Modulating the Acidic and Basic Site Concentration of Metal-Organic Framework Derivatives to Promote the Carbon Dioxide Epoxidation Reaction |
| |
Authors: | Jinhua Ji Hao Liu Zewei Chen Yajun Fu Prof. Weijun Yang Prof. Shuang-Feng Yin |
| |
Affiliation: | College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082 P. R. China |
| |
Abstract: | Metal-organic framework (MOF) is an ideal precursor/template for porous carbon, and its active components are uniformly doped, which can be used in energy storage and catalytic conversion fields. Metal-organic framework PCN-224 with carboxylporphyrin as the ligand was synthesized, and then Zn2+ and Co2+ ions were coordinated in the center of the porphyrin ring by post-modification. Here, PCN-224−ZnCo with different ratios of bimetallic Zn2+/Co2+ ions were used as the precursor, and the metal-nitrogen-carbon(M−N−C) material of PCN-224−ZnCo-950 was obtained by pyrolyzing the precursor at 950 °C in Ar. Because Zn is easy to volatilize at 950 °C, the formed M−N−C materials can reflect different Co contents and different basic site concentrations. The formed material still maintains the original basic framework. With the increase of Zn2+/Co2+ ratio in precursor, the concentration of N-containing alkaline sites in pyrolysis products gradually increase. Compared with the precursor, PCN-224−ZnCo1-950 with Zn2+/Co2+=1 : 1 has greatly improved basicity and suitable acidic/ alkaline site concentration. It can be efficiently used to carbon dioxide absorption and catalyze the cycloaddition of CO2 with epoxide. More importantly, the current method of adjusting the acidic/basic sites in M−N−C materials through volatilization of volatile metals can provide an effective strategy for adjusting the catalysis of MOF derivatives with porphyrin structure. |
| |
Keywords: | carbon dioxide conversion cycloaddition metal-organic frameworks metalloporphyrin pyrolysis |
|
|