漂浮型Ag2CrO4-g-C3N4-TiO2/膨胀珍珠岩可见光催化材料除藻性能

宋靖珂; 王学江; 王佳忆; 王鑫

doi:10.13801/j.cnki.fhclxb.20200928.006

漂浮型Ag₂CrO₄-g-C₃N₄-TiO₂/膨胀珍珠岩可见光催化材料除藻性能

doi: 10.13801/j.cnki.fhclxb.20200928.006

宋靖珂^1,,
王学江^2, ,,
王佳忆^2,,
王鑫^3,

1.
河南师范大学　环境学院，黄淮水环境与污染防治教育部重点实验室，河南省环境污染控制重点实验室，新乡 453007
2.
同济大学　环境科学与工程学院，污染控制与资源化国家重点实验室，上海 200092
3.
华南师范大学　物理与电信工程学院，广东省高效绿色能源与环保材料工程技术研究中心，广东省量子调控工程与材料重点实验室，广州 510006

基金项目: 河南师范大学博士科研启动项目(5101219170135)；河南师范大学博士后科研经费(5101219470222)

详细信息

通讯作者:
王学江，教授，研究方向为水污染控制及资源化利用　E-mail：wangxj@tongji.edu.cn

中图分类号: X524；O643.36；O644.1
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出版历程
- 收稿日期: 2020-07-23
- 录用日期: 2020-09-24
- 网络出版日期: 2020-09-29
- 刊出日期: 2021-06-23

Photocatalytic inactivation of algae using floating visible-light-responsive photocatalyst Ag₂CrO₄-g-C₃N₄-TiO₂/modified expanded perlite

SONG Jingke^1
,,
WANG Xuejiang^{2
, ,},
WANG Jiayi^2
,,
WANG Xin^3
,

1.
Henan Key Laboratory for Environmental Pollution Control, Key Laboratory of Yellow River and Huai River Water Environment and Pollution Control, Ministry of Education, School of Environment, Henan Normal University, Xinxiang 453007, China
2.
State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
3.
Guangdong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, Guangdong Engineering Technology Research Center of Efficient Green Energy and Environment Protection Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006, China

摘要

摘要: 以Al₂O₃改性的膨胀珍珠岩(mEP)为载体，采用溶胶凝胶-浸渍沉积法制备Ag₂CrO₄-g-C₃N₄-TiO₂/mEP漂浮型可见光催化材料。对制备的光催化材料使用XRD、N₂吸附/脱附、FESEM-EDS、XPS和UV-vis DRS等分析方法进行材料表征。实验结果表明，不同的Ag₂CrO₄含量可对复合催化剂的晶型和比表面积产生影响，过高的Ag₂CrO₄可在催化剂的表面形成团聚颗粒不利于催化剂对藻细胞的吸附和光催化灭活。以铜绿微囊藻为处理对象，光催化剂中Ag₂CrO₄/TiO₂的理论摩尔比为0.05，初始藻细胞浓度为2.75×10⁶ cells/mL时，单纯暗吸附8 h藻细胞的去除率为10.3%，在吸附和光催化的协同作用下，藻细胞的去除率可达81.88%。光催化除藻过程中起主要作用的为光生空穴h⁺，该催化剂在重复利用三次后对藻细胞仍有72.19%的去除率，催化剂有较好的稳定性。
- Ag₂CrO₄ /
- g-C₃N₄ /
- 可见光催化 /
- 漂浮 /
- 除藻
Abstract: Based on Al₂O₃ modified expanded perlite (mEP), floating visible-light responsive photocatalysts Ag₂CrO₄-g-C₃N₄-TiO₂/mEP were prepared via a sol-gel-impregnation deposition method. The synthesized photocatalysts were characterized using XRD, N₂ adsorption/desorption, FESEM-EDS, XPS and UV-vis DRS. The results show that the concentration of Ag₂CrO₄ has influence on the crystal structure and specific surface area of the photocatalysts. High concentration of Ag₂CrO₄could form agglomerated particles on the surface of the photocatalyst which are not conductive to the adsorption and photocatalytic inactivation of algae. When the theoretical molar ratio of Ag₂CrO₄/TiO₂ is 0.05 and the initial algal cell concentration of Microcystis aeruginosa is 2.75×10⁶ cells/mL, the removal rate of algal after adsorption for 8 h was 10.3%. Under the synergistic effect of adsorption and photocatalysis, the removal rate of algal could reach 81.88%. The inactivation of algae cell mainly ascribed to the attack by the photo-generated holes (h⁺). The removal rate of algae could reach to 72.19% after three successive cycles which indicated the stability of the photocatalst.
- Ag₂CrO₄ /
- g-C₃N₄ /
- visible-light photocatalysis /
- floating /
- algae removal

