<p>Graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) has been widely applied in advanced oxidation processes based on persulfate (PS) for photocatalytic degradation aqueous pollutants, yet it still suffers from limitations such as weak redox capability, low electrical conductivity and severe charge recombination. In this study, via building a confined environment, the doped-C and nitrogen vacancy (Nv) were simultaneously introduced in g-C<sub>3</sub>N<sub>4</sub> through one-step calcination. Compared to CN-M derived from melamine, the urea-derived CN-U exhibits higher concentrations of doped-C and Nv, which leads to the different band structures. The valence band (VB) and conduction band (CB) of CN-M shift more positively than those for CN-U with ΔE<sub>VB</sub> and ΔE<sub>CB</sub> being 0.31 and 0.36 eV, respectively. As a result, a Z-type g-C<sub>3</sub>N<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> homojunction (CN-UM) derived from the mixture of urea and melamine was constructed with the minimum resistance, the lowest charge recombination rate and the high redox capacity retained. The tetracycline degradation efficiency and degradation rate constant by CN-UM coupling with PS reach 99% and 0.08989 min<sup>−1</sup>, respectively, after irradiation for 60 min, along with the excellent cycling stability. The active species h<sup>+</sup>, ·O<sub>2</sub><sup>−</sup>, ·OH and <InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(\rm{SO}_{4^{\cdot\,-}}\)</EquationSource> <EquationSource Format="MATHML"><math display="block"> <msub> <mrow> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <msup> <mn>4</mn> <mrow> <mo>⋅</mo> <mspace width="thinmathspace" /> <mo>−</mo> </mrow> </msup> </mrow> </msub> </math></EquationSource> </InlineEquation> play roles during the degradation process, with the contributions from h<sup>+</sup> and ·O<sub>2</sub><sup>−</sup> higher than those from ·OH and <InlineEquation ID="IEq2"> <EquationSource Format="TEX">\(\rm{SO}_{4^{\cdot\,-}}\)</EquationSource> <EquationSource Format="MATHML"><math display="block"> <msub> <mrow> <mi mathvariant="normal">S</mi> <mi mathvariant="normal">O</mi> </mrow> <mrow> <msup> <mn>4</mn> <mrow> <mo>⋅</mo> <mspace width="thinmathspace" /> <mo>−</mo> </mrow> </msup> </mrow> </msub> </math></EquationSource> </InlineEquation>.</p>

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One step construction of N-vacancy-rich carbon doped g-C3N4/g-C3N4Z-type homojunction and its coupling with persulfate for tetracycline degradation

  • Ze-min Zhu,
  • Guo-dong Zheng,
  • Yong-hua Zhou,
  • Li-miao Chen,
  • Qiu-mei Wu,
  • Tie-chui Yuan

摘要

Graphitic carbon nitride (g-C3N4) has been widely applied in advanced oxidation processes based on persulfate (PS) for photocatalytic degradation aqueous pollutants, yet it still suffers from limitations such as weak redox capability, low electrical conductivity and severe charge recombination. In this study, via building a confined environment, the doped-C and nitrogen vacancy (Nv) were simultaneously introduced in g-C3N4 through one-step calcination. Compared to CN-M derived from melamine, the urea-derived CN-U exhibits higher concentrations of doped-C and Nv, which leads to the different band structures. The valence band (VB) and conduction band (CB) of CN-M shift more positively than those for CN-U with ΔEVB and ΔECB being 0.31 and 0.36 eV, respectively. As a result, a Z-type g-C3N4/g-C3N4 homojunction (CN-UM) derived from the mixture of urea and melamine was constructed with the minimum resistance, the lowest charge recombination rate and the high redox capacity retained. The tetracycline degradation efficiency and degradation rate constant by CN-UM coupling with PS reach 99% and 0.08989 min−1, respectively, after irradiation for 60 min, along with the excellent cycling stability. The active species h+, ·O2, ·OH and \(\rm{SO}_{4^{\cdot\,-}}\) S O 4 play roles during the degradation process, with the contributions from h+ and ·O2 higher than those from ·OH and \(\rm{SO}_{4^{\cdot\,-}}\) S O 4 .