Synthesis · Conductive MOFs as bifunctional oxygen electrocatalysts for all-solid-state Zn-air batteries

8 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Hydrothermal

2 · Synthesis method of conductive MOFs

Metal precursorsNi(OAc)2.4H2O, 10 mg

Linker precursorsHHTP, 7 mg

Solventsdeionized water, 4.0 mL

Atmospherenot specified

Temperature85

Time12

Work-upCooled naturally to room temperature; crystals washed with deionized water (3 x 5 mL) and acetone (3 x 5 mL).

Activationnot specified

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	7 mg	2 · Synthesis method of conductive MOFs
Metal Source	Ni(OAc)2.4H2O	10 mg	2 · Synthesis method of conductive MOFs
Solvent	deionized water	4.0 mL	2 · Synthesis method of conductive MOFs

Complete recipeSource: SI

Route 2: Hydrothermal

3 · Synthesis method of conductive MOFs · Table S1

Metal precursorsNi(OAc)2.4H2O, 9.9 mg; RuCl3 solution, 0.21 mL of 0.4 mg/mL

Linker precursorsHHTP, 7 mg

Solventsdeionized water, 3.79 mL plus aqueous RuCl3 solution

Atmospherenot specified

Temperature85

Time12

Work-upSame processing method as [Ni6(HHTP)3(H2O)x]n: natural cooling, washing with water and acetone.

Activationnot specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	7 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	Ni(OAc)2.4H2O	9.9 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	RuCl3	0.21 mL · 0.4 mg/mL	3 · Synthesis method of conductive MOFs · Table S1
Solvent	deionized water	3.79 mL	3 · Synthesis method of conductive MOFs · Table S1

Complete recipeSource: SI

Route 3: Hydrothermal

3 · Synthesis method of conductive MOFs · Table S1

Metal precursorsNi(OAc)2.4H2O, 9.7 mg; RuCl3 solution, 0.63 mL of 0.4 mg/mL

Linker precursorsHHTP, 7 mg

Solventsdeionized water, 3.37 mL plus aqueous RuCl3 solution

Atmospherenot specified

Temperature85

Time12

Work-upSame processing method as [Ni6(HHTP)3(H2O)x]n: natural cooling, washing with water and acetone.

Activationnot specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	7 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	Ni(OAc)2.4H2O	9.7 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	RuCl3	0.63 mL · 0.4 mg/mL	3 · Synthesis method of conductive MOFs · Table S1
Solvent	deionized water	3.37 mL	3 · Synthesis method of conductive MOFs · Table S1

Complete recipeSource: Both

Route 4: Hydrothermal

3 · Synthesis method of conductive MOFs · Table S1

Metal precursorsNi(OAc)2.4H2O, 9.5 mg; RuCl3 solution, 1.05 mL of 0.4 mg/mL

Linker precursorsHHTP, 7 mg

Solventsdeionized water, 2.95 mL plus aqueous RuCl3 solution

Atmospherenot specified

Temperature85

Time12

Work-upSame processing method as [Ni6(HHTP)3(H2O)x]n: natural cooling, washing with water and acetone.

Activationnot specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	7 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	Ni(OAc)2.4H2O	9.5 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	RuCl3	1.05 mL · 0.4 mg/mL	3 · Synthesis method of conductive MOFs · Table S1
Solvent	deionized water	2.95 mL	3 · Synthesis method of conductive MOFs · Table S1

Complete recipeSource: SI

Route 5: Drop Cast

4 · Zn-air batteries

SolventsH2O:ethanol = 1:1 v/v

Additives5% Nafion, KOH electrolyte, Zn(OAc)2 for rechargeable batteries

Atmosphereair cathode in Zn-air cell

Substrate orientationNi foam and gas-diffusion layer

Oxidant / reductantZn powder anode; oxygen from air cathode

Work-upNi foams washed with 1 M HCl, absolute ethanol and distilled water; catalyst ink dropped onto Ni foam/gas-diffusion layer and kept in vacuum container for 30 min.

Activationvacuum container for 30 min after coating

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	[Ni5.7Ru0.3(HHTP)3(H2O)x]n catalyst	5 mg	4 · Zn-air batteries
Additive	5% Nafion	50 uL · 5%	4 · Zn-air batteries
Solvent	H2O:ethanol	950 uL · 1:1 v/v	4 · Zn-air batteries
Electrolyte	KOH solution	6 M	4 · Zn-air batteries
Electrolyte	Zn(OAc)2	0.2 M for rechargeable Zn-air batteries	4 · Zn-air batteries

Complete recipeSource: SI

Route 6: Drop Cast

3 · Electrochemical characterizations

SolventsH2O

Additives5% Nafion, 40 uL

AtmosphereO2 or N2 saturated 0.1 M KOH during testing

Substrate orientationGC-RDE, 0.1256 cm2

Work-up5 mg catalyst and 40 uL 5% Nafion dispersed in 960 uL H2O and ultrasonicated for 30 min; 10 uL ink dropped onto GC-RDE.

Activationnot specified

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	[Ni5.7Ru0.3(HHTP)3(H2O)x]n catalyst	5 mg	3 · Electrochemical characterizations
Additive	5% Nafion	40 uL · 5%	3 · Electrochemical characterizations
Solvent	H2O	960 uL	3 · Electrochemical characterizations

Complete recipeSource: SI

Route 7: Other

4-5 · Zn-air batteries

SolventsH2O

AdditivesPVA, KOH, zinc acetate

Atmosphereair cathode in all-solid-state Zn-air cell

Temperature95; -20

Time2; 0.667; 2

Substrate orientationsandwich cell with catalyst-supported air diffusion layer

Oxidant / reductantZn powder anode; oxygen from air cathode

Work-upPVA gel electrolyte prepared by stirring 1 g PVA in 10 mL H2O at 95 C for 2 h, adding 1 mL 18 M KOH containing 0.02 M zinc acetate, stirring 40 min, freezing at -20 C for 2 h, thawing to room temperature.

Activationfreeze-thaw gel formation

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	[Ni5.7Ru0.3(HHTP)3(H2O)x]n catalyst	2 mg/cm2 loading	4-5 · Zn-air batteries
Additive	PVA powder	1 g	4-5 · Zn-air batteries
Solvent	H2O	10 mL	4-5 · Zn-air batteries
Electrolyte	KOH	1 mL solution · 18 M	4-5 · Zn-air batteries
Electrolyte	zinc acetate	in 1 mL KOH solution · 0.02 M	4-5 · Zn-air batteries

Complete recipeSource: SI

Route 8: Hydrothermal

3 · Synthesis method of conductive MOFs · Table S1

Metal precursorsNi(OAc)2.4H2O, 9.0 mg; RuCl3 solution, 2.1 mL of 0.4 mg/mL

Linker precursorsHHTP, 7 mg

Solventsdeionized water, 1.9 mL plus aqueous RuCl3 solution

Atmospherenot specified

Temperature85

Time12

Work-upSame processing method as [Ni6(HHTP)3(H2O)x]n: natural cooling, washing with water and acetone.

Activationnot specified

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	7 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	Ni(OAc)2.4H2O	9.0 mg	3 · Synthesis method of conductive MOFs · Table S1
Metal Source	RuCl3	2.1 mL · 0.4 mg/mL	3 · Synthesis method of conductive MOFs · Table S1
Solvent	deionized water	1.9 mL	3 · Synthesis method of conductive MOFs · Table S1