Copper-Based Two-Dimensional Conductive Metal–Organic Framework Thin Films for Ultrasensitive Detection of Perfluoroalkyls in Drinking Water

Roh, Heejung; Quill, Tyler J.; Chen, Gan; Gong, Huaxin; Cho, Yeongsu; Kulik, Heather J.; Bao, Zhenan; Salleo, Alberto; Gumyusenge, Aristide

doi:10.1021/acsnano.4c16212

Copper-Based Two-Dimensional Conductive Metal–Organic Framework Thin Films for Ultrasensitive Detection of Perfluoroalkyls in Drinking Water

Journal Article · Sat Feb 08 00:00:00 EST 2025 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.4c16212· OSTI ID:2575236

Roh, Heejung ^[1]; ^[2]; Chen, Gan ^[2]; ^[2]; Cho, Yeongsu ^[1]; ^[1]; ^[2]; Salleo, Alberto ^[2]; ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Perfluoroalkyls (PFAS) continue to emerge as a global health threat making their effective detection and capture extremely important. Though metal–organic frameworks (MOFs) have stood out as a promising class of porous materials for sensing PFAS, detection limits remain insufficient and a fundamental understanding of detection mechanisms warrants further investigation. Here, in this study, we show the use of a 2D conductive MOF film based on copper hexahydroxy triphenylene (Cu-HHTP) to fabricate chemiresistive sensing devices for detecting PFAS in drinking water. We further show ultrasensitive detection using electrochemical impedance spectroscopy. Owing to excellent electrostatic attractions and electrochemical interactions between the copper-based MOF and PFAS, confirmed by high-resolution spectroscopy and theoretical simulations, the MOF-based sensor reported herein exhibits excellent affinity and sensitivity toward perfluorinated acids at concentrations as low as 0.002 ng/L.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515

