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. 2024 Jul 10;25(14):7585.
doi: 10.3390/ijms25147585.

Structure Engineering of Ni/SiO2 Vegetable Oil Hydrogenation Catalyst via CeO2

Margarita Gabrovska  1 , Dimitrinka Nikolova  1 , Vojkan Radonjić  2 , Daniela Karashanova  3 , Aleksandra Baeva  4 , Tsvetomila Parvanova-Mancheva  1 , Peter Tzvetkov  4 , Evangeliya Petrova  1 , Gabriella Zarkova  1 , Jugoslav Krstić  2
Affiliations

Structure Engineering of Ni/SiO2 Vegetable Oil Hydrogenation Catalyst via CeO2

Margarita Gabrovska et al. Int J Mol Sci. .

Abstract

Inspired by our finding that metallic Ni particles could be uniformly distributed on a reduced CeO2 surface and stabilized on Ce3+ sites, we suppose a possible improvement in the activity and selectivity of the MgNi/SiO2 vegetable oil hydrogenation catalyst by increasing the surface metal Ni availability via modification by ceria. The proposed approach involved the addition of a CeO2 modifier to the SiO2 carrier and as a catalyst component. Evaluation of the structure, reducibility, and surface and electronic states of the CeO2-doped MgNi/SiO2 catalyst was performed by means of the Powder X-ray diffraction (PXRD), Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS) combined with High-resolution transmission electron microscopy (HRTEM), Temperature-programmed reduction with hydrogen (H2-TPR), and H2-chemisortion techniques. So far, no studies related to this approach of designing Ni/SiO2 catalysts for the partial hydrogenation of vegetable oil have been reported. The added ceria impact was elucidated by comparing fatty acid compositions obtained by the catalysts at an iodine value of 80. In summary, tuning the hydrogenation performance of Ni-based catalysts can be achieved by structural reconstruction using 1 wt.% CeO2. The introduction mode changed the selectivity towards C18:1-cis and C18:0 fatty acids by applying ceria as a carrier modifier, while hydrogenation activity was improved upon ceria operation as the catalyst dopant.

Keywords: CeO2 doping effect; HRTEM; Ni/SiO2 catalysts; SEM-EDS; fatty acids composition; partial hydrogenation of sunflower oil.

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Conflict of interest statement

The authors declare no conflicts of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of the data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
SEM images of the morphology and EDS elemental mapping at magnification 100×: (a) Ni-red; (b) MgNi-red; (c) CeMgNi-red; (d) MgNi-Ce-red.
Figure 2
Figure 2
EDS elemental mapping of Ni at magnification 100×: (a) Ni-red; (b) MgNi-red; (c) CeMgNi-red; (d) MgNi-Ce-red.
Figure 3
Figure 3
TEM images at magnification 40,000× and HRTEM images at magnification 600,000× of the reduced samples: (a,b) Ni-red; (c,d) MgNi-red; (e,f) CeMgNi-red; (g,h) MgNi-Ce-red.
Figure 3
Figure 3
TEM images at magnification 40,000× and HRTEM images at magnification 600,000× of the reduced samples: (a,b) Ni-red; (c,d) MgNi-red; (e,f) CeMgNi-red; (g,h) MgNi-Ce-red.
Figure 4
Figure 4
SAED patterns with insets of the Ni nanoparticle size distribution derived from HRTEM of the reduced samples: (a) Ni-red; (b) MgNi-red; (c) CeMgNi-red; (d) MgNi-Ce-red.
Figure 5
Figure 5
PXRD patterns of the ex situ reduced samples.
Figure 6
Figure 6
H2-TPR profiles of (a) all precursors in the range 50–900 °C, (b) Ni and MgNi precursors after isothermal reduction at 430 and 490 °C, and (c) CeMgNi and MgNi-Ce precursors after isothermal reduction at 430 and 490 °C.
Figure 7
Figure 7
Sunflower oil hydrogenation activity vs. reaction time of the studied catalysts.
Figure 8
Figure 8
Change in the composition of (a) C18:1-cis, (b) C18:2-cis, (c) C18:1-trans, and (d) C18:2-trans FAs vs. IV during partial sunflower oil hydrogenation using different catalysts.
Figure 8
Figure 8
Change in the composition of (a) C18:1-cis, (b) C18:2-cis, (c) C18:1-trans, and (d) C18:2-trans FAs vs. IV during partial sunflower oil hydrogenation using different catalysts.
Figure 9
Figure 9
Comparison among the selected data from the characterization of the reduced samples.
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