Preparation and performance study of CaFe2O4-based composite photocatalysts

doi:10.19965/j.cnki.iwt.2020-0483

Abstract

Abstract:

CaFe₂O₄/CaSO₄/Fe₂O₃ ternary composite photocatalyst was synthesized by one⁃step hydrothermal method. The sample only contained CaFe₂O₄，CaSO₄ and Fe₂O₃，without other impurities. CaFe₂O₄/CaSO₄/Fe₂O₃ ternary composite photocatalyst was flower⁃like，mainly composed of some fine particles bonding together. The band gap（E _g） of Fe₂O₃，CaFe₂O₄，CaSO₄，and ternary composite CaFe₂O₄/CaSO₄/Fe₂O₃ photocatalyst were 1.83，1.85，3.69/4.29 and 1.35/2.64 eV，respectively. Compare with Fe₂O₃，CaFe₂O₄and CaSO₄，the ternary composite CaFe₂O₄/CaSO₄/Fe₂O₃ photocatalyst had strong absorption capacity of UV-visible light，strong charge transfer ability and high separation efficiency，and was a potential UV-visible photocatalyst. The comparative study of photocatalytic experiment showed that ternary composite CaFe₂O₄/CaSO₄/Fe₂O₃ photocatalyst had strong UV-visible photocatalytic activity in the degradation of methyl orange organic dyes. Cyclic degradation experiments showed that CaFe₂O₄/CaSO₄/Fe₂O₃ ternary composite photocatalyst had high stability. In the photocatalytic degradation process，the synergistic effects of hole，hydroxyl radical and superoxide radical made the ternary composite CaFe₂O₄/CaSO₄/Fe₂O₃ photocatalyst had high photocatalytic activity.

Key words: hydrothermal method, photocatalyst, light absorption capacity, methyl orange, hydroxyl radical

摘要：

采用一步水热法合成了CaFe₂O₄/CaSO₄/Fe₂O₃三元复合光催化剂。样品中仅含有CaFe₂O₄、CaSO₄和Fe₂O₃，无其他杂质存在。CaFe₂O₄/CaSO₄/Fe₂O₃三元复合光催化剂呈花状，主要由一些细颗粒黏连而成。结果表明，Fe₂O₃、CaFe₂O₄、CaSO₄和CaFe₂O₄/CaSO₄/Fe₂O₃三元复合光催化剂的带隙能（E _g）分别为1.83、1.85、3.69/4.29、 1.35/2.64 eV； CaFe₂O₄/CaSO₄/Fe₂O₃具有较强的紫外可见光吸收能力、较强的电荷转移能力及较高的分离效率，是一种潜在的紫外可见光催化剂。光催化对比实验表明，CaFe₂O₄/CaSO₄/Fe₂O₃三元复合光催化剂在降解甲基橙有机染料方面具有较强的紫外可见光催化活性。循环降解实验表明，CaFe₂O₄/CaSO₄/Fe₂O₃三元复合光催化剂具有高的稳定性。在光催化降解过程中，空穴、羟基自由基和超氧自由基的协同作用使该催化剂具有高的光催化活性。

关键词: 水热法, 光催化剂, 光吸收能力, 甲基橙, 羟基自由基

CLC Number:

O643.36
X703

Chunyan ZHANG, Zheyu LIU. Preparation and performance study of CaFe₂O₄-based composite photocatalysts[J]. Industrial Water Treatment, 2022, 42(2): 104-110.

张春燕, 刘哲语. CaFe₂O₄基复合光催化剂的制备及性能研究[J]. 工业水处理, 2022, 42(2): 104-110.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2020-0483

https://www.iwt.cn/EN/Y2022/V42/I2/104

Figures/Tables 10

Fig. 1 XRD of photocatalysts

Fig. 2 SEM（a）and HRTEM（b）of CaFe₂O₄/CaSO₄/Fe₂O₃

Fig. 3 UV-Vis absorption spectrum（a）and the relation curve of （αhν）²-hν（b~c）

Fig. 4 Impedance spectroscopy（a）and photocurrent density（b）

Fig. 5 Photocatalytic degradation curves（a）and first⁃order kinetics curves（b）under UV irradiation

Fig. 6 Photocatalytic degradation curves（a）and first⁃order kinetics curves（b）under visible light irradiation

Fig. 7 Stability（a） and XRD patterns（b）of CaFe₂O₄/CaSO₄/Fe₂O₃ in cycle experiment

