β-NaYF4:Yb3+,Tm3+/g-C3N4复合水凝胶材料的制备及其应用

doi:10.16085/j.issn.1000-6613.2022-0184

化工进展 ›› 2022, Vol. 41 ›› Issue (6): 3146-3154.DOI: 10.16085/j.issn.1000-6613.2022-0184

β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄复合水凝胶材料的制备及其应用

陈彰旭¹^,²^,³(), 陈冰冰¹^,²^,³, 王荣财¹^,²^,³, 叶晨光¹^,²^,³, 郑炳云¹^,²^,³

^1.莆田学院环境与生物工程学院，福建莆田 351100
^2.福建省新型污染物生态毒理效应与控制重点实验室，福建莆田 351100
^3.福建省高校生态环境及其信息图谱重点实验室，福建莆田 351100

收稿日期:2022-01-28 修回日期:2022-03-04 出版日期:2022-06-10 发布日期:2022-06-21
通讯作者: 陈彰旭
作者简介:陈彰旭（1977—），男，博士，副教授，硕士生导师，研究方向为环境功能材料。E-mail：xuzhangchen@163.com。
基金资助:
国家自然科学基金(51778598);福建省自然科学基金(2015J01644);国家级大学生创新项目(202011498004);2018年福建省科技特派员资金项目;2021年莆田市科技特派员资金项目;福建省教育厅A类项目(JAT200537)

Preparation and application of β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄ composite hydrogel

CHEN Zhangxu¹^,²^,³(), CHEN Bingbing¹^,²^,³, WANG Rongcai¹^,²^,³, YE Chenguang¹^,²^,³, ZHENG Bingyun¹^,²^,³

^1.College of Environmental and Biological Engineering, Putian University, Putian 351100, Fujian, China
^2.Fujian Provincial Key Laboratory of Ecology-Toxicological Effects & Control for Emerging Contaminants, Putian 351100, Fujian, China
^3.Key Laboratory of Ecological Environment and Information Atlas, Fujian Provincial University, Putian 351100, Fujian, China

Received:2022-01-28 Revised:2022-03-04 Online:2022-06-10 Published:2022-06-21
Contact: CHEN Zhangxu

摘要/Abstract

摘要：

为了有效解决日益严重的水污染问题，本文研究了β-NaYF₄: Yb³⁺, Tm³⁺/g-C₃N₄复合材料的制备及其在可见光下催化降解亚甲基蓝模拟废水的最佳工艺条件。首先，利用溶剂热法合成了β-NaYF₄: Yb³⁺, Tm³⁺，再将煅烧法制备的 g-C₃N₄加入聚丙烯酸/聚乙烯醇水溶液，后滴入饱和硼酸溶液获得β-NaYF₄: Yb³⁺, Tm³⁺/g-C₃N₄/聚丙烯酸/聚乙烯醇复合水凝胶。利用X射线衍射仪、场发射扫描电子显微镜、紫外-可见分光光度计、热重分析仪、全自动比表面积微孔孔隙分析仪等进行表征；利用正交试验L₁₆(4⁵)考察复合材料的投加量、复合材料的比例、温度、亚甲基蓝溶液的pH、光照时间等因素，探索降解亚甲基蓝的最佳工艺条件。正交试验结果表明：光照时间为20.0h、pH为7.00、复合材料的投加量0.25g、温度20.0℃、复合材料活性组分β-NaYF₄: Yb³⁺, Tm³⁺与g-C₃N₄的比例为1∶4，此时对30.0mg/L亚甲基蓝降解率达到94.84%，循环降解亚甲基蓝模拟废水4次后的降解率仍高达为86.22%。

关键词: β-NaYF₄:Yb³⁺,Tm³⁺, 氮化碳, 水凝胶, 亚甲基蓝, 复合材料, 催化, 降解, 再生

Abstract:

To deal with the problem of water pollution effectively, the preparation of β-NaYF₄: Yb³⁺, Tm³⁺/g-C₃N₄ composites and the optimum conditions for photocatalytic degrading methylene blue wastewater under visible light were studied. β-NaYF₄: Yb³⁺, Tm³⁺ and g-C₃N₄ were synthesized by solvothermal method and calcinations method, respectively. Then, β-NaYF₄: Yb³⁺, Tm³⁺ and g-C₃N₄ were mixed and added into the solution of polyacrylic acid-polyvinyl alcohol. The β-NaYF₄: Yb³⁺, Tm³⁺/g-C₃N₄/PAA/PVA composite hydrogel was formed by adding the above mixed solution to the saturated borate aqueous solution dropwise with hard stirring. The products were characterized by X-ray diffractometer, field emission scanning electron microscope, UV-visible spectrophotometer, thermal gravimetric analyzer and specific surface area microporous pore analyzer and so on. The orthogonal experiment L₁₆ (4⁵) was used to explore the optimal conditions for degrading methylene blue. The results showed that the degradation rate of methylene blue in 30mg/L was 94.84% under the optimal conditions of the illumination time 20.0 h, the pH value 7.00, the dosage of composite materials 0.25 g, the temperature 20.0℃ and the ratio of active material β-NaYF₄: Yb³⁺, Tm³⁺ to g-C₃N₄ 1∶4. Moreover, the degradation rate of methylene blue in simulated wastewater was still up to 86.22% after 4 recycles. This study revealed that the prepared composite had a good practical value for the application in wastewater treatment.

