Alkali Metal Cations Induce Pseudo-outer-sphere Oxygen Reduction Reaction Mechanism in Electrolyte-Catalyst Synergy
Bibliographic record
Abstract
Alkali metal cations (AMCs) are known to play pivotal roles in modulating electrocatalytic systems, significantly affecting the oxygen reduction reaction (ORR). While their macroscopic effects are well recognized, the molecular-level interactions of AMCs at the electrochemical interface remain poorly understood. Here, using constant-potential ab initio molecular dynamics simulations, we uncover that AMCs (Li +, Na +, and K + ) act as molecular switches that trigger a pseudo-outer-sphere ORR mechanism. In this mechanism, surface-adsorbed water molecules serve as dynamic bridges that simultaneously mediate interfacial electron transfer and proton transport. As a result, the reactive zone extends beyond the catalyst surface, overcoming the spatial constraints of traditional inner-sphere pathways. Crucially, H 2 O 2 is generated directly within the outer Helmholtz plane via reduction of AMC-O 2 complexes, effectively bypassing the catalyst surface and avoiding over-reduction. This results in significantly enhanced selectivity and production efficiency. Our results demonstrate that AMCs activate interfacial coupling to unlock alternative reaction pathways, while concurrently elucidating the critical yet often overlooked role of solute molecules in governing electrocatalytic behavior. This work establishes a framework for the understanding of electrolyte-catalyst coupling and provides principles for designing next-generation electrochemical systems.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".