Synthesis and Characteristics of Functional Mesoporous Metal-Organic Frameworks with Immobilized Phosphotungstic Acid
HAO Jinlei1, ZHANG Guihua2, WANG Yan1,3, WAN Jinquan1,3, MA Yongwen1,3, HUANG Liyan1
1 School of Environment and Energy, South China University of Technology, Guangzhou 510006; 2 Huizhou Institute of Environmental Science, Huizhou 516001; 3 State Key Laboratory of Pulp and Paper Engineering, Guangzhou 510640
Abstract: Obtaining large pore carriers to immobilize phosphotungstic acid (PTA) is of great significance for the catalytic conversion of big molecular substances. In this study, the surfactant cetyltrimethylammonium bromide (CTAB) was applied as a structure-directing agent for metal-organic frameworks (MOFs). MIL-101(Cr) was synthesized with -NH2 and -Cl to realize its functiona-lization, and well-dispersed PTA on MIL-101(Cr) was obtained. It was found that with the addition of CTAB, although the obtained samples maintained the MIL-101 structure, their crystal growth became poor gradually with adding amount of CTAB and possessed great thermal stability. MOFs’ surface areas and pore sizes increased with the increase of CTAB. Samples switched from microporous structure to micro-mesoporous structure when MOFs coexisted with the adding of CTAB. Moreover, the mesoporous structures increased along with the increase of CTAB. When the adding amount of CTAB was 5.4 mmol, the optimum mesoporous ratio reached the peak with about 87%, mainly with pore sizes of 3.9 nm and 46.1 nm. The addition of CTAB would not interfere with the electrostatic interaction between -NH2 and PTA, but the amount of immobilized PTA increased first and then decreased with the increase of CTAB. The immobilized PTA reached the maximum at CTAB equals to 3.6 mmol. As the amount of loading PTA, the glucose yield of cellulose hydrolysis catalyzed has same trend. The yield of glucose can reach 76.35% of the catalytic effect compared with same amount of non-immobilized PTA. After three consecutive catalytic hydrolysis of microcrystalline cellulose samples, the glucose yield decreased by only about 5%, indicating that grafted -NH2 exerts its function of immobilization PTA by electrostatic interaction and reduces the loss of PTA.
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2018, Vol. 32 
