| SEM, NaCl-Cu (+−+−) | atomic steps and well-defined square terraces |
|---|---|
| Surface characterization CV, NaCl-Cu (+−+−) | well-defined peaks at +0.37 V, +0.41 V, and +0.46 V vs RHE, corresponding to Cu(100), Cu(110), and Cu(111), respectively; two broad features at −0.1 V and +0.1 V, tentatively assigned to OH− adsorption on extended terrace domains of the (100) and (111) facet orientations, respectively |
| Pb UPD, NaCl-Cu (+−+−) | (100), 4 %; (310), 27 %; (110), 23 %; (111), 46 %; Rf = 2.6 |
| SEM, NaCl-Cu (−++−) | surface uniformly covered by spherical particles exhibiting multi-faceted crystalline features, with an average diameter of 1–3 µm |
| Surface characterization CV, NaCl-Cu (−++−) | cathodic peak at −0.1 V vs RHE, associated with the (100) terraces; peak at +0.1 V vs RHE, attributed to (111) terraces; signals at +0.37 V, +0.41 V, and +0.46 V vs RHE, corresponding to (100), (110) defect sites, and (111) small terraces, respectively |
| Pb UPD, NaCl-Cu (−++−) | (100), 5 %; (310), 33 %; (110), 15 %; (111), 47 %; Rf = 2.5 |
| Surface characterization CV, KI-Cu (+−+−) | crossing point at approximately −0.6 V vs SCE; prominent signal between −0.2 V and 0.0 V vs RHE, tentatively assigned to the (100) crystallographic motif |
| Pb UPD, KI-Cu (+−+−) | (100), 5 %; (310), 38 %; (110), 15 %; (111), 43 %; Rf = 2.5 |
| SEM, KI-Cu (−++−) | sponge-like surface texture characterized by a highly porous and irregular nanostructure |
| Surface characterization CV, KI-Cu (−++−) | peaks at +0.37 V and +0.41 V vs RHE, corresponding to (100) and (110) surface facets, respectively; the (111) signal at +0.46/+0.48 V vs RHE was considerably less intense; peak at +0.1 V vs RHE, attributed to extended (111) terraces |
| Pb UPD, KI-Cu (−++−) | (high index), 10 %; (100), 26 %; (310), 22 %; (110), 35 %; (111), 7 %; Rf = 8.2 |
| In-situ Raman spectroscopy, NaCl-Cu (+−+−) | 190–350 cm⁻¹, assigned to the CuO Ag mode; 120–190 cm⁻¹, corresponding to convoluted Cu2O/CuCl vibrational features; deconvoluted spectral features centered at ~140 and ~160 cm⁻¹, assigned to the Cu2O T1u (TO-LO) and CuCl (LO) modes, respectively |
| In-situ Raman spectroscopy, KI-Cu (+−+−) | 430–620 cm⁻¹, assigned to the Cu2O T2g and T1u modes; 120–190 cm⁻¹ and 250–430 cm⁻¹, corresponding to convoluted Cu2O/CuI vibrational features; deconvoluted signal centered at ~120 cm⁻¹, assigned to the γ-CuI (TO) mode; signal centered at ~150 cm⁻¹, including possible Cu2O T1u (TO-LO), γ-CuI (LO), and I3− ν3 modes; deconvoluted Cu–O vibration from Cu2O centered at ~215 cm⁻¹ |
| In-situ Raman spectroscopy during stripping | fast disappearance of CuCl and CuO signals; CuI signals remained after 20 stripping cycles |
Andrea Conte, Sebastián Murcia-López, Camilo Arturo Mesa, Sara Bonacchi, Sabrina Antonello, María Escudero-Escribano. “Halide-directed nanostructuring of copper unraveled by multivariate analysis.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.10001930/v2