Synthesis · Partial selenium surface modulation of metal organic framework assisted cobalt sulfide hollow spheres for high performance bifunctional oxygen electrocatalysis and rechargeable zinc-air batteries

7 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

2 (render p002) · 2.3 Synthesis of MOF CoS2 hollow spheres

Metal precursorshollow ZIF-67 spheres

Linker precursors2-methylimidazole-derived ZIF-67 precursor

Solventsnone reported for melt diffusion step

Additivessulfur powder

Atmosphereinert atmosphere reactor

Temperature500

Time3

Oxidant / reductantsulfur powder, ZIF-67:S weight ratio 2:1

Work-upHollow ZIF-67 spheres mixed with sulfur powder for 15 min before heating; post-heating workup not reported.

ActivationHeated at 500 degC for 3 h with heating rate 2 degC min-1.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	synthesized hollow ZIF-67 spheres	weight ratio to S powder 2:1	2 (render p002) · 2.3 Synthesis of MOF CoS2 hollow spheres
Other	S powder	weight ratio ZIF-67:S = 2:1	2 (render p002) · 2.3 Synthesis of MOF CoS2 hollow spheres

Vague recipeSource: Main

Route 2: Other

4 (render p004) · 3.1 Synthesis, morphological and structural characterizations · Fig. S3 and Fig. S4a referenced

Metal precursorshollow ZIF-67 spheres

Linker precursors2-methylimidazole-derived ZIF-67 precursor

Additivespure Se

Atmospherenot fully specified for this control; likely analogous inert high-temperature route

Oxidant / reductantpure selenium

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	hollow ZIF-67 precursor	not reported	4 (render p004) · 3.1 Synthesis, morphological and structural characterizations · Fig. S3 and Fig. S4a referenced
Other	pure Se	not reported	4 (render p004) · 3.1 Synthesis, morphological and structural characterizations · Fig. S3 and Fig. S4a referenced

Partial recipeSource: Main

Route 3: Drop Cast

3 (render p003) · 2.5 Electrochemical measurements

Metal precursorssynthesized Se-doped MOF CoS2 hollow spheres

Solventsethanol 200 uL; deionized water 250 uL

AdditivesNafion 50 uL

Atmosphereambient drying in electrical oven

Temperature60

Substrate orientationclean carbon cloth, 1.0 cm x 1.0 cm

Work-up5 mg catalyst, ethanol, water and Nafion ultrasonicated 30 min; 50 uL ink drop-cast on carbon cloth.

ActivationDried at 60 degC.

Scalability contextCatalyst loading estimated 0.5 mg cm-2.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	synthesized material	5 mg	3 (render p003) · 2.5 Electrochemical measurements
Solvent	ethanol	200 uL	3 (render p003) · 2.5 Electrochemical measurements
Solvent	deionized water	250 uL	3 (render p003) · 2.5 Electrochemical measurements
Additive	Nafion	50 uL	3 (render p003) · 2.5 Electrochemical measurements

Partial recipeSource: Main

Route 4: Drop Cast

3 (render p003) · 2.5.1 For ORR measurements

Metal precursorsSe-doped MOF CoS2 hollow spheres

Solvents1 mL isopropyl alcohol and DI water (1:1)

Additives10 uL of 5% Nafion solution

Atmosphereambient

Time1 h sonication

Substrate orientationRDE diameter 5.0 mm, area 0.19625 cm2

Work-up2.5 mg catalyst dispersed and sonicated; nearly 30 uL ink drop-coated onto RDE.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	catalyst	2.5 mg	3 (render p003) · 2.5.1 For ORR measurements
Additive	5% Nafion solution	10 uL · 5%	3 (render p003) · 2.5.1 For ORR measurements
Solvent	isopropyl alcohol and DI water (1:1)	1 mL · 1:1	3 (render p003) · 2.5.1 For ORR measurements

Partial recipeSource: Main

Route 5: Other

2 (render p002) · 2.4 Synthesis of Se doped MOF CoS2 hollow spheres · Fig. 1

Metal precursorshollow ZIF-67 spheres

Linker precursors2-methylimidazole-derived ZIF-67 precursor

Solventsnone reported for sulfuration/selenization step

Additivessulfur powder and selenium powder

Atmosphereinert atmosphere reactor

Temperature500

Time3

Oxidant / reductantS powder 0.08 g plus Se powder 0.02 g replacing S powder 0.1 g

Work-upProcedure similar to MOF CoS2 route; post-heating workup not reported.

ActivationHeated at 500 degC for 3 h with heating rate 2 degC min-1.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	synthesized hollow ZIF-67 spheres	not reported in section 2.4	2 (render p002) · 2.4 Synthesis of Se doped MOF CoS2 hollow spheres · Fig. 1
Other	S powder	0.08 g	2 (render p002) · 2.4 Synthesis of Se doped MOF CoS2 hollow spheres · Fig. 1
Other	Se powder	0.02 g	2 (render p002) · 2.4 Synthesis of Se doped MOF CoS2 hollow spheres · Fig. 1

Partial recipeSource: Main

Route 6: Other

2 (render p002) · 2.2 Synthesis of ZIF-67 hollow spheres

Metal precursorsCobalt(II) sulfate heptahydrate, 20 mmol CoSO4.7H2O

Linker precursors2-methylimidazole, 160 mmol 2-MIM

Solvents100% methanol, 400 mL for cobalt sulfate solution and 400 mL for 2-MIM solution

AdditivesSulfate anions from cobalt sulfate; no separate additives reported

Atmosphereambient/not specified

Temperatureroom temperature for mixing; 60 for drying

Timeovernight drying; precipitation/mixing time not reported

Oxidant / reductantnone reported

Work-up2-Methylimidazole solution mixed with cobalt sulfate solution; purple precipitates washed multiple times with methanol and water.

ActivationDried overnight at 60 degC.

Scalability contextLarge volumes reported: 400 mL methanol solutions for each precursor.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cobalt sulfate heptahydrate (CoSO4.7 H2O)	20 mmol	2 (render p002) · 2.2 Synthesis of ZIF-67 hollow spheres
Linker	2-methylimidazole (2-MIM)	160 mmol	2 (render p002) · 2.2 Synthesis of ZIF-67 hollow spheres
Solvent	100% methanol	400 mL + 400 mL · 100%	2 (render p002) · 2.2 Synthesis of ZIF-67 hollow spheres

Partial recipeSource: Main

Route 7: Other

3 and 10 (render p003 and p010) · 2.6 Aqueous Zn-air batteries; 3.5 · Fig. 8

Metal precursorsSe-doped MOF CoS2 hollow spheres; commercial Zn foil

Solventsaqueous electrolyte

Additives6.0 M KOH / 0.2 M zinc acetate electrolyte

Atmosphereair cathode

Substrate orientationSe-doped MOF CoS2 loaded in carbon cloth as air cathode; Zn foil anode

Oxidant / reductantair/O2 at cathode; Zn foil anode

Work-upHomemade electrochemical Zn-air cell assembled.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	commercial Zn foil	0.25 mm thick	3 and 10 (render p003 and p010) · 2.6 Aqueous Zn-air batteries; 3.5 · Fig. 8
Other	Se doped CoS2 spheres air cathode	not reported	3 and 10 (render p003 and p010) · 2.6 Aqueous Zn-air batteries; 3.5 · Fig. 8
Electrolyte	KOH / zinc acetate	6.0 M KOH / 0.2 M zinc acetate	3 and 10 (render p003 and p010) · 2.6 Aqueous Zn-air batteries; 3.5 · Fig. 8