以淀粉为模板多孔纳米氧化铈的制备及其催化性能研究

赵国峥; 李长波; 廉畅; 裴芳; 王晨昊; 付国玲

doi:10.13198/j.issn.1001-6929.2018.08.10

以淀粉为模板多孔纳米氧化铈的制备及其催化性能研究

doi: 10.13198/j.issn.1001-6929.2018.08.10

1.
辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
2.
东北制药集团股份有限责任公司, 辽宁沈阳 110027
3.
中船第九设计研究院工程有限公司, 上海 200063
4.
大连东达环境集团春柳河污水处理有限公司, 辽宁大连 116000

基金项目:

国家水体污染控制与治理科技重大专项 2012ZX07202-002

详细信息

作者简介:
赵国峥(1981-), 女, 黑龙江双城人, 讲师, 硕士, 主要从事石化行业水污染控制及资源化技术研究, lnpulcb@126.com

中图分类号: X703.1
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- 被引次数: 0
出版历程
- 收稿日期: 2018-03-15
- 修回日期: 2018-08-15
- 刊出日期: 2019-01-25

Synthesis of Porous Nano Cerium Oxide Using Starch as Template and Their Catalytic Performance Investigation

1.
College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Northeast Pharmaceutical Co., Ltd., Shenyang 110027, China
3.
China Shipbuilding Ninth Design & Research Institute Engineering Co., Ltd., Shanghai 200063, China
4.
Dalian Dongda Environment Group Chun Liu River Sewage Treatment Company Limited, Dalian 116000, China

Funds:

National Major Science and Technology Program for Water Pollution Control and Treatment, China 2012ZX07202-002

摘要

摘要: 为获得多孔纳米CeO₂（氧化铈），以淀粉为生物模板，以Ce（NO₃）₃·6H₂O为铈源，在温和条件下制备出海绵状的多孔纳米CeO₂，同时考察了焙烧温度、碱液、铈源投加量对样品形貌的影响.利用XRD（X射线衍射光谱）、SEM（扫描电镜）、N₂吸附-脱附等表征手段对合成的多孔纳米CeO₂进行物相组成、微观形貌及孔径大小分布的分析.通过湿式催化过氧化试验，探究其对腈纶废水中有机物COD_Cr的催化降解性能.结果表明：①所制备的多孔纳米CeO₂具有多孔结构，孔径分布范围为2~4 nm，孔容为0.225 cm³/g，BET比表面积为256.426 m²/g；②多孔纳米CeO₂的最佳制备条件为1 g淀粉溶解于20 mL水中，加入0.02 mol Ce（NO₃）₃·6H₂O，以5%的氨水调节前驱体混合液pH，以1℃/min升至400℃，焙烧4 h，得到海绵状的多孔纳米CeO₂.③以不同形貌的CeO₂作为湿式催化反应中的催化剂，催化降解腈纶废水中有机物，其中以制备的多孔纳米CeO₂催化性能最佳，COD_Cr去除率可达82.5%.研究显示，焙烧温度、碱液、铈源投加量均可影响样品的形貌，在湿式催化过氧化处理腈纶废水试验中，多孔纳米CeO₂能显著提高废水COD_Cr的去除率.
- 淀粉 /
- 多孔纳米CeO₂ /
- 催化剂 /
- 湿式催化过氧化
Abstract: In order to obtain porous nano CeO₂(cerium oxide), starch and Ce(NO₃)₃·6H₂O were employed as a biotemplate agent and cerium source, respectively. The porous nano CeO₂ was synthesized under mild conditions. Subsequently, the influence of calcination temperature and dosage of alkali and Ce(NO₃)₃·6H₂O on the morphology of the porous nano CeO₂ were investigated. The synthesized CeO₂ was characterized by X-ray diffraction (XRD), N₂ adsorption-desorption, and scanning electron microscopy (SEM). Furthermore, the catalytic performance was studied through the treatment of acrylic fiber wastewater by a catalytic wet peroxide oxidation method. The results indicated that:(1) The nano CeO₂ had a porous structure and with pore size between 2-4 nm, pore volume of 0.225 cm³/g and BET surface area of 256.426 m²/g. (2) The optimum conditions for the preparation of the porous nano CeO₂ were:dissolution of 1 g starch in 20 mL water followed by addition of 0.02 mol Ce(NO₃)₃·6H₂O; pH adjustment of the precursor mixture using an aqueous solution of ammonia (5%); and calcination at 400℃ for 4 h with the heating rate of 1℃/min in air. A nano CeO₂ with cavernous porous structure was obtained. (3) CeO₂ with different morphologies was used as catalyst in wet catalytic reactions for degrading refractory organic matters in acrylic wastewaters. The best catalytic efficiency was obtained with the prepared porous nano CeO₂, and the removal rate of COD_Cr reached 82.5%. In conclusion, the morphology of the CeO₂ was affected by the calcination temperature and dosage of alkali and Ce(NO₃)₃·6H₂O. This porous nano CeO₂ can be used as an effective catalyst for treatment of acrylic wastewaters in wet catalytic peroxidation processes. The removal efficiency of COD_Cr could be significantly improved.
- soluble starch /
- porous nano cerium oxide /
- catalyst /
- wet catalytic peroxide

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图 1 多孔纳米CeO₂的XRD分析

Figure 1. XRD analysis of porous nano CeO₂

下载: 全尺寸图片幻灯片

图 2 多孔纳米CeO₂的N₂吸附-脱附曲线

Figure 2. N₂ adsorption desorption curve of porous nano CeO₂

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图 3 多孔纳米CeO₂孔径分布曲线

Figure 3. Pore diameter distribution of porous nano CeO₂

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图 4 不同焙烧温度制得多孔纳米CeO₂的SEM

Figure 4. SEM images of porous nano CeO₂ obtained at different temperatures

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图 5 不同碱液制得多孔纳米CeO₂的SEM

Figure 5. SEM images of porous nano CeO₂ obtained from different lye

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图 6 不同Ce(NO₃)₃ ·6H₂O投加量制得多孔纳米CeO₂的SEM

Figure 6. SEM image of porous nano CeO₂ at different dosage of Ce(NO₃)₃ ·6H₂O

下载: 全尺寸图片幻灯片

图 7 COD_Cr去除率比对

注：a—未加CeO₂；b—分析纯CeO₂；c—无孔纳米CeO₂；d—多孔纳米CeO₂.

Figure 7. Comparison chart of COD_Cr removal efficiency

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