Synthesis · Self-Nanocavity-Confined Halogen Anions Boosting the High Selectivity of the Two-Electron Oxygen Reduction Pathway over Ni-Based MOFs

5 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

SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Metal precursors0.027 mmol Ni(NO3)2.6H2O in 4 mL distilled water

Linker precursors0.019 mmol HITP in 20 mL dimethyl sulfoxide

Solvents20 mL dimethyl sulfoxide; 4 mL distilled water; 10 mL ethanol-water solution with volume ratio 9:1

Additives0.6 mmol NH4Br inferred from 'same process' with corresponding ammonium salt; 100 uL NH3.H2O added dropwise

Atmospherenot specified

Temperature50 deg C preheating; 60 deg C reaction and drying

Time10 min ultrasonication, 10 min after metal addition, 12 h reaction, overnight drying

Work-upblack powder collected by centrifuging, washed with distilled water and ethanol several times

Activationdried under vacuum at 60 deg C overnight

Scalability contextBatch solution/flask synthesis; no scale-up data reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP	0.019 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Metal Source	Ni(NO3)2.6H2O	0.027 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	dimethyl sulfoxide	20 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	distilled water	4 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Additive	NH4Br	0.6 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	ethanol-water solution	10 mL · 9:1 volume ratio	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Base	NH3.H2O	100 uL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Complete recipeSource: Both

Route 2: Solvothermal

SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Metal precursors0.027 mmol Ni(NO3)2.6H2O in 4 mL distilled water

Linker precursors0.019 mmol HITP in 20 mL dimethyl sulfoxide

Solvents20 mL dimethyl sulfoxide; 4 mL distilled water; 10 mL ethanol-water solution with volume ratio 9:1

Additives0.6 mmol NH4Cl inferred from 'same process' with corresponding ammonium salt; 100 uL NH3.H2O added dropwise

Atmospherenot specified

Temperature50 deg C preheating; 60 deg C reaction and drying

Time10 min ultrasonication, 10 min after metal addition, 12 h reaction, overnight drying

Work-upblack powder collected by centrifuging, washed with distilled water and ethanol several times

Activationdried under vacuum at 60 deg C overnight

Scalability contextBatch solution/flask synthesis; no scale-up data reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP	0.019 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Metal Source	Ni(NO3)2.6H2O	0.027 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	dimethyl sulfoxide	20 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	distilled water	4 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Additive	NH4Cl	0.6 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	ethanol-water solution	10 mL · 9:1 volume ratio	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Base	NH3.H2O	100 uL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Complete recipeSource: Both

Route 3: Solvothermal

SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Metal precursors0.027 mmol Ni(NO3)2.6H2O in 4 mL distilled water

Linker precursors0.019 mmol HITP in 20 mL dimethyl sulfoxide

Solvents20 mL dimethyl sulfoxide; 4 mL distilled water; 10 mL ethanol-water solution with volume ratio 9:1

Additives0.6 mmol NH4F; 100 uL NH3.H2O added dropwise

Atmospherenot specified

Temperature50 deg C preheating; 60 deg C reaction and drying

Time10 min ultrasonication, 10 min after metal addition, 12 h reaction, overnight drying

Work-upblack powder collected by centrifuging, washed with distilled water and ethanol several times

Activationdried under vacuum at 60 deg C overnight

Scalability contextBatch solution/flask synthesis; no scale-up data reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP	0.019 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Metal Source	Ni(NO3)2.6H2O	0.027 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	dimethyl sulfoxide	20 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	distilled water	4 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Additive	NH4F	0.6 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	ethanol-water solution	10 mL · 9:1 volume ratio	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Base	NH3.H2O	100 uL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Complete recipeSource: Both

Route 4: Solvothermal

SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Metal precursors0.027 mmol Ni(NO3)2.6H2O in 4 mL distilled water

Linker precursors0.019 mmol HITP in 20 mL dimethyl sulfoxide

Solvents20 mL dimethyl sulfoxide; 4 mL distilled water; 10 mL ethanol-water solution with volume ratio 9:1

Additives0.6 mmol NH4I inferred from 'same process' with corresponding ammonium salt; 100 uL NH3.H2O added dropwise

Atmospherenot specified

Temperature50 deg C preheating; 60 deg C reaction and drying

Time10 min ultrasonication, 10 min after metal addition, 12 h reaction, overnight drying

Work-upblack powder collected by centrifuging, washed with distilled water and ethanol several times

Activationdried under vacuum at 60 deg C overnight

Scalability contextBatch solution/flask synthesis; no scale-up data reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP	0.019 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Metal Source	Ni(NO3)2.6H2O	0.027 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	dimethyl sulfoxide	20 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	distilled water	4 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Additive	NH4I	0.6 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	ethanol-water solution	10 mL · 9:1 volume ratio	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Base	NH3.H2O	100 uL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Complete recipeSource: SI

Route 5: Solvothermal

SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts

Metal precursors0.027 mmol Ni(NO3)2.6H2O in 4 mL distilled water

Linker precursors0.019 mmol HITP in 20 mL dimethyl sulfoxide

Solventsdimethyl sulfoxide; distilled water; ethanol-water solution was omitted with the ammonium-salt step for pristine Ni MOF not fully detailed

Additives100 uL NH3.H2O added dropwise

Atmospherenot specified

Temperature50 deg C preheating; 60 deg C reaction and drying

Time10 min ultrasonication, 10 min after metal addition, 12 h reaction, overnight drying

Work-upblack powder collected by centrifuging, washed with distilled water and ethanol several times

Activationdried under vacuum at 60 deg C overnight

Scalability contextBatch solution/flask synthesis; no scale-up data reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP	0.019 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Metal Source	Ni(NO3)2.6H2O	0.027 mmol	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	dimethyl sulfoxide	20 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Solvent	distilled water	4 mL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts
Base	NH3.H2O	100 uL	SI p.S2 · Preparation of X-Ni (X = F, Cl, Br, I) and Ni MOF catalysts