Materials Research Express

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Photocatalytic and catalytic degradation of organic dye by uncapped and

capped ZnS quantum dots
To cite this article before publication: Asma Rafiq et al 2019 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/aaff8e

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Page 1 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-111684.R1

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3 Photocatalytic and Catalytic Degradation of Organic Dye by Uncapped and Capped ZnS
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5 Quantum dots
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A. Rafiqa, M. Imranb,c, M. Ikrama*, M. Nazd, M. Aqeela, H. Majeede, S. G. Hussainf, S. Alia,g
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a
10 Solar Cell Applications Research Lab, Department of Physics, Government College University
11 Lahore, 54000, Pakistan
12 b
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, 29 Zhongguancun
13 East Road, Haidian District, Beijing 100190, China
14 c
University of Chinese Academy of Sciences, Beijing 100190, China
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16 Biochemistry Lab, Depatment of Chemistry, Government College University Lahore, 54000,

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17 Punjab, Pakistan.
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18 Department of Botany, Government College University, Lahore, 54000, Punjab, Pakistan.
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19 Department of Physics, King Faisal University, Al-Ahsa 31982, Saudi Arabia
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Department of Physics, Riphah Institute of Computing and Applied Sciences (RICAS), Riphah
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22 International University, 14 Ali Road, Lahore, Pakistan
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*Corresponding Author Email: dr.muhammadikram@gcu.edu.pk
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ABSTRACT
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30 ZnS quantum dots were prepared with different concentrations of 2-mercaptoethanol as a
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32 capping agent by simple and fast co-precipitation method. The synthesized nanopowders were
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34 characterized using various analytical chemistry as well as image visualizing techniques to
35 elucidate the changes in structure and shape of quantum dots. The lowest average estimated
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37 crystallite size of ZnS quantum dot was 4.2 nm that showed relevancy to 2-Mercaptoethanol
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amount. X-ray diffraction (XRD) confirmed purity of nanosized ZnS with cubic and
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rhombohedral crystalline structures. Upon capping increased absorption around 300 nm was
42 recorded by UV-Vis spectroscopy that suggests ZnS interaction with 2-mercaptoethanol. The
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44 surface morphology of capped ZnS showed nanorod shape with agglomeration of particles
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46 confirmed by field emission electron microscopy (FESEM). The presence of functional groups
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47 and strong chemical bonding at the interface of quantum dots was confirmed by fourier
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49 transform infrared spectroscopy (FTIR). However, thermal analysis revealed no decomposition
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51 till 200 °C evidenced by DSC-TGA that suggests its high temperature stability. Moreover,
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53 uncapped ZnS quantum dot showed extensive methylene blue (MB) dye degradation with
54 maximum absorption peak (λmax) at 664 nm that suggests visible light activity. The synthesized
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3 ZnS quantum dots has strong potential to be used as effective dye degradation agents in textile,
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5 tanneries and leather industries.
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7 Keywords: Capping; 2-mercaptoethanol; nanoparticle; FESEM; catalysis; dye
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11 1. INTRODUCTION
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13 Nanotechnology advancements has opened up new doors of exploration in science and
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15 engineering fields [1]. Variety of semiconducting nanomaterials owing electrical, optical and
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17 surface properties have attracted the attention of researchers throughout the world. These
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nanostructures have potentially be used in film coatings, photoelectric devices, filters, sensors,
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20 delivery of drugs and chemical catalysis [2]. Among these nanostructures, quantum dots (QDs)
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22 are smaller than bulk Bohr excitonic radii yields high photoluminescence (PL) property and
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display blue shift in the optical transition [3].

Recently, photocatalytic features of inorganic semiconductors exhibited huge attraction and

interest of researchers [4]. In dye degradation, semiconductor photocatalyst is preferred because
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of sustained and fundamentally applied research in environmental remediation [5]. Synthetic
31 dyes release organic compounds in industrial manufacturer in leather, tanning, food processing,
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33 plastic, glass, paints, cosmetic, textile and pharmaceutics causing environment pollution [6]. Dye
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35 residues impart color to the wastewater even with small concentration level and form a class of
36 grave and glaring grave contaminants. In the present context, the catalytic reduction studies of
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38 these dyes commence greater consequence as most of dyes are proven as toxic when inhaled/
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40 ingested orally and cause health hazards skin and eye irritation in humans. These synthetic dyes
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have adverse effects to the environment; including the ability to deplete oxygen in the surface
43 waters [7].
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46 On the contrary, removal of industrial dyes is toxic and carcinogenic metabolites leads to
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47 water contamination in addition to producing environmental problem for the world [8]. Besides,
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49 water soluble formulations are more harmful as they create direct impact on living beings.
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51 Primarily, organic dyes in waste water coming out from textile and other industries have the
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53 major influence on it. Various dyes are nontoxic but when mix with water; form highly toxic
54 complexes easily in the water wastage and pollute it [9]. Thus new strategies to tackle dye
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56 contaminated waste water should be investigated and opted to recycle water [10].
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3 Photocatalysis (organic – inorganic) has attracted the attention of researchers due to non-
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5 destructive inorganic compounds [11]. Heterogeneous photocatalysis has been considered as a
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7 most cost effective alternative for water remediation among numerous chemical, physical, and
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biological methods for treatment of wastewaters, [12] The semiconductor during photocatalysis

