Synthesis · Mo-Based crystal POMOFs with a high electrochemical capacitor performance

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Hydrothermal

p002 / article p.13027 · Experimental - Synthesis of compound 1

Metal precursorsH3[PMo12O40].6H2O; Cu(Ac)2.2H2O

Linker precursorsbtx (C12H12N6)

SolventsH2O (15 mL); Mill-Q water used in work

Additivestriethylamine (TEA, C6H15N, 0.03 mL); pH adjusted with 1.0 M HCl/NaOH

Atmosphereautogenous pressure in 25 mL PTFE-lined stainless-steel container

Temperature160

Time72

Oxidant / reductantTEA acts as reductant to reduce Cu(II) to Cu(I), according to synthesis analysis

Work-upSlow cooling to room temperature at 10 C h-1; yellow block crystals filtered, washed with water, dried at room temperature

Activationnone reported beyond room-temperature drying

Scalability context25 mL Teflon-lined reactor; yield 40% based on Mo.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	H3[PMo12O40].6H2O	0.2320 g (0.12 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 1
Metal Source	Cu(Ac)2.2H2O	0.0479 g (0.24 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 1
Linker	btx (C12H12N6)	0.0433 g (0.18 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 1
Solvent	H2O	15 mL	p002 / article p.13027 · Experimental - Synthesis of compound 1
Base	triethylamine (TEA, C6H15N)	0.03 mL	p002 / article p.13027 · Experimental - Synthesis of compound 1
Acid	HCl/NaOH for pH adjustment	to pH 2.0 · 1.0 M	p002 / article p.13027 · Experimental - Synthesis of compound 1

Complete recipeSource: Main

Route 2: Hydrothermal

p002 / article p.13027 · Experimental - Synthesis of compound 2

Metal precursorsH3[PMo12O40].6H2O; CuCl

Linker precursorsbtx (C12H12N6)

SolventsH2O (15 mL)

AdditivespH adjusted with 1.0 M HCl/NaOH

Atmosphereautogenous pressure in 25 mL PTFE-lined stainless-steel container

Temperature160

Time72

Oxidant / reductantPOM is reduced while Cu(I) is oxidised to Cu(II), according to synthesis analysis

Work-upSlow cooling to room temperature at 10 C h-1; green block crystals filtered, washed with water, dried at room temperature

Activationnone reported beyond room-temperature drying

Scalability context25 mL Teflon-lined reactor; yield 46% based on Mo.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	H3[PMo12O40].6H2O	0.2320 g (0.12 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 2
Metal Source	CuCl	0.0238 g (0.24 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 2
Linker	btx	0.0433 g (0.18 mmol)	p002 / article p.13027 · Experimental - Synthesis of compound 2
Solvent	H2O	15 mL	p002 / article p.13027 · Experimental - Synthesis of compound 2
Acid	HCl/NaOH for pH adjustment	to pH 2.0 · 1.0 M	p002 / article p.13027 · Experimental - Synthesis of compound 2

Partial recipeSource: SI

Route 3: Hydrothermal

p005 · Supporting information - Synthesis of Cu-MOF · Figure S9-2

Metal precursorsCu(Ac)2.2H2O inferred from identical compound 1 method; POM omitted

Linker precursorsbtx

SolventsH2O; exact volume not restated in SI, inferred from compound 1 method

AdditivesTEA and pH-adjusting acid/base inferred from identical compound 1 method; POM omitted

Atmosphereautogenous pressure inferred from compound 1 method

Temperature160 inferred synthesis; 80 drying

Time72 inferred synthesis; 5 drying

Work-upGreen powder collected, washed with distilled water three times, dried at 80 C for 5 h

Activationnone beyond drying

Scalability contextControl preparation described only by reference to compound 1 route.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu source from compound 1 route, likely Cu(Ac)2.2H2O	not restated in SI	p005 · Supporting information - Synthesis of Cu-MOF · Figure S9-2
Linker	btx	not restated in SI	p005 · Supporting information - Synthesis of Cu-MOF · Figure S9-2
Solvent	H2O	not restated in SI	p005 · Supporting information - Synthesis of Cu-MOF · Figure S9-2
Base	TEA from compound 1 route, inferred	not restated in SI	p005 · Supporting information - Synthesis of Cu-MOF · Figure S9-2

Complete recipeSource: Main

Route 4: Drop Cast

p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes

Metal precursorscompound 1

Solventswater (0.5 mL)

Additivesacetylene black; Nafion solution

Atmosphereambient / room temperature

Temperatureroom temperature

Time4 total drying hours

Substrate orientationGCE surface, 3 mm diameter

Work-upSonicated slurry; 10 uL deposited onto GCE, dried 3 h; 2.5 uL Nafion deposited, dried 1 h

Activationnone reported

Scalability contextLaboratory drop-cast three-electrode preparation.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	compound 1	2.5 mg	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Additive	acetylene black	2.5 mg	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Solvent	water	0.5 mL	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Additive	Nafion solution	2.5 uL	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes

Complete recipeSource: Main

Route 5: Drop Cast

p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes

Metal precursorscompound 2

Solventswater (0.5 mL)

Additivesacetylene black; Nafion solution

Atmosphereambient / room temperature

Temperatureroom temperature

Time4 total drying hours

Substrate orientationGCE surface, 3 mm diameter

Work-upSonicated slurry; 10 uL deposited onto GCE, dried 3 h; 2.5 uL Nafion deposited, dried 1 h

Activationnone reported

Scalability contextLaboratory drop-cast three-electrode preparation.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	compound 2	2.5 mg	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Additive	acetylene black	2.5 mg	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Solvent	water	0.5 mL	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes
Additive	Nafion solution	2.5 uL	p002-p003 / article pp.13027-13028 · Experimental - Preparation of the working electrodes

Complete recipeSource: SI

Route 6: Other

p005 · Supporting information - Synthesis of PMo@TBAB · Figure S9-1

Metal precursorsPMo12 parent POM

Solventsdistilled water (20 mL + 5 mL)

Additivestetrabutylammonium bromide (TBAB)

Atmosphereambient, under stirring

Temperature80 drying

Time5 drying

Work-upSuspension filtered; precipitate collected, washed with distilled water three times, dried at 80 C for 5 h

Activationnone beyond drying

Scalability contextSmall-batch control preparation.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	PMo12	0.1160 g (0.06 mmol)	p005 · Supporting information - Synthesis of PMo@TBAB · Figure S9-1
Additive	tetrabutylammonium bromide (TBAB)	0.0580 g (0.18 mmol)	p005 · Supporting information - Synthesis of PMo@TBAB · Figure S9-1
Solvent	distilled water	20 mL + 5 mL	p005 · Supporting information - Synthesis of PMo@TBAB · Figure S9-1