HTML全文

图 1 TiO₂/Al₂O₃改性膨胀珍珠岩(mEP)、g-C₃N₄-TiO₂/mEP及Ag₂CrO₄-g-C₃N₄-TiO₂/mEP系列材料的XRD图谱 (a)，EP、mEP及Ag₂CrO₄-g-C₃N₄-TiO₂/mEP系列材料的N₂吸附脱附曲线 (b)

Figure 1. XRD patterns of TiO₂/Al₂O₃ modified expanded perlite (mEP), g-C₃N₄-TiO₂/mEP and Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-x% (x=1, 5, 10, 15) (a) , N₂ sorption-desorption isotherms of EP, mEP and Ag₂CrO₄-g-C₃N₄-TiO₂/mEP- x% (x=1, 5, 10, 15) (b)

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图 2 Ag₂CrO₄与TiO₂不同摩尔比的Ag₂CrO₄-g-C₃N₄-TiO₂/mEP复合材料的FESEM图像

Figure 2. FESEM images of Ag₂CrO₄-g-C₃N₄-TiO₂/mEP with different Ag₂CrO₄toTiO₂ mole ratios ((a) 1%; (b) 5%; (c) 10%; (d) 15%)

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图 3 Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5%的SEM图像 (a)及Ag (b)、Cr (c) 和Ti (d) 的面扫描能谱图

Figure 3. SEM image of Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5% (a) and element mapping of Ag (b), Cr (c) and Ti (d)

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图 4 Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5%的XPS图谱

Figure 4. XPS spectra of Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5%

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图 5 TiO₂/mEP、g-C₃N₄-TiO₂/mEP及Ag₂CrO₄-g-C₃N₄-TiO₂/mEP系列材料的紫外-可见光吸收光谱

Figure 5. UV-vis diffuses reflectance spectra of TiO₂/mEP, g-C₃N₄-TiO₂/mEP and Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-x% (x=1, 5, 10, 15)

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图 6 TiO₂/mEP、g-C₃N₄-TiO₂/mEP及Ag₂CrO₄-g-C₃N₄-TiO₂/mEP系列材料对藻细胞的吸附 (a) 和光催化去除 (b)

Figure 6. Comparisons of adsorption (a) and photo-inactivation (b) in solution of algae cells by TiO₂/mEP, g-C₃N₄-TiO₂/mEP and Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-x%(x=1, 5, 10, 15)

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图 7 光催化除藻过程中活性基团分析

Figure 7. Effects of different reactive species scavengers on the photocatalytic inactivation of algae under visible-light irradiation

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图 8 Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5%光催化剂重复利用性能

Figure 8. Changes in the efficiency of Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-20% for the inactivation of algae in three cycles

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表 1 EP、mEP及Ag₂CrO₄-g-C₃N₄-TiO₂/mEP系列材料的比表面积、孔径及孔容

Table 1. Specific surface area, average pore diameter and total pore volume of EP, mEP and Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-x%(x=1, 5, 10, 15)

