Synthesis · Electrodeposition of Ni/Cu Bimetallic Conductive Metal–Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc–Air Batteries

5 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Electrochemical

Synthesis of M3(HITP)2 samples

Metal precursorsNiCl2.6H2O/CuSO4 mixture, Ni/Cu = 0/1; total metal salt mixture 10 mg

Linker precursorsHITP.6HCl (1 mg)

Solvents2 mL deionized water for linker; 18 mL deionized water + 20 mL ethanol for metal salts

Additivesnone reported beyond electrolyte constituents; carbon cloth pretreated with H2SO4 solution

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time10

Substrate orientationpretreated carbon cloth working electrode in three-electrode cell; carbon rod counter electrode; saturated calomel reference electrode

Oxidant / reductantcathodic water reduction generates OH- proto-base; constant current -1 mA cm-2

Work-upCarbon cloths pretreated with H2SO4 solution, deionized water and absolute ethanol; post-deposition washing/drying not reported.

ActivationNo separate activation reported.

Scalability contextBinder-free film growth directly on carbon cloth; authors describe the method as facile, mild and cost-effective.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl (2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride)	1 mg · dissolved in 2 mL deionized water	Synthesis of M3(HITP)2 samples
Metal Source	NiCl2.6H2O/CuSO4 mixture (Ni/Cu feed ratio 0/1)	10 mg total · dissolved in 18 mL water + 20 mL ethanol	Synthesis of M3(HITP)2 samples
Solvent	deionized water	2 mL + 18 mL	Synthesis of M3(HITP)2 samples
Solvent	ethanol	20 mL	Synthesis of M3(HITP)2 samples
Acid	H2SO4 solution for carbon cloth pretreatment	not reported · not reported	Synthesis of M3(HITP)2 samples
Electrolyte	mixed HITP.6HCl and metal salt electrosynthesis solution	40 mL total nominal solvent volume plus solutes · not directly reported	Synthesis of M3(HITP)2 samples

Partial recipeSource: Both

Route 2: Electrochemical

Synthesis of M3(HITP)2 samples

Metal precursorsNiCl2.6H2O/CuSO4 mixture, Ni/Cu = 1/1; total metal salt mixture 10 mg

Linker precursorsHITP.6HCl (1 mg)

Solvents2 mL deionized water for linker; 18 mL deionized water + 20 mL ethanol for metal salts

Additivesnone reported beyond electrolyte constituents; carbon cloth pretreated with H2SO4 solution

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time10

Substrate orientationpretreated carbon cloth working electrode in three-electrode cell; carbon rod counter electrode; saturated calomel reference electrode

Oxidant / reductantcathodic water reduction generates OH- proto-base; constant current -1 mA cm-2

Work-upCarbon cloths pretreated with H2SO4 solution, deionized water and absolute ethanol; post-deposition washing/drying not reported.

ActivationNo separate activation reported.

Scalability contextBinder-free film growth directly on carbon cloth; authors describe the method as facile, mild and cost-effective.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl (2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride)	1 mg · dissolved in 2 mL deionized water	Synthesis of M3(HITP)2 samples
Metal Source	NiCl2.6H2O/CuSO4 mixture (Ni/Cu feed ratio 1/1)	10 mg total · dissolved in 18 mL water + 20 mL ethanol	Synthesis of M3(HITP)2 samples
Solvent	deionized water	2 mL + 18 mL	Synthesis of M3(HITP)2 samples
Solvent	ethanol	20 mL	Synthesis of M3(HITP)2 samples
Acid	H2SO4 solution for carbon cloth pretreatment	not reported · not reported	Synthesis of M3(HITP)2 samples
Electrolyte	mixed HITP.6HCl and metal salt electrosynthesis solution	40 mL total nominal solvent volume plus solutes · not directly reported	Synthesis of M3(HITP)2 samples

Partial recipeSource: Both

Route 3: Electrochemical

Synthesis of M3(HITP)2 samples

Metal precursorsNiCl2.6H2O/CuSO4 mixture, Ni/Cu = 2/1; total metal salt mixture 10 mg

Linker precursorsHITP.6HCl (1 mg)

Solvents2 mL deionized water for linker; 18 mL deionized water + 20 mL ethanol for metal salts

Additivesnone reported beyond electrolyte constituents; carbon cloth pretreated with H2SO4 solution

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time10

Substrate orientationpretreated carbon cloth working electrode in three-electrode cell; carbon rod counter electrode; saturated calomel reference electrode

Oxidant / reductantcathodic water reduction generates OH- proto-base; constant current -1 mA cm-2

Work-upCarbon cloths pretreated with H2SO4 solution, deionized water and absolute ethanol; post-deposition washing/drying not reported.

ActivationNo separate activation reported.

