Molekul.
Vol.
No.
July 2024: 352 Ae 359 Articles MOLEKUL eISSN: 2503-0310 https://doi.
org/10.
20884/1.
Preparation of Oil Palm Leaves Ash-Supported Titania for the Elimination of Safranin-O Dye in Water Salprima Yudha S1,2*.
Morina Adfa1,2.
Swadexi Istiqphara3.
Aswin Falahudin1.
Muhamad Alvin Reagen1 Department of Chemistry.
Faculty of Mathematics and Natural Sciences.
Universitas Bengkulu.
Kandang Limun.
Kota Bengkulu 38122.
Indonesia Research Center of Sumatra Natural Products and Functional Materials (RC-SuNaPFuM.
Universitas Bengkulu.
Kandang Limun.
Kota Bengkulu, 38122.
Indonesia Department of Electrical Engineering.
Institut Teknologi Sumatera (ITERA).
Way Huwi.
Kecamatan Jati Agung.
Kabupaten Lampung Selatan.
Province of Lampung.
Indonesia.
*Corresponding author email: salprima@unib.
2022@gmail.
Received January 15, 2024.
Accepted April 19, 2024.
Available online July 20, 2024 ABSTRACT.
The objective of this study was to develop an approach for incorporating titanium oxide or titania into oil palm leaves ash (OPLA) using a simple procedure.
The study process comprised the mixing of oil palm leaves (OPL) powder and titanium tetraisopropoxide in chloroform solvent, followed by the elimination of the solvent to obtain a solid residue.
Subsequently, the residue obtained was calcined at 500 AC for 5 hours, leading to the production of a yellow-light powder.
The results of product characterization using X-ray diffraction (XRD) and scanning electron microscopy analysis showed the presence of titanium oxide in OPLA.
In addition, the wide diffractogram detected in XRD analysis revealed the presence of a silica peak.
The un-sharp peaks in the regions of 25.
6A, 38.
2A, 47.
9A, 54.
5A, and 62.
9A showed that the TiO2 particles were pure anatase, and no peaks of other TiO2-anatase phases were detected.
Analysis using SEM showed that the surface of the material obtained was irregular and tended to have a hollow shape, while energy dispersive X-ray analysis revealed a SiO2 content of approximately 73%.
However, the titanium element or titania was not detected possibly due to its small The material obtained also had a good catalytic activity for safranin-O dye elimination under sunlight irradiation, which served as the activation energy source.
Based on these findings, the use of OPLA .
side product of oil palm plantation.
could be evaluated economically due to its effective role in the catalytic process despite the addition of a small amount of titania catalyst.
Keywords: Oil palm leaves ash, titania, safranin-O, sunlight irradiation.
INTRODUCTION
Waste biomaterials are substances with the potential to be utilized as attractive supporting materials due to their widespread availability, non-toxic nature, and cost-effectiveness.
In addition, biomasses or their derivative compounds have similar properties and can facilitate the dispersion of metal and/or metal oxide particles, leading to enhanced stability and recoverability of small particles.
Certain biomasses are widely recognized as silica sources (Vaibhav et al.
, 2015.
Permatasari et al.
, 2016.
Patel et , 2017.
Rovani et al.
, 2018.
Sapave et al.
, 2018.
Nasdiyanto et al.
, 2.
, and have been used as supporting materials for metals or metal oxides, including in the standard preparation of TiO2AeSiO2 composites using commercially available SiO2 precursors (Pierpaoli et al.
, 2.
For example, silica obtained from rice husk ash and rice straw was used in the production of TiO2AeSiO2 composites as photocatalysts for dye discoloration (Yang et al.
, 2016.
Choi et al.
, 2.
Recent studies have shown that incorporating nanoscale TiO2 into black rice husks can enhance the compressive strength of rice husk mortars (Noorvand et al.
, 2.
In addition, there has been significant progress in this field of study, particularly regarding the use of alternative biomasses as silica sources in ceramic materials preparation (Hubadillah et al.
Hossain et al.
, 2018.
Danewalia et al.
, 2018.
Singh et al.
, 2.
Among the limited agricultural resources containing silica in their biomasses, oil palm has been reported to be the most demanded.
Oil palm leaves (OPL) are widely recognized for their rich silica precursor content, which can be used for various purposes (Onoja et al.
, 2017.
Onoja et al.
, 2.
response to the imperative for advancing materials exploration through the use of diverse local natural resources, several preliminary investigations were carried out using OPL as silica precursors.
These investigations have yielded materials with unique properties and showed significant potential for fundamental studies (Yudha S et al.
, 2020.
