Journal Article

PUBDB-2026-02649

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Selectivity and Active State Formation During Pulsed CO$_2$ Electroreduction in Cation‐Modified Electrolyte

Liberra, E.Extern* ; Bai, L.Extern* ; Wagner, T.Extern* ; Etxebarria, A.Extern* ; Jacobse, L.Extern* ; Rüscher, M.Extern* ; Ortega, E. ; Timoshenko, J.Extern* ; Bergmann, A. (Corresponding author)Extern* ; Roldan Cuenya, B. (Corresponding author)Extern*

2026
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/celc.202500459  doi:10.3204/PUBDB-2026-02649

Abstract: Pulsed CO2 reduction reaction (CO2RR) is a viable approach to steer selectivity between C1 and C2+ products as well as hydrocarbons and oxygenates via intermittent Cu oxidation. Here, we report on the catalytic influence of alkali metal cations using oxide-derived Cu nanocrystals based on comprehensive electrocatalytic testing and time-resolved in situ X-ray absorption spectroscopy and diffraction. Typical cation-dependent selectivity trends were observed at optimal potentiostatic conditions, while pulsed operation significantly reduces hydrogen and formate selectivity and introduces a discontinuous shift in product selectivity not directly following the ionic radius. K+/Cs+ exhibits enhanced ethanol formation with a weaker enhancement of methane compared to Li+/Na+. Our in situ studies revealed dynamic structural catalyst responses to potential modulation and cation identity, with a quantitative link of the lattice parameter to the cation size but not their effective ionic radius, which includes the hydration shell. Importantly, this trend is also linked to the enhanced C2+ formation under potentiostatic CO2RR, while under pulsed CO2RR, not the Cu(I) but Cu(II) formation kinetics, facilitating Cu dissolution, influences selectivity. Overall, our results demonstrate that cations modulate both the electrode (surface) structure and thus, the electronic environment of Cu, but also its dynamicity, thereby governing the mechanistic pathway and selectivity of CO2RR.

Note: eutsche Forschungsgemeinschaft (DFG,German Research Foundation), project no. 327886311-SPP 2080. (BMBF) under grant no. 03EW0015B(CATLAB)

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Contributing Institute(s):

1. FS DOOR-User (FS DOOR-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. FS-Proposal: I-20250446 (I-20250446) (I-20250446)
3. FS-Proposal: I-20230966 (I-20230966) (I-20230966)

Experiment(s):

1. PETRA Beamline P21.2 (PETRA III)
2. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2026

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