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

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

Abstract

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

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

CLC Number:

TS207.3

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.

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.

Figures/Tables 13

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

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

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

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

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

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

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

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

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

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

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

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

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

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

利用钛有机骨架材料制备微米级TiO₂色谱填料

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References 18

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