cMOF Evidence Base

Synthesis evidence

Stabilization of Hexaaminobenzene in a 2D Conductive Metal-Organic Framework for High Power Sodium Storage

Park J., Lee M., Feng D. et al. · Journal of the American Chemical Society · 2018 · 10315-10323

8 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

main p.10321 · Experimental Section

Metal precursorsCobalt nitrate hexahydrate [Co(NO3)2.6H2O], 21.0 mg (0.072 mmol), dissolved in 6 mL water.
Linker precursorsHAB.3HCl, 10 mg (0.036 mmol), in 5 mL H2O, added before base.
SolventsWater: 6 mL cobalt solution plus 5 mL HAB solution.
AdditivesNH4OH, 6 M aqueous; 60 uL (0.36 mmol, 10 equiv to HAB) for Co-HAB-A10; 3-8 equiv for Co-HAB-A3 to Co-HAB-A8.
AtmosphereOpen air; stirring at 300 rpm.
TemperatureRT reaction; dried at 80 C
Time1 h reaction; 3 h drying unless otherwise noted
Substrate orientationnot_applicable
Oxidant / reductantOpen air; NH4OH used for deprotonation/partial oxidation after metal-linker complexation.
Work-upDark navy solids filtered and washed with copious water and acetone.
ActivationDried under vacuum at 80 C for 3 h unless otherwise noted.
Scalability contextBatch amounts are milligram-scale; authors report systematic variation of base equivalents to tune crystallinity and yield.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecobalt nitrate hexahydrate [Co(NO3)2.6H2O]21.0 mg (0.072 mmol) · in 6 mL watermain p.10321 · Experimental Section
LinkerHAB.3HCl10 mg (0.036 mmol) · in 5 mL H2Omain p.10321 · Experimental Section
Baseaqueous ammonium hydroxide (NH4OH)60 uL for A10; varied 3-8 equiv for other A-series samples · 6 Mmain p.10321 · Experimental Section
Solventwater11 mL totalmain p.10321 · Experimental Section
Complete recipeSource: SI

Route 2: Other

SI p.S4 · Effect of sequence of base addition · Fig. S1

Metal precursorsCobalt nitrate hexahydrate [Co(NO3)2.6H2O], 21.0 mg (0.072 mmol), dissolved in 6 mL water.
Linker precursorsHAB.3HCl, 10 mg (0.036 mmol), in 5 mL H2O.
SolventsWater: 6 mL for cobalt salt plus 5 mL for HAB.3HCl solution.
AdditivesNH4OH, 60 uL of 6 M aqueous solution (0.36 mmol, 10 equiv to HAB), added before linker.
AtmosphereAir; stirred at 300 rpm.
Temperatureroom temperature; dried at 80 C
Time1 h reaction; 3 h drying
Substrate orientationnot_applicable
Oxidant / reductantOpen air; base-assisted deprotonation/partial oxidation proposed generally.
Work-upFiltered, washed with copious water and acetone.
ActivationDried under vacuum at 80 C for 3 h.
Scalability contextSmall-vial scale only; route disfavoured because it yields Co(OH)2 impurity.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecobalt nitrate hexahydrate [Co(NO3)2.6H2O]21.0 mg (0.072 mmol) · in 6 mL waterSI p.S4 · Effect of sequence of base addition · Fig. S1
LinkerHAB.3HCl10 mg (0.036 mmol) · in 5 mL H2OSI p.S4 · Effect of sequence of base addition · Fig. S1
Baseaqueous ammonium hydroxide (NH4OH)60 uL (0.36 mmol; 10 equiv to HAB) · 6 MSI p.S4 · Effect of sequence of base addition · Fig. S1
Solventwater11 mL totalSI p.S4 · Effect of sequence of base addition · Fig. S1
Complete recipeSource: Both

Route 3: Solvothermal

SI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4

Metal precursorsCobalt nitrate hexahydrate [Co(NO3)2.6H2O], 105 mg (0.36 mmol).
Linker precursorsHAB.3HCl, 50 mg (0.18 mmol), in 5 mL H2O.
Solvents25 mL DMF and 20 mL water for cobalt solution, plus 5 mL H2O for HAB.3HCl; described as DMF/water mixture (1:1, v/v).
AdditivesNH4OH, 180 uL of 6 M aqueous solution (1.08 mmol, 6 equiv to HAB), added immediately after linker.
AtmosphereOpen air; stirring.
Temperature75 C reaction; 80 C drying
Time15 min preheat; 2 h reaction; 3 h drying
Substrate orientationnot_applicable
Oxidant / reductantOpen air; NH4OH base added immediately; no separate oxidant/reductant reported.
Work-upDark navy solids filtered and washed with copious amounts of water and acetone.
ActivationDried under vacuum at 80 C for 3 h.
Scalability contextMilligram-scale round-bottom-flask synthesis; DMF cosolvent chosen to slow MOF growth and improve crystallinity.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecobalt nitrate hexahydrate [Co(NO3)2.6H2O]105 mg (0.36 mmol) · in 25 mL DMF + 20 mL waterSI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4
LinkerHAB.3HCl50 mg (0.18 mmol) · in 5 mL H2OSI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4
Baseaqueous ammonium hydroxide (NH4OH)180 uL (1.08 mmol; 6 equiv to HAB) · 6 MSI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4
SolventN,N-dimethylformamide (DMF)25 mLSI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4
Solventwater25 mL totalSI p.S6 · Co-HAB Synthesis using mixed solvent · Fig. S4
Partial recipeSource: Both

