|Salprima Yudha S||Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Bengkulu, Jalan W.R. Supratman, Kandang Limun, Bengkulu 38371, Indonesia|
|Aswin Falahudin||Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Bengkulu, Jalan W.R. Supratman, Kandang Limun, Bengkulu 38371, Indonesia|
|Asdim||Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Bengkulu, Jalan W.R. Supratman, Kandang Limun, Bengkulu 38371, Indonesia|
|Jeong In Han||Department of Chemical and Biochemical Engineering, Dongguk University-Seoul 30, Pildong-ro 1 gil, Jung-gu, Seoul 04620, Republic of Korea|
A new synthetic method for the preparation of titania (TiO2) was developed. The synthesis involved utilizing dammar gum as the natural soft template, chloroform (CHCl3) as the reaction solvent, and titanium tetraisopropoxide (TTIP) as the main precursor. The results show that the methodology described herein is an efficient alternative for the preparation of titania with larger surface areas up to 58.1 m2 g-1 for TiO2 from the TTIP-dammar gum/CHCl3/H2O reaction system, and 56.2 m2 g-1 for TiO2 from the TTIP-dammar gum/CHCl3 reaction system. Both surface areas are larger than that of the pure TTIP/CHCl3/H2O product (5.56 m2 g-1). In addition, the as-prepared TiO2, which uses dammar gum as a soft template, exhibited higher photocatalytic activity toward rhodamine B degradation compared to the as-prepared TiO2 in the absence of dammar gum.
Dammar-gum; Photocatalyst; Soft template; Titania
Owing to its remarkable physical and chemical properties, titanium dioxide (TiO2) or titania, is well known as one of the most desired semiconductor materials. It is known that all phase types of titania (anatase, rutile, and brookite) are effective as photocatalysts under ultra-violet (UV) light irradiation (Jing et al., 2011). A number of synthetic approaches for TiO2 have been reported widely (Slamet et al., 2017; Kusrini et al., 2019). A popular and efficient strategy includes development of this material on various templates (Xie et al., 2016; Niu et al., 2018). For instance, application of resorcinol-formaldehyde resin as a template for the preparation of a TiO2 hollow nanostructure has recently been described. It has been shown that hollow titania has good activity as a photocatalyst for the degradation of rhodamine B under UV radiation. This result indicates that the hollow titania structure is important for its catalytic activity (Tang et al., 2013). Alginate has also been claimed as a good sacrificial soft template for the synthesis of specific pores and nanoparticles. In particular, the role of alginate as a template for nucleation and the formation of porous TiO2 has been described (Yu et al., 2016).
Other methods of obtaining mesoporous TiO2 include reacting titanium isopropoxide in the presence of a semi-rigid template, such as a rod-shaped virus bacteriophage, M13. TiO2 was obtained using this methodology and was shown to exhibit good stability, particularly in the anatase phase when the calcination temperature elevated to 800°C (Hernández-Gordillo et al., 2018). Furthermore, the poly(butyl methacrylate) (PBMA) colloidal crystal template has also been developed to synthesize titania using a sol-dipping template method. The TiO2 that was obtained using this procedure was shown to have a meso-scale pore structure, which was indicated by the many holes that were formed following the calcination procedure used to remove the template (Zhang et al., 2012).
Other research shows that utilizing different bio templates results in the formation of different crystal phases of TiO2, even at calcination temperatures of up to 750°C. TiO2 was obtained in the anatase phase when albumen and yeast were used as templates. In contrast, when dandelion pollen was utilized, only the rutile phase was isolated (Bao et al., 2012). A variety of concentrations of rice straw (lignocellulosic waste material) were investigated as soft templates when using the sol-gel methodology. A synthetic modification procedure was carried out to alter the pore volume and size of the TiO2 (Ramimoghadam et al., 2014).
