Synthesis · Missing-Linker 2D Conductive Metal Organic Frameworks for Rapid Gas Detection

8 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

2 · Synthesis of missing-linker M-HAB

Metal precursorsCo(NO3)2.6H2O, 0.072 mmol

Linker precursorsoxidized HAB, 0.035 mmol aqueous solution, 5 mL

Solventsaqueous reaction medium; DI water and methanol washes

Additivestriethylamine, 4 vol% aqueous solution, 5 mL

AtmosphereHAB oxidized in air; dried under nitrogen; activated under vacuum

Temperature30 deg C ligand oxidation; 100 deg C activation

Time240 h ligand oxidation; 12 h reaction; 12 h activation

Oxidant / reductantair/O2 slow oxidation of HAB ligand

Work-upcentrifuged, decanted, washed with DI water and then methanol three times

Activationdried at room temperature under nitrogen, then vacuum activated at 100 deg C for 12 h

Scalability contextSame M-HAB procedure as aNi-HAB; scale-up not discussed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	0.072 mmol	2 · Synthesis of missing-linker M-HAB
Linker	oxidized HAB	0.035 mmol in 5 mL aqueous solution	2 · Synthesis of missing-linker M-HAB
Base	triethylamine	5 mL · 4 vol% aqueous solution	2 · Synthesis of missing-linker M-HAB

Complete recipeSource: SI

Route 2: Other

2 · Synthesis of missing-linker M-HAB

Metal precursorsCuCl2.2H2O, 0.072 mmol

Linker precursorsoxidized HAB, 0.035 mmol aqueous solution, 5 mL

Solventsaqueous reaction medium; DI water and methanol washes

Additivestriethylamine, 4 vol% aqueous solution, 5 mL

AtmosphereHAB oxidized in air; dried under nitrogen; activated under vacuum

Temperature30 deg C ligand oxidation; 100 deg C activation

Time240 h ligand oxidation; 12 h reaction; 12 h activation

Oxidant / reductantair/O2 slow oxidation of HAB ligand

Work-upcentrifuged, decanted, washed with DI water and then methanol three times

Activationdried at room temperature under nitrogen, then vacuum activated at 100 deg C for 12 h

Scalability contextSame M-HAB procedure as aNi-HAB; scale-up not discussed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuCl2.2H2O	0.072 mmol	2 · Synthesis of missing-linker M-HAB
Linker	oxidized HAB	0.035 mmol in 5 mL aqueous solution	2 · Synthesis of missing-linker M-HAB
Base	triethylamine	5 mL · 4 vol% aqueous solution	2 · Synthesis of missing-linker M-HAB

Complete recipeSource: Both

Route 3: Other

2 · Synthesis of missing-linker M-HAB

Metal precursorsFe(NO3)3.9H2O, 0.072 mmol in SI; main text lists Fe(NO3)3.6H2O

Linker precursorsoxidized HAB, 0.035 mmol aqueous solution, 5 mL

Solventsaqueous reaction medium; DI water and methanol washes

Additivestriethylamine, 4 vol% aqueous solution, 5 mL

AtmosphereHAB oxidized in air; dried under nitrogen; activated under vacuum

Temperature30 deg C ligand oxidation; 100 deg C activation

Time240 h ligand oxidation; 12 h reaction; 12 h activation

Oxidant / reductantair/O2 slow oxidation of HAB ligand

Work-upcentrifuged, decanted, washed with DI water and then methanol three times

Activationdried at room temperature under nitrogen, then vacuum activated at 100 deg C for 12 h

Scalability contextSame M-HAB procedure as aNi-HAB; scale-up not discussed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Fe(NO3)3.9H2O	0.072 mmol	2 · Synthesis of missing-linker M-HAB
Linker	oxidized HAB	0.035 mmol in 5 mL aqueous solution	2 · Synthesis of missing-linker M-HAB
Base	triethylamine	5 mL · 4 vol% aqueous solution	2 · Synthesis of missing-linker M-HAB

Complete recipeSource: SI

Route 4: Drop Cast

3 · Fabrication of the sensory devices · Figure S2

Metal precursorspre-synthesized aNi-HAB sample

Linker precursorscontained in pre-synthesized aNi-HAB

Solventsdeionized water dispersion, 0.5 mg/mL

Atmosphereambient device fabrication; sensing under dry N2/analyte mixtures

Temperature80 deg C pre-test hotplate treatment

Time0.167 h pre-test hotplate treatment

Substrate orientationSi chip with pre-patterned Ti-Au (20/50 nm) electrodes

Work-updrop-cast to form chemiresistive device

Activationtreated at 80 deg C on hotplate for 10 min before each sensing test

Scalability contextDevice-level drop-casting; film thickness/volume not reported.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	aNi-HAB dispersion	0.5 mg/mL · 0.5 mg/mL	3 · Fabrication of the sensory devices · Figure S2

