High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks

Austin M. Evans; Nathan P. Bradshaw; Brian Litchfield; Michael J. Strauss; Bethany Seckman; Matthew R. Ryder; Ioannina Castano; Christopher Gilmore; Nathan C. Gianneschi; Catherine R. Mulzer; Mark C. Hersam; William R. Dichtel

doi:10.1002/adma.202004205

High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks

Austin M. Evans, Nathan P. Bradshaw, Brian Litchfield, Michael J. Strauss, Bethany Seckman, Matthew R. Ryder, Ioannina Castano, Christopher Gilmore, Nathan C. Gianneschi, Catherine R. Mulzer, Mark C. Hersam, William R. Dichtel

Neutron & X-Ray Scattering, & Thermophys

Research output: Contribution to journal › Article › peer-review

70 Scopus citations

Abstract

2D covalent organic frameworks (2D COFs) are a unique materials platform that combines covalent connectivity, structural regularity, and molecularly precise porosity. However, 2D COFs typically form insoluble aggregates, thus limiting their processing via additive manufacturing techniques. In this work, colloidal suspensions of boronate-ester-linked 2D COFs are used as a spray-coating ink to produce large-area 2D COF thin films. This method is synthetically general, with five different 2D COFs prepared as colloidal inks and subsequently spray-coated onto a diverse range of substrates. Moreover, this approach enables the deposition of multiple 2D COF materials simultaneously, which is not possible by polymerizing COFs on substrates directly. When combined with stencil masks, spray-coated 2D COFs are rapidly deposited as thin films larger than 200 cm² with line resolutions below 50 µm. To demonstrate that this deposition scheme preserves the desirable attributes of 2D COFs, spray-coated 2D COF thin films are incorporated as the active material in acoustic sensors. These 2D-COF-based sensors have a 10 ppb limit-of-quantification for trimethylamine, which places them among the most sensitive sensors for meat and seafood spoilage. Overall, this work establishes a scalable additive manufacturing technique that enables the integration of 2D COFs into thin-film device architectures.

Original language	English
Article number	2004205
Journal	Advanced Materials
Volume	32
Issue number	42
DOIs	https://doi.org/10.1002/adma.202004205
State	Published - Oct 1 2020

Bibliographical note

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Funding

A.M.E. and N.P.B. contributed equally to this work. The authors acknowledge the Army Research Office for a Multidisciplinary University Research Initiatives (MURI) award under grant number W911NF-15-1-0447. N.P.B. and A.M.E. also acknowledge the Department of Energy (Grant DE-SC0019356) for support of the 2D COF spray coating work. A.M.E. (DGE-1324585), M.J.S. (DGE-1842165), I.C. (DGE-1842165), and N.P.B. were supported by National Science Foundation Graduate Research Fellowships. A.M.E., M.J.S., and I.C were supported by Ryan Fellowships provided by the International Institute of Nanotechnology. N.P.B. and M.C.H. acknowledge the Department of Energy (Grant DE-SC0019356) and the National Science Foundation (Grant DMR-1720139) for support of the 2D COF spray coating work. M.R.R. acknowledges the U.S. Department of Energy Office of Science (Basic Energy Sciences) for research funding and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility, operated under Contract No. DE-AC02-05CH11231, for access to supercomputing resources. Parts of this work were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 and Sector 8 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and the Dow Chemical Company. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, both U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE- AC0206CH11357. This work has also made use of the IMSERC, EPIC, Keck II, and NUANCE facilities at Northwestern University, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the Keck Foundation, the State of Illinois, and International Institute for Nanotechnology (IIN). A.M.E. and N.P.B. contributed equally to this work. The authors acknowledge the Army Research Office for a Multidisciplinary University Research Initiatives (MURI) award under grant number W911NF‐15‐1‐0447. N.P.B. and A.M.E. also acknowledge the Department of Energy (Grant DE‐SC0019356) for support of the 2D COF spray coating work. A.M.E. (DGE‐1324585), M.J.S. (DGE‐1842165), I.C. (DGE‐1842165), and N.P.B. were supported by National Science Foundation Graduate Research Fellowships. A.M.E., M.J.S., and I.C were supported by Ryan Fellowships provided by the International Institute of Nanotechnology. N.P.B. and M.C.H. acknowledge the Department of Energy (Grant DE‐SC0019356) and the National Science Foundation (Grant DMR‐1720139) for support of the 2D COF spray coating work. M.R.R. acknowledges the U.S. Department of Energy Office of Science (Basic Energy Sciences) for research funding and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility, operated under Contract No. DE‐AC02‐05CH11231, for access to supercomputing resources. Parts of this work were performed at the DuPont‐Northwestern‐Dow Collaborative Access Team (DND‐CAT) located at Sector 5 and Sector 8 of the Advanced Photon Source (APS). DND‐CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and the Dow Chemical Company. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, both U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐ AC0206CH11357. This work has also made use of the IMSERC, EPIC, Keck II, and NUANCE facilities at Northwestern University, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐1542205), the MRSEC program (NSF DMR‐1720139) at the Materials Research Center, the Keck Foundation, the State of Illinois, and International Institute for Nanotechnology (IIN).

