Bi2MoO6/WO3复合光催化材料的合成及其可见光催化性能

但智钢; 肖经浩; 姚旭

doi:10.13801/j.cnki.fhclxb.20210526.005

Bi₂MoO₆/WO₃复合光催化材料的合成及其可见光催化性能

doi: 10.13801/j.cnki.fhclxb.20210526.005

但智钢^1, ,,
肖经浩^{1, 2,},
姚旭²

1.
中国环境科学研究院　国家环境保护生态工业重点实验室，北京 100012
2.
湖北大学　物理与电子科学学院，武汉 430062

基金项目: 国家重点研究计划项目(2019YFC1904201)

详细信息

通讯作者:
但智钢，博士，研究员，博士生导师，研究方向为工业固废处理与资源化　E-mail：dash_2001@163.com

中图分类号: O614
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出版历程
- 收稿日期: 2021-04-02
- 修回日期: 2021-05-10
- 录用日期: 2021-05-18
- 网络出版日期: 2021-05-26
- 刊出日期: 2022-04-01

Synthesis and visible light photocatalytic properties of Bi₂MoO₆/WO₃ composite photocatalysts

DAN Zhigang^{1
, ,},
XIAO Jinghao^{1, 2
,},
YAO Xu²

1.
State Environmental Protection Key Laboratory of Eco-Industry, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
2.
Faculty of Physics & Electronic Sciences, Hubei University, Wuhan 430062, China

摘要

摘要: 采用水热法成功制备了不同Bi₂MoO₆含量的Bi₂MoO₆/WO₃复合光催化剂，利用XRD、SEM、UV-Vis、EIS和PL对样品进行了微观结构、形貌、光吸收特性、光谱响应和光电流的测试与表征，并考察了Bi₂MoO₆/WO₃复合材料光催化分解水制氧的活性。结果表明，Bi₂MoO₆/WO₃复合样品的光催化活性明显高于纯WO₃和Bi₂MoO₆样品。在模拟太阳光照射下，15%Bi₂MoO₆/WO₃复合催化剂的光催化产氧效率是纯WO₃的产氧效率的2.3倍，以Fe(NO₃)₃·9H₂O为牺牲剂时，复合催化剂的产氧效率可达到107 μmol/(g·h)，且具有良好的循环稳定性。分析发现Bi₂MoO₆/WO₃复合样品中Bi₂MoO₆颗粒与WO₃纳米棒的异质结结构提高了光生载流子传输和转移效率，减少了光生电子-空穴对的复合几率，因此有助于增强光催化活性。
- Bi₂MoO₆ /
- WO₃ /
- 纳米棒 /
- 复合光催化剂 /
- 光催化产氧
Abstract: Bi₂MoO₆/WO₃ composite photocatalysts with various Bi₂MoO₆ amounts were successfully synthesized by hydrothermal method. The microstructure, morphologies, optical absorption properties and spectral response of Bi₂MoO₆/WO₃ composites were measured and characterized by XRD, SEM, UV-Vis, EIS and PL. Moreover, the photocatalytic activities of the samples were further investigated. The results show that the photocatalytic activity of the 15%Bi₂MoO₆/WO₃ composite is obviously higher than that of the pure WO₃ and Bi₂MoO₆: the photocatalytic oxygen production efficiency of the Bi₂MoO₆/WO₃ is 2.3 times that of the pure WO₃. The oxygen production efficiency of composite catalyst obtained 107 μmol/(g·h) after introducing Fe(NO₃)₃·9H₂O assacrificial agent and exhibited good cycling stability. It is inferred that the Bi₂MoO₆ nanoparticle-WO₃ nanorod heterojunction structure improves the transport and transfer efficiency of photo-generated carriers, reduces the recombination probability of electron-hole pairs, which is helpful to enhance the photocatalytic activity.
- Bi₂MoO₆ /
- WO₃ /
- nanorods /
- composite photocatalyst /
- photocatalytic oxygen production

HTML全文

图 1 WO₃ (a)、Bi₂MoO₆ (b)、10%Bi₂MoO₆/WO₃ (c)、15%Bi₂MoO₆/WO₃ (d) 和20%Bi₂MoO₆/WO₃ (e) 的SEM图像

Figure 1. SEM images of WO₃ (a), Bi₂MoO₆ (b), 10%Bi₂MoO₆/WO₃ (c), 15%Bi₂MoO₆/WO₃ (d) and 20%Bi₂MoO₆/WO₃ (e)

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图 2 纯WO₃、Bi₂MoO₆及不同Bi₂MoO₆比例Bi₂MoO₆/WO₃复合样品的XRD图谱

Figure 2. XRD patterns of pure WO₃, Bi₂MoO₆ and Bi₂MoO₆/WO₃ composites with different contents of Bi₂MoO₆