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10 absorbs light energy greater than band gap that caused excitation from valence to conduction band and
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12 electron hole pairs generated due to charge separation that produced free radicals. These free radicals
13 (OH) oxidize organic materials and resulted in pollutants degradation [13].
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16 Recently, semiconductor nanostructures have been widely studied to explore

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size dependent optical properties and potential applications in various fields like photocatalysis
19 and optical sensitization [14]. Nano-photocatalysts showed superior activities compared to bulk
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21 couterparts due to increased redox potential as a result of greater surface to volume ratio.
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However, efficient photocatalyst having dye degradation potential has light visible region
adsorption, appropriate band gap and flat band potential. [15].

Transition metal sulfides, particularly zinc sulphide-ZnS has unique catalytic functions due to
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electron–hole pairs generation by photo excitation. It is chemically stable, environmentally safe,
30 nontoxic and highly negative reduction potentials of excited electrons relative to other transition
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32 metal oxides TiO2 and ZnO [16]. The sulphide nanostructures have been proved efficient
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34 photocatalyst due to easier access of electron hole pairs on behalf of photoexcitation [17]. The
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high negative reduction potential of excited electron in aqueous solution is due to higher
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37 conduction band position in photocatalyst [18]. Likewise, NPs showed excellent photocatalytic
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39 activity due to trapped holes aroused due to sulphides surface defects [19].
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41 So far, several surface modifications of nanoparticles have been carried out by different
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43 functionalized/capping agents such as L-cysteine, thioglycolic acid ,3-mercaptopropionic acid
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45 ,thioacetamide, trioctylphosphine oxide, trioctylphosphine, mercaptosilane, bovine serum
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albumin, glutathione, dihydrolipoic acid , and polymer coating [20-26]. Earlier, capping agent
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48 and selective solvent have been used for ZnS fabrication processes [27] to control the size.
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50 Functionalization of nanostructures surface through chemical agent can modify photocatalytic
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52 activities, morphology, toxicity, particle size, optical properties as well as mechanical stability.
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53 However, currently researchers are focusing on size role in tuning the optoelectronic properties
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55 without capping agent against agglomeration leading to larger particles [28].
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3 Therefore, we aimed to evaluate the influence of capping agent 2-mercaptoethanol on
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5 structural, thermal, morphological, optical and catalytic properties of ZnS. However, nanosized
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7 ZnS was prepared using water based chemical precipitation at room temperature. Photocatalytic
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and catalytic degradation of organic dye methyl blue-(MB) was investigated using uncapped and

