Cathodic Corrosion at the Bismuth–Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction

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ACS proof PDF. Canonical curation with VOR pdf_path is on 2018jonnathan-medina-ram-chem-mater-2-cathodic-corrosion (papers/MedinaRamon_ChemMat_2018.pdf).

Summary¶

This entry registers the ACS proof PDF papers/MedinaRamon_ChemMat_2018_proof.pdf for Chemistry of Materials DOI 10.1021/acs.chemmater.8b00050, “Cathodic Corrosion at the Bismuth–Ionic Liquid Electrolyte Interface under Conditions for CO₂ Reduction.” The extract (normalized/extracts/2018medinaramon-venue-research-2_p1-2.txt) contains the article abstract and the start of the Introduction, establishing the combined experimental and computational scope: in situ X-ray reflectivity on Bi(001) films that initially contain a native Bi₂O₃ layer reduced to Bi⁰ during cyclic voltammetry in acetonitrile with BMIM⁺ electrolytes; loss of roughly 60% of the Bi(001) Bragg reflectivity during a potential sweep between about −1.5 and −1.9 V versus Ag/AgCl attributed to roughly 4–10% thinning and roughly 40% decrease in lateral domain size, largely reversible on the anodic scan; and repeated cycling enhancing thinning and roughening, suggesting partial dissolution under negative polarization. The abstract states that molecular dynamics with ReaxFF and DFT calculations indicate stronger binding of imidazolium cations than tetrabutylammonium (TBA⁺) as the potential and surface charge become more negative, that ReaxFF predicts greater disorder for negatively charged Bi(001) with imidazolium and substantial Bi migration from the surface, and that DFT shows Bi···[Im]⁺ complexes favoring dissolution from step edges between about −1.65 and −1.95 V while desorption from a flat terrace requires about −2.25 V. The scientific narrative, figure references, and full Methods are maintained on 2018jonnathan-medina-ram-chem-mater-2-cathodic-corrosion because the proof file can differ subtly in layout from the journal PDF.

Methods¶

The proof extract continues into the Experimental section opener, listing BMIM triflate (≥98%) from Sigma-Aldrich used as received and solutions prepared in acetonitrile at 100 mM, with comparison experiments using TBA-based electrolytes (for example TBAPF₆ and TBAOTf sources named in the text layer). Experimental XR electrochemical cells, potential programs, and surface-sensitive fitting procedures appear in the main article. ReaxFF simulations use a Bi/ionic-liquid parameterization developed in the study to explore binding and restructuring at the electrified interface, while DFT calculations address cluster or complex energetics referenced in the text. Full computational details—supercell sizes, charge models, thermostat choices, and convergence settings—should be read from 2018jonnathan-medina-ram-chem-mater-2-cathodic-corrosion rather than inferred from this duplicate proof path alone.

MD application (proof-ingest note)¶

ReaxFF molecular dynamics on Bi(001) with imidazolium vs TBA⁺ motifs parallels the main article narrative. Engine / code: N/A — MD engine not restated on this duplicate proof page—confirm alongside LAMMPS/other notes on [[2018jonnathan-medina-ram-chem-mater-2-cathodic-corrosion]]. Ensemble: NVT-class sampling for the interfacial ReaxFF segments per the VOR Methods summary on the sibling page. Timestep / duration / thermostat / barostat: N/A — not transcribed from this proof PDF—use the VOR Methods. PBC: slab models implied by the Bi(001) focus (exact padding/freeze in PDF). Temperature / pressure / electric field / enhanced sampling: N/A — MD-stage details not duplicated here beyond what appears in the abstract on the sibling VOR page.

Findings¶

The peer-reviewed article ties imidazolium-related surface disorder and bismuth migration to cathodic corrosion under the investigated potentials; the proof extract’s abstract already quantifies XR reflectivity loss, thinning, and domain-size trends during BMIM scans and contrasts behavior with TBA-based electrolytes where the dramatic restructuring was not observed. The Introduction reproduced in the extract recounts prior in situ XR on Bi thin films during CO₂ reduction and frames the present work as coordinated XR, RRDE, ReaxFF, and potential-dependent DFT to explain atomic-level restructuring. Because this slug duplicates the science under a proof pdf_path, automated PDF-to-text pipelines may reorder captions relative to the final issue; when quoting layer electron densities or Bi occupancy metrics, anchor numbers to the VOR PDF or to tables in 2018medinaramos-venue-microsoft-word rather than to this proof file.

Limitations¶

Proof PDFs may not match final figure numbering. Prefer the non-proof PDF for long-term maintenance.

Relevance to group¶

Multi-institution collaboration including van Duin (ReaxFF) and Argonne beamline science for electrified interfaces.

When diffing this proof against the VOR PDF, pay attention to author affiliations and compound labels that ACS sometimes reformats during production; those cosmetic edits do not change the core electrochemistry but can break naive string-based extract alignment in automation scripts.

Citations and evidence anchors¶

https://doi.org/10.1021/acs.chemmater.8b00050