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内电场增强S型异质结N-C3N4/BiOClxI1−x的制备及其光催化性能

徐凯旋 亢玉龙 高晓明 贺红斌 袁中强 胡亚楠

徐凯旋, 亢玉龙, 高晓明, 等. 内电场增强S型异质结N-C3N4/BiOClxI1−x的制备及其光催化性能[J]. 复合材料学报, 2023, 40(9): 5134-5144. doi: 10.13801/j.cnki.fhclxb.20221209.002
引用本文: 徐凯旋, 亢玉龙, 高晓明, 等. 内电场增强S型异质结N-C3N4/BiOClxI1−x的制备及其光催化性能[J]. 复合材料学报, 2023, 40(9): 5134-5144. doi: 10.13801/j.cnki.fhclxb.20221209.002
XU Kaixuan, KANG Yulong, GAO Xiaoming, et al. Preparation of S-type heterojunction N-C3N4/BiOClxI1−x with internal electric field and enhanced photocatalytic properties[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5134-5144. doi: 10.13801/j.cnki.fhclxb.20221209.002
Citation: XU Kaixuan, KANG Yulong, GAO Xiaoming, et al. Preparation of S-type heterojunction N-C3N4/BiOClxI1−x with internal electric field and enhanced photocatalytic properties[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5134-5144. doi: 10.13801/j.cnki.fhclxb.20221209.002

内电场增强S型异质结N-C3N4/BiOClxI1−x的制备及其光催化性能

doi: 10.13801/j.cnki.fhclxb.20221209.002
基金项目: 陕西省自然科学基金(2022 QFY07-03)
详细信息
    通讯作者:

    高晓明,博士,教授,硕士生导师,研究方向为光催化 E-mail:ydgaoxm@126.com

  • 中图分类号: X75;TB332

Preparation of S-type heterojunction N-C3N4/BiOClxI1−x with internal electric field and enhanced photocatalytic properties

Funds: Natural Science Foundation of Shaanxi Province (2022 QFY07-03)
  • 摘要: 采用一步水热法使固溶体BiOClxI1−x静电自组装在N掺杂的氮化碳(N-C3N4)表面,制备了N-C3N4/BiOClxI1−x S型异质结。通过XRD、XPS、SEM、TEM、FTIR、UV-Vis等技术对样品的晶型、形貌、结构、元素组成、表面官能团、光学性质等进行了表征,并考察了N-C3N4/BiOClxI1−x光催化氧化有机污染物与还原Cr(VI)的活性。结果表明,N-C3N4/BiOClxI1−x具有强的光吸收,在N-C3N4与BiOClxI1−x界面处形成的内电场抑制了电子-空穴对的复合。在可见光照射下,20%N-BiOCl0.5I0.5呈现出优异的光催化活性,2.5 h内苯酚的降解率达到98.53%;1 h内Cr(VI)的还原率达到99.11%。20%N-BiOCl0.5I0.5在5次循环后表现出良好的稳定性。3 h内20%N-BiOCl0.5I0.5可见光降解苯酚的总有机碳(TOC)去除率为80.21%。结合捕获实验、ESR、DFT计算等表明,N-C3N4/BiOClxI1−x活性归因于S型异质结的形成、N-C3N4和BiOClxI1−x之间的内部电场及能带弯曲和库仑力的存在,加速了光生载流子的空间分离和有序电子流。

     

  • 图  1  (a) BiOClxI1−x的XRD图谱;(b) BiOClxI1−x在2θ=25°~37°的XRD图谱;(c) N-C3N4/BiOClxI1−x的XRD图谱;(d) 样品的FTIR图谱;(e) N-C3N4的Zeta谱图;(f) BiOCl0.5I0.5的Zeta谱图

    Figure  1.  (a) XRD patterns of BiOClxI1−x; (b) XRD patterns of BiOClxI1−x at 2θ=25°-37°; (c) XRD patterns of N-C3N4/BiOClxI1−x; (d) FTIR spectra of the as-prepared samples; (e) Zeta spectra of N-C3N4; (f) Zeta spectra of BiOCl0.5I0.5

