Cobalt polyoxometalate-derived CoWO4 oxygen-evolving catalysts for efficient electrochemical and photoelectrochemical water oxidation

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Title
Cobalt polyoxometalate-derived CoWO4 oxygen-evolving catalysts for efficient electrochemical and photoelectrochemical water oxidation
Author
Han, YujinChoi, KeunsuOh, HyeonmyeongKim, ChanseokJeon, DasonLee, CheolminLee, Jun HeeRyu, Jungki
Issue Date
2018-11
Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
Citation
JOURNAL OF CATALYSIS, v.367, pp.212 - 220
Abstract
Highly efficient water-oxidation catalysts (WOCs) were readily prepared through the simple heat treatment of cobalt-containing polyoxometalate [Co4(H2O)2(PW9O34)2]10− (POM). The annealing of soluble POM molecules at high temperatures in air led to the formation of insoluble nanoparticles, of which the crystal structure and catalytic activity can be controlled by the annealing temperature. POMs were converted to amorphous and crystalline CoWO4 nanoparticles when annealed at 400 and 500 °C, respectively. Interestingly, amorphous CoWO4 nanoparticles exhibited excellent catalytic activity near the neutral pH of pH 8.0, making them superior to both pristine POM and POM-derived crystalline CoWO4 nanoparticles. X-ray absorption and photoelectron spectroscopies combined with density functional theory (DFT) calculations revealed that their outstanding performance was resulted from the generation of large amounts of oxygen vacancies upon annealing, leading to the optimum distance between the nearest Co ions for the Langmuir-Hinshelwood (LH) mechanism. Based on these findings, we could readily immobilize CoWO4-based WOCs on the surfaces of various electrodes for efficient electrochemical and photoelectrochemical water oxidation through the annealing of POMs pre-adsorbed onto the desired electrode surface. This study may provide insights not only for the synthesis of efficient electrocatalysts derived from POMs but also for their immobilization onto the desired electrode surface for practical applications.
URI
https://scholarworks.unist.ac.kr/handle/201301/24933
URL
https://www.sciencedirect.com/science/article/pii/S0021951718303580
DOI
10.1016/j.jcat.2018.09.011
ISSN
0021-9517
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