Photocatalyst	Specific surface area/(m²·g⁻¹)	Average pore size/mm	Total pore volume/(cm³·g⁻¹)
EP	2.3	10.4	0.006
mEP	66.5	2.5	0.041
Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-1%	73.4	3.0	0.055
Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-5%	37.2	4.7	0.044
Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-10%	33.6	4.1	0.027
Ag₂CrO₄-g-C₃N₄-TiO₂/mEP-15%	42.5	3.6	0.033

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参考文献(25)

[1]	SHAO J H, GU J D, PENG L, et al. Modification of cyanobacterial bloom-derived biomass using potassium permanganate enhanced the removal of microcystins and adsorption capacity toward cadmium (II)[J]. Journal of Hazardous Materials,2014,272:83-88. doi: 10.1016/j.jhazmat.2014.03.013
[2]	BRIAND J F, ROBILLOT C, QUIBLIER-LLOBÉRAS C, et al. Environmental context of Cylindrospermopsis raciborskii (Cyanobacteria) blooms in a shallow pond in France[J]. Water Research,2002,36(13):3183-3192. doi: 10.1016/S0043-1354(02)00016-7
[3]	GAO Z W, PENG X J, ZHANG H M, et al. Montmorillonite-Cu(II)/Fe(III) oxides magnetic material for removal of cyanobacterial Microcystis aeruginosa and its regeneration[J]. Desalination,2009,247(1-3):337-345. doi: 10.1016/j.desal.2008.10.006
[4]	SUN F, PEI H Y, HU W R, et al. The lysis of Microcystis aeruginosa in AlCl₃ coagulation and sedimentation processes[J]. Chemical Engineering Journal,2012,193:196-202.
[5]	DONG C L, CHEN W, LIU C. Flocculation of algal cells by amphoteric chitosan-based flocculant[J]. Bioresource Technology,2014,170:239-247. doi: 10.1016/j.biortech.2014.07.108
[6]	WANG Z P, CHEN Y Q, XIE P C, et al. Removal of Microcystis aeruginosa by UV-activated persulfate: Performance and characteristics[J]. Chemical Engineering Journal,2016,300:245-253. doi: 10.1016/j.cej.2016.04.125
[7]	PINHO L X, AZEVEDO J, BRITO A, et al. Effect of TiO₂ photocatalysis on the destruction of microcystis aeruginosa cells and degradation of cyanotoxins microcystin-LR and cylindrospermopsin[J]. Chemical Engineering Journal,2015,268:144-152. doi: 10.1016/j.cej.2014.12.111
[8]	SONG J, WANG X, MA J, et al. Visible-light-driven in situ inactivation of microcystis aeruginosa with the use of floating g-C₃N₄ heterojunction photocatalyst: Performance, mechanisms and implications[J]. Applied Catalysis B: Environmental,2018,226:83-92. doi: 10.1016/j.apcatb.2017.12.034
[9]	SONG J, WANG X, MA J, et al. Removal of microcystis aeruginosa and microcystin-LR using a graphitic-C₃N₄/TiO₂ floating photocatalyst under visible light irradiation[J]. Chemical Engineering Journal,2018,348:380-388. doi: 10.1016/j.cej.2018.04.182
[10]	RODRIGUEZ-GONZALEZ V, ALFARO S O, TORRES-MARTINEZ L M, et al. Silver-TiO₂ nanocomposites: Synthesis and harmful algae bloom UV-photoelimination[J]. Applied Catalysis B-Environmental,2010,98(3-4):229-234. doi: 10.1016/j.apcatb.2010.06.001
[11]	CHEN Y F, HUANG W X, HE D L, et al. Construction of heterostructured g-C₃N₄/Ag/TiO₂ Microspheres with enhanced photocatalysis performance under visible-light irradiation[J]. ACS Applied Materials & Interfaces,2014,6(16):14405-14414.
[12]	WANG X, WANG X, ZHAO J, et al. Efficient visible light-driven in situ photocatalytic destruction of harmful alga by worm-like N, P co-doped TiO₂/expanded graphite carbon layer (NPT-EGC) floating composites[J]. Catalysis Science & Technology,2017,7:2335-2346.
