Organophosphorus Binding Thermodynamics in Metal–Organic Frameworks: Interplay between Oxidation State, Lewis Acidity, and Node Structure

Fahy, Kira M.; Hou, Bang; Garg, Palak; Lee, Seryeong; Smoljan, Courtney S.; Shehab, Mohammad K.; Kirlikovali, Kent O.; Farha, Omar K.

doi:10.1021/acsami.5c06791

Organophosphorus Binding Thermodynamics in Metal–Organic Frameworks: Interplay between Oxidation State, Lewis Acidity, and Node Structure

Journal Article · Tue Jun 24 00:00:00 EDT 2025 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5c06791· OSTI ID:3007818

^[1]; Hou, Bang ^[1]; Garg, Palak ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Northwestern University, Evanston, IL (United States)

Organophosphorus compounds, including nerve agents and pesticides, represent a class of toxic chemicals causing harm to troops, civilians, and the environment. Metal–organic frameworks (MOFs) have emerged as a class of highly porous, crystalline, tunable materials adept at both capturing and catalytically neutralizing these harmful toxins. In particular, MOFs whose nodes display strong Lewis acidic character can hydrolyze such chemicals nearly instantaneously. However, without the help of a basic buffer to regenerate the active site, the benign organophosphorus product strongly binds to the node and prevents catalyst turnover. Here, we investigate a series of MOFs whose nodes contain metals of varying Lewis acidities and employ isothermal titration calorimetry (ITC) to directly measure the heat from the binding of an organophosphorus probe molecule, allowing the construction of a full thermodynamic binding profile (ΔH, ΔS, ΔG, K_a). We couple this with potentiometric titrations and solid state ³¹P magic angle spinning (MAS) NMR to gain a clearer picture of how node identity, structure, and Lewis acidity interplay to impact binding strength and favorability. Furthermore, this study is the first to integrate these three complementary techniques to investigate binding interactions in MOFs, further showcasing the viability of ITC for probing MOF systems, which is still relatively underexplored.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States); University of Chicago, IL (United States)

Sponsoring Organization:: National Science Foundation Graduate Research Fellowship (NSF GRFP); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023383

OSTI ID:: 3007818

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 27 Vol. 17; ISSN 1944-8244; ISSN 1944-8252