Other Award/Contract Number:: ECCS-2026822
ITE-2345076
DGE-1656518

OSTI ID:: 2575236

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 6 Vol. 19; ISSN 1936-086X; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Electrically Conductive Metal–Organic Framework Thin Film‐Based On‐Chip Micro‐Biosensor: A Platform to Unravel Surface Morphology‐Dependent Biosensing Chen, Xin; Dong, Junjie; Chi, Kai Advanced Functional Materials, Vol. 31, Issue 51 https://doi.org/10.1002/adfm.202102855	journal	September 2021
Face‐to‐Face Growth of Wafer‐Scale 2D Semiconducting MOF Films on Dielectric Substrates Liu, Youxing; Wei, Yanan; Liu, Minghui Advanced Materials, Vol. 33, Issue 13 https://doi.org/10.1002/adma.202007741	journal	February 2021
[Cu ₃ (C ₆ Se ₆ )] _n : The First Highly Conductive 2D π–d Conjugated Coordination Polymer Based on Benzenehexaselenolate Cui, Yutao; Yan, Jie; Chen, Zhijun Advanced Science, Vol. 6, Issue 9 https://doi.org/10.1002/advs.201802235	journal	March 2019
Cu ₃ (hexaiminotriphenylene) ₂ : An Electrically Conductive 2D Metal-Organic Framework for Chemiresistive Sensing Campbell, Michael G.; Sheberla, Dennis; Liu, Sophie F. Angewandte Chemie International Edition, Vol. 54, Issue 14 https://doi.org/10.1002/anie.201411854	journal	February 2015
Layer-by-Layer Assembled Conductive Metal-Organic Framework Nanofilms for Room-Temperature Chemiresistive Sensing Yao, Ming-Shui; Lv, Xiao-Jing; Fu, Zhi-Hua Angewandte Chemie International Edition, Vol. 56, Issue 52 https://doi.org/10.1002/anie.201709558	journal	November 2017
2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves Song, Xiaoyu; Wang, Xinyue; Li, Yusen Angewandte Chemie International Edition, Vol. 59, Issue 3 https://doi.org/10.1002/anie.201911543	journal	November 2019
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Advanced analysis of copper X-ray photoelectron spectra: Advanced analysis of copper X-ray photoelectron spectra Biesinger, Mark C. Surface and Interface Analysis, Vol. 49, Issue 13 https://doi.org/10.1002/sia.6239	journal	May 2017
Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian Theoretical Chemistry Accounts, Vol. 117, Issue 4 https://doi.org/10.1007/s00214-007-0250-5	journal	January 2007
Coordination compounds of 1,4-dihydroxybenzoquinone and its homologues. Structures and properties Kitagawa, S. Coordination Chemistry Reviews, Vol. 224, Issue 1-2 https://doi.org/10.1016/S0010-8545(01)00369-1	journal	January 2002
Dissecting π-conjugated covalent-coupling over conductive MOFs toward efficient two-electron oxygen reduction Sun, Xuan; Li, Yuanli; Su, Hui Applied Catalysis B: Environmental, Vol. 317 https://doi.org/10.1016/j.apcatb.2022.121706	journal	November 2022
Analytical chemistry of perfluoroalkylated substances Voogt, P.; Saez, M. TrAC Trends in Analytical Chemistry, Vol. 25, Issue 4 https://doi.org/10.1016/j.trac.2005.10.008	journal	April 2006
Metal–organic frameworks for electrochemical applications Liu, Wei; Yin, Xue-Bo TrAC Trends in Analytical Chemistry, Vol. 75 https://doi.org/10.1016/j.trac.2015.07.011	journal	January 2016
Electron Beam Patterning of Metal–Organic Frameworks Miao, Yurun; Tsapatsis, Michael Chemistry of Materials, Vol. 33, Issue 2 https://doi.org/10.1021/acs.chemmater.0c04204	journal	January 2021
Efficient Removal of Per- and Polyfluoroalkyl Substances from Water with Zirconium-Based Metal–Organic Frameworks Li, Rui; Alomari, Shefa; Stanton, Robert Chemistry of Materials, Vol. 33, Issue 9 https://doi.org/10.1021/acs.chemmater.1c00324	journal	April 2021
Ammonia Capture via an Unconventional Reversible Guest-Induced Metal-Linker Bond Dynamics in a Highly Stable Metal–Organic Framework Lyu, Pengbo; Wright, Ashley M.; López-Olvera, Alfredo Chemistry of Materials, Vol. 33, Issue 15 https://doi.org/10.1021/acs.chemmater.1c01838	journal	July 2021
Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00067	journal	March 2017
Electronic Devices Using Open Framework Materials Allendorf, Mark D.; Dong, Renhao; Feng, Xinliang Chemical Reviews, Vol. 120, Issue 16 https://doi.org/10.1021/acs.chemrev.0c00033	journal	July 2020
Understanding the Adsorption of PFOA on MIL-101(Cr)-Based Anionic-Exchange Metal–Organic Frameworks: Comparing DFT Calculations with Aqueous Sorption Experiments Liu, Kai; Zhang, Siyu; Hu, Xiyue Environmental Science & Technology, Vol. 49, Issue 14 https://doi.org/10.1021/acs.est.5b00802	journal	July 2015
Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater Barzen-Hanson, Krista A.; Roberts, Simon C.; Choyke, Sarah Environmental Science & Technology, Vol. 51, Issue 4 https://doi.org/10.1021/acs.est.6b05843	journal	February 2017
