Synthesis · A 2D copper-imidazolate framework without thermal treatment as an efficient ORR electrocatalyst for Zn-air batteries

6 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

5 · II.3 Scale-up synthesis · Fig. S3

Metal precursorsCuCl2 aqueous precursor, scaled relative to optimised recipe

Linker precursorsICA aqueous precursor, scaled relative to optimised recipe

Solventswater; methanol workup

AdditivesCTAB

Atmosphereambient air; room temperature

TemperatureRT

Time15 h

Work-upsame as optimised route

ActivationNo calcination or thermal activation reported.

Scalability contextFinal synthesis volume increased from 10 mL to 100 mL; yielded 105 mg. 30x scale decreased crystallinity and particle-size homogeneity.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuCl2	scaled 10x · 25 mM in optimised recipe	5 · II.3 Scale-up synthesis · Fig. S3
Linker	ICA	scaled 10x · 50 mM in optimised recipe	5 · II.3 Scale-up synthesis · Fig. S3
Additive	CTAB	scaled 10x · 0.25 mM solution in optimised recipe	5 · II.3 Scale-up synthesis · Fig. S3

Partial recipeSource: SI

Route 2: Other

5 · II.2 Influence of the copper precursor and solvent · Fig. S2

Metal precursorsCu(NO3)2 used instead of CuCl2

Linker precursorsimidazole-2-carboxaldehyde under the optimised procedure

Solventswater; methanol workup as in optimised procedure

AdditivesCTAB as in optimised procedure

Atmosphereambient air; room temperature

TemperatureRT

Time15 h

Work-upsame workup as optimised synthesis implied

ActivationNo calcination or thermal activation reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	not separately specified · implied 25 mM Cu(II)	5 · II.2 Influence of the copper precursor and solvent · Fig. S2
Linker	imidazole-2-carboxaldehyde (ICA)	not separately specified · implied 50 mM	5 · II.2 Influence of the copper precursor and solvent · Fig. S2
Additive	CTAB	not separately specified · optimised conditions	5 · II.2 Influence of the copper precursor and solvent · Fig. S2

Complete recipeSource: Both

Route 3: Other

4 · II.1 Optimized synthetic procedure · Fig. S1

Metal precursorscopper(II) chloride, CuCl2, aqueous solution (4 mL, 25 mM)

Linker precursorsimidazole-2-carboxaldehyde (ICA), aqueous solution (4 mL, 50 mM)

Solventswater for reaction; methanol for washing/solvent exchange and redispersion

Additivescetyltrimethylammonium bromide (CTAB), 4 mL, 0.25 mM; optimum final CTAB concentration reported as 0.1 mM

Atmosphereambient air; room temperature

TemperatureRT; ICA solution heated to 80 C only for dissolution; vacuum drying at 60 C for 18 h mentioned in TGA discussion

Time15 h growth after 5 min stirring

Work-upcentrifugation at 10000 RCF for 5 min; washed three times with methanol to remove water and CTAB; vacuum-dried and redispersed in methanol

ActivationNo thermal activation/calcination; solvent exchange with methanol and mild vacuum drying remove solvent molecules.

Scalability contextMain text and SI report scale-up to 105 mg nanosheets at 10x reaction volume.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper(II) chloride (CuCl2; Sigma Aldrich #451665)	4 mL · 25 mM	4 · II.1 Optimized synthetic procedure · Fig. S1
Linker	imidazole-2-carboxaldehyde (ICA; Sigma Aldrich #272000)	4 mL aqueous solution · 50 mM	4 · II.1 Optimized synthetic procedure · Fig. S1
Additive	cetyltrimethylammonium bromide (CTAB; Sigma Aldrich #H5882)	4 mL · 0.25 mM solution; optimum final concentration 0.1 mM	4 · II.1 Optimized synthetic procedure · Fig. S1
Solvent	water	reaction solvent	4 · II.1 Optimized synthetic procedure · Fig. S1
Solvent	methanol	wash solvent; redispersion solvent · 2 mg mL-1 final stock dispersion	4 · II.1 Optimized synthetic procedure · Fig. S1

Complete recipeSource: SI

Route 4: Drop Cast

28 · VI.1 Description of two types of Zn-air batteries · Fig. S32B

Metal precursorspreformed 2DCIF nanosheets

Solventsmethanol for 2DCIF ink; isopropanol in Nafion overcoat

Additives5% Nafion/isopropanol solution; PVDF binder in carbon disk

Atmosphereambient temperature drying

Temperature80 C hot pressing for carbon disk fabrication; ambient drying after drop-casting

Time1 min hot pressing

Substrate orientationhomemade carbon disk

Work-upcarbon disks hot-pressed from carbon black and 10% PVDF at 250 bar for 1 min; 2DCIF ink drop-cast and Nafion-coated

Activationnone

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2DCIF methanolic dispersion	25 uL · 15 mg mL-1	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32B
Additive	PVDF	10%	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32B
Other	carbon black	carbon disk component	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32B
Additive	Nafion/isopropanol solution	one drop · 5%	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32B

Complete recipeSource: SI

Route 5: Drop Cast

28 · VI.1 Description of two types of Zn-air batteries · Fig. S32A

Metal precursorspreformed 2DCIF nanosheets

Solventsmethanol for 2DCIF ink; isopropanol in Nafion overcoat

Additives5% Nafion/isopropanol solution

Atmosphereambient temperature drying

Temperatureambient

Substrate orientationSigracet BC 35 carbon paper

Work-updrop-cast 25 uL of 15 mg mL-1 2DCIF dispersion; dry; coat with one drop of 5% Nafion/isopropanol

Activationnone

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2DCIF methanolic dispersion	25 uL · 15 mg mL-1	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32A
Additive	Nafion/isopropanol solution	one drop · 5%	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32A
Other	Sigracet BC 35 carbon paper	0.63 cm2 active area in contact with electrolyte	28 · VI.1 Description of two types of Zn-air batteries · Fig. S32A

Complete recipeSource: SI

Route 6: Drop Cast

3 · I. General information; Electrocatalytic measurements · Fig. 3

Metal precursorspreformed 2DCIF nanosheets

Solventsmethanol

Additivesnone; Pt/C control also prepared without Nafion

Atmosphereambient handling; dried at 4 C

Temperature4

Timeovernight drying

Substrate orientationglassy carbon disk electrode, 5 mm diameter

Work-up25 uL of 2 mg mL-1 dispersion cast onto clean GC surface and dried overnight

Activationnone

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2DCIF methanolic dispersion	25 uL · 2 mg mL-1	3 · I. General information; Electrocatalytic measurements · Fig. 3
Solvent	methanol	Not specified	3 · I. General information; Electrocatalytic measurements · Fig. 3