Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74
Abstract
Elucidating the interaction between coadsorbed H2O and NH3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH3 adsorption in humid environments. Nevertheless, molecular competition between NH3 and H2O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH3 and H2O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH3/H2O ratio, the incoming NH3 is capable of displacing metal-bound H2O and moving it to secondary adsorption sites due to the stronger binding of NH3 compared with H2O. Interestingly, the reverse process of H2O displacing metal-bound NH3 is also possible upon increasing water concentration. Our calculations show that H2O exchanging the preabsorbed NH3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding betweenmore »
- Authors:
-
- Univ. of Texas at Dallas, Richardson, TX (United States)
- Wake Forest Univ., Winston-Salem, NC (United States)
- Rutgers Univ., Piscataway, NJ (United States)
- Texas A & M Univ., College Station, TX (United States)
- Publication Date:
- Research Org.:
- Wake Forest Univ., Winston-Salem, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1901705
- Grant/Contract Number:
- SC0019902
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 17; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Adsorption; Binding energy; Metal organic frameworks; Metals; Molecules
Citation Formats
Tan, Kui, Ullah, Saif, Pandey, Haardik, Cedeño-Morales, Eder M., Wang, Hao, Wang, Kunyu, Zhou, Hong-Cai, Li, Jing, and Thonhauser, Timo. Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74. United States: N. p., 2022.
Web. doi:10.1021/acs.chemmater.2c01637.
Tan, Kui, Ullah, Saif, Pandey, Haardik, Cedeño-Morales, Eder M., Wang, Hao, Wang, Kunyu, Zhou, Hong-Cai, Li, Jing, & Thonhauser, Timo. Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74. United States. https://doi.org/10.1021/acs.chemmater.2c01637
Tan, Kui, Ullah, Saif, Pandey, Haardik, Cedeño-Morales, Eder M., Wang, Hao, Wang, Kunyu, Zhou, Hong-Cai, Li, Jing, and Thonhauser, Timo. Wed .
"Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74". United States. https://doi.org/10.1021/acs.chemmater.2c01637. https://www.osti.gov/servlets/purl/1901705.
@article{osti_1901705,
title = {Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74},
author = {Tan, Kui and Ullah, Saif and Pandey, Haardik and Cedeño-Morales, Eder M. and Wang, Hao and Wang, Kunyu and Zhou, Hong-Cai and Li, Jing and Thonhauser, Timo},
abstractNote = {Elucidating the interaction between coadsorbed H2O and NH3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH3 adsorption in humid environments. Nevertheless, molecular competition between NH3 and H2O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH3 and H2O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH3/H2O ratio, the incoming NH3 is capable of displacing metal-bound H2O and moving it to secondary adsorption sites due to the stronger binding of NH3 compared with H2O. Interestingly, the reverse process of H2O displacing metal-bound NH3 is also possible upon increasing water concentration. Our calculations show that H2O exchanging the preabsorbed NH3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H2O and displaced NH3. Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH3 are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm–1) and considerable intensity decrease, which arises from the freezing of NH3 vibrations by coadsorbed H2O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH3 removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.},
doi = {10.1021/acs.chemmater.2c01637},
journal = {Chemistry of Materials},
number = 17,
volume = 34,
place = {United States},
year = {Wed Aug 24 00:00:00 EDT 2022},
month = {Wed Aug 24 00:00:00 EDT 2022}
}
Works referenced in this record:
Abatement of ammonia and amines from waste gases: a summary
journal, March 2003
- Busca, G.; Pistarino, C.
