Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66

Rebecca H. Palmer, Jian Liu, Chung Wei Kung, Idan Hod, Omar K. Farha, Joseph T Hupp

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.

Original languageEnglish
Pages (from-to)4707-4714
Number of pages8
JournalLangmuir
Volume34
Issue number16
DOIs
Publication statusPublished - Apr 24 2018

Fingerprint

Metals
discrete cosine transform
metals
Charge transfer
delivery
chemical energy
Chronoamperometry
Molecules
electrocatalysts
Electrocatalysts
solar energy
electric power
Crystallites
Solar energy
crystallites
Cyclic voltammetry
installing
molecules
constrictions
diffusion coefficient

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66. / Palmer, Rebecca H.; Liu, Jian; Kung, Chung Wei; Hod, Idan; Farha, Omar K.; Hupp, Joseph T.

In: Langmuir, Vol. 34, No. 16, 24.04.2018, p. 4707-4714.

Research output: Contribution to journalArticle

Palmer, Rebecca H. ; Liu, Jian ; Kung, Chung Wei ; Hod, Idan ; Farha, Omar K. ; Hupp, Joseph T. / Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66. In: Langmuir. 2018 ; Vol. 34, No. 16. pp. 4707-4714.
@article{86d3c684480b4e5bb455d8f43f0d59ae,
title = "Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66",
abstract = "Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20{\%} of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.",
author = "Palmer, {Rebecca H.} and Jian Liu and Kung, {Chung Wei} and Idan Hod and Farha, {Omar K.} and Hupp, {Joseph T}",
year = "2018",
month = "4",
day = "24",
doi = "10.1021/acs.langmuir.7b03846",
language = "English",
volume = "34",
pages = "4707--4714",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "16",

}

TY - JOUR

T1 - Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66

AU - Palmer, Rebecca H.

AU - Liu, Jian

AU - Kung, Chung Wei

AU - Hod, Idan

AU - Farha, Omar K.

AU - Hupp, Joseph T

PY - 2018/4/24

Y1 - 2018/4/24

N2 - Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.

AB - Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.

UR - http://www.scopus.com/inward/record.url?scp=85045909322&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85045909322&partnerID=8YFLogxK

U2 - 10.1021/acs.langmuir.7b03846

DO - 10.1021/acs.langmuir.7b03846

M3 - Article

VL - 34

SP - 4707

EP - 4714

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 16

ER -