Performance study of Fe(III)-doped BiOCl photocatalyst for degradation of tetracycline hydrochloride
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摘要: 盐酸四环素(TC-HCl)结构稳定，可通过排泄物释放到水环境，对水生系统和人体健康构成潜在威胁。BiOCl作为备受关注的光催化材料之一，太阳光利用率低和光生电子-空穴对复合率高的问题限制了其发展应用。本文在不添加表面活性剂的情况下，采用一锅溶剂热法合成了由二维纳米片自组装的Fe掺杂BiOCl多孔微球，研究其对TC-HCl的降解性能。结果表明：Fe掺杂缩小了BiOCl的禁带宽度，从而提高其光吸收强度并拓宽其光响应范围至可见光区；Fe掺杂加速了光生载流子的分离，提升了BiOCl的光催化性能。制得的0.15-Fe/BiOCl对TC-HCl (30 mg/L)的去除效果最佳，经暗吸附和光催化过程后去除率可达92%。本文结合实验结果阐述了Fe掺杂BiOCl在可见光下光催化降解TC-HCl的机制，分析了导致循环活性降低的原因，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，并为改善材料循环活性提供了可行的见解。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 accelerated the separation of photogenerated carriers and improved the photocatalytic performance of BiOCl. The 0.15-Fe/BiOCl had the best removal effect on TC-HCl (30 mg/L), and the removal rate could 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 is revealed in this study, and the reasons for the reduction of cycling activity are analyzed, which provides 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.
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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)；BiOCl和0.15-Fe/BiOCl的FTIR图谱：4000~400 cm−1 (c)和600~450 cm−1 (d)
Figure 1. XRD patterns of BiOCl and 0.15-Fe/BiOCl：5°-80° (a) and 32°-34° (b); FTIR spectra of BiOCl and 0.15-Fe/BiOCl：4000-400 cm−1 (c) and 600-450 cm−1 (d)
图 2 BiOCl (a)和0.15-Fe/BiOCl (b)的SEM图像；(c) 0.15-Fe/BiOCl的EDS图像
Figure 2. SEM images of BiOCl (a) and 0.15-Fe/BiOCl (b); (c) EDS diagram of 0.15-Fe/BiOCl
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. XPS spectra of BiOCl and 0.15-Fe/BiOCl sample: (a) Bi4f; (b) Cl2p; (c) O1s; (d) Fe2p; (e) Survey spectra
图 5 BiOCl和0.15-Fe/BiOCl的UV-Vis DRS图谱(a)、带隙图(b)、VB-XPS图(c)
α—Absorption coefficient; h—Planck constant; ν—Frequency
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的瞬态光电流响应(PC) (a)和电化学阻抗谱(EIS) (b)
Figure 6. Transient photocurrent responses (PC) (a) and electrochemical impedance spectra (EIS) (b) of BiOCl and 0.15-Fe/BiOCl
图 7 BiOCl和Z-Fe/BiOCl的可见光降解盐酸四环素(TC-HCl) 曲线(a)和对应样品的准一级动力学拟合(b)
Ct/C0—Photocatalytic activity of TC-HCl degradation; k—Apparent rate constants
Figure 7. Visible light degradation curves (a) and quasi-first-order kinetic fitting (b) of tetracycline hydrochloride (TC-HCl) by BiOCl and Z-Fe/BiOCl
图 8 不同TC-HCl浓度下0.15-Fe/BiOCl的可见光降解曲线
Figure 8. TC-HCl concentrations effect of operating conditions on visible light degradation by 0.15-Fe/BiOCl
图 9 (a) 不同pH对0.15-Fe/BiOCl可见光降解TC-HCl的影响；(b) 不同pH下0.15-Fe/BiOCl的Zeta电位值
pHZPC—pH of the zero point of charge
Figure 9. (a) pH effect of operating conditions on visible light degradation of TC-HCl by 0.15-Fe/BiOCl; (b) Zeta potential values of 0.15-Fe/BiOCl at different pH
图 10 (a) 添加不同捕获剂对0.15-Fe/BiOCl光催化效果的影响；(b) 0.15-Fe/BiOCl样品5, 5-二甲基-1-吡咯啉-N-氧化物(DMPO)-•O2 −和2, 2, 6, 6-四甲基-4-甲基哌啶(TEMPO)-h+ 的ESR图谱
IPA—Isopropyl alcohol; SO—Sodium oxalate; AA—Ascorbic acid
Figure 10. (a) Effect of adding different capture agents on the photocatalytic effect of 0.15-Fe/BiOCl; (b) ESR spectra of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO)-•O2 − and 2, 2, 6, 6-tetramethylpiperidine (TEMPO)-h+ in 0.15-Fe/BiOCl samples
图 11 0.15-Fe/BiOCl光催化机制示意图
TCH+—Oxidised products of TC-HCl; Eg—Band gap; CB—Conductionband; VB—Valence band
Figure 11. Schematic diagram of the photocatalytic mechanism of 0.15-Fe/BiOCl
图 12 (a) 0.15-Fe/BiOCl循环性能；首次反应前后0.15-Fe/BiOCl样品的XRD图谱(b)、SEM图像(c)和XPS图谱：Bi4f (d)；O1s (e)
Figure 12. (a) Cycle performance of 0.15-Fe/BiOCl; XRD patterns (b), SEM images (c) and XPS spectra of 0.15-Fe/BiOCl samples before and after the first reaction: Bi4f (d), O1s (e)
表 1 BiOCl和0.15-Fe/BiOCl的比表面积(SBET)、孔容(Vp)和孔径数据
Table 1. Specific surface area (SBET), total pore volume (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 
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