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

Abstract

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:
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)
OSTI Identifier:
1493738
Alternate Identifier(s):
OSTI ID: 1469235; OSTI ID: 1498866
Report Number(s):
BNL-211361-2019-JAAM
Journal ID: ISSN 2050-7488; JMCAET; 146984
Grant/Contract Number:  
AC02-06CH11357; SC0012445; SC0012704
Resource 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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., 2018. 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. Wed . "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/1493738.
@article{osti_1493738,
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}
}

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Cited by: 2 works
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Figures / Tables:

Fig. 1 Fig. 1: Proposed mechanism for the acid-catalysed (A) cyclic carbonate synthesis from epoxides and CO2 in the presence of a tetraalkylammonium halide (bromide).

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Works referenced in this record:

Benzene, Toluene, and Xylene Transport through UiO-66: Diffusion Rates, Energetics, and the Role of Hydrogen Bonding
journal, June 2018

  • Grissom, Tyler G.; Sharp, Conor H.; Usov, Pavel M.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 28
  • DOI: 10.1021/acs.jpcc.8b03356

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

Warming caused by cumulative carbon emissions towards the trillionth tonne
journal, April 2009

  • Allen, Myles R.; Frame, David J.; Huntingford, Chris
  • Nature, Vol. 458, Issue 7242
  • DOI: 10.1038/nature08019

Interaction parameters for the uptake of sulfur mustard mimics into polyurethane films
journal, June 2017


Interpenetrating Metal–Metalloporphyrin Framework for Selective CO 2 Uptake and Chemical Transformation of CO 2
journal, June 2016


Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals
journal, May 2011

  • Schaate, Andreas; Roy, Pascal; Godt, Adelheid
  • Chemistry - A European Journal, Vol. 17, Issue 24
  • DOI: 10.1002/chem.201003211

Adsorption and diffusion in thin films of nanoporous metal–organic frameworks: ferrocene in SURMOF Cu2(ndc)2(dabco)
journal, January 2013

  • Heinke, Lars; Wöll, Christof
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 23
  • DOI: 10.1039/c3cp50578b

Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge?
journal, August 2011

  • Cokoja, Mirza; Bruckmeier, Christian; Rieger, Bernhard
  • Angewandte Chemie International Edition, Vol. 50, Issue 37
  • DOI: 10.1002/anie.201102010

Molecular approaches to the electrochemical reduction of carbon dioxide
journal, January 2012

  • Finn, Colin; Schnittger, Sorcha; Yellowlees, Lesley J.
  • Chem. Commun., Vol. 48, Issue 10
  • DOI: 10.1039/C1CC15393E

Metal organic framework based catalysts for CO 2 conversion
journal, January 2017

  • Maina, James W.; Pozo-Gonzalo, Cristina; Kong, Lingxue
  • Materials Horizons, Vol. 4, Issue 3
  • DOI: 10.1039/C6MH00484A

Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks
journal, June 2015

  • Zhou, Wencai; Wöll, Christof; Heinke, Lars
  • Materials, Vol. 8, Issue 6
  • DOI: 10.3390/ma8063767

Metal-Organic Frameworks for CO 2 Chemical Transformations
journal, October 2016


The role of reticular chemistry in the design of CO2 reduction catalysts
journal, February 2018


Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination
journal, October 2013

  • Feng, Dawei; Chung, Wan-Chun; Wei, Zhangwen
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja408084j

Metalloporphyrin-based organic polymers for carbon dioxide fixation to cyclic carbonate
journal, January 2015

  • Chen, Aibing; Zhang, Yunzhao; Chen, Jinzhu
  • Journal of Materials Chemistry A, Vol. 3, Issue 18
  • DOI: 10.1039/C5TA00993F

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

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation
journal, January 2018

  • Zhu, Jie; Usov, Pavel M.; Xu, Wenqian
  • Journal of the American Chemical Society, Vol. 140, Issue 3
  • DOI: 10.1021/jacs.7b10643

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

Metal–Organic Frameworks (MOFs)
journal, January 2014

  • Zhou, Hong-Cai “Joe”; Kitagawa, Susumu
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS90059F

An alkaline-resistant Ag( i )-anchored pyrazolate-based metal–organic framework for chemical fixation of CO 2
journal, January 2018

  • Yang, Huimin; Zhang, Xu; Zhang, Guiyang
  • Chemical Communications, Vol. 54, Issue 35
  • DOI: 10.1039/C8CC01461B

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

Honeycomb Metal–Organic Framework with Lewis Acidic and Basic Bifunctional Sites: Selective Adsorption and CO 2 Catalytic Fixation
journal, March 2018

  • Li, Xiu-Yuan; Ma, Li-Na; Liu, Yang
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 13
  • DOI: 10.1021/acsami.8b01291

Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks
journal, June 2014

  • Guillerm, Vincent; Weseliński, Łukasz J.; Belmabkhout, Youssef
  • Nature Chemistry, Vol. 6, Issue 8
  • DOI: 10.1038/nchem.1982

Structure activity relationships in metal–organic framework catalysts for the continuous flow synthesis of propylene carbonate from CO 2 and propylene oxide
journal, January 2018

  • James, Bryant R.; Boissonnault, Jake A.; Wong-Foy, Antek G.
  • RSC Advances, Vol. 8, Issue 4
  • DOI: 10.1039/C7RA13245J

A novel method to measure diffusion coefficients in porous metal–organic frameworks
journal, January 2010

  • Zybaylo, Olexandra; Shekhah, Osama; Wang, Hui
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 28
  • DOI: 10.1039/b927601g

Investigation of the molecular transport of aliphatic and aromatic esters into engineering polymer membranes
journal, May 1994


A versatile sample-environment cell for non-ambient X-ray scattering experiments
journal, July 2008

  • Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles
  • Journal of Applied Crystallography, Vol. 41, Issue 4
  • DOI: 10.1107/S0021889808020165

Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms
journal, September 2005

  • Orr, James C.; Fabry, Victoria J.; Aumont, Olivier
  • Nature, Vol. 437, Issue 7059
  • DOI: 10.1038/nature04095

The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion
journal, July 2017

  • Trickett, Christopher A.; Helal, Aasif; Al-Maythalony, Bassem A.
  • Nature Reviews Materials, Vol. 2, Issue 8
  • DOI: 10.1038/natrevmats.2017.45

Ionic liquid tethered post functionalized ZIF-90 framework for the cycloaddition of propylene oxide and CO 2
journal, January 2016

  • Tharun, Jose; Bhin, Kyung-Mi; Roshan, Roshith
  • Green Chemistry, Vol. 18, Issue 8
  • DOI: 10.1039/C5GC02153G

The surface barrier phenomenon at the loading of metal-organic frameworks
journal, July 2014

  • Heinke, Lars; Gu, Zhigang; Wöll, Christof
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5562

Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009

  • Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001679

Verwendung von Schwingquarzen zur W�gung d�nner Schichten und zur Mikrow�gung
journal, April 1959


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