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- Diaz-Morales, Oscar, et al.
(författare)
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Catalytic effects of molybdate and chromate–molybdate films deposited on platinum for efficient hydrogen evolution
- 2023
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Ingår i: Journal of chemical technology and biotechnology (1986). - : Wiley. - 0268-2575 .- 1097-4660. ; 98:5, s. 1269-1278
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Tidskriftsartikel (refereegranskat)abstract
- BACKGROUND: Sodium chlorate (NaClO3) is extensively used in the paper industry, but its production uses strictly regulated highly toxic Na2Cr2O7 to reach high hydrogen evolution reaction (HER) Faradaic efficiencies. It is therefore important to find alternatives either to replace Na2Cr2O7 or reduce its concentration.RESULTS: The Na2Cr2O7 concentration can be significantly reduced by using Na2MoO4 as an electrolyte co-additive. Na2MoO4 in the millimolar range shifts the platinum cathode potential to less negative values due to an activating effect of cathodically deposited Mo species. It also acts as a stabilizer of the electrodeposited chromium hydroxide but has a minor effect on the HER Faradaic efficiency. X-ray photoelectron spectroscopy (XPS) results show cathodic deposition of molybdenum of different oxidation states, depending on deposition conditions. Once Na2Cr2O7 was present, molybdenum was not detected by XPS, as it is likely that only trace levels were deposited. Using electrochemical measurements and mass spectrometry we quantitatively monitored H2 and O2 production rates. The results indicate that 3 μmol L−1 Na2Cr2O7 (contrary to current industrial 10–30 mmol L−1) is sufficient to enhance the HER Faradaic efficiency on platinum by 15%, and by co-adding 10 mmol L−1 Na2MoO4 the cathode is activated while avoiding detrimental O2 generation from chemical and electrochemical reactions. Higher concentrations of Na2MoO4 led to increased oxygen production.CONCLUSION: Careful tuning of the molybdate concentration can enhance performance of the chlorate process using chromate in the micromolar range. These insights could be also exploited in the efficient hydrogen generation by photocatalytic water splitting and in the remediation of industrial wastewater.
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| 2. |
- Endrodi, Balazs, et al.
(författare)
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In situ formed vanadium-oxide cathode coatings for selective hydrogen production
- 2019
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Ingår i: Applied Catalysis B. - : Elsevier. - 0926-3373 .- 1873-3883. ; 244, s. 233-239
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Tidskriftsartikel (refereegranskat)abstract
- Electrode selectivity towards hydrogen production is essential in various conversion technologies for renewable energy, as well as in different industrial processes, such as the electrochemical production of sodium chlorate. In this study we present sodium metavanadate as a solution additive, inducing selective cathodic formation of hydrogen in the presence of various other reducible species such as hypochlorite, chlorate, oxygen, nitrate, hydrogen-peroxide and ferricyanide. During electrolysis a vanadium-oxide coating forms from the reduction of sodium metavanadate, explaining the observed enhanced selectivity. The hydrogen evolution reaction proceeds without significantly altered kinetics on such in situ modified electrode surfaces. This suggests that the reaction takes place at the interface between the electrode surface and the protective film, which acts as a diffusion barrier preventing the unwanted species to reach the electrode surface.
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