Abstract: Direct mixing (de novo) and Solvent Assisted Ligand Exchange (SALE) are the main methods used for the synthesis of Mixed-Linker Zeolitic Imidazolate Frameworks (ML-ZIFs). ML-ZIFs with combined -NO2 and -Br/-Cl functionalities were prepared via both synthetic routes. Thereafter the CO2 uptake of the ML-ZIFs were compared, as well as their abilities to fixate CO2 with epoxide substrates. The de novo synthesis resulted in ML-ZIFs with SOD topologies, 60: 40 (-NO2: -Br/-Cl) functionality ratios, higher porosities, better thermal stability and higher CO2 uptake than equivalent SALE products. SALE resulted in smaller ML-ZIF crystallites, only ～ 10% incorporation of -Br/-Cl functionalized imidazolate linkers, and phase change during activation. ML-ZIF-7Cl, obtained from direct mixing, resulted in the highest CO2 uptake (90 cm3 g-1), in line with its higher porosity. ML-ZIF-7Cl, in combination with tetrabutylammonium bromide (TBAB), showed a high catalytic activity (TOF of 446 h-1) for the fixation of CO2 with propylene oxide and was reusable for up to 4 cycles without loss in activity.
Keywords:
Zeolitic imidazolate frameworks (ZIFs) ; Solvent assisted ligand exchange (SALE) ; De Novo synthesis ; CO2 uptake ; CO2 fixation
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[2] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
2
[ 67-56-1 ]
[ 124-38-9 ]
[ 75-56-9 ]
[ 108-32-7 ]
[ 57-55-6 ]
[ 107-98-2 ]
[ 1589-47-5 ]
[ 616-38-6 ]
Yield
Reaction Conditions
Operation in experiment
13.2%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
12.5%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
5.8%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
23%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
7.8%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[2] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[3] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[4] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[5] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
[6] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
[7] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[8] Frontiers of Chemistry in China, 2011, vol. 6, # 1, p. 21 - 30
3
[ 67-56-1 ]
[ 124-38-9 ]
[ 75-56-9 ]
[ 108-32-7 ]
[ 57-55-6 ]
[ 107-98-2 ]
[ 1589-47-5 ]
Yield
Reaction Conditions
Operation in experiment
52.4%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin?1, and further reached 220°C at the rate of 30°Cmin?1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
 and De Novo Synthetic Routes on CO2 Uptake and Fixation by Mixed-Linker Zeolitic Imidazolate Frameworks.png)