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图 3 纯WO₃、Bi₂MoO₆及不同Bi₂MoO₆比例Bi₂MoO₆/WO₃复合样品的紫外-可见漫反射图谱 (a) 及对应的Tauc’s曲线图 (b)

Figure 3. UV-vis DRS spectra (a) and Tauc’s plots (b) of pure WO₃, Bi₂MoO₆ and Bi₂MoO₆/WO₃ composites with different contents of Bi₂MoO₆

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图 4 模拟太阳光照射下WO₃、Bi₂MoO₆及不同复合比例Bi₂MoO₆/WO₃样品的光催化产氧性能 (a) 和牺牲剂对15%Bi₂MoO₆/WO₃样品产氧性能的影响 (b)

Figure 4. Performance of photocatalytic oxygen production for WO₃, Bi₂MoO₆ and Bi₂MoO₆/WO₃ composites with different contents of Bi₂MoO₆(a) and effect of sacrificial agents on the oxygen production performance of 15%Bi₂MoO₆/WO₃(b)

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图 5 WO₃、Bi₂MoO₆及不同复合比例Bi₂MoO₆/WO₃的电化学阻抗谱 (a)、光致发光图谱 (b) 及光电流响应 (c)

Figure 5. EIS spectra (a), PL spectra (b) and photocurrent response (c) of WO₃, Bi₂MoO₆ and Bi₂MoO₆/WO₃ composites with different contents of Bi₂MoO₆

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图 6 Bi₂MoO₆/WO₃复合材料光催化产氧机制

Figure 6. Mechanism of photocatalytic oxygen production of Bi₂MoO₆/WO₃ composite

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表 1 Bi₂MoO₆/WO₃的命名

Table 1. Naming of Bi₂MoO₆/WO₃

Sample	Mass ratio of Bi₂MoO₆：WO₃/%
5%Bi₂MoO₆/WO₃	5
10%Bi₂MoO₆/WO₃	10
15%Bi₂MoO₆/WO₃	15
20%Bi₂MoO₆/WO₃	20

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表 2 WO₃和Bi₂MoO₆的能带位置计算结果

Table 2. Calculated band position values of Bi₂MoO₆ and WO₃

Sample	X/eV	E_e/eV	E_CB /eV	E_VB/eV	E_g/eV
WO₃	6.57	4.5	+0.88	+3.46	2.78
Bi₂MoO₆	5.55	4.5	−0.25	+2.35	2.60
Notes: X—Electronegativity of the semiconductor; E_e—Energy of free electrons on the hydrogen scale; E_CB—Conduct band edge potential; E_VB—Valence band-edge potential; E_g—Band gap energy.

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参考文献(22)

