Castner A.T., Johnson B.A., Cohen S.M. et al. · Journal of the American Chemical Society · 2021 · 7991-7999
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 authors claim this is the first MOF that contains both an enzyme active-site model and an energy-matched redox mediator, mimicking the separated catalytic and electron-transport functions in [FeFe] hydrogenases.
Caveat: Novelty claim is author-stated; database extraction did not independently verify all prior literature.
p007 / article p.7997 · Conclusions · Linked to 5 structured results
PCN-700_NDI_FeFe composite electrodes generate detectable H2 under aqueous controlled-potential electrolysis, substantially above the carbon black/Nafion blank.
Caveat: HER was explicitly described as not the main focus; no turnover frequency or Faradaic efficiency was reported in the extracted documents.
p006 / article p.7996 · Electrochemical Characterization in the Presence of Acid · Figures S33-S35 · Linked to 4 structured results
The low BET surface area and Type IV hysteretic isotherm of PCN-700_NDI_FeFe may arise from Fe2 complex degradation during 85 C activation and consequent pore clogging.
Caveat: This is an author-proposed explanation in the SI, not directly proven.
p019 / SI p.19 · BET analysis · Figure S17 · Linked to 2 structured results
AcOH changes the PCN-700_NDI_FeFe voltammogram in a way consistent with proton-coupled Fe2 redox chemistry, while PCN-700_NDI_ta does not show the same anodic second-wave response.
Caveat: The overall second-wave charge remains below the expected three-electron response.
p006 / article p.7996 · Electrochemical Characterization in the Presence of Acid · Figure 5 · Linked to 3 structured results
Charge transport in PCN-700_NDI_FeFe is nonlinear: successive charging leads to attractive interactions, restricted counterion mobility, and apparent diffusion coefficients that are not constant.
Caveat: Transport inference is from voltammetric response in composite electrodes rather than direct solid-state conductivity.
p001 / article p.7991 · Abstract · Linked to 9 structured results
The FeFe linker contribution overlaps with the second NDI reduction, and not all expected reductions are visible because the MOF has limited electron and counterion uptake capacity.
Caveat: Assignment relies on comparison to homogeneous linkers and integrated CV charge rather than direct spectroelectrochemical identification inside the MOF.
p005 / article p.7995 · Electrochemical Characterization · Figures 3, S29 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| carbon black/Nafion blank electrode ink | carbon black plus Nafion binder | unknown · CompositeNon-MOF electrode background control. | p021 / SI p.21 · Electrolysis for HER |
| [FeFe](dcbdt)(CO)6 | [FeFe](dcbdt)(CO)6Molecular diiron carbonyl active-site mimic · dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate | 0D · Model SystemMolecular [FeFe] hydrogenase active-site model and dicarboxylated linker for SLI into PCN-700_NDI. | p002 / article p.7992 · Introduction · Figure 1b |
| NDI-OMe | Naphthalene diimide-N,N-bis(propanoate methyl ester)Molecular NDI model compound | 0D · Model SystemHomogeneous molecular redox-active NDI model used for electrochemical comparison. | p004 / SI p.4 · Linker Synthesis and Characterization · Figure S5 |
| PCN-700 | Zr6O4(OH)8(H2O)4 SBUs with Me2dpdc linkersZr6O4(OH)8(H2O)4 secondary building units · Me2dpdc = 2,2'-dimethyldiphenyl-4,4'-dicarboxylate | 3D · PristinePCN-700 is an 8-connected Zr-MOF related to UiO-67, with four linker-vacant pockets per node set that can be filled by sequential linker installation. | p002 / article p.7992 · Synthesis and Characterization · Figure 1b |
| PCN-700_NDI | PCN-700 with NDI-COOH installed into large linker-vacant pocketsZr6O4(OH)8(H2O)4 secondary building units · Me2dpdc plus naphthalene diimide-N,N-bis(propanoate) linker | 3D · PristinePostsynthetically inserted NDI linker in PCN-700; NMR shows partial occupation of vacant sites. | p003 / article p.7993 · Synthesis and Characterization · Figure S10, Table S1 |