[13]	PARK H, PARK Y, KIM W, et al. Surface modification of TiO₂ photocatalyst for environmental applications[J]. Journal of Photochemistry and Photobiology C: Photochemistry Reviews,2013,15:1-20. doi: 10.1016/j.jphotochemrev.2012.10.001
[14]	ZHOU J, ZHANG M, ZHU Y. Photocatalytic enhancement of hybrid C₃N₄/TiO₂ prepared via ball milling method[J]. Physical Chemistry Chemical Physics,2015,17(5):3647-3652. doi: 10.1039/C4CP05173D
[15]	ZHANG Y, LU J N, HOFFMANN M R, et al. Synthesis of g-C₃N₄/Bi₂O₃/TiO₂ composite nanotubes: Enhanced activity under visible light irradiation and improved photoelectrochemical activity[J]. Rsc Advances,2015,5(60):48983-48991. doi: 10.1039/C5RA02750K
[16]	XU D F, CHENG B, WANG W K, et al. Ag₂CrO₄/g-C₃N₄/graphene oxide ternary nanocomposite Z-scheme photocatalyst with enhanced CO₂ reduction activity[J]. Applied Catalysis B-Environmental,2018,231:368-380. doi: 10.1016/j.apcatb.2018.03.036
[17]	WANG X, WANG X J, ZHAO J F, et al. Adsorption-photocatalysis functional expanded graphite C/C composite for in-situ photocatalytic inactivation of Microcystis aeruginosa[J]. Chemical Engineering Journal,2018,341:516-525. doi: 10.1016/j.cej.2018.02.054
[18]	LI P, SONG Y, YU S. Removal of Microcystis aeruginosa using hydrodynamic cavitation: Performance and mechanisms[J]. Water Research,2014,62:241-248. doi: 10.1016/j.watres.2014.05.052
[19]	HOU Y, ZUO F, MA Q, et al. Ag₃PO₄ oxygen evolution photocatalyst employing synergistic action of Ag/AgBr nanoparticles and graphene sheets[J]. Journal of Physical Chemistry C,2015,116(38):20132-20139.
[20]	DENG Y, TANG L, ZENG G, et al. Facile fabrication of a direct Z-scheme Ag₂CrO₄/g-C₃N₄ photocatalyst with enhanced visible light photocatalytic activity[J]. Journal of Molecular Catalysis A Chemical,2016,421:209-221. doi: 10.1016/j.molcata.2016.05.024
[21]	SOOFIVAND F, MOHANDES F, SALAVATI-NIASARI M. Silver chromate and silver dichromate nanostructures: Sonochemical synthesis, characterization, and photocatalytic properties[J]. Materials Research Bulletin,2013,48(6):2084-2094. doi: 10.1016/j.materresbull.2013.02.025
[22]	WANG X, WANG X J, ZHAO J F, et al. Solar light-driven photocatalytic destruction of cyanobacteria by F-Ce-TiO₂/expanded perlite floating composites[J]. Chemical Engineering Journal,2017,320:253-263. doi: 10.1016/j.cej.2017.03.062
[23]	XU H, ZHAO H, SONG Y, et al. g-C₃N₄/Ag₃PO₄ composites with synergistic effect for increased photocatalytic activity under the visible light irradiation[J]. Materials Science in Semiconductor Processing,2015,39:726-734. doi: 10.1016/j.mssp.2015.04.013
[24]	MA S, ZHAN S, JIA Y, et al. Enhanced disinfection application of Ag-modified g-C₃N₄ composite under visible light[J]. Applied Catalysis B: Environmental,2016,186:77-87. doi: 10.1016/j.apcatb.2015.12.051
[25]	WANG X, WANG X J, ZHAO J F, et al. An alternative to in situ photocatalytic degradation of microcystin-LR by worm-like N, P co-doped TiO₂/expanded graphite by carbon layer (NPT-EGC) floating composites[J]. Applied Catalysis B: Environmental,2017,206:479-489. doi: 10.1016/j.apcatb.2017.01.046