Accepted Manuscript

Facile synthesis of Zinc Vanadate Zn3(VO4)2 for highly efficient visible light assisted
photocatalytic activity

Muhammad Munir Sajid, Naveed Akthar Shad, Sadaf Bashir Khan, Zhengjun Zhang,
Nasir Amin
PII: S0925-8388(18)33806-4
DOI: 10.1016/j.jallcom.2018.10.134
Reference: JALCOM 47952

To appear in: Journal of Alloys and Compounds

Received Date: 18 August 2018

Revised Date: 11 October 2018
Accepted Date: 12 October 2018

Please cite this article as: M.M. Sajid, N.A. Shad, S.B. Khan, Z. Zhang, N. Amin, Facile synthesis of Zinc
Vanadate Zn3(VO4)2 for highly efficient visible light assisted photocatalytic activity, Journal of Alloys and
Compounds (2018), doi: https://doi.org/10.1016/j.jallcom.2018.10.134.

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Facile Synthesis of Zinc Vanadate Zn3(VO4)2 for highly efficient visible light

assisted Photocatalytic activity

Muhammad Munir Sajida,c*, Naveed Akthar Shada,b, Sadaf Bashir Khanc, Zhengjun Zhangd,

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Nasir Amin*a

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a
Department of Physics, Government College University Allama Iqbal Road, Faisalabad,

38000, Pakistan.

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b
National Institute for Biotechnology and Genetic Engineering (NIBGE), P.O. Box. 577, Jhang

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Road Faisalabad, Pakistan.
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c
The State Key Laboratory for New Ceramics & Fine Processing, School of Materials Science &

Engineering, Tsinghua University, Beijing, China, 100084.

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d
Advanced Key Laboratory for New Ceramics, School of Materials Science & Engineering,
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Tsinghua University, Beijing, China, 100084.

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*Corresponding Author

*
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Email: nasir786a@yahoo.com
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ABSTRACT

Zinc Vanadate Zn3(VO4)2 nanoplates with width and thickness 300 ~ 500nm and 50 ~

75nm diameter were synthesized by the facile modified hydrothermal method. Which containing

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mixing of Ammonia metavanadate (NH4VO3) powder with zinc acetate (Zn(CH3COO)2.2H2O),

in the presence of CTAB and N, N-dimethyl formamide (DMF), the pH was adjusted around 5

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and white precipitates were obtained. The potential of Zn3(VO4)2 photocatalyst was investigated

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by degrading Congo Red (CR) and Crystal Violet (CV) dyes using a UV-visible

spectrophotometer. These Zinc vanadate nanoplates (ZnVO-Nps) showed enhanced dye removal

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(100%) due to reduced band gap 2.68eV and high surface area (84m²/g). The Photoluminescence
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measurement showed the ZnVO-Nps potential for blue/green visible optical devices. These result

showed that ZnVO-Nps have higher photocatalytic degradation due to the large surface area and
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porosity; it is proposed that the ZnVO-Nps demonstrated the high-level application for the

degradation of organic pollutants under visible light irradiation.

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Keywords: Zinc Vanadate; Nanoplates; Hydrothermal Method; Organic dyes; Crystal Violet
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(CV); Congo Red (CR); and Photocatalysis

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1. Introduction

Recently, heterogeneous photocatalysis has gained significant importance in the field of eco-

friendly technology, [1] in green chemistry [2] and in evolving Advanced Oxidation Processes

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(AOPs) primarily for air and wastewater remediation.[3, 4] Different methods, such as

coagulation, filtration, [5] adsorption and photocatalytic technology are reported for the removal

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of organic pollutants from the aqueous medium. [6, 7] In the content of these techniques,

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photocatalytic skill has gained much attraction owing to its simple methodology, the simplicity

of design and high efficiency. [8] A high-quality photocatalyst must adsorb reactants and absorb

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light preferably in the visible or near UV region of the electromagnetic spectrum. [9] To
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correctly utilize photo visible radiation and minimize environmental contamination, exploration

of photocatalysis of low-cost materials comprises fascinating and inspirational work.[10, 11]

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Transition metal oxides such as vanadate (vanadium oxide) based material are capable of
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pseudo-capacitance execution, due to their mechanical stability, low cost, high energy density
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and catalysis.[12-14] Recently Zn3(VO4)2 is an interesting and potential candidate for

heterogeneous photocatalysis Owing to it has extraordinary chemical constancy, low optical

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damage, comparatively higher catalytic activity, and affordable trade availability.[15] Numerous

routes have been established for the fabrication of vanadate based material photocatalyst
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including thermal decomposition, co-precipitation, sol-gel method,[16-20] solid-solid transition,

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[21] microwave-assisted,[22] solve-thermal,[15] hydrothermal,[23] [24] laser ablation

process[25] or solution-solid growth.[26]

