TY - JOUR
T1 - Synthetic Origin-Dependent catalytic activity of Metal-Organic Frameworks
T2 - Unprecedented demonstration with ZIF-8 s on CO2 cycloaddition reaction
AU - Lee, Gihoon
AU - Lee, Minseong
AU - Jeong, Yanghwan
AU - Jang, Eunhee
AU - Baik, Hionsuck
AU - Chul Jung, Ji
AU - Choi, Jungkyu
N1 - Funding Information:
This work was supported by the C1 Gas Refinery Program (2018M3D3A1A01018004) and the Super Ultra Low Energy and Emission Vehicle Engineering Research Center (SULEEV ERC) (2016R1A5A1009592) through the National Research Foundation of Korea (NRF) funded by the Korea Government (Ministry of Science and ICT; MSIT). TEM characterizations were conducted at the Seoul Center in the Korea Basic Science Institute (KBSI).
Funding Information:
This work was supported by the C1 Gas Refinery Program (2018M3D3A1A01018004) and the Super Ultra Low Energy and Emission Vehicle Engineering Research Center (SULEEV ERC) (2016R1A5A1009592) through the National Research Foundation of Korea (NRF) funded by the Korea Government (Ministry of Science and ICT; MSIT). TEM characterizations were conducted at the Seoul Center in the Korea Basic Science Institute (KBSI).
Publisher Copyright:
© 2022 The Authors
PY - 2022/5/1
Y1 - 2022/5/1
N2 - In this study, the catalytic activities of three types of zeolitic imidazolate framework-8 (ZIF-8) (two types were synthesized in aqueous and methanolic media, while the other was commercially available) with respect to CO2 cycloaddition to epichlorohydrin were evaluated. Surprisingly, only the ZIF-8 that was synthesized in an aqueous medium showed a marked catalytic performance, leading to the generation of the desired product, chloropropene carbonate. On the contrary, the other two types of ZIF-8 showed little to no catalytic activity. It is conjectured that the water molecules occluded inside the as-synthesized ZIF-8 triggered the dissociation of Zn-N bonds, resulting in a concomitant transformation to a new, dense phase. Accordingly, it is plausible that dissociated Zn or N species were formed during the reaction. In particular, we found that the dissociated N species arising from the dissociation of Zn-N bonds were pyrrolic and pyridinic, while the dissociated Zn species were bound to hydroxyl groups. Finally, complementary interpretation of CO2– and NH3-based temperature-programmed desorption and NH3-adsorbed Fourier transform infrared spectroscopy results revealed that the dissociated Zn species connected with hydroxyl groups, observed only in the ZIF-8 synthesized in an aqueous medium, served simultaneously as Lewis acids and bases and, thus, were crucial to the CO2 cycloaddition reaction.
AB - In this study, the catalytic activities of three types of zeolitic imidazolate framework-8 (ZIF-8) (two types were synthesized in aqueous and methanolic media, while the other was commercially available) with respect to CO2 cycloaddition to epichlorohydrin were evaluated. Surprisingly, only the ZIF-8 that was synthesized in an aqueous medium showed a marked catalytic performance, leading to the generation of the desired product, chloropropene carbonate. On the contrary, the other two types of ZIF-8 showed little to no catalytic activity. It is conjectured that the water molecules occluded inside the as-synthesized ZIF-8 triggered the dissociation of Zn-N bonds, resulting in a concomitant transformation to a new, dense phase. Accordingly, it is plausible that dissociated Zn or N species were formed during the reaction. In particular, we found that the dissociated N species arising from the dissociation of Zn-N bonds were pyrrolic and pyridinic, while the dissociated Zn species were bound to hydroxyl groups. Finally, complementary interpretation of CO2– and NH3-based temperature-programmed desorption and NH3-adsorbed Fourier transform infrared spectroscopy results revealed that the dissociated Zn species connected with hydroxyl groups, observed only in the ZIF-8 synthesized in an aqueous medium, served simultaneously as Lewis acids and bases and, thus, were crucial to the CO2 cycloaddition reaction.
KW - CO cycloaddition
KW - CO utilization
KW - Structural transformation
KW - Zeolitic imidazolate framework-8
UR - http://www.scopus.com/inward/record.url?scp=85124043120&partnerID=8YFLogxK
U2 - 10.1016/j.cej.2022.134964
DO - 10.1016/j.cej.2022.134964
M3 - Article
AN - SCOPUS:85124043120
SN - 1385-8947
VL - 435
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 134964
ER -