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10 capped ZnS.
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13 2. EXPERIMENTAL DETAILS
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15 2.1. Materials
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Zinc nitrate 6-hydrate (Zn(NO)3)2 .6H2 O- 97%) was obtained from Panreac, sodium
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19 sulphide pentahydrate (Na2S.5H2O- 98%) was purchased from Daejung and sodium borohydride
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21 (NaBH4 -98.0%) were received from Sigma Aldrich. Methyl blue (MB) and capping agent 2-
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2.2 Synthesis of ZnS Quantum Dots
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Mercaptoethanol were purchased from BDH Laboratories supplies and AppliChem respectively.
All chemicals purchased were of analytical grade and used without any additional processing.
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30 Homogenous solutions of 0.1M Zn(NO3).4H2O and Na2S.5H2O were dissolved
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individually in water (50 ml) under stirring for 30 minutes as reported [29]. Solution of
33 Na2S.5H2O was added dropwise in zinc nitrate mixture. During drop wise mixing, precipitation
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35 occurred. The concentration of precipitation increased with amount of sodium sulphide solution
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37 under vigorous stirring for 15 minutes subsequently centrifuged at 40000 rpm for 5 minutes. The
38 precipitated particles were filtered and washed several times with deionized water to remove any
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40 traces of adhered impurities. To obtain nascent ZnS QDs, the washed particles were dried at
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42 60°C for 24 hours in vacuum oven. In order to synthesize 2-mercaptoethanol (HOCH2CH2SH)
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capped ZnS, above steps were carried out according to calculated 2.5 ml and 5 ml stoichiometric
45 ratio as shown in Fig. 1.
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48 The prepared samples of different capped molar concentration namely ZnS(A), ZnS(B) and
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50 ZnS(C) correspond to 0 ml, 2.5 ml and 5 ml respectively were used in further study.
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35 Fig. 1: Steps involved in the synthesis of ZnS QDs
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2.3. Catalytic reduction of Methylene Blue with uncapped and capped ZnS QDs
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The catalytic activity was determined in terms of degradation of Methylene blue (MB) in
43 NaBH4 presence. MB is a cationic thiazine dye extensively used in analytical chemistry as a
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45 redox indicator. [30]. MB in oxidized form is blue and is colorless when reduced. MB solution
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(1mM) was diluted with sufficient amount of deionized water (DIW) in the quartz cell. NaBH4
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solution (0.1M, 400 μL) and QDs (uncapped and capped, 400 μL) solution were added to
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50 prepared aqueous MB solution to evaluate the catalytic degradation of dye. The reaction progress
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52 was measured spectrophotometrically and absorption spectra were monitored at regular intervals
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54 at room temperature. Decolorization of MB in the presence of NaBH4 signifies reduction of MB
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3 as shown in Fig. 2. However, sodium borohydride being reducing agent failed to reduce MB
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5 effectively because of its significant redox-potential variation [31-32].
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30 Fig. 2: Schematic representation of catalytic process
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2.4 Photo-Catalytic Activity Process
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34 Photocatalytic activity of uncapped and capped ZnS QDs was studied by degradation of
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36 synthetic MB dye in aqueous solution. A mercury lamp (400 W) having principal wavelength of
37 400-700 nm was used as the visible light source. 5mg/500 mL aqueous solution of MB dye was
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39 exposed to dark (30 min) for sufficient physical absorption. 30 mg of nanocatalyst (QDs) were
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41 added to 30 mL MB solution and exposed to mercury lamp under continuous stirring. To avoid
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excessive heating, the distance between surface of the solution and light source was maintained
44 at 15 cm. 2 ml of solution from reaction mixture was withdrawn at regular interval of 20 min to
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46 determine the dye concentration using UV-Vis spectrophotometer (200-800 nm). The absorbance
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48 of MB at λmax = 664 nm was recorded from UV–Vis absorption spectra. The decrease in
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50 absorbance of dye after irradiation at λmax for regular time intervals provided decolorization rate
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and hence photodegradation efficiency of NPs, was calculated as
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6 Where Ao and At are initial and absorbance at time t (irradiation time) [33].
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8 2.5. Characterization
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The size and phase orientation of ZnS QDs was done using PAN Analytical Xpert PRO X-ray
12 diffraction (XRD) withCu Kα radiation (0.154 nm) and 2θ ranged from 20°- 80º. UV-Vis
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14 spectrophotometer (Genesys 10S) was used to measure the absorption and catalytic reduction of
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16 capped and uncapped ZnS QDs. The presence of functional groups was acquired using fourier

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transform infrared spectroscopy-FTIR (Perkin Elmer spectrometer). Microstructures and surface
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19 morphology were obtained using JSM-6460LV field emission scanning electron microscope
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21 (FESEM coupled with Energy -dispersive X-ray spectroscopy (EDX). Raman Spectra were
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obtained with DXR Raman microscope (Thermo Scientific) with a diode laser at 532nm (6 mV).
However, thermal changes were analyzed via differential scanning calorimetry- thermal
gravimetric analysis (DSC/TGA) Model # Q600 with T.A instruments.
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30 3. RESULTS AND DISCUSSION
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34 The determination of phase composition, structure and particle size is very important to
35 examine the physical properties of prepared samples [34]. The X-ray diffractograms of prepared
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37 ZnS (A-C) are shown in Fig. 3. The observed diffraction peaks are indexed and patterns
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confirmed the cubic zinc blende crystal structure of ZnS [35]. XRD pattern revealed that
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improved crystallinity with capping and well matched with JCPDS (Card no: 01-080-0020) [36].
42 The broadening of peaks confirmed the formation of nanocrystals in control sample (ZnS) [37].
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44 Quite sharp peaks of ZnS appeared with capping agent are indexed to rhombohedral phase of
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46 ZnS (JCPDS, card no. 01-089-2200 and 01-089-2179). Furthermore, few small peaks were
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47 observed in capped samples which may be attributed to surface capping of particles [38]. The
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49 crystalline ZnS size was estimated using Scherrer equation D = 0.9 λ/ (βcosθ), where D is
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51 crystalline size, λ is incident X-rays wavelength, θ is the diffraction angle of (111) peak of cubic
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phase and β is half-width [39].
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3 The average estimated crystallite size from half width of diffraction peaks using Debye–
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5 Scherer equation is 4.2, 49, 29.6 nm respectively. It can be seen with increasing amount of 2-
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7 Merceptoethanol, crystallite size of ZnS QDs increased.
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36 Fig.3: XRD pattern of uncapped and capped ZnS QDs
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41 investigations [40]. UV–vis absorption spectra confirmed the optical properties, absorption
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43 range, size, and band gap of semiconductor QDs [41]. Therefore, size as well as effectiveness of
44 2-hydroxyethanthiol capping agent on stabilization and formation of QDs in aqueous media UV-
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46 vis spectroscopy was used Fig. 4a. The absorption increased with amount of capped materials
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48 compared to uncapped (ZnS A). The increased absorption is attributed to large concentration of
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vacancies and interstitial ions in capped samples [42].
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Fig.4: Absorption spectra of prepared samples (a) and band gap energy (b)

