cMOF Evidence Base

Synthesis evidence

Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO2 Reduction

Li X., Surendran Rajasree S., Gude V. et al. · Angewandte Chemie - International Edition · 2023 · e202219046

9 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

5 · Fabrication of MOF-assembled working electrode

Metal precursorsMOF catalyst containing 0.5 umol molecular catalyst
Solventswater/isopropanol mixed solvent, 2:1
Work-upDisperse catalyst in water/isopropanol and drop-cast on graphite sheet electrode
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherMOF catalystsame as described above5 · Fabrication of MOF-assembled working electrode
Solventwater and isopropanol2:15 · Fabrication of MOF-assembled working electrode
Complete recipeSource: SI

Route 2: Other

4 · Synthetic procedure of cobalt porphyrin and phthalocyanine

Metal precursorscobalt acetate tetrahydrate, 12 g, 0.05 mol
Linker precursorstrimellitic anhydride; phthalic anhydride
Solventsnitrobenzene, 100 mL; KOH aqueous solution; DMF/acetone 3:1 chromatography solvent
Additivesurea; ammonium molybdate; 0.5 M HCl wash; 2 M HCl acidification
Temperature200
Time15 h initial reflux; 24 h KOH reflux
Work-upFilter dark purple solid; wash sequentially with ethyl ether, 0.5 M HCl, MeOH, and water; reflux in 1 M KOH; acidify to pH 2; filter; wash with water; purify by column chromatography using DMF/acetone 3:1
Show 8 structured reagent records
RoleReagentAmount / concentrationSource
Linkertrimellitic anhydride1.2 g (6.25 mmol)4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Linkerphthalic anhydride6.5 g (43.9 mmol)4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Additiveurea30 g (0.5 mol)4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Metal Sourcecobalt acetate tetrahydrate12 g (0.05 mol)4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Additiveammonium molybdate0.25 g (1.3 mmol)4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Solventnitrobenzene100 mL4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
BaseKOH solution100 mL · 1 M aq4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
AcidHCl2 M4 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Complete recipeSource: SI

Route 3: Other

4 · Synthesis of molecular catalyst installed NU-1000

Metal precursorsactivated NU-1000; CoPc-COOH
Linker precursorsCoPc-COOH; NU-1000 TBAPy framework
SolventsDMF, 4 mL for CoPc-COOH solution; acetone wash
Temperature80
Time72
Work-upCentrifugation; thorough DMF washing; acetone washing three times; vacuum drying at room temperature
ActivationActivated NU-1000 used as starting framework
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherCoPc-COOH20 mg (0.036 mmol)4 · Synthesis of molecular catalyst installed NU-1000
Otheractivated NU-100080 mg4 · Synthesis of molecular catalyst installed NU-1000
SolventDMF4 mL4 · Synthesis of molecular catalyst installed NU-1000
Solventacetone3 washes4 · Synthesis of molecular catalyst installed NU-1000
Partial recipeSource: SI

Route 4: Other

4 · Synthesis of molecular catalyst installed NU-1000

Metal precursorsactivated NU-1000; CoPc-COOH
Linker precursorsCoPc-COOH; NU-1000 TBAPy framework
SolventsDMF; acetone wash
Temperature80
Time72
Work-upSame as CoPc@NU-1000-H: centrifugation; DMF washing; acetone washing; vacuum drying at room temperature
ActivationActivated NU-1000 used as starting framework
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherCoPc-COOH10 mg of CoPc-COOH (20 mg, 0.036 mmol) was used instead4 · Synthesis of molecular catalyst installed NU-1000
Otheractivated NU-1000same as CoPc@NU-1000-H4 · Synthesis of molecular catalyst installed NU-1000
SolventDMFNot specified4 · Synthesis of molecular catalyst installed NU-1000
SolventacetoneNot specified4 · Synthesis of molecular catalyst installed NU-1000
Complete recipeSource: SI

