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<p>In this study, TiC/TCN (tubular g-C<sub>3</sub>N<sub>4</sub>) composite photocatalysts with Schottky heterojunction structure were prepared by a simple physical milling and one-step calcination process. The degradation efficiency of the photocatalytic system was tested under simulated sunlight irradiation using Tetracycline solution (TC) and Ciprofloxacin solution (CIP) as target pollutants. The prepared composite photocatalysts were analyzed and discussed in detail by various characterization methods such as X-ray diffraction (XRD), field emission electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), N<sub>2</sub> adsorption–desorption isotherms and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS). The TiC component serves as an efficient electron mediator, uniformly distributed across the tubular g-C<sub>3</sub>N<sub>4</sub> (TCN) substrate to establish a TiC/TCN Schottky-type heterojunction. The efficient inhibition of the photogenerated electron and hole recombination rate can be primarily ascribed to the unique tubular structure, enlarged specific surface area and reduced band gap energy of the composite photocatalyst. The results of photocatalytic experiments revealed that pure TiC and BCN exhibited relatively low photocatalytic activity, while the coupling of TCN with TiC significantly enhanced the photocatalytic performance of the resulting TiC/TCN. The optimum 6% TiC/TCN sample could remove TC and CIP up to 91.3% and 88.1%. After four consecutive cycle photocatalytic stability tests, the removal rates of TC and CIP could still be retained at 87.2% and 83.6%, respectively, indicating that the 6% TiC/TCN sample demonstrated exceptional structural integrity and recyclability. Through radical trapping experiments, the photocatalytic process was conclusively demonstrated to be primarily governed by superoxide radicals (<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10854_2025_15015_Article_IEq1.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="30" /> </InlineMediaObject> <EquationSource Format="TEX">\(\cdot {\text{O}}_{2}^{ - }\)</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mo>·</mo> <msubsup> <mtext>O</mtext> <mrow> <mn>2</mn> </mrow> <mo>-</mo> </msubsup> </mrow> </math></EquationSource> </InlineEquation>) and photogenerated holes (h⁺) as dominant reactive species. Based on these experimental results, the photocatalytic mechanism was proposed. The present work provides an efficient and simple idea for constructing a TiC/TCN Schottky heterojunction, demonstrating promising potential for practical implementation in photocatalytic degradation of persistent pharmaceutical contaminants.</p>

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In-situ calcination synthesis of 2D/1D TiC/g-C3N4 composite photocatalysts with enhanced degradation of antibiotics under simulated sunlight

  • 期刊论文

  • 发表日期：

    2025年6月10日

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  • Haojie Zhang,
  • Jinsong Xie,
  • Zezhong Xu,
  • Hongdian Lu,
  • Kunhong Hu

摘要

In this study, TiC/TCN (tubular g-C3N4) composite photocatalysts with Schottky heterojunction structure were prepared by a simple physical milling and one-step calcination process. The degradation efficiency of the photocatalytic system was tested under simulated sunlight irradiation using Tetracycline solution (TC) and Ciprofloxacin solution (CIP) as target pollutants. The prepared composite photocatalysts were analyzed and discussed in detail by various characterization methods such as X-ray diffraction (XRD), field emission electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), N2 adsorption–desorption isotherms and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS). The TiC component serves as an efficient electron mediator, uniformly distributed across the tubular g-C3N4 (TCN) substrate to establish a TiC/TCN Schottky-type heterojunction. The efficient inhibition of the photogenerated electron and hole recombination rate can be primarily ascribed to the unique tubular structure, enlarged specific surface area and reduced band gap energy of the composite photocatalyst. The results of photocatalytic experiments revealed that pure TiC and BCN exhibited relatively low photocatalytic activity, while the coupling of TCN with TiC significantly enhanced the photocatalytic performance of the resulting TiC/TCN. The optimum 6% TiC/TCN sample could remove TC and CIP up to 91.3% and 88.1%. After four consecutive cycle photocatalytic stability tests, the removal rates of TC and CIP could still be retained at 87.2% and 83.6%, respectively, indicating that the 6% TiC/TCN sample demonstrated exceptional structural integrity and recyclability. Through radical trapping experiments, the photocatalytic process was conclusively demonstrated to be primarily governed by superoxide radicals ( \(\cdot {\text{O}}_{2}^{ - }\) · O 2 - ) and photogenerated holes (h⁺) as dominant reactive species. Based on these experimental results, the photocatalytic mechanism was proposed. The present work provides an efficient and simple idea for constructing a TiC/TCN Schottky heterojunction, demonstrating promising potential for practical implementation in photocatalytic degradation of persistent pharmaceutical contaminants.