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Synergistic Bimetallic PdNi Nanoparticles: Enhancing Glycerol Electrooxidation while Preserving C3 Product Selectivity
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-9181-9825
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-9385-7577
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Electrochemical conversion of glycerol offers a promising route to synthesise 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 towards 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 25%) 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.

Keywords [en]
alkaline, electrocatalysis, density functional theory, HPLC, value-added products
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-339633OAI: oai:DiVA.org:kth-339633DiVA, id: diva2:1812221
Note

QC 20231115

Available from: 2023-11-15 Created: 2023-11-15 Last updated: 2023-11-15Bibliographically approved
In thesis
1. From Facets to Flow: The Electrooxidation of Glycerol on Pd-based catalysts
Open this publication in new window or tab >>From Facets to Flow: The Electrooxidation of Glycerol on Pd-based catalysts
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Glycerol, a by-product of biodiesel refineries, has uses in industries such as cosmetics, food, and pharmaceuticals. However, its usage is small compared to the amount of glycerol produced from biodiesel production. Therefore, there is an opportunity to use glycerol, an important platform chemical, as a cheap feedstock for the synthesis of valuable chemicals. These chemicals can be formed in aqueous media through the glycerol electrooxidation reaction (GEOR) on the anode with hydrogen gas concurrently generated on the cathode. This thesis focuses on the GEOR in alkaline media on Pd and PdNi catalysts. 

The works compiled here evaluate the GEOR using electrochemical methods such as cyclic voltammetry, galvanostatic polarisation curves, chronoamperometry and chronopotentiometry. Pd and PdNi catalysts were fabricated through chemical synthesis, and electrodeposition onto Ni substrates. Singularly oriented Pd crystal facets were studied, showing those approximating Pd (111) as the most active. Similarly faceted bimetallic PdNi nanoparticles proved significantly more active than pure Pd. Effects of mass transport, studied for Pd/NiRDE and PdNi/NiRDE, indicated performance effects linked to diffusion and underutilisation of thicker catalyst layers. In aerated solutions, industrially relevant current densities were achieved on PdNi/Nifoam in concentrated electrolytes at elevated temperatures for extended periods. The analysis of glycerol oxidation products, formed during steady state measurements, was done using high performance liquid chromatography. The two major products were consistently shown to be glycerate and lactate. This work, covering many aspects of the GEOR, shows that Pd-based catalysts have potential for future industrial application.

Abstract [sv]

Glycerol, en biprodukt från biodieselraffinaderier, har användningsområden i industrier som producerar kosmetika, livsmedel och läkemedel. Dess användning är dock liten jämfört med mängden glycerol som produceras från biodieselproduktion. Därför finns det en möjlighet att använda glycerol, en viktig plattformskemikalie, som ett billigt råmaterial för syntes av värdefulla kemikalier. Dessa kemikalier kan bildas i vattenlösning genom glycerolelektrooxidationsreaktionen (GEOR) på anoden samtidigt vätgas genereras på katoden. Denna avhandling fokuserar på GEOR på Pd- och PdNi-katalysatorer i alkaliska medier.

Detta arbete inkluderar studier av GEOR med hjälp av elektrokemiska metoder som cyklisk voltammetri, galvanostatiska polarisationskurvor, kronoamperometri och kronopotentiometri. Pd- och PdNi-katalysatorer tillverkades genom kemisk syntes och elektrodeposition på Ni-substrat. Singulärt orienterade Pd-kristallfacetter studerades och visade att de som närmar sig Pd (111) var de mest aktiva. Bimetalliska PdNi-nanopartiklar med liknande fasetter visade sig vara betydligt mer aktiva än ren Pd. Effekter av masstransport, som studerades för Pd/NiRDE och PdNi/NiRDE, indikerade prestandaeffekter kopplade till diffusion och underutnyttjande av tjockare katalysatorskikt. I luftade lösningar uppnåddes industriellt relevanta strömtätheter på PdNi/Nifoam i koncentrerade elektrolyter vid förhöjda temperaturer under längre perioder. Analysen av glyceroloxidationsprodukter, bildade vid stationära mätningat, gjordes med hjälp av högupplösande vätskekromatografi. De två huvudprodukterna visades konsekvent vara glycerat och laktat. Detta arbete, som täcker många aspekter av GEOR, visar att Pd-baserade katalysatorer har potential för framtida industriell tillämpning. 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2023. p. 95
Series
TRITA-CBH-FOU ; 2023:52
Keywords
glycerol, electrooxidation, palladium, nickel, alkaline, HPLC, RDE, glycerol, elektrooxidation, palladium, nickel, alkalisk, HPLC, RDE
National Category
Chemical Sciences Physical Chemistry Materials Chemistry Other Chemistry Topics
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-339635 (URN)978-91-8040-752-6 (ISBN)
Public defence
2023-12-08, D2, Lindstedtsvägen 9, https://kth-se.zoom.us/meeting/register/u5cqfuigpj4jE9EaFkO3TgvRFk7joTndod0B, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Foundation for Strategic Research, EM16-0010
Note

QC 20231116

Available from: 2023-11-16 Created: 2023-11-15 Last updated: 2025-04-24Bibliographically approved

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White, JaiMartín-Yerga, DanielCornell, Ann M.

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