Route 5: Drop Cast

5 · Fabrication of MOF-assembled working electrode

Metal precursorsMOF catalyst containing 0.5 umol molecular catalyst
SolventsNafion solution, 80 uL, 5%
Additivescarbon black powder, 2 mg
Work-upUltrasonic dispersion; drop-cast 10 uL ink over 1 cm x 1 cm deposition area on graphite sheet electrode
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherMOF catalystcalculated amount containing 0.5 umol molecular catalysts5 · Fabrication of MOF-assembled working electrode
Additivecarbon black powder2 mg5 · Fabrication of MOF-assembled working electrode
AdditiveNafion solution80 uL · 5%5 · Fabrication of MOF-assembled working electrode
Vague recipeSource: Both

Route 6: Solvothermal

2 · Results and Discussion

SolventsHCl-DMSO solution for modulator removal
Additivesphenyl-benzoate modulators removed
Temperatureroom temperature
ActivationTreat as-synthesised NU-1000 with HCl-DMSO solution at room temperature
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
SolventDMSONot specified2 · Results and Discussion
AcidHClNot specified2 · Results and Discussion
Partial recipeSource: SI

Route 7: Other

3 · Synthetic procedure of cobalt porphyrin and phthalocyanine

Metal precursorscobalt chloride hexahydrate, 310 mg, 1.3 mmol
Linker precursorsTPPH2-COOEt, 100 mg, 0.13 mmol
SolventsDMF, 30 mL; CHCl3 for redissolution; DCM chromatography eluent
Atmosphereargon
Temperaturereflux
Timeovernight
Work-upCool to room temperature; add water to precipitate; filter; wash with water 3 times; redissolve in CHCl3; column chromatography with pure DCM
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTPPH2-COOEt100 mg (0.13 mmol)3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Metal Sourcecobalt chloride hexahydrate310 mg (1.3 mmol)3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
SolventDMF30 mL3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
SolventCHCl3Not specified3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
SolventDCMNot specified3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Complete recipeSource: SI

Route 8: Other

3 · Synthetic procedure of cobalt porphyrin and phthalocyanine

Metal precursorsTPP(Co)-COOEt cobalt porphyrin intermediate
SolventsTHF/MeOH 1:1, 20 mL total; water 20 mL
AdditivesKOH, 308 mg in 10 mL aqueous solution; 0.5 M HCl to pH 2
Temperaturereflux
Timeovernight
Work-upRemove organic solvents under vacuum; add water; acidify to pH 2; collect precipitate by filtration; wash with water twice; dry under vacuum
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherTPP(Co)-COOEt90 mg (0.11 mmol)3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
BaseKOH308 mg (5.5 mmol) · in 10 mL aqueous solution3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
SolventTHF and MeOH20 mL · 1:1 volume ratio3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
AcidHCl0.5 M3 · Synthetic procedure of cobalt porphyrin and phthalocyanine
Complete recipeSource: SI

Route 9: Other

4 · Synthesis of molecular catalyst installed NU-1000

Metal precursorsactivated NU-1000; TPP(Co)-COOH
Linker precursorsTPP(Co)-COOH; NU-1000 TBAPy framework
SolventsDMF, 5 mL for TPP(Co)-COOH plus 5 mL for NU-1000; acetone wash
Temperature80
Time72
Work-upCentrifugation; thorough DMF washing; acetone washing five times; vacuum drying at room temperature
ActivationActivated NU-1000 used as starting framework
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OtherTPP(Co)-COOH45 mg (0.054 mmol)4 · Synthesis of molecular catalyst installed NU-1000
Otheractivated NU-1000100 mg (0.045 mmol SBU)4 · Synthesis of molecular catalyst installed NU-1000
SolventDMF10 mL total4 · Synthesis of molecular catalyst installed NU-1000
Solventacetonefive washes4 · Synthesis of molecular catalyst installed NU-1000