Influence of the B<sup>3+</sup> Cation Nature on the Properties of Cu<i>B</i>O<sub>2</sub> Oxides (<i>B</i>=Mn, Co, Cr, Fe, and Ga) with a Delafossite/Crednerite Structure

The paper presents an investigation into the physicochemical and catalytic properties of Cu<i>B</i>O<sub>2</sub> oxides with a delafossite/crednerite-type structure, exploring the dependence on the nature of the <i>B</i><sup>3+</sup> cation (Mn<sup>3+</sup>, Co<sup>3+</sup>, Cr<sup>3+</sup>, Fe<sup>3+</sup>, and Ga<sup>3+</sup>). The catalytic properties in CO oxidation were examined in conjunction with structural data, surface composition, the distribution of surface metal states, and the reactivity of oxygen. The selection of synthesis conditions was tailored to yield crystallized Cu<i>B</i>O<sub>2</sub> particles exhibiting either a delafossite or crednerite structure, depending on the nature of the <i>B</i><sup>3+</sup> cation nature. Thermal stability increases in the following order: CuMnO<sub>2</sub> < CuCrO<sub>2</sub> ≈ CuFeO<sub>2</sub> ≈ CuCoO<sub>2</sub> < CuGaO<sub>2</sub>. Heating of all the studied mixed oxides in the CO + O<sub>2</sub> mixture to 250 °C did not cause changes in the phase composition and structural characteristics. The highest catalytic activity near room temperature was observed for CuMnO<sub>2</sub> and CuCrO<sub>2</sub>. A correlation was established between the catalytic activity of Cu<i>B</i>O<sub>2</sub> and the reactivity of surface oxygen, presumably attributed to the pronounced lability of the redox transitions between the Cu<sup>1+</sup>/Cu<sup>2+</sup> and B<sup>n+</sup>/B<sup>m+</sup> pairs. The transformation of the delafossite/crednerite into a spinel structure can cause both deactivation (<i>B</i> = Fe and Co) and significant catalytic activation (<i>B</i> = Mn and Cr) in low-temperature CO oxidation.

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Publication Details

Journal
Inorganic Chemistry
Published
2025-06-30
DOI
https://doi.org/10.1021/acs.inorgchem.5c01254
Citations
2
Primary Topic
Copper-based nanomaterials and applications
Type
article
Field-Weighted Citation Impact
1.04

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article

Influence of the B3+ Cation Nature on the Properties of CuBO2 Oxides (B=Mn, Co, Cr, Fe, and Ga) with a Delafossite/Crednerite Structure

Nikolai A. Sokovikov, Svetlana V. Cherepanova, Vera M. Metalnikova, Tatyana Yu. Kardash et al.
2 citations
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Copper-based nanomaterials and applications
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article

Influence of the B3+ Cation Nature on the Properties of CuBO2 Oxides (B=Mn, Co, Cr, Fe, and Ga) with a Delafossite/Crednerite Structure

Nikolai A. Sokovikov, Svetlana V. Cherepanova, Vera M. Metalnikova, Tatyana Yu. Kardash, А. И. Боронин, Dmitry A. Svintsitskiy, Ekaterina S. Kvasova
article en
2 citations

Abstract

The paper presents an investigation into the physicochemical and catalytic properties of Cu<i>B</i>O<sub>2</sub> oxides with a delafossite/crednerite-type structure, exploring the dependence on the nature of the <i>B</i><sup>3+</sup> cation (Mn<sup>3+</sup>, Co<sup>3+</sup>, Cr<sup>3+</sup>, Fe<sup>3+</sup>, and Ga<sup>3+</sup>). The catalytic properties in CO oxidation were examined in conjunction with structural data, surface composition, the distribution of surface metal states, and the reactivity of oxygen. The selection of synthesis conditions was tailored to yield crystallized Cu<i>B</i>O<sub>2</sub> particles exhibiting either a delafossite or crednerite structure, depending on the nature of the <i>B</i><sup>3+</sup> cation nature. Thermal stability increases in the following order: CuMnO<sub>2</sub> < CuCrO<sub>2</sub> ≈ CuFeO<sub>2</sub> ≈ CuCoO<sub>2</sub> < CuGaO<sub>2</sub>. Heating of all the studied mixed oxides in the CO + O<sub>2</sub> mixture to 250 °C did not cause changes in the phase composition and structural characteristics. The highest catalytic activity near room temperature was observed for CuMnO<sub>2</sub> and CuCrO<sub>2</sub>. A correlation was established between the catalytic activity of Cu<i>B</i>O<sub>2</sub> and the reactivity of surface oxygen, presumably attributed to the pronounced lability of the redox transitions between the Cu<sup>1+</sup>/Cu<sup>2+</sup> and B<sup>n+</sup>/B<sup>m+</sup> pairs. The transformation of the delafossite/crednerite into a spinel structure can cause both deactivation (<i>B</i> = Fe and Co) and significant catalytic activation (<i>B</i> = Mn and Cr) in low-temperature CO oxidation.

Inorganic ChemistryVol. 64(27)
Novosibirsk State University (RU), Boreskov Institute of Catalysis (RU)
Russian Science Foundation
Openalex Percentile: Top 24%
Copper-based nanomaterials and applications
1.04
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