Synthesis · Conductive Metal-Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries

6 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

S6 · The synthesis of compound 2 · Scheme S2

Linker precursors1,2-dimethoxybenzene

Solventsconcentrated nitric acid (65%)

Atmospherenot specified

Temperature0 degC addition; then 80 degC

Time5

Oxidant / reductantHNO3 nitration

Work-upcool to room temperature; filter yellow precipitate; wash with deionised water until neutral pH; dry

Scalability context24.98 g product, 108.6 mmol, 92% yield reported.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Acid	concentrated nitric acid	100 mL · 65%	S6 · The synthesis of compound 2 · Scheme S2
Linker	1,2-Dimethoxybenzene	15 mL, 16.26 g	S6 · The synthesis of compound 2 · Scheme S2

Complete recipeSource: SI

Route 2: Other

S6 · The synthesis of compound 3 · Scheme S2

Linker precursorscompound 2 / 1,2-dimethoxy-4,5-dinitrobenzene

Solventsethanol

AdditivesPd/C catalyst

Atmospherenitrogen

Temperature0 degC addition; then 80 degC

Time5

Oxidant / reductanthydrazine monohydrate reductant

Work-upcool; filter; wash with ethanol three times; concentrate filtrate

Scalability context1.21 g product, 7.19 mmol, 82% yield reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Compound 2	2.0 g, 8.76 mmol	S6 · The synthesis of compound 3 · Scheme S2
Solvent	ethanol	40 mL	S6 · The synthesis of compound 3 · Scheme S2
Additive	Pd/C catalyst	200 mg	S6 · The synthesis of compound 3 · Scheme S2
Reductant	hydrazine monohydrate	4.26 mL, 87.6 mmol	S6 · The synthesis of compound 3 · Scheme S2

Complete recipeSource: SI

Route 3: Other

S6 · The synthesis of compound 4 · Scheme S2

Linker precursorscompound 3 and hexaketocyclohexane octahydrate

Solventsacetic acid

Atmosphereargon

Temperature120

Time24

Work-upcool to room temperature; wash several times with methanol, acetone, and water; dry under vacuum

Scalability context0.62 g product, 1.09 mmol, 43% yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4,5-dimethoxybenzene-1,2-diamine Compound 3	1.5 g, 8.92 mmol	S6 · The synthesis of compound 4 · Scheme S2
Linker	hexaketocyclohexane octahydrate	0.796 g, 2.55 mmol	S6 · The synthesis of compound 4 · Scheme S2
Solvent	acetic acid	40 mL	S6 · The synthesis of compound 4 · Scheme S2

Complete recipeSource: SI

Route 4: Other

S7 · The synthesis of HAN-6OH · Scheme S2

Linker precursorscompound 4

Solventsdeionised water workup

Additivespyridine hydrochloride

Atmospherenot specified

Temperature230; drying at 120

Time4; drying 12

Work-upcool naturally; add 100 mL deionised water; centrifuge; wash black precipitate with excess deionised water until neutral

Activationdry at 120 degC for 12 h

Scalability context0.35 g product, 70% yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Compound 4	0.5 g, 0.89 mmol	S7 · The synthesis of HAN-6OH · Scheme S2
Additive	pyridine hydrochloride	20 g, 173 mmol	S7 · The synthesis of HAN-6OH · Scheme S2
Solvent	deionized water	100 mL	S7 · The synthesis of HAN-6OH · Scheme S2

Complete recipeSource: SI

Route 5: Drop Cast

S1-S2 · Electrochemical Measurements

Solventswater implied by CMC/SBR binder; exact slurry solvent not explicitly stated

AdditivesSuper-P conductive carbon; CMC/SBR binder

Atmospherecell assembly in Ar glovebox with O2 and H2O below 0.1 ppm

Temperature70

Time12

Substrate orientationCu foil current collector

Work-upslurry applied onto Cu foil and dried under vacuum

Scalability contextActive material loading approximately 1-1.5 mg cm-2.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	active materials	60 wt part	S1-S2 · Electrochemical Measurements
Additive	Super-P	30 wt part	S1-S2 · Electrochemical Measurements
Additive	CMC/SBR binder, mass ratio 1:1	10 wt part	S1-S2 · Electrochemical Measurements
Electrolyte	KFSI in EC:EMC	5 M; EC:EMC v:v 1:1	S1-S2 · Electrochemical Measurements
Other	potassium metal counter electrode	Not specified	S1-S2 · Electrochemical Measurements

Complete recipeSource: Both

Route 6: Solvothermal

S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1

Metal precursorsCopper(II) nitrate trihydrate

Linker precursorsHAN-6OH

Solvents2 mL deionised water, 100 uL methanol, 100 uL DMF

Additives74 uL ethylenediamine

Atmospheredegassed by three freeze-pump-thaw cycles; Schlenk tube

Temperature120

Time48

Work-upcool to room temperature; wash multiple times with DMF, acetone, and water

Activationdry overnight under vacuum at 120 degC

Scalability contextMain text gives solution reaction; SI gives milligram scale quantities.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Copper (II) nitrate trihydrate	19.2 mg, 0.083 mmol	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1
Linker	HAN-6OH	26.4 mg, 0.055 mmol	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1
Solvent	deionized water	2 mL	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1
Solvent	methanol	100 uL	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1
Solvent	DMF	100 uL	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1
Base	ethylenediamine	74 uL	S7 · The synthesis of HAN-Cu-MOF · Figure 1a; Scheme S1