Route 4: Other

main p.10321 · Experimental Section · Fig. 4

Metal precursorsCo-HAB powders as active material.
Linker precursorsCo-HAB powders as active material.
SolventsNMP slurry solvent implied by standard preparation; exact solvent not restated for high-loading route.
AdditivesPTFE binder instead of PVDF; carbon black retained at same 90:5:5 mass ratio.
AtmosphereVacuum drying; cell atmosphere not specified.
Temperature70 C drying if standard procedure was followed
Timeovernight drying if standard procedure was followed
Substrate orientationCu foil current collector
Oxidant / reductantNa metal anode/counter electrode during cell testing.
Work-upPrepared as high mass loading electrodes with PTFE binder, then tested in Na cells.
Activationnone beyond vacuum drying
Scalability contextActive mass loading increased from 1.3 to 9.6 mg cm^-2.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherCo-HAB powders90 wt% of electrode solidsmain p.10321 · Experimental Section · Fig. 4
Additivecarbon black5 wt%main p.10321 · Experimental Section · Fig. 4
AdditivePTFE binder5 wt%main p.10321 · Experimental Section · Fig. 4
Complete recipeSource: SI

Route 5: Other

SI p.S9 · Electrical conductivity measurement · Fig. S6

Metal precursorsAs-synthesised Co-HAB powder.
Linker precursorsAs-synthesised Co-HAB powder.
SolventsNone reported for pressing.
AdditivesNone reported.
AtmosphereEvacuated to ca. few 10^-4 mbar for 24 h before measurement.
Temperature25 C measurement
Time24 h evacuation before measurement
Substrate orientationglass slide during four-point probe measurement
Oxidant / reductantnone
Work-upCold isostatic pressing using MTI Corporation pressing equipment.
ActivationVacuum evacuation before measurement.
Scalability contextPellet geometry 3.175 mm diameter, 200-300 um thickness.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
OtherCo-HAB powderpellet, 3.175 mm diameterSI p.S9 · Electrical conductivity measurement · Fig. S6
Partial recipeSource: SI

Route 6: Drop Cast

SI p.S8 · UV-Vis-NIR spectrum of Co-HAB · Fig. S5

Metal precursorsAs-synthesised Co-HAB powder (metal precursor not used in this processing step).
Linker precursorsAs-synthesised Co-HAB powder.
SolventsWater dispersion.
AdditivesNone reported.
AtmosphereNot specified.
Temperatureroom temperature evaporation implied
Timenot specified
Substrate orientationquartz substrate
Oxidant / reductantnone
Work-upWater evaporated before measurement.
Activationnone reported
Scalability contextAnalytical film preparation only.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Otheras-synthesized Co-HABnot specifiedSI p.S8 · UV-Vis-NIR spectrum of Co-HAB · Fig. S5
Solventwaternot specifiedSI p.S8 · UV-Vis-NIR spectrum of Co-HAB · Fig. S5
Complete recipeSource: Both

Route 7: Other

SI p.S2 · Materials and instrumentation

Metal precursorsCo-HAB powders as active material.
Linker precursorsCo-HAB powders as active material.
SolventsN-methyl-2-pyrrolidone (NMP) added to slurry.
AdditivesCarbon black conductive additive (Super P, TIMCAL) and PVDF binder.
AtmosphereDried under vacuum; electrochemical cells assembled with Na metal and 1 M NaPF6/DEGDME electrolyte (assembly atmosphere not specified).
Temperature70 C drying; testing temperature not specified
Time1 h slurry stirring; overnight drying
Substrate orientationCu foil current collector; 1 cm2 circular disks
Oxidant / reductantNa metal anode/counter electrode during cell testing.
Work-upSlurry coated on Cu foil, dried at 70 C overnight under vacuum, cut into 1 cm2 disks.
Activationnone beyond vacuum drying
Scalability contextTypical electrode mass 1-1.5 mg.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
OtherCo-HAB powders90 wt% of electrode solidsSI p.S2 · Materials and instrumentation
Additivecarbon black conductive additive (Super P, TIMCAL)5 wt%SI p.S2 · Materials and instrumentation
AdditivePVDF binder5 wt%SI p.S2 · Materials and instrumentation
SolventN-methyl-2-pyrrolidone (NMP)added to mixtureSI p.S2 · Materials and instrumentation
ElectrolyteNaPF6 in diethylene glycol dimethyl ethercoin cell electrolyte · 1 MSI p.S2 · Materials and instrumentation
Vague recipeSource: Main

Route 8: Unknown

main p.10321 · Results and Discussion · Fig. S12

Metal precursorsNi source not specified in this paper.
Linker precursorsHAB implied by material name Ni-HAB; exact precursor not specified here.
SolventsNot specified; electrochemical testing conditions identical to Co-HAB are stated.
AdditivesElectrode formulation not specified; likely analogous Co-HAB electrode formulation but not explicitly stated.
AtmosphereNot specified.
Temperaturenot specified
Timenot specified
Substrate orientationNa half-cell electrode
Oxidant / reductantNa metal cell for testing.
Work-upnot specified
Activationnot specified
Scalability contextOnly electrochemical comparison reported.