[1]	GHOLAMI P, KHATAEE A, BHATNAGAR A, et al. Synthesis of N-doped magnetic WO_3-x@mesoporous carbon using a diatom template and plasma modification: Visible-light-driven photocatalytic activities[J]. ACS Applied Materials Interfaces,2021,13(11):13072-13086. doi: 10.1021/acsami.0c21076
[2]	刘成宝, 唐飞, 朱晨, 等. WO₃-Ag/石墨相 C₃N₄ Z型复合光催化剂的合成及其光催化性能[J]. 复合材料学报, 2021, 38(1):209-220. LIU C B, TANG F, ZHU C, et al. Preparation and photocatalytic properties of WO₃-Ag/graphitic C₃N₄ Z-scheme composite photocatalyst[J]. Journal of Composite Materials,2021,38(1):209-220(in Chinese).
[3]	WANG F, VALENTIN C, PACCHIONI G. Doping of WO₃ for photocatalytic water splitting: Hints from density functional theory[J]. Journal of Physical Chemistry C,2012,116(16):8901-8909. doi: 10.1021/jp300867j
[4]	LI S, WANG J, XIA Y, et al. Boosted electron-transfer by coupling Ag and Z-scheme heterostructures in CdSe-Ag-WO₃-Ag for excellent photocatalytic H₂ evolution with simultaneous degradation[J]. Chemical Engineering Journal,2021,417:129298. doi: 10.1016/j.cej.2021.129298
[5]	ZHAO Y, ZHANG Y, YE Z, et al. CdS-dots decorated WO₃ nanorods photocatalyst with highly ordered interfacial structure for enhanced photocatalytic activities via Z-scheme mechanism[J]. International Journal of Hydrogen Energy,2021,46:9040-9051. doi: 10.1016/j.ijhydene.2021.01.023
[6]	ZHOU Q, SONG Y, LI N, et al. Direct dual Z-scheme Bi₂WO₆/GQDs/WO₃ inverse opals for enhanced photocatalytic activities under visible light[J]. ACS Sustainable Chemistry & Engineering,2020,21:7921-7927.
[7]	WANG X, SUN M, MURUGANAN T, et al. Electrochemically self-doped WO₃/TiO₂ nanotubes for photocatalytic degradation of volatile organic compounds[J]. Applied Catalysis B: Environmental,2020,260:118205. doi: 10.1016/j.apcatb.2019.118205
[8]	LING Y, DAI Y. Direct Z-scheme hierarchical WO₃/BiOBr with enhanced photocatalytic degradation performance under visible light[J]. Applied Surface Science,2020,509:145201. doi: 10.1016/j.apsusc.2019.145201
[9]	ZHANG B, LI J, GAO Y, et al. To boost photocatalytic activity in selective oxidation of alcohols on ultrathin Bi₂MoO₆ nanoplates with Pt nanoparticles as cocatalyst[J]. Journal of Catalysis,2017,345:96-103. doi: 10.1016/j.jcat.2016.11.023
[10]	YANG X, XIANG Y, QU Y, et al. Novel in situ fabrication of conjugated microporous poly(benzothiadiazole)-Bi₂MoO₆ Z-scheme heterojunction with enhanced visible light photocatalytic activity[J]. Journal of Catalysis,2017,345:319-328. doi: 10.1016/j.jcat.2016.11.014
[11]	MA T, WU J, MI Y, et al. Novel Z-Scheme g-C₃N₄/C@ Bi₂MoO₆ composite with enhanced visible-light photocatalytic activity for β-naphthol degradation[J]. Separation and Purification Technology,2017,183:54-65. doi: 10.1016/j.seppur.2017.04.005
[12]	GOVINDARAJ T, MAHENDRAN C, MARNADU R, et al. The remarkably enhanced visible-light-photocatalytic activity of hydrothermally synthesized WO₃ nanorods: An effect of Gd doping[J]. Ceramics International,2021,47:4267-4278. doi: 10.1016/j.ceramint.2020.10.004
[13]	JI Z, WU J, JIA T, et al. In-situ growth of TiO₂ phase junction nanorods with Ti³⁺ and oxygen vacancies to enhance photocatalytic activity[J]. Materials Research Bulletin,2021,140:111291. doi: 10.1016/j.materresbull.2021.111291
[14]	HUANG S, LONG Y, RUAN S, et al. Enhanced photocatalytic CO₂ reduction in defect-engineered Z-scheme WO_3-x/g-C₃N₄ heterostructures[J]. ACS Omega,2019,13:15593-15599.
[15]	MA H, HE Y, LI X, et al. In situ loading of MoO₃ clusters on ultrathin Bi₂MoO₆ nanosheets for synergistically enhanced photocatalytic NO abatement[J]. Applied Catalysis B: Environmental,2021,292:120159. doi: 10.1016/j.apcatb.2021.120159
[16]	AMANO F, ISHINAGA E, YAMAKAT A. Effect of particle size on the photocatalytic activity of WO₃ particles for water oxidation[J]. The Journal of Physical Chemistry C,2013,117(44):22584-22590. doi: 10.1021/jp408446u
[17]	LI S, WANG C, CHEN X, et al. Photocatalytic degradation of antibiotics using a novel Ag/Ag₂S/ Bi₂MoO₆ plasmonic p-n heterojunction photocatalyst: mineralization activity, degradation pathways and boosted charge separation mechanism[J]. Chemical Engineering Journal,2021,415:128991. doi: 10.1016/j.cej.2021.128991
[18]	KOHANTORABI M, MOUSSAVI G, MOHAMMADI S, et al. Photocatalytic activation of peroxymonosulfate (PMS) by novel mesoporous Ag/ZnO@NiFe₂O₄ nanorods, inducing radical-mediated acetaminophen degradation under UVA irradiation[J]. Chemosphere,2021,277:130271. doi: 10.1016/j.chemosphere.2021.130271
[19]	QIN Y, LU J, MENG F, et al. Rationally constructing of a novel 2D/2D WO₃/Pt/g-C₃N₄ Schottky-Ohmic junction towards efficient visible-light-driven photocatalytic hydrogen evolution and mechanism insight[J]. Journal of Colloid and Interface Science,2021,586:576-587. doi: 10.1016/j.jcis.2020.10.123
[20]	XUE C, ZHANG P, SHAO G, et al. Effective promotion of spacial charge separation in direct Z-scheme WO₃/CdS/WS₂ tandem heterojunction with enhanced visible-light-driven photocatalytic H₂ evolution[J]. Chemical Engineering Journal,2020,398:125602. doi: 10.1016/j.cej.2020.125602
[21]	JIA J, JIANG C, ZHANG X, et al. Urea-modified carbon quantum dots as electron mediator decorated g-C₃N₄/WO₃ with enhanced visible-light photocatalytic activity and mechanism insight[J]. Applied Surface Science,2019,45:143524.
[22]	TIAN J, HAO P, WEI N, et al. 3D Bi₂MoO₆ nanosheet/TiO₂ nanobelt heterostructure: Enhanced photocatalytic activities and photoelectochemistry performance[J]. ACS Catalysis,2015,5:4530-4536. doi: 10.1021/acscatal.5b00560