Assessing the Effectiveness of Point-of-Use Residential Drinking Water Filters for Perfluoroalkyl Substances (PFASs) Herkert, Nicholas J.; Merrill, John; Peters, Cara Environmental Science & Technology Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.estlett.0c00004	journal	February 2020
Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants Hu, Xindi C.; Andrews, David Q.; Lindstrom, Andrew B. Environmental Science & Technology Letters, Vol. 3, Issue 10 https://doi.org/10.1021/acs.estlett.6b00260	journal	August 2016
Probing the Sorption of Perfluorooctanesulfonate Using Mesoporous Metal–Organic Frameworks from Aqueous Solutions Barpaga, Dushyant; Zheng, Jian; Han, Kee Sung Inorganic Chemistry, Vol. 58, Issue 13 https://doi.org/10.1021/acs.inorgchem.9b00380	journal	May 2019
Active Sites in Copper-Based Metal–Organic Frameworks: Understanding Substrate Dynamics, Redox Processes, and Valence-Band Structure Duke, Audrey S.; Dolgopolova, Ekaterina A.; Galhenage, Randima P. The Journal of Physical Chemistry C, Vol. 119, Issue 49 https://doi.org/10.1021/acs.jpcc.5b08053	journal	November 2015
2D MOFs with Ni(II), Cu(II), and Co(II) as Efficient Oxygen Evolution Electrocatalysts: Rationalization of Catalytic Performance vs Structure of the MOFs and Potential of the Redox Couples Goswami, Anindita; Ghosh, Debanjali; Chernyshev, Vladimir V. ACS Applied Materials & Interfaces, Vol. 12, Issue 30 https://doi.org/10.1021/acsami.0c07268	journal	July 2020
Screening and Discrimination of Perfluoroalkyl Substances in Aqueous Solution Using a Luminescent Metal–Organic Framework Sensor Array Chen, Beining; Yang, Zhengshuang; Qu, Xiaolei ACS Applied Materials & Interfaces, Vol. 13, Issue 40 https://doi.org/10.1021/acsami.1c15528	journal	October 2021
Metal–Organic Framework-Based Microfluidic Impedance Sensor Platform for Ultrasensitive Detection of Perfluorooctanesulfonate Cheng, Yu H.; Barpaga, Dushyant; Soltis, Jennifer A. ACS Applied Materials & Interfaces, Vol. 12, Issue 9 https://doi.org/10.1021/acsami.9b22445	journal	February 2020
Polydopamine Coating of a Metal–Organic Framework with Bi-Copper Sites for Highly Selective Electroreduction of CO₂ to C₂₊ Products Zhao, Zhen-Hua; Zhu, Hao-Lin; Huang, Jia-Run ACS Catalysis, Vol. 12, Issue 13 https://doi.org/10.1021/acscatal.2c02002	journal	June 2022
Electrochemical Sensing of Perfluorooctanesulfonate (PFOS) Using Ambient Oxygen in River Water Clark, Rebecca B.; Dick, Jeffrey E. ACS Sensors, Vol. 5, Issue 11 https://doi.org/10.1021/acssensors.0c01894	journal	November 2020
Rapid and Label-Free Detection of Interferon Gamma via an Electrochemical Aptasensor Comprising a Ternary Surface Monolayer on a Gold Interdigitated Electrode Array Ding, Shaowei; Mosher, Curtis; Lee, Xian Y. ACS Sensors, Vol. 2, Issue 2 https://doi.org/10.1021/acssensors.6b00581	journal	January 2017
MOFs for the Sensitive Detection of Ammonia: Deployment of fcu-MOF Thin Films as Effective Chemical Capacitive Sensors Assen, Ayalew H.; Yassine, Omar; Shekhah, Osama ACS Sensors, Vol. 2, Issue 9 https://doi.org/10.1021/acssensors.7b00304	journal	August 2017
Highly Defective UiO-66 Materials for the Adsorptive Removal of Perfluorooctanesulfonate Clark, Chelsea A.; Heck, Kimberly N.; Powell, Camilah D. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 7 https://doi.org/10.1021/acssuschemeng.8b05572	journal	March 2019
Peer Reviewed: Perfluorochemical Surfactants in the Environment Giesy, John P.; Kannan, Kurunthachalam Environmental Science & Technology, Vol. 36, Issue 7 https://doi.org/10.1021/es022253t	journal	April 2002
van der Waals Volumes and Radii Bondi, A. The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451 https://doi.org/10.1021/j100785a001	journal	March 1964
Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit? Farha, Omar K.; Eryazici, Ibrahim; Jeong, Nak Cheon Journal of the American Chemical Society, Vol. 134, Issue 36, p. 15016-15021 https://doi.org/10.1021/ja3055639	journal	August 2012
Integrated Photocatalytic Reduction and Oxidation of Perfluorooctanoic Acid by Metal–Organic Frameworks: Key Insights into the Degradation Mechanisms Wen, Yinghao; Rentería-Gómez, Ángel; Day, Gregory S. Journal of the American Chemical Society, Vol. 144, Issue 26 https://doi.org/10.1021/jacs.2c04341	journal	June 2022
Molecular Cu Electrocatalyst Escalates Ambient Perfluorooctanoic Acid Degradation Sinha, Soumalya; Chaturvedi, Ashwin; Gautam, Rajeev K. Journal of the American Chemical Society, Vol. 145, Issue 50 https://doi.org/10.1021/jacs.3c08352	journal	December 2023
Electrochemical Reduction of Perfluorooctanoic Acid (PFOA): An Experimental and Theoretical Approach Calvillo Solís, Jonathan J.; Sandoval-Pauker, Christian; Bai, David Journal of the American Chemical Society, Vol. 146, Issue 15 https://doi.org/10.1021/jacs.4c00443	journal	April 2024
