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Phenolic resin derivatized TiO2-walnut shell carbon hybrid materials for solar photocatalytic phenol removal

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Abstract

As a toxic organic pollutant in industrial wastewaters, phenol wastewater treatment is investigated extensively. TiO2 based photocatalysts are widely used for such applications, due to its ecofriendly properties, ease of preparation, low toxicity and recycle stability. In this study, phenolic-resin-modified TiO2 (PF/TiO2), TiO2/WSC (Walnut shell carbon) and PF/TiO2/WSC hybrid composites were successfully synthesized by a sol-gel method. The obtained TiO2-based composites were characterized by BET, XRD, SEM, FTIR and XPS techniques. The phase characterization results showed that the TiO2 phase was anatase in the PF/TiO2/WSC (300 °C, 2 h) composite. TiO2 was uniformly loaded on the surface of the WSC, as revealed by a shift in the Ti binding energy. Ti–O–C bonds are formed in the prepared TiO2/WSC and PF/TiO2/WSC (300 °C, 2 h) photocatalyst. Using a catalyst dosage of 2.0 g/L and an initial phenol concentration of 80 mg/L, the 10%PF/30%TiO2/WSC composite showed the best activity with 88% degradation obtained under sunlight for 150 min. The active species of PF/TiO2/WSC photocatalytic degradation of phenol were ·OH and ·O2−, and a photocatalytic degradation mechanism was proposed. The synergistic system of WSC adsorption and the superior photocatalytic performance of phenolic-resin-modified TiO2 achieved high degradation efficiency of pollutants in water. This research provides an environmentally friendly method for utilizing agricultural wastes and applies a new idea for solar photocatalytic removal of pollutants.

Graphical Abstract

Reaction Mechanism for phenol degradation over 10%PF/30%/TiO2/WSC: Based on the results of the structure characterizations and the natural sunlight photocatalytic activity results of the prepared 10%PF/30%/TiO2/WSC, a possible synergistic effect between TiO2 and WSC on the enhancement of photocatalytic activity is proposed. Walnut shell activated carbon, as a strong biomass adsorbent, provides enrichment effect for TiO2 photocatalysis, and provides channels for TiO2 electron transport, reducing the electron-hole recombination rate. And TiO2 photocatalytic degradation could give the walnut shell carbon new adsorption sites, to form the systematic effect of adsorption and photocatalytic efficiency. When the 10%PF/30%/TiO2/WSC photocatalyst irradiated by natural sunlight, the electrons (e−) in the valence band (VB) of TiO2 will be excited by energy and transfer to the conduction band (CB) to generate photogenerated electrons, which will generate photogenerated holes (hv+), also form superoxide radical (·O2−) and hydroxyl radical (·OH). These radicals can oxidize phenol into para-benzoquinone, and finally mineralize into small molecules H2O and CO2. It has been extensively approved that carbon doping would introduce a mid band-gap state close to the TiO2 valence bond, and also can increase phenol removal efficiency significantly.

Highlights

  • Phenolic resin modified TiO2 (PF/TiO2), TiO2/WSC (Walnut shell carbon) and PF/TiO2/WSC hybrid composites were prepared by sol-gel method, and the obtained TiO2-based composites were used for phenol removal

  • The obtained PF/TiO2/WSC (300 °C, 2 h) composite material retains the layered pores structure and the anatase TiO2 phase walnut shell carbon. TiO2 is uniformly loaded on the surface of the walnut shell carbon to make the binding energy of Ti has shifted. Also Ti–O–C bonds are found in the PF/TiO2 and PF/TiO2 /WSC (300 °C, 2h) composite structure.

  • 10%PF/30%TiO2/WSC composite showed the best activity when the catalyst dosage was 2g/L, the initial phenol concentration was 80 mg/L, and its degradation rate was 88.14% under sunlight for 150 min.

  • The synergistic system of walnut shell carbon adsorption and the superior photocatalytic performance of phenolic resin modified TiO2 achieves high degradation efficiency of pollutants in water and provides a new idea for solar photocatalytic pollutants removal in water.

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Acknowledgements

The present study was supported by the Joint Project of Basic Agricultural Research Fund of Yunnan Province (2018FG001-051) and Open fund of Key Laboratory of State Forestry and Grassland Administration on Highly-Efficient Utilization of Forestry Biomass Resources in Southwest China (2023-GC03).

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Authors and Affiliations

  1. Key Laboratory of State Forestry and Grassland Administration on Highly-Efficient Utilization of Forestry Biomass Resources in Southwest China (Southwest Forestry University), Kunming, 650224, PR China

    Tao Li, Jinyuan Zhang, Shiping Zhou, Fengchuan Li & Huijuan Li

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  1. Tao Li
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  2. Jinyuan Zhang
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  3. Shiping Zhou
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  4. Fengchuan Li
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Contributions

Tao Li contributed significantly to analysis and manuscript preparation, prepared the Figs. 1–9. Jinyuan Zhang contributed to make the graphs in the manuscript. Shiping Zhou performed the data analyses; Fengchuang Li performed the experiment and prepared Figs. 10–12. Huijuan Li contributed to the conception of the study and wrote the manuscript. All authors reviewed the manuscript.

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Correspondence to Huijuan Li.

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Li, T., Zhang, J., Zhou, S. et al. Phenolic resin derivatized TiO2-walnut shell carbon hybrid materials for solar photocatalytic phenol removal. J Sol-Gel Sci Technol (2024). https://doi.org/10.1007/s10971-024-06370-4

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