Li X., Surendran Rajasree S., Gude V. et al. · Angewandte Chemie - International Edition · 2023 · e202219046
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.
Post-electrolysis checks did not indicate sizeable cobalt macrocycle leaching, but CoPc@NU-1000-h loses about 20-25% electrocatalytic current, possibly due to leaching of electroactive TBAPy linkers.
Caveat: Some stability evidence is qualitative or figure-based; current loss mechanism is proposed rather than directly proven.
17 · Stability · Figures S22-S27 · Linked to 4 structured results
CoPc-COO and TPP(Co)-COO are installed at Zr-oxo SBUs in a bidentate mode that creates the 3676 cm-1 locked hydroxy-aqua node signature.
Caveat: Assignment relies on DRIFTS signatures and prior literature for NU-1000 node chemistry.
3 · Results and Discussion · Figure 2 · Linked to 2 structured results
TPP(Co)@NU-1000 suffers from thermodynamically unfavourable second-electron transfer because the TPP(Co) Co(I/0) potential is far more negative than the NU-1000 reduction potential.
Caveat: Redox potentials of Co species were taken from homogeneous DMF measurements and converted/reported against RHE.
4 · Results and Discussion · Linked to 4 structured results
Charge delivery from NU-1000 to the installed molecular catalyst, rather than CO2 adsorption or local environment, is the determinant factor for the different CO selectivities.
Caveat: Electrocatalysis occurs on composite electrodes with carbon/Nafion for many measurements; the CA Dhop analysis used binder-free films to reduce this complication.
5 · Results and Discussion · Linked to 6 structured results
Installed CoPc can participate in the charge-hopping pathway as a redox relay, increasing Dhop and lowering MOF charge-transfer resistance.
Caveat: The authors note they cannot exclude CoPc-CoPc redox hopping at 0.5 CoPc per node loading.
5 · Results and Discussion · Linked to 6 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| CoPc-COOH | Not specifiedCo(II) phthalocyanine centre · carboxyphthalocyanine ligand | 0D · UnknownMolecular cobalt phthalocyanine catalyst precursor for SALI installation. | 4 · Synthetic procedure of cobalt porphyrin and phthalocyanine · Figure SCh2 |
| CoPc@NU-1000 | Not specifiedZr(IV)6-oxo SBUs bearing node-installed CoPc-carboxylate · TBAPy framework linkers plus carboxyphthalocyanine cobalt(II) guest catalyst | 3D · CompositeSALI-installed cobalt phthalocyanine macrocycle anchored at Zr-oxo nodes in NU-1000 mesopores. | 2 · Results and Discussion · Figure 1 |
| NU-1000 | Not specifiedZr(IV)6-oxo secondary building units · carboxy-terminated tetraphenylpyrene, TBAPy | 3D · PristineHydrolytically stable pyrene-based zirconium MOF with 1D mesopore channels along the c axis. | 1 · Introduction |
| TPP(Co)-COOH | Not specifiedCo(II) porphyrin centre · 2-((4'-carboxylic)phenyl)-5,10,15,20-tetraphenylporphyrin | 0D · UnknownMolecular cobalt porphyrin catalyst precursor for SALI installation. | 3 · Synthetic procedure of cobalt porphyrin and phthalocyanine · Scheme S1 |
| TPP(Co)@NU-1000 | Not specifiedZr(IV)6-oxo SBUs bearing node-installed TPP(Co)-carboxylate · TBAPy framework linkers plus carboxyphenyl tetraphenylporphyrin cobalt(II) guest catalyst | 3D · CompositeSALI-installed cobalt tetraphenylporphyrin macrocycle anchored at Zr-oxo nodes in NU-1000 mesopores. | 2 · Results and Discussion · Figure 1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| CoPc-COOHresearch_0383__mat__mat_copc_cooh | Powder · Composite Component · Unknown | molecular catalyst precursor | 4 · Synthetic procedure |
| CoPc@NU-1000-h binder-free CA electroderesearch_0383__mat__mat_copc_nu1000 | Electrode · Composite Sample · Guest Loaded | drop-cast MOF catalyst dispersed in water/isopropanol without Nafion or carbon blackgraphite sheet electrode | 5 · Electrochemistry |
| CoPc@NU-1000-h carbon/Nafion electroderesearch_0383__mat__mat_copc_nu1000 | Electrode · Composite Sample · Composite | drop-cast MOF ink with carbon black and Nafiongraphite sheet electrode | 5 · Electrochemistry |
| CoPc@NU-1000-hresearch_0383__mat__mat_copc_nu1000 | Powder · Target Sample · Guest Loaded | high CoPc loading SALI powder | 2 · Results and Discussion |
| CoPc@NU-1000-l binder-free CA electroderesearch_0383__mat__mat_copc_nu1000 | Electrode · Composite Sample · Guest Loaded | drop-cast MOF catalyst dispersed in water/isopropanol without Nafion or carbon blackgraphite sheet electrode | 5 · Results and Discussion · Figure 6d |
| CoPc@NU-1000-l carbon/Nafion electroderesearch_0383__mat__mat_copc_nu1000 | Electrode · Composite Sample · Composite | drop-cast MOF ink with carbon black and Nafiongraphite sheet electrode | 5 · Electrochemistry |
| CoPc@NU-1000-lresearch_0383__mat__mat_copc_nu1000 | Powder · Target Sample · Guest Loaded | low CoPc loading SALI powder | 2 · Results and Discussion |
| PM6 model of CoPc@NU-1000research_0383__mat__mat_copc_nu1000 | Model · Model System · Model | truncated NU-1000 segment with CoPc-COOH anchored to Zr-oxo SBU | 6 · Computational methods |
| PM6 model of TPP(Co)@NU-1000research_0383__mat__mat_tppco_nu1000 | Model · Model System · Model | truncated NU-1000 segment with TPP(Co)-COOH anchored to Zr-oxo SBU | 6 · Computational methods |
| activated NU-1000research_0383__mat__mat_nu1000 | Powder · Pristine Control · Pristine Framework | microcrystalline NU-1000 activated by removal of phenyl-benzoate modulators | 2 · Results and Discussion |
| NU-1000 carbon/Nafion electroderesearch_0383__mat__mat_nu1000 | Electrode · Pristine Control · Composite | NU-1000 with carbon black and Nafion on graphite sheetgraphite sheet electrode | 6 · Results and Discussion · Figure 7 |
| TPP(Co)-COOHresearch_0383__mat__mat_tppco_cooh | Powder · Composite Component · Unknown | molecular catalyst precursor | 3 · Synthetic procedure |
| TPP(Co)@NU-1000 binder-free CA electroderesearch_0383__mat__mat_tppco_nu1000 | Electrode · Composite Sample · Guest Loaded | drop-cast MOF catalyst dispersed in water/isopropanol without Nafion or carbon blackgraphite sheet electrode | 4 · Results and Discussion · Figure 6d |
| TPP(Co)@NU-1000 carbon/Nafion electroderesearch_0383__mat__mat_tppco_nu1000 | Electrode · Composite Sample · Composite | drop-cast MOF ink with carbon black and Nafiongraphite sheet electrode | 5 · Electrochemistry |
| TPP(Co)@NU-1000research_0383__mat__mat_tppco_nu1000 | Powder · Target Sample · Guest Loaded | SALI powder | 4 · Synthesis of molecular catalyst installed NU-1000 |