Funders	Funder number
DOE Office of Science
E.I. DuPont de Nemours & Co.
IIN
International Institute for Nanotechnology
International Institute of Nanotechnology
National Energy Research Scientific Computing Center
Soft and Hybrid Nanotechnology Experimental	NSF ECCS‐1542205
U.S. Department of Energy Office of Science
National Science Foundation
U.S. Department of Energy	DE‐SC0019356, DGE‐1842165, DGE‐1324585
Army Research Office	W911NF‐15‐1‐0447
W. M. Keck Foundation
Dow Chemical Company
DuPont
Office of Science
Basic Energy Sciences
Argonne National Laboratory	DE‐ AC0206CH11357
Northwestern University
Materials Research Science and Engineering Center, Harvard University	NSF DMR‐1720139
International Institute for Nanotechnology, Northwestern University	DMR‐1720139
National Energy Research Scientific Computing Center	DE‐AC02‐05CH11231

Keywords

acoustic sensors
additive manufacturing
covalent organic framework (COF)
solution processing
thin-films

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/adma.202004205

Cite this

Evans, A. M., Bradshaw, N. P., Litchfield, B., Strauss, M. J., Seckman, B., Ryder, M. R., Castano, I., Gilmore, C., Gianneschi, N. C., Mulzer, C. R., Hersam, M. C., & Dichtel, W. R. (2020). High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks. Advanced Materials, 32(42), Article 2004205. https://doi.org/10.1002/adma.202004205

@article{3c96eedae3c644e6962c901819e82217,

title = "High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks",

abstract = "2D covalent organic frameworks (2D COFs) are a unique materials platform that combines covalent connectivity, structural regularity, and molecularly precise porosity. However, 2D COFs typically form insoluble aggregates, thus limiting their processing via additive manufacturing techniques. In this work, colloidal suspensions of boronate-ester-linked 2D COFs are used as a spray-coating ink to produce large-area 2D COF thin films. This method is synthetically general, with five different 2D COFs prepared as colloidal inks and subsequently spray-coated onto a diverse range of substrates. Moreover, this approach enables the deposition of multiple 2D COF materials simultaneously, which is not possible by polymerizing COFs on substrates directly. When combined with stencil masks, spray-coated 2D COFs are rapidly deposited as thin films larger than 200 cm2 with line resolutions below 50 µm. To demonstrate that this deposition scheme preserves the desirable attributes of 2D COFs, spray-coated 2D COF thin films are incorporated as the active material in acoustic sensors. These 2D-COF-based sensors have a 10 ppb limit-of-quantification for trimethylamine, which places them among the most sensitive sensors for meat and seafood spoilage. Overall, this work establishes a scalable additive manufacturing technique that enables the integration of 2D COFs into thin-film device architectures.",

keywords = "acoustic sensors, additive manufacturing, covalent organic framework (COF), solution processing, thin-films",

author = "Evans, {Austin M.} and Bradshaw, {Nathan P.} and Brian Litchfield and Strauss, {Michael J.} and Bethany Seckman and Ryder, {Matthew R.} and Ioannina Castano and Christopher Gilmore and Gianneschi, {Nathan C.} and Mulzer, {Catherine R.} and Hersam, {Mark C.} and Dichtel, {William R.}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2020",

month = oct,

day = "1",

doi = "10.1002/adma.202004205",

language = "English",

volume = "32",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "wiley",

number = "42",

}

TY - JOUR

T1 - High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks

AU - Evans, Austin M.

