Performance study of Fe(III)-doped BiOCl photocatalyst for degradation of tetracycline hydrochloride
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摘要:
光催化技术可以利用太阳能实现难降解污染物的有效降解，具有节能、无毒、成本低等特点，已成为科学家关注和研究的新前沿。BiOCl具有良好的能带结构和独特的层状结构，可实现对有机污染物的有效降解。但是，太阳光利用率低、光生电子-空穴复合率高的问题严重限制其发展及应用。因此，为了提高可见光响应能力并降低光生电子-空穴复合率，有必要对BiOCl进行改性。为克服光催化剂上述缺点，本研究在较短时间内制备了Fe掺杂改性的0.15-Fe/BiOCl材料。Fe的引入显著缩短了禁带宽度，拓宽了其可见光响应范围，降低了光生载流子复合率，有效提高了太阳光利用率以及光生电子-空穴对的分离效率。制备的样品在对盐酸四环素具有优异的去除效果，经暗吸附和光催化过程后去除率可达92%。催化剂失活后，其Fe-O断裂、吸附氧/晶格氧比值升高和晶格氧的大量损失可能会降低其循环性能。文章为制备具有高效光催化活性的过渡金属掺杂BiOCl材料提供了一种有前景的方法，为提高材料的循环活性提供了可行的见解。 0.15-Fe/BiOCl光催化机制示意图(a)；BiOCl和Z-Fe/BiOCl的可见光降解盐酸四环素曲线(b)Schematic diagram of the photocatalytic mechanism of 0.15-Fe/BiOCl(a); Visible light degradation curves of tetracycline hydrochloride by BiOCl and Z-Fe/BiOCl(b) Abstract: Tetracycline hydrochloride (TC-HCl), which can be released into the aquatic environment through excreta, poses a potential threat to aquatic systems and human health due to its stable structure and difficult biodegradability. As one of the photocatalytic materials of great interest, BiOCl development applications are limited by the low solar light utilization and the hight rate of photogenerated electron-hole recombination. In this study, Fe-doped BiOCl porous microspheres self-assembled from two-dimensional nanosbeets were synthesized by a one-pot solvothermal method without the addition of surfactants, and the degradation properties for TC-HCl was investigated. The results showed that Fe doping narrowed the forbidden band width of BiOCl, thereby improving the light absorption intensity and broadening the photoresponse range to the visible region. Fe doping accelerates the separation of photogenerated carriers and improves the photocatalytic performance of BiOCl. The 0.15-Fe/BiOCl has the best removal effect on TC-HCl (30 mg/L), and the removal rate can reach 92% after dark adsorption and photocatalysis. Combined with the experimental results, the mechanism of photocatalytic degradation of TC-HCl by Fe-doped BiOCl under visible light was revealed in this study, and the reasons for the reduction of cycling activity were analyzed, which provided a promising method for the preparation of transition metal-doped BiOCl materials with high photocatalytic activity and feasible insights for improving the cycling activity of materials.-
Key words:
- BiOCl /
- Fe-doped /
- Fe/BiOCl /
- photocatalysis /
- tetracycline hydrochloride
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图 1 BiOCl和0.15-Fe/BiOCl的XRD图谱：5°-80°(a)和32°-34°(b)；FT-IR图谱：4000 cm−1-400 cm−1(c)和600 cm−1-450 cm−1(d)
