Synthesis · Selective reduction of CO2 by conductive MOF nanosheets as an efficient co-catalyst under visible light illumination

4 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets

Metal precursorsNiCl2.6H2O, 0.056 mmol in 10 mL ultrapure water.

Linker precursorsHITP.HCl, 0.038 mmol in 10 mL ultrapure water.

SolventsUltrapure water; acetone for reflux workup.

AdditivesConcentrated NH3.H2O, 600 uL, 14 mol L-1.

AtmosphereAir during 65 C reaction.

Temperature65 C reaction; 150 C vacuum drying.

Time2 h reaction; 24 h water reflux; 3 h acetone reflux; 12 h vacuum drying.

Work-upCentrifuged, refluxed in ultrapure water for 24 h with water refreshed each 12 h, refluxed in acetone for 3 h.

ActivationDried under vacuum at 150 C for 12 h.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HITP.HCl	0.038 mmol	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets
Metal Source	NiCl2.6H2O	0.056 mmol	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets
Solvent	ultrapure water	10 mL for solution A and 10 mL for solution B	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets
Base	concentrated NH3.H2O	600 uL · 14 mol L-1	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets
Solvent	acetone	reflux workup	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets

Complete recipeSource: Main

Route 2: Other

main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl

Metal precursorsFe powder in bromination step; Pd2(dba)3 catalyst for amination step.

Linker precursorsTriphenylene precursor to HITP.6HCl.

SolventsPhNO2; toluene; THF; aqueous HCl; washing with EtOH, acetone, CHCl3 and petroleum ether/ethyl acetate.

AdditivesBr2, rac-BINAP, C4H9ONa, Ph2C=NH, HCl.

AtmosphereN2 purge for bromination and Pd/rac-BINAP amination steps.

Temperature210 C for 3 h; 110 C for 30 min then 110 C for 12 h; room temperature for HCl deprotection.

Time3 h bromination; 0.5 h catalyst preheat; 12 h amination; 0.5 h HCl deprotection; dried overnight.

Oxidant / reductantBr2 brominating reagent; Fe powder present in bromination step.

Work-upFiltered, washed with EtOH/acetone/CHCl3, rotary evaporated; CH2Cl2 wash/filter; silica chromatography PE:EA (4:1); HCl precipitation, centrifuged and washed with PE three times.

ActivationDried in vacuum oven overnight.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	triphenylene	4.3 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Reductant	Fe powder	1.8 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Solvent	PhNO2	15 mL reaction solution	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Oxidant	Br2	2.23 mL	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Additive	Pd2(dba)3	0.68 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Additive	rac-BINAP	1.38 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Base	C4H9ONa	22.7 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Additive	Ph2C=NH	20.5 mmol	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl
Acid	aqueous HCl	2 mL · 2.0 M	main pp.2-3, article pp.340-341 · 2.2.1. Synthesis of HITP.6HCl

Partial recipeSource: Main

Route 3: Drop Cast

main p.3, article p.341 · 2.5. Electrochemical measurements

Metal precursorsNi3(HITP)2 powder.

Linker precursorsHITP already incorporated in Ni3(HITP)2.

SolventsEthanol, 0.25 mL.

Additives50 uL Nafion solution; 0.5 mg Ketjen carbon black.

Temperatureoven drying temperature not specified

Time60 min ultrasound; drying time not specified

Substrate orientationCarbon paper, 1 cm2.

Work-upInk painted onto carbon paper and dried in oven.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2	1 mg	main p.3, article p.341 · 2.5. Electrochemical measurements
Solvent	ethanol	0.25 mL	main p.3, article p.341 · 2.5. Electrochemical measurements
Additive	Nafion solution	50 uL	main p.3, article p.341 · 2.5. Electrochemical measurements
Additive	carbon black (Ketjen black)	0.5 mg	main p.3, article p.341 · 2.5. Electrochemical measurements

Partial recipeSource: Main

Route 4: Other

main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets

Metal precursorsBulk Ni3(HITP)2.

Linker precursorsHITP already incorporated in bulk Ni3(HITP)2.

SolventsAcetonitrile, 15 mL.

Temperatureroom temperature not explicitly specified

Time24 h sonication

Work-upNo post-sonication separation details provided in the main text.

Scalability context30 mg bulk MOF per 15 mL acetonitrile batch.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	bulk Ni3(HITP)2	30 mg	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets
Solvent	acetonitrile	15 mL	main p.3, article p.341 · 2.2.2. Synthesis of Ni3(HITP)2 nanosheets