Synthesis · A Triptycene-Based 2D MOF with Vertically Extended Structure for Improving the Electrocatalytic Performance of CO2 to Methane

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: Drop Cast

4 · 2.4 The electrochemical reduction of CO2

Solventsisopropanol (0.15 mL) and H2O (0.05 mL)

Additives20 uL of 5 wt% Nafion

Substrate orientation5 mm diameter glassy carbon disk

Work-upSonicate ink for 1 min; drop 5 uL onto GC disk to form working electrode.

ActivationElectrolyte saturated with CO2 or Ar by bubbling for 30 min before electrolysis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2D-vc-MOF(Cu) catalyst	2 mg	4 · 2.4 The electrochemical reduction of CO2
Additive	Nafion	20 uL · 5 wt%	4 · 2.4 The electrochemical reduction of CO2
Solvent	isopropanol	0.15 mL	4 · 2.4 The electrochemical reduction of CO2
Solvent	H2O	0.05 mL	4 · 2.4 The electrochemical reduction of CO2

Complete recipeSource: Both

Route 2: Solvothermal

3 · 2.1.1-2.1.5 · Figures S1-S6

Metal precursorsCu(OAc)2.H2O, 3 equivalents

Linker precursorsHHTC, 2 equivalents

Solventsscreened H2O/MeOH, H2O/DEF, MeOH/DEF, MeOH/1,4-dioxane, H2O/DMAc, H2O/DMF, H2O/NMP, H2O/DMSO; solvent ratios H2O/DEF = 1:3, 1:2, 1:1, 3:1

Additivesscreened TBAH, DBU, NMP, NH3.H2O, KOH, NaOH, TEA, EDA; NaOH amount varied 1-20 uL of 4 M solution

Atmosphereoxygen volume varied; freeze-thaw cycle used for anaerobic condition

Temperature60, 80, 100, 120 screened; 80 optimal

Time12, 24, 72, 120, 168 screened; 120 optimal

Oxidant / reductantO2 volume crucial for crystallinity

Work-upGeneral route filters cooled mixture, washes with H2O and acetone, dries at 60 deg C under vacuum for 12 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Copper acetate monohydrate (Cu(OAc)2.H2O)	3 equiv in main text; 0.03 mmol in SI general procedure	3 · 2.1.1-2.1.5 · Figures S1-S6
Linker	HHTC	2 equiv in main text; 0.02 mmol in SI general procedure	3 · 2.1.1-2.1.5 · Figures S1-S6
Solvent	mixed solvent screen	1.5 mL	3 · 2.1.1-2.1.5 · Figures S1-S6
Base	TBAH, DBU, NMP, NH3.H2O, KOH, NaOH, TEA, or EDA	varied according to SI sections 2.1.1-2.1.4 · TBAH 1 M; KOH/NaOH 4 M; NH3.H2O 25 wt%	3 · 2.1.1-2.1.5 · Figures S1-S6

Complete recipeSource: Both

Route 3: Solvothermal

3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption

Metal precursorsCu(OAc)2 / copper acetate monohydrate, 0.03 mmol, 6 mg

Linker precursorsHHTC, 0.02 mmol, 7 mg

Solvents1.5 mL H2O/DEF (v/v = 1:2)

Additives1 uL of 4 M NaOH

Atmosphereair/oxygen present; anaerobic freeze-thaw condition gave amorphous solid with Cu2O nanoparticles

Temperature80

Time120

Oxidant / reductantO2 in reaction vessel acts as partial oxidant for HHTC/semiquinone formation

Work-upCool to room temperature, filter, wash with H2O (10 mL x 5) and acetone (10 mL x 3), dry at 60 deg C under vacuum for 12 h.

ActivationFor gas adsorption: immerse in anhydrous acetone for 2 days with solvent exchange three times per day, centrifuge, dry at 60 deg C under vacuum for 12 h, evacuate at 25 deg C for 12 h.

Scalability contextReported yield 44%; small-vial recipe uses milligram-scale reagents.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2 / copper acetate monohydrate	0.03 mmol, 6 mg	3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption
Linker	2,3,6,7,14,15-hexahydroxyltriptycene (HHTC)	0.02 mmol, 7 mg	3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption
Solvent	H2O/DEF	1.5 mL; v/v = 1:2	3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption
Base	NaOH	1 uL · 4 M	3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption
Oxidant	O2	ambient vial headspace; optimisation tested 0, 0.5, 1.5, and 3.5 mL O2	3-4 · 2.1.6 The optimal synthetical procedure; 2.2 adsorption

Partial recipeSource: Main

Route 4: Unknown

4 · The e-CO2RR Performance of 2D-vc-MOF(Cu)