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Title: Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO 2

Abstract

Realization of heterogeneous electrochemical CO 2-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 CO 2 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 (~10 15 sites/cm 2). The chemical products of the reduction, obtained with ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

Authors:
 [1];  [2];  [1];  [2];  [3];  [4]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of California at San Diego, La Jolla, CA (United States)
  3. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
  4. Northwestern Univ., Evanston, IL (United States); Argonne National Lab., Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1224208
Alternate Identifier(s):
OSTI ID: 1224209
Grant/Contract Number:  
AC02-06CH11357; SC0001059; FA9550-10-1-0572
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; electrocatalysis; metal organic frameworks; Fe-porphyrin; solar fuel; redox conductivity

Citation Formats

Hod, Idan, Sampson, Matthew D., Deria, Pravas, Kubiak, Clifford P., Farha, Omar K., and Hupp, Joseph T. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b01767.
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. United States. doi:10.1021/acscatal.5b01767.
Hod, Idan, Sampson, Matthew D., Deria, Pravas, Kubiak, Clifford P., Farha, Omar K., and Hupp, Joseph T. Fri . "Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2". United States. doi:10.1021/acscatal.5b01767. https://www.osti.gov/servlets/purl/1224208.
@article{osti_1224208,
title = {Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2},
author = {Hod, Idan and Sampson, Matthew D. and Deria, Pravas and Kubiak, Clifford P. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {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. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.},
doi = {10.1021/acscatal.5b01767},
journal = {ACS Catalysis},
issn = {2155-5435},
number = ,
volume = ,
place = {United States},
year = {2015},
month = {9}
}

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Works referencing / citing this record:

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  • DOI: 10.1002/chem.201701613

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  • DOI: 10.1039/c6dt04208b

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  • Popov, Damir A.; Luna, John M.; Orchanian, Nicholas M.
  • Dalton Transactions, Vol. 47, Issue 48
  • DOI: 10.1039/c8dt00125a

An acetylenedicarboxylato-bridged Mn( ii )-based 1D coordination polymer: electrochemical CO 2 reduction and magnetic properties
journal, January 2019

  • Dutta, Basudeb; Maity, Suvendu; Ghosh, Soumen
  • New Journal of Chemistry, Vol. 43, Issue 13
  • DOI: 10.1039/c8nj06387g

Trace water accelerating the CO 2 cycloaddition reaction catalyzed by an indium–organic framework
journal, January 2018

  • Hou, Sheng-Li; Dong, Jie; Jiao, Zhuo-Hao
  • Inorganic Chemistry Frontiers, Vol. 5, Issue 7
  • DOI: 10.1039/c8qi00260f

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journal, January 2019

  • Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04680a

Double role of metalloporphyrins in catalytic bioinspired supramolecular metal–organic frameworks (SMOFs)
journal, July 2018


New homodinuclear tris(3-alkylpyrazolyl)borate complexes of Co II and Ni II with a tetraacetylethane dianion as a bridging ligand
journal, October 2016

  • Mikhalyova, Elena A.; Trofimenko, Swiatoslaw; Zeller, Matthias
  • Acta Crystallographica Section C Structural Chemistry, Vol. 72, Issue 11
  • DOI: 10.1107/s205322961601398x

Inorganic coordination polymer quantum sheets@graphene oxide composite photocatalysts: Performance and mechanism
journal, July 2019

  • Li, Shixiong; Mo, Qiaoling; Lai, Xiaoxia
  • Journal of Materials Research, Vol. 34, Issue 18
  • DOI: 10.1557/jmr.2019.207

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journal, June 2019

  • Li, Jun-Hong; Wang, Yi-Sen; Chen, Yu-Chuan
  • Applied Sciences, Vol. 9, Issue 12
  • DOI: 10.3390/app9122427