Synthesis · Solid-solid interface growth of conductive metal-organic framework nanowire arrays and their supercapacitor application

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Cvd

main p.2-3, article pp.244-245 · Synthesis of Cu3(HHTP)2 NWAs on Cu foils; Results and discussion · Fig. 1a

Metal precursorsSolid Cu foil substrate/current collector

Linker precursors1-3 mg HHTP in quartz boat in high-temperature zone

SolventsNo liquid solvent in the growth chamber; oxygenated water provides Ar/O-H2O flow

AtmosphereInitial evacuation to 1 Torr; argon/oxygenated water (Ar/O-H2O) mixture flow of 10 sccm during low-temperature step

TemperatureHigh-temperature zone 325 C at 25 C min-1 for 30 min; low-temperature zone 100 C for a period of time, explicitly 1 h in results discussion

Time0.5 h high-temperature sublimation; 1 h low-temperature reaction stated in Results and discussion

Substrate orientationPretreated Cu foils downstream in another quartz boat at low-temperature zone

Oxidant / reductantO2 in oxygenated water oxidises HHTP; HHTP quinone form converts Cu to Cu2+; H2O assists crystallisation

Work-upSlowly cooled to room temperature; washed thoroughly with ethanol and deionised water 5 times; dried under N2 stream. For mass measurement, dried under vacuum at 100 C for 30 h.

ActivationFor N2 sorption, products scraped from NWA/Cu foils heated to 100 C under vacuum for 10 h.

Scalability contextAuthors state the dual-temperature zone CVD method is expected to be useful for various conductive MOFs; mass loading tunable from 0.40 to 2.0 mg cm-2.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	pretreated Cu foil	round slices, F = 1.2 cm for electrode samples	main p.2-3, article pp.244-245 · Synthesis of Cu3(HHTP)2 NWAs on Cu foils; Results and discussion · Fig. 1a
Linker	HHTP	1-3 mg	main p.2-3, article pp.244-245 · Synthesis of Cu3(HHTP)2 NWAs on Cu foils; Results and discussion · Fig. 1a
Oxidant	oxygenated water in Ar/O-H2O mixture	10 sccm gas mixture flow	main p.2-3, article pp.244-245 · Synthesis of Cu3(HHTP)2 NWAs on Cu foils; Results and discussion · Fig. 1a
Other	argon	carrier gas in Ar/O-H2O mixture	main p.2-3, article pp.244-245 · Synthesis of Cu3(HHTP)2 NWAs on Cu foils; Results and discussion · Fig. 1a

Complete recipeSource: Main

Route 2: Other

main p.2, article p.244 · Preparation of powder electrodes

Metal precursorsCu3(HHTP)2 powders

SolventsN-methyl-2-pyrrolidone solution

AdditivesPolyvinylidene fluoride binder, Cu3(HHTP)2:PVDF = 80:20 w/w

AtmosphereVacuum drying

Temperature80

Time12 h stirring; 12 h vacuum drying

Substrate orientationCoated on Cu foil, F = 1.2 cm

Work-upSticky slurry coated on Cu foil and dried at 80 C under vacuum for 12 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HHTP)2 powders	mass loading 1.0 mg cm-2	main p.2, article p.244 · Preparation of powder electrodes
Additive	polyvinylidene fluoride	80:20 w/w Cu3(HHTP)2:PVDF	main p.2, article p.244 · Preparation of powder electrodes
Solvent	N-methyl-2-pyrrolidone solution	Not specified	main p.2, article p.244 · Preparation of powder electrodes

Complete recipeSource: Main

Route 3: Solvothermal

main p.2, article p.244 · Synthesis of Cu3(HHTP)2 powders

Metal precursorsCopper acetate monohydrate, 0.2 mmol

Linker precursorsHHTP, 0.1 mmol

Solvents5 mL water/N,N-dimethylformamide (DMF), v:v = 1:1

Temperature85

Time12

Work-upCooled naturally to room temperature; crystallite powders collected and washed thoroughly with ethanol and deionised water 5 times; dried under nitrogen stream.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate monohydrate	0.2 mmol	main p.2, article p.244 · Synthesis of Cu3(HHTP)2 powders
Linker	HHTP	0.1 mmol	main p.2, article p.244 · Synthesis of Cu3(HHTP)2 powders
Solvent	water/N,N-dimethylformamide (DMF)	5 mL, v:v = 1:1	main p.2, article p.244 · Synthesis of Cu3(HHTP)2 powders

Partial recipeSource: SI

Route 4: Cvd

SI p.S15 · Figure S13 caption · Fig. S13

Metal precursorsPretreated Fe foils

Linker precursorsHexahydroxybenzene (HHB) in high-temperature zone

SolventsNo liquid solvent in chamber; oxygenated water provides Ar/O-H2O flow

AtmosphereEvacuated to 1 Torr; argon/oxygenated water (Ar/O-H2O) mixture flow of 10 sccm

TemperatureHigh-temperature zone 250 C at 25 C min-1 for 60 min; low-temperature zone 100 C

Time1 h high-temperature step; low-temperature period not specified

Substrate orientationPretreated Fe foils in another quartz boat downstream of the low-temperature zone

Oxidant / reductantOxygenated water atmosphere

Scalability contextReported only as a generality demonstration for solid-solid interface growth.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	pretreated Fe foils	Not specified	SI p.S15 · Figure S13 caption · Fig. S13
Linker	hexahydroxybenzene (HHB)	Not specified	SI p.S15 · Figure S13 caption · Fig. S13
Oxidant	oxygenated water in Ar/O-H2O mixture	10 sccm mixture flow	SI p.S15 · Figure S13 caption · Fig. S13

Complete recipeSource: Main

Route 5: Other

main p.2, article p.244 · Fabrication of the supercapacitor

Metal precursorsTwo Cu3(HHTP)2 NWA electrodes

Solvents1 M KCl aqueous electrolyte

AdditivesWaterman separator membrane

Time10 h standing before testing

Substrate orientationTwo identical round slices, F = 1.2 cm, used as positive and negative electrodes

Work-upAssembled by applying suitable pressure; allowed to stand for 10 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HHTP)2 NWA electrodes	two identical round slices; mass loading 1.0 mg cm-2	main p.2, article p.244 · Fabrication of the supercapacitor
Electrolyte	KCl aqueous electrolyte	1 M	main p.2, article p.244 · Fabrication of the supercapacitor
Additive	separator membrane (waterman)	one piece	main p.2, article p.244 · Fabrication of the supercapacitor