability tests and measured the photocatalytic efficiency of MZN,
N. Tripathy et al. / Ceramics International 42 (2016) 9519–9526 9525
Fig. 7. (a) Stability test and (b) FESEM image of MZN photocatalysts after five successive re-uses for RhB photodegradation.
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