Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2

Idan Hod, Matthew D. Sampson, Pravas Deria, Clifford P. Kubiak, Omar K. Farha, Joseph T Hupp

Research output: Contribution to journalArticle

238 Citations (Scopus)

Abstract

Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal-organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (∼1015 sites/cm2). The chemical products of the reduction, obtained with ∼100% Faradaic efficiency, are mixtures of CO and H2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

Original languageEnglish
Pages (from-to)6302-6309
Number of pages8
JournalACS Catalysis
Volume5
Issue number11
DOIs
Publication statusPublished - Nov 6 2015

Fingerprint

Porphyrins
Metals
Catalysts
Carbon Monoxide
Catalysis
Fluxes
Thin films
Electrodes

Keywords

  • CO reduction
  • electrocatalysis
  • Fe-porphyrin
  • metal organic frameworks
  • redox conductivity
  • solar fuel

ASJC Scopus subject areas

  • Catalysis

Cite this

Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2 . / Hod, Idan; Sampson, Matthew D.; Deria, Pravas; Kubiak, Clifford P.; Farha, Omar K.; Hupp, Joseph T.

In: ACS Catalysis, Vol. 5, No. 11, 06.11.2015, p. 6302-6309.

Research output: Contribution to journalArticle

Hod, Idan ; Sampson, Matthew D. ; Deria, Pravas ; Kubiak, Clifford P. ; Farha, Omar K. ; Hupp, Joseph T. / Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2 In: ACS Catalysis. 2015 ; Vol. 5, No. 11. pp. 6302-6309.
@article{70c3cddb3b394951aa248d6c1f657fde,
title = "Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2",
abstract = "Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal-organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (∼1015 sites/cm2). The chemical products of the reduction, obtained with ∼100{\%} Faradaic efficiency, are mixtures of CO and H2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.",
keywords = "CO reduction, electrocatalysis, Fe-porphyrin, metal organic frameworks, redox conductivity, solar fuel",
author = "Idan Hod and Sampson, {Matthew D.} and Pravas Deria and Kubiak, {Clifford P.} and Farha, {Omar K.} and Hupp, {Joseph T}",
year = "2015",
month = "11",
day = "6",
doi = "10.1021/acscatal.5b01767",
language = "English",
volume = "5",
pages = "6302--6309",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2

AU - Hod, Idan

AU - Sampson, Matthew D.

AU - Deria, Pravas

AU - Kubiak, Clifford P.

AU - Farha, Omar K.

AU - Hupp, Joseph T

PY - 2015/11/6

Y1 - 2015/11/6

N2 - Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal-organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (∼1015 sites/cm2). The chemical products of the reduction, obtained with ∼100% Faradaic efficiency, are mixtures of CO and H2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

AB - Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal-organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (∼1015 sites/cm2). The chemical products of the reduction, obtained with ∼100% Faradaic efficiency, are mixtures of CO and H2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

KW - CO reduction

KW - electrocatalysis

KW - Fe-porphyrin

KW - metal organic frameworks

KW - redox conductivity

KW - solar fuel

UR - http://www.scopus.com/inward/record.url?scp=84946854794&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84946854794&partnerID=8YFLogxK

U2 - 10.1021/acscatal.5b01767

DO - 10.1021/acscatal.5b01767

M3 - Article

AN - SCOPUS:84946854794

VL - 5

SP - 6302

EP - 6309

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 11

ER -