Sol-gel synthesis of TiO2 on Co3O4-coated sporopollenin exine microcapsules (SECs) and photocatalytic performance of new semiconductor heterojunction material.

In this study, a new approach was developed to prepare mesoporous hybrid TiO2/Co3O4 coated on Juglans sporopollenin exine microcapsules (SECs). TiO2 was synthesized on Co3O4-coated SECs used as substrate, by sol-gel method. The obtained semiconductor/semiconductor hetero-junction hybrid materials were characterized with X-ray diffractometry (XRD), UV-Vis absorption spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), particle size distribution, specific surface area, and zeta potential measurements. Photocatalytic performances of hybrid materials were tested for Reactive Black 5 dye under both UV and visible light. Equilibrium pH of the solution containing 10 mg/L Reactive Black 5 dye and 0.1% wt/v TiO2/Co3O4 was around 4.7. After irradiation in the solar box, more than 98% of the Reactive Black 5 was photocatalytically degraded within 60 min.

Different Plant Sporopollenin Exine Capsules and Their Multifunctional Usage.

Sporopollenin exine capsules (SECs) are highly resistant to heat and various acids and bases. They are also cheap, highly porous, eco-friendly polymer biomaterials with stable microencapsulation capacity. Due to their strong and uniquely shaped exine layers, they can allow growth on metal oxide materials, as a biotemplate for use in different applications. In this study, first, a single SEC extraction method was applied to three different pollens from Pinus, Fraxinus excelsior, and Tilia. Scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) analysis, and thermogravimetric/differential thermal analysis (TGA/DTA) measurements both before and after the extraction process were performed to observe changes in surface area, morphology, porous structure, and degradation properties. The protein content and removal were analyzed by elemental and spectrophotometric analyses. Then, SECs were loaded by passive and centrifuge loading for drug delivery, and the loading capacities were analyzed by Fourier transform infrared spectroscopy and spectrophotometry. The method was successful in opening the pores and maintaining the structural integrity of SECs. It was determined that the morphology and porosity affected the encapsulation efficiency. According to the loading capacities, Tilia SECs were the most efficient SECs for both loading methods. In addition, three different SECs were hydrothermally coated with cobalt and then heat-treated to obtain a metal oxide structure. A CO3O4 supercapacitor electrode constructed using CO3O4-F. excelsior SEC powder had the best surface area parameters. The electrode showed a maximum specific capacity of 473 F/g for over 3000 continuous cycles of galvanostatic charge-discharge (GCD).

Juglans Sporopollenin for High-Performance Supercapacitor Electrode Design.

Recently, plant pollen has been used as a source of activated carbon to produce carbon-containing supercapacitor electrodes. However, in this study, pollen was used as a biotemplate with a completely different approach. As a biotemplate, pollen offers a wide range of varieties in terms of exterior, porosity, shape, and size. An electrode formed by the use of metal oxide grown on the pollen exine layer (sporopollenin microcapsules) as the active substance will inevitably exhibit good electrochemical capacitive properties. Juglans male flowers have been distinguished by dissection from anthers. Isolation of pollen grains from anthers was carried out using sieving from suitable sieves (45-200 µm). Juglans sporopollenin exine microcapsules (SECs) were separated from the intine and protoplasm by acetolysis in combination with reflux. The solution containing SECs, metal ions, and Ni foam was put into a Teflon-lined hydrothermal container, and then, it was reacted at 120 °C for 15 h. The resulting precipitate, as well as the Ni foam, was heat-treated at 300 and 360 °C for 3 h in air. The raw pollen, chemically treated pollen, and cobalt-coated SEC (CoSEC) and CoSEC/Ni foam were characterized using scanning electron microscopy, Brunauer-Emmett-Teller surface area analysis, thermogravimetric analysis, and X-ray diffraction techniques. Two different types of supercapacitor electrode designs, with the use of exine microcapsules of Juglans sporopollenin, were performed for the first time. The maximum specific capacitance was up to 1691 F g-1 at 5 A g-1.