DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Kinetics of cooperative CO2 adsorption in diamine-appended variants of the metal–organic framework Mg2(dobpdc)

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/d0sc01087a · OSTI ID:1607826
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division

Carbon capture and sequestration is a key element of global initiatives to minimize anthropogenic greenhouse gas emissions. Although many investigations of new candidate CO2 capture materials focus on equilibrium adsorption properties, it is also critical to consider adsorption/desorption kinetics when evaluating adsorbent performance. Diamine-appended variants of the metal–organic framework Mg2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising materials for CO2 capture because of their cooperative chemisorption mechanism and associated step-shaped equilibrium isotherms, which enable large working capacities to be accessed with small temperature swings. However, the adsorption/desorption kinetics of these unique materials remain understudied. More generally, despite the necessity of kinetics characterization to advance adsorbents toward commercial separations, detailed kinetic studies of metal–organic framework-based gas separations remain rare. Here, we systematically investigate the CO2 adsorption kinetics of diamine-appended Mg2(dobpdc) variants using a thermogravimetric analysis (TGA) assay. In particular, we examine the effects of diamine structure, temperature, and partial pressure on CO2 adsorption and desorption kinetics. Importantly, most diamine-appended Mg2(dobpdc) variants exhibit an induction period prior to reaching the maximum rate of CO2 adsorption, which we attribute to their unique cooperative chemisorption mechanism. In addition, these materials exhibit inverse Arrhenius behavior, displaying faster adsorption kinetics and shorter induction periods at lower temperatures. Using the Avrami model for nucleation and growth kinetics, we determine rate constants for CO2 adsorption and quantitatively compare rate constants among different diamine-appended variants. Overall, these results provide guidelines for optimizing adsorbent design to facilitate CO2 capture from diverse target streams and highlight kinetic phenomena relevant for other materials in which cooperative chemisorption mechanisms are operative.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
Grant/Contract Number:
SC0019992; SC0001015; FWP-00006194; GM120799; AC02-05CH11231
OSTI ID:
1607826
Alternate ID(s):
OSTI ID: 1677407; OSTI ID: 1756345
Journal Information:
Chemical Science, Vol. 11, Issue 25; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

References (52)

