Electrocatalytic Properties of Calcium Titanate, Strontium Titanate, and Strontium Calcium Titanate Powders Synthesized by Solution Combustion Technique

Electrocatalytic Properties of Calcium Titanate, Strontium Titanate, and Strontium Calcium Titanate Powders Synthesized by Solution Combustion Technique

Hindawi Advances in Materials Science and Engineering Volume 2019, Article ID 1612456, 7 pages https://doi.org/10.1155/2019/1612456 Research Article Electrocatalytic Properties of Calcium Titanate, Strontium Titanate, and Strontium Calcium Titanate Powders Synthesized by Solution Combustion Technique Oratai Jongprateep ,1,2 Nicha Sato ,1 Ratchatee Techapiesancharoenkij,1,2 and Krissada Surawathanawises1 1Department of Materials Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, !ailand 2Materials Innovation Center, Faculty of Engineering, Kasetsart University, Bangkok 10900, !ailand Correspondence should be addressed to Oratai Jongprateep; [email protected] Received 29 October 2018; Accepted 13 February 2019; Published 4 April 2019 Academic Editor: Alexander Kromka Copyright © 2019 Oratai Jongprateep et al. *is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Calcium titanate (CaTiO3), strontium titanate (SrTiO3), and strontium calcium titanate (SrxCa1−xTiO3) are widely recognized and utilized as dielectric materials. *eir electrocatalytic properties, however, have not been extensively examined. *e aim of this research is to explore the electrocatalytic performance of calcium titanate, strontium titanate, and strontium calcium titanate, as potential sensing materials. Experimental results revealed that CaTiO3, SrTiO3, and Sr0.5Ca0.5TiO3 powders synthesized by the solution combustion technique consisted of submicrometer-sized particles with 2 specific surface areas ranging from 4.19 to 5.98 m /g. Optical bandgap results indicated that while CaTiO3 and SrTiO3 had bandgap energies close to 3 eV, Sr0.5Ca0.5TiO3 yielded a lower bandgap energy of 2.6 eV. Cyclic voltammetry tests, measured in 0.1 M sodium nitrite, showed oxidation peaks occurring at 0.58 V applied voltage. *e highest peak current was observed in Sr0.5Ca0.5TiO3 powder. *e superior electrocatalytic performance of Sr0.5Ca0.5TiO3 might be attributed to lower bandgap energy, which consequently facilitates higher electron transfer. Electrocatalytic performance of Sr0.5Ca0.5TiO3 was subsequently reexamined in a wider concentration range of sodium nitrite. *e results revealed that the material responded linearly to nitrite solution in the range of 0.1 mM to 0.1 M and exhibited sensitivity ranging from 3.117 to 0.040 μA/mM, in the entire tested nitrite concentrations. *e results suggest that Sr0.5Ca0.5TiO3 could also be used for nitrite detection. 1. Introduction treatment, which involved antibiomicrobial action and water splitting [8–10]. Other known usages of perovskite Calcium titanate, strontium titanate, and strontium materials include the production of solar cells and gas calcium titanate are perovskite-structured ceramics often sensing as well as biosensing devices [11, 12]. Since exploited in fabrication of electronic devices. In general, nonenzymatic sensors used in food chemical or human perovskite-structured titanate, such as CaTiO3, SrTiO3, fluid detection are generally produced from semi- BaTiO3, and FeTiO3, have relatively wide bandgap en- conductor materials with bandgap energy values ranging ergies ranging between 2.8 and 3.6 eV [1–6]. Bandgap from 2.3 to 3.4 eV, considering perovskite’s bandgap energies can be modified to suit the intended application energy characteristics, the materials have great potential through doping [7]. Perovskite materials, owing to their for electrochemical sensors [13, 14]. high stability, good electrical response, and bandgap Food chemical contaminant and toxicants are of great energy capability to be tailored, have been developed for importance. For example, the food additive nitrite is a utilization in photocatalytic applications as in wastewater commonly used chemical in curing meat and usually 2 Advances in Materials Science and Engineering found in processed foods such as sausage, bacons, and 2 2 (αhυ) � hυ − Eg(αhυ) � hυ − Eg; (1) drinks. Consumption of nitrite in high concentrations can adversely affect human health. Nitrite is known as a where α is the absorption coefficient, Eg is the energy (eV), h potential carcinogenic substance [15, 16]. It has been is Planck’s constant (Js), and υ is the wave frequency. reported that nitrite can reduce oxygen exchange in Electrocatalytic activities of the powders were de- haemoglobin and oxygen-carrying capacity with adverse termined using a Metrohm AutoLab Potentiostat health effects especially in pregnant women and infants (PGSTAT302N). Cyclic voltammetry technique was [17, 18]. performed on the working electrode containing the Nitrite detection via the