Competitive Adsorption of NH3 and H2O in Metal–Organic Framework Materials: MOF-74

Tan, Kui; Ullah, Saif; Pandey, Haardik; Cedeño-Morales, Eder M.; Wang, Hao; Wang, Kunyu; Zhou, Hong-Cai; Li, Jing; Thonhauser, Timo

doi:10.1021/acs.chemmater.2c01637

Title: Competitive Adsorption of NH₃ and H₂O in Metal–Organic Framework Materials: MOF-74

Journal Article · Wed Aug 24 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c01637· OSTI ID:1901705

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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)

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.

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Research Organization:: Wake Forest Univ., Winston-Salem, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0019902

OSTI ID:: 1901705

Journal Information:: Chemistry of Materials, Vol. 34, Issue 17; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (62)

Abatement of ammonia and amines from waste gases: a summary Busca, G.; Pistarino, C. Journal of Loss Prevention in the Process Industries, Vol. 16, Issue 2 https://doi.org/10.1016/S0950-4230(02)00093-1	journal	March 2003
Metal–organic frameworks (MOFs): potential and challenges for capture and abatement of ammonia Vikrant, Kumar; Kumar, Vanish; Kim, Ki-Hyun Journal of Materials Chemistry A, Vol. 5, Issue 44 https://doi.org/10.1039/C7TA07847A	journal	January 2017
Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks Wang, Hao; Lustig, William P.; Li, Jing Chemical Society Reviews, Vol. 47, Issue 13 https://doi.org/10.1039/C7CS00885F	journal	January 2018
Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review Khan, Nazmul Abedin; Hasan, Zubair; Jhung, Sung Hwa Journal of Hazardous Materials, Vol. 244-245 https://doi.org/10.1016/j.jhazmat.2012.11.011	journal	January 2013
Effects of high ammonia loads on nitrogen mass balance and treatment performance of a biotrickling filter Tsang, Yiu Fai; Wang, Lei; Chua, Hong Process Safety and Environmental Protection, Vol. 98 https://doi.org/10.1016/j.psep.2015.08.008	journal	November 2015
Evaluation of MOFs for air purification and air quality control applications: Ammonia removal from air Jasuja, Himanshu; Peterson, Gregory W.; Decoste, Jared B. Chemical Engineering Science, Vol. 124 https://doi.org/10.1016/j.ces.2014.08.050	journal	March 2015
Toxic gas removal – metal–organic frameworks for the capture and degradation of toxic gases and vapours Barea, Elisa; Montoro, Carmen; Navarro, Jorge A. R. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C3CS60475F	journal	January 2014
Enhanced Adsorption of Ammonia on Metal-Organic Framework/Graphite Oxide Composites: Analysis of Surface Interactions Petit, Camille; Bandosz, Teresa J. Advanced Functional Materials, Vol. 20, Issue 1, p. 111-118 https://doi.org/10.1002/adfm.200900880	journal	January 2010
Highly effective ammonia removal in a series of Brønsted acidic porous polymers: investigation of chemical and structural variations Barin, Gokhan; Peterson, Gregory W.; Crocellà, Valentina Chemical Science, Vol. 8, Issue 6 https://doi.org/10.1039/C6SC05079D	journal	January 2017
Ammonia Storage by Reversible Host-Guest Site Exchange in a Robust Metal-Organic Framework Godfrey, Harry G. W.; da Silva, Ivan; Briggs, Lydia Angewandte Chemie International Edition, Vol. 57, Issue 45 https://doi.org/10.1002/anie.201808316	journal	October 2018
Exceptional ammonia uptake by a covalent organic framework Doonan, Christian J.; Tranchemontagne, David J.; Glover, T. Grant Nature Chemistry, Vol. 2, Issue 3, p. 235-238 https://doi.org/10.1038/nchem.548	journal	February 2010
Metal-organic frameworks with high capacity and selectivity for harmful gases Britt, D.; Tranchemontagne, D.; Yaghi, O. M. Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11623-11627 https://doi.org/10.1073/pnas.0804900105	journal	August 2008
High Ammonia Uptake of a Metal–Organic Framework Adsorbent in a Wide Pressure Range Kim, Dae Won; Kang, Dong Won; Kang, Minjung Angewandte Chemie International Edition, Vol. 59, Issue 50 https://doi.org/10.1002/anie.202012552	journal	November 2020
Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture Rieth, Adam J.; Wright, Ashley M.; Dincă, Mircea Nature Reviews Materials, Vol. 4, Issue 11 https://doi.org/10.1038/s41578-019-0140-1	journal	September 2019
Controlled Gas Uptake in Metal–Organic Frameworks with Record Ammonia Sorption Rieth, Adam J.; Dincă, Mircea Journal of the American Chemical Society, Vol. 140, Issue 9 https://doi.org/10.1021/jacs.8b00313	journal	February 2018