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal-Organic Framework Moon, Su-Young; Liu, Yangyang; Hupp, Joseph T. Angewandte Chemie International Edition, Vol. 54, Issue 23 https://doi.org/10.1002/anie.201502155	journal	May 2015
Leveraging Isothermal Titration Calorimetry to Explore Structure–Property Relationships of Protein Immobilization in Metal–Organic Frameworks Tai, Tzu‐Yi; Sha, Fanrui; Wang, Xiaoliang Angewandte Chemie International Edition, Vol. 61, Issue 37 https://doi.org/10.1002/anie.202209110	journal	August 2022
Metal–Organic Framework Composites for Theragnostics and Drug Delivery Applications Osterrieth, Johannes W. M.; Fairen‐Jimenez, David Biotechnology Journal, Vol. 16, Issue 2 https://doi.org/10.1002/biot.202000005	journal	May 2020
Mechanistic Studies of Metal Aqua Ions: A Semi-Historical Perspective Lincoln, Stephen?F. Helvetica Chimica Acta, Vol. 88, Issue 3 https://doi.org/10.1002/hlca.200590036	journal	March 2005
Water exchange on metal ions: experiments and simulations Helm, L.; Merbach, A. E. Coordination Chemistry Reviews, Vol. 187, Issue 1 https://doi.org/10.1016/S0010-8545(99)90232-1	journal	June 1999
Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts Wasson, Megan C.; Buru, Cassandra T.; Chen, Zhijie Applied Catalysis A: General, Vol. 586 https://doi.org/10.1016/j.apcata.2019.117214	journal	September 2019
Recent advances in luminescent metal–organic frameworks (LMOFs) based fluorescent sensors for antibiotics Raja Lakshmi, Pandi; Nanjan, Pandurangan; Kannan, Sukanya Coordination Chemistry Reviews, Vol. 435 https://doi.org/10.1016/j.ccr.2021.213793	journal	May 2021
Strategies for Pore Engineering in Zirconium Metal-Organic Frameworks Feng, Liang; Day, Gregory S.; Wang, Kun-Yu Chem, Vol. 6, Issue 11 https://doi.org/10.1016/j.chempr.2020.09.010	journal	November 2020
Insight into organophosphate chemical warfare agent simulant hydrolysis in metal-organic frameworks Ploskonka, Ann M.; DeCoste, Jared B. Journal of Hazardous Materials, Vol. 375 https://doi.org/10.1016/j.jhazmat.2019.04.044	journal	August 2019
Catalytic Degradation of an Organophosphorus Agent at Zn–OH Sites in a Metal–Organic Framework Mian, Mohammad Rasel; Islamoglu, Timur; Afrin, Unjila Chemistry of Materials, Vol. 32, Issue 16 https://doi.org/10.1021/acs.chemmater.0c02373	journal	August 2020
Topological Characterization of Metal–Organic Frameworks: A Perspective Glasby, Lawson T.; Cordiner, Joan L.; Cole, Jason C. Chemistry of Materials, Vol. 36, Issue 19 https://doi.org/10.1021/acs.chemmater.4c00762	journal	July 2024
Exploring the Role of Hexanuclear Clusters as Lewis Acidic Sites in Isostructural Metal–Organic Frameworks Lyu, Jiafei; Zhang, Xuan; Li, Peng Chemistry of Materials, Vol. 31, Issue 11 https://doi.org/10.1021/acs.chemmater.9b00960	journal	May 2019
Techno-economic Analysis of Metal–Organic Frameworks for Hydrogen and Natural Gas Storage DeSantis, Daniel; Mason, Jarad A.; James, Brian D. Energy & Fuels, Vol. 31, Issue 2 https://doi.org/10.1021/acs.energyfuels.6b02510	journal	January 2017
Hydrolysis of Organophosphorus Agents Catalyzed by Cobalt Nanoparticles Supported on Three-Dimensional Nitrogen-Doped Graphene Li, Yanfang; Yan, Jiawei; Yu, Daobo Inorganic Chemistry, Vol. 60, Issue 23 https://doi.org/10.1021/acs.inorgchem.1c02217	journal	November 2021
Low-Temperature Catalytic Transfer Hydrogenation of Biomass-Derived Furfural over Irreversibly Adsorbed and Highly Dispersed Zr(IV) Species Cen, Shuangshuang; Li, Lei; Li, Yanan Inorganic Chemistry, Vol. 63, Issue 29 https://doi.org/10.1021/acs.inorgchem.4c02156	journal	July 2024
Synergistic Catalysis by Lewis Acid and Base Sites on ZrO ₂ for Meerwein–Ponndorf–Verley Reduction Komanoya, Tasuku; Nakajima, Kiyotaka; Kitano, Masaaki The Journal of Physical Chemistry C, Vol. 119, Issue 47 https://doi.org/10.1021/acs.jpcc.5b08355	journal	November 2015
Product Inhibition and the Catalytic Destruction of a Nerve Agent Simulant by Zirconium-Based Metal–Organic Frameworks Liao, Yijun; Sheridan, Thomas; Liu, Jian ACS Applied Materials & Interfaces, Vol. 13, Issue 26 https://doi.org/10.1021/acsami.1c05062	journal	June 2021
Role of Metal–Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation Fahy, Kira M.; Sha, Fanrui; Reischauer, Susanne ACS Applied Materials & Interfaces, Vol. 16, Issue 23 https://doi.org/10.1021/acsami.4c05016	journal	June 2024
Zirconium-Based Metal–Organic Frameworks for the Catalytic Hydrolysis of Organophosphorus Nerve Agents Kirlikovali, Kent O.; Chen, Zhijie; Islamoglu, Timur ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.9b20154	journal	January 2020
