Synthesis · 3D self-branched zinc-cobalt Oxide@N-doped carbon hollow nanowall arrays for high-performance asymmetric supercapacitors and oxygen electrocatalysis

11 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Other

654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Metal precursorsCo-MOF/CTs

Linker precursors2-methylimidazole in Co-MOF

AtmosphereAr; air

Temperature700; 250

Time2; 1.5

Substrate orientationCo-MOF/CTs piece

Oxidant / reductantair oxidation after Ar carbonization

Work-upsame procedure as ZnCo2O4@NC/CTs, using Co-MOF/CTs precursor

Activationsame carbonization/oxidation sequence as target ZnCo2O4@NC/CTs

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co-MOF/CTs	one piece	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs
Other	Ar	Not specified	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs
Oxidant	air	Not specified	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Complete recipeSource: Main

Route 2: Other

654 · 2.1. Preparation of Co-MOF/CTs

Metal precursorsCo(NO3)2.6H2O

Linker precursors2-methylimidazole (C4H6N2)

SolventsDI water

Atmosphereambient; vacuum oven drying

Temperatureroom temperature; 60

Time6; overnight

Substrate orientationpretreated carbon textiles, both ends and back side protected with cellulose tape

Work-upsample taken out, cleaned with DI water

Activationdried in a vacuum oven at 60 C overnight

Scalability contextReported as a simple solution-based method at room temperature.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	0.582 g	654 · 2.1. Preparation of Co-MOF/CTs
Linker	2-methylimidazole (C4H6N2)	1.3 g	654 · 2.1. Preparation of Co-MOF/CTs
Solvent	DI water	40 mL for solution A; 40 mL for solution B	654 · 2.1. Preparation of Co-MOF/CTs
Other	pretreated carbon textiles	1.5 x 5.0 x 0.033 cm3	654 · 2.1. Preparation of Co-MOF/CTs

Partial recipeSource: Both

Route 3: Other

SI p.12 · Part 3 Figures · Fig. S8

Metal precursorsCo(NO3)2.6H2O

Linker precursors2-methylimidazole (C4H6N2)

SolventsDI water

Atmosphereambient room-temperature ageing; vacuum oven drying

Temperatureroom temperature; 60

Time1.5; 3.0; 4.5; 6.0; overnight drying

Substrate orientationpretreated CTs immersed with both ends and back side protected by cellulose tape

Work-upcleaned with DI water

Activationdried in a vacuum oven at 60 C overnight

Scalability contextSame growth also demonstrated on Fe foil, Ni foam and graphite paper.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	0.582 g	SI p.12 · Part 3 Figures · Fig. S8
Linker	2-methylimidazole (C4H6N2)	1.3 g	SI p.12 · Part 3 Figures · Fig. S8
Solvent	DI water	40 mL for solution A; 40 mL for solution B	SI p.12 · Part 3 Figures · Fig. S8

Complete recipeSource: Main

Route 4: Other

654 · 2.1. Preparation of Co-MOF/CTs

Solventsconcentrated nitric acid (70%); distilled water

Atmosphereair oven

Temperatureroom temperature; 70

Timeovernight; 5

Substrate orientationcarbon textiles substrate

Oxidant / reductantnitric acid

Work-uprinsed with DI water until pH 7.0

Activationdried in hot air oven at 70 C for 5 h

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Acid	concentrated nitric acid	70%	654 · 2.1. Preparation of Co-MOF/CTs
Solvent	distilled (DI) water	Not specified	654 · 2.1. Preparation of Co-MOF/CTs

Complete recipeSource: SI

Route 5: Drop Cast

Part 1 Supplementary method

Metal precursorsFe3O4@r-GO nanocomposite powder

Linker precursorsnone

SolventsN-methylpyrrolidinone (NMP)

Additivesacetylene black; polyvinylidene fluoride (PVDF)

Atmospherevacuum oven drying

Temperature120

Timeovernight

Substrate orientationcarbon textiles, 1.5 x 5.0 x 0.033 cm3

Work-upslurry coated onto carbon textiles using a small spatula

Activationdried at 120 C in a vacuum oven overnight

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe3O4@r-GO	80 wt% of solids	Part 1 Supplementary method
Additive	acetylene black	10 wt% of solids	Part 1 Supplementary method
Additive	polyvinylidene fluoride (PVDF)	10 wt% of solids	Part 1 Supplementary method
Solvent	N-methylpyrrolidinone (NMP)	Not specified	Part 1 Supplementary method

