超分子前驱体制备磷掺杂三维g-C3N4及光催化性能
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辽宁石油化工大学

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X703;O644.1

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辽宁省教育厅2022年度科研项目 项目编号:LJKMZ20220721


Supramolecular precursors for the preparation of phosphorus-doped three-dimensional g-C3N4 and photocatalytic performance
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LiaoNing Petrochemical University

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    摘要:

    采用超分子自组装法和化学沉淀法,以三聚氰胺、三聚氰酸为原料,以磷酸铵为P掺杂剂,制备P掺杂三维石墨相氮化碳(g-C3N4)MNP-x(x表示当三聚氰胺为0.01 mol时磷酸铵的添加质量,下同),通过XRD、FTIR、XPS、SEM、UV-Vis和光致发光(PL)等对MNP-x进行表征,运用光催化降解染料罗丹明B(RhB)反应来评价MNP-x的光催化性能,使用自由基捕获剂验证光催化反应中起作用的活性基团,并推测反应机理。结果表明,最佳条件下制备的MNP-0.08,相较未掺杂P的g-C3N4(MN),SEM显示,MNP-0.08形貌由一维管状变为三维花束状;XPS证实,P原子取代部分C原子掺杂到g-C3N4结构单元;PL显示,MNP-0.08提高了电子-空穴对(e--h+)的分离能力;UV-Vis显示,MNP-0.08改变了能带结构,价带(VB)从1.96 eV变为2.00 eV,导带(CB)从0.7 eV变为0.75 eV,,能带间隙值(Eg)从2.66 eV变为2.75 eV;经验证,?O2-作为主要的活性基团使MNP-0.08光催化降解RhB能力得到提高,反应速率常数(k)为0.02816 min-1,是MN(k=0.00955 min-1)的2.95倍;能带结构改变、P作为富电子中心促进载流子分离和P掺杂诱导高电荷转移并使受激电子局部化,这三种协同效应使MNP比MN具备更高的光催化性能。

    Abstract:

    Supramolecular self-assembly and chemical precipitation methods were used to prepare P-doped three-dimensional graphitic phase carbon nitride (g-C3N4) MNP-x using melamine and cyanuric acid as raw materials and ammonium phosphate as a P-dopant (x denotes the added mass of ammonium phosphate when the melamine is 0.01 mol, the same below), and characterisation of MNP-x was performed by XRD, FTIR, XPS, SEM, UV-Vis and photoluminescence (PL), etc. The photocatalytic degradation of the dye rhodamine B (RhB) reaction was applied to evaluate the photocatalytic performance of MNP-x. A free radical trapping agent was used to verify the reactive groups that play a role in the photocatalytic reaction and to speculate the reaction mechanism. The results showed that MNP-0.08 prepared under optimal conditions, compared to the undoped P-doped g-C3N4(MN), SEM showed that the MNP-0.08 morphology changed from a one-dimensional tubular to a three-dimensional bouquet; XPS confirmed that the P atoms replaced some of the C atoms doped into the g-C3N4 structural unit; PL showed that MNP-0.08 improved the electron-hole pair (e-,h+) separation; UV-Vis showed that MNP-0.08 changed the energy band structure, the valence band (VB) from 1.96 eV to 2.00 eV, and the conduction band (CB) from 0.7 eV to 0.75 eV,,and the energy band gap value (Eg) from 2.66 eV to 2.75 eV; it was verified that -O2- as the main reactive group makes the MNP-0.08 photocatalytic degradation of RhB was improved with a reaction rate constant (k) of 0.02816 min-1, which was 2.95 times higher than that of MN (k=0.00955 min-1); the synergistic effects of the change in energy band structure, P as an electron-rich centre to promote carrier separation, and P doping to induce a high charge transfer and localize excited electrons made MNP possess a much higher photocatalytic performance than MN with higher photocatalytic performance.

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刘京津,赵 华,李会鹏,蔡天凤.超分子前驱体制备磷掺杂三维g-C3N4及光催化性能[J].精细化工,2024,41(7):

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  • 收稿日期:2023-07-07
  • 最后修改日期:2023-10-23
  • 录用日期:2023-10-09
  • 在线发布日期: 2024-07-11
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