- Journal of Loss Prevention in the Process Industries, Vol. 16, Issue 2
Metal–organic frameworks (MOFs): potential and challenges for capture and abatement of ammonia
journal, January 2017
- Vikrant, Kumar; Kumar, Vanish; Kim, Ki-Hyun
- Journal of Materials Chemistry A, Vol. 5, Issue 44
Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks
journal, January 2018
- Wang, Hao; Lustig, William P.; Li, Jing
- Chemical Society Reviews, Vol. 47, Issue 13
Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review
journal, January 2013
- Khan, Nazmul Abedin; Hasan, Zubair; Jhung, Sung Hwa
- Journal of Hazardous Materials, Vol. 244-245
Effects of high ammonia loads on nitrogen mass balance and treatment performance of a biotrickling filter
journal, November 2015
- Tsang, Yiu Fai; Wang, Lei; Chua, Hong
- Process Safety and Environmental Protection, Vol. 98
Evaluation of MOFs for air purification and air quality control applications: Ammonia removal from air
journal, March 2015
- Jasuja, Himanshu; Peterson, Gregory W.; Decoste, Jared B.
- Chemical Engineering Science, Vol. 124
Toxic gas removal – metal–organic frameworks for the capture and degradation of toxic gases and vapours
journal, January 2014
- Barea, Elisa; Montoro, Carmen; Navarro, Jorge A. R.
- Chem. Soc. Rev., Vol. 43, Issue 16
Enhanced Adsorption of Ammonia on Metal-Organic Framework/Graphite Oxide Composites: Analysis of Surface Interactions
journal, January 2010
- Petit, Camille; Bandosz, Teresa J.
- Advanced Functional Materials, Vol. 20, Issue 1, p. 111-118
Highly effective ammonia removal in a series of Brønsted acidic porous polymers: investigation of chemical and structural variations
journal, January 2017
- Barin, Gokhan; Peterson, Gregory W.; Crocellà, Valentina
- Chemical Science, Vol. 8, Issue 6
Ammonia Storage by Reversible Host-Guest Site Exchange in a Robust Metal-Organic Framework
journal, October 2018
- Godfrey, Harry G. W.; da Silva, Ivan; Briggs, Lydia
- Angewandte Chemie International Edition, Vol. 57, Issue 45
Exceptional ammonia uptake by a covalent organic framework
journal, February 2010
- Doonan, Christian J.; Tranchemontagne, David J.; Glover, T. Grant
- Nature Chemistry, Vol. 2, Issue 3, p. 235-238
Metal-organic frameworks with high capacity and selectivity for harmful gases
journal, August 2008
- Britt, D.; Tranchemontagne, D.; Yaghi, O. M.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11623-11627
High Ammonia Uptake of a Metal–Organic Framework Adsorbent in a Wide Pressure Range
journal, November 2020
- Kim, Dae Won; Kang, Dong Won; Kang, Minjung
- Angewandte Chemie International Edition, Vol. 59, Issue 50
Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture
journal, September 2019
- Rieth, Adam J.; Wright, Ashley M.; Dincă, Mircea
- Nature Reviews Materials, Vol. 4, Issue 11
Controlled Gas Uptake in Metal–Organic Frameworks with Record Ammonia Sorption
journal, February 2018
- Rieth, Adam J.; Dincă, Mircea
- Journal of the American Chemical Society, Vol. 140, Issue 9
A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs
journal, April 2019
- Wang, Yanxiang; Zhao, Xiang; Yang, Huajun
- Angewandte Chemie International Edition, Vol. 58, Issue 19
Ammonia Capture within Isoreticular Metal–Organic Frameworks with Rod Secondary Building Units
journal, August 2019
- Moribe, Shinya; Chen, Zhijie; Alayoglu, Selim
- ACS Materials Letters, Vol. 1, Issue 4
Ammonia adsorption and its effects on framework stability of MOF-5 and MOF-177
journal, August 2010
- Saha, Dipendu; Deng, Shuguang
- Journal of Colloid and Interface Science, Vol. 348, Issue 2, p. 615-620
Synergistic Effect of Mixed Oxide on the Adsorption of Ammonia with Metal–Organic Frameworks
journal, May 2016
- Mounfield, William P.; Taborga Claure, Micaela; Agrawal, Pradeep K.
- Industrial & Engineering Chemistry Research, Vol. 55, Issue 22
Acid loaded porphyrin-based metal–organic framework for ammonia uptake
journal, January 2015
- Wilcox, Oliver T.; Fateeva, Alexandra; Katsoulidis, Alexandros P.
