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- Terekhina, Irina, 1994-
(författare)
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On selective glycerol valorisation : Exploring the performance of facet-controlled nanoelectrocatalysts
- 2024
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- As the biodiesel industry's growth skyrocketed in the past 20 years, it resulted in the accumulation of its main by-product—glycerol. Despite its extensive applications in the pharmaceutical industry, medicine, cosmetics, agriculture, and food industries, the supply exceeds the demand. Hence, glycerol, being abundant and cheap, has emerged as a promising feedstock for producing value-added chemicals. One of the tactics to generate those products is the glycerol electrooxidation reaction (GEOR), where glycerol is oxidised at the anode and hydrogen gas is generated at the cathode.In the present thesis, noble metal-based nanoparticles were synthesised, characterised, and evaluated in alkaline media as catalysts for the GEOR. In order to assess and optimise the electrocatalytic performance and selectivity of the GEOR toward three-carbon (C3) products, different parameters like the morphology and composition of the catalyst, exposed crystallographic facets, electrolyte composition and electrolysis potential were studied.The centre of the attention of the research covered were Pd, Pd-Ni, Pt and Pt-Co nanoparticles with an octahedral, rhombic dodecahedral, and cubic shape and more irregular shapes. Cubic-shaped catalysts with {100} faces were the best-performing among the investigated systems. In addition, alloying of Pd and Pt with non-noble Ni and Co improved the efficiency of the GEOR compared to their noble monometallic counterparts while generally retaining the selectivity of C3 products mostly represented by glycerate and lactate.
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| 2. |
- White, Jai, et al.
(författare)
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Synergistic Bimetallic PdNi Nanoparticles : Enhancing Glycerol Electrooxidation While Preserving C3 Product Selectivity
- 2024
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Ingår i: ACS Applied Energy Materials. - 2574-0962. ; 7:5, s. 1802-1813
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemical conversion of glycerol offers a promising route to synthesize value-added glycerol oxidation products (GOPs) from an abundant biomass-based resource. While noble metals provide a low overpotential for the glycerol electrooxidation reaction (GEOR) and high selectivity toward three-carbon (C3) GOPs, their efficiency and cost can be improved by incorporating non-noble metals. Here, we introduce an effective strategy to enhance the performance of Pd nanoparticles for the GEOR by alloying them with Ni. The resulting PdNi nanoparticles show a significant increase in both specific activity (by almost 60%) and mass activity (by almost 35%) during the GEOR at 40 °C. Additionally, they exhibit higher resistance to deactivation compared to pure Pd. Analysis of the GOPs reveals that the addition of Ni into Pd does not compromise the selectivity, with glycerate remaining at around 60% of the product fraction and the other major product being lactate at around 30%. Density functional theory calculations confirm the reaction pathways and the basis for the higher activity of PdNi. This study demonstrates a significant increase in the GEOR catalytic performance while maintaining the selectivity for C3 GOPs, using a more cost-effective nanocatalyst.
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