cMOF Evidence Base

Synthesis evidence

Mimicking the Electron Transport Chain and Active Site of [FeFe] Hydrogenases in One Metal-Organic Framework: Factors That Influence Charge Transport

Castner A.T., Johnson B.A., Cohen S.M. et al. · Journal of the American Chemical Society · 2021 · 7991-7999

7 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: SI

Route 1: Drop Cast

p021 / SI p.21 · Electrolysis for HER

Solvents2-propanol in MOF ink
Additivescarbon black and Nafion 117
Atmosphereair drying
Temperatureroom temperature
Timeovernight drying
Substrate orientationcarbon mesh paper cut to approximately 1 x 2 cm; approximately 1 cm2 coated
Work-upSame MOF ink preparation as GC electrode; 40 uL painted onto carbon mesh and dried overnight in air.
ActivationDried overnight in air.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN_NDI_FeFe MOF ink40 uL paintedp021 / SI p.21 · Electrolysis for HER
Additivecarbon blackin inkp021 / SI p.21 · Electrolysis for HER
AdditiveNafionin inkp021 / SI p.21 · Electrolysis for HER
Complete recipeSource: SI

Route 2: Drop Cast

p021 / SI p.21 · MOF-modified Electrode Preparation

Solvents2-propanol (0.5 mL)
Additivescarbon black (4 mg), 0.5% v/v Nafion 117
Atmosphereair drying
Temperatureroom temperature
Timeovernight drying after at least 20 min sonication
Substrate orientationpolished 7 mm glassy carbon disc; working area exposed using Teflon tape
Work-upGC electrodes polished with alumina down to 0.05 um, rinsed, sonicated in EtOH for 3 min, dried, then coated with 10 uL ink.
ActivationDried in air overnight.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN-700_NDI_FeFe1 mgp021 / SI p.21 · MOF-modified Electrode Preparation
Additivecarbon black4 mgp021 / SI p.21 · MOF-modified Electrode Preparation
Solvent2-propanol0.5 mLp021 / SI p.21 · MOF-modified Electrode Preparation
AdditiveNafion 1170.5% v/vp021 / SI p.21 · MOF-modified Electrode Preparation
Complete recipeSource: SI

Route 3: Drop Cast

p021 / SI p.21 · MOF-modified Electrode Preparation

Solvents2-propanol (0.5 mL)
Additivescarbon black (4 mg), 0.5% v/v Nafion 117
Atmosphereair drying
Temperatureroom temperature
Timeovernight drying after at least 20 min sonication
Substrate orientationpolished 7 mm glassy carbon disc; working area exposed using Teflon tape
Work-upGC electrodes polished with alumina down to 0.05 um, rinsed, sonicated in EtOH for 3 min, dried, then coated with 10 uL ink.
ActivationDried in air overnight.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN-700_NDI_ta1 mgp021 / SI p.21 · MOF-modified Electrode Preparation
Additivecarbon black4 mgp021 / SI p.21 · MOF-modified Electrode Preparation
Solvent2-propanol0.5 mLp021 / SI p.21 · MOF-modified Electrode Preparation
AdditiveNafion 1170.5% v/vp021 / SI p.21 · MOF-modified Electrode Preparation
Complete recipeSource: Both

Route 4: Other

p012 / SI p.12 · SLI 2.2: [FeFe](dcbdt)(CO)6 into PCN_NDI

Metal precursorsPreformed PCN-700_NDI plus molecular [FeFe](dcbdt)(CO)6 linker
Linker precursors[FeFe](dcbdt)(CO)6 (4 eq in SI; 2 eq in main text)
SolventsDegassed H2O (8 mL); degassed acetone wash
AtmosphereAr, dark, deoxygenated solvent
Temperatureroom temperature
Time24
Work-upAfter incorporation, suspended in fresh degassed H2O for at least 3 h in the dark three times; then washed with degassed acetone in the dark until no colour observed in wash solvent.
ActivationPCN-700_NDI dried under vacuum before insertion; BET activation at 85 C may degrade Fe2 complex.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN-700_NDI (dried under vacuum)Not specifiedp012 / SI p.12 · SLI 2.2: [FeFe](dcbdt)(CO)6 into PCN_NDI
Linker[FeFe](dcbdt)(CO)64 eq in SI; 2 eq in main textp012 / SI p.12 · SLI 2.2: [FeFe](dcbdt)(CO)6 into PCN_NDI
Solventdegassed H2O8 mLp012 / SI p.12 · SLI 2.2: [FeFe](dcbdt)(CO)6 into PCN_NDI
Solventdegassed acetonewash solventp012 / SI p.12 · SLI 2.2: [FeFe](dcbdt)(CO)6 into PCN_NDI
Complete recipeSource: Both