Chemiresistive Sensor Arrays from Conductive 2D Metal–Organic Frameworks Campbell, Michael G.; Liu, Sophie F.; Swager, Timothy M. Journal of the American Chemical Society, Vol. 137, Issue 43 https://doi.org/10.1021/jacs.5b09600	journal	October 2015
Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework Darago, Lucy E.; Aubrey, Michael L.; Yu, Chung Jui Journal of the American Chemical Society, Vol. 137, Issue 50 https://doi.org/10.1021/jacs.5b10385	journal	December 2015
2D Conductive Iron-Quinoid Magnets Ordering up to T _c = 105 K via Heterogenous Redox Chemistry DeGayner, Jordan A.; Jeon, Ie-Rang; Sun, Lei Journal of the American Chemical Society, Vol. 139, Issue 11 https://doi.org/10.1021/jacs.7b00705	journal	March 2017
Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal–Organic Framework Park, Jihye; Hinckley, Allison C.; Huang, Zhehao Journal of the American Chemical Society, Vol. 140, Issue 44 https://doi.org/10.1021/jacs.8b06666	journal	September 2018
Perspective on Fluorocarbon Chemistry Lemal, David M. The Journal of Organic Chemistry, Vol. 69, Issue 1 https://doi.org/10.1021/jo0302556	journal	January 2004
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
A Smooth Solvation Potential Based on the Conductor-Like Screening Model York, Darrin M.; Karplus, Martin The Journal of Physical Chemistry A, Vol. 103, Issue 50 https://doi.org/10.1021/jp992097l	journal	December 1999
Conductive 2D metal-organic framework for high-performance cathodes in aqueous rechargeable zinc batteries Nam, Kwan Woo; Park, Sarah S.; dos Reis, Roberto Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12857-4	journal	October 2019
Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance Feng, Dawei; Lei, Ting; Lukatskaya, Maria R. Nature Energy, Vol. 3, Issue 1 https://doi.org/10.1038/s41560-017-0044-5	journal	January 2018
Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks Dou, Jin-Hu; Arguilla, Maxx Q.; Luo, Yi Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00847-7	journal	November 2020
A sensitive electrochemical immunosensor for label-free detection of Zika-virus protein Kaushik, Ajeet; Yndart, Adriana; Kumar, Sanjeev Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-28035-3	journal	June 2018
MOF-based electronic and opto-electronic devices Stavila, V.; Talin, A. A.; Allendorf, M. D. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00096J	journal	January 2014
Metal–organic framework sorbents for the removal of perfluorinated compounds in an aqueous environment Sini, Karima; Bourgeois, Damien; Idouhar, Madjid New Journal of Chemistry, Vol. 42, Issue 22 https://doi.org/10.1039/C8NJ03312A	journal	January 2018
Copper-based metal–organic frameworks for CO₂reduction: selectivity trends, design paradigms, and perspectives Nwosu, Ugochukwu; Siahrostami, Samira Catalysis Science & Technology, Vol. 13, Issue 13 https://doi.org/10.1039/D3CY00408B	journal	January 2023
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
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
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
A smooth, nonsingular, and faithful discretization scheme for polarizable continuum models: The switching/Gaussian approach Lange, Adrian W.; Herbert, John M. The Journal of Chemical Physics, Vol. 133, Issue 24 https://doi.org/10.1063/1.3511297	journal	December 2010
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
Geometry optimization made simple with translation and rotation coordinates Wang, Lee-Ping; Song, Chenchen The Journal of Chemical Physics, Vol. 144, Issue 21 https://doi.org/10.1063/1.4952956	journal	June 2016
The ORCA quantum chemistry program package Neese, Frank; Wennmohs, Frank; Becker, Ute The Journal of Chemical Physics, Vol. 152, Issue 22 https://doi.org/10.1063/5.0004608	journal	June 2020
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors Boys, S.F.; Bernardi, F. Molecular Physics, Vol. 19, Issue 4, p. 553-566 https://doi.org/10.1080/00268977000101561	journal	October 1970
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
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
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
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
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
PFOA and Cancer in a Highly Exposed Community: New Findings from the C8 Science Panel Nicole, Wendee Environmental Health Perspectives, Vol. 121, Issue 11-12 https://doi.org/10.1289/ehp.121-A340	journal	November 2013

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Copper-Based Two-Dimensional Conductive Metal–Organic Framework Thin Films for Ultrasensitive Detection of Perfluoroalkyls in Drinking Water

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