Organic contaminants such as dyes releases from the fast growth of industries like textile,

food, mining, petrochemical or leather industries create a great threat to the environment.[27, 28]
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Photocatalytic nanomaterials play a significant role in order to degrade these pollutants. Zinc

vanadate based nanostructures are currently under intensive investigations due to their

degradation characteristic in visible light illumination irradiation.[29, 30] Wang et al. described

the preparation of Zn3V2O8 by solid-state reaction and its photocatalytic activity as O2 evolution

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was evaluated.[31] The Zn3V2O7(OH)2(H2O)2 was also synthesised with success and used for

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photocatalyst to degrade organic pollutant under UV-light radiation. The photocatalytic

efficiency of the Zn3(VO4)2 nanostructure formed via calcination of Zn3V2O7(OH)2(H2O)2 was

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three times than the sample prepared by solid-state reaction. [32] Zn3(VO4)2 nanostructures with

distinct respected morphological characteristics have been acknowledged to show good

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photocatalytic degradation of MB dye and 4-nitrophenol (4-NP). [15, 30, 33]
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According to our knowledge, only a few reports are in the literature on the preparation of
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Zn3(VO4)2 nanostructures and its photocatalytic degradation application by using costly,

difficult, toxic chemicals and at low temperature with the chemical route. Keeping in
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consideration, the substantial role of Zn3(VO4)2 in several applications, it is necessary to grow a

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cost-effective and facile method for the preparation and to explore the capacity as photocatalysis

degradation materials for future applications. In the present study, we successfully prepared
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nanoplates of Zn3(VO4)2 by the facile modified hydrothermal method and characterized by

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several resources, such as Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray

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(EDX) spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), Brunauer–

Emmett–Teller (BET) surface area and pore size analyser, X-ray Photoelectron Spectroscopy

(XPS), UV–vis Diffuse Reflectance Spectra (DRS), Photoluminescence (PL), and Electronic

Paramagnetic Resonance (EPR) analysis. The enhanced photocatalytic response of the as-

prepared Zn3(VO4)2 nanoplates was evaluated and observed by the degradation of congo red and
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crystal violet organic dyes under visible light. Our work offered novel linear perspective for

efficient photocatalyst that can degrade different organic dyes in visible light irradiation and

contributed direction for designing more effective photocatalysts in future for treating dye

effluents and industrial wastewater.

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2. Experimental methods

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All substances have been of analytical grade and purity was used besides any further

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purification. Ammonium metavanadate (NH4VO3), zinc acetate (Zn(CH3COO)2.2H2O) and

cetyltrimethylammonium bromide (CTAB) had been bought from Sigma Aldrich. In a common

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method, 1.4037 g of Ammonia Vanadate, 1.3170g of zinc acetate and 0.8163 g of CTAB were
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dissolved in 40 mL N, N-dimethyl formamide (DMF), Oxalic acid (C2H2O4) was added drops

wise as a chelating agent respectively under vigorous stirring for 2 hr. Oxalic acid turns the
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solution colour into yellowish that suggests chelation from oxalate anions to metal cations.
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Sodium hydrate (NaOH) was used to adjust the pH at 5 of the solution. The change of colour

from yellow to bluish indicating the reduction of V5+ into V4+ .[34-37] It's far a recognized fact
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that (DMF) can absorb water from the precursor materials to produce NH(CH3)2 and HCOOH,
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this HCOOH further serves as reducing agent and result in a final product of Zn3(VO4)2 with

V3+ [38]. The mixture was transferred to a 100 mL autoclave with a Teflon line. The autoclave
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used to maintain at 180˚C for 20 hours after that the autoclave was cooled openly in the air. The
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white precipitates had been filtered, washed with deionized water and ethanol for many times

and dried at 80˚C for 8h. Growth procedure for the hydrothermal synthesis of Zn3(VO4)2

nanoplates is shown in Figure 1.

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Figure 1: Growth procedure for the synthesis of Zn3(VO4)2 nanoplates.
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2.1 Characterization
The Rigaku 2500 X-ray diffractometer is used to analyze the crystallinity, phase and plate
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size of synthesis nanoplates. The morphological study of plates was checked by Field Emission
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Scanning Electron Microscopy (SEM, JSM-6460, Japan) working at operating voltage of 20 KV;

whereas the elemental analysis of the nanoplates was examined by Energy-Dispersive X-ray
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spectroscopy (EDX) Bruker Alpha spectrophotometer is used to study the attached functional
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groups with nanoplates. The absorbance spectra of organic dyes (CR, CV) were measured by

using Perkin Elmer lambda 35 UV-Vis-spectrophotometer. The Fourier transform infrared by

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FT-IR Spectrometer Nicolet iS50, ranges from 400 to 4000 cm-1. Porosity and Brunauer–
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Emmett–Teller (BET) surface areas of the products were evaluated by multi-point BET method

using adsorption data. The photoluminescence (PL) analysis was measured on Horiba Scientific

Fluoromax-4 spectrofluorometer. Electronic Paramagnetic Resonance (EPR) testing was

performed on ESR-JES-FA 2010 spectrometer.