electrochemical technique using synthesized powder and multiwalled carbon nanotube nonenzymatic sensors requires materials with high elec- (MWCNT) within the voltage range of −0.8 to 0.8 V, at the trocatalytic activities. Enhancement of electrocatalytic ac- scan rate of 0.01 V/s. Pt was used as the counterelectrode, tivities can be achieved through chemical composition while Ag/AgCl as the reference electrode. *e working control, microstructure refining, and material electronic electrode was activated in 0.1 M sodium hydroxide so- structure tailoring [19, 20]. lution. Detection of nitrite was conducted in sodium Doping is one of the processes to improve perovskite’s nitrite solution with the concentration range of 0.1 to electrochemical performance through structure alteration. 100 mM. *e working electrode was prepared by mixing Distortion of the material structure often occurs as a result of the synthesized powders with the multiwalled carbon the introduction of dopants into the crystal lattice sites. *is nanotubes at the ratio 1 :1 by weight and subsequently is also accompanied by an increase of charged ions [21]. underwent the hydrothermal process at 120°C for 5 hours. Microstructure control also enhances electrocatalytic ac- *e mixture was drop onto the 1 cm by 1 cm stainless steel tivity. Fine and porous particulates with an increased surface substrate. area also create more active sites for reactions and conse- quently results in improved sensing performance [22, 23]. 3. Results and Discussion According to Zhu et al., refined microstructure also facili- tates mobility of electrons between sensing materials and 3.1. Chemical Composition. Upon calcination, the synthe- substance for detection [24, 25]. sized powders were tested for their chemical compositions *is study, therefore, aims at studying electrocatalytic using the X-ray diffraction technique. *e Sr-Ti-O powders performance of calcium titanate, strontium titanate, and exhibit the peaks corresponding to strontium titanate strontium calcium titanate synthesized by the solution (JCPDS 082-0230), as shown in Figure 1. For the Ca-Ti-O combustion technique. Relationships among chemical powders, the compositional analysis showed a single phase compositions, microstructure, bandgap energies, and elec- corresponding to calcium titanate, CaTiO3 (JCPDS 082- trocatalytic properties of the materials were also examined. 0229). Strontium calcium titanate, SrxCa1−xTiO3 (JCPDS 089-8032), was observed in the Sr-Ca-Ti-O powders. Low 2. Materials and Methods intensity peaks corresponding to anatase titanium dioxide (JCPDS 084-1285) were observed in the calcium titanate and Calcium titanate, strontium titanate, and strontium calcium strontium calcium titanate powder. titanate were synthesized by the solution combustion X-ray diffraction patterns were also utilized in the technique. *e initial reagents consisting of calcium nitrate semiquantitative analysis. Fraction of the main phase (Deajung), strontium nitrate (Deajung), and titanium di- (SrxCa1−xTiO3 (x � 0, 0.5, and 1)) to the total powder con- oxide (Sigma-Aldrich) in nitric acid (Univar) were mixed to tent, defined as F, was determined as follows: attain an aqueous solution of 0.54 M concentration. Initi- pure mix I /I �Aimpurity ation of combustion was facilitated by glycine (Deajung), F � ; (2) A Ipure Imix A A which was added to the prepared aqueous solution, at a purity −()/ � purity − impurity� temperature of about 400°C. *e powders obtained from the where F is the weight faction of the primary phase to the total solution combustion process were subsequently calcined at powder, Imix is the integrated intensity of pure phase and 900°C for 3 hours. secondary phase, Ipure is the integrated intensity of pure Chemical composition and microstructural analysis of phase, A is the mass attenuation factor of titanium the calcined powder were conducted using an X-ray dif- impurity dioxide (anatase), and A is the mass attenuation factor fractometer (Philips, X’Pert) and a scanning electron mi- purity of SrTiO or Sr Ca TiO . croscope (FEI, Quanta 450), respectively. ImageJ software 3 x 1−x 3 *e semiquantitative analysis revealed that content of was employed in particle size analysis, whereas Brunauer– the secondary phase contained in the synthesized powder Emmett–Teller (Micrometrics, 3 Flex) was utilized in the was minimal. *e titanium dioxide present in the synthe- measurement of specific surface area of the powders. sized powder did not exceed 1.25 wt.%. *e trivial quantity Optical bandgap energy measurement was conducted of the secondary phase seemed to have not contributed to using a UV-Vis spectrophotometer (UV-1700). *e significant electrocatalytic activity alterations. measurements of optical transmission were conducted within the wavelength ranging between 300

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