Route 5: Other

p012 / SI p.12 · SLI 1: NDI-COOH into PCN-700

Metal precursorsPreformed PCN-700
Linker precursorsNDI-COOH (10 eq)
SolventsDMF (8 mL); Soxhlet extraction with acetone
Temperature75
Time24
Work-upPCN-700 dried under vacuum, suspended with NDI-COOH in DMF by gentle aspiration; after incubation, Soxhlet extracted with acetone for at least 18 h.
ActivationPCN-700 dried under vacuum before insertion.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN-700 (dried under vacuum)Not specifiedp012 / SI p.12 · SLI 1: NDI-COOH into PCN-700
LinkerNDI-COOH10 eq in SI; 5 eq per desired vacant site in main textp012 / SI p.12 · SLI 1: NDI-COOH into PCN-700
SolventDMF8 mLp012 / SI p.12 · SLI 1: NDI-COOH into PCN-700
SolventacetoneSoxhlet extraction solventp012 / SI p.12 · SLI 1: NDI-COOH into PCN-700
Complete recipeSource: Both

Route 6: Other

p012 / SI p.12 · SLI 2.1: ta into PCN-700_NDI

Metal precursorsPreformed PCN-700_NDI
Linker precursorsterephthalic acid (ta, 4 eq in SI; 2 eq per desired vacant site in main text)
SolventsDMF (8 mL); Soxhlet extraction with acetone
Temperatureroom temperature
Time24
Work-upPCN-700_NDI dried under vacuum, suspended with ta in DMF by gentle aspiration; stirred at RT for 24 h; Soxhlet extracted with acetone for at least 18 h.
ActivationPCN-700_NDI dried under vacuum before insertion.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherPCN-700_NDI (dried under vacuum)Not specifiedp012 / SI p.12 · SLI 2.1: ta into PCN-700_NDI
Linkerta4 eq in SI; 2 eq per desired vacant site in main textp012 / SI p.12 · SLI 2.1: ta into PCN-700_NDI
SolventDMF8 mLp012 / SI p.12 · SLI 2.1: ta into PCN-700_NDI
SolventacetoneSoxhlet extraction solventp012 / SI p.12 · SLI 2.1: ta into PCN-700_NDI
Complete recipeSource: Both

Route 7: Solvothermal

p012 / SI p.12 · PCN-700 MOF Preparation

Metal precursorsZrCl4 (0.120 g, 0.51 mmol)
Linker precursorsMe2dpdc linker (0.180 g, 0.67 mmol)
SolventsDMF (11.45 mL)
AdditivesTFA (0.55 mL, 7.18 mmol)
Temperature120
Time72
Work-upMixture sonicated, 2 mL aliquots charged into 4 mL vials; resulting crystals washed with fresh DMF three times and stored in DMF.
ActivationBulk powder samples dried under active vacuum at room temperature prior to measurements; BET samples activated at 85 C under active vacuum (1 x 10^-4 Pa).
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl40.120 g, 0.51 mmolp012 / SI p.12 · PCN-700 MOF Preparation
LinkerMe2dpdc linker (2)0.180 g, 0.67 mmolp012 / SI p.12 · PCN-700 MOF Preparation
SolventDMF11.45 mLp012 / SI p.12 · PCN-700 MOF Preparation
AcidTFA0.55 mL, 7.18 mmolp012 / SI p.12 · PCN-700 MOF Preparation