Toward Base Heterogenization: A Zirconium Metal–Organic Framework/Dendrimer or Polymer Mixture for Rapid Hydrolysis of a Nerve-Agent Simulant Chen, Zhijie; Islamoglu, Timur; Farha, Omar K. ACS Applied Nano Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsanm.8b02292	journal	February 2019
Solvent Mediated Interactions on Alkene Epoxidations in Ti-MFI: Effects of Solvent Identity and Silanol Density Torres, Chris; Potts, David S.; Flaherty, David W. ACS Catalysis, Vol. 13, Issue 13 https://doi.org/10.1021/acscatal.3c01073	journal	June 2023
Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks Rimoldi, Martino; Howarth, Ashlee J.; DeStefano, Matthew R. ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b02923	journal	December 2016
Nanosizing a Metal–Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis Li, Peng; Moon, Su-Young; Guelta, Mark A. ACS Nano, Vol. 10, Issue 10 https://doi.org/10.1021/acsnano.6b04996	journal	October 2016
Metal–Organic Framework Materials as Chemical Sensors Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K. Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125 https://doi.org/10.1021/cr200324t	journal	September 2011
Decontamination of Adsorbed Chemical Warfare Agents on Activated Carbon Using Hydrogen Peroxide Solutions Osovsky, Ruth; Kaplan, Doron; Nir, Ido Environmental Science & Technology, Vol. 48, Issue 18 https://doi.org/10.1021/es502981y	journal	August 2014
Superacidity in Sulfated Metal–Organic Framework-808 Jiang, Juncong; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 37 https://doi.org/10.1021/ja507119n	journal	September 2014
A Hafnium-Based Metal–Organic Framework as an Efficient and Multifunctional Catalyst for Facile CO₂ Fixation and Regioselective and Enantioretentive Epoxide Activation Beyzavi, M. Hassan; Klet, Rachel C.; Tussupbayev, Samat Journal of the American Chemical Society, Vol. 136, Issue 45, p. 15861-15864 https://doi.org/10.1021/ja508626n	journal	October 2014
Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery Horcajada, Patricia; Serre, Christian; Maurin, Guillaume Journal of the American Chemical Society, Vol. 130, Issue 21 https://doi.org/10.1021/ja710973k	journal	May 2008
Isothermal Titration Calorimetry to Explore the Parameter Space of Organophosphorus Agrochemical Adsorption in MOFs Drout, Riki J.; Kato, Satoshi; Chen, Haoyuan Journal of the American Chemical Society, Vol. 142, Issue 28 https://doi.org/10.1021/jacs.0c04668	journal	July 2020
Insights into Catalytic Hydrolysis of Organophosphonates at M–OH Sites of Azolate-Based Metal Organic Frameworks Mian, Mohammad Rasel; Chen, Haoyuan; Cao, Ran Journal of the American Chemical Society, Vol. 143, Issue 26 https://doi.org/10.1021/jacs.1c03901	journal	June 2021
What Is Being Measured with P-Bearing NMR Probe Molecules Adsorbed on Zeolites? Bornes, Carlos; Fischer, Michael; Amelse, Jeffrey A. Journal of the American Chemical Society, Vol. 143, Issue 34 https://doi.org/10.1021/jacs.1c05014	journal	August 2021
Separation of Aromatic Hydrocarbons in Porous Materials Idrees, Karam B.; Li, Zhao; Xie, Haomiao Journal of the American Chemical Society, Vol. 144, Issue 27 https://doi.org/10.1021/jacs.2c03114	journal	July 2022
Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis Syed, Zoha H.; Mian, Mohammad Rasel; Patel, Roshan Journal of the American Chemical Society, Vol. 144, Issue 37 https://doi.org/10.1021/jacs.2c05290	journal	September 2022
Unlocking New Topologies in Zr-Based Metal–Organic Frameworks by Combining Linker Flexibility and Building Block Disorder Koschnick, Charlotte; Terban, Maxwell W.; Frison, Ruggero Journal of the American Chemical Society, Vol. 145, Issue 18 https://doi.org/10.1021/jacs.2c13731	journal	April 2023
Air-Stable Cu(I) Metal–Organic Framework for Hydrogen Storage Sengupta, Debabrata; Melix, Patrick; Bose, Saptasree Journal of the American Chemical Society, Vol. 145, Issue 37 https://doi.org/10.1021/jacs.3c06393	journal	September 2023
Thermodynamic Insights into Phosphonate Binding in Metal–Azolate Frameworks Fahy, Kira M.; Lee, Seryeong; Akpinar, Isil Journal of the American Chemical Society, Vol. 146, Issue 8 https://doi.org/10.1021/jacs.3c14643	journal	February 2024
A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO ₂ Removal and Air Capture Using Physisorption Bhatt, Prashant M.; Belmabkhout, Youssef; Cadiau, Amandine Journal of the American Chemical Society, Vol. 138, Issue 29 https://doi.org/10.1021/jacs.6b05345	journal	July 2016
