Synthesis of Ni-doped ceria nanoparticles and their unusual surface reduction in hydrogen

Barreau, Mathias; Chen, D.; J., Zhang,; Papaefthimiou, Vasiliki; Petit, C.; Salusso, Davide; Borfecchia, Elisa; Turczyniak-Surdacka, Sylwia; Sobczak, Kamil; Mauri, Silvia; Braglia, Luca; Torelli, Piero; Zafeiratos, Spyridon

doi:10.1016/j.mtchem.2022.101011

Cited by 9 publications

(15 citation statements)

References 61 publications

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“…The commonly used sol–gel methods generally involve long and complex synthesis procedures [ 4 , 15 , 16 , 17 ]. On the contrary, direct precursor calcination has shown a great potential for the direct preparation of catalysts [ 18 , 19 , 20 , 21 , 22 ]. In the latter approach, promising results have been reported for direct calcination of metal–organic frameworks (MOFs) at moderate temperatures (300–500 °C) [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ].…”

Section: Introductionmentioning

confidence: 99%

“…They are separated by about 2000 cm −1 and the 2 F 5/2 → 2 F 7/2 electronic transition is observed in the infrared range at 2127 cm −1 [ 14 , 41 , 42 , 43 , 44 , 45 , 46 ]. The presence/absence of this absorption band was then related to the occurrence of Ce 3+ and it has been recently used to qualitatively monitor cerium reduction in a NiCeO 2 sample [ 18 ]. From the infrared viewpoint, the hydroxyl stretching vibration could also be used to selectively monitor Ce 3+ formation on the catalyst surface.…”

Section: Introductionmentioning

confidence: 99%

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MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

et al. 2023

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The development of Ce-based materials is directly dependent on the catalyst surface defects, which is caused by the calcination steps required to increase structural stability. At the same time, the evaluation of cerium’s redox properties under reaction conditions is of increasing relevant importance. The synthesis of Ce-UiO-66 and CeZr-UiO-66 and their subsequent calcination are presented here as a simple and inexpensive approach for achieving homogeneous and stable CeO2 and CeZrOx nanocrystals. The resulting materials constitute an ideal case study to thoroughly understand cerium redox properties. The Ce3+/Ce4+ redox properties are investigated by H2-TPR experiments exploited by in situ FT-IR and Ce M5-edge AP-NEXAFS spectroscopy. In the latter case, Ce3+ formation is quantified using the MCR-ALS protocol. FT-IR is then presented as a high potential/easily accessible technique for extracting valuable information about the cerium oxidation state under operating conditions. The dependence of the OH stretching vibration frequency on temperature and Ce reduction is described, providing a novel tool for qualitative monitoring of surface oxygen vacancy formation. Based on the reported results, the molecular absorption coefficient of the Ce3+ characteristic IR transition is tentatively evaluated, thus providing a basis for future Ce3+ quantification through FT-IR spectroscopy. Finally, the FT-IR limitations for Ce3+ quantification are discussed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

et al. 2023

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“…A clear modification of sXAS peaks in reaction mixture as compared to the prior state in H 2 is noticed, while the peak shape evolves as the temperature increases. The sXAS spectra are simulated by linear combination of reference peaks following the methodology developed in our recent work [28] (see also Figure S13). As shown in Figure 4a during H 2 ‐activation nickel is partially reduced to Ni 0 /NiCe (spectra at the light‐blue background).…”

Section: Resultsmentioning

confidence: 99%

“…This finding is not only important to explain the reactivity of NiCeO x but can also rationalize our previous findings showing a net enhancement in the NiCeO x reducibility in H 2 as compared to CeO x . [28] For CO 2 activation, our DFT results show that CO 2 can be bound to surface OH groups on both hydroxylated-CeO 2 (100) and Ni-doped hydroxylated-CeO 2 (100) surfaces to form strongly adsorbed carbonate intermediates (E ads is about À 5 eV) (Figure 5g and h). According to the Sabatier principle, intermediates with either too strong or too weak adsorption are not favourable to catalytic reactions.…”

Section: First Principles Calculations and Apxps Experiments To Ratio...mentioning

confidence: 90%

“…The ceria cubic fluorite lattice parameter (α) of calcined catalyst is 5.414 Å which is somewhat higher than undoped ceria nanoparticles of similar sizes. [28,32] This indicates that Ni ions occupies interstitial positions in the ceria lattice (interstitial sites), since the substitution of Ce 4 + lattice sites with the smaller Ni ions would have led to lattice contraction (i.e. decrease of α).…”

Section: Textural and Physicochemical Characterization Of Niceo Xmentioning

confidence: 99%

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Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity

Barreau

Saluso

et al. 2023

Angewandte Chemie

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CO 2 hydrogenation to methane is gaining increasing interest as one of the most promising ways to store intermittent renewable energy in the form of chemical fuels. Ni particles supported on CeO 2 represent a highly efficient, stable and inexpensive catalyst for this reaction. Herein, Ni-doped CeO 2 nanoparticles were tested for CO 2 methanation showing an extremely high Ni mass-specific activity and CH 4 selectivity. Operando characterization reveals that this performance is tightly associated with ionic Νi and Ce 3 + surface sites, while formation of metallic Ni does not seem to considerably promote the reaction. Theoretical calculations confirmed the stability of interstitial ionic Ni sites on ceria surfaces and highlighted the role of Ce-O frustrated Lewis pair (FLP), Ni-O classical Lewis pair (CLP) and Ni-Ce pair sites to the activation of H 2 and CO 2 molecules. To a large extent, the theoretical predictions were validated by in situ spectroscopy under H 2 and CO 2 : H 2 gaseous environments.

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Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity

Barreau

Saluso

et al. 2023

Angew Chem Int Ed

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Synthesis of Ni-doped ceria nanoparticles and their unusual surface reduction in hydrogen

Cited by 9 publications

References 61 publications

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity

Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity

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Synthesis of Ni-doped ceria nanoparticles and their unusual surface reduction in hydrogen

Cited by 9 publications

References 61 publications

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy

Ionic Nickel Embedded in Ceria with High Specific CO2 Methanation Activity

Ionic Nickel Embedded in Ceria with High Specific CO2 Methanation Activity

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Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity

Ionic Nickel Embedded in Ceria with High Specific CO₂ Methanation Activity