A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs Wang, Yanxiang; Zhao, Xiang; Yang, Huajun Angewandte Chemie International Edition, Vol. 58, Issue 19 https://doi.org/10.1002/anie.201901343	journal	April 2019
Ammonia Capture within Isoreticular Metal–Organic Frameworks with Rod Secondary Building Units Moribe, Shinya; Chen, Zhijie; Alayoglu, Selim ACS Materials Letters, Vol. 1, Issue 4 https://doi.org/10.1021/acsmaterialslett.9b00307	journal	August 2019
Ammonia adsorption and its effects on framework stability of MOF-5 and MOF-177 Saha, Dipendu; Deng, Shuguang Journal of Colloid and Interface Science, Vol. 348, Issue 2, p. 615-620 https://doi.org/10.1016/j.jcis.2010.04.078	journal	August 2010
Synergistic Effect of Mixed Oxide on the Adsorption of Ammonia with Metal–Organic Frameworks Mounfield, William P.; Taborga Claure, Micaela; Agrawal, Pradeep K. Industrial & Engineering Chemistry Research, Vol. 55, Issue 22 https://doi.org/10.1021/acs.iecr.6b01045	journal	May 2016
Acid loaded porphyrin-based metal–organic framework for ammonia uptake Wilcox, Oliver T.; Fateeva, Alexandra; Katsoulidis, Alexandros P. Chemical Communications, Vol. 51, Issue 81 https://doi.org/10.1039/C5CC06209H	journal	January 2015
Postsynthetic Modification of a Metal–Organic Framework for Stabilization of a Hemiaminal and Ammonia Uptake Morris, William; Doonan, Christian J.; Yaghi, Omar M. Inorganic Chemistry, Vol. 50, Issue 15, p. 6853-6855 https://doi.org/10.1021/ic200744y	journal	August 2011
Computational Screening of Functional Groups for Ammonia Capture in Metal–Organic Frameworks Kim, Ki Chul; Yu, Decai; Snurr, Randall Q. Langmuir, Vol. 29, Issue 5 https://doi.org/10.1021/la3045237	journal	January 2013
Insights into Adsorption of NH ₃ on HKUST-1 Metal–Organic Framework: A Multitechnique Approach Borfecchia, Elisa; Maurelli, Sara; Gianolio, Diego The Journal of Physical Chemistry C, Vol. 116, Issue 37 https://doi.org/10.1021/jp305756k	journal	September 2012
MOF-74 building unit has a direct impact on toxic gas adsorption Grant Glover, T.; Peterson, Gregory W.; Schindler, Bryan J. Chemical Engineering Science, Vol. 66, Issue 2, p. 163-170 https://doi.org/10.1016/j.ces.2010.10.002	journal	January 2011
High volumetric uptake of ammonia using Cu-MOF-74/Cu-CPO-27 Katz, Michael J.; Howarth, Ashlee J.; Moghadam, Peyman Z. Dalton Transactions, Vol. 45, Issue 10 https://doi.org/10.1039/C5DT03436A	journal	January 2016
High and Reversible Ammonia Uptake in Mesoporous Azolate Metal–Organic Frameworks with Open Mn, Co, and Ni Sites Rieth, Adam J.; Tulchinsky, Yuri; Dincă, Mircea Journal of the American Chemical Society, Vol. 138, Issue 30 https://doi.org/10.1021/jacs.6b05723	journal	July 2016
Water Stability and Adsorption in Metal–Organic Frameworks Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S. Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612 https://doi.org/10.1021/cr5002589	journal	September 2014
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 Tan, Kui; Zuluaga, Sebastian; Gong, Qihan Chemistry of Materials, Vol. 27, Issue 6 https://doi.org/10.1021/acs.chemmater.5b00315	journal	March 2015
Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13871	journal	December 2016
Screening the Effect of Water Vapour on Gas Adsorption Performance: Application to CO ₂ Capture from Flue Gas in Metal-Organic Frameworks Chanut, Nicolas; Bourrelly, Sandrine; Kuchta, Bogdan ChemSusChem, Vol. 10, Issue 7 https://doi.org/10.1002/cssc.201601816	journal	March 2017
Water and Metal–Organic Frameworks: From Interaction toward Utilization Liu, Xinlei; Wang, Xuerui; Kapteijn, Freek Chemical Reviews, Vol. 120, Issue 16 https://doi.org/10.1021/acs.chemrev.9b00746	journal	May 2020
Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang Chemistry of Materials, Vol. 27, Issue 3, p. 668-678 https://doi.org/10.1021/cm502760q	journal	January 2015
Power of Infrared and Raman Spectroscopies to Characterize Metal-Organic Frameworks and Investigate Their Interaction with Guest Molecules Hadjiivanov, Konstantin I.; Panayotov, Dimitar A.; Mihaylov, Mihail Y. Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00487	journal	December 2020
Defect Termination in the UiO-66 Family of Metal–Organic Frameworks: The Role of Water and Modulator Tan, Kui; Pandey, Haardik; Wang, Hao Journal of the American Chemical Society, Vol. 143, Issue 17 https://doi.org/10.1021/jacs.1c01408	journal	April 2021
Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration Tan, Kui; Nijem, Nour; Canepa, Pieremanuele Chemistry of Materials, Vol. 24, Issue 16 https://doi.org/10.1021/cm301427w	journal	August 2012
