Functionalized Mesoporous Polymers with Enhanced Performance as Reference Electrode Frits

Evan L. Anderson; Stacey A. Saba; Dylan J. Loomis; Phil Buhlmann; Marc A Hillmyer

doi:10.1021/acsanm.7b00058

Functionalized Mesoporous Polymers with Enhanced Performance as Reference Electrode Frits

Evan L. Anderson, Stacey A. Saba, Dylan J. Loomis, Phil Buhlmann, Marc A Hillmyer

Chemistry (Twin Cities)

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

9 Scopus citations

Abstract

Mesoporous glasses (10 nm pores) and macroporous polymers (1 μm pores) are often used as frits in the fabrication of aqueous reference electrodes. These frits function as salt bridges that allow for electrical contact between the sample and reference solutions while slowing cross contamination of the two solutions. Unfortunately, mesoporous glass and macroporous polymer frits used for these purposes inherently result in sample-dependent potentials or in rapid cross contamination of the sample and reference solutions, respectively. To address these issues, we synthesized mesoporous polymer frits, with much smaller pore sizes (10 nm) and electrically neutral hydrophilic pore walls. These monoliths were prepared from a bicontinuous, microphase-separated, and cross-linked block polymer precursor, that is, poly(lactide)-b-poly(isoprene)-b-poly(styrene-co-divinylbenzene), PLA-b-PI-b-P(S-co-DVB). The PLA serves as a selectively etchable sacrificial block, the PI provides latent reactive sites on the pore walls, and the P(S-co-DVB) forms the mechanically robust matrix. Subjecting the PI repeat units in the monoliths to epoxidation and subsequent hydrolysis reactions renders the pore walls hydrophilic and uncharged, permitting the use of the polymer as a porous frit material in reference electrodes with aqueous electrolyte solutions. This monolith chemistry allows for reference electrodes with reduced flow rates that approach those of mesoporous glass frits and thus mitigated cross contamination. Moreover, reference electrode potential variations are reduced across a large range of electrolyte concentrations.

Original language	English (US)
Pages (from-to)	139-144
Number of pages	6
Journal	ACS Applied Nano Materials
Volume	1
Issue number	1
DOIs	https://doi.org/10.1021/acsanm.7b00058
State	Published - Jan 26 2018

Bibliographical note

Funding Information:
The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont Northwestern Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725) and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science Office of Basic Energy Science (Contract No. DE-AC02-06CH11357).

Funding Information:
The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota, which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont−Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725), and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science (Contract No. DE-AC02-06CH11357).

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

electrochemical measurements
polymerization-induced microphase separation
porous frits
porous polymers
reference electrodes

Access

10.1021/acsanm.7b00058

OpenUrl availability

Full text

Cite this

@article{3564bb21a89449a897bb3c36c67d2fbe,

title = "Functionalized Mesoporous Polymers with Enhanced Performance as Reference Electrode Frits",

abstract = "Mesoporous glasses (10 nm pores) and macroporous polymers (1 μm pores) are often used as frits in the fabrication of aqueous reference electrodes. These frits function as salt bridges that allow for electrical contact between the sample and reference solutions while slowing cross contamination of the two solutions. Unfortunately, mesoporous glass and macroporous polymer frits used for these purposes inherently result in sample-dependent potentials or in rapid cross contamination of the sample and reference solutions, respectively. To address these issues, we synthesized mesoporous polymer frits, with much smaller pore sizes (10 nm) and electrically neutral hydrophilic pore walls. These monoliths were prepared from a bicontinuous, microphase-separated, and cross-linked block polymer precursor, that is, poly(lactide)-b-poly(isoprene)-b-poly(styrene-co-divinylbenzene), PLA-b-PI-b-P(S-co-DVB). The PLA serves as a selectively etchable sacrificial block, the PI provides latent reactive sites on the pore walls, and the P(S-co-DVB) forms the mechanically robust matrix. Subjecting the PI repeat units in the monoliths to epoxidation and subsequent hydrolysis reactions renders the pore walls hydrophilic and uncharged, permitting the use of the polymer as a porous frit material in reference electrodes with aqueous electrolyte solutions. This monolith chemistry allows for reference electrodes with reduced flow rates that approach those of mesoporous glass frits and thus mitigated cross contamination. Moreover, reference electrode potential variations are reduced across a large range of electrolyte concentrations.",

keywords = "electrochemical measurements, polymerization-induced microphase separation, porous frits, porous polymers, reference electrodes",

author = "Anderson, {Evan L.} and Saba, {Stacey A.} and Loomis, {Dylan J.} and Phil Buhlmann and Hillmyer, {Marc A}",

note = "Funding Information: The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont Northwestern Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725) and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science Office of Basic Energy Science (Contract No. DE-AC02-06CH11357). Funding Information: The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota, which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont−Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725), and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science (Contract No. DE-AC02-06CH11357). Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2018",

month = jan,

day = "26",

doi = "10.1021/acsanm.7b00058",

language = "English (US)",

volume = "1",

pages = "139--144",

journal = "ACS Applied Nano Materials",

issn = "2574-0970",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Functionalized Mesoporous Polymers with Enhanced Performance as Reference Electrode Frits

AU - Anderson, Evan L.