The band gap energy of QDs was determined from absorption spectrum as shown in Fig. 4b,
according to the equation
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Where αo, hυ, and Eg are a constant, photon energy, and optical band gap of the QDs,
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33 respectively [43]. The bandgap of ZnS nanostructures was reduced from 3.8 to 3.69 and 3.45eV
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35 in the presence of capping (4b). This reduction in band gap is due to increase in particles size
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37 well cover the reported [41].
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39 Energy dispersive X-ray spectroscopy (EDX) is a very good tool to study the chemical
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41 composition of the synthesized material. Fig. 5 (a-c) shows the EDX spectrum of ZnS (A-C)
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quantum dots respectively. The presence of Zn and S is confirmed and no impurity is observed
44 in the spectrum. This indicates that purity of ZnS QDs prepared by fast co-precipitation
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33 Fig 5(a-c). EDX patterns of different ratios of capped ZnS (A-C)
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36 Fig. 6 (a-c) show typical FESEM images of ZnS and 2-mercaptoethanol capped ZnS
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38 nanopowders. From FESEM images, it is observed that ZnS nanostructures showed higher
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40 agglomeration of small and large ZnS nanostructures than capped nanostructures (a-b).
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Alternatively, the morphology of small amount of capped synthesized product showed rod-
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32 Fig. 6. FESEM images of uncapped and capped ZnS nanostructures
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36 To further investigate the nature of ZnS QDs, HRTEM and SAED patterns are presented in
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39 confirms the observation from X-ray diffractograms. As seen, it is difficult to determine the size
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41 of particles accurately due to narrow size distribution of ZnS QDs. This suggests compact
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coverage of 2 mercaptoethanol on ZnS particles and avoided agglomeration [22]. However, few
44 aggregated particles lead to bigger size. Aggregates in TEM observations pointed to solvent
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Fig. 7. HRTEM images (a-d) and corresponding SAED pattern (b-d inset) of uncapped and
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41 ZnS-QDs were submerged in MB dye solution before irradiation for 30 min to assure
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adsorption attained equilibrium. The degradation of MB by NaBH4 was performed in the
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44 presence and absence of ZnS. Firstly, reference sample (dye solution) was conducted with
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46 NaBH4 and observed slower degradation rate. Subsequently, minute quantity of catalyst in
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48 solution (dye +NaBH4) was added, degradation rate enhanced rapidly which indicates immense
49 catalytic effect of ZnS QDs. Degradation of dye with ZnS and capped under UV-Vis
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in the presence of ZnS QDs within 40 min that suggest their efficient photocatalyst action (7a).
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3 The cause of degradation is due to rapid formation of electron–hole pairs during photo-
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5 excitation of ZnS-QDs and negative reduction potential associated with excited electrons. From
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7 literature, ZnS QDs <10 nm exhibited 63 % degradation of MB dye for 300 min under UV
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irradiation [44]. Pourahmad [45] reported 45 % degradation after 20 min of irradiation with ZnS,

