3D flower-shaped MoS2/O-g-C3N4 Z-type heterojunction enhances the photocatalyst degradation of bisphenol A
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摘要: 光催化降解是一种很有应用前景的污染物处理方法。采用溶剂热法制备了3D/2D二硫化钼负载氧掺杂石墨相氮化碳(MoS2/O-g-C3N4)复合材料，通过XRD、XPS、SEM、TEM、FTIR和PL等表征了MoS2与O-g-C3N4之间Z型异质结的成功构建。在模拟太阳光下，当MoS2的负载量为0.2%时，MoS2/O-g-C3N4的光催化活性最高，双酚A (BPA)的降解率为92.6%，是纯g-C3N4的7倍。此外，MoS2和O-g-C3N4之间界面的紧密接触和相互的协同效应，显著增强了光催化反应活性位点和可见光吸收能力，有效提高了光生载流子的分离。根据液相质谱联用仪(LC-MS)和自由基捕获实验，提出了0.2%MoS2/O-g-C3N4异质结复合材料降解BPA可能的光催化降解机制。本研究为制备高效异质结光催化剂提供了新的方法。Abstract: Photocatalytic degradation was considered as a promising strategy for the elimination of hazardousorganic pollutants. In this work, a binary 3D/2D molybdenum disulfide supported oxygen-doped graphite carbon nitride (MoS2/O-g-C3N4) heterojunctions was successfully fabricated by using a facile hydrothermal strategy. Meanwhile, the as-prepared photocatalysts were characterized by XRD, XPS, SEM, TEM, FTIR and PL. By these characterized observed the formation of Z-type heterojunction between MoS2 and O-g-C3N4. Under visible light irradiation, when the loading of MoS2 was 0.2%, MoS2/O-g-C3N4 exhibited better photocatalytic activity, and the degradation rate of bisphenol A (BPA) is 92.6%, which is 7 times higher than that of pure g-C3N4. In addition, the close contact and mutual synergistic effect of the interface between MoS2 and O-g-C3N4 significantly enhance the photocatalytic reaction active sites and visible light absorption capacity, and effectively improve the separation of photogenerated carriers. Using liquid chromatography-mass spectrometry technology (LC-MS) and capturing experimental results, the possible photocatalytic mechanism of the 0.2%MoS2/O-g-C3N4 heterojunction composite material degrading crystal violet were proposed. This research provides a new method for the preparation of high-efficiency heterojunction photocatalysts.
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Key words:
- MoS2 /
- graphite carbon nitride /
- Z-type heterojunction /
- photocatalysis /
- mutual synergistic
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图 1 (a) 石墨相氮化碳(g-C3N4)、氧掺杂g-C3N4 (O-g-C3N4)、MoS2和X%MoS2/O-g-C3N4的XRD图谱(插图为g-C3N4和O-g-C3N4的放大图)；g-C3N4 (b)、O-g-C3N4 (c) 和0.2%MoS2/O-g-C3N4 (d) 的TEM图像
Figure 1. (a) XRD patterns of graphite carbon nitride (g-C3N4), oxygen-doped g-C3N4 (O-g-C3N4), MoS2 and X%MoS2/O-g-C3N4 (Illustration is an enlarged view of g-C3N4 and O-g-C3N4); TEM images of g-C3N4 (b), O-g-C3N4 (c) and 0.2%MoS2/O-g-C3N4(d)
图 2 (a) 0.2%MoS2/O-g-C3N4的XPS全谱；(b) g-C3N4、O-g-C3N4、MoS2和0.2%MoS2/O-g-C3N4的C1s谱；(c) O-g-C3N4和0.2%MoS2/O-g-C3N4的N1s谱；(d) g-C3N4、O-g-C3N4和0.2%MoS2/O-g-C3N4的O1s谱；(e) MoS2和0.2%MoS2/O-g-C3N4的Mo3d谱；(f) MoS2和0.2%MoS2/O-g-C3N4的S2p谱