Complete recipeSource: SI

Route 6: Solvothermal

Part 1 Supplementary method

Metal precursorsFe(NO3)3.9H2O; FeCl3.6H2O

Linker precursorsnone

SolventsDI water

Additivesr-GO; NaNO3

AtmosphereAr during final annealing

Temperature50; 60; 450

Time2; 12; 2

Work-upcentrifugation, DI-water washing several times, vacuum freeze-drying

Activationannealed at 450 C for 2 h in Ar atmosphere

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	r-GO	10 mg initially; 15 mg freeze-dried powders in second step	Part 1 Supplementary method
Metal Source	Fe(NO3)3.9H2O	1.0 g	Part 1 Supplementary method
Metal Source	FeCl3.6H2O	0.432 g	Part 1 Supplementary method
Additive	NaNO3	0.864 g	Part 1 Supplementary method
Solvent	DI water	100 mL; 35 mL	Part 1 Supplementary method

Complete recipeSource: Main

Route 7: Other

655 · 2.5. Electrochemical characterization

Metal precursorsZnCo2O4@NC/CTs cathode; Fe3O4@r-GO/CTs anode

SolventsDI water

AdditivesPVA; KOH

Atmosphereambient assembly

Temperature85; room temperature

Time3; 0.167

Substrate orientationtwo electrodes assembled face-to-face

Work-upelectrodes immersed in PVA-KOH gel electrolyte and left at room temperature for 10 min

ActivationPVA-KOH gel solidified; device packed and tested

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	PVA	3.0 g	655 · 2.5. Electrochemical characterization
Solvent	DI water	30 mL	655 · 2.5. Electrochemical characterization
Electrolyte	KOH solution	10 mL · 4 M	655 · 2.5. Electrochemical characterization
Other	ZnCo2O4@NC/CTs and Fe3O4@r-GO/CTs electrodes	two pieces of electrodes	655 · 2.5. Electrochemical characterization

Complete recipeSource: Main

Route 8: Other

654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Metal precursorsZnCo-MOF/CTs

Linker precursorsorganic ligands in ZnCo-MOF precursor

Atmosphereair

Temperature400

Time2

Substrate orientationZnCo-MOF/CTs piece

Oxidant / reductantair oxidation

Activationannealed in air at 400 C for 2 h with ramp rate 1.5 C min-1

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ZnCo-MOF/CTs	one piece	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs
Oxidant	air	Not specified	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Complete recipeSource: Main

Route 9: Other

654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Metal precursorsZnCo-MOF/CTs

Linker precursorsorganic ligands in ZnCo-MOF precursor

AtmosphereAr; air

Temperature700; 250

Time2; 1.5

Substrate orientationZnCo-MOF/CTs piece

Oxidant / reductantair oxidation after Ar carbonization

Work-upcooling to room temperature between annealing steps

ActivationAr annealing at 700 C for 2 h followed by air annealing at 250 C for 1.5 h; both ramp rates 1.5 C min-1

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ZnCo-MOF/CTs	one piece	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs
Other	Ar	Not specified	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs
Oxidant	air	Not specified	654 · 2.3. Preparation of 3D self-branched ZnCo2O4@NC/CTs

Complete recipeSource: Main

Route 10: Other

654 · 2.2. Preparation of ZnCo-MOF/CTs

Metal precursorsCo-MOF/CTs; Zn(NO3)2.6H2O

Linker precursors2-methylimidazole retained from Co-MOF

Solventsethanol

Atmospherevacuum oven drying

Temperatureroom temperature; 60

Time0.5; 10

Substrate orientationCo-MOF/CTs piece immersed in Zn nitrate ethanol solution

Work-upwashed with ethanol several times

Activationdried in vacuum oven at 60 C for 10 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	0.3 g	654 · 2.2. Preparation of ZnCo-MOF/CTs
Solvent	ethanol	60 mL	654 · 2.2. Preparation of ZnCo-MOF/CTs
Other	Co-MOF/CTs	one piece	654 · 2.2. Preparation of ZnCo-MOF/CTs

Complete recipeSource: Both

Route 11: Other

654 · 2.2. Preparation of ZnCo-MOF/CTs · Fig. S6-S7

Metal precursorsCo-MOF/CTs; Zn(NO3)2.6H2O

Linker precursors2-methylimidazole retained from Co-MOF

Solventsethanol

Atmospherevacuum oven drying

Temperatureroom temperature; 60

Time0.167; 0.333; 0.5; 1.0; 10 h drying

Substrate orientationCo-MOF/CTs immersed in Zn nitrate ethanol solution

Work-upwashed with ethanol several times

Activationdried in vacuum oven at 60 C for 10 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	0.3 g	654 · 2.2. Preparation of ZnCo-MOF/CTs · Fig. S6-S7
Solvent	ethanol	60 mL	654 · 2.2. Preparation of ZnCo-MOF/CTs · Fig. S6-S7
Other	Co-MOF/CTs	one piece	654 · 2.2. Preparation of ZnCo-MOF/CTs · Fig. S6-S7