CeO2改性WO3/g-C3N4光催化氧化脱硫性能

doi:10.11949/0438-1157.20191332

摘要/Abstract

摘要：

以钨酸铵、六水硝酸铈、尿素为原料，采用熔融法制备CeO₂-WO₃/g-C₃N₄催化剂，并对样品进行XRD、UV-Vis、TEM、PL和XPS表征。结果表明：CeO₂的引入可以提高WO₃在g-C₃N₄上的分散度，抑制光生电子空穴对的复合，同时Ce⁴⁺/Ce³⁺良好的储氧放氧能力有利于氧空位和活性氧的生成，从而有利于WO₃/g-C₃N₄催化剂的催化性能。在以高压钠灯模拟可见光源的条件下，以过氧化羟基异丙苯为氧化剂，考察了CeO₂的加入量对催化剂氧化二苯并噻吩(DBT)性能的影响，结果表明：最佳的CeO₂引入量为5%(质量分数)，在80℃、氧硫摩尔比(O/S)为5.0的反应条件下，反应180 min时DBT在WO₃/g-C₃N₄和CeO₂-WO₃/g-C₃N₄催化剂的作用下转化率分别为72.9%和86.4%，且改性后的催化剂可以循环使用8次而催化活性没有明显降低。

关键词: CeO₂, 分布, 储氧放氧能力, 氧空位, 氧化, 催化剂

Abstract:

Using ammonium tungstate, cerium nitrate hexahydrate, and urea as raw materials, CeO₂-WO₃ / g-C₃N₄ catalyst was prepared by the melt method, and the samples were characterized by XRD, UV-Vis, TEM, PL, and XPS. XRD characterization results show that the introduction of CeO₂ can improve the dispersion of active component WO₃ on g-C₃N₄, and XPS characterization indicates the good oxygen storage and release capacity of Ce⁴⁺/Ce³⁺ is conducive to the formation of oxygen vacancy and reactive oxygen species. The PL characterization also indicates that the introduction of CeO₂ can capture electrons and thus inhibits photogenic electron hole pair recombination. The introduction of the CeO₂ for the catalytic activity of compound photocatalysis was investigated by oxidation and desulfurization experiment, the high-pressure sodium lamp was used to simulate visible light source, using the mixture of n-heptane and dibenzothiophene (DBT) as a simulation oil. Experimental results show that in 80℃, O/S molar ratio 5.0, 5% (mass fraction) CeO₂ payload, 180 min of reaction conditions, the introduction of CeO₂ catalyst on the oxidation of DBT in n-heptane conversion rate was 86.4%, higher than WO₃/g-C₃N₄ on the oxidation of DBT conversion rate 72.9%. The characterization results and oxidation desulfurization experiments showed that the introduction of CeO₂ could interact well with WO₃/g-C₃N₄, thus improving the activity of the composite photocatalyst.

Key words: CeO₂, distribution, oxygen storage and release capacity, oxygen vacancy, oxidation, catalyst

中图分类号:

TQ 028.8

刘帅, 李学雷, 王烁天, 李旭贺, 王彦娟, 苑兴洲, 张健, 封瑞江. CeO₂改性WO₃/g-C₃N₄光催化氧化脱硫性能[J]. 化工学报, 2020, 71(4): 1618-1626.

Shuai LIU, Xuelei LI, Shuotian WANG, Xuhe LI, Yanjuan WANG, Xingzhou YUAN, Jian ZHANG, Ruijiang FENG. WO₃/g-C₃N₄ modified by CeO₂ and its oxidation and desulfurization properties[J]. CIESC Journal, 2020, 71(4): 1618-1626.