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3. Result and Discussion

SEM micrographs of as-prepared Zn3(VO4)2 nanoplates are displayed in Figure 2 shows

cross-sectional and top sight SEM images taken at low magnification while images (inset) taken

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at high magnification, display nanoplates with width and thickness 300 ~ 500nm and 50 ~ 75nm.

Our results resemble in literature with yaung yu et al., who synthesized pyrovanadate nanosheets

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by hydrothermal method at 200˚C with width 400–500 nm and its thickness is nearly about 100

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nm [39]. It is perceived that this formation of nanoplates is because of chelation of metal cations

in the solution.

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Figure 2: SEM image at low magnification, and high magnification of Zn3(VO4)2 nanoplates
hydrothermally synthesized at 180˚C.
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Energy dispersive X-ray spectroscopic (EDX) technique was used to evaluate the chemical

composition of Zn3(VO4)2 nanoplates. The result of EDX investigation is displayed in Figure 3.

It confirms that Zn3(VO4)2 consists of only Zn, O, and V. No other impurity is detected in the

obtained product within the detection limit. The atomic ratio was found to be 14.12:28.61:57.27,

which closed to the stoichiometric ratio of Zn3(VO4)2.

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Figure 3: EDX analysis of Zn3(VO4)2 nanoplates synthesis at 180˚C.

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The synthesized ZnVO-Nps were further characterized by X-ray powder diffraction
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technique for phase purity as shown in Figure 4. The intense peaks reflect strong crystal quality

of Zn3(VO4)2, the strongest peak at position 34.33 All the peaks matched well with listed
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together with JCPDS No. 11-0288 and no secondary phase or impurity peaks were observed
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indicating the phase purity of the obtained product, which is consistent with previously reported
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results in the literature.

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Figure 4: The XRD pattern for the as-synthesized Zn3(VO4)2 nanoplates at 180 ˚C.
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X-ray photoelectron spectroscopy is a versatile tool for the evaluation of chemical

composition and purity of the product so for further superficial chemical analysis of the

Zn3(VO4)2 nanoplates was examined by XPS, Figure 5(a) Indicating the obtained results as it can

be seen from the XPS spectrum that our sample is composed of Zn, V, and O elements. The

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binding energies of Zn 2p core levels from resolution XPS spectra revealed at 1021.4 and

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1044.60 eV for Zn 2p3/2 and Zn 2p1/2 of this sample as indicated in Figure. 5(b), 517.13 and

524.64 eV for V 2p3/2 and V2p1/2 as shown in Figure 5(c), and for O 2s the typical 530.4 eV was

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observed as represented in Figure 5(d), respectively. These results are in good consistent with

those reported.[40, 41] [32]From the above detailed XPS spectra peaks, the outputs from XRD,

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EDX confirming the products are pure Zn3(VO4)2.
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Figure 5: (a) wide scan total XPS spectrum of the Zn3(VO4)2 nanoplates sample, (b) For Zn 2p;
(c) For V 2p and (d) For O 1s.
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FTIR spectrum of Zn3(VO4)2 nanoplates is shown in Figure 6. The peaks at 455 cm-1 and

996 cm-1, are assigned to symmetric (V–O–Zn) and (V–O–V) while peaks at 774 cm-1 are

attributing to asymmetric (V–O–Zn) and (V–O–V). The peaks at 1625 cm−1, 3481 cm-1 is

attributed due to the stretching and bending vibration of H–O–H from H2O molecule absorbed by

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the surface of the Zn3(VO4)2 plates. These peaks are consistent with the previously reported

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values.

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Figure 6: FTIR spectrum of the as-prepared Zn3(VO4)2 nanoplates

4. Photocatalytic activity
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The photocatalytic mechanism typically contains three steps: absorption of a photon

having energy equal or greater than photocatalyst band gap energy, second generation and

recombination of electron-hole pairs, number three and finally Oxidation and reduction

occurrences at photocatalyst surface. Schematic representation for the creation of holes and
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electrons in the Zn3(VO4)2 nanomaterial upon imposing visible light for successive

mineralization of CR and CV dyes is shown in Figure 7. When photons of energy equable/higher

than its band-gap energy of photocatalyst, it interacts with photocatalyst and electron-hole (ehp)

pairs are generated and separated. The excited electron reacts with adsorbate oxygen specks O2

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to make electronically involved superoxide anion radicals (O2-•). Although the stimulated holes

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in the valance band oxidize −OH preceding to the generation of hydroxyl radical species (•OH),

[42] this hydroxyl •OH radical being a very robust oxidizing agent would oxidize the dye

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molecules to the mineral remaining products, i.e. CO2, H2O.[43]

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Figure 7: Photocatalysis mechanism for the degradation of dyes.

