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Title: Stabilization of reactive Co 4O 4 cubane oxygen-evolution catalysts within porous frameworks

Abstract

A major challenge to the implementation of artificial photosynthesis (AP), in which fuels are produced from abundant materials (water and carbon dioxide) in an electrochemical cell through the action of sunlight, is the discovery of active, inexpensive, safe, and stable catalysts for the oxygen evolution reaction (OER). Multimetallic molecular catalysts, inspired by the natural photosynthetic enzyme, can provide important guidance for catalyst design, but the necessary mechanistic understanding has been elusive. In particular, fundamental transformations for reactive intermediates are difficult to observe, and well-defined molecular models of such species are highly prone to decomposition by intermolecular aggregation. Here, we present a general strategy for stabilization of the molecular cobalt-oxo cubane core (Co 4O 4) by immobilizing it as part of metal–organic frameworks, thus preventing intermolecular pathways of catalyst decomposition. These materials retain the OER activity and mechanism of the molecular Co 4O 4analog yet demonstrate unprecedented long-term stability at pH 14. Here, the organic linkers of the framework allow for chemical fine-tuning of activity and stability and, perhaps most importantly, provide “matrix isolation” that allows for observation and stabilization of intermediates in the water-splitting pathway.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [4]; ORCiD logo [1];  [1];  [5];  [6];  [6];  [7]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Columbia Univ., New York, NY (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of California, Berkeley, CA (United States)
  5. Rensselaer Polytechnic Inst., Troy, NY (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1523541
Alternate Identifier(s):
OSTI ID: 1532442
Grant/Contract Number:  
AC02-05CH1123; SC0004993; AC02-05CH11231; AC02-76SF00515; SC0012704; DMR-1420634; DGE-1106400
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 24; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
artificial photosynthesis; mechanism; OER; cubane; MOF

Citation Formats

Nguyen, Andy I., Van Allsburg, Kurt M., Terban, Maxwell W., Bajdich, Michal, Oktawiec, Julia, Amtawong, Jaruwan, Ziegler, Micah S., Dombrowski, James P., Lakshmi, K. V., Drisdell, Walter S., Yano, Junko, Billinge, Simon J. L., and Tilley, T. Don. Stabilization of reactive Co4O4 cubane oxygen-evolution catalysts within porous frameworks. United States: N. p., 2019. Web. doi:10.1073/pnas.1815013116.
Nguyen, Andy I., Van Allsburg, Kurt M., Terban, Maxwell W., Bajdich, Michal, Oktawiec, Julia, Amtawong, Jaruwan, Ziegler, Micah S., Dombrowski, James P., Lakshmi, K. V., Drisdell, Walter S., Yano, Junko, Billinge, Simon J. L., & Tilley, T. Don. Stabilization of reactive Co4O4 cubane oxygen-evolution catalysts within porous frameworks. United States. doi:10.1073/pnas.1815013116.
Nguyen, Andy I., Van Allsburg, Kurt M., Terban, Maxwell W., Bajdich, Michal, Oktawiec, Julia, Amtawong, Jaruwan, Ziegler, Micah S., Dombrowski, James P., Lakshmi, K. V., Drisdell, Walter S., Yano, Junko, Billinge, Simon J. L., and Tilley, T. Don. Wed . "Stabilization of reactive Co4O4 cubane oxygen-evolution catalysts within porous frameworks". United States. doi:10.1073/pnas.1815013116.
@article{osti_1523541,
title = {Stabilization of reactive Co4O4 cubane oxygen-evolution catalysts within porous frameworks},
author = {Nguyen, Andy I. and Van Allsburg, Kurt M. and Terban, Maxwell W. and Bajdich, Michal and Oktawiec, Julia and Amtawong, Jaruwan and Ziegler, Micah S. and Dombrowski, James P. and Lakshmi, K. V. and Drisdell, Walter S. and Yano, Junko and Billinge, Simon J. L. and Tilley, T. Don},
abstractNote = {A major challenge to the implementation of artificial photosynthesis (AP), in which fuels are produced from abundant materials (water and carbon dioxide) in an electrochemical cell through the action of sunlight, is the discovery of active, inexpensive, safe, and stable catalysts for the oxygen evolution reaction (OER). Multimetallic molecular catalysts, inspired by the natural photosynthetic enzyme, can provide important guidance for catalyst design, but the necessary mechanistic understanding has been elusive. In particular, fundamental transformations for reactive intermediates are difficult to observe, and well-defined molecular models of such species are highly prone to decomposition by intermolecular aggregation. Here, we present a general strategy for stabilization of the molecular cobalt-oxo cubane core (Co4O4) by immobilizing it as part of metal–organic frameworks, thus preventing intermolecular pathways of catalyst decomposition. These materials retain the OER activity and mechanism of the molecular Co4O4analog yet demonstrate unprecedented long-term stability at pH 14. Here, the organic linkers of the framework allow for chemical fine-tuning of activity and stability and, perhaps most importantly, provide “matrix isolation” that allows for observation and stabilization of intermediates in the water-splitting pathway.},
doi = {10.1073/pnas.1815013116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 24,
volume = 116,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1815013116

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