Synthesis · Overcoming Diffusion Limitation of Faradaic Processes: Property-Performance Relationships of 2D Conductive Metal-Organic Framework Cu3(HHTP)2 for Reversible Lithium-Ion Storage

4 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2

Metal precursors127 mg Cu(NO3)2.3H2O (0.53 mmol, 1.75 eq.; Sigma Aldrich, 99.0%)

Linker precursors130 mg H6HHTP (0.3 mmol, 1 eq.)

Solvents8.4 mL deionised water for linker dispersion; 2 mL deionised water for copper nitrate solution; water and ethanol washes; Soxhlet extraction as for rod-like MOF

Additives1.02 mL 25% ammonia solution, corresponding to 15 mmol and 50 eq. NH3

AtmosphereNot specified for synthesis; drying/activation under rough or reduced vacuum

Temperature85; electrode-active material later dried at 60

Time24 h synthesis; Soxhlet extraction duration not restated but stated to be like rod-like procedure

Oxidant / reductantOxygen is proposed as oxidant in the reaction scheme, but no controlled oxidant atmosphere is specified for synthesis.

Work-upCooled to RT, diluted to 40 mL, centrifuged 10 min at 9500 rpm, washed twice with 40 mL deionised water and once with 40 mL ethanol, dried at rough vacuum overnight, Soxhlet washed.

ActivationLike rod-like MOF Soxhlet workup; final product dried, with 60 C chosen as activation/drying temperature for investigated electrodes.

Scalability contextAmmonia modulator redirects crystal growth laterally to thin flakes.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6HHTP	130 mg; 0.3 mmol; 1 eq.	S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2
Metal Source	Cu(NO3)2.3H2O	127 mg; 0.53 mmol; 1.75 eq. · 99.0%	S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2
Solvent	deionized water	8.4 mL plus 2 mL and washing volumes	S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2
Base	ammonia solution	1.02 mL; 15 mmol NH3; 50 eq. · 25%	S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2
Solvent	ethanol	40 mL final wash; Soxhlet solvent as for rod-like route	S-2 to S-3 · 1.1.2 Flake-like Cu3(HHTP)2

Complete recipeSource: SI

Route 2: Drop Cast

S-5 · 1.3 Electrode preparation

Metal precursorsFlake-like Cu3(HHTP)2 powder active material

Solvents1.6 mL anhydrous N-methyl-2-pyrrolidone

AdditivesCarbon black Super C65 and PVDF binder

AtmosphereDry-room labelling after drying; cells assembled in Ar glovebox

Temperature60 for final Schlenk drying

TimePVDF dissolution 30 min; homogenisation 30 min; final drying 20 h

Substrate orientationCast onto 20 um aluminium foil; Be disc used for in situ XRD electrodes

Work-upCast with 100 um wet-film thickness, vacuum dried overnight, punched into 12 mm electrodes and dried again under <0.05 mbar at 60 C.

ActivationElectrodes dried on Schlenk line under reduced pressure <0.05 mbar at 60 C for 20 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	flake-like Cu3(HHTP)2	100 mg; 60 wt% active material in final paste	S-5 · 1.3 Electrode preparation
Additive	carbon black Super C65	50 mg; 30 wt%	S-5 · 1.3 Electrode preparation
Additive	PVDF Solef PVdF 5130	16.7 mg; 10 wt%	S-5 · 1.3 Electrode preparation
Solvent	anhydrous N-methyl-2-pyrrolidone	1.6 mL · 99.8%	S-5 · 1.3 Electrode preparation

Complete recipeSource: SI

Route 3: Solvothermal

S-2 · 1.1.1 Rod-like Cu3(HHTP)2

Metal precursors180 mg copper trifluoroacetylacetonate (Cu3(F3Acac)2; 0.486 mmol, 1.5 eq.; Sigma Aldrich)

Linker precursors105 mg H6HHTP (0.324 mmol, 1 eq.; TCI Chemicals)

Solvents15 mL deionised water and 15 mL 1-propanol; acetone and ethanol used in washing; 250 mL boiling ethanol used for Soxhlet extraction

AtmosphereNot specified for synthesis; activation under reduced pressure/fine vacuum

Temperature85; activation at RT then 60

Time24 h synthesis; Soxhlet 24 h; final vacuum drying 20 h at RT and 20 h at 60 C

Oxidant / reductantOxygen is proposed as oxidant in the reaction scheme, but no controlled oxidant atmosphere is specified for synthesis.

Work-upCooled to RT, diluted to 40 mL, centrifuged 10 min at 9500 rpm, washed twice with 40 mL acetone and once with 40 mL ethanol, dried under reduced pressure, Soxhlet extracted in ethanol.

ActivationPre-dried under <1 mbar overnight, then Schlenk line fine vacuum <0.05 mbar at RT for 20 h and 60 C for 20 h.

Scalability contextMain text notes rod-like particles may have small outgrowths caused by 10- to 30-fold upscaling or surface sensitivity.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6HHTP	105 mg; 0.324 mmol; 1 eq.	S-2 · 1.1.1 Rod-like Cu3(HHTP)2
Metal Source	copper triflouroacetylacetonate (Cu3(F3Acac)2)	180 mg; 0.486 mmol; 1.5 eq.	S-2 · 1.1.1 Rod-like Cu3(HHTP)2
Solvent	deionized water	15 mL plus transfer/wash water	S-2 · 1.1.1 Rod-like Cu3(HHTP)2
Solvent	1-propanol	15 mL · 99.7%	S-2 · 1.1.1 Rod-like Cu3(HHTP)2
Solvent	acetone	40 mL wash repeated twice	S-2 · 1.1.1 Rod-like Cu3(HHTP)2
Solvent	ethanol	40 mL wash; 250 mL Soxhlet extraction	S-2 · 1.1.1 Rod-like Cu3(HHTP)2

Complete recipeSource: SI

Route 4: Drop Cast

S-5 · 1.3 Electrode preparation

Metal precursorsRod-like Cu3(HHTP)2 powder active material

Solvents1.6 mL anhydrous N-methyl-2-pyrrolidone

AdditivesCarbon black Super C65 and PVDF binder

AtmosphereDry-room labelling after drying; cells assembled in Ar glovebox

Temperature60 for final Schlenk drying

TimePVDF dissolution 30 min; homogenisation 30 min; final drying 20 h

Substrate orientationCast onto 20 um aluminium foil; Be disc used for in situ XRD electrodes

Work-upCast with 100 um wet-film thickness, vacuum dried overnight, punched into 12 mm electrodes and dried again under <0.05 mbar at 60 C.

ActivationElectrodes dried on Schlenk line under reduced pressure <0.05 mbar at 60 C for 20 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	rod-like Cu3(HHTP)2	100 mg; 60 wt% active material in final paste	S-5 · 1.3 Electrode preparation
Additive	carbon black Super C65	50 mg; 30 wt%	S-5 · 1.3 Electrode preparation
Additive	PVDF Solef PVdF 5130	16.7 mg; 10 wt%	S-5 · 1.3 Electrode preparation
Solvent	anhydrous N-methyl-2-pyrrolidone	1.6 mL · 99.8%	S-5 · 1.3 Electrode preparation