Yudha S et Preparation of Oil Palm Leaves Ash-Supported Titania Salprima Yudha S.
, et al.
, 2.
Several studies have also explored the use of oil palm waste, particularly charcoal derived from oil palm shells as supporting materials for a nickel catalyst in the cracking of methyl ester from used cooking oil (Nazarudin et al.
, 2.
At present, various reports have explored different composites comprising TiO2 and supporting materials, primarily focusing on catalytic applications for contaminant degradation in aqueous environments.
For example.
TiO2-zeolite and TiO2-silica composites have been developed as catalysts for the degradation of diverse pollutants, such as safranin-O (SO) (Dong et , 2012.
Ekka et al.
, 2.
In addition.
TiO2-zeolite composites showed efficacy in degrading SO, methylene blue (MB), and 2,4-dinitroaniline (DNA) within a photocatalytic system.
Adsorption on the photocatalyst surface represents a crucial step in the degradation process, with kinetic studies showing that the adsorption of SO conforms to the Langmuir equation (Faghihian & Bahranifard, 2.
Zeolite-supported TiO2 also showed effectiveness in the degradation of red safranin within a fixed-bed reactor designed for water treatment (Rismanchian et , 2.
Therefore, the objective of this study was to fabricate titania incorporated into oil palm leaf ash (OPLA) by using a solid-state reaction at high temperatures .
AC).
The samples obtained were then analyzed using scanning electron microscopy, energy dispersive X-ray spectroscopy.
X-ray diffraction, and Fourier transform infrared spectroscopy.
The catalytic behaviors of the samples for degradation of SO under solar light irradiation experiments were also A total of 3 g of OPL powder was placed in a crucible, followed by the addition of 50 mL chloroform and stirring using a magnetic stirrer.
The reaction mixture was allowed to run for 30 minutes while being stirred to ensure that the OPL powder was completely dissolved in the solvent.
While the mixture was still being stirred, 1 mL of TTIP was added.
After stirring for 30 minutes, the mixture was allowed to stand at room temperature overnight.
The crucible was wrapped in aluminum foil with small holes to ensure slow evaporation of the chloroform.
The crucible was inserted into the furnace, and the heating temperature was adjusted to achieve a temperature rise of 500AC in two hours from room temperature.
The reaction is allowed to continue at 500 AC for 5 hours.
After that, the cooling process was carried out gradually over a period of 24 hours.
The product of the solid-solid reaction was characterized by a variety of commonly used X-ray diffraction (XRD Mini-Flex.
Rigak.
SEM, and energy-dispersive X-ray (EDX) (JEOL JSM 6510 LA) were used for phase, surface, and FTIR spectrophotometer (Compact FT-IR Alpha 2.
Bruke.
was used to determine the vibration patterns generated by the resulting material.
Experiments were performed on 10 mL of SO solutions .
with 2 treatments, namely with and without The resulting experiments comprised .
SO without catalyst under dark condition .
UV irradiation ( = 254 n.
, .
SO without catalyst under dark condition .
, .
SO without catalyst under dark condition .
UV irradiation .
sunlight irradiation .
SO with TiO2-OPLA catalyst under dark condition .
SO with TiO2-OPLA catalyst under dark condition .
UV irradiation .
, and .
SO with TiO2-OPLA catalyst under dark condition .
UV irradiation .
sunlight irradiation .
, with 10 mg catalyst for each treatment.
The spectrophotometer equipped with Agilent-60 at 519 Figure 1 presents a full schematic diagram of the synthetic pathway and the property analysis, including its application as a photocatalyst.
EXPERIMENTAL SECTION
Materials The tetra-isopropoxide (TTIP) from Sigma Aldrich, as well as hydrochloric acid, nitric acid, and sodium hydroxide from Merck.
In addition, the biomass of OPL was obtained from an oil palm plantation farmer, and all glassware was rinsed with an aqua regia solution.
Procedure After cleaning the OPL with distilled water, the samples were dried and crushed with a juice mixer.
Figure 1.
The synthetic processes of TiO2-OPLA, characterization, and its application Molekul.
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July 2024: 352 Ae 359
RESULTS AND DISCUSSION
Synthesis of TiO2-OPLA OPL powder in chloroform solvent had a brownish-green color, and the color of the mixture changed to a blackish brown after the addition of TTIP.
In addition, the reaction mixture of OPL powder and TTIP was heated at 500 AC for 5 hours to produce a reddish-white powder, as shown in Figure 2.
Characterization The XRD analysis in Figure 3 showed that when OPL powder was heated with TTIP precursor, amorphous products, such as TiO2 and OPL ash containing silica (SiO.
were produced.