    图  2  BiOCl0.5I0.5和20%N-BiOCl0.5I0.5的HR-XPS图谱

    Figure  2.  HR-XPS spectra of BiOCl0.5I0.5 and 20%N-BiOCl0.5I0.5

    图  3  BiOI (a)、BiOCl0.5I0.5 (b) 的SEM图像;(c) 20%N-BiOCl0.5I0.5局部放大图像

    Figure  3.  SEM images of BiOI (a), BiOCl0.5I0.5 (b); (c) Partial enlargement of 20%N-BiOCl0.5I0.5

    d—Thickness of nanosheets

    图  4  ((a)~(c)) 20%N-BiOCl0.5I0.5的TEM图像;((d)~(j)) 20%N-BiOCl0.5I0.5的EDS图谱、Bi、Cl、O、I、N、C图谱

    Figure  4.  ((a)-(c)) TEM images of 20%N-BiOCl0.5I0.5; ((d)-(j)) EDS, Bi, Cl, O, I, N and C mapping of 20%N-BiOCl0.5I0.5

    图  5  (a) N-BiOClxI1−x的UV-Vis漫反射图谱;(b) BiOClxI1−x的带隙

    Figure  5.  (a) UV-Vis DRS diffuse reflection map of N-BiOClxI1−x; (b) Band gap of N-BiOClxI1−x

    图  6  N-C3N4 (a) 和BiOCl0.5I0.5 (b) 的Mott-Schottky曲线;(c) 能带结构

    Figure  6.  Mott-Schottky curves N-C3N4 (a) and BiOCl0.5I0.5 (b); (c) Band structure

    C−2—Interfacial capacitance

    图  7  (a) 苯酚的光催化降解曲线;((b), (c))光催化还原六价铬曲线和表观速率常数;(d) 20%N-BiOCl0.5I0.5循环降解苯酚稳定性测试;(e) 20%N-BiOCl0.5I0.5在5个循环前后的XRD图谱;(f) 20%N-BiOCl0.5I0.5可见光降解苯酚的TOC去除率

    Figure  7.  (a) Photocatalytic degradation curve of phenol; ((b), (c)) Photocatalytic reduction curve and apparent rate constant of Cr(Ⅵ); (d) Recycling use of 20%N-BiOCl0.5I0.5 for phenol degradation; (e) XRD patterns of before and after five cycles of 20%N-BiOCl0.5I0.5 for for phenol degradation; (f) Removal rate of TOC of phenol over 20%N-BiOCl0.5I0.5

    C0—Initial solution concentration; Ct—Solution concentration at time t; K—Apparent rate constant; TOC0—Total organic carbon of initial solution; TOC—Total organic carbon of solution at time t

    图  8  20%N-BiOCl0.5I0.5的•O2测试 (a)、•OH测试 (b)、h+测试 (c)

    Figure  8.  ESR spectra of •O2(a), •OH(b), h+ (c) of 20%N-BiOCl0.5I0.5

    图  9  (a) N-C3N4理论模型;(b) N-C3N4的功函数;(c) BiOCl0.5I0.5的功函数;((d)~(e)) 20%N-BiOCl0.5I0.5三维电子密度差图

    Figure  9.  (a) N-C3N4 theoretical model; (b) N-C3N4 of work function calculation; (c) BiOCl0.5I0.5 of work function calculation; ((d)-(e)) Three-dimensional charge density differences of 20%N-BiOCl0.5I0.5

    Φ—Work function

    图  10  光催化降解机制图:(a) II型异质结;(b) S型异质结

    Figure  10.  Photocatalytic degradation mechanism: (a) Type II heterojunction; (b) S-scheme heterojunction

    NHE—Normal hydrogen electrode; IEF—Inerenal Electric Field; EVAC—Vacuum level; Ef—Flat band potential; Eg—Energy band

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出版历程
  • 收稿日期:  2022-10-17
  • 修回日期:  2022-11-20
  • 录用日期:  2022-11-26
  • 网络出版日期:  2022-12-12
  • 刊出日期:  2023-09-15

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