Synthesis · Bismuth-based conductive MOF/COF hybrids enable efficient electrochemical heavy metal ion quantification

6 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Drop Cast

4 · 2.4

Metal precursorsBi-HHTP/COF suspension contains Bi(III) sites

Linker precursorsBi-HHTP/COF hybrid

SolventsDMF suspension; ultrapure water and ethanol sonication during GCE pretreatment

Additivesalumina slurry for polishing

Atmosphereair drying at room temperature

Temperatureroom temperature drying; infrared lamp drying temperature not reported

Timenot reported

Substrate orientationglassy carbon electrode, d = 3 mm

Oxidant / reductantnone reported

Work-upGCE polished with 1.0 to 0.05 um alumina slurry, sonicated in ultrapure water and ethanol, air-dried; 3 uL suspension drop-cast; dried under infrared lamp

Activationinfrared-lamp drying

Scalability contextSmall-area drop-cast electrode fabrication only.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Bi-HHTP/COF	3 uL suspension · 3 mg mL-1	4 · 2.4
Solvent	DMF	not reported · suspension solvent	4 · 2.4
Other	glassy carbon electrode	d = 3 mm	4 · 2.4
Additive	alumina slurry	not reported · 1.0 to 0.05 um	4 · 2.4
Solvent	ultrapure water	not reported	4 · 2.4
Solvent	ethanol	not reported	4 · 2.4

Partial recipeSource: Main

Route 2: Other

4 · 2.3.3

Metal precursorsBi-HHTP component contains Bi(III)

Linker precursorspreformed Bi-HHTP and preformed TPB-DVA COF

SolventsDMF

Additivesnone reported

Atmospherenot reported

Temperaturenot reported; ultrasonication likely room temperature

Time1 h ultrasonication

Oxidant / reductantnone reported

Work-upnot reported in main text

Activationnot reported in main text

Scalability contextMass ratios varied; optimal sensing ratio reported as Bi-HHTP:COF = 1:1.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Bi-HHTP	different mass ratios; optimal 1:1 reported in Results	4 · 2.3.3
Other	COF	different mass ratios; optimal 1:1 reported in Results	4 · 2.3.3
Solvent	DMF	not reported	4 · 2.3.3

Partial recipeSource: Main

Route 3: Drop Cast

4 · 2.4

Metal precursorsBi-HHTP contains Bi(III)

Linker precursorsBi-HHTP

SolventsDMF presumed by similar method

Additivesalumina slurry for GCE polishing

Atmosphereair drying at room temperature

Temperaturenot reported

Timenot reported

Substrate orientationglassy carbon electrode, d = 3 mm

Oxidant / reductantnone reported

Work-upprepared by similar drop-cast method to Bi-HHTP/COF/GCE

Activationinfrared-lamp drying presumed by similar method

Scalability contextControl electrode only.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Bi-HHTP	not separately reported · similar method	4 · 2.4
Other	glassy carbon electrode	d = 3 mm	4 · 2.4

Partial recipeSource: Main

Route 4: Solvothermal

4 · 2.3.1

Metal precursorsBismuth (III) acetate (186 mg)

Linker precursors2,3,6,7,10,11-hexahydroxytriphenylene (80 mg)

SolventsDI water (80 mL); deionized water workup (150 mL)

Additivesnone reported

Atmospherenot reported

Temperature85 C reaction; 50 C aqueous washing/stirring; vacuum drying temperature not reported

Time12 h stirring before autoclave; overnight reaction; 24 h stirred workup; 12 h vacuum drying

Oxidant / reductantnone reported

Work-upcentrifuged 6000 rpm 6 min; suspended in 150 mL DI water; heated/stirred 24 h with water changed every 6 h; centrifuged 8000 rpm 6 min

Activationvacuum drying for 12 h

Scalability contextDescribed as high-yield in conclusions but no isolated yield or scale-up test reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Bismuth (III) acetate	186 mg	4 · 2.3.1
Linker	2,3,6,7,10,11-hexahydroxytriphenylene	80 mg	4 · 2.3.1
Solvent	DI water	80 mL	4 · 2.3.1
Solvent	deionized water	150 mL	4 · 2.3.1

Partial recipeSource: Main

Route 5: Drop Cast

4 · 2.4

Metal precursorsnone

Linker precursorsCOF

SolventsDMF presumed by similar method

Additivesalumina slurry for GCE polishing

Atmosphereair drying at room temperature

Temperaturenot reported

Timenot reported

Substrate orientationglassy carbon electrode, d = 3 mm

Oxidant / reductantnone reported

Work-upprepared by similar drop-cast method to Bi-HHTP/COF/GCE

Activationinfrared-lamp drying presumed by similar method

Scalability contextControl electrode only.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	COF	not separately reported · similar method	4 · 2.4
Other	glassy carbon electrode	d = 3 mm	4 · 2.4

Partial recipeSource: Main

Route 6: Solvothermal

4 · 2.3.2

Metal precursorsnone

Linker precursorsTPB (0.252 g); DVA (0.2 g)

Solvents100 mL o-dichlorobenzene/n-butanol mixture, volume ratio 1/1

Additives2 mL acetic acid (6 M)

Atmospherenitrogen atmosphere

Temperature110 C reaction; 80 C drying

Time48 h reaction; 24 h drying

Oxidant / reductantnone reported

Work-upwashed with ethanol

Activationdrying at 80 C for 24 h

Scalability contextNo yield or scale-up test reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,3,5-tris(4-aminophenyl) benzene (TPB)	0.252 g	4 · 2.3.2
Linker	4-benzenedicarboxaldehyde (DVA)	0.2 g	4 · 2.3.2
Solvent	o-dichlorobenzene/n-butanol	100 mL · volume ratio 1/1	4 · 2.3.2
Acid	acetic acid	2 mL · 6 M	4 · 2.3.2
Solvent	ethanol	not reported · washing solvent	4 · 2.3.2