Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemical Engineering and Macromolecules Innovation Inst.
Nanjing Univ. of Technology (China). State Key Lab. of Materials-Oriented Chemical Engineering (MCE) and College of Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry and Macromolecules Innovation Inst.
Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO2 uptake capacity (up to ~9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO2 with epoxides, including sterically hindered epoxides. Thus, the MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.
Zhu, Jie, et al. "A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO<sub>2</sub> Adsorption and Chemical Fixation." Journal of the American Chemical Society, vol. 140, no. 3, Dec. 2017. https://doi.org/10.1021/jacs.7b10643
Zhu, Jie, Usov, Pavel M., Xu, Wenqian, Celis-Salazar, Paula J., Lin, Shaoyang, Kessinger, Matthew C., Landaverde-Alvarado, Carlos, Cai, Meng, May, Ann M., Slebodnick, Carla, Zhu, Dunru, Senanayake, Sanjaya D., & Morris, Amanda J. (2017). A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO<sub>2</sub> Adsorption and Chemical Fixation. Journal of the American Chemical Society, 140(3). https://doi.org/10.1021/jacs.7b10643
Zhu, Jie, Usov, Pavel M., Xu, Wenqian, et al., "A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO<sub>2</sub> Adsorption and Chemical Fixation," Journal of the American Chemical Society 140, no. 3 (2017), https://doi.org/10.1021/jacs.7b10643
@article{osti_1421945,
author = {Zhu, Jie and Usov, Pavel M. and Xu, Wenqian and Celis-Salazar, Paula J. and Lin, Shaoyang and Kessinger, Matthew C. and Landaverde-Alvarado, Carlos and Cai, Meng and May, Ann M. and Slebodnick, Carla and others},
title = {A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO<sub>2</sub> Adsorption and Chemical Fixation},
annote = {Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO2 uptake capacity (up to ~9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO2 with epoxides, including sterically hindered epoxides. Thus, the MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.},
doi = {10.1021/jacs.7b10643},
url = {https://www.osti.gov/biblio/1421945},
journal = {Journal of the American Chemical Society},
issn = {ISSN 0002-7863},
number = {3},
volume = {140},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2017},
month = {12}}
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Argonne National Laboratory (ANL); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357; SC0012446; SC0012704
OSTI ID:
1421945
Alternate ID(s):
OSTI ID: 1430863
Report Number(s):
BNL--203399-2018-JAAM; 141320
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 3 Vol. 140; ISSN 0002-7863
