Comparison of the photocatalytic activity of perovskite structures: Bismuth, barium, and zinc titanate nanostructures for photodegradation of methylene blue from water

https://doi.org/10.1016/j.jphotochem.2020.113104Get rights and content

Highlights

  • Synthesis of different TiO2-based nanostructures and improving their photocatalytic performances.

  • A comparison reported on the photocatalytic activity of differently prepared perovskite nanostructures.

  • A full structural, optical, and morphological analysis were reported.

  • Utilizing bandgap engineering strategy for obtaining the best performance for removing MB from water.

Abstract

This study was conducted to improve the photocatalytic performance of TiO2 in the visible light range using TiO2 based nanostructures. For this purpose, TiO2 nanostructures were prepared by using the microwave-assisted technique and then used to prepare barium titanate (BaTiO3), bismuth titanate (Bi4Ti3O12), and zinc titanate (ZnTiO3) nanostructures. The thermal, structural, purity, surface morphology, and optical studies were conducted through the TGA/DTA, XRD, EDX, FE-SEM, and UV–vis analyses. The crystallite sizes of TiO2, bismuth titanate, barium titanate, and zinc titanate nanostructures were obtained 45, 32, 32, and 29 nm respectively. The optical band gap of prepared samples was evaluated at 3.65, 2.65, 2.80, and 3.80 eV, respectively. The photocatalytic activity of the perovskite nanostructures on methylene blue degradation was evaluated and the results showed that bismuth titanate nanostructures with smaller bandgap have higher photocatalytic activity among prepared samples in the visible light range.

Introduction

The applications of different dyes and solvents in various industries such as textile, paint, petrochemicals, and the widespread use of herbicides, pesticides in agriculture have raised the growing concern of scientific communities and the environmental authority’s around the world. These organic pollutants cause environmental problems, contaminates drinking water, surface water, and endanger aquatic life. Therefore, eliminating these toxic pollutants from water and the environment is a necessity for global communities. Finding efficient and low-cost methods for the treatment of industrial, wastewater containing non-decomposable organic material is one of the urgent needs. One of the most efficient, easy, and low-cost methods is the use of a photocatalytic oxidation process for detoxification of toxic and hazardous pollutants as well as drinking water. Methylene blue is one of the organic cationic dyes that, widely used in medical, textile, paint, and petroleum technology and enters the drinking water cycle through the sewage of these industries [[1], [2], [3]].

Metal oxides are semiconductor materials that have been widely used in multiple fields for example electronics, storage devices of power, and information [4], non-linear optics [5], catalyst [6], etc. The photocatalytic activity of some of these materials, such as ZnO, TiO2, SnO2, and CdS have been investigated to solve the water problem. Most of these materials have only been active in the UV range due to their wide bandgap [[7], [8], [9]].

Perovskite compounds such as Bi4Ti3O12, BaTiO3, ZnTiO3, CaTiO3, and SrTiO3 due to their piezoelectric, ferroelectric, piezoelectric properties are used as catalyst electrodes in fuel cells, sensors, memory devices, and spintronics applications. As well as, these compounds are efficient and suitable candidates for the replacement of TiO2 due to advantages such as non-toxicity, chemical stability, and good photocatalytic activity in the visible region [[10], [11], [12]]. In this work, three titanium dioxide-based materials, namely Bi4Ti3O12, BaTiO3, and ZnTiO3 have been prepared and their structural, optical, and photocatalytic properties have been studied and compared.

Bismuth titanate has several crystal phases, such as Bi12TiO20, Bi4Ti3O12, Bi2Ti2O7, and due to interesting properties, such as ferroelectric, special electro-optical properties, high dielectric constant has been widely used in ultrasonic sensors, storage devices [13], optical memory, optoelectrical components [14], optical displays [15], and piezoelectric ceramics [16]. Various photocatalytic applications of this material have been reported in the literature. W. Zhao et al. prepared Bi4Ti3O12 nanostructures using the molten salt method. they compared the photocatalytic activity of Bi4Ti3O12 and TiO2 nanostructures for degradation of the methylene blue under visible light irradiation [17]. J. F. Ren et al. synthesized Bi12TiO20 nanostructures in an ionic liquid by hydrothermal process and evaluated the influence of ionic liquid on the photocatalytic activity of the prepared nanostructures to remove methylene orange [18].

R. He et al. reviewed some of the carried-out studies on the photocatalytic activity of bismuth-based materials such as Bi12TiO20, Bi4Ti3O12, Bi2Ti2O7, etc. on various dyes. they discussed and summarized the effective parameters on photocatalytic activity such as surface morphology, surface modification, stoichiometry, conventional heterojunctions, and doping [19].