Scalability contextBinder-free film growth directly on carbon cloth; authors describe the method as facile, mild and cost-effective.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl (2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride)	1 mg · dissolved in 2 mL deionized water	Synthesis of M3(HITP)2 samples
Metal Source	NiCl2.6H2O/CuSO4 mixture (Ni/Cu feed ratio 2/1)	10 mg total · dissolved in 18 mL water + 20 mL ethanol	Synthesis of M3(HITP)2 samples
Solvent	deionized water	2 mL + 18 mL	Synthesis of M3(HITP)2 samples
Solvent	ethanol	20 mL	Synthesis of M3(HITP)2 samples
Acid	H2SO4 solution for carbon cloth pretreatment	not reported · not reported	Synthesis of M3(HITP)2 samples
Electrolyte	mixed HITP.6HCl and metal salt electrosynthesis solution	40 mL total nominal solvent volume plus solutes · not directly reported	Synthesis of M3(HITP)2 samples

Partial recipeSource: Both

Route 4: Electrochemical

Synthesis of M3(HITP)2 samples

Metal precursorsNiCl2.6H2O/CuSO4 mixture, Ni/Cu = 3/1; total metal salt mixture 10 mg

Linker precursorsHITP.6HCl (1 mg)

Solvents2 mL deionized water for linker; 18 mL deionized water + 20 mL ethanol for metal salts

Additivesnone reported beyond electrolyte constituents; carbon cloth pretreated with H2SO4 solution

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time10

Substrate orientationpretreated carbon cloth working electrode in three-electrode cell; carbon rod counter electrode; saturated calomel reference electrode

Oxidant / reductantcathodic water reduction generates OH- proto-base; constant current -1 mA cm-2

Work-upCarbon cloths pretreated with H2SO4 solution, deionized water and absolute ethanol; post-deposition washing/drying not reported.

ActivationNo separate activation reported.

Scalability contextBinder-free film growth directly on carbon cloth; authors describe the method as facile, mild and cost-effective.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl (2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride)	1 mg · dissolved in 2 mL deionized water	Synthesis of M3(HITP)2 samples
Metal Source	NiCl2.6H2O/CuSO4 mixture (Ni/Cu feed ratio 3/1)	10 mg total · dissolved in 18 mL water + 20 mL ethanol	Synthesis of M3(HITP)2 samples
Solvent	deionized water	2 mL + 18 mL	Synthesis of M3(HITP)2 samples
Solvent	ethanol	20 mL	Synthesis of M3(HITP)2 samples
Acid	H2SO4 solution for carbon cloth pretreatment	not reported · not reported	Synthesis of M3(HITP)2 samples
Electrolyte	mixed HITP.6HCl and metal salt electrosynthesis solution	40 mL total nominal solvent volume plus solutes · not directly reported	Synthesis of M3(HITP)2 samples

Partial recipeSource: Both

Route 5: Electrochemical

Synthesis of M3(HITP)2 samples

Metal precursorsNiCl2.6H2O/CuSO4 mixture, Ni/Cu = 1/0; total metal salt mixture 10 mg

Linker precursorsHITP.6HCl (1 mg)

Solvents2 mL deionized water for linker; 18 mL deionized water + 20 mL ethanol for metal salts

Additivesnone reported beyond electrolyte constituents; carbon cloth pretreated with H2SO4 solution

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time10

Substrate orientationpretreated carbon cloth working electrode in three-electrode cell; carbon rod counter electrode; saturated calomel reference electrode

Oxidant / reductantcathodic water reduction generates OH- proto-base; constant current -1 mA cm-2

Work-upCarbon cloths pretreated with H2SO4 solution, deionized water and absolute ethanol; post-deposition washing/drying not reported.

ActivationNo separate activation reported.

Scalability contextBinder-free film growth directly on carbon cloth; authors describe the method as facile, mild and cost-effective.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.6HCl (2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride)	1 mg · dissolved in 2 mL deionized water	Synthesis of M3(HITP)2 samples
Metal Source	NiCl2.6H2O/CuSO4 mixture (Ni/Cu feed ratio 1/0)	10 mg total · dissolved in 18 mL water + 20 mL ethanol	Synthesis of M3(HITP)2 samples
Solvent	deionized water	2 mL + 18 mL	Synthesis of M3(HITP)2 samples
Solvent	ethanol	20 mL	Synthesis of M3(HITP)2 samples
Acid	H2SO4 solution for carbon cloth pretreatment	not reported · not reported	Synthesis of M3(HITP)2 samples
Electrolyte	mixed HITP.6HCl and metal salt electrosynthesis solution	40 mL total nominal solvent volume plus solutes · not directly reported	Synthesis of M3(HITP)2 samples