This was shown by the widening of the silica diffractogram, as well as the absence of sharp TiO2 diffractogram Less sharp peaks in the regions of 25.
6A, 38.
9A, 54.
5A, and 62.
9A showed that the TiO2 particles were pure anatase (JCPDS 21-1.
The results of this study also showed that no peaks of other TiO2 phases were detected.
This was consistent with previous studies, establishing that heating the precursor in the open air by the calcination method at a low temperature of 600 AC produced TiO2 in the anatase phase (Zhai, et al.
, 1.
In addition, the material could possibly contain compounds or impurities, even in trace amounts, because the experiment was performed on untreated OPL.
This was evident through the presence of unidentified small peaks in the XRD.
SEM analysis (Figures 4a and 4.
showed that the product was generally in the form of small powders in the shape of hollow materials.
EDX analysis (Figure 4.
showed the presence of significant amounts of silica .
2%) in the indicated area but no titanium oxide.
This could be caused by the trace amount of TiO2 trapped in the SiO2 matrix, but the XRD peaks were sufficient to show that the resulting material contained TiO2 (Hong, et al.
, 2.
The FTIR analysis of the resulting material revealed the presence of SiO2, as shown in Figure 5.
The SiO2 was indicated by the absorption peak at 1108 cmOe1, which showed the presence of a specific Si-O-Si bond.
The material also contained a Ti-O-Si interaction due to a peak at 805 cmOe1.
This finding was consistent with previous studies, reporting that pure SiO2 did not show a peak in the region, and other reports showed the presence of Ti-O-Si bonds in the 800Ae1200 cm-1 range (Huang et al.
, 2.
In addition, the wide peak in the 3422 cmOe1 regions revealed that the material was easily absorbed by moisture due to its correlation with the stretching vibrations of hydroxyl groups and water molecules.
The peak was also supported by the presence of a second peak at 1630 cmOe1, which revealed the bending vibration of the same molecule.
Figure 2.
Physical change of the reaction mixture .
after calcination Figure 3.
XRD pattern of TiO2-OPLA Preparation of Oil Palm Leaves Ash-Supported Titania Salprima Yudha S.
, et al.
Figure 4.
SEM pattern of TiO2-OPLA .
5000y and .
EDX pattern of TiO2-OPLA Figure 5.
FTIR spectrum of TiO2-OPLA Molekul.
Vol.
No.
July 2024: 352 Ae 359 Catalytic Applications Safranin-O (SO) is a dye derived from phenazine, which poses a significant threat to aquatic life when present in wastewater (Jyoti et al.
, 2.
This textile dye not only raises environmental concerns but also serves as a good candidate for photocatalytic studies due to its high stability to visible light (Sydorchuk et al.
In this study, the elimination of SO in wastewater was explored using TiO2-OPLA as a catalyst under UV and sunlight irradiation.
The experimental procedures started with the preparation of multiple concentrations of SO solution, including 3, 6, 9, 12, and 15 ppm, followed by measurement of their absorbance with a UV-Vis spectrophotometer.
Subsequently, these concentrations were plotted to produce a linear regression equation based on the absorbance values obtained.
The linear regression equation was then used to determine the change in the concentration of the solutions that had been subjected to treatment with a catalyst and irradiation.
The results of the UV-Vis spectrophotometry analysis of SO samples given different treatments are presented in Figure 6.
Based on the results, there was no significant difference between the solutions treated without the TiO2-OPLA catalyst in dark conditions .
and those treated using a combination of dark conditions and sunlight irradiation .
hours and 3 hour.
, as shown in Figures 6a and 6b.
This finding suggested that the stability of SO remained unaffected under sunlight irradiation.
However.
SO without catalyst under dark conditions .
UV irradiation .
, and sunlight irradiation .
experienced a decrease in absorbance, leading to an elimination efficiency of 56% (Figure 6.
Although UV irradiation induced a photolysis reaction for SO, the yield obtained was relatively low.
The results revealed that the addition of 10 mg of TiO2-OPLA catalyst under dark conditions .
led to a slight decrease in absorbance, with an elimination efficiency of 21% (Figure 6.
The findings suggested that the presence of catalyst powder in the solution led to a decrease in absorbance due to the adsorption process.
This was consistent with the previous studies, reporting that the initial stage of the heterogeneous catalytic reactions comprised the adsorption of treated molecules on and/or into the catalyst (Vydrine, 2.
Exposure to UV light for 3 hours activated the TiO2-OPLA catalyst, leading to a reduction in absorbance due to the photocatalysis process (Figure 6.
limination efficiency: 29.
5%).
