坡缕石-Cd<sub>0.5</sub>Zn<sub>0.5</sub>S/Zn-Fe LDH复合材料的制备及其光催化性能

胡美凤; 唐忠家; 文娜; 常玥; 查飞

doi:10.13801/j.cnki.fhclxb.20220705.003

坡缕石-Cd_0.5Zn_0.5S/Zn-Fe LDH复合材料的制备及其光催化性能

doi: 10.13801/j.cnki.fhclxb.20220705.003

胡美凤¹,
唐忠家¹,
文娜¹,
常玥^{1, 2, 3, ,},
查飞¹

1.
西北师范大学　化学化工学院，兰州 730070
2.
生态功能高分子材料教育部重点实验室，兰州 730070
3.
甘肃省高分子材料重点实验室，兰州 730070

基金项目: 国家自然科学基金(21865031)

详细信息

通讯作者:
常玥，博士，教授，硕士生导师，研究方向为功能材料的制备及应用　E-mail: cy70@sin.com

中图分类号: O611.3；TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2022-05-18
- 修回日期: 2022-06-21
- 录用日期: 2022-06-24
- 网络出版日期: 2022-07-06
- 刊出日期: 2023-05-15

Preparation of palygorskite-Cd_0.5Zn_0.5S/Zn-Fe LDH composite and its photocatalytic performance

HU Meifeng¹,
TANG Zhongjia¹,
WEN Na¹,
CHANG Yue^{1, 2, 3
, ,},
ZHA Fei¹

1.
College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, China
2.
Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Lanzhou 730070, China
3.
Key Laboratory of Polymer Materials of Gansu Province, Lanzhou 730070, China

Funds: National Natural Science Foundation of China (21865031)

摘要

摘要: 为解决Cd_0.5Zn_0.5S易光腐蚀的缺点，两步水热法制备了坡缕石(PGS)负载Cd_0.5Zn_0.5S/Zn-Fe 层状双金属氢氧化物(LDH)复合材料(PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH)，通过Zn-Fe LDH和PGS提高光生载流子的分离效率。利用XRD、SEM、TEM、UV-Vis DRS和PL对材料的结构、形貌及光学性能进行了表征。电镜图像显示，片状Zn-Fe LDH表面附着针状PGS与颗粒状Cd_0.5Zn_0.5S。紫外-可见漫反射光谱表明PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH吸光区域比Cd_0.5Zn_0.5S宽，吸收边缘从560 nm红移至605 nm。PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH在光催化降解结晶紫(CV)中表现出良好的光催化活性，催化活性高于Cd_0.5Zn_0.5S和Zn-Fe LDH。当PGS 与Cd_0.5Zn_0.5S/Zn-Fe LDH质量比为50%时，可见光照射60 min， 20 mg PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH对20 mg/L结晶紫溶液的去除率为97.5%，${\text{•}} {\rm{O}}_2^{-}$、•OH是光催化降解的主要活性物种，且5次循环实验后仍然保持较高活性。此外，制备的复合材料对孔雀石绿(MG)、酸性品红(AF)、罗丹明B(RhB)、甲基橙(MO)、亚甲基蓝(MB)等染料均表现出较好的光降解效果。
- Cd_0.5Zn_0.5S/Zn-Fe LDH /
- 坡缕石 /
- 光催化剂 /
- 降解 /
- 染料
Abstract: To solve easy photocorrosion of Cd_0.5Zn_0.5S, palygorskite (PGS) supported Cd_0.5Zn_0.5S/Zn-Fe layered double hydroxides (LDH) composites (PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH) were prepared by a two-step hydrothermal method. The aim is to improve the separation efficiency of photogenerated carriers using Zn-Fe LDH and PGS. Its crystal phase, micromorphology and optical properties were characterized by XRD, SEM, TEM, UV-Vis DRS and PL. The electron microscope images show that the needle-like PGS and graininess Cd_0.5Zn_0.5S are attached on the surface of Zn-Fe LDH. UV-visible diffuse reflectance spectroscopies confirm that the PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH has a wider absorption range than Cd_0.5Zn_0.5S. That absorption range has a red shift from 560 nm to 605 nm. The photocatalytic activity of PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH is higher than those of Cd_0.5Zn_0.5S and Zn-Fe LDH in the degradation of crystal violet. The photocatalyst with mass ratio of PGS to Cd_0.5Zn_0.5S/Zn-Fe LDH of 50%, the removal rate of 20 mg/L crystal violet is 97.5% by 20 mg of PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH for 60 min. ${\text{•}}{\rm{O}}_2^{-} $ and •OH groups are the main active species in photodegradatlon reaction. The photocatalytic activity of composite is well retained after five cycles. Meanwhile, the composite shows good photocatalytic activity in the degradations of various dyes including malachite green (MG), acid fuchsin (AF), Rhodamine B (RhB), methyl orange (MO) and methylene blue (MB).
- Cd_0.5Zn_0.5S/Zn-Fe LDH /
- palygorskite /
- photocatalyst /
- degradation /
- dye

HTML全文

图 1 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3、Cd_0.5Zn_0.5S/Zn-Fe LDH 3、Cd_0.5Zn_0.5S、Zn-Fe LDH和PGS的XRD图谱