The BET surface area was evaluated by Brunauer-Emmett-Teller (BET, ASAP-2020)

using adsorption isotherms in relative pressure at (P/Po) ranges from 0.05 to 0.25, the BET

surface area of ZnVO-Nps is 84 m2/g, which is obviously high, owing to regular orientation of

pores in the structure and showing highly crystalline nature of nanoplates.[44] Zn3(VO4)2
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nanoplates possessing large surface area represents a higher tendency to adsorb dyes which

improve the response of photocatalytic degradation for the dyes. The pore size was calculated by

desorption isotherms, the Barret-Joyner-Halender (BJH) method, [45-47] an average pore size of

9 nm can be seen from the differential pore size distribution curve in inset of Figure 8(a), The

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pore size dispersion of powder displays intense peak about 4 nm to 6 nm, due to antiparticle

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gaps, and nonporous in the fabrications of Zn3(VO4)2 nanoplates. This type of uniformly

homogenous well defined nonporous structure is suitable for photocatalysis as it offers effective

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pathways to reactant molecules and byproducts. BET results prove that the hysteresis is the H3

type which associates with slit shape capillaries having wide frames and reduced stems of plate-

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like group atoms. The lamellar pore slit shape pores construction clearly indicates the presence
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of mesopores within the structure. Thus, the Zn3(VO4)2 oxide is an extremely highly crystalline

mesopores material. Tauc’s plot method used to calculate ZnVO-Np optical band gap of 2.68 eV
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as shown in Figure 8(b), which is quite similar to the previously reported.[15]

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Figure 8: (a) Nitrogen adsorption-desorption curve for surface area measurement of Zn3(VO4)2
nanoplates (b) Tauc plot for Zn3(VO4)2 composite
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Congo red (C32H22N6Na2O6S2) is a benzene derivative dye known carcinogenic

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compound and extensively used to treat leather articles, textiles and some foods. It has a harmful
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effect on human, aquatic life as well as on land. Crystal violet (C25H30ClN3) is the mixture of

tetramethyl, pentamethyl, hexamethyl and pararosanilines, commonly used in textile industries

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for colour purposes. It is poisonous in nature because it yields toxic output as carbon monoxide,
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carbon dioxide, nitrogen oxides and hydrogen chlorides and has harmful effects on human,

agricultural and on aquatic life. [11] [48] The photocatalytic reaction of as-synthesized ZnVO-

Nps was evaluated by photocatalytic degradation of CR and CV dyes under visible light

irradiation. The chemical structure of Congo red and crystal violet is shown in Figure 9.
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Figure 9: Chemical Structure of Congo red (CR) and Crystal Violet (CV) dyes.
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For a photocatalytic response, the ZnVO-Nps have been used to the degradation of CR

and CV organic dyes under Visible radiation; for comparison, the photocatalytic response of CR
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and CV was also investigated by the usage of ZnVO-Nps without visible light and visible light
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without ZnVO-Nps catalyst, individually. The initial Congo red, Crystal violet and ZnVO-Nps
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concentration are 10 mg/L CR, 10 mg/L CV and 10 mg/10 mL solution, separately.

The typical absorption peak from Congo Red (CR) is turned up at 496 nm, Similarly, the
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peculiar absorption peak of CV is situated at 582 nm. The intensity level of the peak decreased

evidently on the increase in time of the visible light illumination. Congo red dye concentration
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step-downs to 0 mg/L after visible light irradiating for 2.5h. The colour of CR dye solution
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transfers from bright Red to colourless, we repeated the photocatalytic experiment for three times

and the evaluated error bar is inserted in 10(c). Figure 11a indicates the CV absorption ratio

subsequently at classified interval conditions. The CV C/Co ratio decreased to zero within 60
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mints. The colour of the CV solution alters from deep blue to colourless each time as we

repeated the experiment for three times, the error bar graph is illustrated in Figure. 11(c).

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Figure 10: (a) Absorption bands of CR solution at illuminated times taking 50mL CR solution

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under visible light, (b) CR concentration ratio treated with ZnVO-Nps solution at different
irradiation time, (c) Error bar graph for photocatalytic measurement of CR solution.
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Figure 11: (a) Absorption spectra of CV solution at different interval carrying 10mL CV solution
under visible light, (b) CV concentration ratio treated with ZnVO-Nps solution at different
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irradiation time, (c) Error bar graph for photocatalytic measurement of CV solution.
To realize the role of the visible light on the photocatalytic reaction for Congo red and
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crystal violet dye, the degradation percentage was also evaluated under visible light without any
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photocatalyst. From the Figure (10b, 11b) it can be seen that there is no photocatalytic activity

for both dyes solution with visible light without ZnVO-Nps. On the other hand, the ZnVO-Nps

bear very little photocatalytic response for dyes without visible light irradiation. The graphical

record between C/Co ratio and radiation time as Figure 10(b) and 11(b) shows the CR

photodegradation is about 25.31 in 2.5 h and CV photodecompose ratio represents nearly 22.06%
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in 60 mints respectively. Thus, it’s evident that the photocatalytic activities for CR and CV

degradation are specific by visible light radiation assisted.[15, 45] The photocatalytic reaction

considered to be related particularly activated kind of peroxide (O2¯) then hydroxyl (•OH) created

from electrons and holes coming to the surface of the water.[38] When the ZnVO-Nps oxidize

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the water due to low band gap the activation energy instantly overcome the band hole using

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ZnVO-Nps and give superior photocatalytic efficiency under visible radiation.