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12 MB dye within 30 min and enhanced degradation can be ascribed to capping of ZnS.
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14 The MB degradation mechanism by ZnS nanostructures is shown as follows: when irradiated
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hole during excitation oxidize dye molecule directly into reactive intermediates [33]. Though,
hydroxyl radical formation favored during decomposition of water by hole. Eqs (2) and (3)
explains this phenomenon.
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37 Alternatively, negative reduction potential associated with conduction
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band converts molecular oxygen into superoxide radical, which in turn assists
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degradation of organic dye compounds.
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50 Resultant superoxide and hydroxyl radical react with dye
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31 Fig. 8. Catalytic degradation of methylene blue by NaBH4 at different time intervals
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33 QDs were used for degradation of MB dye as a function of time for uncapped and capped
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35 ZnS is represented in Fig.9 (a-d). It is observed that uncapped ZnS photocatalysis showed higher
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activities relative to capped. Degradation continuously increased with time and maximum
38 absorption peak (λmax) of MB was observed at 664 nm. Band gap showed visible-light activity of
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40 photocatalyst. Moreover, other than band gap, crystal structure, the particle size, degree of
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42 crystallinity and surface area of semiconductor QDs also have effect on the transportation of
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photo-generated electrons, holes and their photo catalyst performance too [46].
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35 The thermal properties of pure and capped nanopowders were recorded using DSC/TGA
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37 analysis from room temperature (RT) to 1000 °C in air with ramp rate (10 °C /min) as shown in
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Fig. 10(a-c). The thermal properties of pure and capped nanopowders were recorded using
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40 DSC/TGA analysis from RT to 1000 °C in air with ramp rate (10 °C /min) as shown in Fig. 6(a-
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42 c). The DSC/TGA curve of ZnS (9a) showed initially 12 % mass loss occurred between 0-200 °C
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44 and is attributed to water evaporation from nanostructures [47]. The mass increment start from
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46 200-350 °C corresponds to thermal oxidation and formation of Zn2SO4. The final decomposition
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47 temperature is between 600-1000 °C represents decomposition of Zn2SO4 to ZnO and SO2. The
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49 DSC/TGA curve of capped ZnS has different degradation pattern relative to uncapped ZnS 9(b-
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51 c). With small amount of capped sample (9b), TGA curve showed initial mass loss around 5 %
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upto 200 °C mostly due to removal of water used during fabrication and water of crystallization,
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3 mass increment observed at 360 °C due to zinc sulfate/ zinc oxy-sulfate formation. A sharp
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5 significant decrease in mass loss ~ 35 % at 425 °C was observed correspond to exothermal peak
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Fig.10 (a-c): DSC/TGA curve of pure and capped ZnS (2.5 and 5ml) respectively
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48 Uncapped and 2-mercaptoethanol capped ZnS QDs were examined using FTIR spectra (Fig.
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50 11). This spectrum displays IR absorption due to several vibration modes. The formation of new
51 bands and shift in existing bands in adsorbed 2-mercaptoethanol indicates binding mode. The
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53 broad peak at 3433 cm-1 corresponds to (O-H) and 3000–2800 cm-1 bands due to C–H symmetric
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7 amines [48]. All above functional groups appeared due to organic solvents used during synthesis,
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40 Fig.11: FTIR spectra of pure and capped ZnS (2.5 and 5ml) respectively.
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44 Fig.12 represents the Raman spectra of prepared capped and uncapped ZnS QDs under
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green excitation (λ= 514 nm). The prepared ZnS nanopowder exhibits (last spectrum from
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47 bottom) peaks at 177, 348 and 1045 cm-1 are well matched with reported [49]. Upon capping (2nd
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49 and 3rd spectrum from bottom), several peaks at lower wave numbers such as (1400 cm-1) and
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51 main peak around 2932 cm-1 was found [50]. The peak intensity (2932 cm-1) increased with
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Fig.12: Raman spectra of pure and capped ZnS (A, B and C) respectively.
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34 4. CONCLUSION
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37 The current study is presenting novel, short and fast co-precipitation method for the
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39 preparation of visible light catalytic material named ZnS QDs. The obtained QDs had cubic and
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41 rhombohedral crystalline structures in size ranged from 4.2-29.6 nm having band gap energies
42 3.8-3.45 eV. Crystallite size variations caused changes in band gap that suggests suitable
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44 materials for organic pollutants. However, FESEM confirmed agglomerated particles of
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46 uncapped ZnS and rod shape in case of capped. The capped ZnS QDs showed excellent potential
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in organic dyes degradation and could serve as catalyst. The same process could be successfully
49 employed for creating different optical and Raman properties by doping with suitable transition
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51 metal impurities. The results obtained with capping agent are future guidelines for ZnS QDs
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53 preparation in order to tune band gap, modern optoelectronic technology and in other industrial
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3 ACKNOWLEDGMENT: The authors are thankful to higher education commission (HEC),
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5 Pakistan for financial support.
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7 Conflict of Interest: The authors declared this manuscript has no conflict of interest.
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