Complete recipeSource: Both

Route 5: Other

2 · Synthesis of missing-linker M-HAB

Metal precursorsNiCl2.6H2O, 0.072 mmol

Linker precursorsoxidized HAB, 0.035 mmol aqueous solution, 5 mL; oxidized by keeping HAB in air at 30 deg C for 10 days

Solventswater from aqueous triethylamine and oxidized HAB solutions; DI water and methanol washes

Additivestriethylamine, 4 vol% aqueous solution, 5 mL

AtmosphereHAB oxidation in air; dried under nitrogen protection; activated under vacuum

Temperature30 deg C ligand oxidation; room temperature precipitation/drying; 100 deg C activation

Time240 h ligand oxidation; 12 h reaction; 12 h activation

Oxidant / reductantair/O2 slow oxidation of HAB ligand

Work-upcentrifuged, decanted, washed with DI water and then methanol three times

Activationdried at room temperature under nitrogen, then vacuum activated at 100 deg C for 12 h

Scalability contextSimple vial precipitation without stirring; scale-up not discussed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2.6H2O	0.072 mmol	2 · Synthesis of missing-linker M-HAB
Linker	oxidized HAB	0.035 mmol in 5 mL aqueous solution	2 · Synthesis of missing-linker M-HAB
Base	triethylamine	5 mL · 4 vol% aqueous solution	2 · Synthesis of missing-linker M-HAB
Oxidant	air/O2	10 days exposure · ambient air	2 · Synthesis of missing-linker M-HAB

Complete recipeSource: Both

Route 6: Hydrothermal

2-3 · Preparation of Crystalline Ni-HAB

Metal precursorsNi(NO3)2.6H2O, 0.055 mmol

Linker precursorsHAB.3HCl, 0.036 mmol in 2 mL degassed H2O

Solventsdegassed H2O; methanol storage/wash

Additives0.4 mL of 14 M NH4OH in 2 mL degassed H2O

Atmospheredegassed water; loosely capped vial

Temperature65

Time2

Work-upcentrifuged, decanted, washed with 5 mL deionized water three times and 5 mL methanol three times

Activationkept in 3 mL methanol; no vacuum activation reported for cNi-HAB

Scalability contextSmall scintillation-vial synthesis; scale-up not discussed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	0.055 mmol	2-3 · Preparation of Crystalline Ni-HAB
Linker	HAB.3HCl	0.036 mmol in 2 mL degassed H2O	2-3 · Preparation of Crystalline Ni-HAB
Base	NH4OH	0.4 mL in 2 mL degassed H2O · 14 M	2-3 · Preparation of Crystalline Ni-HAB

Partial recipeSource: SI

Route 7: Drop Cast

3 · Fabrication of the sensory devices

Metal precursorspre-synthesized cNi-HAB sample

Linker precursorscontained in pre-synthesized cNi-HAB

Solventsdevice dispersion solvent not separately specified; fabricated as above

Atmosphereambient device fabrication; sensing under dry N2/analyte mixtures

Temperature80 deg C pre-test hotplate treatment

Time0.167 h pre-test hotplate treatment

Substrate orientationSi chip with pre-patterned Ti-Au (20/50 nm) electrodes

Work-upfabricated as for aNi-HAB sensory device

Activationtreated at 80 deg C on hotplate for 10 min before each sensing test

Scalability contextDevice-level drop-casting; volume/thickness not reported.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	cNi-HAB dispersion	not separately reported · fabricated as above	3 · Fabrication of the sensory devices

Partial recipeSource: Main

Route 8: Other

433 · Relative humidity detection · Figure 4a,b

Metal precursorsaNi-HAB film device

Linker precursorscontained in aNi-HAB; Nafion perfluorosulfonate layer added

SolventsNafion deposition solvent not reported

AdditivesNafion mass fractions tested; 1% optimal

Atmospherenot reported

Substrate orientationas-prepared aNi-HAB MOF film on chemiresistive chip

Work-upNafion layer deposited on top of the MOF film

Activationnot reported beyond standard device pre-test treatment

Scalability contextFunctional overlayer concept; deposition method details are limited.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Additive	Nafion	1% mass fraction optimal; 0, 0.1, 0.5, 1% tested	433 · Relative humidity detection · Figure 4a,b