Table 1 E _g，electronegativity，E _CB and E _VB of CaFe₂O₄，CaSO₄ and Fe₂O₃

样品	E _g/eV	X/eV	E _CB/eV	E _VB/eV
CaFe₂O₄	1.85	5.30	-0.30	1.90
CaSO₄	3.94	5.95	-0.52	3.42
Fe₂O₃	1.83	5.89	0.475	2.305

Fig. 8 Photocatalytic mechanism of CaFe₂O₄/CaSO₄/Fe₂O₃

Fig. 9 Effect of different quenching agents on degradation rate of methyl orange

References 23

1	申玉芳，龙飞，邹正光. 半导体光催化技术研究进展［J］. 材料导报，2006，20（6）：28-31. doi:10.3321/j.issn:1005-023X.2006.06.008
	SHEN Yufang， LONG Fei， ZOU Zhengguang. Developments of photocatalytic semiconductors［J］. Materials Reports，2006，20（6）：28-31. doi:10.3321/j.issn:1005-023X.2006.06.008
2	李金火，朱德贵，薛宗岳，等. 二氧化钛-活性炭复合光催化材料的制备及表征［J］. 无机盐工业，2008，40（11）：28-30. doi:10.3969/j.issn.1006-4990.2008.11.010
	LI Jinhuo， ZHU Degui， XUE Zongyue，et al. Preparation and characterization of photocatalytic material of TiO₂ -active carboncomposi⁃te［J］. Inorganic Chemicals Industry，2008，40（11）：28-30. doi:10.3969/j.issn.1006-4990.2008.11.010
3	李跃军，曹铁平，梅泽民，等. Gd-N共掺杂SrTiO₃/TiO₂复合纳米纤维制备及光催化性能［J］. 无机化学学报，2019，35（1）：82-88. doi:10.11862/CJIC.2019.011
	LI Yuejun， CAO Tieping， MEI Zhemin，et al. Preparation and photocatalytic activity of Gd-N co⁃doped SrTiO₃/TiO₂ composite nanofibers［J］. Chinese Journal of Inorganic Chemistry，2019，35（1）：82-88. doi:10.11862/CJIC.2019.011
4	薛红艳. 纳米铁酸钙的光催化活性与催化机理研究［J］. 无机盐工业，2017，49（9）：85-88.
	XUE Hongyan. Photocatalytic activity and mechanism of nano-CaFe₂O₄ ［J］. Inorganic Chemicals Industry，2017，49（9）：85-88.
5	马富，赵红建. 一种合成超顺磁CaFe₂O₄纳米颗粒的新方法及其络合机理［J］. 无机盐工业，2018，50（11）：67-71. doi:10.1016/j.inoche.2018.01.009
	MA Fu， ZHAO Hongjian. A novel method for synthesis of superparamagnetic CaFe₂O₄ nanoparticles and its chelation mechani⁃sms［J］. Inorganic Chemicals Industry，2018，50（11）：67-71. doi:10.1016/j.inoche.2018.01.009
6	ZHANG Zhijie， WANG Wenzhong. Solution combustion synthesis of CaFe₂O₄ nanocrystal as a magnetically separable photocatalyst［J］. Materials Letter，2014，133：212-215. doi:10.1016/j.matlet.2014.07.050
7	DOM R， SUBASRI R， RADHA K，et al. Synthesis of solar active nanocrystalline ferrite，MFe₂O₄（M：Ca，Zn，Mg）photocatalyst by microwave irradiation［J］. Solid State Communications，2011，151（6）：470-473. doi:10.1016/j.ssc.2010.12.034
8	WANG Yujuan， SONG Jingjing. Synthesized and photocatalytic mechanism of the NiO supported YMnO₃ nanoparticles for photocatalytic degradation of the methyl orange dye［J］. Zeitschrift Für Physikalische Chemie，2020，234：153-170. doi:10.1515/zpch-2019-1392
9	亓峰. 碳酸钙/铁酸钙复合催化剂制备及其催化性能［J］. 无机盐工业，2018，50（3）：77-80.
	QI Feng. Preparation and catalytic performance of composite CaCO₃/CaFe₂O₄ catalyst［J］. Inorganic Chemicals Industry，2018，50（3）：77-80.
10	CAO Zhengheng， WANG Caiqin， CHEN Jun. Synthesis and photocatalytic property of p-n junction YMnO₃/SrTiO₃ composites［J］. Materials Research Express，2018，5：115512. doi:10.1088/2053-1591/aadec0
11	WU Yizhang， ZHOU Xuan， LI Mengmeng，et al. 2D/3D interface engineering：Direct Z-scheme g-C₃N₄/YMnO₃ heterojunction for reinforced visible⁃light photocatalytic oxidation［J］. Journal of Materials Science：Materials in Electronics，2019，30：17601-17611. doi:10.1007/s10854-019-02109-y
