高比表面积二氧化锆的合成及其催化应用

doi:10.16085/j.issn.1000-6613.2018-1106

摘要/Abstract

摘要：

二氧化锆（ZrO₂）是一种优异的催化材料，同时具有表面酸碱性，易产生氧空位，耐高温、抗腐蚀，机械强度高。然而传统方法合成的二氧化锆比表面积和孔容较小，限制了其应用。本文介绍了近年来高比表面积多孔二氧化锆的合成方法和技术，包括模板法、MOF热解法、静电纺丝等以及提高其热稳定性的措施，同时简述了其在催化领域的应用。研究表明，此类高比表面积的二氧化锆可以提高负载金属分散度，加强金属-载体相互作用，进而提高催化剂活性和稳定性，同时其粒径大小、形貌、孔结构均会影响其催化性能。高效低成本合成热稳定的高比表面积二氧化锆并对对其形貌和结构进行精准调控，将使其未来具有更广的催化应用前景。

关键词: 二氧化锆, 比表面积, 催化, 多孔材料, 纳米材料

Abstract:

Zirconium dioxide (ZrO₂) is an excellent catalytic material, due to its high-temperature resistance, corrosion resistance and high mechanical strength. Besides, it has both acid and basic sites on the surface and is able to produce oxygen vacancy. However, ZrO₂ prepared by conventional methods has low surface area and pore volume, which may limit its broad applications. The recent preparation methods or techniques of high-surface-area ZrO₂, including templating methods, MOF pyrolysis, and electrostatic spinning,so as to improve its thermal stability and to extend its applications in catalysis are reviewed. The studies showed that the porous ZrO₂ can improve the dispersion of the supported metal and the metal-support interaction, giving rise to the enhanced activity and stability of the catalysts. Meanwhile, its particle size, morphology and pore structure also have effects on the catalytic performance. The high-efficient and low-cost preparation methods of thermal stable high-surface-area ZrO₂, and the accurate regulation of its morphology or structure, will give it a broader catalytic application prospect in the future.

Key words: zirconium dioxide（ZrO₂）, specific surface area, catalysis, porous materials, nanomaterials

中图分类号:

O643.3

朱杰, 李文慧, 刘邦荐, 慕旻辰, 郭新闻. 高比表面积二氧化锆的合成及其催化应用[J]. 化工进展, 2019, 38(01): 315-323.

Jie ZHU, Wenhui LI, Bangjian LIU, Minchen MU, Xinwen GUO. Preparation of high-surface-area ZrO₂ and its application in catalysis[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 315-323.

图/表 8

表1 模板法合成的高比表面积ZrO2

锆源	模板	比表面积 /m²·g^-1	孔容 /cm³·g^-1	孔径 /nm	晶型	文献
氧氯化锆	F127	97	0.14	4.1	四方相	[11]
四氯化锆	CTAB	573	0.76	5.2	单斜相	[12]
氧氯化锆	SDS	113	—	5.0	单斜相	[13]
正丁醇锆	F127	124	0.16	4.8	四方相	[14]
氧氯化锆	SBA-15	248	0.30	3.0~4.0	四方相	[15]
氧氯化锆	KIT-6	391	0.54	3.4	四方相	[16]
四氯化锆	多孔SiO₂	293	0.60	7.3	四方相	[17]
UiO-66	UiO-66	174	0.21	5.0~8.0	四方相	[18]

图1 以P123为软模板结合静电纺丝技术合成ZrO2纤维示意图[19]

图2 “表面铸造”法合成ZrO2纳米管示意图[16]

图3 球形和块状有序介孔二氧化锆的透射电镜照片、吸附等温线和孔径分布曲线

图4 热解UiO-66制备高比表面积ZrO2的示意图[18]及NH2-UiO-66和含氮Co/ZrO2催化剂电镜照片

图5 添加硅氧烷合成热稳定的多孔ZrO2示意图[36]

图6 球形中空Ni/ZrO2催化剂催化辛酸脱氧反应示意图[42]及多孔ZrO2骨架负载Ni催化生物质加氢示意图[43]

图7 高比表面积多孔Ni/ZrO2催化二氧化碳甲烷干重整反应[4]

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