TY - JOUR
T1 - Isothermal Titration Calorimetry to Explore the Parameter Space of Organophosphorus Agrochemical Adsorption in MOFs
AU - Drout, Riki J.
AU - Kato, Satoshi
AU - Chen, Haoyuan
AU - Son, Florencia A.
AU - Otake, Ken Ichi
AU - Islamoglu, Timur
AU - Snurr, Randall Q.
AU - Farha, Omar K.
N1 - Funding Information:
O.K.F. and R.Q.S. gratefully acknowledge support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003). R.J.D. gratefully acknowledges the International Institute for Nanotechnology for providing financial support through the Ryan Fellowship. The authors appreciate the efforts of Ashlee Howarth, Marek Majewski, and Lee Robison, who initially explored glyphosate adsorption in MOFs. We thank Arabela Grigorescu of the Northwestern Keck Biophysics Facility for providing invaluable assistance with ITC instrument set up and data optimization. The authors also employed the X-ray diffractometers and NMR spectrometers in the IMSERC facility at Northwestern University, which receives support from the NSF (CHE-1048773 and DMR-0521267); the SHyNE Resource (NSF NNCI-1542205); the State of Illinois; and the International Institute for Nanotechnology. ICP-OES metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center. The computing resources were provided by the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science user facility supported by the Office of Science of the U.S. Department of Energy (DE AC02-05CH11231), and the Quest high-performance computing facility at Northwestern University.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/7/15
Y1 - 2020/7/15
N2 - The expansion of manufacturing and commercial agriculture alongside rapid globalization have resulted in the widespread contamination of freshwater supplies with chemical toxins including persistent organic pollutants. Effective mitigation of such pollution is paramount to the safeguarding of human health, animal and aquatic life, and the environment. Currently, adsorption is the most economically viable water purification strategy. Owing to their crystallinity and modular nature, metal-organic frameworks (MOFs) are an excellent platform material for systematically investigating the physical and chemical properties which govern adsorption processes. X-ray diffraction techniques provide atomically precise descriptions of toxin-MOF interactions, while liquid-phase adsorption isotherms readily allow for the determination of uptake capacity and kinetics; however, determination of the thermodynamics of toxin-MOF interactions in aqueous media remains tedious. Herein, we add isothermal titration calorimetry (ITC) to our arsenal of techniques for characterizing adsorption mechanisms in MOFs. With this method, we are able to directly quantify the full thermodynamic profile of a chemical process (Ka, ΔG, ΔH, TΔS), providing critical details to support the rational design of next-generation sorbents. We demonstrate the suitability of ITC through our exploration of the parameter space of organophosphorus agrochemical adsorption in zirconium-based MOFs.
AB - The expansion of manufacturing and commercial agriculture alongside rapid globalization have resulted in the widespread contamination of freshwater supplies with chemical toxins including persistent organic pollutants. Effective mitigation of such pollution is paramount to the safeguarding of human health, animal and aquatic life, and the environment. Currently, adsorption is the most economically viable water purification strategy. Owing to their crystallinity and modular nature, metal-organic frameworks (MOFs) are an excellent platform material for systematically investigating the physical and chemical properties which govern adsorption processes. X-ray diffraction techniques provide atomically precise descriptions of toxin-MOF interactions, while liquid-phase adsorption isotherms readily allow for the determination of uptake capacity and kinetics; however, determination of the thermodynamics of toxin-MOF interactions in aqueous media remains tedious. Herein, we add isothermal titration calorimetry (ITC) to our arsenal of techniques for characterizing adsorption mechanisms in MOFs. With this method, we are able to directly quantify the full thermodynamic profile of a chemical process (Ka, ΔG, ΔH, TΔS), providing critical details to support the rational design of next-generation sorbents. We demonstrate the suitability of ITC through our exploration of the parameter space of organophosphorus agrochemical adsorption in zirconium-based MOFs.
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U2 - 10.1021/jacs.0c04668
DO - 10.1021/jacs.0c04668
M3 - Article
C2 - 32614581
AN - SCOPUS:85088150359
SN - 0002-7863
VL - 142
SP - 12357
EP - 12366
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 28
ER -
