Synthesis · Drawing sensors with ball-milled blends of metal-organic frameworks and graphite

14 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

3 of 17 · Materials 2.2 · Figure 1B

Solventsnone

Additivesgraphite

Atmosphereambient conditions

Temperatureroom temperature

Time5 min milling; 1 min compression

Work-upball milled in 5 mL steel jar with two 4 mm steel balls at 30 Hz; compressed in 6 mm die at 6.9 MPa for 1 min; 3 mm cylinder also compressed at 1.7 MPa for 1 min

Scalability context90 mg MOF plus 10 mg graphite; 9:1 by mass

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pure Co3HHTP2 MOF	90 mg	3 of 17 · Materials 2.2 · Figure 1B
Additive	99.995% pure graphite, average particle size 2-15 um	10 mg	3 of 17 · Materials 2.2 · Figure 1B

Complete recipeSource: Both

Route 2: Other

5-6 of 17 · Results 3.1 · Table S1; Figure S4

Atmosphereambient

Temperatureroom temperature

Time1 min

Work-upMOF powder compressed into 6 mm pellet

Scalability contextabout 90 mg powder per pellet

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Co3HHTP2 powder	~90 mg	5-6 of 17 · Results 3.1 · Table S1; Figure S4

Complete recipeSource: Main

Route 3: Hydrothermal

3 of 17 · Materials 2.1 · Figure 1A

Metal precursorsCo acetate, 1.23 mmol

Linker precursorsHHTP, 0.62 mmol

Solventsdeionized water, 28 mL; water and acetone washes

Atmospherenot specified; ambient air implied

Temperature85

Time24 h after 10 min sonication; 2 h cooling

Work-upvacuum filtration; washed with deionized water (3 x 50 mL) and acetone (3 x 50 mL)

Activationdried overnight under reduced pressure (4000 Pa) at 85 C

Scalability contextgeneral 100 mL round-bottom flask procedure; SI absent so any SI refinements are not checked

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co acetate	1.23 mmol	3 of 17 · Materials 2.1 · Figure 1A
Linker	2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)	0.62 mmol	3 of 17 · Materials 2.1 · Figure 1A
Solvent	deionized water	28 mL; wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A
Solvent	acetone	wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A

Complete recipeSource: Both

Route 4: Other

3 of 17 · Materials 2.2 · Figure 1B

Solventsnone

Additivesgraphite

Atmosphereambient conditions

Temperatureroom temperature

Time5 min milling; 1 min compression

Work-upball milled in 5 mL steel jar with two 4 mm steel balls at 30 Hz; compressed in 6 mm die at 6.9 MPa for 1 min; 3 mm cylinder also compressed at 1.7 MPa for 1 min

Scalability context90 mg MOF plus 10 mg graphite; 9:1 by mass

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pure Cu3HHTP2 MOF	90 mg	3 of 17 · Materials 2.2 · Figure 1B
Additive	99.995% pure graphite, average particle size 2-15 um	10 mg	3 of 17 · Materials 2.2 · Figure 1B

Complete recipeSource: Both

Route 5: Other

10-11 of 17 · Results 3.4.4 · Figures S18-S19

Metal precursorsCu acetate-derived Cu3HHTP2

Linker precursorsHHTP

Solventswater for MOF synthesis; none for ball milling

Additivesgraphite

Atmosphereambient for storage/fabrication unless otherwise noted

Temperature85 for MOF synthesis; room temperature for milling and sensing

Time24 h MOF synthesis; 5 min milling

Substrate orientationpaper devices with gold electrodes

Work-uptwo independently prepared 200 mg-scale HHTP batches; each 90 mg Cu3HHTP2 ball milled with 10 mg graphite and abraded into devices

Scalability contextbatch-to-batch and scale-dependent variants: 200 mg and 800 mg HHTP scales

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3HHTP2	90 mg for blending; prepared on 200 mg or 800 mg HHTP scale	10-11 of 17 · Results 3.4.4 · Figures S18-S19
Additive	graphite	10 mg	10-11 of 17 · Results 3.4.4 · Figures S18-S19

Complete recipeSource: Both

Route 6: Other

5-6 of 17 · Results 3.1 · Table S1; Figure S4

Atmosphereambient

Temperatureroom temperature

Time1 min

Work-upMOF powder compressed into 6 mm pellet

Scalability contextabout 90 mg powder per pellet

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Cu3HHTP2 powder	~90 mg	5-6 of 17 · Results 3.1 · Table S1; Figure S4

Complete recipeSource: Main

Route 7: Hydrothermal

3 of 17 · Materials 2.1 · Figure 1A

Metal precursorsCu acetate, 1.23 mmol

Linker precursorsHHTP, 0.62 mmol

Solventsdeionized water, 28 mL; water and acetone washes

Atmospherenot specified; ambient air implied

Temperature85

Time24 h after 10 min sonication; 2 h cooling

Work-upvacuum filtration; washed with deionized water (3 x 50 mL) and acetone (3 x 50 mL)

Activationdried overnight under reduced pressure (4000 Pa) at 85 C

Scalability contextgeneral 100 mL round-bottom flask procedure; SI absent so any SI refinements are not checked

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu acetate	1.23 mmol	3 of 17 · Materials 2.1 · Figure 1A
Linker	2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)	0.62 mmol	3 of 17 · Materials 2.1 · Figure 1A
Solvent	deionized water	28 mL; wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A
Solvent	acetone	wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A

