Synthesis · Immobilization of N-(3-aminopropyl)-imidazole through MOFs in proton conductive membrane for elevated temperature anhydrous applications

4 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2

Metal precursorsFeCl3.6H2O (540.6 mg, 2.0 mmol)

Linker precursorsdimethyl aminoterephthalate (0.324 g, 1.5 mmol)

SolventsDMF (15 mL for linker solution + 15 mL for FeCl3 solution); CH2Cl2 wash; CHCl3 storage; hot ethanol activation

Additivesnone reported; route avoided HF mineralizer

Atmospherenot specified

Temperature110 deg C synthesis; 100 deg C DMF treatment; 80 deg C hot ethanol treatment

Time24 h synthesis; 8 h DMF treatment; 8 h hot ethanol treatment; overnight vacuum drying

Work-upcooled below 2 deg C/min, filtered, washed with DMF and CH2Cl2 several times, dried under vacuum at room temperature overnight

Activationtreated with DMF at 100 deg C and hot ethanol at 80 deg C for 8 h each; activated by guest exchange and stored in CHCl3

Scalability contextBatch autoclave powder synthesis; no scale-up data reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl3.6H2O	540.6 mg; 2.0 mmol	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2
Linker	dimethyl aminoterephthalate	0.324 g; 1.5 mmol	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2
Solvent	DMF	30 mL total	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2
Solvent	CH2Cl2	wash, several times	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2
Solvent	ethanol	hot ethanol activation	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2
Solvent	CHCl3	storage solvent	p002 · 2.2.1 Synthesis of activated Fe-MIL-101-NH2

Complete recipeSource: Main

Route 2: Other

p002 · 2.2.2 Preparation of MOFs>NAPI

Metal precursorsactivated Fe-MIL-101-NH2 MOFs (200 mg)

Linker precursorsN-(3-aminopropyl)-imidazole (NAPI, 1 mL)

Solventsneat NAPI; no separate solvent reported

Atmospherenot specified

Temperatureroom temperature adsorption; 150 deg C vacuum drying

Time60 min stirring; 24 h vacuum drying

Work-upsolid collected by centrifuge and dried under vacuum (1.2 x 10^-1 mbar) at 150 deg C for 24 h

Activationactivated MOFs were used from route_fe_mil101_nh2_solvothermal

Scalability contextImmersion/adsorption of powder into liquid NAPI; no scale-up data reported.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MOFs	200 mg	p002 · 2.2.2 Preparation of MOFs>NAPI
Additive	N-(3-aminopropyl)-imidazole (NAPI)	1 mL	p002 · 2.2.2 Preparation of MOFs>NAPI

Complete recipeSource: SI

Route 3: Other

p001 · SI 1 Leaching of NAPI from MOFs

Metal precursorsMOFs>NAPI (100 mg)

Linker precursorsresidual NAPI in Fe-MIL-101-NH2

SolventsCHCl3 (100 mL soak; ca. 5-10 mL wash)

Atmospherenot specified

Temperatureroom temperature

Time1 h soak; overnight vacuum drying

Work-upcentrifuged off, washed by CHCl3, dried under vacuum at room temperature overnight

Scalability contextLeaching/retention test only.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOFs>NAPI	100 mg	p001 · SI 1 Leaching of NAPI from MOFs
Solvent	CHCl3	100 mL soak; ca. 5-10 mL wash	p001 · SI 1 Leaching of NAPI from MOFs

Partial recipeSource: Main

Route 4: Drop Cast

p002 · 2.2.3 Preparation of PEMs

Metal precursorsMOFs>NAPI or MOFs/MOFs>NAPI powder

Linker precursorsSPPO; PPO-SO2Cl intermediate; NAPI in MOF; NaOH

SolventsDMF; thionyl chloride-DMF reflux medium; NMP; water; 1 M HCl aqueous solution

AdditivesNaOH solution (0.1 mol/L); HCl (1 M) post-treatment

Atmospherenot specified

Temperaturereflux for chlorosulfonylation; 80 deg C solvent evaporation; 60 deg C heat treatment and vacuum drying; room temperature HCl treatment

Time20 min ultrasonication; 3 days stirring; 12 h at 80 deg C; 2 h at 60 deg C; 24 h in 1 M HCl

Substrate orientationcast onto flat glass

Work-upfiltered and washed after chlorosulfonylation; membrane removed by flushing with distilled water, heated, acid-treated, washed with DI water and vacuum-dried

Activationfinal vacuum drying at 60 deg C

Scalability contextSolution-cast membrane; no casting area or precise component masses reported for membrane formulations.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	SPPO	not specified	p002 · 2.2.3 Preparation of PEMs
Solvent	DMF	not specified	p002 · 2.2.3 Preparation of PEMs
Other	thionyl chloride	not specified	p002 · 2.2.3 Preparation of PEMs
Other	PPO-SO2Cl	not specified	p002 · 2.2.3 Preparation of PEMs
Solvent	NMP	not specified	p002 · 2.2.3 Preparation of PEMs
Other	MOFs/MOFs>NAPI	6% encapsulated MOFs for typical conductivity sample; exact mass not specified	p002 · 2.2.3 Preparation of PEMs
Base	NaOH solution	not specified · 0.1 mol/L	p002 · 2.2.3 Preparation of PEMs
Acid	HCl aqueous solution	24 h treatment · 1 M	p002 · 2.2.3 Preparation of PEMs