Synthesis · Co 3 O 4 @Cu-Based Conductive Metal–Organic Framework Core–Shell Nanowire Electrocatalysts Enable Efficient Low-Overall-Potential Water Splitting

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

p007 / journal p.6581 · Fabrication of Co3O4@CuCAT

Metal precursorsCu(C5H4F3O2)2, 50 mg; preformed Co3O4 on carbon cloth

Linker precursorsHHTP, 35 mg

Solventswater, 40 mL; 1-methyl-2-pyrrolidone (NMP), 2 mL

AdditivesNMP cosolvent/additive; no separate base reported

Atmospherenot specified; sealed Teflon-lined autoclave

Temperature85 deg C

Time12 h

Substrate orientationCo3O4 electrode, 3 x 4 cm, immersed in dark solution in 50 mL Teflon-lined autoclave

Oxidant / reductantnot specified

Work-upcool to room temperature; wash as-prepared sample with water several times; dry under vacuum

Activationpreformed Co3O4 NWAs from route_co3o4_nwa_cc

Scalability context3 x 4 cm Co3O4 electrode coated in a 50 mL autoclave; no continuous or larger-scale process reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(C5H4F3O2)2	50 mg	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Linker	HHTP	35 mg	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Solvent	water	40 mL	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Solvent	1-methyl-2-pyrrolidone (NMP)	2 mL	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Other	Co3O4 nanowire-array electrode	3 x 4 cm; Co3O4/Cu(C5H4F3O2)2 weight ratio 2:1	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT

Partial recipeSource: Main

Route 2: Solvothermal

p007 / journal p.6581 · Fabrication of Co3O4@CuCAT

Metal precursorsCu(C5H4F3O2)2; preformed Co3O4 on carbon cloth

Linker precursorsHHTP

Solventswater/NMP as in optimal coating route

AdditivesNMP

Atmospherenot specified; sealed autoclave

Temperature85 deg C

Time12 h inferred from optimal route; variant sentence states synthesized at 85 deg C

Substrate orientationCo3O4 nanowire-array electrode immersed in Cu/HHTP solution

Oxidant / reductantnot specified

Work-upnot separately stated; assumed same wash/dry as optimal route

Activationpreformed Co3O4 NWAs

Scalability contextOnly weight ratios are reported for variants; exact masses per variant are not listed.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(C5H4F3O2)2	varied; ratios 8:1, 4:1, 1:1, 1:2 versus Co3O4	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Linker	HHTP	not separately specified for variants	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Solvent	water	not separately specified for variants	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Solvent	NMP	not separately specified for variants	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT
Other	Co3O4 nanowire-array electrode	varied by weight ratio	p007 / journal p.6581 · Fabrication of Co3O4@CuCAT

Complete recipeSource: Main

Route 3: Hydrothermal

p007 / journal p.6581 · Fabrication of Co3O4

Metal precursorsCo(NO3)2·6H2O, 6 mmol

Solventswater, 40 mL; carbon cloth rinsed with acetone, ethanol, and water after nitric-acid activation

Additivesurea, 30 mmol; NH4F, 18 mmol; concentrated nitric acid activation of carbon cloth

Atmospherestatic air during annealing

Temperature100 deg C hydrothermal growth; 60 deg C drying; 400 deg C annealing

Time30 min stirring; 8 h hydrothermal; 10 h drying; 3 h annealing

Substrate orientationcarbon cloth 3 x 4 cm2 in 50 mL Teflon-lined stainless-steel autoclave

Oxidant / reductantthermal dehydration/oxidation of Co(OH)F precursor in air

Work-upcool to room temperature; wash carbon cloth with ethanol and water; dry at 60 deg C for 10 h; anneal precursor in clean crucible

Activationcarbon cloth activated with concentrated nitric acid and rinsed thoroughly