Figure 1. XRD patterns of 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3, Cd_0.5Zn_0.5S/Zn-Fe LDH 3, Cd_0.5Zn_0.5S, Zn-Fe LDH and PGS

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图 2 Zn-Fe LDH (a)、Cd_0.5Zn_0.5S (b)、Cd_0.5Zn_0.5S/Zn-Fe LDH 3 (c)、PGS (d)和50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3 (e)的SEM图像；50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3的TEM图像((f), (g))及EDS能谱图(h)

Figure 2. SEM images of Zn-Fe LDH (a), Cd_0.5Zn_0.5S (b), Cd_0.5Zn_0.5S/Zn-Fe LDH 3 (c), PGS (d) and 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3 (e); TEM images ((f), (g)) and EDS spectrum (h) of 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3

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图 3 不同光催化材料的紫外-可见漫反射光谱(a)和相应的禁带宽度图(b)

α—Absorption coefficient; hν—Photon energy

Figure 3. UV-vis DRS (a) and band gap diagram (b) of different materials

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图 4 Zn-Fe LDH、Cd_0.5Zn_0.5S、Cd_0.5Zn_0.5S/Zn-Fe LDH及50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3的光致发光光谱

Figure 4. PL spectra of Zn-Fe LDH, Cd_0.5Zn_0.5S, Cd_0.5Zn_0.5S/Zn-Fe LDH and 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3

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图 5 Cd_0.5Zn_0.5S、Zn-Fe LDH和Cd_0.5Zn_0.5S/Zn-Fe LDH复合材料对染料的光催化活性((a), (b))及光催化降解反应动力学(c)

Figure 5. Photocatalytic activity of Cd_0.5Zn_0.5S, Zn-Fe LDH and Cd_0.5Zn_0.5S/Zn-Fe LDH composites for dyes ((a), (b)) and photocatalytic degradation reaction kinetics (c)

C_t—Concentration after time t of degradation; C₀—Initial concentration; MB—Methylene blue; CV—Crystal violet; RhB—Rhodamine B; AF—Acid fuchsin; MG—Malachite green; MO—Methyl orange

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图 6 PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3对CV的光催化活性(a)及50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3对染料降解率(b)

TC—Tetracycline

Figure 6. Photocatalytic activity of PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3 on CV (a) and removal rate of 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3 for dyes (b)

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图 7 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3光催化循环实验

Figure 7. Photocatalysis cycle experiment of 50%PGS-Cd_0.5Zn_0.5S/ Zn-Fe LDH 3

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图 8 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3对混合染料的降解(a)及紫外-可见光谱(b)

Figure 8. Degradation of mixed dyes by 50%PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH 3 (a) and UV-Vis spectra (b)

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图 9 Cd_0.5Zn_0.5S (a)和Zn-Fe LDH (b)的MS图谱

Figure 9. MS maps of Cd_0.5Zn_0.5S (a) and Zn-Fe LDH (b)

C⁻²—Space charge capacitance

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图 10 PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH的活性物种捕获实验

EDTA-2Na—Ethylenediamine tetraacetic acid disodium salt; BQ—Benzoquinone; IPA—Isopropyl alcohol

Figure 10. Trapping experiments for active species of PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH

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图 11 PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH光催化降解CV的机制

NHE—Normal hydrogen electrode

Figure 11. Photocatalytic degradation mechanism of CV by PGS-Cd_0.5Zn_0.5S/Zn-Fe LDH

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表 1 Cd_0.5Zn_0.5S/Zn-Fe层状双金属氢氧化物(LDH)复合材料的命名

Table 1. Nomenclature of Cd_0.5Zn_0.5S/Zn-Fe layered double hydroxides (LDH) composites

Sample	Mass of Zn-Fe LDH/g	Mass ratio of Cd_0.5Zn_0.5S to Zn-Fe LDH
Cd_0.5Zn_0.5S/Zn-Fe LDH 1	0.052	7∶1
Cd_0.5Zn_0.5S/Zn-Fe LDH 2	0.104	7∶2
Cd_0.5Zn_0.5S/Zn-Fe LDH 3	0.156	7∶3
Cd_0.5Zn_0.5S/Zn-Fe LDH 4	0.208	7∶4
Cd_0.5Zn_0.5S/Zn-Fe LDH 5	0.260	7∶5

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表 2 坡缕石(PGS)-Cd_0.5Zn_0.5S/Zn-Fe LDH复合材料的命名

Table 2. Naming of palygorskite (PGS)-Cd_0.5Zn_0.5S/Zn-Fe LDH composites

Sample	Mass ratio of PGS/wt%	Mass ratio of Cd_0.5Zn_0.5S/ Zn-Fe LDH 3/wt%
30%PGS-Cd_0.5Zn_0.5S/ Zn-Fe LDH 3	30	100
40%PGS-Cd_0.5Zn_0.5S/ Zn-Fe LDH 3	40	100
50%PGS-Cd_0.5Zn_0.5S/ Zn-Fe LDH 3	50	100
60%PGS-Cd_0.5Zn_0.5S/ Zn-Fe LDH 3	60	100

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