Preparation of graphene oxide load Ag3PO4@polyaniline composite and its photocatalytic performance
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摘要: 为了解决Ag3PO4严重的光腐蚀问题，采用化学吸附法制备了核壳结构的聚苯胺(PANI)包覆磷酸银(Ag3PO4@PANI)，并用氧化石墨烯(GO)作为Ag3PO4@PANI复合光催化剂的载体，通过PANI和GO的协同作用提升了载流子的分离效率。当GO与Ag3PO4@PANI质量比为4%时，催化剂在24 min内降解苯酚的去除率可达98.1%，18 min内对环丙沙星(CIP)的去除率可达90.3%，15 min内对四环素(TC)的去除率可达98.6%，在5 min内对各类染料的去除率为100%。经过6次重复反应，Ag3PO4@PANI/GO仍保持较好的稳定性。自由基捕获实验证实•h+和•O2−是光催化降解的主要活性物种。实验结果表明，PANI与Ag3PO4之间形成了核壳结构，GO的引入提升了电子的传输速率，PANI和GO对Ag3PO4的协同作用促进了光生电子-空穴的分离，进而提升了Ag3PO4的稳定性和光催化活性。Abstract: To solve severe photocorrosion of Ag3PO4, which was used to prepare a core-shell Ag3PO4@polyaniline (PANI) composite photocatalyst by chemisorption, and graphene oxide (GO) was used as the carrier of Ag3PO4@PANI composite photocatalyst, reaching the superior carrier separation efficiency via synergetic effect of GO and PANI. The photocatalyst with mass ratio of GO to Ag3PO4@PANI of 4% shows visible light activity for the degradation of phenol, ciprofloxacin (CIP), tetracycline (TC) and dyes of 98.1%, 90.3%, 98.6% and 100% in 24 min, 18 min, 15 min and 5 min, respectively. Even after six repeat reactions, Ag3PO4@PANI/GO still maintain a high degradation rate. The trapping experiments confirm that •h+ and •O2 are the main active species in the photocatalytic degradation. The experimental results show that a core-shell structure is formed between PANI and Ag3PO4, the introduction of GO increases the electron transport rate, and the synergistic effect of PANI and GO on Ag3PO4 promotes the separation of photogenerated electrons and holes, thereby improving the stability of Ag3PO4 and photocatalytic activity.
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Key words:
- Ag3PO4 /
- graphene oxide /
- core-shell /
- photocatalyst /
- degradation /
- phenol /
- antibiotic /
- dye
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图 1 PANI、GO、Ag3PO4、Ag3PO4@PANI和Ag3PO4@PANI/GO的XRD图谱
Figure 1. XRD patterns of PANI, GO, Ag3PO4, Ag3PO4@PANI and Ag3PO4@PANI/GO
图 3 PANI、Ag3PO4、Ag3PO4@PANI和Ag3PO4@PANI/4%GO的FTIR (a) 和Raman图谱 (b)
Figure 3. FTIR (a) and Raman (b) spectra of PANI, Ag3PO4, Ag3PO4@PANI and Ag3PO4@PANI/4%GO
图 4 纯Ag3PO4 (a)、Ag3PO4@PANI (b) 和Ag3PO4@PANI/GO (c) 的SEM图像；Ag3PO4@PANI (d) 和Ag3PO4@PANI/4%GO (e) 的TEM图像；Ag3PO4@PANI/4%GO的EDS能谱图 (f)
Figure 4. SEM images of Ag3PO4 (a), Ag3PO4@PANI (b) and Ag3PO4@PANI/GO (c); TEM images of Ag3PO4@PANI (d) and Ag3PO4@PANI/4%GO (e); EDS spectrum of Ag3PO4@PANI/4%GO (f)
图 6 Ag3PO4和Ag3PO4@PANI/4%GO的N2吸附-解吸等温线
Figure 6. N2 adsorption-desorption isotherms of Ag3PO4 and Ag3PO4@PANI/4%GO
图 7 PANI、Ag3PO4、Ag3PO4@PANI和Ag3PO4@PANI/4%GO的UV-Vis (a)、Kubelka-Munk图 (b)、PL图 (c)、EIS图 (d) 和光电流响应图 (e)
Figure 7. UV-Vis diffuse reflectance spectra (a), plot of (αhν)1/2 vs. hν (b), Photoluminescence spectrum (c), EIS of Nyquist plots (d) and photocurrent responses (e) of PANI, Ag3PO4, Ag3PO4@PANI and Ag3PO4@PANI/4%GO
图 8 PANI、Ag3PO4、Ag3PO4@PANI和Ag3PO4@PANI/GO可见光下降解苯酚曲线 (a)、降解环丙沙星(CIP)曲线 (b)；Ag3PO4@PANI/GO降解四环素(TC)、罗丹明B(RhB)、亚甲基蓝(MB)、亚甲基红(MR)和亚甲基橙 (MO)的曲线 (c)；Ag3PO4@PANI/4%GO降解苯酚 (d)、CIP (e) 和TC (f) 的紫外-可见吸收光谱曲线
Figure 8. Under visible light curves of degradation of phenol (a), curves of degradation of ciprofloxacin (CIP) (b) of PANI, Ag3PO4, Ag3PO4@PANI and Ag3PO4@PANI/GO; Curves of degradation of tetracycline (TC), rhodamine B (RhB), methylene blue (MB), methylene red (MR) and methylene orange (MO) by Ag3PO4@PANI/GO (c); Degradation of phenol (d), CIP (e) and TC (f) by Ag3PO4@PANI/4%GO ultraviolet-visible absorption spectrum curves
Ct—Concentration after time t of degradation; C0—Initial concentration
图 9 Ag3PO4@PANI/4%GO 进行6次光催化循环降解苯酚的图谱 (a)、循环实验前后样品的XRD图谱 (b)
Figure 9. Reusability tests with Ag3PO4@PANI/4%GO using phenol (a) and XRD patterns before and after reusability tests (b)
图 10 (a) Ag3PO4@PANI/4%GO的活性物种捕获实验；(b) Ag3PO4@PANI/4%GO、Ag3PO4和Ag3PO4@PANI的Mott–Schottky曲线
Figure 10. (a) Trapping experiments for active species of Ag3PO4@PANI/4%GO; (b) Mott–Schottky curves obtained for Ag3PO4@PANI/4%GO, Ag3PO4 and Ag3PO4@PANI
AO—Ammonium oxalate; TBA—Tertiary butyl alcohol; PBQ—Benzoquinone; C—Interface capacitance
图 11 Ag3PO4@PANI/GO光催化降解污染物的机制
Figure 11. Schematic illustration of electronehole separation over Ag3PO4@PANI/GO
ECB—Conduction band potential; EVB—Valence band potential; LUMO—Lowest unoccupied molecular orbital; HOMO—Highest occupied molecular orbital
表 1 Ag3PO4@聚苯胺(PANI)/氧化石墨烯(GO)复合材料的命名
Table 1. Naming of Ag3PO4@polyaniline (PANI)/graphene oxide (GO) composites
Sample Mass ratio
of GO/%Mass ratio of
Ag3PO4@PANI/%Ag3PO4@PANI/2%GO 2 100 Ag3PO4@PANI/4%GO 4 100 Ag3PO4@PANI/6%GO 6 100 Ag3PO4@PANI/8%GO 8 100 Ag3PO4@PANI/10%GO 10 100 
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