The Chemistry of CO ₂ Capture in an Amine-Functionalized Metal–Organic Framework under Dry and Humid Conditions Flaig, Robinson W.; Osborn Popp, Thomas M.; Fracaroli, Alejandro M. Journal of the American Chemical Society, Vol. 139, Issue 35 https://doi.org/10.1021/jacs.7b06382	journal	August 2017
Theoretical Predictions of ³¹ P NMR Chemical Shift Threshold of Trimethylphosphine Oxide Absorbed on Solid Acid Catalysts Zheng, Anmin; Zhang, Hailu; Lu, Xin The Journal of Physical Chemistry B, Vol. 112, Issue 15 https://doi.org/10.1021/jp709739v	journal	April 2008
Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites Xiao, Dianne J.; Bloch, Eric D.; Mason, Jarad A. Nature Chemistry, Vol. 6, Issue 7 https://doi.org/10.1038/nchem.1956	journal	May 2014
Hydrothermal Synthesize of HF-Free MIL-100(Fe) for Isoniazid-Drug Delivery Simon, Meta A.; Anggraeni, Erlina; Soetaredjo, Felycia Edi Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-53436-3	journal	November 2019
Synthesis and catalytic properties of MIL-100(Fe), an iron( iii ) carboxylate with large pores Horcajada, Patricia; Surblé, Suzy; Serre, Christian Chem. Commun., Issue 27 https://doi.org/10.1039/B704325B	journal	January 2007
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration Klet, Rachel C.; Liu, Yangyang; Wang, Timothy C. Journal of Materials Chemistry A, Vol. 4, Issue 4 https://doi.org/10.1039/C5TA07687K	journal	January 2016
Photochemistry and photophysics of MOFs: steps towards MOF-based sensing enhancements Dolgopolova, Ekaterina A.; Rice, Allison M.; Martin, Corey R. Chemical Society Reviews, Vol. 47, Issue 13 https://doi.org/10.1039/C7CS00861A	journal	January 2018
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework Islamoglu, Timur; Otake, Ken-ichi; Li, Peng CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/C8CE00455B	journal	January 2018
Metal–organic framework nanoparticles for arsenic trioxide drug delivery Ettlinger, Romy; Sönksen, Marthe; Graf, Monika Journal of Materials Chemistry B, Vol. 6, Issue 40 https://doi.org/10.1039/C8TB01899E	journal	January 2018
The surface chemistry of metal–organic frameworks and their applications Forgan, Ross S. Dalton Transactions, Vol. 48, Issue 25 https://doi.org/10.1039/C9DT01710K	journal	January 2019
Suitability of a diamine functionalized metal–organic framework for direct air capture Bose, Saptasree; Sengupta, Debabrata; Malliakas, Christos D. Chemical Science, Vol. 14, Issue 35 https://doi.org/10.1039/D3SC02554C	journal	January 2023
Metal–organic framework materials as catalysts Lee, JeongYong; Farha, Omar K.; Roberts, John Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459 https://doi.org/10.1039/b807080f	journal	January 2009
Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites Britt, D.; Furukawa, H.; Wang, B. Proceedings of the National Academy of Sciences, Vol. 106, Issue 49, p. 20637-20640 https://doi.org/10.1073/pnas.0909718106	journal	November 2009
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel Science, Vol. 295, Issue 5554, p. 469-472 https://doi.org/10.1126/science.1067208	journal	January 2002
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
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
U.N. Taps Special Labs to Investigate Syrian Attack Enserink, M. Science, Vol. 341, Issue 6150 https://doi.org/10.1126/science.341.6150.1050	journal	September 2013
A scalable metal-organic framework as a durable physisorbent for carbon dioxide capture Lin, Jian-Bin; Nguyen, Tai T. T.; Vaidhyanathan, Ramanathan Science, Vol. 374, Issue 6574 https://doi.org/10.1126/science.abi7281	journal	December 2021
Thermodynamic equilibrium and kinetic fundamentals of oxide dissolution in aqueous solution Wang, Jianwei Journal of Materials Research, Vol. 35, Issue 8 https://doi.org/10.1557/jmr.2020.81	journal	April 2020

Similar Records

Role of Metal–Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation

Journal Article · Sat Jun 01 20:00:00 EDT 2024 · ACS Applied Materials and Interfaces · OSTI ID:2467583

Polymer Tacticity Effects in Polymer–Lanthanide Chelation Thermodynamics

Journal Article · Sun Nov 12 19:00:00 EST 2023 · Macromolecules · OSTI ID:2377630

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications

Journal Article · Sun Jul 04 20:00:00 EDT 2021 · Chemical Science · OSTI ID:1815529

Related Subjects

Lewis acidity
binding
isothermal titration calorimetry
metal−organic framework
solid state NMR
water exchange rate

Organophosphorus Binding Thermodynamics in Metal–Organic Frameworks: Interplay between Oxidation State, Lewis Acidity, and Node Structure

Citation Formats

References (56)

Similar Records

Related Subjects