图/表 13

图1 g-C3N4、WO3、CeO2、WO3/g-C3N4和CeO2-WO3/g-C3N4样品的XRD谱图

Fig.1 XRD patterns of g-C3N4,WO3,CeO2,WO3/g-C3N4 and CeO2-WO3/g-C3N4a—g-C3N4; b—WO3; c—CeO2; d—WO3(20% mass fraction)/g-C3N4; e—CeO2(2% mass fraction)-WO3(20% mass fraction)/g-C3N4; f—CeO2(5% mass fraction)-WO3(20% mass fraction)/g-C3N4; g—CeO2(8% mass fraction)-WO3(20% mass fraction)/g-C3N4; h—CeO2(10% mass fraction)-WO3(20% mass fraction)/g-C3N4

表1 催化剂WO3组分晶粒数据

Table 1 Crystal data of WO3 components of catalyst

催化剂	WO₃结晶度/%	WO₃平均晶粒尺寸 / nm
WO₃(20%质量分数)/g-C₃N₄	76.39	66.3
CeO₂(2%质量分数)-WO₃(20%质量分数)/g-C₃N₄	46.92	46.4
CeO₂(5%质量分数)-WO₃(20%质量分数)/g-C₃N₄	20.63	30.3
CeO₂(8%质量分数)-WO₃(20%质量分数)/g-C₃N₄	10.49	27.5
CeO₂(10%质量分数)-WO₃(20%质量分数)/g-C₃N₄	2.71	18.6

图2 g-C3N4、WO3/g-C3N4和CeO2-WO3/g-C3N4样品的TEM图

Fig.2 TEM images of g-C3N4,WO3/g-C3N4 and CeO2-WO3/g-C3N4

图3 g-C3N4、WO3、WO3/g-C3N4和CeO2-WO3/g-C3N4样品的UV-Vis谱图

Fig.3 UV-Vis spectra of g-C3N4,WO3,WO3/g-C3N4 and CeO2-WO3/g-C3N4a—WO3/g-C3N4; b—CeO2-WO3/g-C3N4; c—WO3; d—g-C3N4

图4 g-C3N4、WO3/g-C3N4、CeO2-WO3/g-C3N4样品的PL谱图

Fig.4 PL spectra of g-C3N4,WO3/g-C3N4,CeO2-WO3/g-C3N4a—g-C3N4; b—WO3/g-C3N4; c—CeO2-WO3/g-C3N4

图5 CeO2-WO3/g-C3N4的XPS谱图

Fig.5 XPS spectra of CeO2-WO3/g-C3N4

表2 催化剂XPS峰面积数据

Table 2 XPS peak area data of catalyst

催化剂	O_β/(O_α+O_β) 浓度比/%	O_β/O_α浓度比/%	Ce³⁺/(Ce³⁺+Ce⁴⁺)摩尔比/%
CeO₂	5.67	6.3	42.11
WO₃/g-C₃N₄	14.09	16.4	—
CeO₂-WO₃/g-C₃N₄	54.49	84.1	63.78

图6 不同催化剂的氧化脱硫效果

Fig.6 Oxidative desulfurization effect of different catalysts(reaction conditions: 80℃, O/S =5.0, payload of CeO2 5% (mass))

图7 催化剂负载量对DBT转化率的影响

Fig.7 Effect of catalyst loading on conversion rate of DBT(reaction conditions: 80℃, O/S =5.0, 180 min)

图8 温度对DBT转化率的影响

Fig.8 Effect of temperature on conversion rate of DBT（reaction conditions: O/S =5.0, 180 min, payload of CeO2 5% (mass)）

图9 氧硫摩尔比对DBT在反应体系中的影响

Fig.9 Influence of oxygen-sulfur mole ratio on DBT in reaction system(reaction conditions: 80℃, 180 min, payload of CeO2 5% (mass))

图10 CeO2(5%质量分数)-WO3(20%质量分数)/g-C3N4催化剂的循环使用性能

Fig.10 Catalytic performances of fresh and reused CeO2(5%,mass fraction)-WO3(20% ,mass fraction)/g-C3N4(reaction conditions: 80℃, O/S=5, 180 min, payload of CeO2 5% (mass))

图11 CeO2(5%质量分数)-WO3(20%质量分数)/g-C3N4催化剂光催化机理示意图

Fig.11 Schematic diagram of photocatalytic mechanism of CeO2(5% mass fraction)-WO3(20% mass fraction)/g-C3N4 catalyst

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CeO₂改性WO₃/g-C₃N₄光催化氧化脱硫性能

WO₃/g-C₃N₄ modified by CeO₂ and its oxidation and desulfurization properties

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