Meanwhile, exposure to sunlight for 1 hour caused a significant decrease in absorbance and an elimination efficiency of 56%, as shown in Figure 6f.
The results revealed that the TiO2 catalyst played an important role in accelerating the elimination of SO compounds in the presence of sunlight irradiation compared to UV This observation was in line with previous studies, where the degradation of methylene blue and congo-red was more effective in the presence of TiO2 under sunlight compared to UV light due to the fast recombination of electrons and holes, which reduced the elimination rate (Bharati et al.
, 2.
Based on the analysis results in Figure 6, sunlight had a substantial influence on increasing the catalytic performance of the catalyst.
Consequently, subsequent experiments focused on the use of sunlight as an inducer in SO photocatalysis and as an energy source for the activation of TiO2-OPLA in the photocatalytic elimination of SO.
The UV-Vis spectrophotometry analysis findings are presented in Figure 7.
Figure 6.
UVAevisible spectra of decomposition of SO dye under some reaction conditions: .
SO without catalyst under dark condition .
UV irradiation .
SO without catalyst under dark condition .
SO without catalyst under dark condition .
UV irradiation .
sunlight irradiation .
SO with TiO2-OPLA catalyst under dark condition .
SO with TiO2-OPLA catalyst under dark condition .
UV irradiation .
SO with TiO2-OPLA catalyst under dark condition .
UV irradiation .
sunlight irradiation .
Preparation of Oil Palm Leaves Ash-Supported Titania Salprima Yudha S.
, et al.
Figure 7.
UVAevisible spectra of decomposition of SO dye under two reaction conditions:
SO TiO2-OPLA catalyst under sunlight irradiation .
SO without any catalyst under sunlight irradiation .
Figure 8.
Plausible Reaction Mechanism for Degradation of SO by TiO2-OPLA The SO solution treated with the TiO2-OPLA catalyst exhibited nearly complete elimination (Figure Meanwhile, the untreated solution exposed to sunlight for 2 hours showed photolysis with an elimination efficiency of 55.
8% (Figure 7.
The synergistic interaction between TiO2-OPLA particles .
hich contain a large quantity of SiO.
and sunlight indicated the potential of OPL waste to be used as a precursor for the production of active catalyst support However, this study predominantly focused on the exploration of catalyst activity in degrading SO compounds without exploring the kinetics and analysis of equilibrium isotherms.
From a technical and economic standpoint, the use of sunlight was more profitable due to its constant availability and the non-use of expensive equipment.
Several catalytic mechanisms through which TiO2-SiO2 composites degraded some essential chemicals have been thoroughly described (Yang et al.
, 2011.
Musaev et al.
Salgado et al.
, 2019.
Panwar et al.
, 2.
These mechanisms could be used to explain SO elimination by TiO2-OPLA because OPLA contained a large amount of SiO2, which produced a plausible mechanism for the current photocatalytic reaction, as shown in Figure 8.
Figure 8 shows that the presence of sunlight irradiation on the surface of titania particles causes the excitation of electrons and leaves holes.
The process of electron excitation and the presence of holes could cause reactions that produce AOH radicals in water.
These radicals broke down the SO compound by starting hydroxylation reactions and breaking the ring, which made the compound break down into simpler, less harmful compounds.
CONCLUSIONS
In conclusion, the use of OPL as a natural source of silica and the incorporation of titanium oxide could be easily fabricated by a solid-state reaction at 500 AC.
The resulting material showed that titanium oxide .
s anatas.
was not completely crystalline compared to silica, which was generally amorphous.
TiO2-OPLA was a material with an irregular shape with good catalytic activity against the elimination of SO when tested outdoors .
nder sunlight irradiatio.
The good degradation process reached 56% when SO was treated with the TiO2-OPLA catalyst under dark conditions, followed by UV and sunlight irradiation for 22 h, 3 h, and 1 h, respectively.
Meanwhile, the maximum yield for the degradation process was Molekul.
Vol.
No.
July 2024: 352 Ae 359 sufficient in the presence of TiO2-SiO2 under sunlight irradiation, which almost degraded safranin-O.
ACKNOWLEDGEMENTS
This work was financially supported by Kementerian Pendidikan, kebudayaan.
Riset dan Teknologi (Kemendikbudriste.
Republik of Indonesia, under a scheme Penelitian Dasar - Fiscal 2021.
contract between Kemendikbudristek and Lembaga Penelitian dan Pengabdian (LPPM) Universitas Bengkulu (UNIB), number 106/E4.
1/AK.
PT/2021
(July 12, 2.
and derivative contract between the principal investigator (PI) and LPPM UNIB, number 2179/UN30.
15/PG/2021 (July 13, 2.
REFERENCES