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A soft molecular single-source precursor approach to synthesize a nanostructured Co 9 S 8 (pre)catalyst for efficient water oxidation and biomass valorization

The molecular single-source precursor (SSP) route has emerged as a promising avenue for synthesizing highly efficient electro(pre)catalysts tailored for both oxygen evolution (OER) and organic electrooxidation reactions. This study introduces a novel [Co II (PyHS) 4 (OTf) 2 ] molecular complex, offe...

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Published in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2024-11, Vol.12 (44), p.30522-30533
Main Authors: Dasgupta, Basundhara, Ghosh, Suptish, Walter, Carsten, Budde, Markus S., Marquardt, Georg J., Chen, Han-Hsu, Breithaupt, Markus G. M., Yilmaz, Tolga, Garmatter, Christoph, Ahamad, Tamanna, Zebger, Ingo, Driess, Matthias, Menezes, Prashanth W.
Format: Article
Language:English
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Summary:The molecular single-source precursor (SSP) route has emerged as a promising avenue for synthesizing highly efficient electro(pre)catalysts tailored for both oxygen evolution (OER) and organic electrooxidation reactions. This study introduces a novel [Co II (PyHS) 4 (OTf) 2 ] molecular complex, offering a facile route to access the nanocrystalline Co 9 S 8 phase. Upon application in alkaline OER, Co 9 S 8 displayed remarkably high electrocatalytic activity across various metrics, including overpotentials, Tafel slopes, faradaic efficiency, charge transfer resistance, turnover frequency, electrochemical surface area, Co-redox active sites, and long-term stability at industrially relevant current densities (for 80 h at 100 mA cm −2 ) outperforming its Co-based counterparts under identical conditions. In-depth analysis employing several ex situ techniques revealed the complete leaching of sulfur and irreversible reconstruction of Co 9 S 8 into a cobalt oxyhydroxide active phase during the OER. Moreover, quasi in situ Raman spectroscopy provided insights into the presence of Co IV O 2 active species under operational OER conditions, along with the formation of the Co superoxide intermediate. Beyond OER applications, the Co 9 S 8 -derived active phase demonstrated notable efficiency in catalyzing the selective oxidation of biomass-derived glycerol and furan-2-carboxaldehyde to formate and furan-2-carboxylic acid, respectively, achieving yields exceeding 80%, with excellent reusability. A full hybrid-water electrolysis cell has been developed, wherein biomass valorization with Co 9 S 8 , coupled with H 2 production, resulted in a significant improvement in energy efficiency compared to conventional water-splitting.
ISSN:2050-7488
2050-7496
DOI:10.1039/D4TA05436A