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Figure 12: Photoluminescence (PL) spectrum of ZnVO-Nps at room temperature

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Figure 12 shows the PL spectra of Zn3(VO4)2 nanoplates evaluated at room temperature

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applying the excitation wavelength of 325 nm. Strong emission spectra from 480 to 550 nm are
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obtained in the PL spectrum. The blue emission centre placed at 492 (2.52 eV). It is found from

the previous PL literature survey that Zinc vanadate show new energy levels inside the band gap

of nanostructures that can be stimulated by Zn-vacancy, O-vacancy, zinc interstitial and O-

interstitial. This type of Vacancies produce newly energy levels in the bandgap of nanomaterials;

these new energy levels are called deep energy levels (DEL). [49, 50] The sharp and strong peak
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might be due to these new vacancies or defects which are attributed due to the charge transition

in the VO4. [51, 52] This PL study endows the promise of Zn3(VO4)2 with nanoplates

morphology could be an excellent candidate for blue/green visible light emitting devices, in the

optical and another field. Diffusion of the ehp charge carry on at the surface of the ZnVO-Nps

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and the photocatalytic reactions may be described as in following equations.[53]

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ZnVO-Nps + hν ZnVO-Nps (e- + h+) (1)

H2O + h+ OH¯ + H+

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(2)

O2 + e- O-2 (3)

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The photocatalytic degradation method of the ZnVO-Nps is the direct absorption
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procedure of a photon with the aid of the energy band gap. It is well-known that photocatalytic

response may be additionally affected by the competition between recombination and the charge
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separation approaches and photoluminescence emission spectra had been extensively used to
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observe the rate of charge recombination. [54, 55]

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Figure 13 DMPO spin-trapping EPR spectra for (a) DMPO-O2− and (b) DMPO-OH under
visible light irradiation
In order to evaluate the effect of the active species during the photocatalytic activity,
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electron paramagnetic resonance (EPR) technique was applied to scavenge the relevant active

species. [56-59] From Figure 13, not only the six characteristic peaks of the DMPO–O2 adducts
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were observed, but the four characteristic peaks of DMPO–OH adducts (1: 2: 2: 1) quartet
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pattern were also observed under irradiation of the composite dispersion with visible radiation.

Figure 13 display (0 mint Dark) that here no EPR signals appears when the reaction is carried out

in the dark while, the signals with intensities corresponding to the characteristic peaks of

DMPO–O2 and DMPO–OH adducts were observed under visible light. The intensity of the
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signals gradually step-ups with prolonged reaction time, indicating that •O2 and OH• are formed

as active species in the presence of Zn3(VO4)2 composites. The probability of forming OH• is

much lowered than that of •O2, while, hydroxyl radical is an extremely strong oxidizing agent,

which takes the degradation process to either partial or complete mineralization of various

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organic pollutants. [24] [55] It shows that the reactive •O2 plays the major role and OH• play

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minor roles in the photocatalytic degradation of CR and CV dye.

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Table: 1 Comparison of Photocatalytic activity of some photocatalysts and Current Zn3(VO4)2
for degradation of CR and CV dye under visible light irradiation.

Powder Dye Efficiency Time Reference

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P-25, Degussa CR 85% 240 mint [60]

P-25, Degussa CR 87.9% 180 mint [61]

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P-25, Degussa CR 67% 120 mint [62]

P-25, Degussa CR 88 % 165 mint [63]

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Fe3O4/CuO CR 99% 300 mint [64]

SnO2/CdS CR 97% 240 mint [65]
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Zn3(VO4)2 nanoplates CR 100% 150 mint Present Work

P-25, Degussa CV 49% 60 mint [66]
ZnO CV 95% 300 mint [67]
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CdS/CdTiO3–TiO2 CV 61% 180 mint [68]

Ag3VO4/g-C3N4 CV 34% 150 mint [69]

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Cd-Al/C CV 52% 180mint [70]

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Bi7O9I3/GO CV 96% 1440 mint [71]

Zn3(VO4)2 CV 100% 60 mint Present Work

nanoplates
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5. Conclusion

In summary, Zn3(VO4)2 nanoplates were successfully synthesized using the simple

hydrothermal method. The as-synthesized nanoplates exhibit good photocatalytic degradation

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performance on CR and CV dyes under visible light irradiation. This degradation may be

attributed due to the better surface area, massive energetic sites and visible light absorption