AU - Saba, Stacey A.

AU - Loomis, Dylan J.

AU - Buhlmann, Phil

AU - Hillmyer, Marc A

N1 - Funding Information: The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont Northwestern Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725) and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science Office of Basic Energy Science (Contract No. DE-AC02-06CH11357). Funding Information: The authors thank Dr. J. Hollinger for the synthesis of the RAFT agent and Dr. M. Mousavi for helpful discussions. This work was supported by the National Science Foundation (Grant Nos. DMR-1609459 and CHE-1710024). E.L.A. thanks the Lester C. and Joan M. Krogh Endowed Fellowship and ACS Division of Analytical Chemistry and Eastman Summer Fellowship. S.A.S. thanks the NSF GRFP and the Louise T. Dosdall Fellowship (UMN) for support. Parts of this work were performed in the Characterization Facility, Univ. of Minnesota, which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont−Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by E. I. DuPont de Nemours, The Dow Chemical Company, the U.S. National Science Foundation (DMR-9304725), and the State of Illinois through the Department of Commerce and the Board of Higher Education (IBHE HECA NWU 96). Use of Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science (Contract No. DE-AC02-06CH11357). Publisher Copyright: © 2017 American Chemical Society.

PY - 2018/1/26

Y1 - 2018/1/26

N2 - Mesoporous glasses (10 nm pores) and macroporous polymers (1 μm pores) are often used as frits in the fabrication of aqueous reference electrodes. These frits function as salt bridges that allow for electrical contact between the sample and reference solutions while slowing cross contamination of the two solutions. Unfortunately, mesoporous glass and macroporous polymer frits used for these purposes inherently result in sample-dependent potentials or in rapid cross contamination of the sample and reference solutions, respectively. To address these issues, we synthesized mesoporous polymer frits, with much smaller pore sizes (10 nm) and electrically neutral hydrophilic pore walls. These monoliths were prepared from a bicontinuous, microphase-separated, and cross-linked block polymer precursor, that is, poly(lactide)-b-poly(isoprene)-b-poly(styrene-co-divinylbenzene), PLA-b-PI-b-P(S-co-DVB). The PLA serves as a selectively etchable sacrificial block, the PI provides latent reactive sites on the pore walls, and the P(S-co-DVB) forms the mechanically robust matrix. Subjecting the PI repeat units in the monoliths to epoxidation and subsequent hydrolysis reactions renders the pore walls hydrophilic and uncharged, permitting the use of the polymer as a porous frit material in reference electrodes with aqueous electrolyte solutions. This monolith chemistry allows for reference electrodes with reduced flow rates that approach those of mesoporous glass frits and thus mitigated cross contamination. Moreover, reference electrode potential variations are reduced across a large range of electrolyte concentrations.

AB - Mesoporous glasses (10 nm pores) and macroporous polymers (1 μm pores) are often used as frits in the fabrication of aqueous reference electrodes. These frits function as salt bridges that allow for electrical contact between the sample and reference solutions while slowing cross contamination of the two solutions. Unfortunately, mesoporous glass and macroporous polymer frits used for these purposes inherently result in sample-dependent potentials or in rapid cross contamination of the sample and reference solutions, respectively. To address these issues, we synthesized mesoporous polymer frits, with much smaller pore sizes (10 nm) and electrically neutral hydrophilic pore walls. These monoliths were prepared from a bicontinuous, microphase-separated, and cross-linked block polymer precursor, that is, poly(lactide)-b-poly(isoprene)-b-poly(styrene-co-divinylbenzene), PLA-b-PI-b-P(S-co-DVB). The PLA serves as a selectively etchable sacrificial block, the PI provides latent reactive sites on the pore walls, and the P(S-co-DVB) forms the mechanically robust matrix. Subjecting the PI repeat units in the monoliths to epoxidation and subsequent hydrolysis reactions renders the pore walls hydrophilic and uncharged, permitting the use of the polymer as a porous frit material in reference electrodes with aqueous electrolyte solutions. This monolith chemistry allows for reference electrodes with reduced flow rates that approach those of mesoporous glass frits and thus mitigated cross contamination. Moreover, reference electrode potential variations are reduced across a large range of electrolyte concentrations.

KW - electrochemical measurements

KW - polymerization-induced microphase separation

KW - porous frits

KW - porous polymers

KW - reference electrodes

UR - http://www.scopus.com/inward/record.url?scp=85069469436&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85069469436&partnerID=8YFLogxK

U2 - 10.1021/acsanm.7b00058

DO - 10.1021/acsanm.7b00058

M3 - Article

AN - SCOPUS:85069469436

SN - 2574-0970

VL - 1

SP - 139

EP - 144

JO - ACS Applied Nano Materials

JF - ACS Applied Nano Materials

IS - 1

ER -

Functionalized Mesoporous Polymers with Enhanced Performance as Reference Electrode Frits

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this