| PCN-700_NDI_FeFe | PCN-700 with NDI linker and [FeFe](dcbdt)(CO)6 linker installedZr6O4(OH)8(H2O)4 secondary building units · Me2dpdc, NDI-COOH, and [FeFe](dcbdt)(CO)6 where dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate | 3D · PristineBiomimetic dual-functional PCN-700 framework placing NDI mediator and FeFe active-site mimic in predetermined pockets. | p004 / article p.7994 · Synthesis and Characterization · Figures 2, S7, S8 |
| PCN-700_NDI_ta | PCN-700 with NDI and terephthalate linkers installedZr6O4(OH)8(H2O)4 secondary building units · Me2dpdc, NDI-COOH, and ta = terephthalic acid/terephthalate | 3D · PristineDual-linker PCN-700 control containing NDI mediator and terephthalate instead of FeFe active-site linker. | p003 / article p.7993 · Synthesis and Characterization · Figure S11, Table S1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| carbon black/Nafion blank carbon-mesh electroderesearch_0180__mat__binder_blank | Electrode · Pristine Control · Composite | Background ink without MOF, composed only of carbon black and Nafion, deposited for HER blank comparison.carbon mesh paper | p021 / SI p.21 · Electrolysis for HER · Figure S34 |
| [FeFe](dcbdt)(CO)6 homogeneous solutionresearch_0180__mat__fefe_dcbdt_model | Model · Model System · Model | 1 mM solution in DMF with 0.5 M KPF6; sparged with Ar before CV.glassy carbon working electrode for solution CV | p023 / SI p.23 · MOF-modified Electrode Preparation and Electrochemical Characterization · Figure S24 |
| NDI-OMe homogeneous solutionresearch_0180__mat__ndi_ome_model | Model · Model System · Model | 1 mM solution in DMF with 0.5 M KPF6; sparged with Ar before CV.glassy carbon working electrode for solution CV | p002 / SI p.2 · General Materials and Methods · Figure S23 |
| PCN-700_NDI_FeFe MOF/carbon black/Nafion carbon-mesh HER electroderesearch_0180__mat__pcn_700_ndi_fefe | Electrode · Composite Sample · Composite | 40 uL MOF ink painted onto approximately 1 cm2 carbon mesh electrode and dried overnight in air.carbon mesh paper, approximately 1 x 2 cm; approximately 1 cm2 coated area | p021 / SI p.21 · Electrolysis for HER · Figures S33-S35 |
| PCN-700_NDI_FeFe MOF/carbon black/Nafion glassy-carbon electroderesearch_0180__mat__pcn_700_ndi_fefe | Electrode · Composite Sample · Composite | Ink of 1 mg MOF and 4 mg carbon black in 0.5 mL 2-propanol containing 0.5% v/v Nafion 117; sonicated at least 20 min, 10 uL drop-cast, dried in air overnight.7 mm glassy carbon disc | p021 / SI p.21 · MOF-modified Electrode Preparation |
| PCN-700_NDI_FeFe powderresearch_0180__mat__pcn_700_ndi_fefe | Powder · Target Sample · Guest Loaded | PCN-700_NDI treated with [FeFe](dcbdt)(CO)6 in degassed water at room temperature under Ar in the dark for 24 h; washed with degassed water and acetone until wash solvent was colourless. | p012 / SI p.12 · MOF Preparation and Characterization · Figures S7, S17, S18, S21, S26-S36 |
| PCN-700_NDI powderresearch_0180__mat__pcn_700_ndi | Powder · Pristine Control · Guest Loaded | PCN-700 dried under vacuum, treated with NDI-COOH in DMF at 75 C for 24 h, then Soxhlet-extracted with acetone. | p012 / SI p.12 · MOF Preparation and Characterization · Figure S10 |
| PCN-700_NDI_ta MOF/carbon black/Nafion glassy-carbon electroderesearch_0180__mat__pcn_700_ndi_ta | Electrode · Composite Sample · Composite | Ink of 1 mg MOF and 4 mg carbon black in 0.5 mL 2-propanol containing 0.5% v/v Nafion 117; sonicated at least 20 min, 10 uL drop-cast, dried in air overnight.7 mm glassy carbon disc | p021 / SI p.21 · MOF-modified Electrode Preparation |
| PCN-700_NDI_ta powderresearch_0180__mat__pcn_700_ndi_ta | Powder · Pristine Control · Guest Loaded | PCN-700_NDI dried under vacuum, treated with terephthalic acid in DMF at room temperature for 24 h, then Soxhlet-extracted with acetone. | p012 / SI p.12 · MOF Preparation and Characterization · Figures S11, S15, S16, S20, S25 |
| PCN-700 MOF powder/crystalsresearch_0180__mat__pcn_700 | Powder · Pristine Control · Pristine Framework | Solvothermal PCN-700 crystals washed with fresh DMF and stored in DMF until use; dried under vacuum for subsequent insertion or characterisation. | p012 / SI p.12 · MOF Preparation and Characterization · Figures S7, S9, S13, S14, S19 |