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Title: Water oxidation by size selected Co27 clusters supported on Fe2O3

Journal Article · · ChemSusChem
ORCiD logo [1];  [1];  [2];  [2];  [3];  [3];  [4];  [4];  [5]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Argonne National Lab. (ANL), Argonne, IL (United States). Argonne-Northwestern Solar Energy Research (ANSER) Center
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Sciences Division
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Nanoscience and Technology Division
+ Show Author Affiliations

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co-27) deposited on hematite (Fe2O3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co-27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination at the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co-27 clusters is Fe2O3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co-27/Fe2O3 material is significantly improved when the samples are annealed (with the clusters already deposited). Given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0001059
OSTI ID:
1352624
Alternate ID(s):
OSTI ID: 1356628
Journal Information:
ChemSusChem, Vol. 9, Issue 20; ISSN 1864-5631
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

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Cited By (3)

Metal Nanoclusters: New Paradigm in Catalysis for Water Splitting, Solar and Chemical Energy Conversion journal March 2019
Perspective: Size selected clusters for catalysis and electrochemistry journal March 2018
Study on the Adsorption and Activation Behaviours of Carbon Dioxide over Copper Cluster (Cu 4 ) and Alumina-Supported Copper Catalyst (Cu 4 /Al 2 O 3 ) by means of Density Functional Theory journal December 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fe2O3
electrocatalysis
photoelectrocatalysis
subnanometer cobalt cluster
water oxidation