Johnson B.A., Castner A.T., Agarwala H. et al. · Chemical Science · 2025 · 5214-5222
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
The Zn(NDI)@FTO thin films are assigned to the reported Zn(NDI) phase by SEM thickness/morphology and PXRD peaks at 5.1 and 10.3 degrees.
Caveat: The full synthesis/structure recipe is inherited from previous reports; no CIF is assigned in this extraction package.
p025 / SI page S25 · Figures · Figure S4 · Linked to 3 structured results
The [Co(bpy)3]3+ / reduced-NDI cross reaction is fast enough on the diffusion timescale to satisfy the assumptions of the steady-state analytical model.
Caveat: Marcus estimate uses approximations including f12 near unity and work-term cancellation.
p019 / SI page S19 · 4.2.2 Marcus theory and DFT calculations · Linked to 4 structured results
When mobile ion concentration is low relative to redox-active linker concentration, an electric field develops in the film and migration enhances the electron-hopping flux/current rather than merely limiting it.
Caveat: The 1.5-fold enhancement is an asymptotic low-ion model limit; the experimental beta value is 0.5.
p006 / journal page 5219 · Results and discussion · Fig. 3 · Linked to 3 structured results
Steady-state catalytic CV with a freely diffusing acceptor minimises net counterion flux and better isolates the intrinsic electron-hopping diffusion coefficient De of Zn(NDI) films.
Caveat: The extracted De can still be influenced by microscopic effects such as solvation, ion pairing and ion-coupled electron transfer.
p008 / journal page 5221 · Conclusion · Linked to 3 structured results
Transient potential-step Cottrell analysis overestimates the electron-hopping diffusion coefficient because ion diffusion-migration and electric-field effects contribute to the measured current.
Caveat: Magnitude of overestimation depends on ion diffusivity and bulk ion-to-linker concentration ratios.
p007 / journal page 5220 · Results and discussion · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| 1D planar redox-film Poisson-Nernst-Planck model | modelNDI/NDI radical anion redox sites represented as P/Q | 1D · Model SystemAnalytical reaction-diffusion-migration model for a planar redox film with immobilised redox species and mobile acceptor/counterions. | p005 / SI page S5 · 3.2 Steady-state catalytic mechanism |
| [Co(bpy)3]3+ / [Co(bpy)3]2+ | [Co(bpy)3]3+ / [Co(bpy)3]2+Co coordination complex · 2,2'-bipyridyl ligands | 0D · Model SystemFreely diffusing molecular electron acceptor/product used to impose steady-state catalytic conditions in Zn(NDI) films. | p003 / journal page 5216 · Results and discussion · Fig. 1d |
| Zn(NDI) | Zn(NDI)tetrahedral Zn nodes · naphthalenediimide dipyrazolate linker (NDI) | 3D · PristineZn-based redox-conducting MOF with ca. 16 A wide 1D channels; thin films on FTO assigned by matching PXRD peaks and SEM morphology. | p003 / journal page 5216 · Results and discussion · Fig. 1c |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| bare FTO control electroderesearch_0667__mat__mat_zn_ndi | Electrode · Pristine Control · Unknown | bare FTO working electrode in 0.5 M LiClO4/DMF with [Co(bpy)3]3+bare FTO | p027 / SI page S27 · Figures · Figure S8 |
| DFT molecular redox modelsresearch_0667__mat__mat_co_bpy_acceptor | Model · Model System · Model | DFT-optimised NDI, NDI radical anion, [Co(bpy)3]3+ and [Co(bpy)3]2+ in DMF COSMO | p020 / SI page S20 · 4.2.3 DFT computational details |
| [Co(bpy)3]3+ on glassy carbonresearch_0667__mat__mat_co_bpy_acceptor | Electrode · Model System · Model | 3 mM [Co(bpy)3]3+ in 0.5 M LiClO4/DMF0.071 cm2 glassy carbon disk working electrode | p028 / SI page S28 · Figures · Figure S9 |
| analytical planar redox-film modelresearch_0667__mat__mat_analytical_model | Model · Model System · Model | Poisson-Nernst-Planck / reaction-diffusion model with NDI linker P/Q, [Co(bpy)3]3+ acceptor and mobile counterions1D planar film boundary at conducting electrode and film-solution interface · df = 1 um used for simulations | p010 / SI page S10 · 3.4 Derivation of steady-state current response with electromigration |
| Zn(NDI)@FTO thin filmresearch_0667__mat__mat_zn_ndi | Thin Film · Target Sample · Pristine Framework | MOF thin film on FTO, cycled in 0.5 M LiClO4/DMF at 50 mV s-1 until current stabilised before measurementfluorine-doped tin oxide (FTO), 7 ohm/sq · approximately 1 um | p003 / SI page S3 · Materials and methods |