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Glycerol Electrooxidation at Industrially Relevant Current Densities Using Electrodeposited PdNi/Nifoam Catalysts in Aerated Alkaline Media
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-9181-9825
Institute of Chemical, Environmental and Bioscience Engineering, TUW Vienna University of Technology, 1060, Vienna, Austria.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0002-9385-7577
Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden.
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2023 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 170, no 8, article id 086504Article in journal (Refereed) Published
Abstract [en]

Through glycerol electrooxidation, we demonstrate the viability of using a PdNi catalyst electrodeposited on Ni foam to facilitate industrially relevant rates of hydrogen generation while concurrently providing valuable organic chemicals as glycerol oxidation products. This electrocatalyst, in a solution of 2 M NaOH and 1 M glycerol at 80 °C, enabled current densities above 2000 mA cm−2 (in a voltammetric sweep) to be obtained in atmospheres of both air and N2. Repeated potential cycling under an aerated atmosphere to these exceptional current densities indicated a high stability of the catalyst. Through steady state polarisation curves, 1000 mA cm−2 was reached below an anodic potential of 0.8 V vs RHE. Chronoamperometry showed glycerate and lactate being the major oxidation products, with increased selectivity for lactate at the expense of glycerate in aerated systems. Aerated atmospheres were demonstrated to consistently increase the apparent Faradaic efficiency to >100%, as determined by the concentration of oxidation products in solution. The excellent performance of PdNi/Ni in aerated solutions suggests that O2 removal from the electrolyte is not needed for an industrial glycerol electrooxidation process, and that combining electrochemical and chemical glycerol oxidation, in the presence of dissolved O2, presents an important process advantage.

Place, publisher, year, edition, pages
The Electrochemical Society , 2023. Vol. 170, no 8, article id 086504
National Category
Physical Chemistry Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-334940DOI: 10.1149/1945-7111/acee27ISI: 001049747200001Scopus ID: 2-s2.0-85168440809OAI: oai:DiVA.org:kth-334940DiVA, id: diva2:1792727
Note

QC 20230830

Available from: 2023-08-30 Created: 2023-08-30 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, DanielLundberg, HelenaHenriksson, GunnarCornell, Ann

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