AU - Bradshaw, Nathan P.

AU - Litchfield, Brian

AU - Strauss, Michael J.

AU - Seckman, Bethany

AU - Ryder, Matthew R.

AU - Castano, Ioannina

AU - Gilmore, Christopher

AU - Gianneschi, Nathan C.

AU - Mulzer, Catherine R.

AU - Hersam, Mark C.

AU - Dichtel, William R.

PY - 2020/10/1

Y1 - 2020/10/1

N2 - 2D covalent organic frameworks (2D COFs) are a unique materials platform that combines covalent connectivity, structural regularity, and molecularly precise porosity. However, 2D COFs typically form insoluble aggregates, thus limiting their processing via additive manufacturing techniques. In this work, colloidal suspensions of boronate-ester-linked 2D COFs are used as a spray-coating ink to produce large-area 2D COF thin films. This method is synthetically general, with five different 2D COFs prepared as colloidal inks and subsequently spray-coated onto a diverse range of substrates. Moreover, this approach enables the deposition of multiple 2D COF materials simultaneously, which is not possible by polymerizing COFs on substrates directly. When combined with stencil masks, spray-coated 2D COFs are rapidly deposited as thin films larger than 200 cm2 with line resolutions below 50 µm. To demonstrate that this deposition scheme preserves the desirable attributes of 2D COFs, spray-coated 2D COF thin films are incorporated as the active material in acoustic sensors. These 2D-COF-based sensors have a 10 ppb limit-of-quantification for trimethylamine, which places them among the most sensitive sensors for meat and seafood spoilage. Overall, this work establishes a scalable additive manufacturing technique that enables the integration of 2D COFs into thin-film device architectures.

AB - 2D covalent organic frameworks (2D COFs) are a unique materials platform that combines covalent connectivity, structural regularity, and molecularly precise porosity. However, 2D COFs typically form insoluble aggregates, thus limiting their processing via additive manufacturing techniques. In this work, colloidal suspensions of boronate-ester-linked 2D COFs are used as a spray-coating ink to produce large-area 2D COF thin films. This method is synthetically general, with five different 2D COFs prepared as colloidal inks and subsequently spray-coated onto a diverse range of substrates. Moreover, this approach enables the deposition of multiple 2D COF materials simultaneously, which is not possible by polymerizing COFs on substrates directly. When combined with stencil masks, spray-coated 2D COFs are rapidly deposited as thin films larger than 200 cm2 with line resolutions below 50 µm. To demonstrate that this deposition scheme preserves the desirable attributes of 2D COFs, spray-coated 2D COF thin films are incorporated as the active material in acoustic sensors. These 2D-COF-based sensors have a 10 ppb limit-of-quantification for trimethylamine, which places them among the most sensitive sensors for meat and seafood spoilage. Overall, this work establishes a scalable additive manufacturing technique that enables the integration of 2D COFs into thin-film device architectures.

KW - acoustic sensors

KW - additive manufacturing

KW - covalent organic framework (COF)

KW - solution processing

KW - thin-films

UR - http://www.scopus.com/inward/record.url?scp=85090976732&partnerID=8YFLogxK

U2 - 10.1002/adma.202004205

DO - 10.1002/adma.202004205

M3 - Article

C2 - 32939866

AN - SCOPUS:85090976732

SN - 0935-9648

VL - 32

JO - Advanced Materials

JF - Advanced Materials

IS - 42

M1 - 2004205

ER -

High-Sensitivity Acoustic Molecular Sensors Based on Large-Area, Spray-Coated 2D Covalent Organic Frameworks

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this