Figure 1. XRD patterns of BiOCl and 0.15-Fe/BiOCl：5°-80°(a) and 32°-34°(b)；FT-IR patterns of BiOCl and 0.15-Fe/BiOCl：4000 cm−1-400 cm−1 (c) and 600 cm−1-450 cm−1(d)
图 2 BiOCl(a)和0.15-Fe/BiOCl(b)的SEM图像；0.15-Fe/BiOCl的EDS图(c)
Figure 2. SEM image of BiOCl (a) and 0.15-Fe/BiOCl(b)；EDS diagram of 0.15-Fe/BiOCl (c)
图 3 BiOCl和0.15-Fe/BiOCl的N2吸附-解吸等温线曲线(a)和BJH法的孔径分布图(b)
Figure 3. N2 adsorption-desorption isotherm curves of BiOCl and 0.15-Fe/BiOCl (a) and pore size distribution by BJH method (b)
图 4 BiOCl和0.15-Fe/BiOCl的XPS图谱：(a) Bi4f；(b) Cl2p；(c) O1s；(d) Fe2p；(e) 全谱
Figure 4. The XPS spectra of BiOCl and 0.15-Fe/BiOCl samples: (a) Bi4f, (b) Cl2p, (c) O1s, (d) Fe2p, (e) survey spectra respectively
图 5 BiOCl和0.15-Fe/BiOCl的UV-vis DRS图(a)、带隙图(b)、VB-XPS图(c)
Figure 5. UV-Vis diffuse reflectance spectrum(a), band gap diagram(b), and VB-XPS (c) of BiOCl and 0.15-Fe/BiOCl
图 6 BiOCl和0.15-Fe/BiOCl的(a)PC和(b)EIS(Ω)图谱
Figure 6. (a)PC and (b)EIS (Ω) plots of BiOCl and 0.15-Fe/BiOCl
图 7 BiOCl和Z-Fe/BiOCl的可见光降解TC-HCl曲线(a)和对应样品的准一级动力学拟合(b)
Figure 7. Visible light degradation curves of TC-HCl by BiOCl and Z-Fe/BiOCl (a), quasi-first-order kinetic fitting of corresponding samples(b)
图 8 不同TC-HCl浓度下0.15-Fe/BiOCl的可见光降解TC-HCl曲线
Figure 8. TC-HCl concentrations effect of operating conditions on visible light degradation of TC-HCl by 0.15-Fe/BiOCl
图 9 不同pH对0.15-Fe/BiOCl可见光降解TC-HCl (TC-HCl：30 mg/L；光催化剂：0.50 g/L)的影响(a)；不同pH下0.15-Fe/BiOCl的Zeta电位值(b)
Figure 9. pH effect of operating conditions on visible light degradation of TC-HCl by 0.15-Fe/BiOCl (a)；Zeta potential values of 0.15-Fe/BiOCl at different pH(b)
图 10 添加不同捕获剂对0.15-Fe/BiOCl光催化效果的影响(a)；0.15-Fe/BiOCl样品DMPO-•O2−和TEMPO-h+ 的ESR光谱(b)
Figure 10. The effect of adding different capture agents on the photocatalytic effect of 0.15-Fe/BiOCl (a), ESR spectra of DMPO-•O2− and TEMPO-h+ in 0.15-Fe/BiOCl samples (b)
图 11 0.15-Fe/BiOCl光催化机制示意图
Figure 11. Schematic diagram of the photocatalytic mechanism of 0.15-Fe/BiOCl
图 12 0.15-Fe/BiOCl循环性能(a)；首次反应前后0.15-Fe/BiOCl样品的XRD图谱(b)、SEM图(c)和XPS图谱：Bi4f(d)，O1s (e)
Figure 12. Cycle performance of 0.15-Fe/BiOCl(a); XRD patterns (b), SEM patterns(c) and XPS patterns of 0.15-Fe/BiOCl samples before and after the first reaction: Bi4f (d), O1s (e)
表 1 BiOCl和0.15-Fe/BiOCl的SBET、Vp和孔径数据
Table 1. SBET, Vp and pore size data for BiOCl and 0.15-Fe/BiOCl
Sample SBET
/(m²·g−1)Vp
/(cm3·g−1)Pore Size/
nmBiOCl 26.96 0.087 16.65 0.15-Fe/BiOCl 70.75 0.164 11.22 Notes: SBET: Specific surface are; Vp: Total pore volume 
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