Rapid synthesis of tetragonal zirconia nanoparticles by microwave-solvothermal route and its photocatalytic activity towards organic dyes and hexavalent chromium in single and binary component systems
Graphical abstract
Introduction
Nanometric ZrO2 is an important class of multifunctional material with wide range of technological and interdisciplinary applications in various fields such as transparent and optical devices, fuel cells, sensor, coating, advanced ceramics, catalysis/photocatalysis, sorbent, energy conversion and storage and biomedical applications [[1], [2], [3], [4], [5], [6], [7], [8], [9], [10]]. ZrO2 exhibits three polymorphic forms as monoclinic (m), tetragonal (t) and cubic (c) with temperature dependent stabilities in the range RT – 1170 °C, 1170–2370 °C and above 2370 °C, respectively. ZrO2 with relatively large band gap energy (∼ 5.0 eV), high chemical and photothermal stability, high corrosive resistance and negative value of the conduction band potential (-1.0 V vs. NHE), shows good photocatalytic performance under UV light irradiation for various heterogeneous photochemical reactions, as well as water splitting [[11], [12], [13]]. However, the wide bandgap and the recombination of photogenerated electron-hole pairs prevent its photocatalytic applications in the visible light region. It has been reported that besides doping with metals/non-metals, the synthetic routes greatly influence the band gap energy of ZrO2 [1,10,14,15]. The band gap values of ZrO2 can be narrowed down to 2.3 eV depending on the preparation methods [1,14,15]. Recently, oxygen-deficient black zirconia (ZrO2-x) with bandgap as low as ∼1.5 eV has been prepared from white ZrO2 via a controlled magnesiothermic reduction in 5 % H2/Ar for solar light absorption [16]. As a result, studies on photocatalytic performance of ZrO2 NPs have attracted a great deal of interest recently [8,[2], [3], [4], [5], [6], [7], [8], [9], [10],14,[16], [17], [18], [19], [20], [21], [22], [23]]. It has also been observed that the catalytic performance of ZrO2 is not only sensitive to its crystal phase but also related to its size and morphology [9,10,24,25]. For instance the metastable t-ZrO2 exhibits superior catalytic and mechanical properties than when it is in the monoclinic phase (m-ZrO2) [24]. The phase formation and the morphology of the ZrO2 nanoparticles are largely dependent on the methods of synthesis. Several physical and chemical methods such as sol-gel, microwave, hydrothermal, solvothermal, co precipitation, surfactant templating, flame spray pyrolysis etc. have been effectively used for controlled synthesis of t-ZrO2 with different morphology including nanoparticles, nanorods, nanotubes etc. at mild temperature [1,3,[19], [20], [21], [22],[26], [27], [28], [29], [30], [31], [32], [33]]. Synthesis of t-ZrO2 with low band gap energy showing higher photocatalytic activity is still a challenge.
Ultrafine polymer stabilized nanocrystalline t-ZrO2 powders and t-ZrO2 NPs have been successfully synthesised by microwave-assisted hydrothermal [1] and microwave-assisted sol-gel [30] methods. Hydrothermal route has been effectively used in the preparation of tetragonal ZrO2 NPs [31] and star-like ZrO2 nanostructures [21]. Calcinations of flower-like hierarchical ZrO2, prepared by hydrothermal process using Zr(SO4)2.4H2O and CH3COONa as the raw materials, yielded tetragonal zirconia nanostructures [22]. To the best of our knowledge, this is the only report discussing about the synthesis of t-ZrO2 via rapid one-step microwave-assisted solvothermal route. Microwave assisted synthesis has advantages of production of smaller nanoparticles with narrow size distribution in short duration. The present work is a part of our ongoing research to use microwave-assisted hydrothermal/solvothermal route for the preparation of various potential inorganic ceramics [34,35].
Degradation of organic dyes under UV or visible light irradiation has been commonly used to evaluate the catalytic efficiency of different photocatalysts [[36], [37], [38], [39], [40]]. Dyes, a common constituent of waste water, are indiscriminately discharged as effluents into the environment by different industries such as textile, leather, food and paper. Due to their toxicity and possible carcinogenicity and mutagenicity, it is essential to remove the dye material from effluents before their discharge into the water stream. Heterogeneous photocatalytic treatment using a wide variety of photocatalytic materials have been extensively used to solve this problem.
Hexavalent chromium (Cr(VI)), another common inorganic water contaminant, has been widely used in leather tanning, dye production industries besides other industries such as steel production, electroplating, etc. [41,42]. Cr(VI) is not only highly toxic but also carcinogens posing danger to human health and environment. Apart from conventional methods of treatment, such as chemical reduction/precipitation, ion exchange, electrolysis, adsorption, etc., removal of Cr(VI) through photocatalytic reduction has been explored using different photocatalysts [23]. Photoreduction of Cr(VI) at pH > 6.0 precipitates the reduced Cr(III) species as its hydroxide; the catalyst can be recovered by subsequent acidification. In this context, removal of both dyes and hexavalent chromium is important as well as beneficial.
In this paper, we reported the synthesis of t-ZrO2 NPs via a rapid and one-step microwave-solvothermal route characterised by the use of various physicochemical methods. Further, the photocatalytic efficiency t-ZrO2 NPs was evaluated for degradation of two potentially harmful and structurally different dyes such as bromophenol blue and eosin yellow as well as reduction of Cr(VI).
Section snippets
Materials
Analytical grade chemicals and reagents were used as received without further purification. Zirconyl oxynitrate (CDH), 1,4-butanediol (Spectrochem) were used for synthesis of ZrO2. Bromophenol Blue (BRB), Eosin Yellow (EY) and K2Cr2O7 (CDH) were used as received in photocatalytic experiments. Double distilled water was used in all experiments.
Synthesis of ZrO2
ZrO2 nanoparticles (NPs) were synthesised through microwave mediated solvothermal process. In a typical lot, ZrO(NO3)2 (0.70 g) and 1,4 butanediol (20 mL)
XRD analysis
The XRD patterns of the synthesized ZrO2 NPs are shown in Fig. 1. The most emerging diffraction peaks in the XRD patterns are indexed to tetragonal ZrO2 (t-ZrO2) phase corresponding to (111), (200), (220), (311), and (222) crystalline planes (JCPDS Card No. 02-0733) and also matches well with those reported for t-ZrO2 [21,24,[27], [28], [29]]. Peaks of no other phases (especially, monoclinic phase) are observed in the XRD patterns indicating formation of a single crystalline tetragonal phase.
Conclusion
Single phase tetragonal ZrO2 NPs (t-ZrO2) was successfully synthesised by microwave solvothermal method and its structural, morphological and optical behaviours were investigated. Tetragonal phase purity of synthesised sample was confirmed from XRD, Raman and HR-TEM analyses. The ZrO2 NPs showed band gap energy of 3.67 eV which is comparable to those prepared by other methods with similar size. The photocatalytic efficiency of as synthesized samples was tested for degradation of two
CRediT authorship contribution statement
Sanjibani Mishra: Investigation, Visualization. A.K Debnath: Resources, Data curation. K.P Muthe: Resources, Data curation. Nigamananda Das: Supervision, Methodology, Writing - review & editing. P. Parhi: Supervision, Methodology, Writing - original draft, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work is funded and supported by BRNS, India (Grant no. 2013/ 37C/53/BRNS/2152). Miss S. Mishra acknowledges BRNS for fellowship. Financial support to the Centre of Excellence in Environment and Public Health by Government of Odisha under OHEPEE (Grant No. 26913/HED/HE-PTC-WB-02-17) is gratefully acknowledged.
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