Moving Beyond Adsorption Capacity in Design of Adsorbents for CO 2 Capture from Ultradilute Feeds: Kinetics of CO 2 Adsorption in Materials with Stepped Isotherms journal December 2018
Strong CO2 Binding in a Water-Stable, Triazolate-Bridged Metal−Organic Framework Functionalized with Ethylenediamine
  • Demessence, Aude; D’Alessandro, Deanna M.; Foo, Maw Lin
  • Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8784-8786 https://doi.org/10.1021/ja903411w
journal July 2009
Analysis and Status of Post-Combustion Carbon Dioxide Capture Technologies journal October 2011
Unusual Inverse Temperature Dependence on Reaction Rate in the Asymmetric Autocatalytic Alkylation of Pyrimidyl Aldehydes journal November 2010
Equilibrium and absorption kinetics of carbon dioxide by solid supported amine sorbent journal February 2011
Modification of the Mg/DOBDC MOF with Amines to Enhance CO 2 Adsorption from Ultradilute Gases journal April 2012
Suitability of a Solid Amine Sorbent for CO 2 Capture by Pressure Swing Adsorption journal May 2011
Preparation and CO2 adsorption of amine modified Mg–Al LDH via exfoliation route journal January 2012
“Molecular Basket” Sorbents for Separation of CO 2 and H 2 S from Various Gas Streams journal April 2009
Putting an ultrahigh concentration of amine groups into a metal–organic framework for CO 2 capture at low pressures journal January 2016
Postsynthetic Covalent Modification of a Neutral Metal−Organic Framework journal October 2007
Negative activation energies and curved Arrhenius plots. 1. Theory of reactions over potential wells journal December 1984
Adsorption of CO 2 on Amine-Functionalized Y-Type Zeolites journal February 2010
A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism journal September 2017
Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica journal July 2012
CO2 capture on polyethylenimine-impregnated hydrophobic mesoporous silica: Experimental and kinetic modeling journal September 2011
Kinetics of Phase Change. I General Theory journal December 1939
Carbon capture and storage update journal January 2014
Photochemical Removal of Mercury from Flue Gas journal October 2002
Elucidating CO 2 Chemisorption in Diamine-Appended Metal–Organic Frameworks journal December 2018
Fine-Tuning of the Carbon Dioxide Capture Capability of Diamine-Grafted Metal-Organic Framework Adsorbents Through Amine Functionalization journal December 2016
Reversible adsorption of carbon dioxide on amine surface-bonded silica gel journal December 1995
Direct Air Capture of CO 2 Using Amine Functionalized MIL-101(Cr) journal August 2016
Convex Arrhenius plots and their interpretation journal January 2001
Determination of the isothermal nucleation and growth parameters for the crystallization of thin Ge2Sb2Te5 films journal September 2002
Polyamine-appended porous organic polymers for efficient post-combustion CO2 capture journal February 2019
Synthesis of Fluidized CO 2 Sorbents Based on Diamine Coordinated to Metal-Organic Frameworks by Direct Conversion of Metal Oxides Supported on Mesoporous Silica journal June 2018
An ethylenediamine-grafted Y zeolite: a highly regenerable carbon dioxide adsorbent via temperature swing adsorption without urea formation journal January 2016
The three activation energies with isothermal transformations: applications to metallic glasses journal September 1981
CO 2 /H 2 O Adsorption Equilibrium and Rates on Metal−Organic Frameworks: HKUST-1 and Ni/DOBDC journal September 2010
Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal–Organic Framework journal October 2017
Application of a High-Throughput Analyzer in Evaluating Solid Adsorbents for Post-Combustion Carbon Capture via Multicomponent Adsorption of CO 2 , N 2 , and H 2 O journal April 2015
Overcoming double-step CO 2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg 2 (dobpdc) journal January 2018
Enthalpy versus Entropy in Chlorocarbene/Alkene Addition Reactions journal April 2008
A mechanistic rationalization of unusual kinetic behavior in proline-mediated C–O and C–N bond-forming reactions journal January 2006
Modeling adsorption of CO2 on amine-functionalized mesoporous silica. 2: Kinetics and breakthrough curves journal July 2010
Amine-modified MCM-41 mesoporous silica for carbon dioxide capture journal August 2011
Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption journal January 2011
Polyamine-Tethered Porous Polymer Networks for Carbon Dioxide Capture from Flue Gas journal June 2012
A jump in an Arrhenius plot can be the consequence of a phase transition: The binding of ATP to myosin subfragment 1 journal March 1983
Exceptional CO 2 working capacity in a heterodiamine-grafted metal–organic framework journal January 2015
Pore Surface Engineering with Controlled Loadings of Functional Groups via Click Chemistry in Highly Stable Metal–Organic Frameworks journal August 2012
Controlling Cooperative CO 2 Adsorption in Diamine-Appended Mg 2 (dobpdc) Metal–Organic Frameworks journal July 2017
Negative activation enthalpies in the kinetics of protein folding. journal September 1995
A Tailor-Made Interpenetrated MOF with Exceptional Carbon-Capture Performance from Flue Gas journal April 2019
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks journal March 2015
Capture of Carbon Dioxide from Air and Flue Gas in the Alkylamine-Appended Metal–Organic Framework mmen-Mg2(dobpdc) journal April 2012
Diamine-functionalized metal–organic framework: exceptionally high CO 2 capacities from ambient air and flue gas, ultrafast CO 2 uptake rate, and adsorption mechanism journal January 2014
Kinetics Studies of CO 2 Adsorption/Desorption on Amine-Functionalized Multiwalled Carbon Nanotubes journal July 2014
Warning signs for stabilizing global CO 2 emissions journal November 2017
Theoretical studies of halocarbene cycloaddition selectivities journal January 1985
Diamine-Functionalization of a Metal-Organic Framework Adsorbent for Superb Carbon Dioxide Adsorption and Desorption Properties journal April 2018

Figures / Tables (11)