Synthesis · Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal-Organic Framework Incorporating Nickel Bis(diimine) Units

5 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

S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2

Linker precursorsTriphenylene, then brominated compound 1, protected imine compound 2

SolventsNitrobenzene, diethyl ether, dichlorobenzene, degassed toluene, dichloromethane, ethyl acetate/hexane chromatography, THF

AdditivesIron shavings, bromine, Pd2(dba)3, racemic-BINAP, benzophenone imine, sodium tert-butoxide, HCl

AtmosphereNitrogen stream and freeze-pump-thaw cycles for synthesis of compound 2; other steps not inert.

Temperature205 C reflux for bromination; 110 C preheat and reflux for Buchwald-type amination; room temperature acid deprotection

Timeovernight stand plus 2 h reflux for compound 1; overnight reflux for compound 2; 0.5 h after acid addition for compound 3

Oxidant / reductantBromine for bromination; HCl for deprotection

Work-upEther precipitation/rinsing, dichlorobenzene recrystallisation/chilling, Celite filtration, column chromatography, centrifugation, THF washing, drying.

Scalability contextMulti-step ligand precursor route taken from literature.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	triphenylene	4.95 mmol; 1.13 g	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Additive	iron shavings	1.78 mmol; 100 mg	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Oxidant	liquid bromine	42.6 mmol; 2.2 mL	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Solvent	nitrobenzene	40 mL	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Additive	tris(dibenzylidenacetone)dipalladium(0)	0.343 mmol; 314 mg	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Additive	racemic-BINAP	0.686 mmol; 427 mg	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Additive	benzophenone imine	11.1 mmol; 1.9 mL	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Base	sodium tert-butoxide	11.1 mmol; 1.1 g	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2
Acid	hydrochloric acid	1.98 mmol; 1.0 mL · 2.0 M	S5-S6 · 2.2 The Synthesis of 2,3,6,7,10,11-Triphenylenehexamine · Scheme S2

Complete recipeSource: SI

Route 2: Drop Cast

S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27

SolventsEthanol for Ni3(HITP)2 ink; NMP for PVFc/carbon black counter-electrode ink

AdditivesPVFc and carbon black in counter electrode; ionic liquid [Bmim][TF2N] electrolyte

AtmosphereDevice atmosphere varied by test gas: 1-100% CO2, N2/O2/humid air mixtures

Temperatureambient / 298 K for device tests

Time0.5 h sonication for ink; 20 min vacuum drying for working electrode

Substrate orientationCarbon fibre paper

Oxidant / reductantPotential swing: -1.4 V capture and 1.1 V release

Work-upDrop-cast onto CFP and vacuum dry; counter electrode dried under vacuum at 80 C.

Scalability contextSingle-electrode lab device; authors propose stacked-cell engineering for scale-up.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2	20 mg	S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27
Solvent	ethanol	1 mL	S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27
Other	carbon fibre paper	working-electrode substrate	S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27
Additive	PVFc and carbon black	50 mg:50 mg in 2 mL NMP	S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27
Electrolyte	1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide	Not specified	S18-S19 · 10.3 Cyclic CO2 Capture and Release of Ni3(HITP)2 · Figures S19-S27

Complete recipeSource: Both

Route 3: Other

S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2

Metal precursorsNi(OAc)2.4H2O, 13.8 mg, 0.056 mmol

Linker precursorsHATP.6HCl, 20 mg, 0.038 mmol

SolventsWater, 10 mL for nickel solution and 10 mL for HATP solution

AdditivesConcentrated aqueous ammonia, 0.6 mL, 14 mol L-1

AtmosphereOpen beaker; air exposure implied

Temperature65

Time2

Work-upFiltered precipitate; washed with water (30 mL x 3), ethyl alcohol (30 mL x 3), and acetone (30 mL x 3).

ActivationDried under house vacuum for 6 h. Separate BET activation used H2O/ethanol soaking at 40 C and 80 C vacuum drying.

Scalability contextBatch recipe in 20 mL vial/open beaker; no scale-up demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	13.8 mg; 0.056 mmol	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2
Linker	HATP.6HCl	20 mg; 0.038 mmol	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2
Solvent	water	20 mL total	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2
Base	concentrated aqueous ammonia (NH4OH)	0.6 mL · 14 mol L-1	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2
Solvent	ethyl alcohol	30 mL x 3 wash	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2
Solvent	acetone	30 mL x 3 wash	S6-S7 · 2.3 The Synthesis of the MOF Ni3(HITP)2

Complete recipeSource: SI

Route 4: Drop Cast

S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16

SolventsEthanol for Ni(DIB)2/CB ink; NMP for PVFc/CB counter electrode

AdditivesCarbon black, PVFc, [Bmim][TF2N] ionic liquid electrolyte

Atmosphere100% CO2 for solid-state cyclic test

Temperatureambient / 298 K

Time0.5 h sonication; 20 min vacuum drying for working electrode

Substrate orientationCarbon fibre paper

Oxidant / reductantPotential swing: -1.4 V capture and 1.1 V release

Work-upDrop-cast working and counter electrodes; counter electrode dried under vacuum at 60 C before use.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni(DIB)2	13.5 mg	S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16
Additive	carbon black	13.5 mg	S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16
Solvent	ethanol	1 mL	S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16
Additive	PVFc and carbon black	30 mg PVFc and 30 mg carbon black	S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16
Electrolyte	1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide	Not specified	S16-S17 · 10.2 Cyclic CO2 Capture and Release of Ni(DIB)2 · Figure S16

Complete recipeSource: Both

Route 5: Other

S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1

Metal precursorsNickel(II) chloride, 10 g

Linker precursorso-phenylenediamine / DAB, 6 g

SolventsWater; warm water; acetone for washing/Soxhlet purification

AdditivesConcentrated aqueous ammonia, 30 mL

AtmosphereOpen vessel; not inert

Temperatureroom temperature for coupling; warm water used for DAB solution

Time24 h stirring; then Soxhlet extraction continued for three days after deep blue extract appeared

Work-upFiltered precipitate; washed with water and acetone; dried; Soxhlet extraction with acetone; crystals filtered, washed with acetone and vacuum dried.

Scalability contextGram-scale quantities reported for NiCl2 and o-phenylenediamine.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel(II) chloride	10 g	S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1
Linker	o-phenylenediamine (DAB)	6 g	S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1
Solvent	water	30 mL for NiCl2; 800 mL warm water for DAB	S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1
Base	concentrated aqueous ammonia	30 mL	S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1
Solvent	acetone	wash and Soxhlet extraction solvent	S4 · 2.1 The Synthesis of Ni(DIB)2 · Scheme S1