Scalability contextSubstrate-scale 3 x 4 cm2 carbon cloth in a 50 mL autoclave; no larger-scale synthesis reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	6 mmol	p007 / journal p.6581 · Fabrication of Co3O4
Base	urea	30 mmol	p007 / journal p.6581 · Fabrication of Co3O4
Additive	NH4F	18 mmol	p007 / journal p.6581 · Fabrication of Co3O4
Solvent	water	40 mL	p007 / journal p.6581 · Fabrication of Co3O4
Acid	concentrated nitric acid	not specified · concentrated	p007 / journal p.6581 · Fabrication of Co3O4
Other	carbon cloth	3 x 4 cm2	p007 / journal p.6581 · Fabrication of Co3O4

Complete recipeSource: Main

Route 4: Solvothermal

p007 / journal p.6581 · Fabrication of CuCAT

Metal precursorsCu(C5H4F3O2)2, 50 mg

Linker precursorsHHTP, 35 mg

Solventswater, 40 mL; NMP, 2 mL

AdditivesNMP cosolvent/additive; no separate base reported

Atmospherenot specified; sealed Teflon-lined autoclave

Temperature85 deg C

Time12 h plus overnight drying

Substrate orientationpowder synthesis; later dispersion cast onto CC for electrode sample

Oxidant / reductantnot specified

Work-upcool to room temperature; centrifuge product; dry overnight; cast powder dispersion onto CC and dry overnight for electrode

Activationnone reported

Scalability context50 mL autoclave batch; no yield or scale-up reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(C5H4F3O2)2	50 mg	p007 / journal p.6581 · Fabrication of CuCAT
Linker	HHTP	35 mg	p007 / journal p.6581 · Fabrication of CuCAT
Solvent	water	40 mL	p007 / journal p.6581 · Fabrication of CuCAT
Solvent	1-methyl-2-pyrrolidone (NMP)	2 mL	p007 / journal p.6581 · Fabrication of CuCAT
Other	carbon cloth for cast electrode	1 x 1 cm2 geometric area	p007 / journal p.6581 · Fabrication of CuCAT

Complete recipeSource: Main

Route 5: Drop Cast

p008 / journal p.6582 · Electrochemical measurements

Metal precursorscommercial IrO2, ca. 2 mg

Solventswater, 1 mL

Additives0.1% Nafion, 30 uL (text OCR shows 30 mL but this is likely microlitre in the rendered page)

Atmospherenot specified

Temperatureroom temperature drying overnight (temperature not specified)

Timeovernight drying

Substrate orientationcarbon cloth, geometric area 1 x 1 cm2

Oxidant / reductantnot applicable

Work-upultrasonically disperse IrO2 in water/Nafion; transfer dispersion onto CC; dry overnight

Activationnone reported

Scalability contextBenchmark electrode fabrication only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	commercial IrO2	ca. 2 mg	p008 / journal p.6582 · Electrochemical measurements
Solvent	water	1 mL	p008 / journal p.6582 · Electrochemical measurements
Additive	Nafion	30 uL inferred from rendered page/common notation; OCR says 30 mL · 0.1 %	p008 / journal p.6582 · Electrochemical measurements
Other	carbon cloth	1 x 1 cm2	p008 / journal p.6582 · Electrochemical measurements

Complete recipeSource: Main

Route 6: Drop Cast

p008 / journal p.6582 · Electrochemical measurements

Metal precursorscommercial 20% Pt/C, ca. 2 mg

Solventswater, 1 mL

Additives0.1% Nafion, 30 uL (text OCR shows 30 mL but this is likely microlitre in the rendered page)

Atmospherenot specified

Temperatureroom temperature drying overnight (temperature not specified)

Timeovernight drying

Substrate orientationcarbon cloth, geometric area 1 x 1 cm2

Oxidant / reductantnot applicable

Work-upultrasonically disperse Pt/C in water/Nafion; transfer dispersion onto CC; dry overnight

Activationnone reported

Scalability contextBenchmark electrode fabrication only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	commercial 20% Pt/C	ca. 2 mg · 20 % Pt/C	p008 / journal p.6582 · Electrochemical measurements
Solvent	water	1 mL	p008 / journal p.6582 · Electrochemical measurements
Additive	Nafion	30 uL inferred from rendered page/common notation; OCR says 30 mL · 0.1 %	p008 / journal p.6582 · Electrochemical measurements
Other	carbon cloth	1 x 1 cm2	p008 / journal p.6582 · Electrochemical measurements