12	WANG Xixin， LI Yang， LIU Maocheng，et al. Fabrication and electrochemical investigation of MWO₄（M=Co，Ni）nanoparticles as high⁃performance anode materials for lithium⁃ion batteries［J］. Ionics，2018，24（2）：363-372. doi:10.1007/s11581-017-2200-0
13	GAO Huajing， YANG Hua， WANG Shifa. Comparative study on optical and electrochemical properties of MFe₂O₄（M=Mg，Ca，Ba）nanoparticles［J］. Transactions of Indian Ceramic Society，2018，77（3）：150-160. doi:10.1080/0371750x.2018.1512381
14	LIN Jie， ZONG Ruilong， ZHOU Mi，et al. Photoelectric catalytic degradation of methylene blue by C₆₀-modified TiO₂ nanotube array［J］. Applied Catalysis B：Environmental，2009，89（3/4）：425-431. doi:10.1016/j.apcatb.2008.12.025
15	ZHU Shengbao， XU Tongguang， FU Hongbo，et al. Synergetic effect of Bi₂WO₆ photocatalyst with C₆₀ and enhanced photoactivity under visible irradiation［J］. Environmental Science & Technology，2007，41（17）：6234-6239. doi:10.1021/es070953y
16	LIU Zhifu， ZHAO Zhigang， MIYAUCHI M. Efficient visible light active CaFe₂O₄/WO₃ based composite photocatalysts：Effect of interfacial modification［J］. The Journal of Physical Chemistry C，2009，113（39）：17132-17137. doi:10.1021/jp906195f
17	KADARI A， MAHI K， MOSTEFA R，et al. Optical and structural properties of Mn doped CaSO₄ powders synthesized by sol-gel process［J］. Journal of Alloys and Compounds，2016，688（Part A）：32-36. doi:10.1016/j.jallcom.2016.07.040
18	MEHRAJ O， PIRZADA B M，MIR N A，et al. A highly efficient visible⁃light⁃driven novel p-n junction Fe₂O₃/BiOI photocatalyst：Surface decoration of BiOI nanosheets with Fe₂O₃ nanoparticles［J］. Applied Surface Science，2016，387：642-651. doi:10.1016/j.apsusc.2016.06.166
19	TACHIKAWA T， FUJITSUKA M， MAJIMA T. Mechanistic insight into the TiO₂ photocatalytic reactions：Design of new photocatalysts［J］. The Journal of Physical Chemistry C，2007，111（14）：5259-5275. doi:10.1021/jp069005u
20	ARAI T， YANAGIDA M， KONISHI Y，et al. Efficient complete oxidation of acetaldehyde into CO₂ over CuBi₂O₄/WO₃ composite photocatalyst under visible and UV light irradiation［J］. The Journal of Physical Chemistry C，2007，111（21）：7574-7577. doi:10.1021/jp0725533
21	胡金山，王欢，刘利，等. 高效Ag@AgBr等离子体光催化剂的制备及可见光活性研究［J］. 分子催化，2013，27（5）：452-458.
	HU Jinshan， WANG Huan， LIU Li，et al. Preparation of highly efficient Ag@AgBr plasmonic photocatalyst and its photocatalytic performance under visible light［J］. Journal of Molecular Catalysis，2013，27（5）：452-458.
22	ZHANG Hanzhuo， XUE Junsheng， HAN Jinxun，et al. Photo⁃assisted Fenton reactions and growth evolution of crack⁃urchined CuBi₂O₄ microspheres assembled by nanorods［J］. Ceramics International，2020，46（15）：23742-23748. doi:10.1016/j.ceramint.2020.06.148
23	刘晓艳，刘莲，吴俊峰，等. Fenton/过硫酸盐降解水中的4-乙酰氨基酚［J］. 工业水处理，2018，38（10）：25-28. doi:10.11894/1005-829x.2018.38(10).025
	LIU Xiaoyan， LIU Lian， WU Junfeng，et al. Degradation of acetaminophen in water by Fenton/persulfate system［J］. Industrial Water Treatment，2018，38（10）：25-28. doi:10.11894/1005-829x.2018.38(10).025

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CaFe₂O₄基复合光催化剂的制备及性能研究

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