Synthesis · Atomically Precise Integration of Multiple Functional Motifs in Catalytic Metal-Organic Frameworks for Highly Efficient Nitrate Electroreduction

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF

Metal precursorsIn(NO3)3.4.5H2O, 0.020 g, 0.052 mmol in main text; SI text has amount omitted but same reagent.

Linker precursorsH4TTFTB, 0.013 g, 0.034 mmol in main text; SI text lists 0.17 mmol, likely OCR/source inconsistency.

Solvents0.5 mL H2O, 2 mL DMF, 0.5 mL ethanol.

Additives0.4 mL CH3COOH.

AtmosphereNot specified.

Temperature120

Time72

Work-upCooled to room temperature at 5 C h-1; red octahedral crystals filtered and washed with DMF and acetone three times.

ActivationNo activation reported.

Scalability contextSingle-crystal solvothermal batch; 0.018 g product, 82.57% yield based on H4TTFTB.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	In(NO3)3.4.5H2O	0.020 g, 0.052 mmol · in 0.5 mL H2O	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF
Linker	H4TTFTB	0.013 g, 0.034 mmol · in 2 mL DMF	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF
Solvent	DMF	2 mL	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF
Solvent	H2O	0.5 mL	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF
Solvent	ethanol	0.5 mL	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF
Acid	CH3COOH	0.4 mL	main p.10, article p.2774 · Methods: Synthesis of Compound 3D In-MOF

Complete recipeSource: Both

Route 2: Solvothermal

SI p.2 · Synthesis of compound In4

Metal precursorsIn(NO3)3.4H2O, 0.010 g, 0.027 mmol in 0.3 mL H2O.

Linker precursorsm-H4TTFTB, 0.010 g, 0.014 mmol; 4,4'-bipy, 0.010 g, 0.064 mmol.

Solvents2 mL DMF and 0.3 mL H2O.

Additives0.15 mL CH3COOH.

AtmosphereNot specified.

Temperature120

Time24

Work-upAllowed to cool to room temperature; red block crystals filtered and washed three times with DMF and acetone.

ActivationNo activation reported.

Scalability contextSingle-crystal solvothermal batch; 0.005 g product, 29% yield based on m-H4TTFTB.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	In(NO3)3.4H2O	0.010 g, 0.027 mmol · in 0.3 mL H2O	SI p.2 · Synthesis of compound In4
Linker	m-H4TTFTB	0.010 g, 0.014 mmol · in 2 mL DMF	SI p.2 · Synthesis of compound In4
Additive	4,4'-bipy	0.010 g, 0.064 mmol · in 2 mL DMF	SI p.2 · Synthesis of compound In4
Solvent	DMF	2 mL	SI p.2 · Synthesis of compound In4
Solvent	H2O	0.3 mL	SI p.2 · Synthesis of compound In4
Acid	CH3COOH	0.15 mL	SI p.2 · Synthesis of compound In4

Complete recipeSource: Both

Route 3: Drop Cast

SI p.6-7 · Electro-catalytic nitrate reduction measurements

Metal precursorsAs-prepared In8 catalyst powder/crystals.

Linker precursorsFramework already synthesised; no free linker added.

SolventsIsopropanol (960 uL) plus Nafion solution (5 wt% in EtOH, 40 uL).

AdditivesNafion binder, 40 uL, 5 wt% in EtOH.

AtmosphereElectrolyte purged with high-purity Ar for 30 min before electrochemical measurement; electrode preparation atmosphere not specified.

Temperatureroom temperature drying

Time0.5 h sonication + 0.5 h sonication + 2 h drying

Substrate orientationCarbon paper electrode, area 1 cm2 immersed.

Work-up100 uL catalyst ink dropped on carbon paper and dried at room temperature for 2 h.

ActivationNo separate activation; 10 CV cycles were used to steady In8 before EIS tests.

Scalability contextElectrode-scale drop-cast preparation; ca. 0.5 mg cm-2 standard loading, with higher loadings studied.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-prepared In8 catalyst	5 mg	SI p.6-7 · Electro-catalytic nitrate reduction measurements
Solvent	isopropanol (IPA)	960 uL	SI p.6-7 · Electro-catalytic nitrate reduction measurements
Additive	Nafion in EtOH	40 uL · 5 wt%	SI p.6-7 · Electro-catalytic nitrate reduction measurements
Other	carbon paper	1 x 2 cm2 paper, 1 x 1 cm2 immersed area	SI p.6-7 · Electro-catalytic nitrate reduction measurements

Complete recipeSource: SI

Route 4: Air Liquid Interface

SI p.5 · Fabrication of the In8 MOF devices · Fig. S63

Metal precursorsAs-prepared In8 suspension in ethanol, about 3 mg mL-1.

Linker precursorsFramework already synthesised; no free linker added.

SolventsEthanol (2 mL), DI water (6.0 mL), n-butanol (2.5 mL), water subphase.

AdditivesPMMA A8 resist; Ti/Au electrodes; no chemical additive to MOF suspension beyond co-solvents.

AtmosphereNot specified.

Temperatureroom temperature

TimeNot specified.

Substrate orientationp++ silicon wafer with 300 nm thermal oxide and pre-patterned Ti/Au electrodes (20/50 nm); electrochemical windows 20 um x 40 um.

Work-upFree-standing film formed on water surface, transferred to substrate, PMMA template removed, second PMMA layer deposited and smaller EBL window opened.

ActivationNo activation reported before ETS; device used for on-chip electrochemistry.

Scalability contextMicrofabricated on-chip device; not a bulk scalable synthesis route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	In8 suspension in ethanol	2 mL · ~3 mg mL-1	SI p.5 · Fabrication of the In8 MOF devices · Fig. S63
Solvent	DI water	6.0 mL plus water subphase · milli-Q filtered	SI p.5 · Fabrication of the In8 MOF devices · Fig. S63
Solvent	n-butanol	2.5 mL	SI p.5 · Fabrication of the In8 MOF devices · Fig. S63
Other	PMMA A8	not specified	SI p.5 · Fabrication of the In8 MOF devices · Fig. S63
Other	Ti/Au electrodes	20/50 nm	SI p.5 · Fabrication of the In8 MOF devices · Fig. S63

Complete recipeSource: Both

Route 5: Solvothermal

SI p.2-3 · Synthesis of compound In8

Metal precursorsIn(NO3)3.4H2O, 0.010 g, 0.027 mmol in 0.5 mL H2O.

Linker precursorsH8TTFOC, 0.010 g, 0.012 mmol in 2 mL DMF.

Solvents2 mL DMF and 0.5 mL H2O.

Additives0.050 mL H2SO4.

AtmosphereNot specified.

Temperature120

Time72

Work-upAllowed to cool to room temperature at 5 C h-1; red block crystals filtered and washed three times with DMF and acetone.

ActivationNo activation reported.

Scalability contextSingle-crystal solvothermal batch; 0.006 g product, 31% yield based on H8TTFOC.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	In(NO3)3.4H2O	0.010 g, 0.027 mmol · in 0.5 mL H2O	SI p.2-3 · Synthesis of compound In8
Linker	H8TTFOC	0.010 g, 0.012 mmol · in 2 mL DMF	SI p.2-3 · Synthesis of compound In8
Solvent	DMF	2 mL	SI p.2-3 · Synthesis of compound In8
Solvent	H2O	0.5 mL	SI p.2-3 · Synthesis of compound In8
Acid	H2SO4	0.050 mL	SI p.2-3 · Synthesis of compound In8