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Title: A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation

Abstract

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 Zr 6 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 CO 2 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 CO 2 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 themore » same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [3];  [1];  [1];  [1]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division
  3. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemical Engineering and Macromolecules Innovation Inst.
  4. Nanjing Univ. of Technology (China). State Key Lab. of Materials-Oriented Chemical Engineering (MCE) and College of Chemical Engineering
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
  6. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry and Macromolecules Innovation Inst.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1430863
Alternate Identifier(s):
OSTI ID: 1421945
Report Number(s):
BNL-203399-2018-JAAM
Journal ID: ISSN 0002-7863; 141320
Grant/Contract Number:  
SC0012704; SC0012445; AC02-06CH11357; 21476115
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 3; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; CO2 fixation; MOFs; metal-cyclam; zirconium

Citation Formats

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., and Morris, Amanda J. A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO2 Adsorption and Chemical Fixation. United States: N. p., 2017. Web. doi: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. A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO2 Adsorption and Chemical Fixation. United States. doi: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., and Morris, Amanda J. Fri . "A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO2 Adsorption and Chemical Fixation". United States. doi:10.1021/jacs.7b10643. https://www.osti.gov/servlets/purl/1430863.
@article{osti_1430863,
title = {A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO2 Adsorption and Chemical Fixation},
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 Zhu, Dunru and Senanayake, Sanjaya D. and Morris, Amanda J.},
abstractNote = {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},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 3,
volume = 140,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Anisotropic displacement ellipsoid drawing (30%) of (a) [CuL(ClO4)2] (1), (b) [NiL](ClO4)2 (3), (c) [CuLCl2] (4) and (d) [NiLCl2]·2DMF (5). Hydrogen atoms were omitted for clarity. Color scheme: C, grey; O, red; N, blue; Ni, light green; Cu, yellow; Cl, green.

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Works referencing / citing this record:

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CCDC 1576954: Experimental Crystal Structure Determination
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Formation of CX Bonds in CO 2 Chemical Fixation Catalyzed by Metal−Organic Frameworks
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