Water Cluster Confinement and Methane Adsorption in the Hydrophobic Cavities of a Fluorinated Metal–Organic Framework Nijem, Nour; Canepa, Pieremanuele; Kaipa, Ushasree Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja400754p	journal	August 2013
Large-Pore Apertures in a Series of Metal-Organic Frameworks Deng, H.; Grunder, S.; Cordova, K. E. Science, Vol. 336, Issue 6084, p. 1018-1023 https://doi.org/10.1126/science.1220131	journal	May 2012
Idiosyncrasies of Co2(dhtp): In situ-annealing by methanol Chmelik, Christian; Mundstock, Alexander; Dietzel, Pascal D. C. Microporous and Mesoporous Materials, Vol. 183 https://doi.org/10.1016/j.micromeso.2013.09.002	journal	January 2014
van der Waals forces in density functional theory: a review of the vdW-DF method Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho Reports on Progress in Physics, Vol. 78, Issue 6 https://doi.org/10.1088/0034-4885/78/6/066501	journal	May 2015
A density functional for sparse matter Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084203	journal	January 2009
Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond Thonhauser, T.; Cooper, Valentino R.; Li, Shen Physical Review B, Vol. 76, Issue 12 https://doi.org/10.1103/PhysRevB.76.125112	journal	September 2007
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks Thonhauser, T.; Zuluaga, S.; Arter, C. A. Physical Review Letters, Vol. 115, Issue 13 https://doi.org/10.1103/PhysRevLett.115.136402	journal	September 2015
Erratum: Van der Waals Density Functional for General Geometries [Phys. Rev. Lett. 92 , 246401 (2004)] Dion, M.; Rydberg, H.; Schröder, E. Physical Review Letters, Vol. 95, Issue 10 https://doi.org/10.1103/PhysRevLett.95.109902	journal	September 2005
Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes Román-Pérez, Guillermo; Soler, José M. Physical Review Letters, Vol. 103, Issue 9 https://doi.org/10.1103/PhysRevLett.103.096102	journal	August 2009
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Phonons and related crystal properties from density-functional perturbation theory Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea Reviews of Modern Physics, Vol. 73, Issue 2 https://doi.org/10.1103/RevModPhys.73.515	journal	July 2001
Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74 Tan, Kui; Zuluaga, Sebastian; Gong, Qihan Chemistry of Materials, Vol. 26, Issue 23 https://doi.org/10.1021/cm5038183	journal	November 2014
Investigation of Acid Sites in a Zeotypic Giant Pores Chromium(III) Carboxylate Vimont, Alexandre; Goupil, Jean-Michel; Lavalley, Jean-Claude Journal of the American Chemical Society, Vol. 128, Issue 10 https://doi.org/10.1021/ja056906s	journal	March 2006
Identification of a wagging vibrational mode of water molecules at the water/vapor interface Perry, Angela; Neipert, Christine; Ridley, Christina Physical Review E, Vol. 71, Issue 5 https://doi.org/10.1103/PhysRevE.71.050601	journal	May 2005
Investigation of NH₃ and NH₄⁺ adsorbed on ZSM-5 zeolites by near and middle infrared spectroscopy Takeuchi, Masato; Tsukamoto, Tatsuya; Kondo, Atsushi Catalysis Science & Technology, Vol. 5, Issue 9 https://doi.org/10.1039/C5CY00753D	journal	January 2015
Infrared Spectroscopy of Ammonia on Iron: Adsorption, Synthesis, and the Influence of Oxygen Iyngaran, Poobalasuntharam; Madden, David C.; King, David A. The Journal of Physical Chemistry C, Vol. 121, Issue 44 https://doi.org/10.1021/acs.jpcc.7b07494	journal	October 2017
Metal-Organic Frameworks for Water Harvesting from Air Kalmutzki, Markus J.; Diercks, Christian S.; Yaghi, Omar M. Advanced Materials, Vol. 30, Issue 37 https://doi.org/10.1002/adma.201704304	journal	April 2018
Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks Dietzel, Pascal D. C.; Johnsen, Rune E.; Blom, Richard Chemistry - A European Journal, Vol. 14, Issue 8 https://doi.org/10.1002/chem.200701370	journal	March 2008
Modulation of Water Vapor Sorption by a Fourth-Generation Metal–Organic Material with a Rigid Framework and Self-Switching Pores Zhang, Shi-Yuan; Jensen, Stephanie; Tan, Kui Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b07290	journal	September 2018
Atomistic Insight into Adsorption, Mobility, and Vibration of Water in Ion-Exchanged Zeolite-like Metal−Organic Frameworks Nalaparaju, A.; Babarao, R.; Zhao, X. S. ACS Nano, Vol. 3, Issue 9 https://doi.org/10.1021/nn900605u	journal	August 2009
The Bending Mode of Water: A Powerful Probe for Hydrogen Bond Structure of Aqueous Systems Seki, Takakazu; Chiang, Kuo-Yang; Yu, Chun-Chieh The Journal of Physical Chemistry Letters, Vol. 11, Issue 19 https://doi.org/10.1021/acs.jpclett.0c01259	journal	September 2020
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006

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