Synthesis · High Proton Mobility with High Directionality in Isolated Channels of MOF-74

6 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

S-5 · Section S2 / Preparation of purely H2O-coordinating Co-MOF-74

Metal precursorspristine Co-MOF-74(Co) crystal sample (0.03 g)

Linker precursorsframework already formed; DOBDC-derived linker

SolventsMeOH (20 mL per exchange), DCM, DDW (10 mL)

Additivesnone reported

Atmospherestored in moisture-free argon-filled glove box prior to use; exchange atmosphere not specified

Temperature60 for MeOH exchange; room temperature for DCM treatment; H2O coordination temperature not specified

TimeMeOH exchange 1 h repeated 6 times; DCM treatment 1 h repeated 7 times; DDW coordination 1 h

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcollected by filtration and dried under vacuum prior to use

ActivationDMF coordination exchanged to MeOH, MeOH removed by DCM, then H2O coordinated at open Co2+ sites

Scalability contextReported for 0.03 g pristine-MOF-74(Co) crystal sample.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pristine-MOF-74(Co) crystal sample	0.03 g	S-5 · Section S2 / Preparation of purely H2O-coordinating Co-MOF-74
Solvent	methanol (MeOH, 99.5%, Daejung)	20 mL	S-5 · Section S2 / Preparation of purely H2O-coordinating Co-MOF-74
Solvent	dichloromethane (DCM, 99.5%, Daejung)	not specified	S-5 · Section S2 / Preparation of purely H2O-coordinating Co-MOF-74
Solvent	distilled deionized water (DDW)	10 mL	S-5 · Section S2 / Preparation of purely H2O-coordinating Co-MOF-74

Complete recipeSource: Both

Route 2: Other

S-5 to S-6 · Section S2 / Base treatment

Metal precursorsH2O-coordinated Co-MOF-74 crystals (0.03 g)

Linker precursorsframework already formed; DOBDC-derived linker

Solvents20 mL pH-adjusted aqueous solution

AdditivesNH4OH solution diluted with DDW at pH 11

Atmosphereambient air drying; treatment atmosphere not otherwise specified

Temperaturenot specified (treatment solution shaken for 1 h)

Time1

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcollected by filtration and dried under ambient air

ActivationpH-control treatment with NH4OH solution diluted with DDW at pH 11

Scalability contextReported for 0.03 g H2O-coordinated crystals in 20 mL solution.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2O-coordinated Co-MOF-74 crystals	0.03 g	S-5 to S-6 · Section S2 / Base treatment
Base	NH4OH solution diluted with DDW at pH 11	20 mL · preadjusted to pH 11	S-5 to S-6 · Section S2 / Base treatment

Complete recipeSource: Both

Route 3: Other

S-5 to S-6 · Section S2 / Acid treatment

Metal precursorsH2O-coordinated Co-MOF-74 crystals (0.03 g)

Linker precursorsframework already formed; DOBDC-derived linker

Solvents20 mL pH-adjusted aqueous solution

AdditivesH2SO4 solution diluted with DDW at pH 3

Atmosphereambient air drying; treatment atmosphere not otherwise specified

Temperaturenot specified (treatment solution shaken for 1 h)

Time1

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcollected by filtration and dried under ambient air

ActivationpH-control treatment with H2SO4 solution diluted with DDW at pH 3

Scalability contextReported for 0.03 g H2O-coordinated crystals in 20 mL solution.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2O-coordinated Co-MOF-74 crystals	0.03 g	S-5 to S-6 · Section S2 / Acid treatment
Acid	H2SO4 solution diluted with DDW at pH 3	20 mL · preadjusted to pH 3	S-5 to S-6 · Section S2 / Acid treatment

Complete recipeSource: Both

Route 4: Other

S-5 to S-6 · Section S2 / Acid treatment

Metal precursorsH2O-coordinated Co-MOF-74 crystals (0.03 g)

Linker precursorsframework already formed; DOBDC-derived linker

Solvents20 mL pH-adjusted aqueous solution

AdditivesH2SO4 solution diluted with DDW at pH 5

Atmosphereambient air drying; treatment atmosphere not otherwise specified

Temperaturenot specified (treatment solution shaken for 1 h)

Time1

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcollected by filtration and dried under ambient air

ActivationpH-control treatment with H2SO4 solution diluted with DDW at pH 5

Scalability contextReported for 0.03 g H2O-coordinated crystals in 20 mL solution.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2O-coordinated Co-MOF-74 crystals	0.03 g	S-5 to S-6 · Section S2 / Acid treatment
Acid	H2SO4 solution diluted with DDW at pH 5	20 mL · preadjusted to pH 5	S-5 to S-6 · Section S2 / Acid treatment

Complete recipeSource: Both

Route 5: Other

S-5 to S-6 · Section S2 / Base treatment

Metal precursorsH2O-coordinated Co-MOF-74 crystals (0.03 g)

Linker precursorsframework already formed; DOBDC-derived linker

Solvents20 mL pH-adjusted aqueous solution

AdditivesNH4OH solution diluted with DDW at pH 9

Atmosphereambient air drying; treatment atmosphere not otherwise specified

Temperaturenot specified (treatment solution shaken for 1 h)

Time1

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcollected by filtration and dried under ambient air

ActivationpH-control treatment with NH4OH solution diluted with DDW at pH 9

Scalability contextReported for 0.03 g H2O-coordinated crystals in 20 mL solution.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2O-coordinated Co-MOF-74 crystals	0.03 g	S-5 to S-6 · Section S2 / Base treatment
Base	NH4OH solution diluted with DDW at pH 9	20 mL · preadjusted to pH 9	S-5 to S-6 · Section S2 / Base treatment

Complete recipeSource: SI

Route 6: Solvothermal

S-5 · Section S2 / Synthesis of Co-MOF-74

Metal precursorsCo(NO3)2.6H2O (0.1189 g, 0.4084 mmol)

Linker precursors2,5-dihydroxyterephthalic acid / DOBDC (0.0482 g, 0.2433 mmol)

SolventsDMF (6.67 mL) for cobalt nitrate; EtOH (6.67 mL) and DDW (6.67 mL) for DOBDC

Additivesnone reported

Atmospheresealed 100 mL glass bottle with PTFE tape; atmosphere not otherwise specified

Temperature100

Time24

Substrate orientationnone

Oxidant / reductantnone reported

Work-upcooled to room temperature, collected, and washed with DMF

Activationnone at this stage; subsequent MeOH/DCM/H2O coordination exchange used for H2O-coordinated samples

Scalability context0.03 g crystal batches used for later exchange/treatment; no scale-up information reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cobalt (II) nitrate (Co(NO3)2.6H2O, >=98%, Aldrich)	0.1189 g, 0.4084 mmol	S-5 · Section S2 / Synthesis of Co-MOF-74
Linker	2,5-dihydroxyterephthalic acid (DOBDC, 97%, Alfa Aesar)	0.0482 g, 0.2433 mmol	S-5 · Section S2 / Synthesis of Co-MOF-74
Solvent	N,N-dimethylformamide (DMF, 99.5%, Daejung)	6.67 mL	S-5 · Section S2 / Synthesis of Co-MOF-74
Solvent	ethanol (EtOH, 94.5%, Daejung)	6.67 mL	S-5 · Section S2 / Synthesis of Co-MOF-74
Solvent	distilled deionized water (DDW)	6.67 mL	S-5 · Section S2 / Synthesis of Co-MOF-74