skip to main content

DOE PAGESDOE PAGES

Title: Insights into CO 2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks

Here, metal–organic frameworks (MOFs) have shown great promise as efficient CO 2 adsorbents, as well as an emerging class of heterogeneous catalysts for conversion of CO 2 to other useful chemicals. In this work, we synthesized and characterized two isostructural hafnium-based MOFs, denoted as Hf-VPI-100 (Cu) and Hf-VPI-100 (Ni). Both frameworks demonstrated high catalytic efficiency for cycloaddition of CO 2 to epoxides under ambient pressure. In situ PXRD, QCM and DRIFTs have been used to probe the interaction between the guest molecules (CO 2/epoxide) and Hf-VPI-100. The crystal structures of these frameworks were preserved during the exposure to CO 2 atmosphere up to 20 bar. The epoxide uptake per unit cell of VPI-100 and diffusion coefficients have been calculated by QCM analysis. Comparison of catalytic efficiency between Hf-VPI-100 and the previously reported Zr-based VPI-100, aided by electronic structure calculations revealed that the open metal centers in the metallocyclam act as the primary Lewis acid sites to facilitate the catalytic conversion of CO 2.
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
BNL-211361-2019-JAAM
Journal ID: ISSN 2050-7488; JMCAET; 146984
Grant/Contract Number:
AC02-06CH11357; SC0012445; SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 44; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1498866
Alternate Identifier(s):
OSTI ID: 1469235; OSTI ID: 1493738

Zhu, Jie, Liu, Jianzhao, Machain, Yered, Bonnett, Brittany, Lin, Shaoyang, Cai, Meng, Kessinger, Matthew C., Usov, Pavel M., Xu, Wenqian, Senanayake, Sanjaya D., Troya, Diego, Esker, Alan R., and Morris, Amanda J.. Insights into CO2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks. United States: N. p., Web. doi:10.1039/C8TA06383D.
Zhu, Jie, Liu, Jianzhao, Machain, Yered, Bonnett, Brittany, Lin, Shaoyang, Cai, Meng, Kessinger, Matthew C., Usov, Pavel M., Xu, Wenqian, Senanayake, Sanjaya D., Troya, Diego, Esker, Alan R., & Morris, Amanda J.. Insights into CO2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks. United States. doi:10.1039/C8TA06383D.
Zhu, Jie, Liu, Jianzhao, Machain, Yered, Bonnett, Brittany, Lin, Shaoyang, Cai, Meng, Kessinger, Matthew C., Usov, Pavel M., Xu, Wenqian, Senanayake, Sanjaya D., Troya, Diego, Esker, Alan R., and Morris, Amanda J.. 2018. "Insights into CO2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks". United States. doi:10.1039/C8TA06383D. https://www.osti.gov/servlets/purl/1498866.
@article{osti_1498866,
title = {Insights into CO2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks},
author = {Zhu, Jie and Liu, Jianzhao and Machain, Yered and Bonnett, Brittany and Lin, Shaoyang and Cai, Meng and Kessinger, Matthew C. and Usov, Pavel M. and Xu, Wenqian and Senanayake, Sanjaya D. and Troya, Diego and Esker, Alan R. and Morris, Amanda J.},
abstractNote = {Here, metal–organic frameworks (MOFs) have shown great promise as efficient CO2 adsorbents, as well as an emerging class of heterogeneous catalysts for conversion of CO2 to other useful chemicals. In this work, we synthesized and characterized two isostructural hafnium-based MOFs, denoted as Hf-VPI-100 (Cu) and Hf-VPI-100 (Ni). Both frameworks demonstrated high catalytic efficiency for cycloaddition of CO2 to epoxides under ambient pressure. In situ PXRD, QCM and DRIFTs have been used to probe the interaction between the guest molecules (CO2/epoxide) and Hf-VPI-100. The crystal structures of these frameworks were preserved during the exposure to CO2 atmosphere up to 20 bar. The epoxide uptake per unit cell of VPI-100 and diffusion coefficients have been calculated by QCM analysis. Comparison of catalytic efficiency between Hf-VPI-100 and the previously reported Zr-based VPI-100, aided by electronic structure calculations revealed that the open metal centers in the metallocyclam act as the primary Lewis acid sites to facilitate the catalytic conversion of CO2.},
doi = {10.1039/C8TA06383D},
journal = {Journal of Materials Chemistry. A},
number = 44,
volume = 6,
place = {United States},
year = {2018},
month = {8}
}

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012
  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie, Vol. 124, Issue 41, p. 10453-10456
  • DOI: 10.1002/ange.201204475

A Hafnium-Based Metal�Organic Framework as an Efficient and Multifunctional Catalyst for Facile CO2 Fixation and Regioselective and Enantioretentive Epoxide Activation
journal, October 2014
  • Beyzavi, M. Hassan; Klet, Rachel C.; Tussupbayev, Samat
  • Journal of the American Chemical Society, Vol. 136, Issue 45, p. 15861-15864
  • DOI: 10.1021/ja508626n