Figure 2. (a) XPS survey of 0.2%MoS2/O-g-C3N4; (b) C1s spectra of g-C3N4, O-g-C3N4, MoS2 and 0.2%MoS2/O-g-C3N4; (c) N1s spectra of O-g-C3N4 and 0.2%MoS2/O-g-C3N4; (d) O1s spectra of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4; (e) Mo3d spectrum of MoS2 and 0.2%MoS2/O-g-C3N4; (f) S2p spectra of MoS2 and 0.2%MoS2/O-g-C3N4
图 3 g-C3N4 (a)、O-g-C3N4 (b)、MoS2 (c) 和0.2%MoS2/O-g-C3N4 (d) 的SEM图像；(e) 0.2%MoS2/O-g-C3N4的元素分布图
Figure 3. SEM images of g-C3N4 (a), O-g-C3N4 (b), MoS2 (c) and 0.2%MoS2/O-g-C3N4 (d); (e) Element mapping images of 0.2%MoS2/O-g-C3N4
图 4 (a) g-C3N4、O-g-C3N4和0.2%MoS2/O-g-C3N4的N2吸附-脱附曲线；(b) g-C3N4、O-g-C3N4、MoS2和0.2%MoS2/O-g-C3N4的FTIR图谱
Figure 4. (a) N2 adsorption-desorption isotherms of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4; (b) FTIR spectra of g-C3N4, O-g-C3N4, MoS2 and 0.2%MoS2/O-g-C3N4
SBET—Specific surface area
图 5 (a) g-C3N4、O-g-C3N4和X%MoS2/O-g-C3N4的UV-vis DRS光谱图；(b) O-g-C3N4、MoS2和0.2%MoS2/O-g-C3N4的(αhv)1/2-hv曲线；(c) g-C3N4、O-g-C3N4和0.2%MoS2/O-g-C3N4的PL光谱图；(d) g-C3N4、O-g-C3N4和0.2%MoS2/O-g-C3N4的电化学阻抗图
Figure 5. (a) UV-vis DRS spectra of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4; (b) Plots of (αhv)1/2 versus band-gap energy (hv) of O-g-C3N4, MoS2 and 0.2%MoS2/O-g-C3N4; (c) PL spectra of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4; (d) Nyquist plots of EIS of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4
图 6 (a) g-C3N4、O-g-C3N4、MoS2和X%MoS2/O-g-C3N4的光催化降解图；(b) g-C3N4、O-g-C3N4、MoS2和X%MoS2/O-g-C3N4的降解动力学曲线；(c) 0.2%MoS2/O-g-C3N4催化剂循环实验；(d) 0.2%MoS2/O-g-C3N4循环前后的XRD图谱；(e) 0.2%MoS2/O-g-C3N4循环前后的FTIR图谱
Figure 6. Photocatalytic degradation diagrams of g-C3N4, O-g-C3N4, MoS2 and X%MoS2/O-g-C3N4; (b) Degradation kinetic curves of g-C3N4, O-g-C3N4, MoS2 and X%MoS2/O-g-C3N4; (c) 0.2%MoS2/O-g-C3N4 catalyst cycle test; (d) XRD patterns before and after cycles of 0.2%MoS2/O-g-C3N4; (e) FTIR spectra before and after cycles of 0.2%MoS2/O-g-C3N4
C—Bisphenol A (BPA) concentration after t time; C0—BPA concentration at the initial time; K—Speed constant; R2—Fit coefficient
图 7 0.2%MoS2/O-g-C3N4复合材料双酚A (BPA)可能的降解途径
Figure 7. Possible degradation pathway of bisphenol A (BPA) under 0.2%MoS2/O-g-C3N4 system
m/z—Relative molecular mass
图 8 不同自由基捕获剂对BPA光降解速率的影响
Figure 8. Effect on photo-degradation rate of BPA with different radical scavengers
BQ—Benzoquinone; EDTA-2Na—Ethylenediaminetetraacetic acid disodium salt; IPA—Isopropanol
图 9 0.2%MoS2/O-g-C3N4对BPA降解机制图的推断
Figure 9. Proposed mechanism of the photocatalytic photodegradation of BPA on 0.2%MoS2/O-g-C3N4
NHE—Normal hydrogen electrode
表 1 g-C3N4、O-g-C3N4和0.2%MoS2/O-g-C3N4的质构特性
Table 1. Textural properties of g-C3N4, O-g-C3N4 and 0.2%MoS2/O-g-C3N4
Sample SBET/(m2·g−1) Pore size/nm g-C3N4 14.94 0.092 O-g-C3N4 48.28 0.313 0.2%MoS2/O-g-C3N4 39.89 0.228 
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