Borges D.D., Devautour-Vinot S., Jobic H. et al. · Angewandte Chemie - International Edition · 2016 · 3919-3924
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.
UiO-66(Zr)-(CO2H)2 reaches superprotonic conductivity under humid conditions, with 2.30 x 10^-3 S cm^-1 at 90 degC and 95% RH.
Caveat: High conductivity is water-mediated and measured on humidified pressed pellets.
2 · Results · Figure 1 · Linked to 3 structured results
Condensation of COOH groups into anhydrides is negligible under the humid impedance conditions.
Caveat: IR under vacuum at 363 K shows only a very weak anhydride band; authors infer humid impedance conditions are less prone to anhydride formation.
7 · Infrared Spectroscopy · Figure S7 · Linked to 2 structured results
At elevated temperature, a hydrogen-bonded water network bridges tetrahedral and octahedral cages, providing a pathway for long-distance proton transfer.
Caveat: Mechanistic picture is derived from MD trajectories supported by QENS dynamics.
4 · Summary · Figure 5 · Linked to 4 structured results
Low-frequency capacitive tails from blocking gold electrodes evidence ionic conducting species, identified as H+ ions.
Caveat: The claim is based on impedance response shape rather than direct ion-selective measurement.
4 · Complex Impedance Spectroscopy · Figure S4 · Linked to 2 structured results
QENS spectra require two dynamical species: a free proton undergoing long-range diffusion and a diffusing/rotating water molecule.
Caveat: Errors in diffusion coefficients grow as broadenings get smaller at lower temperature.
2 · Results · Figure 2 · Linked to 4 structured results
Proton transport is largely governed by a Grotthuss-like mechanism rather than vehicular transport with solvating water molecules.
Caveat: QENS and MD agree on faster proton than water dynamics, though the simulated Ds(CEC) underestimates the QENS proton value.
3 · Results · Figure 3 · Linked to 5 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| UiO-66(Zr)-(CO2D)2 deuterated analogue | Zr6O4(OD)4(O2C-C6D2-CO2-(CO2D)2)6.xD2OZr6 oxo-deuteroxo clusters · deuterium-enriched 1,2,4,5-benzenetetracarboxylate analogue | 3D · PristineUiO-66-type deuterated analogue; SI pattern matching gives space group P23 | 4 · Experimental Section |
| UiO-66(Zr)-(CO2H)2 | Zr6O4(OH)4(O2C-C6H2-CO2-(CO2H)2)6.xH2O (x approximately 16)Zr6 oxo-hydroxo clusters · 1,2,4,5-benzenetetracarboxylate with free CO2H groups | 3D · PristineUiO-66 framework with tetrahedral and octahedral cages connected by narrow triangular windows | 1 · Introduction |
| Fully hydrated UiO-66(Zr)-(CO2H)2 aMS-EVB3 model | One cubic unit cell of UiO-66(Zr)-(CO2H)2 with 80 H2O per unit cell and one excess protonZr6 oxo-hydroxo clusters in flexible-force-field model · 1,2,4,5-benzenetetracarboxylate with free CO2H groups | 3D · Model SystemComputational model of fully hydrated UiO-66(Zr)-(CO2H)2 | 5 · Experimental Section |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| UiO-66(Zr)-(CO2D)2 characterisation powderresearch_0236__mat__uio66_zr_co2d2 | Powder · Target Sample · Pristine Framework | Deuterated analogue after activation; used for PXRD, TGA and N2 sorption characterisation. | 2 · UiO-66(Zr)-(CO2D)2 characterization · Figures S1-S3 |
| desorbed empty MOF QENS backgroundresearch_0236__mat__uio66_zr_co2d2 | Powder · Pristine Control · Pristine Framework | Desorbed sample measured as empty-MOF background for subtraction. | 5 · Experimental Section |
| fully hydrated UiO-66(Zr)-(CO2D)2 QENS sampleresearch_0236__mat__uio66_zr_co2d2 | Powder · Target Sample · Guest Loaded | Fully hydrated after desorption at 373 K; 120 H2O per unit cell; framework scattering reduced by deuteration. | 5 · Experimental Section |
| UiO-66(Zr)-(CO2H)2 pressed pellet for impedanceresearch_0236__mat__uio66_zr_co2h2 | Pellet · Target Sample · Guest Loaded | Powder pressed at 0.6 GPa into pellets; equilibrated 24 h at selected temperature and RH; sandwiched between gold plate electrodes.2.02 mm | 4 · Experimental Section |
| fully hydrated UiO-66(Zr)-(CO2H)2 aMS-EVB3 model systemresearch_0236__mat__uio66_zr_co2h2_model | Model · Model System · Model | NVE simulations after at least 2 ns NVT equilibration; temperatures 300, 350, 400 and 450 K. | 5 · Experimental Section |