Synthesis · Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution

9 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Other

1360 · 2.5. Photocatalytic HER

Additivesurea precursor

Atmospherenot specified

Temperature600

Time4

Activationcalcining urea at 600 °C for 4 h

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	urea	Not specified	1360 · 2.5. Photocatalytic HER

Partial recipeSource: Both

Route 2: Solvothermal

1362 · 3.2. Formation of Homogenous Bimetallic Cobalt Sulfides · Figure 4c,d

Metal precursorsCo-MOF precursor, inferred corresponding MOF route

Linker precursors2-methylimidazole-derived Co-MOF precursor

Solventsethanol

Additivesthioacetamide (TAA)

AtmosphereN2 for final annealing

Temperature120 solvothermal; 350 annealing

Time4 solvothermal; 2 annealing

Oxidant / reductantTAA sulphur source

Work-upcentrifuged and washed with ethanol

Activationannealed under N2 atmosphere

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF	not explicitly repeated for Co3S4	1362 · 3.2. Formation of Homogenous Bimetallic Cobalt Sulfides · Figure 4c,d
Solvent	ethanol	not explicitly repeated for Co3S4	1362 · 3.2. Formation of Homogenous Bimetallic Cobalt Sulfides · Figure 4c,d
Additive	thioacetamide (TAA)	not explicitly repeated for Co3S4	1362 · 3.2. Formation of Homogenous Bimetallic Cobalt Sulfides · Figure 4c,d

Complete recipeSource: SI

Route 3: Other

S4 · 1. Experimental

Metal precursorsCo(NO3)2·6H2O (0.87 g)

Linker precursors2-methylimidazole (1.97 g)

Solventsmethanol, 30 mL for cobalt nitrate solution plus 20 mL for linker solution

Atmosphereambient air not otherwise specified

Temperatureroom temperature; vacuum drying at 50

Time24 h incubation; overnight drying

Work-upcentrifuged; washed with water and methanol in sequence at least three times

Activationdried in vacuum at 50 °C overnight

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	0.87 g	S4 · 1. Experimental
Linker	2-methylimidazole	1.97 g	S4 · 1. Experimental
Solvent	methanol	30 mL + 20 mL	S4 · 1. Experimental

Partial recipeSource: SI

Route 4: Other

S4 · 1. Experimental

Metal precursorsCo(NO3)2·6H2O and Cu(NO3)2·3H2O; analogous to Zn0.30Co2.70-MOF

Linker precursors2-methylimidazole (1.97 g)

Solventsmethanol

Atmosphereambient air not otherwise specified

Temperatureroom temperature

Time24

Work-upcentrifuged and washed with ethanol several times

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	not separately specified	S4 · 1. Experimental
Metal Source	Cu(NO3)2·3H2O	not separately specified	S4 · 1. Experimental
Linker	2-methylimidazole	1.97 g by analogous route	S4 · 1. Experimental
Solvent	methanol	30 mL + 20 mL by analogous route	S4 · 1. Experimental

Complete recipeSource: Both

Route 5: Solvothermal

1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra

Metal precursors80 mg Cu0.30Co2.70-MOF precursor

Linker precursors2-methylimidazole-derived MOF precursor

Solventsethanol, 40 mL

Additivesthioacetamide (TAA), 0.12 g

AtmosphereN2 for final annealing

Temperature120 solvothermal; 350 annealing

Time4 solvothermal; 2 annealing

Oxidant / reductantTAA sulphur source

Work-upcentrifuged and washed with ethanol several times

Activationannealed under N2 atmosphere at 350 °C for 2 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu0.30Co2.70-MOF	80 mg	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Solvent	ethanol	40 mL	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Additive	thioacetamide (TAA)	0.12 g	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra

Partial recipeSource: SI

Route 6: Other

S4 · 1. Experimental

Metal precursorsCo(NO3)2·6H2O and Ni(NO3)2·6H2O; analogous to Zn0.30Co2.70-MOF

Linker precursors2-methylimidazole (1.97 g)

Solventsmethanol

Atmosphereambient air not otherwise specified

Temperatureroom temperature

Time24

Work-upcentrifuged and washed with ethanol several times

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	not separately specified	S4 · 1. Experimental
Metal Source	Ni(NO3)2·6H2O	not separately specified	S4 · 1. Experimental
Linker	2-methylimidazole	1.97 g by analogous route	S4 · 1. Experimental
Solvent	methanol	30 mL + 20 mL by analogous route	S4 · 1. Experimental

Complete recipeSource: Both

Route 7: Solvothermal

1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra

Metal precursors80 mg Ni0.30Co2.70-MOF precursor

Linker precursors2-methylimidazole-derived MOF precursor

Solventsethanol, 40 mL

Additivesthioacetamide (TAA), 0.12 g

AtmosphereN2 for final annealing

Temperature120 solvothermal; 350 annealing

Time4 solvothermal; 2 annealing

Oxidant / reductantTAA sulphur source

Work-upcentrifuged and washed with ethanol several times

Activationannealed under N2 atmosphere at 350 °C for 2 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni0.30Co2.70-MOF	80 mg	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Solvent	ethanol	40 mL	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Additive	thioacetamide (TAA)	0.12 g	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra

Complete recipeSource: SI

Route 8: Other

S4 · 1. Experimental

Metal precursorsCo(NO3)2·6H2O and Zn(NO3)2·6H2O; total Zn + Co fixed at 3 mmol; desired Zn2+/Co2+ ratio

Linker precursors2-methylimidazole (1.97 g)

Solventsmethanol, 30 mL for metal salt solution plus 20 mL for linker solution

Atmosphereambient air not otherwise specified

Temperatureroom temperature

Time24

Work-upcentrifuged and washed with ethanol several times

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	part of 3 mmol total Zn + Co	S4 · 1. Experimental
Metal Source	Zn(NO3)2·6H2O	part of 3 mmol total Zn + Co	S4 · 1. Experimental
Linker	2-methylimidazole	1.97 g	S4 · 1. Experimental
Solvent	methanol	30 mL + 20 mL	S4 · 1. Experimental

Complete recipeSource: Both

Route 9: Solvothermal

1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra

Metal precursors80 mg Zn0.30Co2.70-MOF precursor

Linker precursors2-methylimidazole-derived MOF precursor

Solventsethanol, 40 mL

Additivesthioacetamide (TAA), 0.12 g

AtmosphereN2 for final annealing

Temperature120 solvothermal; 350 annealing

Time4 solvothermal; 2 annealing

Oxidant / reductantTAA sulphur source releasing S2- / H2S in ethanol

Work-upcentrifuged and washed with ethanol several times

Activationannealed under N2 atmosphere at 350 °C for 2 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Zn0.30Co2.70-MOF	80 mg	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Solvent	ethanol	40 mL	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra
Additive	thioacetamide (TAA)	0.12 g	1360 · 2.2. Synthesis of Hollow MxCo3-xS4 Polyhedra