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Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts
Abstract
Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co 3(PO 4)2⋅8 H 2 O, Pak) and phosphate‐containing Co oxide (CoCat). X‐ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5–8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high‐TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high‐TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte‐exposed “outer surface”, within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation.
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Cites
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis
Dau, H., Limberg, C., Reier, T., Risch, M., Roggan, S., & Strasser, P. (2010) · ChemCatChem · doi:10.1002/cctc.201000126 · Cited by 1,783
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Shinagawa, T., Garcia-Esparza, A. T., & Takanabe, K. (2015) · Scientific Reports · doi:10.1038/srep13801 · Cited by 3,287
Bergmann, A., Martinez-Moreno, E., Teschner, D., Chernev, P., Gliech, M., de Araújo, J. F., Reier, T., Dau, H., & Strasser, P. (2015) · Nature Communications · doi:10.1038/ncomms9625 · Cited by 913
Self-citationYu, X., Yu, Z.-Y., Zhang, X.-L., Zheng, Y.-R., Duan, Y., Gao, Q., Wu, R., Sun, B., Gao, M.-R., Wang, G., et al. (2019) · Journal of the American Chemical Society · doi:10.1021/jacs.9b02527 · Cited by 568
Indra, A., Song, T., & Paik, U. (2018) · Advanced Materials · doi:10.1002/adma.201705146 · Cited by 507
Anantharaj, S., & Aravindan, V. (2020) · Advanced Energy Materials · doi:10.1002/aenm.201902666 · Cited by 361
Metadata
- Authors
- González‐Flores, D., Sánchez, I., Zaharieva, I., Klingan, K., Heidkamp, J., Chernev, P., Menezes, P. W., Driess, M., Dau, H., & Montero, M. L.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2015-01-21
- Volume
- 54
- Issue
- 8
- Pages
- 2472-2476
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2151019712
- Cited by
- 180
- References
- 1
- FWCI
- 7.23
- Type
- journal article
- Language
- en
- Open access
- closed
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- González‐Flores, D., Sánchez, I., Zaharieva, I., Klingan, K., Heidkamp, J., Chernev, P., Menezes, P. W., Driess, M., Dau, H., & Montero, M. L. (2015). Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.201409333
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