Utilization of Dammar-Gum as a Soft Template in Titania Synthesis for Photocatalyst

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

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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