Key words: β-NaYF₄: Yb³⁺, Tm³⁺, g-C₃N₄, hydrogel, methylene blue, composites, catalysis, degradation, regeneration

中图分类号:

陈彰旭, 陈冰冰, 王荣财, 叶晨光, 郑炳云. β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄复合水凝胶材料的制备及其应用[J]. 化工进展, 2022, 41(6): 3146-3154.

CHEN Zhangxu, CHEN Bingbing, WANG Rongcai, YE Chenguang, ZHENG Bingyun. Preparation and application of β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄ composite hydrogel[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3146-3154.

图/表 13

参考文献 17

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复合水凝胶中UC/CN质量比	PP复合水溶液质量/g	UC质量 /g	CN质量 /g	代号
1∶4	4.5	0.1	0.4	UCCNPP14
2∶3	4.5	0.2	0.3	UCCNPP23
3∶2	4.5	0.3	0.2	UCCNPP32
4∶1	4.5	0.4	0.1	UCCNPP41
1∶0	4.5	0.5	0	UCCNPP10
0∶1	4.5	0	0.5	UCCNPP01
0∶0	5.0	0	0	UCCNPP00 （PP）
1∶0	0	0.5	0	UC
0∶1	0	0	0.5	CN

复合水凝胶中UC/CN质量比	PP复合水溶液质量/g	UC质量 /g	CN质量 /g	代号
1∶4	4.5	0.1	0.4	UCCNPP14
2∶3	4.5	0.2	0.3	UCCNPP23
3∶2	4.5	0.3	0.2	UCCNPP32
4∶1	4.5	0.4	0.1	UCCNPP41
1∶0	4.5	0.5	0	UCCNPP10
0∶1	4.5	0	0.5	UCCNPP01
0∶0	5.0	0	0	UCCNPP00 （PP）
1∶0	0	0.5	0	UC
0∶1	0	0	0.5	CN

因素水平	光照时间 /h	温度 /℃	pH	复合水凝胶材料投加量/g	复合水凝胶材料中 UC/CN质量比
1	5.0	15.0	5.00	0.10	1∶4（UCCNPP14）
2	10.0	20.0	6.00	0.15	2∶3（UCCNPP23）
3	15.0	25.0	7.00	0.20	3∶2（UCCNPP32）
4	20.0	30.0	8.00	0.25	4∶1（UCCNPP41）

因素水平	光照时间 /h	温度 /℃	pH	复合水凝胶材料投加量/g	复合水凝胶材料中 UC/CN质量比
1	5.0	15.0	5.00	0.10	1∶4（UCCNPP14）
2	10.0	20.0	6.00	0.15	2∶3（UCCNPP23）
3	15.0	25.0	7.00	0.20	3∶2（UCCNPP32）
4	20.0	30.0	8.00	0.25	4∶1（UCCNPP41）

因素	光照时间(A)/h	温度(B)/℃	pH(C)	复合材料投加量(D)/g	复合材料活性组分UC/CN配比(E)	降解率/%
实验1	5.0	15.0	5.00	0.10	1∶4	41.75
实验2	5.0	20.0	6.00	0.15	2∶3	58.71
实验3	5.0	25.0	7.00	0.20	3∶2	67.29
实验4	5.0	30.0	8.00	0.25	4∶1	69.83
实验5	10.0	15.0	6.00	0.20	4∶1	74.03
实验6	10.0	20.0	5.00	0.25	3∶2	74.98
实验7	10.0	25.0	8.00	0.10	2∶3	78.16
实验8	10.0	30.0	7.00	0.15	1∶4	82.54
实验9	15.0	15.0	7.00	0.25	2∶3	84.47
实验10	15.0	20.0	8.00	0.20	1∶4	83.97
实验11	15.0	25.0	5.00	0.15	4∶1	71.04
实验12	15.0	30.0	6.00	0.10	3∶2	71.39
实验13	20.0	15.0	8.00	0.15	3∶2	88.75
实验14	20.0	20.0	7.00	0.10	4∶1	89.41
实验15	20.0	25.0	6.00	0.25	1∶4	89.94
实验16	20.0	30.0	5.00	0.20	2∶3	77.84
验证	20.0	20.0	7.00	0.25	1∶4	94.84
均值1	59.395	72.25	66.403	70.178	74.550
均值2	77.427	76.767	73.517	75.260	74.795
均值3	77.718	76.608	80.928	75.782	75.603
均值4	86.485	75.400	80.178	79.805	76.078
极差	27.090	4.517	14.525	9.627	1.528
因素主次	A＞C＞D＞B＞E
最佳方案	A₄C₃D₄B₂E₄

β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄复合水凝胶材料的制备及其应用

Preparation and application of β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄ composite hydrogel

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