Synthesis · Oxidatively Doped Tetrathiafulvalene-Based Metal-Organic Frameworks for High Specific Energy of Supercapatteries

9 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

p008 / 6628 · 4.1.3

Metal precursorssample 1 crystals

Linker precursorspy-TTF-py/BPDC framework in sample 1

Atmospheresealed large vial containing iodine chips; iodine vapour exposure

Temperatureroom temperature exposure; 60 degC vacuum post-treatment

Time48 h iodine vapour exposure; vacuum overnight

Oxidant / reductantiodine chips / iodine vapour oxidant

Work-upSmall vial removed from large vial; treated under vacuum at 60 degC overnight.

ActivationVacuum at 60 degC overnight after iodine exposure.

Scalability contextGravimetric analysis showed ca. 24% mass increase for 1-ox.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	crystals of 1	not reported	p008 / 6628 · 4.1.3
Oxidant	iodine chips	a few iodine chips	p008 / 6628 · 4.1.3

Partial recipeSource: Main

Route 2: Other

p003 / 6623 · 2.2 Characterization

Metal precursors1-ox

Linker precursorsiodine-treated Ni TTF-BPDC framework

Solventshexane

Atmospherevacuum after washing

Temperature60

Timeovernight

Work-upWashed with hexane repeatedly.

ActivationVacuum at 60 degC overnight.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	1-ox	not reported	p003 / 6623 · 2.2 Characterization
Solvent	hexane	not reported	p003 / 6623 · 2.2 Characterization

Complete recipeSource: Main

Route 3: Solvothermal

p008 / 6628 · 4.1.1

Metal precursorsNi(ClO4)2.6H2O (0.015 mmol, 5.4 mg)

Linker precursorspy-TTF-py (0.01 mmol, 3.6 mg); H2BPDC (0.015 mmol, 2.4 mg)

Solvents1.5 mL CH3CN-DMF mixed solvent, 1:2 by volume

Atmospheresealed thick glass tube; atmosphere not otherwise stated

Temperature120

Time72

Work-upCooled to room temperature; crystals isolated. Further workup not specified.

ActivationNone stated for pristine crystals.

Scalability contextYield 2.4 mg, 34.6% based on py-TTF-py.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(ClO4)2.6H2O	0.015 mmol, 5.4 mg	p008 / 6628 · 4.1.1
Linker	py-TTF-py	0.01 mmol, 3.6 mg	p008 / 6628 · 4.1.1
Linker	H2BPDC	0.015 mmol, 2.4 mg	p008 / 6628 · 4.1.1
Solvent	CH3CN-DMF	1.5 mL, 1:2 v/v	p008 / 6628 · 4.1.1

Partial recipeSource: Main

Route 4: Other

p008 / 6628 · 4.1.4

Metal precursorssample 2 crystals

Linker precursorspy-TTF-py/BPDC framework in sample 2

Atmospheresealed large vial containing iodine chips; iodine vapour exposure, inferred from stated similarity to 1-ox

Temperatureroom temperature exposure; 60 degC vacuum post-treatment, inferred from stated similarity to 1-ox

Time48 h iodine vapour exposure; vacuum overnight, inferred from stated similarity to 1-ox

Oxidant / reductantiodine chips / iodine vapour oxidant

Work-upSimilar to 1-ox; details not restated.

ActivationSimilar to 1-ox; vacuum at 60 degC overnight inferred.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	crystals of 2	not reported	p008 / 6628 · 4.1.4
Oxidant	iodine chips	not restated	p008 / 6628 · 4.1.4

Partial recipeSource: Main

Route 5: Other

p003 / 6623 · 2.2 Characterization

Metal precursors2-ox

Linker precursorsiodine-treated Zn TTF-BPDC framework

Solventshexane

Atmospherevacuum after washing

Temperature60

Timeovernight

Work-upWashed with hexane repeatedly.

ActivationVacuum at 60 degC overnight.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2-ox	not reported	p003 / 6623 · 2.2 Characterization
Solvent	hexane	not reported	p003 / 6623 · 2.2 Characterization

Complete recipeSource: Main

Route 6: Solvothermal

p008 / 6628 · 4.1.2

Metal precursorsZn(ClO4)2.6H2O (0.02 mmol, 7.4 mg)

Linker precursorspy-TTF-py (0.01 mmol, 3.6 mg); H2BPDC (0.015 mmol, 2.4 mg)

Solvents1.6 mL CH3CN-DMF mixed solvent, 1:1 by volume

Atmospheresealed thick glass tube; atmosphere not otherwise stated

Temperature120

Time72

Work-upCooled to room temperature; crystals isolated. Further workup not specified.

ActivationNone stated for pristine crystals.

