Synthesis · Ligand engineering of Co-MOF-74 with hexaaminotriphenylene for enhanced oxygen reduction reaction in zinc-air batteries

6 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Drop Cast

1 · Electrochemical characterizations

Metal precursorsCo-MOF-74 catalyst powder

Solvents950 uL deionized water; 950 uL ethanol; 100 uL Nafion solution

Additives2 mg EC-300J carbon black; Nafion binder

Atmosphereelectrode preparation atmosphere not stated; N2 or O2 purged electrolyte before LSV

Time0.5 h ultrasonication

Substrate orientationRRDE, electrode area 0.247 cm2

Oxidant / reductantO2/N2 saturation for ORR tests

Work-up15 uL catalyst slurry dripped onto clean RRDE, giving 0.242 mg cm-2 loading

Activation100 CV cycles at 100 mV s-1 before LSV

Scalability contextElectrode ink recipe uses 8 mg catalyst and 2 mg carbon black.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF-74 catalyst	8 mg	1 · Electrochemical characterizations
Additive	carbon black EC-300J	2 mg	1 · Electrochemical characterizations
Solvent	deionized water	950 uL	1 · Electrochemical characterizations
Solvent	ethanol	950 uL	1 · Electrochemical characterizations
Additive	Nafion solution	100 uL	1 · Electrochemical characterizations
Electrolyte	KOH solution	1 M	1 · Electrochemical characterizations

Complete recipeSource: SI

Route 2: Drop Cast

1 · Electrochemical characterizations

Metal precursorsCo-MOF-74-HATP catalyst powder

Solvents950 uL deionized water; 950 uL ethanol; 100 uL Nafion solution

Additives2 mg EC-300J carbon black; Nafion binder

AtmosphereN2-saturated 1 M KOH electrolyte for OER tests

Time0.5 h ultrasonication

Substrate orientation1 x 1 cm2 carbon cloth

Oxidant / reductantOER in alkaline electrolyte

Work-updispersion liquid evenly added to carbon cloth and dried; loading 0.5 mg cm-2

Activation50 CV cycles at 100 mV s-1 before LSV

Scalability contextOER electrode loading is 0.5 mg cm-2 on carbon cloth.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF-74-HATP catalyst	8 mg	1 · Electrochemical characterizations
Additive	carbon black EC-300J	2 mg	1 · Electrochemical characterizations
Solvent	deionized water	950 uL	1 · Electrochemical characterizations
Solvent	ethanol	950 uL	1 · Electrochemical characterizations
Additive	Nafion solution	100 uL	1 · Electrochemical characterizations
Electrolyte	KOH electrolyte	1 M	1 · Electrochemical characterizations

Complete recipeSource: SI

Route 3: Drop Cast

1 · Electrochemical characterizations

Metal precursorsCo-MOF-74-HATP catalyst powder

Solvents950 uL deionized water; 950 uL ethanol; 100 uL Nafion solution

Additives2 mg EC-300J carbon black; Nafion binder

Atmosphereelectrode preparation atmosphere not stated; N2 or O2 purged electrolyte before LSV

Time0.5 h ultrasonication

Substrate orientationRRDE, electrode area 0.247 cm2

Oxidant / reductantO2/N2 saturation for ORR tests

Work-up15 uL catalyst slurry dripped onto clean RRDE, giving 0.242 mg cm-2 loading

Activation100 CV cycles at 100 mV s-1 before LSV

Scalability contextElectrode ink recipe uses 8 mg catalyst and 2 mg carbon black.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF-74-HATP catalyst	8 mg	1 · Electrochemical characterizations
Additive	carbon black EC-300J	2 mg	1 · Electrochemical characterizations
Solvent	deionized water	950 uL	1 · Electrochemical characterizations
Solvent	ethanol	950 uL	1 · Electrochemical characterizations
Additive	Nafion solution	100 uL	1 · Electrochemical characterizations
Electrolyte	KOH solution	1 M	1 · Electrochemical characterizations

Partial recipeSource: Main

Route 4: Other

2 · 2.1.3 Synthesis of Co-MOF-74-HATP

Metal precursorspreformed Co-MOF-74

Linker precursorshexaaminotriphenylene (HATP)

Solvents1 mL methanol solution

Atmospherenot stated

Temperature70

Time3 after 10 min ultrasonication

Work-upnot stated

Activationnot stated

Scalability contextSmall-scale post-synthetic ligand-engineering recipe: 20 mg Co-MOF-74, 10 mg HATP, 1 mL methanol.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	above-mentioned Co-MOF-74	20 mg	2 · 2.1.3 Synthesis of Co-MOF-74-HATP
Linker	HATP	10 mg	2 · 2.1.3 Synthesis of Co-MOF-74-HATP
Solvent	methanol solution	1 mL	2 · 2.1.3 Synthesis of Co-MOF-74-HATP

Partial recipeSource: Main

Route 5: Solvothermal

2 · 2.1.2 Synthesis of Co-MOF-74

Metal precursorsCo(NO3)2.6H2O

Linker precursors2,5-dihydroxyterephthalic acid (H4DOBDC)

Solvents90 mL ethanol-DMF-water

Atmospherenot stated

Temperature100

Time24

Work-upwashed with water and ethanol

Activationdried in a vacuum oven at 80 C for 1 day

Scalability contextMetal/linker masses and ethanol/DMF/water ratio are not reported in main or SI text.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	Not specified	2 · 2.1.2 Synthesis of Co-MOF-74
Linker	2,5-dihydroxyterephthalic acid (H4DOBDC)	Not specified	2 · 2.1.2 Synthesis of Co-MOF-74
Solvent	ethanol-DMF-water	90 mL	2 · 2.1.2 Synthesis of Co-MOF-74

Complete recipeSource: SI

Route 6: Other

2 · Zinc-air battery performance test

Metal precursorsCo-MOF-74-HATP@EC-300J cathode catalyst; zinc sheet anode

Solventsaqueous KOH/Zn(CH3COO)2 electrolyte

Additivescarbon paper current collector/cathode substrate

Atmosphereambient air cathode operation implied

Substrate orientationcarbon paper, 1 x 1 cm2

Oxidant / reductantoxygen from air cathode; zinc anode

Work-upcatalyst loaded on carbon paper at 0.6 mg cm-2; assembled against zinc sheet

Activationcharge/discharge stability test used 20 min period: 10 min charge and 10 min discharge

Scalability contextBattery cathode catalyst load is 0.6 mg cm-2; Pt/C control used 0.1 mgPt cm-2.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF-74-HATP@EC-300J	0.6 mg cm-2 on carbon paper	2 · Zinc-air battery performance test
Other	carbon paper	1x1 cm2	2 · Zinc-air battery performance test
Other	zinc sheet	Not specified	2 · Zinc-air battery performance test
Electrolyte	KOH	6.0 M	2 · Zinc-air battery performance test
Electrolyte	Zn(CH3COO)2	0.2 M	2 · Zinc-air battery performance test