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@PHDTHESIS{Bler:1012205,
author = {Bäßler, Jonas Frederik},
othercontributors = {Wessling, Matthias and Ponce De Leon Albarran, Carlos},
title = {{S}elective methanol oxidation for paired electrolysis},
volume = {54},
school = {Rheinisch-Westfälische Technische Hochschule Aachen},
type = {Dissertation},
address = {Aachen},
publisher = {RWTH Aachen University},
reportid = {RWTH-2025-04916},
series = {Aachener Verfahrenstechnik series - AVT.CVT - Chemical
process engineering},
pages = {1 Online-Ressource : Illustrationen},
year = {2025},
note = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
University; Dissertation, Rheinisch-Westfälische Technische
Hochschule Aachen, 2025},
abstract = {Electrochemical processes offer promising routes to
defossilize the chemical industry by integrating low-carbon
electricity. Industrial application is still hindered by
high costs and the challenging transition from lab-scale
research to industrial maturity. Key processes, such as
cathodic hydrogen evolution and CO2 reduction, are typically
paired with the anodic oxygen evolution reaction (OER).
However, the generated oxygen holds little value, and the
electrical costs associated with energy-intensive OER pose a
significant economic barrier. This thesis explores selective
methanol oxidation as a less energy-intensive alternative to
OER for paired electrolysis, which yield value-added
products from both anodic and cathodic reactions.Two paired
processes were studied in electrochemical flow cells:
Methanol oxidation to formaldehyde at platinum paired with
CO2 reduction, and methanol oxidation to formate at
hierarchically structured copper oxide paired with hydrogen
evolution. Investigating both processes at conditions
significantly exceeding previous studies in terms of
electrode area, current density, and product concentration
allowed novel insights into selective methanol oxidation and
revealed crucial interactions within the paired systems.
Furthermore, methanol oxidation was employed to introduce
'feed and bleed' as a versatile alternative to conventional
batch and single-pass operation of electrochemical flow
cells.Methanol oxidation to formaldehyde was strongly
influenced by the oxidation state of the electrode with a
higher Faraday efficiency for oxidized platinum (up to
$58\%),$ but a lower anodic potential for metallic platinum.
Methanol oxidation to formate at optimized conditions
achieved nearly $100\%$ Faraday efficiency and up to $70\%$
yield. The reaction conditions, in particular the
conversion, had a critical impact on the selectivity for
formate. In both paired processes, methanol oxidation
required less electrical energy than conventional OER and
provided value-added products with substantial yields.
Interactions between the anode and cathode side, such as ion
transfer and the crossover of water and reactants were found
to be crucial for the stability of the paired processes,
especially at high product concentrations. Building on the
findings on methanol oxidation, the 'feed and bleed'
operating mode was established enabling the investigation of
reactions in steady state at high product concentration.The
present work highlights the benefits of paired electrolysis
and provides valuable insights on selective methanol
oxidation to formaldehyde and formate with yields and
product concentrations exceeding the previous state of the
art. Challenges arising from high product concentration and
adverse interactions within the paired process were
identified and discussed. The methodological aspects of this
work can be applied to the investigation of other
electrochemical processes under industrially relevant
conditions and thus contribute to the overarching goal of
bringing sustainable processes to industrial application.},
cin = {416110},
ddc = {620},
cid = {$I:(DE-82)416110_20140620$},
pnm = {EFRE 0500077 - ELECTRA - Kompetenzzentrum Industrielle
Elektrochemie (0500077) / BMBF 03SF0589B - Verbundvorhaben
iNEW: Inkubator Nachhaltige Elektrochemische
Wertschöpfungsketten (iNEW) im Rahmen des Gesamtvorhabens
Accelerator Nachhaltige Bereitstellung Elektrochemisch
Erzeugter Kraft- und Wertstoffe mittels Power-to-X (ANABEL)
(03SF0589B) / BMBF 03SF0627B - Verbundvorhaben iNEW2.0: In
iNEW (Inkubator Nachhaltige Elektrochemische
Wertschöpfungsketten) werden neuartige und leistungsfähige
Elektrolyseverfahren zur Anwendung in nachhaltigen
Power-to-X Wertschöpfungsketten erforscht und entwickelt
(03SF0627B)},
pid = {G:(EFRE)0500077 / G:(BMBF)03SF0589B / G:(BMBF)03SF0627B},
typ = {PUB:(DE-HGF)11 / PUB:(DE-HGF)3},
doi = {10.18154/RWTH-2025-04916},
url = {https://publications.rwth-aachen.de/record/1012205},
}
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