skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on December 22, 2018

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

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:
Report Number(s):
BNL-203399-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:
SC0012704; SC0012445; AC02-06CH11357; 21476115
Type:
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)
Research Org:
Brookhaven National Laboratory (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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; MOFs; zirconium; metal-cyclam; CO2 fixation
OSTI Identifier:
1430863