However, the use of natural templates is not only restricted to soft templates. For instance, mesoporous crystalline TiO2 was synthesized using silica KIT-6. The synthetic procedure involved the addition of NaOH to remove the silica template from the desired material (Zhang et al., 2010). Furthermore, a different strategy used pluronic polymeras as the template. A further advantage of using this material was its photocatalytic activity in photo-degradation of orange II under UV irradiation and inert conditions (Xiong et al., 2010). More recently, the synthesis of TiO2 from tetrabutyl titanate was carried out using cotton as a hard template. The annealing temperature was 600°C (2 hours), which afforded the anatase phase of TiO2 (Wang et al., 2015). Other research has shown that TiO2 nanoparticles can be synthesized using polyamidoamine (PAMAM) dendrimer molecules as a template (Peng et al., 2016).
Moreover, it has been demonstrated that combining two or more templates can increase the activity of the obtained titania. The synthesis of a grain size of TiO2 nanotubes, using anodic aluminum oxide membrane as a hard template and a complex of polystyrene-block-polyethylene oxide with titanium isopropoxide, has recently been reported. It was demonstrated that the field emission performance was dependent on the grain size of the TiO2 (Yang et al., 2017). A sol-gel agent made from acrylic acid and N,N’-methylenebis(acrylamide) was also used to synthesize titania, which resulted in the formation of anatase and rutile phases in various ratios. The obtained products were tested as cathode materials for use in a rechargeable aqueous aluminum-ion battery (Ojeda et al., 2017). Furthermore, the common surfactant, cetyltrimethylammonium bromide, was combined with the P123 polymer as a medium to synthesize of TiO2. The synthetic procedure involved using titanium tetrachloride as the precursor and heating the reaction mixture to 550°C for 3 h. The method resulted in the formation of a crystalline rutile phase (Liu et al., 2018).
Biotemplates have not only been used to prepare metal oxides but have also been used as composite precursors. An example of this is the synthesis of porous hierarchal spirulina/TiO2 composite, which resulted in the enhancement of their photocatalytic activity (Tu et al., 2012). Other results show that nano?bril-interconnected cellulose aerogel could be used as a biotemplate for the synthesis of hierarchical porous TiO2 with a highly speci?c surface area (Zhang et al., 2017). In addition, the use of kenaf fiber as a sacrificial template produced nanostructured tubular TiO2 (Osman et al., 2018).
Currents research shows that
dammar gum can be used as a micro-encapsulating material for drugs, such as
diltiazem hydrochloride and ibuprofen, using the oil-in-oil emulsion solvent
evaporation technique. It was demonstrated that encapsulation efficiency
increased as the dammar gum content increased. Unfortunately, the release rates
of the drugs was reduced (Morkhade and Joshi, 2007).
It is known that the materials desired for photocatalysis and photoelectrode purposes
possess two common characteristics: crystallinity and large surface areas (Zhang et al., 2010; Nursama and Muliani, 2012). In
this study, a green, two-step approach for the fabrication of titania was
developed using natural dammar gum as a bio-template, without the addition of
bases, such as NaOH, NH4OH, KOH, or others. Our simple methodology
could be used as an alternative to synthesize TiO2. The dammar gum
was used as a new bio-template for the complexation of the titanium (IV)
isopropoxide (TTIP) precursor, in order to synthesize TiO2.
Furthermore, the synthesized TiO2 that used dammar gum as the soft
template had high photocatalytic activity for rhodamine B degradation.
In conclusion, we report the use of dammar gum as a soft template for the efficient preparation of crystalline photocatalysts with porous structures and large surface areas through the synthesis of anatase TiO2. The described reaction conditions did not require the addition of any base or the use of high temperatures. Furthermore, the obtained product proved to be effective as a photocatalyst in rhodamine B degradation under sunlight irradiation. Further investigations of the obtained titania for other applications are on-going in our laboratory.
We are grateful to the Kementerian Riset, Teknologi dan Pendidikan Tinggi (Kemenristekdikti) Republic of Indonesia for its financial support under the World Class Professor (WCP) Program, fiscal year 2019.
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