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ability of Zn3(VO4)2 nanostructures. UV-visible reflectance analysis study illustrates that

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Zn3(VO4)2 have an energy band gap of 2.68 eV, and these nanoplates have a strong affinity to

absorption of light in the visible region. The Zn3(VO4)2 have large BET surface area 84 m2/g,

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average pore size 9 nm and hysteresis loop of the H3 type which is associated with groups of
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plate-like particles giving lamellar pore structure shows the presence of mesopores in the

structure. The Congo red and Crystal violet with a concentration of 10mg/L are degraded totally
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in 2.5 and 1 hour over 10mg Zn3(VO4)2 nanoplates in 10mL solution respectively. The PL

measurement indicates the potential for blue/green visible optical devices. Thus, Zn3(VO4)2
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nanoplates are good visible light photocatalyst for Congo Red (CR) and Crystal violet (CV) dyes
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degradation under visible light irradiation. Our work proposed new perspectives for efficient

photocatalyst that can degrade different organic dyes under visible light irradiation and gave
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direction for designing more efficient photocatalysts in future for treating dye effluents and
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industrial wastewater.
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Conflict of Interest

There are no conflicts of interest to declare.

Funding Detail

The authors did not receive financial support for this work from any agency.
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Acknowledgements

All the experiments had been performed at Government college university Faisalabad, Pakistan.

SEM, EDX, XPS, BET, Raman, PL and ESR techniques were supported by Dr. Zhengjun Zhang,

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Advanced Key Laboratory for New Ceramics, School of Materials Science & Engineering,

Tsinghua University, Beijing, China, 100084.

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References

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[1] Z. Xing, J. Zhang, J. Cui, J. Yin, T. Zhao, J. Kuang, Z. Xiu, N. Wan, W. Zhou, Applied Catalysis B:
Environmental, (2017).
[2] C.-L. Hsu, J.-H. Lin, D.-X. Hsu, S.-H. Wang, S.-Y. Lin, T.-J. Hsueh, Sensors and Actuators B: Chemical,

U
238 (2017) 150-159.
[3] S.C. Pillai, N.B. McGuinness, C. Byrne, C. Han, J. Lalley, M. Nadagouda, P. Falaras, A.G. Kontos, M.A.
AN
Gracia-Pinilla, K. OShea, Advanced Oxidation Processes for Water Treatment: Fundamentals and
Applications, (2017) 333.
[4] D. Venieri, D. Mantzavinos, Disinfection of Waters/Wastewaters by Solar Photocatalysis, Advances in
Photocatalytic Disinfection, Springer2017, pp. 177-198.
M

[5] Y. Tal, J.E. Watts, H.J. Schreier, Applied and environmental microbiology, 72 (2006) 2896-2904.
[6] Y.-R. Jiang, H.-P. Lin, W.-H. Chung, Y.-M. Dai, W.-Y. Lin, C.-C. Chen, Journal of hazardous materials,
283 (2015) 787-805.
D

[7] C.-W. Siao, H.-L. Chen, L.-W. Chen, J.-L. Chang, T.-W. Yeh, C.-C. Chen, Journal of colloid and interface
science, 526 (2018) 322-336.
TE

[8] J. Zhang, G. Xiao, F.-X. Xiao, B. Liu, Materials Chemistry Frontiers, 1 (2017) 231-250.
[9] C. Li, Z. Sun, R. Ma, Y. Xue, S. Zheng, Microporous and Mesoporous Materials, 243 (2017) 281-290.
[10] M. Baia, K. Gajda-Schrantz, S. Shen, E. Stathatos, International Journal of Photoenergy, 2013 (2013).
[11] A.-H. Lee, Y.-C. Wang, C.-C. Chen, Journal of colloid and interface science, 533 (2019) 319-332.
EP

[12] F.K. Butt, M. Tahir, C. Cao, F. Idrees, R. Ahmed, W.S. Khan, Z. Ali, N. Mahmood, M. Tanveer, A.
Mahmood, ACS applied materials & interfaces, 6 (2014) 13635-13641.
[13] J. Zhu, L. Cao, Y. Wu, Y. Gong, Z. Liu, H.E. Hoster, Y. Zhang, S. Zhang, S. Yang, Q. Yan, Nano letters, 13
C

(2013) 5408-5413.
[14] F.K. Butt, C. Cao, F. Idrees, M. Tahir, R. Hussain, R. Ahmed, W.S. Khan, International Journal of
AC

Hydrogen Energy, 40 (2015) 9359-9364.

