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Electrodeposited PdNi on a Ni rotating disk electrode highly active for glycerol electrooxidation in alkaline conditions
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-9181-9825
Uppsala Univ, Dept Mat Sci & Engn, Angstrom Lab, SE-75103 Uppsala, Sweden..
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry. Department of Chemistry, University of Warwick, UK.ORCID iD: 0000-0002-9385-7577
Uppsala Univ, Dept Mat Sci & Engn, Angstrom Lab, SE-75103 Uppsala, Sweden..
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2022 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 403, article id 139714Article in journal (Refereed) Published
Abstract [en]

The development of alcohol-based electrolysis to enable the concurrent production of hydrogen with low electricity consumption still faces major challenges in terms of the maximum anodic current density achievable. Whilst noble metals enable a low electrode potential to facilitate alcohol oxidation, the deactivation of the catalyst at higher potentials makes it difficult for the obtained anodic current density to compete with water electrolysis. In this work the effect of significant parameters such as mass transport, glycerol and OH- concentration and electrolyte temperature on the glycerol electrooxidation reaction (GEOR) in alkaline conditions on a bimetallic catalyst PdNi/Ni-RDE (Pd0.9Ni0.1) has been studied to discern experimental conditions which maximise achievable anodic current density before deactivation occurs. The ratio of NaOH:glycerol in the electrolyte highly affects the rate of the GEOR. A maximum current density of 793 mA cm(-2) at-0.125 V vs. Hg/HgO through steady state polarisation curves was achieved at a moderate and intermediate rotation rate of 500 RPM in a 2 M NaOH and 1 M glycerol (ratio of 2) electrolyte at 80 & DEG;C. Shown here is a method of catalyst reactivation for enabling the longterm use of the PdNi/Ni-RDE for electrolysis at optimal conditions for extended periods of time (3 h at 300 mA cm(-2) and 10 h at 100 mA cm(-2)). Through scanning electron microscopy (SEM), X-ray photon electron spectroscopy (XPS) and X-ray diffraction (XRD) it is shown that the electrodeposition of Pd and Ni forms an alloy and that after 10 h of electrolysis the catalyst has chemical and structural stability. This study provides details on parameters significant to the maximising of the GEOR current density and the minimising of the debilitating effect that deactivation has on noble metal based electrocatalysts for the GEOR.

Place, publisher, year, edition, pages
Elsevier BV , 2022. Vol. 403, article id 139714
Keywords [en]
Glycerol oxidation, Rotating disk electrode, Palladium nickel, Electrolysis, Hydrogen evolution
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-311530DOI: 10.1016/j.electacta.2021.139714ISI: 000776113700006Scopus ID: 2-s2.0-85121235358OAI: oai:DiVA.org:kth-311530DiVA, id: diva2:1655063
Note

QC 20220429

Available from: 2022-04-29 Created: 2022-04-29 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: 2023-11-22Bibliographically approved

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White, JaiMartín-Yerga, DanielHenriksson, GunnarCornell, Ann M.

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