Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production
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2013
Authors
Lačnjevac, Uroš
Jović, Borka
Gajić Krstajić, Ljiljana

Kovač, Janez

Jović, Vladimir
Krstajić, Nedeljko
Article (Published version)

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The aim of this work was to investigate the possibility of preparation of the composite Cr–MoO2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO2 particles. The content of molybdenum in the deposits was relatively low (0.2–1.5 at.%) and increased with increasing the concentration of suspended MoO2 particles in the bath, in the range from 0 to 10 g dm−3. With further increase in the concentration of MoO2, the content of molybdenum in the coating varied insignificantly.
X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to anal...yze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO2 particles in the bath was raised above 5 g dm−3, the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr2O3 with Cr(3+) valence state on the surface and in the sub-surface region of Cr–MoO2 coatings.
Investigation of the current efficiency for the hydrogen evolution reaction (HER) on Cr–MoO2 cathodes showed that it increased with the increase of the content of MoO2 particles in the coating, exceeding the value of 97% in the solution with the hypochlorite concentration of 0.21 mol dm−3. Under the same conditions, the current efficiency for the HER on Ti and Ti/Cr cathodes is very low (≈20%), and corresponding polarization curves confirmed the fact that the side reaction of hypochlorite reduction takes place in the diffusion-controlled regime on these electrodes. The high selectivity of Cr–MoO2 coating is probably caused by the presence of chromium oxide (hydroxide) formed at the surface of the coating during co-deposition of Cr and MoO2 particles, which prevents hypochlorite reduction on the cathode during the HER.
Keywords:
current efficiency / hypochlorite reduction / selectivity / Cr–MoO2 composite coatingSource:
Electrochimica Acta, 2013, 96, 30, 34-42Publisher:
- Elsevier
Funding / projects:
DOI: 10.1016/j.electacta.2013.02.086
ISSN: 0013-4686
WoS: 000318324900007
Scopus: 2-s2.0-84874944704
Institution/Community
Институт техничких наука САНУ / Institute of Technical Sciences of SASATY - JOUR AU - Lačnjevac, Uroš AU - Jović, Borka AU - Gajić Krstajić, Ljiljana AU - Kovač, Janez AU - Jović, Vladimir AU - Krstajić, Nedeljko PY - 2013 UR - https://dais.sanu.ac.rs/123456789/358 AB - The aim of this work was to investigate the possibility of preparation of the composite Cr–MoO2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO2 particles. The content of molybdenum in the deposits was relatively low (0.2–1.5 at.%) and increased with increasing the concentration of suspended MoO2 particles in the bath, in the range from 0 to 10 g dm−3. With further increase in the concentration of MoO2, the content of molybdenum in the coating varied insignificantly. X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to analyze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO2 particles in the bath was raised above 5 g dm−3, the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr2O3 with Cr(3+) valence state on the surface and in the sub-surface region of Cr–MoO2 coatings. Investigation of the current efficiency for the hydrogen evolution reaction (HER) on Cr–MoO2 cathodes showed that it increased with the increase of the content of MoO2 particles in the coating, exceeding the value of 97% in the solution with the hypochlorite concentration of 0.21 mol dm−3. Under the same conditions, the current efficiency for the HER on Ti and Ti/Cr cathodes is very low (≈20%), and corresponding polarization curves confirmed the fact that the side reaction of hypochlorite reduction takes place in the diffusion-controlled regime on these electrodes. The high selectivity of Cr–MoO2 coating is probably caused by the presence of chromium oxide (hydroxide) formed at the surface of the coating during co-deposition of Cr and MoO2 particles, which prevents hypochlorite reduction on the cathode during the HER. PB - Elsevier T2 - Electrochimica Acta T1 - Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production SP - 34 EP - 42 VL - 96 IS - 30 DO - 10.1016/j.electacta.2013.02.086 UR - https://hdl.handle.net/21.15107/rcub_dais_358 ER -
@article{ author = "Lačnjevac, Uroš and Jović, Borka and Gajić Krstajić, Ljiljana and Kovač, Janez and Jović, Vladimir and Krstajić, Nedeljko", year = "2013", abstract = "The aim of this work was to investigate the possibility of preparation of the composite Cr–MoO2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO2 particles. The content of molybdenum in the deposits was relatively low (0.2–1.5 at.%) and increased with increasing the concentration of suspended MoO2 particles in the bath, in the range from 0 to 10 g dm−3. With further increase in the concentration of MoO2, the content of molybdenum in the coating varied insignificantly. X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to analyze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO2 particles in the bath was raised above 5 g dm−3, the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr2O3 with Cr(3+) valence state on the surface and in the sub-surface region of Cr–MoO2 coatings. Investigation of the current efficiency for the hydrogen evolution reaction (HER) on Cr–MoO2 cathodes showed that it increased with the increase of the content of MoO2 particles in the coating, exceeding the value of 97% in the solution with the hypochlorite concentration of 0.21 mol dm−3. Under the same conditions, the current efficiency for the HER on Ti and Ti/Cr cathodes is very low (≈20%), and corresponding polarization curves confirmed the fact that the side reaction of hypochlorite reduction takes place in the diffusion-controlled regime on these electrodes. The high selectivity of Cr–MoO2 coating is probably caused by the presence of chromium oxide (hydroxide) formed at the surface of the coating during co-deposition of Cr and MoO2 particles, which prevents hypochlorite reduction on the cathode during the HER.", publisher = "Elsevier", journal = "Electrochimica Acta", title = "Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production", pages = "34-42", volume = "96", number = "30", doi = "10.1016/j.electacta.2013.02.086", url = "https://hdl.handle.net/21.15107/rcub_dais_358" }
Lačnjevac, U., Jović, B., Gajić Krstajić, L., Kovač, J., Jović, V.,& Krstajić, N.. (2013). Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production. in Electrochimica Acta Elsevier., 96(30), 34-42. https://doi.org/10.1016/j.electacta.2013.02.086 https://hdl.handle.net/21.15107/rcub_dais_358
Lačnjevac U, Jović B, Gajić Krstajić L, Kovač J, Jović V, Krstajić N. Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production. in Electrochimica Acta. 2013;96(30):34-42. doi:10.1016/j.electacta.2013.02.086 https://hdl.handle.net/21.15107/rcub_dais_358 .
Lačnjevac, Uroš, Jović, Borka, Gajić Krstajić, Ljiljana, Kovač, Janez, Jović, Vladimir, Krstajić, Nedeljko, "Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production" in Electrochimica Acta, 96, no. 30 (2013):34-42, https://doi.org/10.1016/j.electacta.2013.02.086 ., https://hdl.handle.net/21.15107/rcub_dais_358 .