- Chemical Communications, Vol. 51, Issue 81
Postsynthetic Modification of a Metal–Organic Framework for Stabilization of a Hemiaminal and Ammonia Uptake
journal, August 2011
- Morris, William; Doonan, Christian J.; Yaghi, Omar M.
- Inorganic Chemistry, Vol. 50, Issue 15, p. 6853-6855
Computational Screening of Functional Groups for Ammonia Capture in Metal–Organic Frameworks
journal, January 2013
- Kim, Ki Chul; Yu, Decai; Snurr, Randall Q.
- Langmuir, Vol. 29, Issue 5
Insights into Adsorption of NH 3 on HKUST-1 Metal–Organic Framework: A Multitechnique Approach
journal, September 2012
- Borfecchia, Elisa; Maurelli, Sara; Gianolio, Diego
- The Journal of Physical Chemistry C, Vol. 116, Issue 37
MOF-74 building unit has a direct impact on toxic gas adsorption
journal, January 2011
- Grant Glover, T.; Peterson, Gregory W.; Schindler, Bryan J.
- Chemical Engineering Science, Vol. 66, Issue 2, p. 163-170
High volumetric uptake of ammonia using Cu-MOF-74/Cu-CPO-27
journal, January 2016
- Katz, Michael J.; Howarth, Ashlee J.; Moghadam, Peyman Z.
- Dalton Transactions, Vol. 45, Issue 10
High and Reversible Ammonia Uptake in Mesoporous Azolate Metal–Organic Frameworks with Open Mn, Co, and Ni Sites
journal, July 2016
- Rieth, Adam J.; Tulchinsky, Yuri; Dincă, Mircea
- Journal of the American Chemical Society, Vol. 138, Issue 30
Water Stability and Adsorption in Metal–Organic Frameworks
journal, September 2014
- Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
- Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612
Competitive Coadsorption of CO 2 with H 2 O, NH 3 , SO 2 , NO, NO 2 , N 2 , O 2 , and CH 4 in M-MOF-74 (M = Mg, Co, Ni): The Role of Hydrogen Bonding
journal, March 2015
- Tan, Kui; Zuluaga, Sebastian; Gong, Qihan
- Chemistry of Materials, Vol. 27, Issue 6
Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer
journal, December 2016
- Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika
- Nature Communications, Vol. 7, Issue 1
Screening the Effect of Water Vapour on Gas Adsorption Performance: Application to CO 2 Capture from Flue Gas in Metal-Organic Frameworks
journal, March 2017
- Chanut, Nicolas; Bourrelly, Sandrine; Kuchta, Bogdan
- ChemSusChem, Vol. 10, Issue 7
Water and Metal–Organic Frameworks: From Interaction toward Utilization
journal, May 2020
- Liu, Xinlei; Wang, Xuerui; Kapteijn, Freek
- Chemical Reviews, Vol. 120, Issue 16
Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015
- Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
- Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
Power of Infrared and Raman Spectroscopies to Characterize Metal-Organic Frameworks and Investigate Their Interaction with Guest Molecules
journal, December 2020
- Hadjiivanov, Konstantin I.; Panayotov, Dimitar A.; Mihaylov, Mihail Y.
- Chemical Reviews, Vol. 121, Issue 3
Defect Termination in the UiO-66 Family of Metal–Organic Frameworks: The Role of Water and Modulator
journal, April 2021
- Tan, Kui; Pandey, Haardik; Wang, Hao
- Journal of the American Chemical Society, Vol. 143, Issue 17
Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration
journal, August 2012
- Tan, Kui; Nijem, Nour; Canepa, Pieremanuele
- Chemistry of Materials, Vol. 24, Issue 16
Water Cluster Confinement and Methane Adsorption in the Hydrophobic Cavities of a Fluorinated Metal–Organic Framework
journal, August 2013
- Nijem, Nour; Canepa, Pieremanuele; Kaipa, Ushasree
- Journal of the American Chemical Society, Vol. 135, Issue 34
Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012
- Deng, H.; Grunder, S.; Cordova, K. E.