[15] L. Pei, N. Lin, T. Wei, H. Liu, H. Yu, Journal of Alloys and Compounds, 631 (2015) 90-98.
[16] G. Xing, Y. Xu, C. Zhao, Y. Wang, Y. Li, Z. Wu, T. Liu, G. Wu, Powder technology, 213 (2011) 109-115.
[17] L. Zhang, T. Xu, X. Zhao, Y. Zhu, Applied Catalysis B: Environmental, 98 (2010) 138-146.
[18] Y. Yan, J. Wang, M. Hojamberdiev, Z. Lu, B. Ren, Y. Xu, Journal of Alloys and Compounds, 597 (2014)
282-290.
[19] J. Zhou, X. Liu, R. Chen, F. Hu, H. Zou, M. Wei, Dalton Transactions, 42 (2013) 5603-5606.
[20] Y. Guo, X. Yang, F. Ma, K. Li, L. Xu, X. Yuan, Y. Guo, Applied Surface Science, 256 (2010) 2215-2222.
[21] S.A. Mahapure, V.H. Rane, J.D. Ambekar, L.K. Nikam, R. Marimuthu, M.V. Kulkarni, B.B. Kale,
Materials Research Bulletin, 46 (2011) 635-638.
 ACCEPTED MANUSCRIPT

[22] P. Pookmanee, P. Longchin, W. Kangwansupamonkon, R. Puntharod, S. Phanichphant,

Ferroelectrics, 455 (2013) 35-42.
[23] F. Mazloom, M. Masjedi-Arani, M. Ghiyasiyan-Arani, M. Salavati-Niasari, Journal of Molecular
Liquids, 214 (2016) 46-53.
[24] Y.-H. Lee, Y.-M. Dai, J.-Y. Fu, C.-C. Chen, Molecular Catalysis, 432 (2017) 196-209.
[25] A.M. Morales, C.M. Lieber, Science, 279 (1998) 208-211.
[26] G.-T. Zhou, X. Wang, J.C. Yu, Crystal growth & design, 5 (2005) 969-974.

PT
[27] K. Kolomazník, M. Adámek, I. Andel, M. Uhlirova, Journal of Hazardous Materials, 160 (2008) 514-
520.
[28] B. Weiss, Journal of the American Academy of Child Psychiatry, 21 (1982) 144-152.

RI
[29] L. Xiao, Y. Zhao, J. Yin, L. Zhang, Chemistry-A European Journal, 15 (2009) 9442-9450.
[30] F. Duan, W. Dong, D. Shi, M. Chen, Applied Surface Science, 258 (2011) 189-195.
[31] D. Wang, J. Tang, Z. Zou, J. Ye, Chemistry of materials, 17 (2005) 5177-5182.
[32] H. Guo, D. Guo, Z. Zheng, W. Wen, J. Chen, Journal of Materials Research, 29 (2014) 2934-2941.

SC
[33] A.H. Abdullah, W.T. Peng, M.Z. Hussein, Malaysian Journal of Analytical Sciences, 20 (2016) 1338-
1345.
[34] A. Llordes, A.T. Hammack, R. Buonsanti, R. Tangirala, S. Aloni, B.A. Helms, D.J. Milliron, Journal of

U
Materials Chemistry, 21 (2011) 11631-11638.
[35] A.S. Tracey, M.J. Gresser, K.M. Parkinson, Inorganic Chemistry, 26 (1987) 629-638.
AN
[36] J. Hoard, W.R. Scheidt, C.-C. Tsai, Journal of the American Chemical Society, 93 (1971) 3867-3872.
[37] D. Sathyanarayana, C. Patel, Bulletin of the Chemical Society of Japan, 37 (1964) 1736-1740.
[38] L.-j. Mao, C.-y. Liu, J. Li, Journal of Materials Chemistry, 18 (2008) 1640-1643.
[39] Y. Yu, C. Niu, C. Han, K. Zhao, J. Meng, X. Xu, P. Zhang, L. Wang, Y. Wu, L. Mai, Industrial &
M

Engineering Chemistry Research, 55 (2016) 2992-2999.

[40] S.S. Pitale, M. Gohain, I. Nagpure, O. Ntwaeaborwa, B.C. Bezuidenhoudt, H. Swart, Physica B:
Condensed Matter, 407 (2012) 1485-1488.
D

[41] S. Ni, X. Wang, G. Zhou, F. Yang, J. Wang, D. He, Journal of Alloys and Compounds, 491 (2010) 378-
381.
[42] L. Zhang, P. Ghimire, J. Phuriragpitikhon, B. Jiang, A.A. Gonçalves, M. Jaroniec, Journal of colloid and
TE

interface science, 513 (2018) 82-91.

