利用钛有机骨架材料制备微米级TiO2色谱填料

doi:10.3969/j.issn.1006-396X.2021.04.003

摘要/Abstract

摘要：

以钛有机骨架材料（MIL?125(Ti)）作为核和壳材料，通过外延生长法合成了粒径更大、更均匀的核壳材料，即MIL?125(Ti)包覆MIL?125(Ti) (MOFs@MOFs)，再通过煅烧可得到微米级TiO₂色谱填料。考察了核加入质量、壳溶液稀释倍数、反应时间、包覆层数等对包覆效果的影响，得到最佳的制备条件为核加入质量30 mg，不稀释壳溶液，反应24 h，包覆1层。结果表明，利用钛有机骨架材料制备得到的TiO₂色谱填料为锐钛矿型，比表面积76.0 m²/g，粒径可以达到7 μm左右，厚度为2.5 μm左右，不仅保留了其优良的性能，还具备粒径大、可调控多孔结构等特点。此外，该方法操作简便，无需苛刻的合成条件，可操作性强。

关键词: MIL?125(Ti), MOFs@MOFs, 核壳材料, TiO₂色谱填料, 外延生长法

Abstract:

Titanium metal?organic frameworks (MIL?125(Ti)) were used as the core and shell materials.On this basis,a core?shell material with larger and more uniform particle size denoted as MIL?125(Ti) coated MIL?125(Ti) (MOFs@MOFs) was synthesized by the epitaxial growth method, which was then calcined to obtain micron?sized chromatographic packing TiO₂.The preparation conditions,incuding adding amount of core materials,dilution times of shell solution,reaction time,and coating layers,were investigated,which were optimized to be that the amount of core was 30 mg,the shell solution should not be diluted,the reaction time was 24 h,and the coating layer was 1 layer.The results showed that the anatase TiO₂ materials with a specific surface area of 76.0 m²/g,a particle size of about 7 μm,and a thickness of about 2.5 μm,were successfully prepared by MOFs@MOFs,The synthesized TiO₂ not only retained the excellent performance of MOFs@MOFs but also featured a large particle size and adjustable porous structure.In addition,the method was easy to operate without demanding synthesis conditions,and had strong operability.

Key words: MIL?125(Ti), MOFs@MOFs, Core?shell material, Chromatographic packing TiO₂, Epitaxial growth method

中图分类号:

TS207.3

李书启, 刘真真, 李荣, 姜子涛. 利用钛有机骨架材料制备微米级TiO₂色谱填料[J]. 石油化工高等学校学报, 2021, 34(4): 14-20.

Shuqi Li, Zhenzhen Liu, Rong Li, Zitao Jiang. Preparation of Micron⁃Sized Chromatographic Packing TiO₂ by Titanium Organic Frameworks[J]. Journal of Petrochemical Universities, 2021, 34(4): 14-20.

图/表 13

图1 制备MOFs@MOFs及TiO2色谱填料原理示意

Fig.1 Schematic illustration for the syntheses of MOFs@MOFs and TiO2 chromatographic packing

图2 不同核加入质量制备的MOFs@MOFs显微照片（放大倍数400×）

Fig.2 Microscope images of MOFs@MOFs at different additions of MIL?125(Ti)(magnification times 400×)

图3 不同核加入质量制备的MOFs@MOFs的FTIR谱图

Fig.3 FTIR spectra of MOFs@MOFs at different additions of MIL?125(Ti)

图4 不同稀释倍数制备的MOFs@MOFs显微照片（放大倍数400×）

Fig.4 Microscope images of MOFs@MOFs) at different dilution times(magnification times 400×)

图5 不同稀释倍数制备的MOFs@MOFs的FTIR谱图

Fig.5 FTIR spectra of MOFs@MOFs) at different dilution times

图6 不同反应时间制备的MOFs@MOFs显微照片（放大倍数400×）

Fig.6 Microscope images of MOFs@MOFs at different reaction time (magnification times 400×)

图7 不同包覆层数制备的MOFs@MOFs显微照片（放大倍数400×）

Fig.7 Microscope images of MOFs@MOFs at different coating layers (magnification times 400×)

图8 MOFs@MOFs和MIL?125(Ti)以及分别煅烧后制备的TiO2的SEM图像

Fig.8 SEM images of MOFs@MOFs,MIL?125(Ti) and TiO2 prepared after calcination

图9 MOFs@MOFs及煅烧后制备的TiO2的EDS（a） MOFs@MOFs （b） TiO2/MOFs@MOFs

Fig.9 EDS images of MOFs@MOFs and TiO2 prepared after calcination

表1 材料中C、O和Ti元素质量分数

Table 1 Mass fraction of C,O and Ti in each material

材料	w（元素）/%
材料	C	O	Ti
MOFs@MOFs	50.44	34.62	14.95
TiO₂/MOFs@MOFs	6.75	37.20	56.07
MIL⁃125(Ti)	48.33	30.81	14.60
TiO₂/MIL⁃125(Ti)	9.43	41.42	49.15

图10 MOFs@MOFs和MIL?125(Ti) 以及煅烧后制备的TiO2 的XRD谱图（a）煅烧前（b）煅烧后

Fig.10 XRD figures of MOFs@MOFs,MIL?125(Ti) and TiO2 prepared after calcination

图11 TiO2色谱填料的孔径分布、累计孔体积及吸?脱附等温线（a）孔径分布、累计孔体积（b）吸?脱附等温线

Fig.11 Pore size distribution,accumulative pore volume and adsorption/desorption isotherms of TiO2 materials

图12 磷酸肽经分离富集前后的HPLC

Fig.12 HPLC images of phosphopeptides before and after separation and enrichment packing

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利用钛有机骨架材料制备微米级TiO₂色谱填料

Preparation of Micron⁃Sized Chromatographic Packing TiO₂ by Titanium Organic Frameworks

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