- Science, Vol. 336, Issue 6084, p. 1018-1023
Idiosyncrasies of Co2(dhtp): In situ-annealing by methanol
journal, January 2014
- Chmelik, Christian; Mundstock, Alexander; Dietzel, Pascal D. C.
- Microporous and Mesoporous Materials, Vol. 183
van der Waals forces in density functional theory: a review of the vdW-DF method
journal, May 2015
- Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho
- Reports on Progress in Physics, Vol. 78, Issue 6
A density functional for sparse matter
journal, January 2009
- Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007
- Thonhauser, T.; Cooper, Valentino R.; Li, Shen
- Physical Review B, Vol. 76, Issue 12
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
journal, September 2015
- Thonhauser, T.; Zuluaga, S.; Arter, C. A.
- Physical Review Letters, Vol. 115, Issue 13
Erratum: Van der Waals Density Functional for General Geometries [Phys. Rev. Lett. 92 , 246401 (2004)]
journal, September 2005
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 95, Issue 10
Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes
journal, August 2009
- Román-Pérez, Guillermo; Soler, José M.
- Physical Review Letters, Vol. 103, Issue 9
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
High-precision sampling for Brillouin-zone integration in metals
journal, August 1989
- Methfessel, M.; Paxton, A. T.
- Physical Review B, Vol. 40, Issue 6
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001
- Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea
- Reviews of Modern Physics, Vol. 73, Issue 2
Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74
journal, November 2014
- Tan, Kui; Zuluaga, Sebastian; Gong, Qihan
- Chemistry of Materials, Vol. 26, Issue 23
Investigation of Acid Sites in a Zeotypic Giant Pores Chromium(III) Carboxylate
journal, March 2006
- Vimont, Alexandre; Goupil, Jean-Michel; Lavalley, Jean-Claude
- Journal of the American Chemical Society, Vol. 128, Issue 10
Identification of a wagging vibrational mode of water molecules at the water/vapor interface
journal, May 2005
- Perry, Angela; Neipert, Christine; Ridley, Christina
- Physical Review E, Vol. 71, Issue 5
Investigation of NH3 and NH4+ adsorbed on ZSM-5 zeolites by near and middle infrared spectroscopy
journal, January 2015
- Takeuchi, Masato; Tsukamoto, Tatsuya; Kondo, Atsushi
- Catalysis Science & Technology, Vol. 5, Issue 9
Infrared Spectroscopy of Ammonia on Iron: Adsorption, Synthesis, and the Influence of Oxygen
journal, October 2017
- Iyngaran, Poobalasuntharam; Madden, David C.; King, David A.
- The Journal of Physical Chemistry C, Vol. 121, Issue 44
Metal-Organic Frameworks for Water Harvesting from Air
journal, April 2018
- Kalmutzki, Markus J.; Diercks, Christian S.; Yaghi, Omar M.
- Advanced Materials, Vol. 30, Issue 37
Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks
journal, March 2008
- Dietzel, Pascal D. C.; Johnsen, Rune E.; Blom, Richard
- Chemistry - A European Journal, Vol. 14, Issue 8
Modulation of Water Vapor Sorption by a Fourth-Generation Metal–Organic Material with a Rigid Framework and Self-Switching Pores
journal, September 2018
- Zhang, Shi-Yuan; Jensen, Stephanie; Tan, Kui
- Journal of the American Chemical Society, Vol. 140, Issue 39
Atomistic Insight into Adsorption, Mobility, and Vibration of Water in Ion-Exchanged Zeolite-like Metal−Organic Frameworks
journal, August 2009
- Nalaparaju, A.; Babarao, R.; Zhao, X. S.
- ACS Nano, Vol. 3, Issue 9
The Bending Mode of Water: A Powerful Probe for Hydrogen Bond Structure of Aqueous Systems
journal, September 2020
- Seki, Takakazu; Chiang, Kuo-Yang; Yu, Chun-Chieh
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 19
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3