Scalability contextYield 3.9 mg, 55.7% based on py-TTF-py.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(ClO4)2.6H2O	0.02 mmol, 7.4 mg	p008 / 6628 · 4.1.2
Linker	py-TTF-py	0.01 mmol, 3.6 mg	p008 / 6628 · 4.1.2
Linker	H2BPDC	0.015 mmol, 2.4 mg	p008 / 6628 · 4.1.2
Solvent	CH3CN-DMF	1.6 mL, 1:1 v/v	p008 / 6628 · 4.1.2

Complete recipeSource: SI

Route 7: Other

p007 · Electrochemical measurements · Eq. S1

Metal precursors1-ox positive electrode from iodine-doped Ni TTF-BPDC MOF

Linker precursorspy-TTF-py/BPDC framework in 1-ox positrode

Solvents6.0 M KOH aqueous electrolyte

Additivesactivated carbon negative electrode; fibre paper separator

Atmosphereambient assembly not otherwise specified

Temperatureroom temperature measurement

Substrate orientationelectrode coating area 0.5 cm x 0.5 cm for two-electrode configuration

Oxidant / reductantnot applicable

Work-updevice assembled with charge-balanced positive and negative electrodes according to Eq. S1

Activationnone stated beyond electrode vacuum drying

Scalability contextMass ratio balanced by q+ = q- using C x m x deltaV.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	1-ox positive electrode	mass balanced according to Eq. S1	p007 · Electrochemical measurements · Eq. S1
Other	activated carbon negative electrode	mass balanced according to Eq. S1	p007 · Electrochemical measurements · Eq. S1
Electrolyte	KOH aqueous electrolyte	not reported · 6.0 M	p007 · Electrochemical measurements · Eq. S1
Other	fiber paper separator	not reported	p007 · Electrochemical measurements · Eq. S1

Complete recipeSource: SI

Route 8: Other

p007 · Electrochemical measurements · Eq. S1

Metal precursors2-ox positive electrode from iodine-doped Zn TTF-BPDC MOF

Linker precursorspy-TTF-py/BPDC framework in 2-ox positrode

Solvents6.0 M KOH aqueous electrolyte

Additivesactivated carbon negative electrode; fibre paper separator

Atmosphereambient assembly not otherwise specified

Temperatureroom temperature measurement

Substrate orientationelectrode coating area 0.5 cm x 0.5 cm for two-electrode configuration

Oxidant / reductantnot applicable

Work-updevice assembled with charge-balanced positive and negative electrodes according to Eq. S1

Activationnone stated beyond electrode vacuum drying

Scalability contextMass ratio balanced by q+ = q- using C x m x deltaV.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2-ox positive electrode	mass balanced according to Eq. S1	p007 · Electrochemical measurements · Eq. S1
Other	activated carbon negative electrode	mass balanced according to Eq. S1	p007 · Electrochemical measurements · Eq. S1
Electrolyte	KOH aqueous electrolyte	not reported · 6.0 M	p007 · Electrochemical measurements · Eq. S1
Other	fiber paper separator	not reported	p007 · Electrochemical measurements · Eq. S1

Complete recipeSource: SI

Route 9: Other

p006-p007 · Electrochemical measurements

Metal precursorsprepared MOF sample (1, 1-ox, 2 or 2-ox depending on electrode)

Linker precursorsnot applicable at electrode fabrication step

Solventsethanol for slurry preparation; acetone solution and 0.1 M HCl for nickel foam cleaning

AdditivesSuper P conductive carbon; PTFE binder; nickel foam current collector

Atmospherevacuum drying after compaction; otherwise air/ambient not specified

Temperatureroom temperature for electrochemical use; drying temperature not specified

Time12 h vacuum drying after compaction

Substrate orientationnickel foam 1.0 cm x 1.0 cm for three-electrode configuration

Oxidant / reductantnone

Work-upnickel foam ultrasonically cleaned in acetone, then 0.1 M HCl; MOF/Super P/PTFE slurry coated, compacted at 10 MPa and vacuum dried 12 h

Activationvacuum drying 12 h

Scalability contextMOF loading controlled to 2.5 mg cm^-2; MOF:Super P:PTFE = 8:1:1 by weight.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	prepared MOF	loading mass controlled to 2.5 mg cm^-2	p006-p007 · Electrochemical measurements
Additive	Super P	MOF:Super P:PTFE = 8:1:1 by weight	p006-p007 · Electrochemical measurements
Additive	PTFE	MOF:Super P:PTFE = 8:1:1 by weight	p006-p007 · Electrochemical measurements
Solvent	ethanol	not reported	p006-p007 · Electrochemical measurements
Other	nickel foam	1.0 cm x 1.0 cm active area for 3-electrode; foam cut 1.5 cm x 1.0 cm	p006-p007 · Electrochemical measurements
Solvent	acetone solution	not reported	p006-p007 · Electrochemical measurements
Acid	hydrochloric acid	not reported · 0.1 M	p006-p007 · Electrochemical measurements