Complete recipeSource: Both

Route 8: Other

3 of 17 · Materials 2.2 · Figure 1B

Solventsnone

Additivesgraphite

Atmosphereambient conditions

Temperatureroom temperature

Time5 min milling; 1 min compression

Work-upball milled in 5 mL steel jar with two 4 mm steel balls at 30 Hz; compressed in 6 mm die at 6.9 MPa for 1 min; 3 mm cylinder also compressed at 1.7 MPa for 1 min

Scalability context90 mg MOF plus 10 mg graphite; 9:1 by mass

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pure Fe3HHTP2 MOF	90 mg	3 of 17 · Materials 2.2 · Figure 1B
Additive	99.995% pure graphite, average particle size 2-15 um	10 mg	3 of 17 · Materials 2.2 · Figure 1B

Complete recipeSource: Both

Route 9: Other

5-6 of 17 · Results 3.1 · Table S1; Figure S4

Atmosphereambient

Temperatureroom temperature

Time1 min

Work-upMOF powder compressed into 6 mm pellet

Scalability contextabout 90 mg powder per pellet

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Fe3HHTP2 powder	~90 mg	5-6 of 17 · Results 3.1 · Table S1; Figure S4

Complete recipeSource: Main

Route 10: Hydrothermal

3 of 17 · Materials 2.1 · Figure 1A

Metal precursorsFe acetate, 1.23 mmol

Linker precursorsHHTP, 0.62 mmol

Solventsdeionized water, 28 mL; water and acetone washes

Atmospherenot specified; ambient air implied

Temperature85

Time24 h after 10 min sonication; 2 h cooling

Work-upvacuum filtration; washed with deionized water (3 x 50 mL) and acetone (3 x 50 mL)

Activationdried overnight under reduced pressure (4000 Pa) at 85 C

Scalability contextgeneral 100 mL round-bottom flask procedure; SI absent so any SI refinements are not checked

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Fe acetate	1.23 mmol	3 of 17 · Materials 2.1 · Figure 1A
Linker	2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)	0.62 mmol	3 of 17 · Materials 2.1 · Figure 1A
Solvent	deionized water	28 mL; wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A
Solvent	acetone	wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A

Complete recipeSource: Both

Route 11: Other

3-4 and 8 of 17 · Materials 2.3 / Results 3.3 · Figure 1B; Figures S1-S2

Solventsnone

Atmosphereambient during abrasion; dry N2 during sensing

Temperatureroom temperature

Timemanual abrasion; gas exposure 5 min and recovery 10 min during tests

Substrate orientationpaper substrate with evaporated gold electrodes, 1 mm gap

Work-up6 mm pellet pulled along device with 1-5 N force; 3 mm pellet in pencil holder also used; avoid deposition outside electrode gaps

Scalability context15 paper devices per chip; four blends in triplicate plus graphite control

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	M3HHTP2/graphite blended pellet	6 mm pellet or 3 mm pellet	3-4 and 8 of 17 · Materials 2.3 / Results 3.3 · Figure 1B; Figures S1-S2
Other	paper device with gold electrodes	15 devices per chip · 1 mm gap	3-4 and 8 of 17 · Materials 2.3 / Results 3.3 · Figure 1B; Figures S1-S2

Complete recipeSource: Both

Route 12: Other

3 of 17 · Materials 2.2 · Figure 1B

Solventsnone

Additivesgraphite

Atmosphereambient conditions

Temperatureroom temperature

Time5 min milling; 1 min compression

Work-upball milled in 5 mL steel jar with two 4 mm steel balls at 30 Hz; compressed in 6 mm die at 6.9 MPa for 1 min; 3 mm cylinder also compressed at 1.7 MPa for 1 min

Scalability context90 mg MOF plus 10 mg graphite; 9:1 by mass

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pure Ni3HHTP2 MOF	90 mg	3 of 17 · Materials 2.2 · Figure 1B
Additive	99.995% pure graphite, average particle size 2-15 um	10 mg	3 of 17 · Materials 2.2 · Figure 1B

Complete recipeSource: Both

Route 13: Other

5-6 of 17 · Results 3.1 · Table S1; Figure S4

Atmosphereambient

Temperatureroom temperature

Time1 min

Work-upMOF powder compressed into 6 mm pellet

Scalability contextabout 90 mg powder per pellet

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Ni3HHTP2 powder	~90 mg	5-6 of 17 · Results 3.1 · Table S1; Figure S4

Complete recipeSource: Main

Route 14: Hydrothermal

3 of 17 · Materials 2.1 · Figure 1A

Metal precursorsNi acetate, 1.23 mmol

Linker precursorsHHTP, 0.62 mmol

Solventsdeionized water, 28 mL; water and acetone washes

Atmospherenot specified; ambient air implied

Temperature85

Time24 h after 10 min sonication; 2 h cooling

Work-upvacuum filtration; washed with deionized water (3 x 50 mL) and acetone (3 x 50 mL)

Activationdried overnight under reduced pressure (4000 Pa) at 85 C

Scalability contextgeneral 100 mL round-bottom flask procedure; SI absent so any SI refinements are not checked

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni acetate	1.23 mmol	3 of 17 · Materials 2.1 · Figure 1A
Linker	2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)	0.62 mmol	3 of 17 · Materials 2.1 · Figure 1A
Solvent	deionized water	28 mL; wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A
Solvent	acetone	wash 3 x 50 mL	3 of 17 · Materials 2.1 · Figure 1A