Barium titanate(BaTiO3) is a direct bandgap semiconductor (Eg = 3.3 eV) with various phases such as cubic and tetragonal structures [20]. The bending nature of the tetragonal structure reduces the charge recombination and thus increases its photocatalytic efficiency [21]. S. Kappadan et al. prepared the cubic and tetragonal crystal structures of BaTiO3 nanoparticles by the polymeric complex method. They compared the photocatalytic activity of both samples over methylene blue degradation. Their photocatalytic results showed that the catalytic performance of tetragonal phase is higher than the cubic phase. also, they evaluated The photocatalyst stability of samples by four recycling test [20]. J. Liu et.al synthesized BaTiO3 and Ag-BaTiO3 nanotube arrays by the hydrothermal method. They evaluated the photocatalytic activity of prepared films on methyl orange decomposition and investigated the influence of pH and Ag concentration on decomposition ratio [22]. Also, in recent years, the photocatalytic activity of perovskite-like compounds based on bismuth, barium, and bismuth-barium has been reported to remove methylene blue from water. A. Haruna et.al prepared Bi0.65Na0.2Ba0.15FeO3 nanopowders using the sol-gel method at different annealing temperatures and investigated the effect of annealing temperatures on methylene blue degradation. Also, they compared the photocatalytic activity of prepared samples with other photocatalyst materials such as BFO, BFO-Dy, BFO-Gd, BFO-Sm, and TiO2 nanostructures. In the other work, they synthesized the mentioned nanoparticles doped with sodium and potassium metal ions at different annealing temperatures. They investigated the effect of parameters such as pH, the addition of peroxide (H2O2), annealing temperatures, and dopant ratio on photocatalytic activity of prepared samples [23,24].

Zinc titanate is a wide bandgap semiconductor with various phases such as ZnTiO3 (hexagonal), Zn2TiO4 (cubic spinel), and Zn2Ti3O8 (cubic defect spinel) structures that use as a pigment in paints, catalyst in organic transformations, gas sensors, dielectric resonators, reduction of NO and oxidation of CO. ZnTiO3 belongs to the coupled photocatalysts materials(ZnO–TiO2 system) which can increase the photocatalytic performance of TiO2 by decreasing the charge recombination, changing the energy band gap and consequently changing optical response from UV to the visible light range [25,26].

Different preparation methods have been reported for the synthesis of bismuth titanate, barium titanate, and zinc titanate nanostructures such as co-precipitation method, electrochemical method, solid-state method, sol-gel, metal-organic, microwave-assisted method, hydrothermal and hydrolysis [8,19,[26], [27], [28], [29], [30], [31], [32], [33]].

In this study, the microwave-assisted method has been used for the preparation of bismuth titanate, barium titanate, and zinc titanate nanostructures due to advantages such as uniform selective heating, heat distribution, as well as being affordable, fast, safe, and easy preparation [10].

In recent years, the photocatalytic activity of barium, bismuth, and zinc titanate has been extensively studied separately. This research aims to find the compounds based on titanium dioxide to improve the photocatalytic efficiency of titanium dioxide in the visible light range. For this purpose, bismuth titanate, barium titanate, and zinc titanate nanostructures were prepared using a microwave-assisted method, and the photocatalytic activity of them tested on Methylene blue and compared each other. The obtained results showed that bismuth titanate nanostructures, in comparison with the other samples, have lower bandgap energy and higher photocatalytic activity. The bandgap of bismuth titanate, barium titanate, and zinc titanate was obtained 2.65, 2.8, and 3.8 eV, and their photocatalytic activity was evaluated 98 % at 28, 35, and 78 min, respectively.

Section snippets

Synthesis of nanostructures

TiCl4 was purchased from ROYALEX Company (≥ 99 %), Bi(NO3)3.5H2O, was supplied from Rankem Company (≥ 99 %), and (BaCO3)3(≥ 99 %), Zn(CH3COO)2 0.2H2O(≥ 99 %), Methylene blue (C16H18CIN3S.xH2O (x = 2–3)) and NaOH(≥ 99 %) were purchased from Merck Company. The preparation of titanium dioxide nanopowders has been reported in our recently published paper [10].

To the synthesis of the barium titanate nanostructures, initially, 20cc of Barium Carbonate (0.2 M), 20cc of sodium hydroxide (0.2 M), and 20

Thermal, structural and optical characteristics

TGA and DTA measurements have been used to investigate thermal analysis such as phase transitions, absorption, desorption, and thermal decomposition. TGA/DTA profiles of TiO2 nanostructures are shown in Fig. 2(a). As can be seen from Fig. 2(a), the first step of weight loss in the 30−200 °C temperatures range is about 10 %, which is related to the water surface evaporation of the nanopowder. Second weight loss (about 6.7 % weight loss) occurred in the temperature range of 200−430 °C, which is

Conclusion

This study aims to find the highest photocatalytic activity of TiO2-based perovskite materials in the visible light range. For this purpose, three samples of titanate family including bismuth, barium, and zinc titanate were prepared by microwave-assisted method and then their photocatalytic performance was compared with each other. Methylene blue was used to study the photocatalytic activity of the prepared samples. The results showed that the rate constant value of bismuth titanate, barium

CRediT authorship contribution statement

Gholamreza Pirgholi-Givi: Methodology, Investigation, Data curation, Writing - original draft, Formal analysis. Yashar Azizian-Kalandaragh: Writing - original draft, Writing - review & editing, Supervision. Javid Farazin: Methodology, Writing - review & editing.

Declaration of Competing Interest

The authors report no declarations of interest.

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