[43] M.M. Sajid, S.B. Khan, N.A. Shad, N. Amin, Z. Zhang, RSC Advances, 8 (2018) 23489-23498.
[44] G. Yang, S. Li, M. Wu, C. Wang, Journal of Materials Chemistry A, 4 (2016) 10974-10985.
EP

[45] S. Irfan, Y. Shen, S. Rizwan, H.C. Wang, S.B. Khan, C.W. Nan, Journal of the American Ceramic
Society, 100 (2017) 31-40.
[46] S. Irfan, L. Li, A.S. Saleemi, C.-W. Nan, Journal of Materials Chemistry A, 5 (2017) 11143-11151.
[47] S. Fatima, S.I. Ali, M.Z. Iqbal, S. Rizwan, RSC Advances, 7 (2017) 35928-35937.
C

[48] C.-C. Chen, J.-Y. Fu, J.-L. Chang, S.-T. Huang, T.-W. Yeh, J.-T. Hung, P.-H. Huang, F.-Y. Liu, L.-W. Chen,
Journal of colloid and interface science, 532 (2018) 375-386.
AC

[49] L.-L. Yang, Q. Zhao, M. Willander, J. Yang, I. Ivanov, Journal of Applied Physics, 105 (2009) 053503.
[50] M. Wang, Y. Shi, G. Jiang, Materials Research Bulletin, 47 (2012) 18-23.
[51] H. Liu, X. Cheng, H. Liu, J. Yang, J. Cao, Y. Liu, X. Liu, M. Gao, M. Wei, L. Fei, Journal of Materials
Science: Materials in Electronics, 24 (2013) 317-323.
[52] M. Ahmad, C. Pan, J. Zhu, The Journal of Physical Chemistry C, 114 (2010) 2560-2565.
[53] L. Pei, S. Wang, Y. Jiang, Y. Xie, Y. Li, Y. Guo, CrystEngComm, 15 (2013) 7815-7823.
[54] F.-Y. Liu, Y.-R. Jiang, C.-C. Chen, W.W. Lee, Catalysis Today, 300 (2018) 112-123.
[55] F.-Y. Liu, J.-H. Lin, Y.-M. Dai, L.-W. Chen, S.-T. Huang, T.-W. Yeh, J.-L. Chang, C.-C. Chen, Catalysis
Today, 314 (2018) 28-41.
 ACCEPTED MANUSCRIPT

[56] W.W. Lee, C.-S. Lu, C.-W. Chuang, Y.-J. Chen, J.-Y. Fu, C.-W. Siao, C.-C. Chen, RSC Advances, 5 (2015)
23450-23463.
[57] S.-Y. Chou, C.-C. Chen, Y.-M. Dai, J.-H. Lin, W.W. Lee, RSC Advances, 6 (2016) 33478-33491.
[58] C.-C. Chen, C.-T. Yang, W.-H. Chung, J.-L. Chang, W.-Y. Lin, Journal of the Taiwan Institute of
Chemical Engineers, 78 (2017) 157-167.
[59] Y. Hu, D. Li, F. Sun, H. Wang, Y. Weng, W. Xiong, Y. Shao, RSC Advances, 5 (2015) 54882-54889.
[60] M. de Souza, D. Tristao, P. Corio, RSC Advances, 4 (2014) 23351-23358.

PT
[61] W. Anku, S.O.-B. Oppong, S.K. Shukla, P.P. Govender, Acta Chimica Slovenica, 63 (2016) 380-391.
[62] H. Narayan, H. Alemu, D.N. Alotsi, L. Macheli, M. Thakurdesai, S. Jaybhaye, A. Singh,
Nanotechnology Development, 2 (2011) 2.

RI
[63] A. Kar, S. Sain, S. Kundu, A. Bhattacharyya, S. Kumar Pradhan, A. Patra, ChemPhysChem, 16 (2015)
1017-1025.
[64] D. Malwal, P. Gopinath, Catalysis Science & Technology, 6 (2016) 4458-4472.
[65] A. Kar, S. Kundu, A. Patra, RSC Advances, 2 (2012) 10222-10230.

SC
[66] S. Adhikari, R. Gupta, A. Surin, T.S. Kumar, S. Chakraborty, D. Sarkar, G. Madras, RSC Advances, 6
(2016) 80086-80098.
[67] D.R. Shinde, P.S. Tambade, M.G. Chaskar, K.M. Gadave, Drinking Water Engineering and Science, 10

U
(2017) 109.
[68] Y. Li, W. Zhang, L. Li, C. Yi, H. Lv, Q. Song, RSC Advances, 6 (2016) 51374-51386.
AN
[69] S.-M. Lam, J.-C. Sin, A.R. Mohamed, Materials Science in Semiconductor Processing, 47 (2016) 62-
84.
[70] S.A. Khan, S.B. Khan, A.M. Asiri, Scientific reports, 6 (2016) 35107.
[71] S.-Y. Chou, W.-H. Chung, L.-W. Chen, Y.-M. Dai, W.-Y. Lin, J.-H. Lin, C.-C. Chen, RSC Advances, 6
M

(2016) 82743-82758.
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TE
C EP
AC
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Highlights

• First time Zn3(VO4)2 with nanoplates morphology reported for the degradation of dyes.

• Zn3(VO4)2 nanoplates showed excellent visible light driven photocatalytic activity.

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• Crystal violet and Congo red dyes degraded within 60 and 150 mints, respectively.

• Interface of catalyst and dye is a promising factor for photocatalytic degradation.

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• This method provides a simple and cost economical manufacturing process.

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