Synthesis · Boosting electrocatalytic CO2 reduction reaction over viologen-functionalized metal-organic frameworks by enhancement of electron-transfer capacity

7 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)

Metal precursorsHfCl4

Linker precursorsPor(Co) plus methyl viologen

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.03 mmol, 9.6 mg	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)
Linker	Por(Co)	0.027 mmol, 16.47 mg	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)
Additive	Methyl Viologen (MV)	0.003 mmol, 1.32 mg	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)
Solvent	DMF	4 mL	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)
Solvent	H2O	2 mL	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)
Acid	TFA	40 uL	p013 · Section S3 · Synthesis of MV@Por(Co)-MOF(9:1)

Complete recipeSource: Both

Route 2: Solvothermal

p012 · Section S3 · Synthesis of Por(Co)-MOF

Metal precursorsHfCl4

Linker precursorsPor(Co)

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.030 mmol, 9.6 mg	p012 · Section S3 · Synthesis of Por(Co)-MOF
Linker	Por(Co)	0.030 mmol, 18.3 mg	p012 · Section S3 · Synthesis of Por(Co)-MOF
Solvent	DMF	4 mL	p012 · Section S3 · Synthesis of Por(Co)-MOF
Solvent	H2O	2 mL	p012 · Section S3 · Synthesis of Por(Co)-MOF
Acid	TFA	40 uL	p012 · Section S3 · Synthesis of Por(Co)-MOF

Complete recipeSource: Both

Route 3: Solvothermal

p011 · Section S3 · Synthesis of Vg-MOF

Metal precursorsZrOCl2.8H2O

Linker precursors[H2bpybdc]Cl2 (Vg)

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 80 uL

Atmospherenot stated

Temperature100

Time72

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrOCl2.8H2O	0.024 mmol, 8 mg	p011 · Section S3 · Synthesis of Vg-MOF
Linker	[H2bpybdc]Cl2 (Vg)	0.034 mmol, 16 mg	p011 · Section S3 · Synthesis of Vg-MOF
Solvent	DMF	4 mL	p011 · Section S3 · Synthesis of Vg-MOF
Solvent	H2O	2 mL	p011 · Section S3 · Synthesis of Vg-MOF
Acid	TFA	80 uL	p011 · Section S3 · Synthesis of Vg-MOF

Complete recipeSource: Both

Route 4: Solvothermal

p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)

Metal precursorsHfCl4

Linker precursorsPor(Co) and [H2bpybdc]Cl2 (Vg), Por(Co):Vg = 1:1

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.03 mmol, 9.6 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)
Linker	Por(Co)	0.015 mmol, 9.15 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)
Linker	[H2bpybdc]Cl2 (Vg)	0.015 mmol, 7.05 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)
Solvent	DMF	4 mL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)
Solvent	H2O	2 mL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)
Acid	TFA	40 uL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(1:1)

Complete recipeSource: Both

Route 5: Solvothermal

p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)

Metal precursorsHfCl4

Linker precursorsPor(Co) and [H2bpybdc]Cl2 (Vg), Por(Co):Vg = 2:1

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.03 mmol, 9.6 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)
Linker	Por(Co)	0.018 mmol, 11 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)
Linker	[H2bpybdc]Cl2 (Vg)	0.009 mmol, 4.7 mg	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)
Solvent	DMF	4 mL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)
Solvent	H2O	2 mL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)
Acid	TFA	40 uL	p013 · Section S3 · Synthesis of Vg-Por(Co)-MOF(2:1)

Complete recipeSource: Both

Route 6: Solvothermal

p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)

Metal precursorsHfCl4

Linker precursorsPor(Co) and [H2bpybdc]Cl2 (Vg), Por(Co):Vg = 5:1

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.03 mmol, 9.6 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)
Linker	Por(Co)	0.025 mmol, 15.25 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)
Linker	[H2bpybdc]Cl2 (Vg)	0.05 mmol, 2.35 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)
Solvent	DMF	4 mL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)
Solvent	H2O	2 mL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)
Acid	TFA	40 uL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(5:1)

Complete recipeSource: Both

Route 7: Solvothermal

p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)

Metal precursorsHfCl4

Linker precursorsPor(Co) and [H2bpybdc]Cl2 (Vg), Por(Co):Vg = 9:1

Solvents4 mL DMF and 2 mL H2O

AdditivesTFA 40 uL

Atmospherenot stated

Temperature100

Time48

Work-upFiltered; washed with fresh DMF (10 mL x 3); immersed in 10 mL DMF at 80 deg C for 48 h with DMF refreshed every 12 h; acetone wash before drying.

ActivationDMF solvent exchange at 80 deg C for 48 h, acetone wash, drying

Scalability context20 mL glass-vial solvothermal batch; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.03 mmol, 9.6 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)
Linker	Por(Co)	0.027 mmol, 16.47 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)
Linker	[H2bpybdc]Cl2 (Vg)	0.003 mmol, 1.41 mg	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)
Solvent	DMF	4 mL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)
Solvent	H2O	2 mL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)
Acid	TFA	40 uL	p012 · Section S3 · Synthesis of Vg-Por(Co)-MOF(9:1)